Particulate-Filled Polymer Composites

Particulate-Filled
Polymer
Composites
Second Edition
Editor
R.N. Rothon
Rapra Technology Limited

Particulate-Filled Polymer
Composites
2nd Edition
Editor: Roger N. Rothon
rapra TECHNOLOGY
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2003 by

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
2003, Rapra Technology Limited
All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
Every effort has been made to contact copyright holders of any material
reproduced within the text and the authors and publishers apologize if
any have been overlooked.
Cover micrograph of aramid fibre-reinforced polyamide 6,6, reproduced with permission from
P.R. Hornsby, Brunel University, UK.
ISBN: 1-85957-382-7
Typeset by Rapra Technology Limited

Cover printed by The Printing House, Crewe, Cheshire, UK
Printed and bound by Rapra Technology Limited, Shrewsbury, UK
Contents
Preface ................................................................................................................... 1
Contributors .......................................................................................................... 3
1 General Principles Guiding Selection and Use of Particulate Materials ........... 5

1.1 Introduction ........................................................................................... 5
1.2 Basic Characteristics of Particulate Fillers .............................................. 5
1.2.1 Cost ........................................................................................... 6
1.2.2 Chemistry, Composition and Impurities..................................... 7
1.2.3 Density or Specific Gravity ........................................................ 9
1.2.4 Hardness .................................................................................. 10
1.2.5 Abrasiveness ............................................................................ 11
1.2.6 Optical Properties .................................................................... 11
1.2.7 Thermal Properties .................................................................. 14
1.2.8 Particle Shape and Size............................................................. 16
1.2.9 Shape ....................................................................................... 17
1.2.10 Particle Size .............................................................................. 20
1.3 Surface Modification ............................................................................... 26
1.3.1 Stearic Acid and Stearates ........................................................ 26
1.3.2 Coupling Agents ...................................................................... 27
1.3.3 Polymer Modifications............................................................. 27
1.3.4 Direct Bonding ......................................................................... 28
1.4 Particle Packing and the Maximum Packing Fraction .......................... 29
1.4.1 Introduction ............................................................................. 29
1.4.2 Determination of Maximum Packing Fraction (Pf) by Oil
Absorption Procedures............................................................. 29
1.4.3 Particle Packing Theory ........................................................... 30
i
Particulate-Filled Polymer Composites
1.4.4 Applications of Packing Principles to Particulate Filled

Composites .............................................................................. 33
1.5 Interparticle Spacing ............................................................................ 34
1.6 Particle Effects on the Structure of Polymers ........................................ 36
1.6.1 Introduction ............................................................................. 36
1.6.2 Molecular Weight Reduction During Processing ...................... 36
1.6.3 Molecular Weight and Crosslinking Changes due to
Cure Modifications .................................................................. 37
1.6.4 Preferential Adsorption of Polar Species .................................. 37
1.6.5 Formation of an Interphase of Immobilised Polymer ............... 38
1.6.6 Effects on Polymer Conformation due to the Presence of
Particle Surfaces and Interparticle Spacing ............................... 42
1.6.7 Effects on Crystallinity............................................................. 42
References ..................................................................................................... 45
2 Principal Types of Particulate Fillers ............................................................. 53

2.1 Introduction ......................................................................................... 53
2.2 Particulate Fillers from Natural Origins (Mineral Fillers) .................... 53
2.2.1 Introduction ............................................................................. 53
2.2.2 Minerals and Rocks ................................................................. 54
2.2.3 Rocks ....................................................................................... 55
2.2.4 Calcium Carbonate Minerals ................................................... 57
2.2.5 Dolomite .................................................................................. 61
2.2.6 China Clay or Kaolin ............................................................... 61
2.2.7 Calcined Clay .......................................................................... 66
2.2.8 Mica ........................................................................................ 69
2.2.9 Talc .......................................................................................... 70
2.2.10 Montmorillonite (AlMg)8(Si4O10)3-(OH)10.12H2O ................... 72
2.2.11 Barite (BaSO4).......................................................................... 73
2.2.12 Calcium Sulfate Products ......................................................... 74
2.2.13 Wollastonite (CaSiO3) .............................................................. 74
2.2.14 Crystalline Silicas ..................................................................... 76
ii
Contents
2.3 Synthetic Particulate Fillers .................................................................. 78

2.3.1 Carbon Black ........................................................................... 78
2.3.2 Synthetic Silicas ....................................................................... 81
2.3.3 Hydroxides and Basic Carbonates ........................................... 84
2.3.4 Precipitated Calcium Carbonate (PCC) .................................... 96
Acknowledgements ....................................................................................... 96
References ..................................................................................................... 97
3 Analytical Techniques for Characterising Filler Surfaces ............................. 101

3.1 Introduction ....................................................................................... 101
3.2 Acid-Base Theory ............................................................................... 104
3.2.1 Introduction ........................................................................... 104
3.2.2 Gutmann Approach ............................................................... 105
3.2.3 Drago Approach .................................................................... 106
3.2.4 Use in Characterising Fillers .................................................. 106
3.3 Analytical Techniques ........................................................................ 108
3.4 Reactive Techniques ........................................................................... 109
3.4.1 Flow Microcalorimetry .......................................................... 109
3.4.2 Inverse Gas Chromatography ................................................ 119
3.5 Spectroscopic Techniques ................................................................... 124
3.5.1 Introduction ........................................................................... 124
3.5.2 X-Ray Photoelectron Spectroscopy ........................................ 124
3.5.3 Secondary Ion Mass Spectrometry ......................................... 130
3.5.4 Diffuse Reflectance Fourier Transform Infrared Spectroscopy . 134
3.6 Methods for Examining Structural Order in Filler Coatings .............. 145
3.6.1 Wide Angle X-Ray Diffraction ............................................... 145
3.6.2 Differential Scanning Calorimetry ......................................... 146
3.7 Summary ............................................................................................ 147
References ................................................................................................... 148
iii
4 Surface Modification and Surface Modifiers ............................................... 153
4.1 Introduction ....................................................................................... 153
4.2 Reasons for Using Surface Modifiers ................................................. 153
4.3 General Principles of Surface Modification ........................................ 154
4.4 Methods of Using Surface Modifiers .................................................. 155
4.5 Choice of Coating Level ..................................................................... 156
4.6 Techniques for Determining the Amount of Coating Present,

and Assessing the Amount Needed for Mono-layer Coverage ........... 158
4.6.1 Determination of Amount of Additive and its Distribution ... 158
4.6.2 The Monolayer and its Determination .................................. 160
4.6.3 Effects of Processing on the Coating Structure ....................... 163
4.7 Surface Modifier Types ...................................................................... 163
4.7.1 Monomeric Organic Acids and their Salts ............................. 163
4.7.2 Stearic Acid (CH3(CH2)16COOH ........................................... 166
4.7.3 Other Saturated Fatty Acids and Related Substances ............. 170
4.7.4 Effects of Stearic Acid Coating in Composites ....................... 171
4.7.5 Fatty Acid Salts ...................................................................... 173
4.7.6 Unsaturated and other Functional Organic Acids
in Composites ........................................................................ 173
4.7.7 Polymeric Acids and Anhydrides ........................................... 175
4.7.8 Organo-silicon Compounds ................................................... 177
4.7.9 Examples of Silane Coupling Agent Effects in
Filled Polymers ...................................................................... 190
4.7.10 Organo-Titanates and Zirconates .......................................... 191
4.7.11 Aluminates and Zircoaluminates ........................................... 198
4.7.12 Phosphates and Borates ......................................................... 199
4.7.13 Organic Amines and Amino-acids ......................................... 200
4.8 Conclusions ....................................................................................... 200
References ................................................................................................... 201
iv
Contents
5 Compound Preparation, Mixture Characterisation and Process

Enhancement of Particulate-Filled Polymer Compounds ............................. 207
5.1 Introduction ....................................................................................... 207
5.2 Functional Characteristics of Compounding Machinery .................... 209
5.2.1 Transport of Feedstock .......................................................... 210
5.2.2 Melting and Shear Heating .................................................... 213
5.2.3 Mixing ................................................................................... 214
5.2.4 Melt Devolatilisation ............................................................. 217
5.2.5 Melt Pumping and Pressurisation .......................................... 218
5.3 Constructional Design of Compounding Plant ................................... 219
5.3.1 Low and Medium Intensity Premixing Procedures ................. 220
5.3.2 High-Intensity Compounding Machinery .............................. 221
5.4 Characterisation of Filled Compounds .............................................. 228
5.4.1 Introduction ........................................................................... 228
5.4.2 Residence Time Distribution .................................................. 229
5.4.3 Specific Energy Input ............................................................. 231
5.4.4 Screen Pack Analysis .............................................................. 231
5.4.5 Rheological Analysis .............................................................. 232
5.4.6 Ultrasonic Measurement ........................................................ 233
5.4.7 Microstructural Analysis........................................................ 235
5.4.8 Miscellaneous Methods of Analysis ....................................... 239
5.5 Process Enhancement of Particulate Polymer Composites .................. 240
5.5.1 Addition of Rigid Particulate Fillers ....................................... 241
5.5.2 Effects on Polymer Molecular Weight .................................... 243
5.5.3 Short Fibre-Reinforced Thermoplastics Composites .............. 244
5.6 Woodflour and Natural Fibre-Filled Thermoplastics ......................... 246
5.7 Supercritical Fluid Assisted Processing of Filled Compounds ............. 249
5.8 Processing of Thermoset Recyclate Waste Materials .......................... 250
5.9 Preparation of Silicate Layer Polymer Nanocomposites ..................... 251
v
5.10 Conclusions ....................................................................................... 254

References ................................................................................................... 254
6 Effects of Particulate Fillers on Flame Retardant Properties of Composites ... 263

6.1 Introduction ....................................................................................... 263
6.2 General Effects of Fillers on Polymer Flammability ........................... 263
6.3 Fire Retardant Testing........................................................................ 264
6.3.1 Oxygen Index Test (ASTM D2863-87) .................................. 266
6.3.2 Underwriters Laboratory Vertical Burn Test (UL94 -1980) .... 266
6.3.3 Horizontal Burn Test (ASTM D635-88) ................................ 267
6.3.4 Ignitability Test (ISO5657 1986) ........................................... 267
6.3.5 Cone Calorimeter (ASTM E1354, ISO 5660) ........................ 267
6.3.6 Smoke and Corrosive Gas Tests ............................................. 268
6.4 Fire Retardant Fillers that Rely on Endothermic Decomposition ....... 269
6.4.1 Historical Background ........................................................... 269
6.4.2 Potential Endothermic Flame Retardant Fillers ...................... 270
6.4.3 Performance of Endothermic Flame Retardant Fillers ............ 273
6.4.4 Smoke and Corrosive and Toxic Gases .................................. 290
6.5 Nano-Clays ........................................................................................ 296
6.6 Ammonium Polyphosphate (APP) ...................................................... 297
6.7 Fillers for Use in Conjunction with Halogens .................................... 297
References ................................................................................................... 298
7 Particulate Fillers in Elastomers .................................................................. 303

7.1 Introduction ....................................................................................... 303
7.2 Uses of Elastomers ............................................................................. 303
7.3 Elasticity of Rubber ........................................................................... 303
7.4 Formulation of Elastomers ................................................................. 306
7.4.1 General .................................................................................. 306
vi
Contents
7.4.2 Selection of Polymer .............................................................. 306

7.4.3 The Curing System ................................................................. 308
7.4.4 Antioxidants and Antiozonants ............................................. 310
7.4.5 Coupling Agents .................................................................... 311
7.4.6 Process Oils and Plasticisers ................................................... 311
7.4.7 Fillers ..................................................................................... 313
7.4.8 Specialty Additives ................................................................. 314
7.5 The Performance of the Polymer ........................................................ 317
7.5.1 Specification of the Polymer .................................................. 317
7.5.2 Processing Considerations ..................................................... 321
7.5.3 Strength Characteristics of Polymers ...................................... 321
7.5.4 Compounding Considerations ............................................... 322
7.6 The Performance of Fillers ................................................................. 326
7.6.1 Reinforcement of Rubber by Fillers ....................................... 326
7.6.2 Processing Considerations ..................................................... 330
7.6.3 Compounding Considerations ............................................... 333
7.7 Filler Types ........................................................................................ 338
7.7.1 Specification of Fillers for Elastomers .................................... 338
7.7.2 Carbon Black ......................................................................... 340
7.7.3 Synthetic Silicas and Silicates ................................................. 343
7.7.4 Clay Minerals ........................................................................ 344
7.7.5 Calcium Carbonates .............................................................. 346
7.7.6 Alumina Trihydrate ............................................................... 348
7.7.7 Talcs ...................................................................................... 349
7.7.8 Natural Silicas ....................................................................... 349
7.7.9 Barytes and Blanc Fixe ........................................................... 350
7.7.10 Miscellaneous ........................................................................ 350
Acknowledgements ..................................................................................... 350
References ................................................................................................... 351
vii
8 Filled Thermoplastics .................................................................................. 357

8.1 Introduction ....................................................................................... 357
8.1.1 Thermoplastics and Typical Applications .............................. 357
8.1.2 Thermoplastic Composites..................................................... 359
8.2 Bulk and Process Related Properties .................................................. 361
8.2.1 Specific Gravity or Relative Density ....................................... 361
8.2.2 Acoustic Properties ................................................................ 362
8.2.3 Melt Viscosity (MFI) .............................................................. 363
8.2.4 Compounding and Extrusion ................................................. 364
8.2.5 Thermal Conductivity and Specific Heat Capacity ................ 367
8.2.6 Thermal Expansion ................................................................ 368
8.2.7 Electrical Properties ............................................................... 369
8.2.8 Barrier Properties ................................................................... 370
8.3 Mechanical Properties ........................................................................ 371
8.3.1 Introduction ........................................................................... 371
8.3.2 Modulus Tensile and Flexural ............................................. 372
8.3.3 Heat Deflection Temperature (HDT) ..................................... 374
8.3.4 Yield Strength ........................................................................ 375
8.3.5 Impact Strength (Toughness) .................................................. 376
8.4 Effects of Filler on the Polymer Phase ................................................ 380
8.4.1 Introduction ........................................................................... 380
8.4.2 Nucleation ............................................................................. 380
8.4.3 Transcrystallinity ................................................................... 381
8.4.4 Interphase .............................................................................. 382
8.5 Surface Science Aspects ...................................................................... 383
8.5.1 Introduction ........................................................................... 383
8.5.2 Surface Energy and Surface Tension....................................... 383
8.5.3 Wetting and Spreading ........................................................... 384
8.5.4 Adhesion ................................................................................ 384
8.5.5 Dispersion and Agglomeration .............................................. 387
8.5.6 Surface Treatments Dispersants and Coupling Agents ........ 388
viii
Contents
8.6 Aesthetics ........................................................................................... 390

8.6.1 Introduction ........................................................................... 390
8.6.2 Colour/Pigmentation .............................................................. 390
8.6.3 Surface Finish and Gloss ........................................................ 390
8.6.4 Scratch and Abrasion Resistance ........................................... 391
8.7 Stabilisation and Recycleability ......................................................... 392
8.7.1 Introduction ........................................................................... 392
8.7.2 The Effect of Filler Chemistry and Impurities on Stability ..... 393
8.7.3 The Effect of Antioxidant Adsorption on Stability ................ 394
8.7.4 Recycleability ......................................................................... 395
8.8 Uses of Filled Thermoplastics............................................................. 396
8.8.1 Uses of Fillers ......................................................................... 396
8.8.2 Fillers in PVC ......................................................................... 397
8.8.2 Uses of Fillers in Unplasticised PVC ....................................... 401
8.8.3 Uses of Fillers in Polypropylene ............................................. 403
8.8.4 Uses of Fillers in Polyethylene ................................................ 406
8.8.5 The Use of Fillers in Polyamides ............................................ 408
8.8.6 Polybutylene Terephthalate .................................................... 409
8.8.7 Polyethylene Terephthalate .................................................... 410
8.9 Conclusions ....................................................................................... 411
References ................................................................................................... 413
9 Filled Thermosets ........................................................................................ 425

9.1 Introduction ....................................................................................... 425
9.2 Brief Chemistry of Thermoset Polymers ............................................. 427
9.2.1 Free-Radical Chain-Growth Curing Resins ............................ 427
9.2.2 Step Addition Curing Resins .................................................. 435
9.2.3 Condensation Resins .............................................................. 440
9.3 Mechanical Properties ........................................................................ 444
ix
9.3.1 Modulus ................................................................................ 444

9.3.2 Fracture Toughness and Fracture Energy ............................... 450
9.3.3 Failure Stress .......................................................................... 463
9.3.4 Fatigue ................................................................................... 469
9.4 Applications ....................................................................................... 477
9.4.1 Cost Reduction ...................................................................... 477
9.4.2 Modified Mechanical Properties ............................................ 477
9.4.3 Exotherm Control .................................................................. 478
9.4.4 Shrinkage Control .................................................................. 480
9.4.5 Processing Aids ...................................................................... 481
9.4.6 Flame Retardants ................................................................... 482
9.4.7 Metal Fillers ........................................................................... 482
9.4.8 Structural Adhesives .............................................................. 483
References ................................................................................................... 484
10 Composites Using Nano-Fillers ................................................................... 489

10.1 Introduction ....................................................................................... 489
10.2 Scope ................................................................................................. 489
10.3 General Comments ............................................................................ 490
10.4 Nano-Filler Forms ............................................................................. 490
10.4.1 Regular Shapes ...................................................................... 491
10.4.2 Rods, Fibres, etc. ................................................................... 492
10.4.3 Platy Nano-Fillers (Nano-Clays and Related Materials) ........ 493
10.5 Summary and Future Perspectives ...................................................... 510
References ................................................................................................... 511
Abbreviations and Acronyms ...................................................................... 515
Author Index ............................................................................................... 521
Index ........................................................................................................... 527
x
Preface
I was delighted to accept the chance offered by Rapra Technology to produce this updated
second edition of Particulate Filled Polymer Composites, a book first published in 1995.
The first edition had been very well received but has been out of print for some time.
Despite the relatively short time since the publication of the first edition, much has changed
and hence considerable new material has been introduced, including a completely new
chapter covering the latest developments in nano-filler technology.
The use of particulate fillers in polymers has a long history, and they continue to play a
very important role today. Despite the apparent commodity status, the area is still very
dynamic and considerable changes have occurred in applications over the last few years.
The most significant of these have been the dramatic growth in the use of precipitated
silica in energy efficient tyre applications and the emergence of nano-filler technologies.
The multidisciplinary nature of this topic is well illustrated by the scope of the references
in the book. These are drawn from many fields, including: mineralogy, crystallography,
precipitation and crystal growth, powder technology, surface and colloid science, organic
and organo-metallic chemistry, optics, materials science, and polymer science and
technology. It also brings together people from many backgrounds, such as filler producers,
machinery manufacturers, polymer compounders and suppliers of processing aids and
surface modifiers.
Together with my co-authors, I have set out to describe the fundamentals involved in
producing, characterising and using particulate fillers in as clear and concise a way as
possible. The authors have been encouraged to pay particular attention to those areas of
their subjects which their experience shows cause the most confusion, or which are poorly
covered elsewhere. Most importantly, where a topic is controversial, or poorly understood,
they have been encouraged to interpret the existing literature, not merely quote opposing
views, as is often the case. Where possible, use has been made of previously unpublished
work to illustrate key points and extensive literature references are provided so that any
subject can be followed up in depth, if needed.
Chapter 4, on surface modification, is a good example of the approach taken. Most

works concentrate on the organo-silanes. While they are still treated in detail here,
significant space is also given to fatty acids and organo-titanates. Fatty acids are of
considerable commercial importance and exhibit complexities that can cause problems
1
for the unwary. Considerable controversy exists over the mode of action of the organo-
titanates and the available scientific literature is critically reviewed here.
As with any editor, I am very much indebted to my co-authors for their hard work. I am
also indebted to the staff at Rapra Technology, especially Frances Powers, for their help
and support in turning the various contributions into a very well presented composite.
Finally, I would like to express my particular thanks to the late Professor Derek Birchall,
FRS, who first aroused my interest in this area and to the late Hugh Olmstead founder of
Intertech Corporation and to my many friends and colleagues, especially those at
Manchester Metropolitan University, Avecia Limited, Colin Stewart Minchem, CSIRO
Division of Minerals, Electrolux and the Intertech Corporation, who have helped me to
continue this interest in recent years.
Roger N. Rothon
July 2003
2
Contributors
David Ashton Christopher Liauw

ICI Acrylics Manchester Metropolitan University
PO Box 34 Centre For Materials Science Research
Darwen John Dalton Building
Lancashire BB3 1QB Chester Street
Manchester M1 5GD
David Briggs
Siacon Consultants Ltd. Michael Orton
21 Woodfarm Road 24, School Lane
Malvern Hartford
Worcestershire WR14 4RL Cheshire CW8 1PE
Chris DeArmitt Roger Rothon

BASF Aktiengesellschaft Rothon Consultants and
KSP/S-E100 Manchester Metropolitan University
67056 Ludwigshafen 3 Orchard Croft
Germany Guilden Sutton
Chester CH3 7SL
Michael Hancock
6 Poltair Avenue David Skelhorn
St Austell Performance Materials Division
Cornwall PL25 4LY Imerys
100 Mansell Court East
Graham Jackson Suite 300
LGC Ltd. Roswell
The Heath Georgia 30076
Runcorn USA
Cheshire WA7 4QD
Howard Taylor
Peter Hornsby Manchester Metropolitan University
The Wolfson Centre Department of Engineering and
Brunel University Technology
Uxbridge John Dalton Building
Middlesex UB8 3BH Chester Street
Manchester M1 5GD
3
4
1
General Principles Guiding Selection and Use
of Particulate Materials
Roger N. Rothon and Michael Hancock
1.1 Introduction
Particulate-filled polymer composites have a long history and consequently newcomers

to the field usually expect to find an area of well-understood science with few intellectual
challenges remaining. However, they are usually amazed to find that this is far from the
truth in many areas, with few reliable generalisations (but several unreliable ones) available
and much basic information yet to be established. This is largely due to the way in which
the technology has developed, with different filler and polymer combinations tending to
be developed largely piecemeal to meet the specific demands of various industries. The
initial, and to some extent continuing, emphasis on cost reduction has also meant that
many fillers have been poorly characterised.
The purpose of this chapter is to give readers sufficient background so that they may
approach the subject with an open mind and see the whole area as one with stimulating
intellectual challenges, not as an area of mystery and witchcraft. This chapter discusses
how fillers can be characterised and defined with the least ambiguity, and hence how
their behaviour in composites can be understood and hopefully predicted. We also
highlight the principal sources of misunderstandings and the limitations imposed by
commonly used methods of measurement, and explain why and where deviations from
general rules are likely to occur.
1.2 Basic Characteristics of Particulate Fillers
In developing a particulate-filled composite, the formulator needs to be able to answer

the following questions:
1. What property benefits are being sought?
2. What deleterious changes may also occur and can they be tolerated?
3. How easy is the filler to handle and how might it affect processing?
5
4. Are special additives needed?
5. What is the true cost of using the filler, is it justifiable, and are there more cost
effective alternatives?
Important information for answering the above questions includes, cost, purity, particle
size and shape, density, hardness, optical and thermal properties and chemistry. The
primary source of this information should be the filler supplier, although frequently data
may be sparse. A brief description of each factor, its measurement and significance follows.
1.2.1 Cost
In theory this is a fairly simple topic, but one that causes considerable problems for the
unwary. It is widely assumed that polymers are expensive and fillers are cheap, and
many articles on filled polymers start with the statement that fillers are used primarily
to reduce costs. While this can often be the case, these savings are frequently not as
great as anticipated and, in quite a few instances, compound costs, even with the lowest
cost filler, can be higher than the unmodified polymer. There are two principal reasons
for this.
Firstly, the process of compounding filler into polymer costs money in the form of capital
investment, manpower and energy [1]. In cases where compounding is essential, because
other additives such as stabilisers or curatives have to be added to the polymer, then the
cost of incorporating a filler is markedly reduced. In these cases, exemplified by elastomers,
polyvinyl chloride (PVC) and thermosets, the use of fillers is the rule rather than the
exception, unlike the case with, say, polyethylene.
Secondly, prices of fillers and polymers are usually quoted in weight terms, while the
majority of their composites are used on a volume basis. The specific gravity of most
fillers is two to three times that of common polymers and, while raw material savings
may accrue on a weight basis, more mass of the final compound will have to be used to
achieve the same volume than would be the case with the unfilled polymer. When looking
at potential cost savings, comparison of polymer and filler costs must therefore be made
on a volume basis. On this basis one should generally regard the effective raw material
costs of mineral fillers as two to three times their price (by weight). As a consequence
many fillers will not give significant cost savings in the commodity plastics, such as
polypropylene (PP) and this explains why the emphasis today is on achieving specific
effects. However, while fillers may not cheapen a filled composite they may well produce
a cost-property performance that allows the composite to compete against and often
replace more expensive systems.
6
General Principles Guiding Selection and Use of Particulate Materials
1.2.2 Chemistry, Composition and Impurities
While the chemical nature of the filler is frequently of little direct importance to its use in
composites, it plays two important roles, in that it determines the structure of the mineral,
and also the nature of the interaction between polymer and filler. However, away from
these a priori considerations, only in a few cases does the chemical reactivity of the filler
play a significant role in the properties of a composite.
1.2.2.1 Bulk Chemistry
Intrinsically fillers can be divided into two types, reactive and inert. Reactive fillers will
react with their environment. A good example of this is gibbsite (aluminium hydroxide),
which will react with both acidic and basic substances. Aluminium hydroxide also loses
its water of crystallisation at around 200 C and this enables it to provide fire retardancy
in polymer formulations. The silicate minerals: (kaolin, mica, talc, quartz, etc.), are, in
classical chemical terms, virtually inert, only being attacked by very strong acids and
alkalis. The carbonate minerals and the hydroxide minerals are very reactive to acids.
The interactions between the constituent elements in a filler determine its molecular structure
and hence crystallinity, which then dictates all the intrinsic properties of the filler.
1.2.2.2 Surface Chemistry
Filler surface chemistries are of more significance than the bulk ones, as they determine
both the rate of wetting and the strength of interaction with polymers. They are invariably
different from bulk chemistry but, unfortunately, they are poorly characterised for many
fillers. Because of the interest in this very important topic, techniques for surface
characterisation are covered in detail in Chapter 3.
1.2.2.3 Surface Interactions
Polymers have a very much higher (20-30 times) thermal expansion coefficient than
mineral fillers. Thus, in many well-dispersed, hot processed composites, a radial
compressive stress develops as the polymer cools leading to an intimate interaction between
matrix and filler. The value of this stress can be calculated, and depends on both polymer
and filler [2]. Because of this, the interaction will at the very least be mechanical, but
other types will exist depending on the surface chemistry of the filler and also the chemistry
of the polymer.
7
Wettability of filler by polymer is an indication of compatibility between the two. Wettability

by polymer is not readily measured directly, but the effect that the material has on surface
tension of a liquid is a measure of its surface energy. Usually water is chosen as the medium.
Schlumf [3] has reported surface energies for a variety of fillers (Table 1.1). There have
been a wide number of claims that surface energies determine the forces between polymer
chains and different phases, determining mechanical properties of the composite. Adhesion
at a polymer-filler interface has been shown to exert a considerable influence on mechanical
responses, and a correlation between acid-base characteristics of filler and polymer (as
determined by inverse gas chromatography) and properties has been established [4]. Lewis
acid-base interactions between filler and polymer are claimed to be the most important
component in the adhesion of a filler to polymers and thus in determining properties of
composites [5]. For some filler-polymer systems, the strength of interfacial acid-base bonding
may be appreciably enhanced by surface modification of the filler, or by modification of
the polymer, giving large increases in properties.
Table 1.1 Surface energies of fillers and plastics

Material Surface energy (m Jm-2)
Diamond 10,000
Mica 240-500
Glass 1,200
Titanium dioxide 650
Kaolin 500-600
Calcium carbonate 65-70
Stearate coated calcium carbonate 25-30
Talc 65-70
Polymers 15-60
Polypropylene 31
1.2.2.4 Chemical Analysis and Impurities
The purity of a filler is of importance both commercially and technically, i.e., the users
need to know what they are buying, whether it contains components that may be
detrimental to the properties of their product and whether it will cause environmental
problems. Impurities include trace elements that may be on the filler surface or in the
structure of the filler and ancillary minerals, which will have been formed at the same
8
time as the main mineral (see Chapter 2). Sometimes additives from the filler
manufacture may be present, (e.g., surfactants). The form of the impurity can be very
important in determining its importance. Sometimes a potentially detrimental impurity
can be tolerated in relatively high levels, if present in an inert form, but small traces of
the same impurity, if present on the surface in an active form, can be very deleterious.
Examples are certain transition metals, (e.g., iron, manganese, copper), which can
seriously affect colour and thermal stability if present in an active form, even at levels
of a few parts per million. Thus some micas and talcs can contain high levels of iron in
an inert form, which is not detrimental to polymer ageing, while others can have lower
levels of more active material. Some impurities may also pose health hazards, examples
being crystalline silica and asbestos. Fillers are not always analysed for such low-level
impurities and it is a mistake to believe that, if a possible deleterious impurity is not
quoted in a data sheet, it is not present in the product. Conversely, it must be stressed
that, if an element or substance is present in a non-active form, it may have little effect
on polymer properties [6].
It is also necessary to point out that the way chemical composition is presented, can, and
does, cause misunderstandings. Because of the methods of analysis used, many mineral
compositions are quoted as a list of oxides rather than the actual constituent chemical.
Thus a calcium carbonate may be specified as so many percent CaO or a clay may be
reported in terms of SiO2 and Al2O3. This does not imply that any of the oxides are
present in the free state. It should also be recognised that some standard methods of
analysis do not detect very light elements.
1.2.3 Density or Specific Gravity
This is one of the simplest of properties to define, understand and use. Density is mass
per unit volume with SI (Systme Internationale) units of kilograms per cubic meter.
Specific gravity and relative density, the weight of the substance in relation to the weight
of an equivalent volume of water, are often used synonymously. They are dimensionless
but have the same numerical values as density.
Density is determined by the size of the atoms forming the mineral, the closeness with
which they are packed together and by impurities present in the crystal lattice: the heavier
the atoms and the more tightly they are packed together, the higher the density. Thus,
smithsonite, ZnCO3, has a higher specific gravity (4.3) than calcite, CaCO3 (2.7) because
zinc has a much higher atomic mass than calcium, but magnesite, MgCO3, has a higher
specific gravity (3.0-3.2) than calcite despite the fact that magnesium is lighter than
calcium. This is because its ions pack much more closely together. In some fillers air is
deliberately introduced into a matrix to reduce its density.
9
True specific gravities of particulate additives can range from less than 1.0 for hollow
glass beads to over 6.0 for some metallic fillers, but most lie in the range 1.6-2.8, while
common polymers range from 0.9 to 1.4.
Powder densities are of commercial importance, indicating ease of handling, and polymer
compounding, and even affecting plant design. Values for bulk and packing densities are
usually supplied by filler producers and are a measure of how the powder packs under
various conditions. They are determined to some extent by the true density, particle
shape and size of the filler, but the processing involved in its production also plays an
important role. Surface treatments, and the methods used to apply them, can also be
important.
A powder with a low bulk density relative to its true density will contain a great deal of
air. It will flow easily but will be difficult to incorporate into polymers, especially in
equipment such as internal mixers and screw compounders.
1.2.4 Hardness
Hardness is the resistance of a mineral to scratching. It is related to the structure of the

mineral, the strength of the chemical bonds and the density of packing of its constituent
atoms. F. Mohs, a mineralogist drew up a table of hardness in 1812 called the Mohs
Hardness Scale (Table 1.2), which is still used to rank minerals by their resistance or
susceptibility to scratching by other minerals. This scale is widely used for mineral fillers,
but care must be taken in using the data because the scale is not linear, with the differences
becoming greater at the high end. The hardness of most common particulate fillers range
from 1 to 4. Talc is the softest, with a value of one.
Table 1.2 Mohs scale of mineral hardness

1 Talc (softest) 5 Apatite 8 Topaz
2 Gypsum 6 Orthoclase 9 Corundum
3 Calcite 7 Quartz 10 Diamond
4 Fluorite
Hardness must not be confused with toughness, which relates to the ability of the mineral
to resist fracture. Hard minerals can often fracture very easily, for example, by cleavage
along crystal planes.
10
Where mixed fillers are used, if one is much harder than the other, then abrasion of the
softer one may occur. This is of particular importance when hard particulates are used
with easily damaged glass fibres.
Minerals such as talc are soft because they readily delaminate due to weak structural
features (see Chapter 2). Such soft particles can fracture or cleave when polymer
composites are deformed, thus limiting their reinforcing properties [7].
1.2.5 Abrasiveness
Abrasion due to the filler has quite an important role in the processing of filled polymers.
It has several origins. Mohs hardness is a major factor with the harder minerals, such
as quartz and wollastonite (CaSiO3), approaching, or even exceeding the hardness of
the metals used in processing. Large particles and angular particles with sharp edges
are particularly detrimental, probably due to a scratching mechanism, followed by
attrition of the exposed edges. Sometimes the coarse component of a filler may be
predominantly a harder impurity, which leads unfortunately to a combination of the
two mechanisms.
Chemical attack may also be caused by some reactive fillers, leading to etching and
progressive erosion.
1.2.6 Optical Properties
The colour, opacity and gloss of a composite are very important, both aesthetically and
functionally, and will be strongly affected by the incorporation of fillers. When light
strikes any surface, it is subjected to several effects: absorption, scattering, reflection,
polarisation and interference. The extent of each effect is dependent on the nature of
both exit and entrance media, but for all practical purposes only three media, air, filler
and polymer, will be considered here in a superficial treatment. The reader is referred to
works such as by Bohren and Huffman for a detailed explanation [8].
A light ray incident upon an air-solid interface at an angle, i, will be bent or refracted
somewhat normal to the interface, at an angle of refraction, r. A relationship of the
incident angle, i, and the refracted angle, r, sin i/sin r, is constant for a given isotropic
solid. The constant always denoted as n is called the refractive index. The refractive
index of a filler is one of the most important parameters affecting the optical properties
of a filled polymer system and is always quoted relative to air. It is, in fact, a manifestation
of the ratio of the speed of light in air to its speed in the solid.
11
The refractive index of a mineral is the sum of the specific refractive indices of all individual
components normalised for concentrations. Simplifying, it can be said that the refractive
index of a solid is directly related to its density. When light strikes a surface, some will be
reflected with the amount reflected being determined by the density of the constituent
atoms and is thus affected by the refractive index, n. Reflection (r) and transmission (t)
coefficients are given by:
1 n 2
r= t= (1.1)
1+ n 1+ n
To a first approximation this leads to the fraction of incident light being reflected as
simply (n 1)2/(n + 1)2 and approaches zero as the refractive index approaches unity.
The response of a plane surface to an incident beam of light is complicated, as briefly
described previously. Mineral fillers, however, complicate the subject even more deeply
in that they are a priori made up of particles that usually have sizes in the order of the
wavelengths of visible light. Thus large surfaces will reflect and transmit the light waves
but particles will scatter them.
Therefore, light entering a typical powdered filler, comprising many small particles, will
experience reflection, refraction, diffraction and interference at each air - particle interface.
Refraction into the filler particles can lead to absorption of the light (the radiation absorbed
will be converted into another form such as heat) and a measure of this is the absorption
coefficient. The remainder of the light is diffused by scattering and the measure of this is
its scattering coefficient. The colour (sometimes referred to as brightness, reflectance or
whiteness) is related to absorption and scattering coefficients by Kubelka-Munk equations
[9]. The reader is referred to the original paper and to some of the speciality books on
the subject [10] for more details. The level of scattering is very dependent on particle
size, so that finer fillers appear whiter than coarser ones: as an approximation, scattering
in air is at a maximum when the particle size of powder is one-third to one-half the
wavelength of the radiation.
Levels of reflectance and refraction, and hence scattering, are directly related to the
refractive index of the mineral. When incorporated into a polymer matrix, the ratio of
its refractive index to that of the polymer will strongly affect the optical properties of the
composite. As the ratio approaches unity (which is the case for most common polymers
and filler): reflection at the interfaces between filler and polymer approaches zero. This
means that light scattering is reduced dramatically and light absorption becomes obvious.
Mies theory [11] now widely used for particle size determinations from light-scattering
data, predicts that as differences in refractive indices become small, not only does scattering
become less but particle size effects become less and maximum scattering moves to larger
sizes, often several times greater than the wavelength of the light.
12
A filler such as titanium dioxide, having a refractive index much higher than that of the
polymer, will therefore exhibit considerable scattering and will give white products, unless
its absorption coefficient is high in which case dark, opaque composites will be produced
(carbon black or black iron oxide are the ultimate in this instance).
Most fillers are white or off-white powders due to the reflection of visible light. This
reflection consists of two components, absorption and scattering, and, as discussed
previously, most fillers have low absorption but high scattering coefficients. However, the
amount of light scattered depends on the refractive index of the mineral relative to the
medium in which it is measured. In air the differences in refractive indices mean that most
minerals scatter light and appear white. Most plastics, on the other hand, have refractive
indices close to those for minerals (1.5-1.6) and much of the scattering is lost (the light, in
fact cannot see the boundary between filler and polymer). There are a few cases in which
mineral and polymer have almost identical refractive indices. In these instances, scattering
virtually vanishes and the composite becomes almost transparent until loadings are increased
to a level at which particle-particle interaction occurs [12]. This transparency is of
commercial importance in several applications such as silica-filled styrene-butadiene rubber
(SBR) shoe soles, and calcined clay- and glass fibre-filled unsaturated polyester roof panels.
On the other hand, for example, calcite has a refractive index of 1.6, which is sufficiently
different from most of the common plastics for some scattering and hence pigmentation
to occur, but whiteness and opacity will only become very noticeable at high loadings
and with thick products.
With the loss of light scattering, light absorption becomes the dominant optical property
of a mineral-filled plastic. Light is absorbed by transition metal ions, with different
wavelengths being absorbed by different species of ion, and by naturally occurring
organics, which are poly-aromatic species with strong absorption across the whole
spectrum (that is they appear brown or black). The impurities in mineral fillers are mainly
transition metal ions, particularly iron, and humates or lignates. Colours due to these
become frequently more marked in a plastic.
Some minerals exhibit birefringence with refractive indices different in differing directions,
due to an asymmetric crystal structure. Plastics filled with these are dichroic and exhibit
unusual visual appearances.
As well as being a direct cause of the colour in a filled plastic, a filler may indirectly generate
colour by either degrading the polymer (forming radicals and unsaturated species) or by
deactivating antioxidants/stabilisers, etc., used in the polymer. In some cases, breakdown of
filler surface treatments can also generate colour problems. Filler effects can be observed in
most thermoplastics but are particularly relevant in PVC where dehydrochlorination, giving
a polyene conjugated structure, is readily promoted by Lewis acid sites on a mineral surface.
13
During the processing of filled thermoplastics, but particularly during their injection
moulding, white markings are observed at points where high melt strain rates are
encountered. These are especially apparent around the sprue and are very much more
noticeable than for unfilled plastics. Some may be due to water or gas bubbles (splash
markings), some to poor dispersion or filler separation, but most seem to result from
flow patterns. These have been frozen in a strained state before they have had time to
relax due to the high thermal conductivity of filled polymers [13].
When filled polymers are strained, they whiten to some extent. This is partly due to
orientation of polymer chains around filler particles but also to light scattering from
vacuoles formed as the polymer is pulled away from the particle surfaces.
Optical properties can also be affected by the fact that filler particles can affect the
morphology of the plastic by nucleating its crystallisation at the interface. Thus a
composite with different light scattering properties may be obtained.
1.2.6.1 Spectral Absorption
The ultraviolet and visible spectra of the common fillers are largely featureless, unless
there are significant levels of transition metal ions in the mineral, when strong
absorptions will occur. However, the most important practical aspect is the infra-red
(IR) spectrum of a filler. This arises from the nature of the chemical bonds present
and will be unique for each filler type. A common use of IR spectroscopy is as an
analytical tool to identify a filler. An important practical consequence of a fillers IR
absorption is the use of certain fillers in horticultural and agricultural films (see
Chapter 8). Spectra of some of the more common minerals incorporated in a low-
density polyethylene (PE) film are shown in Figure 1.1. Calcium carbonate shows
only two strong absorption bands because the only energy absorptions occur in the
CO3; ion (bending, stretching and deformation modes). Kaolin, a complex alumino-
silicate, shows a much more complicated IR spectrum: after calcining, the
AlOSi bonds rearrange and the resultant product has a very complex IR
pattern with several broad, overlapping bands.
1.2.7 Thermal Properties
Leaving aside the special cases of phase change and decomposition, the principal
thermal properties of interest are specific heat, thermal conductivity and coefficient
of expansion.
14
Figure 1.1 Infra-red spectra of mineral filled polyethylene films
1.2.7.1 Specific Heat
This is usually defined as the energy required to raise 1 gram of material by 1 K with SI
units of J.kg-1.K-1. Specific heats are easily measurable and available for most particulates
[14]. Where they are not, rules exist for estimating the value [7]. The volume specific
heats of most inorganic fillers are similar to the common polymers and the rule of mixtures
gives a good approximation to the values found in composites.
1.2.7.2 Thermal Conductivity
This is the rate at which heat energy is transmitted through a substance, SI units are
W m-1 K-1 but it is usually quoted as cal cm-1K-1. Mineral fillers are about an order of
magnitude more conducting than most polymers, while metallic fillers are even more so.
Filled composites are therefore more conductive in general than the base polymer. The
simple law of mixtures is only applicable at low concentrations because, as with electrical
conductivity, particle-particle contact will occur at high loadings leading to a sudden
15
sharp increase in conductivity, the so-called percolation threshold [15], which is dependent
on particle shape and packing.
This increased conductivity is of considerable importance in some processing operations,

especially injection moulding.
1.2.7.3 Coefficient of Thermal Expansion
As the name implies, this is the rate at which a material changes volume on heating or
cooling. SI units are K-1. Most polymers have coefficients of expansion at least an order of
magnitude greater than mineral fillers: thus mineral-filled composites have lower coefficients
of expansion than unfilled polymers and, in well-annealed systems, the rule of mixtures
applies unless strong bonding occurs between filler and polymer. Some fillers have a negative
coefficient of expansion and are used to achieve composites with zero expansion. Other
fillers show anisotropy, that is they have coefficients that are direction dependent.
The differences in expansion between particle and matrix can result in intimate contact
between them in a composite and consequently considerable stresses occur. These can
have the same properties as chemical bonding at low strains and can mask any effects of
changes in polymer-filler interactions in some tests.
1.2.8 Particle Shape and Size
The importance of these factors is felt at all stages of composite production and use.
They affect powder flow, compounding behaviour, composite viscosity, and mechanical,
thermal and optical properties. Indeed, most of the current predictive equations for the
properties of filled composites use shape and size factors, often determined using model
particles such as glass spheres and flakes. Unfortunately such particles are rare in the real
world and it is important in applying equations to appreciate the limitations imposed by
problems of adequately measuring and describing the morphology of fine particles.
One of the principal difficulties is due to the ability of many fillers to exhibit a variety of
particle shapes and sizes depending on the work done in dispersing them. Their effective
shape and size can therefore vary at any stage of composite formation and use. In principle
one would like to characterise them in situ. This is, however, far less easy than
characterising the initial particulate material itself and one is usually reduced to trying to
carry out measurements under conditions that will represent as near as possible those
encountered in use. In this context, the concept of effective particle, which is the size
and shape achieved in the actual application, is a very useful one to keep in mind and is
returned to later in this chapter.
16
1.2.9 Shape
1.2.9.1 Introduction
Particle shape (as will be discussed in following chapters) is very important in determining
the stiffness, or rigidity, of a composite, the flow and rheology of a melt or liquid, tensile
and impact strength, and the surface smoothness of a component, i.e., many of the
important properties of a composite.
Shape is determined by the genesis of the filler, by its chemistry, its crystal structure and
by the processing it has undergone. Unfortunately, it is usually poorly defined, the literature
abounding with vague terms such as roughly spherical, blocky, irregular, platy, acicular,
etc. Some typical particles likely to be found in fillers are shown in Figure 1.2. All the
fillers commonly used are microscopic in size imposing major difficulties both in how to
measure, and then how to describe and quantify shape in any simple yet meaningful way.
In addition, there are problems of distinguishing between primary particles, agglomerates
and aggregates that occur in a filler, especially in synthetic materials, in which a structure
is sometimes deliberately designed. The subject is complicated further because aggregates
and even particles may break down during processing (see Section 1.2.10.3 for a definition
of these various terms).
Figure 1.2 Some particle types likely to be found in common fillers
17
Despite the complex problems outlined previously, fillers are used because of their shape
in a very wide range of polymers to give specific properties. For example, conventional
clays are used in hose and chemical lining because their shape reduces permeability to
fluids; platy talcs give rigidity to PP; the complex aggregate structure of precipitated
calcium carbonates contributes to the structure of liquid polysulfides; and the special
structured shape of many carbon blacks and synthetic silicas is important to their
performance in elastomers. A further example is the emerging use of very high aspect
ratio, nano-clays as reinforcing, fire retarding and gas and fluid barrier fillers.
1.2.9.2 Origins of Particle Shape
Synthetic products will have their shape determined by their chemical composition and
by the production conditions. For example, precipitated calcium carbonate (CaCO3) can
be produced with different shapes by changing precipitation conditions to produce
aragonite, calcite or vaterite. These conditions can be chosen to produce single crystals
or complicated aggregates, which can be modified during drying and milling. Another
example is the very complex shape of most carbon black particles arising from the partial
fusing and solidification of pyrolysing droplets into three-dimensional chain-like
aggregates during manufacture.
The external shape of a natural mineral is a manifestation of its crystal structure, which
will be briefly discussed in Chapter 2. It is also dependent on the environmental conditions
in which the mineral was formed. If allowed to grow without constraint, then the particles
are bounded by crystal faces, which are disposed in a regular way such that there is a
particular relationship between them in any one mineral species, which is derived from
regular atomic arrangement. However, under pressure, temperature or the effects of
impurities, the crystal may adopt different shapes or habits. These include cubic, fibrous
(fine, long, needles), acicular (needle-like), lamellar (plate-like) and prismatic. It is very
unusual for perfect crystals to be found, but even poorly formed ones will always show
evidence of their intrinsic symmetry.
Many fillers (as will be discussed later) being extracted from the earth or rocks and
processed by fairly simple methods will exhibit the same basic original shapes. Others,
however, may be extracted by complicated routes or involve intensive comminution,
thus altering particle shape. This is determined by the chemical nature and strength of
the bonds between the atoms and groups in the mineral. These depend on electronegative
differences between atoms and the bonding can range from covalent through to ionic.
Two other types of interaction or bonding are important.
Hydrogen forms co-ordinate bonds with atoms with very high electro-negativities, such
as oxygen. This is very important in hydrated minerals such as kaolinite and gibbsite,
18
with layers being bonded together by these relatively weak hydrogen bonds. In neutral
units another weak force, known as Van der Waals bonding, due to non-uniform charge
distributions, bonds group together. The types and strengths of bonds present in the
crystal determine the methods by which the minerals break down on processing. Thus in
the calcite crystal, the weakest bonds exist between the calcium ion and the carbonate
group and these cleave invariably, giving rise to a regular rhombohedral shape. Kaolin
platelets, held by hydrogen bonds, separate more readily from each other rather than
fracture. In talc, magnesium silicate layers are held together by weak Van der Waals
forces and very readily undergo cleavage into progressively thinner plates.
1.2.9.3 Assessment and Measurement of Shape
The shapes outlined previously are very difficult to specify precisely using Euclidean geometry,
but various approaches have been attempted to describe shape, anisotropy and structure as
numbers. Structure is particularly interesting and, while only really recognised currently in
the elastomer field, it probably has significance, as yet overlooked, in other areas.
In synthetic fillers it is sometimes difficult to separate fundamental from aggregate shape

but, where there is sufficient incentive, then ways will usually be found to overcome such
difficulties. Such incentives arose in carbon blacks and more recently in precipitated
silica, where shapes are very complex, but an understanding is critical to their high value
usage in the tyre industry. Much work has been done, especially by Medalia and Heckman
[16], and by Hess and co-workers [17], to develop automatic image analysis procedures.
Using such procedures, all the aspects described previously have been investigated. This
work has much to teach us about other filler particles.
Fractal geometry is now showing great promise for describing the shape of various complex,
irregular particles. As usual, the carbon black industry is leading the way in exploring the
potential of fractals for describing fillers and promising results are already emerging. A
good introduction to fractal geometry and its applications to particles can be found in the
excellent work by Kaye [18], and a number of recent papers have explored the measurement
and significance of fractal dimensions of filler particles including carbon black [19-21].
The importance of measuring structure results from its role in describing the ability of
a particle to trap and partly shield a portion of the polymer matrix from deformation.
This is generally known as an occluded polymer and its presence is important, especially
in many of the unique properties of carbon and silica-filled elastomers. A simplified
picture is given in Figure 1.3 and structure can be thought of as increasing the effective
filler volume. While the carbon black industry is leading the way in using sophisticated
techniques to measure shape and assess structure, they are also prepared to use fairly
simple measurements, and in particular the oil absorption procedure with certain
refinements, to give a quantification of this parameter [22].
19
Figure 1.3 Schematic illustration of the effect of particle structure and occluded polymer
The shape of simple particulate fillers is usually expressed as its aspect ratio (AR),
which is the ratio of the particles diameter to its thickness. Measurement of aspect
ratio is relatively simple for large particles, although time consuming. But, for the
micrometer-sized particles that are normally encountered in fillers used in polymers, it
is difficult, needs expensive equipment (such as scanning electron microscopes), and is
very time consuming, depending on the spread of aspect ratios normally found.
Other techniques are being sought to give an easier, more rapid measurement. Fourty
reports that a comparison of particle-size distribution curves measured by sedimentation
and laser diffraction techniques can give a shape factor [23].
Electrical conductivity of an aqueous suspension of a mineral under flow compared

with it at rest (after the particles have randomised) gives a mean value for AR or a
shape factor. Reasonable agreement with electron microscopy has been found [24].
This complex situation is further complicated by the fact that not only is shape often
dependent on size, but measurement of size is affected by shape. This interdependence
is discussed next and also in the descriptions of individual minerals given in Chapter 2.
1.2.10 Particle Size
Particle size is a very important, property of a filler, but is a particularly complex area
where great confusion still occurs. For an individual, naturally occurring, filler it will
have been determined by the origin and mineralogy of the deposit from which it has
been extracted, by the method used in mining, and by separation procedures used
during processing. For synthetic fillers, size will be determined by the conditions used
20
in its synthesis such as precipitation and possibly by the drying and any coating
procedures. Size is one variable that can be controlled (in theory at least), and its
importance is felt at all stages of composite production and use. Hence, there is
considerable interest in its measurement. Particle size distributions are more useful
than single average values, although the latter have the merit of simplicity. Size is an
easy property to measure reproducibly using a variety of techniques including sieving,
sedimentation, optical scattering and diffraction from particulate suspensions. Each,
however, has a different dependence upon particle dimension and varies with particle
shape. Thus correlation between different minerals measured by different techniques,
in different laboratories is difficult. Again the reader is referred to one of the specialised
books on the subject [25].
The problems arise from the fact that most filler particles are irregular in shape and contain
a wide range of sizes, some of which will be individual particles and others agglomerates
(also with a different shape from the individual particles). In such instances it is not possible
to describe fully the particle size by a few numbers, as is often attempted. Commercially,
most producers will quote two or three values to indicate the size of their fillers (see Section
1.2.10.2 and Chapter 2). Thus the data used in published studies are often a poor
approximation of the real situation and can be very misleading. Wherever possible, the
reader should try to determine and to use the full particle size distribution curve and be
very cautious in interpreting literature studies in which only limited data such as average
particle sizes or surface areas are given. In particular very small amounts of particles above
or below a critical size can sometimes dominate certain properties, (e.g., viscosity, fatigue,
tensile and impact strength) but will not be apparent in many particle size determinations.
An interesting example of the effect of small amounts of oversize particles on the properties
of carbon black-filled elastomers has been given by Gent [26].
1.2.10.2 Particle Size Measurement
As already stated, filler suppliers usually quote three or four properties as a measure of
the particle size:
1. Top cut. This is the size below which the majority (usually 99% or 99.9% by weight)
of the particles are finer.
2. Coarse particles may also be reported as that percentage above a certain size.
3. Average particle size is obtained from particle size distribution curves and is the size that
50% of the particles are below. This can be defined in a variety of ways, e.g., by weight,
volume or number, and care must be taken to understand the definition being used.
21
4. Specific surface area. This is determined by a number of adsorption techniques and is

affected by size, shape and structure of the filler particles.
Coarse particles, i.e., particles above 40 m in size are usually quoted separately and are
measured by screening the filler through standard mesh sieves. This may be carried out
in aqueous suspension or as a dry powder. If the filler is heavily agglomerated then
erroneous results may be obtained especially in dry screening. For accuracy, aqueous
measurements are preferred with the filler being completely dispersed both by mechanical
means and also using a dispersing agent. An idea of the structure and ease of dispersion
of a filler may be obtained by comparing screen residues obtained by both wet and dry
screening. If the filler is hydrophobic, then difficulties will be encountered in wet screening.
These may be overcome by dispersing the filler in an organic liquid such as butanol, but
a wetting agent and a dispersing agent are often both required.
For some applications it is important to know the amount of particles that exceed 10
m. This may be obtained by sieving but practical difficulties due to sieve screen blinding
can occur.
The most widely used techniques in this case involve sedimentation in a fluid, usually
water and applying Stokes law. This states that, under standard equilibrium conditions,
the time, t, taken for a particle to settle to a fixed depth is inversely proportional to the
square root of its spherical diameter, d. This is given in Equation 1.2:
1/ 2
18l
4
d = 10
(
s f gt
) (1.2)
where d is the particle diameter, is the viscosity of the fluid, s and f are the densities
of the solid and the fluid, respectively, g is the gravitational constant and t is the time for
the particle to settle a distance, l.
Diameters obtained in this manner are precise descriptions of the particles but will compare
with the results of other techniques only when the particles are perfectly spherical. In
practice, most fillers have irregularly shaped particles and it is common to interpret
experimental data in terms of theories applicable to spherical particles. Dimensions
obtained are then for equivalent spherical diameters (esd), which are the diameters of
spheres that would give the same behaviour as that obtained from the sample by the
method in question.
Specific surface area is usually measured by the quantitative adsorption of nitrogen

following the procedure originally described by Brunauer, Emmett and Teller, and known
as the BET method (Equation 1.3) [27]:
22
P 1 C 1 P
= + (1.3)
V (Po P ) VmC VmC Po
where V is the volume of gas, under standard conditions, adsorbed at equilibrium pressure,
P; Vm is the volume of gas necessary for monolayer coverage; Po is the saturation pressure;
and C is the BET constant. Often only a single point measurement is made to obtain
surface area, but it is much more reliable to measure adsorptions at several pressures and
then plot P/ V(Po P) against P/Po.
Permeability of a bed of packed particles to a fluid can also be used to give a surface
area [28].
However, there are major sources of difficulty and confusion in describing particle size and
shape. These include adequately defining what subdivision of material is to be described as
the particle, in relying on particle size measurements carried out on the powdered particulate
as an adequate description of it in a composite, and how shape and size interact.
1.2.10.3 Primary Particles, Agglomerates and Aggregates
It surprises many people that a variety of particles can exist in a powder, each of which
can be determined as the particle size under certain conditions of dispersion and
measurement. Moreover, the appropriate particle size for consideration can itself vary
according to whether one is dealing with powder flow, behaviour during compounding
and dispersion, or the properties of the final composite. These different types of particles
are generally described as primary or ultimate particles, agglomerates and aggregates. In
some instances these particle types are readily distinguishable but in others there can be
appreciable overlap. Before discussing the types of particle in detail it is necessary to
clarify the terminology as two contradicting conventions are widely used, and this in
itself is a cause of considerable confusion. The need is to distinguish between collections
of particles that are weakly and strongly bonded together. In this book we shall use the
term agglomerate for weakly bonded particle collections and aggregate for strongly bonded
ones. This is opposed to the views of Kaye [18] based on the derivations of the two
words. The chosen terminology is, however, at least as widely used and is especially
prevalent in the carbon black industry. The reader should always ascertain which
terminology is in use when reading articles in the literature.
An idealised view of particle type and breakdown with work during composite formation
is presented in Figure 1.4. This goes beyond primary particles and considers the case where
fragmentation of these may occur, e.g., hollow glass beads during thermoplastic
compounding. With such simple systems it is usually fairly easy to match the particle sizing
method to the degree of dispersion expected in the composite and obtain realistic answers.
23
Figure 1.4 Idealised view of the way filler particles disperse and of the different forms
of particle types that might be encountered
Unfortunately, many filler systems do not exhibit such simple profiles, and the steps
shown are often less sharp and overlap. Some possibilities are shown in Figure 1.5. A
further complication arises when agglomerates form from initially well-dispersed systems.
These agglomerates are sometimes referred to as flocs and can arise due to loss of colloidal
stability in polymerising systems, or to reticulation (filler network formation) above the
glass transition, especially in cured elastomers, an effect often observed with carbon
blacks. The most difficult situation to deal with is quite frequently met with synthetic
products, especially those formed by precipitation. This is where quite strong, complex
aggregates are present, in addition to agglomerates. These aggregates often break down
slowly, leading to a drawn-out step in the effective size profile. Frequently, they do not
fully break down to primary particles under normal processing conditions. The effective
particle size will then be critically dependent on the exact processing conditions and will
be very difficult to predict in advance. Precipitated calcium carbonates are a good example
where this type of situation is encountered.
Most particle sizing techniques attempt to break down powders to their primary sizes by
use of intensive mixing, ultrasonics and dispersants, but even these can be insufficient.
Curves of the type shown in Figures 1.4 and 1.5 would be very useful for predicting filler
behaviour, especially if the work input could be related to different compounding
procedures. In principle, this should be possible, at least in a semi-quantitative way, by
varying the energy used in dispersing the powder. Such procedures have been found
24
Figure 1.5 Complex particle dispersion behaviour, as often encountered with fine,
precipitated fillers
valuable by one of the authors and some very useful preliminary work of this type has
been reported by Thoma and co-workers [29]. Some typical results obtained by the author
(RR) with a coated precipitated calcium carbonate are given in Table 1.3 (Note only
average particle size values are given for illustrative purposes, the earlier comments about
Table 1.3 Effect of measuring conditions on the apparent particle size of a

coated precipitated calcium carbonate
Average
particle
Measuring Condition Comments
size
(m)
Laser diffraction of organic
20 Detecting agglomerates
dispersion using weak ultrasonics
Laser diffraction of organic
4 Detecting basic aggregate size
dispersion using medium ultrasonics
Laser diffraction of organic Detecting some form of
0.2
dispersion using strong ultrasonics sub-aggregate structure
Electron microscopy 0.07 Detecting primary crystallite size
X-ray line broadening 0.07 Detecting primary crystallite size
25
the dangers of using a single value for a distribution still apply). Furnace-type carbon
blacks provide a good example of the problems involved with concepts and terminology
in this area. Such carbon black particles are formed by partial fusion and solidification
of very small spherical units. These spherical units are generally referred to as the primary
particles. Under no compounding or particle-sizing conditions, however, is it possible to
break down the actual particles completely into these ultimate units. Unfortunately, some
breakdown of the fused structures does occur, depending on the processing conditions,
so that it is not appropriate to consider these fused structures as the ultimate particle
either. In view of these complexities, the best rule is to keep the basic principles as outlined
previously firmly in mind when trying to relate particle size as determined on a powder
to what happens in an actual composite.
As mentioned before, many of the previous problems would be removed if there were simple
and reliable methods for assessing the effective particle size in the polymer matrix. Various
methods can be used including microscopy and contact radiology, both coupled with image
analysis, and recovery from the polymer followed by conventional sizing techniques, although
none are completely satisfactory. A more detailed discussion of some of these aspects will be
found in Chapter 5. In the authors opinions the understanding of filled composites would be
greatly improved by advances in this area.
1.3 Surface Modification
Surface modification of fillers to give improved properties to a polymer composite is a

topic that has received enormous attention over the last 30 years. Improvements in
mechanical properties, dispersion of the filler (which leads to improved properties), improved
rheology and higher filler loading have all been reported to accrue from rendering the
surface more hydrophobic and hence compatible with the polymer or by enabling the filler
to bond covalently, through hydrogen or ionic bonds to the polymer; or by changing the
physical nature of the interface so that energy absorption can occur. This section will deal
mainly with mineral surface interactions. The use of surface modifiers is dealt with at
length in Chapter 4 and specific examples are described in Chapters 2, 7, 8 and 9.
1.3.1 Stearic Acid and Stearates
The most widely used surface modification is treatment with stearic acid. This is believed
to result in a stearate salt coating on most fillers and metal stearates are also used.
Stearic acid will react with basic minerals to give a surface that is covered with strongly
bonded long organic ions (this is discussed in more detail in Chapter 4). Stearic acid-
modified silicates are commercially available but in these cases the stearic acid is almost
26
certainly weakly adsorbed and probably desorbs during melt compounding. Similarly,
metal stearates will form weak bonds with mineral surfaces and desorb from them.
Organo-amines have been used to render silicate surfaces hydrophobic, bonding probably
through strong coordinate bonds. These relatively labile coatings will help improve
dispersion in the initial stages of a compounding operation, before they desorb. They
also give a protective coating to the filler, minimising any polymer degradation that may
occur before stabilisers, antioxidants, etc., are fully dispersed.
1.3.2 Coupling Agents
Surface treatments with bi-functional additives, which form very strong covalent bonds
to the filler and then bond to a polymer by a variety of mechanisms, are widely available.
They are based on organo-metallic compounds with the general formula:
(RI)a M(RII)b (1.4)
where M is a metal ion with valency a + b; RI is an organic group, the choice of which
depends on the polymer in which it is to be used and RII is a group designed to react
with a mineral surface.
The most commonly encountered compounds are organo-silanes [30] and organo-
titanates [31], but others, including organo-zirconates [32], organo-borates [33]
and complexes of chromium [34] have been proposed. R II in most of the coupling
agents is an alkoxy group (methoxy, ethoxy or 2-methoxyethoxy are common),
which is reactive to hydroxyl groups and to water. The preferred reaction mechanism
is for hydrolysis to occur, initially by reaction with environmental or adsorbed
water, with the kinetics being affected by the nature of both the alkoxy and other
reactive groups on the molecule. The organo-metallic hydroxide then condenses
with hydroxyls on the mineral surface or it can form oligomers followed by polymers
by self-condensation reactions [35].
Multiple layers of many coupling agents can be adsorbed onto a mineral surface, with
the packing of the coupling reagent on the surface being determined by the size of the RI
organic group [36]. The structure of these layers can be very complex, with both strongly
and weakly adsorbed species being present. This is discussed in detail in Chapter 4.
1.3.3 Polymer Modifications
To try to improve energy absorption at the interface, and hence improve composite
toughness, modification of the filler with a polymeric, low modulus, interlayer has
27
been reported [37]. There have been many papers published on this technique. Aivazyan
and co-workers [38] review the surface modification of mineral fillers by polymer
deposition, using polymer adsorption from solution, mixing of polymer with dispersed
filler and hetero-coagulation of latex polymer particles on the filler. Good bonds between
coating and filler are often achieved by grafting a reactive group on to the interfacial
polymer before or during filler treatment. Thus, kaolin can be coated with a styrene-
diacetone acrylamide copolymer by dispersing the two monomers with the clay in an
aqueous medium and polymerising with a persulfate catalyst [39].
Unsaturated monomers have been adsorbed on to fillers and then polymerised to give
encapsulated products. The modulus of the polymer could be modified by selecting the
monomer [40]. Acrylic acid-vinyl chloride (1:99) has been polymerised on to calcium
carbonate [41]; reports of the use of 3,5-triacryloxyhexahydro-S-triazine [42], bis-phenol
A and epichlorohydrin [43], methyl methacrylate [44], and acrylic acid [45] have also
been published.
Graft copolymers between unsaturated acids, especially acrylic acid and maleic
anhydride (MA), and polyolefins (PE and PP) are widely used as surface modifiers and
compatibilisers, sometimes in combination with bi-functional coupling agents [46],
for talc, calcium carbonate and calcined clays. Such polymer coatings include
polypropylene-maleic anhydride [47], polypropylene cis-4-cyclohexene-1,2 dicarboxylic
acid [48], polystearyl or polylauryl acrylate [49], polypropylene-acrylic acid, partially
oxidised poly(butane diol) [50] and ethylene-vinyl acetate copolymers [51]. Acid-
containing products can react with basic fillers. With most other types, they will simply
adsorb on to the mineral surface, but they can form esters with some non-basic metal
hydroxyls, notably silanols.
1.3.4 Direct Bonding
Polymers themselves can be grafted on to a mineral surface and the resulting

composites have been reported to be significantly better than simple mixes because
of strong covalent polymer-filler bonds. Composites of clay with ethylene-MA graft
copolymer, in which the anhydride groups interact with the hydroxyl groups on the
surface of the clay, give increased impact strength and flexural modulus compared
with a physical blend of clay and ethylene-MA random copolymers [52].
Polymerisation of monomers can be induced on the mineral by natural catalytic sites
on its surface [53] or by adsorbing polymerisation catalysts on to the mineral prior
to treatment with monomers [54, 55].
28
1.4 Particle Packing and the Maximum Packing Fraction
1.4.1 Introduction
The packing behaviour of particles in a polymer matrix determines at what loading

particle/particle effects become important and is a critical factor in the understanding
and design of polymer composites, especially when highly filled systems are involved.
The maximum packing fraction, Pf, is a particularly useful concept. This is the maximum
volume fraction of particulate that can be incorporated before a continuous network is
developed and voids begin to appear in the composite. In addition to indicating the
maximum practical loadings obtainable, Pf is also useful in understanding and describing
the effect of filler loading on composite properties. Many properties change rapidly as
one approaches Pf, almost in a percolation way, and this parameter is now incorporated
into many mathematical treatments of property-loading dependence [56]. Indeed, it often
goes a long way to explaining why different physical forms of the same filler material
can give markedly differing results at the same loading.
1.4.2 Determination of Maximum Packing Fraction (Pf) by Oil

Absorption Procedures
Despite its utility, Pf is difficult to measure or predict with great precision. This is due to
complex interactions between the particles and the polymer matrix, and the influence of the
fabrication method used. Both of these factors affect the way the particles pack and make
conventional measurements of packing, such as the tap density of the powder, of limited
quantitative value. This is especially true for many typical particulate fillers, which, due to
their fine size and irregular shapes, exhibit particle agglomeration and do not pack well in
the dry state. Such powders often pack considerably better when wetted by suitable liquids,
especially if dispersants are present. These wetting and dispersing effects lie behind the
pragmatic approach of using oil absorption procedures to determine an effective Pf. Originally
introduced for application in putty and paint technology, oil absorption methods rely on
titrating a sample of powder with an oil or other liquid, while continually rubbing and
mixing the mass. End-points are readily detected in these procedures, often defined as the
point at which a putty of a certain consistency is obtained. It is generally believed that at this
point all the particles are dispersed and wetted, and all the gaps between the particles are just
filled with liquid. In practice, only two liquids are used to any extent, linseed oil and phthalate
esters. Both simple manual and instrumental methods are available for determining oil
absorption values. It is important that standard procedures are closely followed if reproducible
results are to be obtained and a number of standards have been issued. The simplest procedure
is the spatula rub-out method, which is embodied in ASTM D281 [57]. A useful description
of its application to particulate fillers has been given by Ferrigno [58].
29
Oil-absorption results are usually quoted as cubic centimetres of oil per 100 grams of
particulate at the end point. Simple mathematical treatment using oil and particle densities
can then convert this to a volume fraction. As a guide, linseed oil absorptions for calcium
carbonate of 20 cm3 100 g-1 and 50 cm3 100 g-1 correspond to filler volume fractions of
0.64 and 0.41, respectively.
The attraction of the oil absorption methods lies in their simplicity and their crude
approximation to polymer processing. Different liquids are also observed to give markedly
different values and this is believed to be due to their respective abilities to wet out and
disperse the particles. Thus in theory, by choosing a liquid of similar properties to the
polymer in question, one should be able to improve the usefulness of the data, although
this does not seem to have been greatly used to date. As mentioned previously, only two
liquids are commonly used and, of these, linseed oil generally gives lower values suggesting
that it wets and disperses particles better than phthalates. The phthalates are popular
because they are widely used as plasticisers in PVC compounds. Liquid paraffins have
been used as model systems for olefinic polymers, and squalane could be used as a model
system for PP.
A detailed study of the oil absorption test and its meaning in terms of particle packing has
been reported by Huisman [59]. He found that the agglomerates present in the original
powder are frequently not fully dispersed during the test, but may be compressed and
reduced in porosity. The degree to which this occurs critically affects the packing and
hence the oil-absorption value. Differences in the degree of compaction obtained go a long
way to explaining variation in oil-absorption values between different operators, and
between manual and instrumental methods, as well as between different liquids. While oil
absorption serves a useful purpose as a guide to the effective value of Pf, great care must be
taken in applying it too literally. In some polymer systems there may be a good match with
the polymer wetting properties and the dispersion procedures. In others this may be very
poor. Oil absorption values are widely used for assessing carbon black properties in the
rubber industry. In this field, special procedures have been developed to attempt to reproduce
the effect of rubber compounding conditions on particle morphology [22].
1.4.3 Particle Packing Theory
Much effort has been devoted to studying the effect of particle size and shape on the
packing properties of powders. Special attention has been given to identifying those
factors that allow high packing fractions to be obtained. This subject is very relevant to
the design of filler systems and the general principles, which often cause considerable
confusion, are outlined here. For greater detail specialist publications such as that by
German should be consulted [60].
30
The packing behaviour of particulate materials depends largely on their particle size,
shape and surface characteristics. The behaviour of model systems with closely defined
size and shape distributions is now well understood. Real particulate materials are much
harder to treat, largely due to the difficulty in determining and describing their size and
shape distributions accurately. Nevertheless, the principles derived for the model systems
can be applied in a semi-quantitative way and appear to work reasonably well.
The aims of particle packing theory are to predict the maximum volume fraction that
can be obtained under a given set of circumstances and the structure of the particle
assembly at this point. The first point to appreciate is that there are several ways of
packing the same collection of particles, each one resulting in a different maximum volume
fraction. The circumstances under which the particles are assembled will determine which
of these structures is obtained in practice. In the extreme case consider a three-dimensional
jigsaw puzzle. With care this can be assembled to give perfect packing with no free space.
This is known as ordered packing. However, if the pieces are put in a container and
shaken, it is extremely unlikely that they will ever discover this perfect packed structure.
Nevertheless, it will be found that, providing there are enough particles, a certain packed
density can be reproducibly obtained implying that some statistically balanced structure
is obtainable. This is known as a random packing situation. More than one ordered and
random packing fraction may be observed with many systems.
Appreciation of the nature of ordered and random packing is important in understanding

the application of packing theory. Ordered packing results in long-range structure as in
a crystal lattice and, although it can sometimes be observed in suspensions of mono-
disperse spherical particles, is not of great importance in our context. As its name implies,
random packing is a statistical process with no long-range structure and it is more relevant
to particulate-filled composites. While some ordered packing configurations can be of
very low density, ordered packing will always be capable of giving higher packing densities
than random packing.
Two classes of random packing are recognised, loose and dense random packing. Loose
packing refers to the sort of packing obtained when particles are randomly assembled under
conditions where they cannot easily move past each other, while in dense random packing,
conditions are such that movement is possible. In powder technology terms, loose random
packing corresponds with a pour density and dense random packing to a tapped density.
The simplest case to consider first is the packing of smooth, regular, mono-sized particles.
This has been well studied for smooth spherical particles, which can readily move past
one another. With these particles a maximum ordered packing fraction of 0.74 has been
established, although other, less dense packings are feasible. Random loose packing
fraction is difficult to predict accurately but is about 0.60. Random dense packing is
more readily predicted and is about 0.64.
31
The theory has been extended quantitatively to a number of regular, non-spherical shapes.
Many of these such as cubes, rectangles and plates can have ordered packing fractions of
unity but most have less dense random packing than spheres, largely due to the difficulty
of the particles moving with respect to one another to optimise packing. Cubic particles
do, however, seem to have a slightly higher random packing density than spheres (about
0.75). Quantification of the packing behaviour of irregular particles is poorly developed
at present but the enhanced interparticle friction soon causes the packing fraction to
decrease as the particles depart from sphericity. Values of 0.50 are not uncommon for
three-dimensional irregular particles. Very low packing fractions (<0.1) are obtained
with high aspect ratio fibres.
The general approach to obtaining high packing fraction powders is to use small particles
to fill in the pores in the packed structure obtained from large particles and then to use
even smaller particles to fill in the remaining pores and so on. A simple view of this is
presented in Figure 1.6. The approach is known as multimodal packing, and much effort
has been devoted to defining the optimum particle size ratios and quantities of the various
modes and the resulting packing fraction obtained.
The case of spherical particles provides the simplest example. As we have already seen,
the maximum ordered packing fraction is 0.74. From geometric principles it can be
shown that this structure has two sizes of pores present, which can be filled by spheres
with 22.5% and 41.4% of the diameter of the largest spheres. This results in an increase
in packing fraction to 0.81.
Unfortunately, such simple geometric calculations are not possible for the more relevant
random packing situation, even when spherical particles are involved. This is because
there will be a random distribution of pore sizes and the small particles will not spread out
evenly among them. In particular, the small particles show a tendency to cluster around the
Figure 1.6 Classical bimodal packing effect
32
surface of the larger ones, increasing their spacing [61]. It can be shown, however, that the
limiting case for random packing of a bimodal distribution of spherical particles of a single
material is achieved at a packing fraction of 0.86. This is obtained with 73% large and
27% small particles and a size ratio of at least 7:1 and preferably up to 20:1 [62]. As with
ordered packing, increasing the number of modes improves the packing, but similar ratios
are needed for each mode. This soon results in an excessively wide particle size distribution
accompanied by ever decreasing benefits. Three modes give a limiting random packed
fraction of 0.91 and the ultimate limiting value appears to be 0.96.
The packing behaviour of multimodal mixtures of irregular particles is very poorly

understood at present, although some empirical studies have been made on simple systems.
Where different sizes of similar shapes are mixed, then improvements in packing similar
to those observed with spheres are usually obtained but starting from a lower level. It
also appears that a wide difference in sizes and a large proportion (by weight) of the
bigger particles is advantageous. Where different shapes are involved then the picture is
very unclear and the packing density may even decrease.
While the multimodal approach is theoretically attractive and is useful for understanding
the general principles, it has some practical limitations. Continuous particle size
distributions are often more readily achieved and less costly and so more relevant. Much
work has gone into trying to predict the optimum shape of distribution for maximum
packing. This is a very complex subject but it has been shown that packing fractions as
good as those obtained from the multimodal approach can be obtained from carefully
controlled continuous particle size distributions. These distributions are hard to define
and are usually developed empirically. They can, however, be looked upon as being derived
from multimodal principles. In general, such distributions are skewed having an abundance
by weight of large particles and a long tail to the fine end.
1.4.4 Applications of Packing Principles to Particulate Filled Composites
The packing principles outlined in the previous section are of great value in preparing
filler size distributions capable of being processed at high loadings in polymeric systems.
In the extreme case monomodal spherical particles can be specially synthesised and mixed
together but this is only worthwhile in a few high value applications, such as light curable
dental resins. More often adjustments are made to the natural particle size distribution
of standard fillers composed of irregular particles to improve the packing. These
adjustments may be by classification to remove certain fractions or by blending in extra
material in specific size ranges. In some instances narrow sieve fractions are prepared
and recombined in set proportions. Where comminution is used to produce fillers then
the processing can be controlled to some extent to produce favourable size distributions.
Practical procedures for producing maximum packing systems were originally worked
33
out by Furnas [63] and have recently been described in some detail by Ferrigno [64]. It
must be borne in mind, however, that other considerations may restrict the particle size
range that can be tolerated in a composite.
While particle distributions prepared according to packing principles generally give the
highest processable loadings in polymers, the prediction of these loadings and the
measurement of the effective maximum packing fraction, is not very easy. As mentioned
earlier a number of different random packing fractions can exist for the same collection
of particles depending on the assembly conditions. Particle packing is usually determined
on a powder, by procedures such as pour or tap density, or by some compression process.
These are not very relevant as the particles used as fillers tend to be relatively fine and
irregular and do not pack well under these conditions. When processed into polymers,
the matrix itself, or additives, together with the compounding procedures, can drastically
alter particle packing behaviour. Different types of packing are also relevant to different
processing conditions. Where flow is required then some sort of random loose packing is
probably the maximum achievable, whereas if the dispersion is subsequently compression
moulded with squeezing out of excess matrix, then a denser random packing becomes
more relevant. Where particles can readily move with respect to one another and a dense
packed arrangement is readily obtained, then the phenomenon of dilatancy, or shear
thickening, may be observed. This is caused by the need for the particles to move to a
more open structure before flow can occur. In such cases processing difficulties may rule
out use of compositions based on the dense packing configuration.
As has been discussed earlier, procedures such as oil absorption, although imperfect,
probably remain the best way of determining a relevant Pf.
1.5 Interparticle Spacing
The distance between filler particles in a polymer matrix is an important consideration,

which often does not receive the attention it deserves. It can be appreciated that composite
properties may be markedly affected when this distance becomes very small. This is
partly because the polymer chains may not now have the full freedom of movement they
would have in the bulk polymer. Equally importantly, if there is a shell of modified
polymer adsorbed on the particles, then at some limiting spacing this shell will overlap
with that on adjacent particles leading to a percolation effect and to this phase dominating
some properties (Figure 1.7). It can also be shown that the critical distance of separation
is likely to be a small number of radii of gyration of polymer chains (20-200 nm).
Interparticle spacing is directly determined by the number of particles present and this
changes markedly with particle size. This is dramatically illustrated in Figure 1.8 by the
micrographs of two poly(methylmethacrylate) composites containing equal volume
fractions of aluminium hydroxide of differing particle size.
34
Figure 1.7 Idealised view of the effect of interparticle distance and of absorbed
polymer on composite structure and properties
Figure 1.8 Scanning electron microscope images of cross-sections of

poly(methylmethacrylate) filled with equal volume fractions of two different particle
size aluminium hydroxide fillers: a) 55% coarse particles, b) 55% fine particles
35
1.6 Particle Effects on the Structure of Polymers
1.6.1 Introduction
There is now considerable evidence that particulate fillers, especially inorganics, can
significantly affect the structure of the matrix polymer itself, and hence the properties of
the final composite. Such effects can vary enormously from system to system and have
largely been overlooked in many studies of filled composites. The existence of these
effects may explain many of the anomalies reported in trying to develop and apply
generalised predictive equations [65].
Matrix modifications can occur in a number of ways and the effect on properties can sometimes
be at least as important as that arising from the much more widely recognised interfacial
bonding effects. Unfortunately, no systematic study of this area has yet been made.
The principal ways in which a particulate phase may affect polymer structure are:
1. Molecular weight reduction during processing.
2. Molecular weight and crosslink modifications due to interference with curing processes.
3. Adsorption of polar, low molecular weight species such as surfactants, plasticisers,

stabilisers and antioxidants and oxidation products.
4. Formation of an immobilised shell of polymer around the particles. Often this shell
is rich in a certain molecular weight fraction, which is then depleted in the matrix.
5. Modification of crystallinity in semi-crystalline polymers.
6. Effects on polymer conformation due to particle surfaces and inter-particle spacing.
A brief description of the various effects together with examples of their importance is
given in the next section.
1.6.2 Molecular Weight Reduction During Processing
It is well known that polymers may undergo mechanochemical degradation during

compounding and moulding operations [66]. Indeed this is an important feature of natural
rubber processing. As most properties are dependent on molecular weight, this can play
an important role in determining final properties and conditions (including the use of
stabilisers) are usually chosen to limit any degradation.
36
As has already been discussed, and will be returned to later, the introduction of a particulate
phase may markedly affect the amount of degradation. The usual effect is for degradation
to be increased due to increased mechanical work, to chemical interactions at the interface
and possibly to deactivation of stabilisers and antioxidants. The effect is most pronounced
under conditions (especially high loadings) where viscosities are high, leading to excessive
shear forces being developed. Such effects have been reported in filled elastomers [67]
and polypropylene [68].
1.6.3 Molecular Weight and Crosslinking Changes due to Cure Modifications
The detailed microstructure of free-radical cured polymers determines their overall

properties, and is governed by the rate of cure and relative rates of various competitive
polymerisation processes such as: initiation, propagation, combination and termination.
Inorganic particles can modify the cure process in several ways. In particular, by lowering
the overall exotherm, they can significantly reduce the cure temperature and kinetics,
thus altering the relative rates of the various processes described above. The surface of
the particles can also play a role by absorbing and altering the stability of the growing
polymers, or by absorbing and altering the activity of the initiator and curative. Most of
these effects have been reported but, unfortunately, structure determination is very difficult
with crosslinked systems and little or no direct evidence for resulting structure changes
has been reported. An example of the effect of different filler particles on the curing of
unsaturated polyesters (and by inference on their structure), as measured by the cure
exotherm, has been given by Plueddemann and Stark [69].
1.6.4 Preferential Adsorption of Polar Species
Polar materials are usually more strongly adsorbed on particulates than is the matrix
polymer and, where present, can displace the polymer altogether from the surface. This
can modify the composite properties in two ways. Firstly, it may lead to a weak interfacial
bond. Secondly, where the polar species was providing a significant matrix function such
as plasticisation, cure modification or flow enhancement, this can be lost.
Good examples of the preferential adsorption of polar materials have been given by
Barnett and Jones [70], Evans and co-workers [71] and by Karlivan and co-workers [72].
Barnett and Jones carried out some elegant and painstaking work on the effect of mineral
fillers on the reinforcement of emulsion-polymerised SBR. This type of elastomer contains
high levels of organic surfactants remaining from the polymerisation process. Certain
mineral fillers gave exceptional and unexpected reinforcement properties, which were
37
demonstrated to be due to the preferential adsorption of these surfactants, resulting in a

significant improvement in the strength of the matrix. This strength improvement was,
at least in part, due to modification of the curing process showing how complex and
inter-related the effects of adding particulates can sometimes be. More recently, Evans
and Rothon have shown how fatty acids prevent the formation of bound rubber when
precipitated calcium carbonate is used as a filler in SBR elastomers. When they are absent,
high levels of bound rubber are formed, accompanied by a marked increase in
reinforcement. Karlivan demonstrated how certain inorganic fillers could be used to
preferentially adsorb low molecular weight polar species produced by thermo-oxidation
of polyolefins. These species tend to form during heat welding of polyolefins to metals
and, by accumulating at the interface, limit the adhesive strength. Their removal markedly
improved adhesion.
1.6.5 Formation of an Interphase of Immobilised Polymer
It is now well established that, in the absence of competing polar species, molecules of
the matrix polymer can be effectively adsorbed on to the surface of a particulate phase,
even when this is an inorganic mineral. The strength of this adsorption can play a key
role in determining composite properties as will be discussed in later chapters.
It is also generally recognised that this adsorbed polymer may have different properties
from the bulk, but the consequences of this for composite properties are often
overlooked. This is partly because, as we shall see, the effects only become significant
at high loadings and with small particles, but also because the adsorbed layers are
hard to detect and characterise. Where they are observed, the effects can be at least as
great as those associated with particle matrix bonding. The principal effect of this
adsorbed layer is to increase the effective size and hence volume fraction of the
particulate phase. A complication that has caused much confusion in the past, and is
only just becoming recognised and understood, is the apparent variability in the thickness
of the immobilised layer according to the method of measurement and the composite
property being studied [73].
Once this difficulty is appreciated, its origins can be clearly understood. Thus, in the
absence of other adsorbing species, there will be a primary layer of strongly adsorbed
polymer at the filler surface. The conformation and properties of this are likely to be
severely modified and probably in all instances it can be regarded as immobilised and
contributing to particle volume. As one moves beyond this layer, the effects due to the
particle do not suddenly disappear but will gradually tail away. This outer region will be
less strongly associated with the particle and may only appear to be immobilised under
certain test conditions.
38
As we shall see, while effects of particles can sometimes extend for large distances, the
immobilised layer thickness generally appears to range from 1 to 50 nm and in many
instances is much less than 10 nm. The effect of various layer thicknesses on the effective
volume of different sized cubic particles is presented in Table 1.4. Only when the layer is
of the order of 50 nm does it have much effect on particles over 1 m in size, but even
thin layers of 10 nm or less have a significant effect on particles about 0.5 m, and this
becomes dramatic as very small particles (0.1 m) are reached. Because of their increased
surface to volume ratio, anisotropic particles such as plates will show greater effects
than those recorded in Table 1.4. Determination of the thickness of immobilised layers is
far from straightforward and can give a variety of answers, as mentioned earlier.
Table 1.4 Calculated effect of surface layers on the apparent volume of various
sized cubic particles
% volume increase for a layer thickness of:
Particle size (m)
1 nm 10 nm 100 nm 1000 nm
0.1 6 73 2600 -
0.5 1.2 12 174 -
1.0 0.6 6 73 2600
5.0 < 0.1 1.2 12 174
10.0 < 0.1 0.6 6 73
The adsorption and conformation of polymer molecules on particle surfaces is of great

interest to colloid scientists, especially with regard to steric stabilisation of dispersions,
and general guidelines can be obtained from their studies. A good description of the
subject can be found in treatise such as that by Napper [74]. It is found that single point
adsorption results in the molecule extending preferentially in a direction perpendicular
to the surface and a layer thickness that approaches a value of twice the radius of gyration
of the free polymer. The radius of gyration is dependent on molecular weight but for our
purposes the effective layer thickness due to this type of conformation will be in the
range of 20-40 nm. With most polymers of interest to us, multipoint attachment is more
likely. This will significantly reduce the layer thickness until, in the limit of flat adsorption,
this can be as low as 1 nm or less.
The most direct method of determining the thickness of adsorbed polymer is by carrying
out adsorption studies, either from a suitable solution of the polymer, or by extracting an
actual composite and determining the residual or bound polymer. Both approaches have
39
been used and the layer thickness is calculated from the volume of adsorbed polymer by
dividing by the surface area of the particulate phase. The bound polymer approach has
been frequently used in studies on carbon black-filled elastomers and several useful reviews
have been published [75]. Unfortunately, the origin of bound polymer is complex and may
be of limited use in characterising effects in the composite itself. Bound layer thicknesses
determined in this way for carbon black-elastomer systems are usually of the order of 1-5
nm. There has been only limited work on determining bound polymer with mineral fillers
and in polymers other than elastomers. Several studies have shown that bound rubber
readily forms with high surface area silicas in elastomers [76], where calculated layer
thicknesses are similar to those reported for carbon blacks. Evans and Rothon have reported
on bound rubber formation with precipitated calcium carbonate in an elastomer system
[71] and again the calculated layer thickness based on their data is less than 5 nm.
Similar low values have been reported by Kosfeld and co-workers for kaolin and zinc
sulfide [77] in a rubber-modified polypropylene and by Lipatov [78] and Boonstra [79]
for silica-filled polyethylene. It is probable that these determinations only detect the
polymer molecules that are strongly attached to the particles, probably in multipoint
fashion. This explains the low values of thickness observed, but it does not necessarily
follow that the immobilised, or modified thickness in composites is not significantly
greater than this.
In addition to bound polymer of the type described previously, polymer may also be
shielded from some deformation processes by being occluded within the particle shape
(See Section 2.8.2) and this is especially important with some carbon blacks.
Viscosity measurements provide another fairly simple method for determining a layer
thickness. For non-agglomerated particles, a fairly simple equation (Equation 1.5) exists
relating relative viscosity of a suspension to the effective volume fraction of the solid phase:
s = 1 + K + K + (1.5)
Where s and are the viscosities of the suspension and the solvent, respectively, K is a
coefficient depending on particle size, shape and concentration, and is the effective
volume concentration. K can be determined in pure solvent without polymer being added
and then used to determine the change in resulting from addition of polymer.
Viscometric determinations of this type tend to give quite high layer thicknesses of the
order of several tens of nanometres. An example of this approach can be found in the
work of Chibowski who studied the adsorption of polyacrylamide of different molecular
weights on to the surface of titanium dioxide from aqueous solution [80]. He found
effective layer thicknesses of 30-70 nm increasing with polymer molecular weight. The
results obtained are, of course, influenced by the solvent. If possible, the measurements
40
should be carried out in a theta solvent, (i.e., one in which the dimensions of the polymer
coil are the same as in the melt).
Various procedures have been applied to composite materials to attempt to determine

the amount and properties of the immobilised layer in situ. Much of the interest in this
has been in the former eastern block countries of Europe and has been reviewed by
Enikolopyan [81]. Among the measurements used have been density, specific heat,
dielectric constant and dynamic mechanical analysis. The general conclusions are that,
as one might expect from reduced configurational entropy, the surface layers are denser
and more rigid than the bulk polymer.
Again most work has been carried out on carbon black-filled elastomers. This has shown
that a slight broadening can be observed in the glass transition of the polymer, which is
interpreted as being that of the surface layers. Deconvolution indicates that the glass
transition of these layers is about 10 C higher than the matrix and the calculated volume
of modified material approximates to a 3 nm layer [82].
Only isolated studies have been reported in other systems. Galeski has carried out thermal
analysis of chalk-filled isotactic polypropylene [83]. Uncoated chalk was found to modify
all the transitions present in the unfilled polymer and to lead to two new transitions
assigned to restricted motion in the interface layers. These effects were largely eliminated
when the chalk was surface treated, confirming their surface origin. No attempt was
made to calculate layer thickness. Gerard and co-workers have reported on the effect of
glass beads in a crosslinked epoxy matrix [84]. They used dynamic mechanical analysis
and found the uncoated beads to reduce the mobility of the polymer, an effect that could
be largely overcome by coating the beads. Analysis of this sort has much to offer and
hopefully will be more widely applied in future work.
Workers such as Pukansky and Tudos have developed procedures for calculating effective
layer thicknesses from the mechanical properties of composites [85]. They have applied
this to calcium carbonate-filled polypropylene and found the effective layer thickness to
vary according to the property being measured. A value of 5 nm was obtained from
Youngs moduli in agreement with the thicknesses expected for strongly bound polymer.
A value of 150 nm was, however, calculated from tensile yield and strength calculations.
It was postulated that the size of the effective interlayer depends on the elongation at
which it is being determined.
The aspect of bound or modified polymer still has many secrets to reveal and its existence
and importance should always be assessed when new polymer/filler combinations are
being developed, especially with high filler loadings and high surface area particles.
41
1.6.6 Effects on Polymer Conformation due to the Presence of Particle

Surfaces and Interparticle Spacing
The properties of polymers depend to a large degree on the conformations available to

their chains. The presence of solid, particulate material can significantly modify these
conformations, even in the absence of any particle-polymer interaction or other effects
such as already discussed.
Firstly, the presence of a solid surface will restrict the conformation of polymer molecules
in its vicinity. This type of effect is widely recognised in colloid science where, as already
mentioned, it has been extensively studied with regard to steric stabilisation of suspensions.
Detailed treatment can be found in works such as those of Napper [74]. The basic findings
are that, in the absence of multipoint attachment, chain molecules respond to this
restriction by expanding in a direction parallel to the surface. This expansion can double
the effective molecular size in that direction.
Secondly, polymer molecules occupy quite considerable volumes, depending on their

molecular weight and temperature. At high filler loadings, especially with ultrafine
particles, the interparticle spacing may be of similar size or smaller. This must mean that
the polymer molecules will be forced to take up a strained conformation and thereby be
considerably modified in their properties.
While these effects are undoubtedly present in particulate composites they have not, to
the authors knowledge, been addressed in any detail so that their significance is still
largely unknown.
1.6.7 Effects on Crystallinity
There is sufficient evidence available to show that particulate fillers can affect the
crystallinity of some polymers and that this may in turn affect mechanical properties.
Despite this, the area has received surprisingly little attention and many studies of filler/
property effects in semi-crystalline polymers do not consider this possibility.
Many thermoplastic materials are semi-crystalline and the precise nature of this
crystallinity plays a major role in determining their properties. In addition to the level of
crystallinity, factors such as crystal phase, crystallite numbers, orientation, size and shape
are all important, but the exact way in which they affect properties is far from understood.
In unfilled polymers the crystallites generally seem to be present in spherulitic aggregates

[86]. Because of hindered motion, thermoplastics have a marked tendency to super cool
before crystallising. The degree of super cooling will itself determine the number of
42
crystallites and will vary according to forming conditions. As a consequence of this super
cooling, thermoplastics are very prone to nucleating effects and specially chosen nucleating
agents are frequently added to ensure rapid crystallisation during forming. Among other
things, this reduces cycle times. In some cases, nucleants may be used to favour certain
crystal phases.
Such nucleating agents are often salts of organic acids and sometimes fine fillers. Their
use does not generally alter the spherulitic nature of the crystallinity, only the size and
number of crystallites. Even so, there can be marked changes in properties accompanying
the use of such nucleants, examples of which are given by Jansen [87]. In particular their
use generally seems to increase impact strength due to the reduction in crystallite size.
Given the importance of crystallinity in determining mechanical and other properties and the
susceptibility of polymers to nucleation, it is pertinent to enquire whether normal filler particles
have any significant effects in this context. This area is surprisingly little studied, but there is
sufficient evidence to show that marked nucleation can occur, although this may vary from
filler to filler, with surface treatment also playing a role. There are also indications that the
type of crystallinity may be affected and thtat there is some circumstantial evidence for a link
between nucleation effects and mechanical properties. This area is, however, not yet well
understood and we are a long way from having a good generalised theory.
The subject is probably best advanced for polymers in contact with glass fibres and
certain platy particles such as sheet silicates. As well as acting as nucleants, this type of
material can alter the type of crystal structure present. Thus, it is now well established
that glass-fibre surfaces can lead to trans-crystallinity. This is the growth of radially
oriented lamellae extending for a few hundred micrometres from the fibre surface. This
topic has been discussed in detail by Thomason [88]. Transcrystallinity is also discussed
in Chapter 8 of this work.
Outside of these areas the picture is much less clear. Straight nucleation affects are easily
detected by thermal analysis techniques. These generally manifest themselves in an earlier
onset temperature and peak temperature, but not necessarily in any increase in total
crystallinity. There are many reports of significant effects for various polymer/filler systems.
Thus, talc has been reported as nucleating PE [89], PP [90] and Nylon 6 [89]. Calcium
carbonate has been reported as nucleating PP [91-93] and PE [94], while sepiolite (Mg4 Si6
O15 (OH)2 . 6H2O) has been reported as nucleating PP [95]. Surface treatment of the filler
particles has also often been found to reduce or eliminate these nucleating effects [89, 96,
97]. One of the authors (RR), has observed similar nucleating effects for aluminium and
magnesium hydroxide in polypropylene and also confirmed the reduction of this effect by
surface treatment. Typical results illustrating these effects are presented in Figure 1.9. What
is far less clear is whether and how these nucleation effects alter the crystal structures
present and whether, like organic nucleants, they alter mechanical properties.
43
Figure 1.9 Effect of magnesium hydroxide fillers on the crystallisation of a

polypropylene copolymer (DSC experiment, cooling at 10 C/min)
There is some evidence for a link with mechanical properties in the work of Hutley
and Darlington [96, 97]. They found a good inverse correlation between the nucleating
ability of fillers such as calcium carbonates and falling weight impact strength in PP.
Surprisingly, the organic nucleants were also found to decrease the impact strength in
line with their nucleating ability, although the opposite effect is usually observed, as
discussed earlier. According to these workers, other mechanical properties were little
affected. Mitsuishi and co-workers have also studied the effect of calcium carbonate
on the nucleation and mechanical properties of PP [91]. They reported significant
correlation with the loss modulus, tensile modulus and tensile impact strength. They
confirmed the decrease of impact strength with increasing nucleating effect reported
by Hutley and Darlington.
Quantifying the effects of the fillers on crystal structure and hence explaining the
mechanical property effects described above is very difficult. This is largely because of
the problems of carrying out direct observations using traditional microscopy procedures
with such highly filled systems. Among the effects that could be looked for are: changes
in total level of crystallinity, changes in crystal phase and its orientation, changes in the
number and size of crystalline particles, and changes in the type of crystalline particle. In
none of these areas is the picture completely clear and the effects obtained probably vary
from system to system. One of the more detailed studies in this field has been by McGenity
and co-workers on calcium carbonate and talc-filled polypropylene [98].
44
While there are some reports of significant effects on the overall level of crystallinity,
most studies show little or no effect [92, 98]. Chacko and co-workers reported that the
effect of calcium carbonate on the crystallinity of polyethylene was dependent on molecular
weight with reduced crystallinity being observed at low molecular weight and no effect
at higher molecular weight [94]. Multiple peaks are often observed in melt cooling studies,
(e.g., Figure 1.9) and have been claimed as evidence for the nucleation of new crystal
phases [92]. When X-ray studies have been carried out, they have usually failed to confirm
this [99], although Murthy did report finding that talc altered the crystal phase present
in Nylon 6 [89]. The present author (RR), also found that reheating of magnesium
hydroxide-filled polypropylene displaying the twin peaks in Figure 1.9 only gave a single
melting peak, suggesting that only one phase was present. On the other hand, fillers have
been reported to increase the amounts of beta-phase in polypropylene [98] and to affect
the crystal phase present in Nylon 6 [89].
The few studies that have been carried out to date strongly suggest that particulate fillers
at normal usage levels markedly disrupt the normal spherulitic morphology. This is not
surprising as the interparticle spacing would probably be insufficient to allow these to
develop properly. There is also some evidence that new forms of crystallinity can be
present associated with the particle surfaces.
Thus Chacko and co-workers [94], report lamellar growths originating from selected
spots on calcite surfaces in polyethylenes and radiating outwards for up to 400 m.
Rybnikar reported similar effects for calcite in polypropylene [93]. In their work,
Kowalewski and Galeski carried out a detailed study of calcium carbonate in
polypropylene including work with large single crystals [92]. They reported that the
effects observed depended on the crystal faces present. A form of trans-crystallinity was
observed on some crystal faces and epitaxial growth was postulated for others.
In summary, it seems clear that particulate fillers can have significant nucleating effects
in semi-crystalline polymers and that this may lead to effects on mechanical properties.
Much work remains to be done to clarify this and provide a clear, coherent description
of the effects involved, however. This would be greatly helped if simple techniques for
determining polymer crystal structures in filled systems were available. It would also be
highly desirable to have a better understanding of how the structure of polymer crystallinity
affects composite properties.
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52
2
Principal Types of Particulate Fillers
Michael Hancock and Roger N. Rothon
2.1 Introduction
One of the fascinations of working in the field of particulate-filled polymer composites is

the wide variety of materials used as fillers, from relatively simple chalks and limestones
to complex rare-earth magnetic powders. Even apparently, mundane, relatively
inexpensive, fillers can vary in subtle, but important, ways according to their precise
origin and method of manufacture, thus adding their interest to the scientific and
technological mind.
In the space available here it is only possible to cover the major fillers and a few of the
less common filler materials, the latter having been selected on the basis of lack of adequate
treatment elsewhere and for illustration of important principles.
2.2 Particulate Fillers from Natural Origins (Mineral Fillers)
2.2.1 Introduction
Mineral fillers are a vital and significant part of the worlds polymer industry. Consumption
in rubber and plastics is currently estimated to be over 2.5 million tonnes per year in
Western Europe. In the first edition of this book growth projections were very bullish
and use in plastics especially was projected to grow at 8-12% per year. On a worldwide
basis, it was predicted that 20 Mt per year would be used in polymers by the year 2000
[1]. However, local and world economies have suffered several blows since 1997 and this
volume has not been reached. As a best guestimate the authors believe that filler use in
polymers currently is about 15 Mt per year.
The majority of use consists of low-cost products in which price is the predominant
specification property. Although this will continue to be an important area for mineral
fillers, increasingly sophisticated applications for plastics, rubbers and composites mean
that the requirements placed on fillers and the specific properties imparted by them will
become more demanding; that is, they will be required to perform as functional additives
conferring specific benefits in applications, which will be narrowly defined. It is therefore
53
important to understand the intrinsic properties of the minerals, how these affect bulk
properties and how these then influence the final filled polymer.
The most important mineral fillers used are carbonates, clays and talcs, while other
silicates are also of interest. Several carbonate minerals are known with some having
potential for use as mineral fillers, although only a few are of industrial importance in
plastic and rubber applications.
Calcite (calcium) and dolomite (calcium-magnesium) are the main carbonate fillers and
are very widespread, being exploited in many countries. The other carbonate mineral of
any importance is, in fact, a mixture of two carbonates: hydromagnesite (a hydrated
basic magnesium carbonate: Mg5(CO3)4(OH)2.4H2O) and Huntite (CaCO3.3MgCO3).
A large, relatively pure deposit is found in Greece and a smaller one in Texas, USA, with
the former being exploited as a filler for paint and paper applications, and as a flame-
retardant filler in plastics and rubber.
Clay minerals are aluminium silicates of either the two-layered kaolinite type or three-
layered montmorillonite type. Only three clay minerals are commonly used in the polymer
industries, kaolinite, montmorillonite and chlorite, and these will be discussed below.
Chlorite, because it usually occurs with talc and has essentially the same properties, is
discussed with that mineral. Talc (magnesium silicate) is widespread but is commonly
found with other magnesium minerals such as magnesite.
For a complete analysis of the worlds industrial minerals, the reader is referred to
publications such as the Minerals Yearbook published by the US Department of the
Interior [2] and The Industrial Minerals Handbook [3].
2.2.2 Minerals and Rocks
Strictly speaking, a mineral is a substance of inorganic origin with definite chemical

composition, which is found in the earths crust. Rocks are naturally occuring mixtures
of minerals. With few exceptions, minerals possess an internal ordered arrangement of
their constituent atoms or groups of atoms, that is, they are crystalline. Some lack any
ordered internal structure and are said to be amorphous.
The arrangements (or motifs) of the atoms are determined by the forces between them;
distances and directions from each other are also determined by these forces. These
arrangements are linked together in a three-dimensional repeating network known as a
lattice. From a consideration of the physics of particles packing around each other, it can
be shown that there are only 14 space lattices possible. These are known as Bravais lattices.
There are also limitations on how the motifs are arranged in the lattice such that they fill
54
all space. There are only 32 possible ways of arranging atoms around a point in a lattice
leading to 230 possible arrangements of objects in space, the so-called space groups. The
forces between the atoms result in specific three-dimensional repeatable orders. The limiting
factors depend on the shape of the unit cell and the environment in which it grows.
The external faces of a mineral are therefore partly an accident of growth: changes imposed
by environmental factors do not alter the fundamental properties of the crystal, although
other effects may be noticed. The regular ordered structure of the crystal means that it
may have different properties in different planes and directions.
The nature of the atoms forming the mineral, the forces between them and their order
determine its fundamental properties such as chemistry, density, optical properties,
hardness and shape. They will also determine the mechanisms by which minerals fracture
and thus play a strong role in determining shape, size and size distribution.
Impurities, which are invariably present in the mineral from its original formation, may
also be present in the crystal and will play a significant role in all the above. Impurities
will also play a major role in determining the surface chemistry of the minerals due to
adsorption of organics or inorganics on to faces. The chemistry of the faces may also be
altered, compared with the bulk, by weathering, and fresh faces that may be formed
during processing may have different adsorption behaviour and different reactivities
than weathered ones.
2.2.3 Rocks
Approximately 2000 minerals are known but relatively few are common, and these are
based mainly on the elements aluminium, calcium, carbon, iron, magnesium, oxygen,
potassium, silicon and sodium. Some elements, such as, sulfur and phosphorus, occur in
localised high concentrations. All other elements are found in trace amounts. Minerals
based on silicates and carbonates dominate and these are the ones mostly used in polymers.
This is illustrated in Table 2.1, which shows the principal mineral fillers used in plastics
in Western Europe. They originate from one of the three main divisions of rocks: igneous,
sedimentary or metamorphic.
Igneous rocks are formed by the cooling and solidification of a molten rock mass. During
cooling, ordered crystallisation occurs. However, minerals may be formed not only by
crystallisation, but may also result from reactions between already formed minerals and
molten ingredients. Minerals may be formed throughout a rock, concentrated in certain
areas, or in very localised veins or strata. The bulk of the silicates such as kaolin, mica,
talc, feldspar, wollastonite and quartz are all found in igneous rocks.
55
Table 2.1 Some types of mineral fillers used in plastics in Europe

Chemical composition
Main mineral (simplistic formulae
Filler (crystalline used for the silicates, Shape
phase) see individual entries
for details)
Natural calcium Aspect ratio about 3:1,
Calcite CaCO3
carbonate blocky
Talc Talc MgSiO3 Platy
China clay Kaolinite Al2O3.2SiO2.2H2O Platy
Calcined clay Metakaolinite Al2Si2O7 Low aspect ratio, platy
Calcined clay Amorphous Al2Si2O7 Low aspect ratio, platy
Alumina
Gibbsite Al(OH)3 Low aspect ratio, platy
trihydrate
Magnesium
Brucite Mg(OH)2 Variable
hydroxide
Wollastonite Wollastonite CaSiO3 Acicular
Mica Muscovite KFeMgAlSiOn Platy
Mica Phlogopite KFeMgAlSiOn Platy
Silica Quartz Si O 2 Cubic
Silica Amorphous SiO2 Aggregated
Sedimentary rocks are derived from weathered rock masses and deposited by the action
of water or other means, or by the sedimentation of bioliths (mineral skeletons, shells,
etc., of plants and animals) into layers, or, rarely, by chemical precipitation. Massive
deposits of china clay or kaolin are found as a result of weathering, followed by movement
and deposition. Limestone, the general term for natural calcium carbonate rocks, is the
most abundant of the sedimentary rocks and is formed by the deposition of countless
skeletons and shells. Gypsum and diatomaceous earths occur widely in sedimentary rocks.
Sedimentary rocks are almost universally found in layered beds, which may have folded
or otherwise been altered by subsequent geological events. Layers will differ from each
other in texture, mineralogy and particle size.
Metamorphic rocks are formed mostly from sedimentary deposits, which have been
subjected to stresses occurring within the earths crust. These forces will cause bending,
breaking, generation of considerable heat and inclusion of magma. The temperatures
56
and pressures involved deform rocks, melt and recrystallise them. By far the most
important metamorphic rock is marble, produced from limestone. Impurities in the
limestone can lead to formation of dolomite, tremolite, wollastonite and phlogopite in
the marble. Brucite (magnesium hydroxide) sometimes is found in metamorphosed
limestone. Other minerals of interest to the polymer industries formed by metamorphic
action are biotite, feldspar and chlorite.
2.2.4 Calcium Carbonate Minerals
2.2.4.1 Properties
Calcium carbonate exists in three crystal modifications, aragonite, calcite and vaterite,
but only the calcite form is of real importance. Because of calcites perfect rhombohedral
cleavage, it is a soft mineral with a Mohs hardness of 3.0. It has a specific gravity of 2.7
and is birefringent having refractive indices of 1.65 and 1.48.
2.2.4.2 Occurrence and Processing
Commercially viable deposits of calcite occur throughout the world. These deposits differ
considerably not only in purity, but in size and genesis, and the variations affect the nature
of a filler produced from them. Over the years various terms have been used to describe
these different materials but the ones in general use today are chalk, limestone and marble.
Chalk formations are soft-textured limestones, which were laid down in the cretaceous
period between 70 and 130 million years ago. Nanofossils are still very commonly found
in these deposits and a typical coccolith (with a diameter of about 8 m) found in a chalk
from Wiltshire in the south of the United Kingdom is shown in Figure 2.1.
Limestone is a consolidated sedimentary calcium carbonate rock. Consolidation may be

due to packing by the overlaying rocks or soil or by recrystallisation of calcite through
the leaching effects of water. The deposits are usually organic in origin being formed by
the deposition of shells and skeletons of marine organisms predominantly coccoliths.
Consolidation pressures may have substantially altered these nanofossils.
Marble is metamorphic limestone. Under high pressures and temperatures in, for example,
volcanic activity, the original calcite (or aragonite) has been recrystallised giving rise to a
coarse-grained rock, which is more dense and harder than chalk. Both limestone and
marble deposits can be heavily contaminated with dolomite, calcium magnesium
carbonate, and magnesite, magnesium carbonate, from the interaction of calcite and
magnesium ions in the sea water in which deposition occurred.
57
Figure 2.1 Coccosphere from a UK chalk deposit
During the formation of the original calcium carbonate deposits, other minerals may
also have been deposited, or organic matter and salts may have percolated through the
rocks under action of ground water. During metamorphic transformation, this will have
been incorporated into the marble structure. Thus, a large proportion of the calcium
carbonate throughout the world is contaminated resulting in dark-coloured marbles and
limestones, of little use to the polymer industry.
However, there are many deposits around the world of sufficient purity and close enough
to the surface that products suitable for use in a wide range of applications can be obtained
by a relatively simple dry-mining operation followed by grinding. Grinding can be carried
out dry or in aqueous suspension depending on the exact nature of the impurities present.
Chalk deposits, as mentioned previously, consist of the skeletal remains of marine animals.
These skeletons consist of rounded calcite crystals around 3 m in size, loosely bonded
together. Grinding operations break these agglomerates into their constituent crystals to
produce fillers with average particle size around 3 m (40 wt% of particles finer than 2
m) and a surface area of around 1 m2 g-1 (Figure 2.2). The top cut will depend on the
energy put into the grinding but, for the plastics industry, is usually around BS 300 mesh.
Coarse particles (above 10 m in diameter) can also be removed by classification. Fine
white powders produced from chalk deposits are very widely known as chalk whitings
or simply whitings.
58
Figure 2.2 Typical particles of a ground UK chalk whiting
Marble deposits can be processed in the same way as chalk but, because marble contains
different sized calcite crystals, or grains, a wider range of particle sized products, with
wider size distributions are obtained, especially as there may be a need to fragment large
crystals. Actual particle sizes will depend on the extent of processing, but typical products
will have a mean value of 3-5 m, with 20-30 wt% finer than 2 m and a specific surface
area around 1 m2g-1.
The colour of products, from whichever rock they are produced depends on the purity of
the deposit and whether selection is used prior to grinding and whether purification
procedures, such as magnetic separation are used during processing. In general, ground
marble powders aimed at the polymer industry are coarser, but whiter than ground whitings.
There are also a large number of products produced from heavily compacted limestone,
which are known as ground limestones. Their average particle-size distributions will be
similar to ground-marble products, while colours can range from fairly pure white to
grey. All of these products, because of the rhombohedral cleavage pattern of calcite crystals,
consist of (mostly) uniform calcite crystals with a fairly symmetrical aspect ratio of 3:1.
Producing even finer products than the above requires very large energy inputs because
of the need to cleave these primary calcite crystals, and energy required is
approximately proportional to the new surface produced by grinding [4]. For example,
59
grinding calcite to obtain particles with 0.25 m equivalent spherical diameter (esd)
will use more than 20 times the energy of reducing it to 5 m. Wet grinding is much
more efficient in dissipating such energies and also in transmitting applied stresses.
The calcite crystals formed by grinding very finely in either wet or dry processes will
have the same aspect ratio, approximately 3:1 as the coarse powders discussed earlier.
Although it is found with a large variety of habits, calcite crystals, in fact, have a
rhombohedral shape, which is independent of its particle size [5]. These calcite crystals
are usually fairly pure calcium carbonate with only traces of transition-metal ions
(iron in particular) occurring in the lattice.
Surface layers may be calcium carbonate, hydroxide or, in freshly broken crystals,
possibly calcium oxide. It is now well established that coccoliths in chalk are coated
with very thin aluminosilicates (smectites and other clay minerals) and organic matter
(humates, etc) [6]. During comminution, compaction or metamorphosis, these coatings
may be disrupted or may still adhere to the calcite surface. Aluminium silicates have
been identified in pure limestones and pure marbles, and have been shown to be
unattached to calcite fragments.
2.2.4.3 Surface Modification
Although it seems that the calcite surface in these fillers is often covered by either organic
materials or silicate minerals, their chemistry is determined by the basic nature of calcium
carbonate and its reactivity towards acids. This is of considerable importance. In particular,
their reaction with fatty or other organic acids, but especially stearic acid, has been used
for many years [7, 8] to improve compatibility with, and dispersion in, polymers. The
coated fillers are much more hydrophobic than uncoated ones, reducing water pick-up,
and they have also been shown to have an effect on polymer morphology, and hence
modifying properties (see Chapter 1).
It is postulated that the stearic acid molecules interact with the calcium carbonate, with
the carboxylate ion reacting with the surface and the organic chains sticking out normal
from the surface. It has been reported that oleic acid, or any other acid, in which the
presence of double bonds alters chain configuration, adsorbs up to a monolayer with the
molecules lying flat on the mineral surface [9].
Much work has been carried out on other surface modifications of calcium carbonate
[10] and a more detailed discussion can be found in Chapter 4. From the authors
experience, many beneficial claims have been made (mostly in patents) for surface
treatments and coupling reactions, but the evidence when examined is flawed. Certainly,
the market place is sceptical of the supposed benefits because very few coupling
agents/surface modifications are used commercially.
60
2.2.4.4 Uses
Calcium carbonate is used in many rubber and plastic applications, mainly to reduce
cost, but ultrafine grades, especially when stearate coated, can give technical advantages,
for example, in polypropylene (PP) mouldings, unplasticised polyvinyl chloride (PVC)
extrusions and polysulfide sealants.
2.2.5 Dolomite
2.2.5.1 Properties, Occurrence and Extraction
The other carbonate mineral in common use as a filler is dolomite: calcium magnesium
carbonate (CaCO3. MgCO3). It is in the trigonal crystal system and is usually found as
rhombohedral crystals with curved composite faces. Dolomite is harder (3.5), denser
(2.85), and slightly more acid resistant than calcite, but in general, the mineral properties
and properties in a polymer are similar.
Dolomite is very widespread with at least 60 producers in 27 countries, but the bulk of
the production goes into building and chemical industries; there are only a handful of
suppliers of fine powders to the polymer industries.
Production is by dry mining and dry grinding, with air classification to remove coarse
particles (down to 10 m).
2.2.5.2 Uses
The uses of dolomite follow the same pattern as calcite, although, because its occurrence
is much less widespread, tonnage is much lower. Ultrafine products (i.e., with an average
particle size of 1 m), are not available. Because dolomite is more difficult to grind than
calcite due to its higher hardness, comminution is more costly.
2.2.6 China Clay or Kaolin
2.2.6.1 Occurrence, Extraction and Properties
Kaolin (Al2O3.2SiO2.2H2O), is probably more widely known as the clay mineral, china
clay [11]. It is found in hydrothermal, residual and sedimentary deposits (probably about
1000 are still commercially worked) around the world with the most important resources
being in Cornwall in SW England and in South Carolina and Georgia in the USA. Large
61
deposits are found, and are being progressively exploited in, for example, Russia, the
Ukraine, the Amazon basin in Brazil, Spain, Australia, Bavaria and Bohemia. There has
been a significant consolidation of the industry in the last few years.
Hydrothermal and residual deposits are classified as primary occurrences, although some
authorities call them secondary as they are found in the rocks from which they have been
formed. Sedimentary deposits are always secondary. The kaolins are formed by the
hydrothermal alteration and weathering of feldspathic igneous and metamorphic rocks
(especially granite) under relatively low temperatures and pressures. The most common
parent minerals are feldspars and muscovite micas. The primary deposits will usually be
mixed with unaltered granite, mica, feldspar and quartz. Secondary deposits are usually
found in layered qualities with very variable purity.
The main primary deposits in SW England and Brazil are exploited by hydraulic mining,
while other small commercial deposits are utilised by a variety of techniques, with varying
levels of sophistication. The most widespread involves dry mining of selected areas
followed by a batch wet-washing and sometimes refining in terms of particle size. Products
are then dried. In hydraulic mining the clay is washed out of the granite matrix using
high-pressure jets of water. Refining into different particle size fractions is carried out by
sedimentation of this aqueous slurry, using the principle of Stokes law for particles falling
through a viscous medium to select the required particle size. To achieve good separation,
the particles must be deflocculated (separated from each other); this is usually achieved
at a neutral pH and by treatment with a polyanion (see below). Mineralogical separation
is also achieved in the refining step with ancillary minerals (mostly feldspar, quartz and
mica) remaining in the coarse fractions. During aqueous processing, products may be
reductively or oxidatively bleached to reduce or remove coloured inorganic (usually
hydrated iron oxides), and organic (humus type materials) coatings on the particle surface.
The clays are then filtered, dried and, for the polymer industries, pulverised to break
down agglomerates, which form during drying.
Sedimentary deposits are mined by a variety of techniques depending on the nature and
extent of the impurities. The simplest and cheapest production route involves dry mining,
crushing and milling. More sophistication is used for air-float products, where the clay
after crushing and grinding passes into an air stream of constant velocity and grit and
coarse particles remain behind. More controlled, purer, products are produced by wet-
refining with the dry-mined clay being dispersed in water, degritted and refined using
hydrocyclones or centrifuges.
Micromineral separation is being used increasingly in both types of production routes

with flotation, selective flocculation and magnetic separation being used to remove
impurities from the clay.
62
Figure 2.3 Stack of kaolinite crystals found in granite
Particle-size distributions (expressed as equivalent spherical diameter, esd) of clays depend

on the inherent particle size of the deposit and the amount of refining that has been
carried out during production. In primary deposits the kaolin plates are usually bound
together in a book-type structure (Figure 2.3) and refining will separate them to a certain
extent. Most commercial products for the polymer industries will be degritted at 300
mesh, so the normal top cut is at least 75 m. More commonly, clays will have been
refined to 20 or 10 m for a range of applications, and speciality products will have a
top cut of 5 m or finer.
Secondary clays are usually very much finer than primary clays and products that are
approximately 100% finer than 5 m can be obtained by a fairly simple air-float or
degritting procedure.
Although kaolin, china clay (and even clay) are often used interchangeably as names, the
main mineral present is usually (but not invariably) kaolinite. In fact some china clays
are sold that contain only 25% kaolinite, but normally kaolins will contain 50-99%
kaolinite with the main impurities being mica, quartz and feldspar. Other silicates, metal
oxides and organic matter are usually found in trace amounts.
Pure kaolinite has the idealised chemical composition Al2 O3.2SiO2.2H2O. It is a crystalline
material with a triclinic form found in microscopic pseudo-hexagonal plates (Figure 2.4),
63
Figure 2.4 Typical kaolinite plates
which readily undergo cleavage. As a consequence it has a low Mohs hardness, between
2.5 and 3, depending on the ancillary minerals present. Its specific gravity is 2.6 and refractive
index is 1.56. Its structure can be regarded as a gibbsite (Al(OH)3), layer bonded to a
siloxane (Si2O5) layer. The silica atom in the siloxane layer is tetrahedrally bound to four
oxygen atoms and the aluminium atom in the gibbsite grouping completes its favoured
octahedral environment by coordinating to three oxygen atoms in the siloxane group.
Thus, one face of this structure comprises oxygen atoms and the other of hydroxyl groups.
These will interact through hydrogen bonding giving a layered kaolinite crystal, which has
a pseudohexagonal platy shape.
The idealised structure described above is invariably spoilt by nature. Isomorphous

substitution of both silica and aluminium ions by transition metals, and particularly by
iron, occurs. This leads to electrical charges occurring on the plates with edges being
positively charged and faces negatively charged; the charges are countered by ions, which
surround the particles in a double layer. (The reader is referred to Jepson [11] and references
therein for a more complete discussion of the properties of clay and kaolinite). Because
of the isomorphous substitution and also because of the occurrence of broken bonds at
the edges, there are both Lewis and Bronsted acid sites on the surface of a kaolinite
particle [12]. These can be very reactive. There is also evidence that some kaolinite particles
are covered with a monolayer of amorphous silicic acid [13], with organic matter [14]
and with hydrated iron oxides [15]. These thin, hexagonal plates have aspect ratios in
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the range 5:1 to 50:1 (but very fine clays can have even higher aspect ratios), which are
dependent on particle size [16]. Aspect ratios of the plates depend on the nature of the
clay deposit with, for example, US clays being chunkier than clays from SW England,
but they are also dependent on the processing used because kaolinite stacks or booklets
readily cleave during processing.
Kaolinite reacts only with very strong acids and bases, is not affected by organic solvents,
and undergoes ion exchange reactions, but from most points of view, it is an inert mineral.
It does undergo a complex series of reactions when heated, which are of commercial
importance and will be discussed fully next.
2.2.6.2 Surface Chemistry and Modification
Although kaolin can be regarded as chemically inert it does have a complicated surface
chemistry. Hydroxyl ions either from the gibbsite layer or from adsorbed gels readily
react with commercial bifunctional silanes [17], titanates or other coupling agents [18].
Kaolinite plates have negatively charged faces and positively charged edges and adsorption
of both positive and negative ions are of great commercial importance. For example,
small amounts of polyanions adsorb on to edges, deflocculating or flocculating the clay
depending on the molecular weight of the polymer, and are an essential feature of its use
in aqueous media (the paper and paint industries especially).
The presence of Lewis and Bronsted acid sites gives rise to a variety of chemical reactions.
Amines, or other Lewis bases, readily adsorb and the use of fatty amines to render the
clay organophilic has been applied for many years to modify properties in a number of
applications [19, 20]. Because of these reactive sites, kaolin will enter into organic reactions
and, of particular interest for plastics, will catalyse the polymerisation of certain
monomers. Sometimes depolymerisation can occur and it can promote the
dehydrochlorination reaction of PVC [21].
2.2.6.3 Uses
China clay is a widely used white filler in the rubber industry. Depending on particle size,
it can be used as a semi-reinforcing filler (hard clay) or a non-reinforcing filler (soft clay)
in such applications as chemical liners, bicycle tyres, conveyor belts, shoe soles, gaskets
and flooring. Its use in plastics is much more limited. In thermoplastics it is used for
speciality antiblocking, in thermosets it is used in urea-, phenol- and melamine
formaldehyde, in unsaturated polyesters, and in epoxy resins.
65
Figure 2.5 Differential thermal analysis trace for a typical china clay
2.2.7 Calcined Clay
When kaolinite is heated (Figure 2.5) to above 500 C it dehydroxylates endothermically,

that is, it loses its water of crystallisation forming metakaolinite. This is then stable up to
980 C, when a defect spinel structure, which is virtually amorphous, forms exothermically.
Above 1100 C there is a slow transformation of the defect spinel with mullite forming
in an amorphous silica matrix.
If the heating is carried out very rapidly, then the outside of the clay particles can fuse,
forming a glass before dehydroxylation occurs. The water formed cannot escape and
forms closed pores, giving a lighter weight aluminosilicate, which still has a defect spinel
structure. Each separate step produces aluminosilicates with unique properties having
considerable commercial importance in the polymer industries.
2.2.7.1 Metakaolin
Above 500 C kaolinite starts to lose its water of crystallisation and, by 650 C,
approximately 90% of this dehydroxylation is complete, leaving residual OH groups
randomly distributed but isolated so that condensation will not occur readily. The product
formed is known as metakaolin. Some crystalline structure is retained [22] but X-ray
diffraction patterns are so diffuse and weak that no better, more recent, identification
has been made. After these structural changes the aluminium, which was originally in
six-fold octahedral sites, occupies four- and five-fold sites almost equally [23].
66
Metakaolin is much more chemically reactive than the kaolinite from which it was formed
[24] and also, deduced from the properties of the polymer composites in which it is used;
it has a very reactive surface. This is probably a consequence of an increase in the number
of Lewis sites due to the reduction in coordination numbers of the aluminium ions and
to the presence of reactive hydroxyls.
2.2.7.2 Calcined Clay
Metakaolin is stable up to 980 C, although between 900 C and 950 C the remaining
OH groups become mobile and condense. This causes the rearrangement of the poorly
crystalline metakaolinite structure to an amorphous defect spinel, which is commonly
called calcined clay. This may also be regarded as formation of poorly crystalline mullite
and a spinel phase with the separation of amorphous silica [25]. However, experimentally,
the material produced up to 1100 C is X-ray amorphous and the various phases suggested
above are deduced from other techniques, such as nuclear magnetic resonance (NMR).
Some isolated hydroxyl ions still remain on the surface of the calcined clay [26] and these
enable it to participate extensively in coupling reactions, which are of considerable
importance (see Section 2.2.7.4).
2.2.7.3 Refractory Material
Above 1100 C the rearrangement of the defect spinel into amorphous silica and mullite
accelerates with the mullite becoming progressively richer in aluminium up to 1500 C.
On cooling the mullite crystallises into needles, which are embedded in an amorphous
aluminosilicate glass. It is a very hard, abrasive mineral, which is virtually inert to all
chemicals and environments.
During calcination, kaolinite plates tend to fuse face-to-face with the consequences that
calcined clays are coarser than the feed clays from which they are produced, but also
have significantly lower aspect ratios, approximately 5:1 (Figure 2.6). Up to a calcining
temperature of 1100 C, cleavage is the preferred mechanism of comminution, but energy
requirements are high. Above 1100 C the rearrangement into defect spinel, amorphous
silica and mullite, and subsequent recrystallisation means that particles become spherical
and undergo fracture on grinding. Metakaolin and the amorphous aluminosilicate
produced at 980-1100 C have approximately the same Mohs hardness of 4.0, specific
gravity 2.6 and refractive index 1.6.
Above 980 C, calcined clays are almost completely inert reacting only with very strong
acids and alkalis under normal conditions. Their surfaces are likewise inert except for
67
Figure 2.6 Particales of clay after calcination at 1100 C
the fact that between 980 and approximately 1100 C there are still some reactive
hydroxyls present. These react readily with hydrolysable groups such as found in the
standard ranges of coupling agents, giving rise to a number of commercial fillers; these
are mostly based on bifunctional silanes.
2.2.7.4 Uses
There is some overlap in the performance of metakaolinite and calcined clay in certain
polymers and hence some contiguous applications such as low-voltage rubber cable
insulation, but there are significant differences, which leads to separate use patterns.
Thus, metakaolinite is mainly used in PVC cable insulation because it improves (uniquely)
the electrical resistivity of plasticised PVC, while calcined clay is used in polyethylene
(PE) film, rubber cables, rubber pharmaceutical applications and rubber extrusions for a
variety of reasons linked to its shape, size and chemical inertness. The refractory product
finds limited use in epoxy and unsaturated polyester mouldings, which have to resist
abrasion and chemical attack.
When silane-treated, calcined clay can be used in polyamide and polybutylterephthalate

(PBT) moulding compounds and in very high-voltage rubber cable insulation. Each
application needs a silane with a different functionality.
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2.2.8 Mica
2.2.8.1 Properties
Mica is the name of a group of phyllosilicate minerals with the generalised chemical
formulation KM(AlSi3O10)(OH)2, where M may be Al, Fe, Mg or combinations of these
metals. All are characterised by a plate morphology and perfect basal cleavage, a
consequence of their layered atomic structure. They are all monoclinic. Crystals are rare
but are usually tabular in form. Their hardness is between 2.0 and 2.5, and specific
gravity between 2.76 and 2.88, both depending on impurity levels. Colour is also variable.
Refractive indices are directionally dependent between 1.56-1.57 ( direction) and 1.60-
1.615 ( direction), so they show strong birefringence.
2.2.8.2 Occurrence and Extraction
There are three commercially important micas: muscovite, which is aluminium rich,
with colours varying from white to silver to pale grey or green; phlogopite, which is rich
in magnesium, and biotite, which is rich in magnesium and iron. Both phlogopite and
biotite are usually darker in colour than muscovite micas. There are also zinnwaldite [a
lithium rich mica: KLiFe2+Al(AlSi2)O10(F, OH)2], and lepidolite K(Li, Al)3(Si, Al)4O10(F,
OH)2, which are widespread but of no commercial importance in the polymer industries.
Muscovite is a widespread and common rock-forming mineral, which is characteristic of

granite. It is therefore commonly found in conjunction with other silicates and silicas
such as kaolinite, feldspar and quartz, sometimes as the major, sometimes as the minor
constituent. Production in these cases is by wet refining followed by flotation.
Muscovite is also found in isolated massive deposits and production follows a dry mining
(for the purest products these may involve hand-selection), grinding route. It is a very
platy mineral that undergoes perfect planar cleavage (see later in this section) but plates
can also undergo fracture. Therefore, both dry grinding and wet grinding are employed
using a variety of grinding media to achieve different particle-size products with different
aspect ratios. Usually careful wet milling, using say a ball mill, is used to give products
with the highest aspect ratios. Commercial deposits occur in Argentina, Brazil, Canada,
France, India, Republic of South Africa, Russia, UK, USA and Zambia.
Phlogopite is also widespread being formed by the metamorphosis of magnesium

limestones, dolomites and tetrabasic rocks. It is found usually in isolated massive deposits
and processing follows a selection, dry mining, grinding procedure. Deposits occur in
Canada, India and Madagascar.
69
Biotite is an important and widely distributed rock-bearing mineral occurring in igneous

rocks and thus is a major impurity in many other silicate minerals. Vermiculite, an
alteration product of biotite and phlogopite, has its mica sheets interlayered with water.
During calcination, exfoliation occurs due to water loss, and this expanded product has
considerable use in heat and sound insulation because it has a very low specific gravity.
Muscovite, ideally KAl2(AlSi3O10)(OH)2, has a dioctahedral structure but with some of

the tetravalent silicon atoms being substituted by aluminium. This leads to negative
charges on the aluminosilicate sheets, which are balanced by cations. Phlogopite and
biotite have trioctahedral structures with, again, aluminium substituting partly for silicon
and subsequent charges balanced by cations. In all three potassium is the common cation.
These layered structures are only bonded weakly through large monovalent cations
and thus micas cleave very readily to, in theory at least, monolayer thickness. Some
rarer micas have more than one silicon atom substituted by aluminium; the extra
negative charge produced by this is balanced by bivalent cations such as calcium.
Stronger bonding occurs and these micas do not cleave so readily, are harder and much
more brittle.
2.2.8.3 Uses
Currently mica is used in phenolic moulding compounds aimed at the electrical industry
and in some polypropylene mouldings. Because of the birefringence exhibited, some
mica is used in decorative articles, sometimes with additional coatings.
2.2.9 Talc
2.2.9.1 Properties of Talc
Pure talc has the chemical composition Mg3(Si4O10)(OH)2. It has a trioctahedral structure
in which an octahedral brucite, Mg(OH)2, sheet is sandwiched between two tetrahedral
siloxane (S2O5) sheets. This structure is electrically neutral and will bond to an adjacent
layer only through Van der Waals forces. Thus talc undergoes cleavage very readily, is
very soft and has a soapy feel. Faces of the layers consist of oxygen atoms, hydroxyl
groups are only found at broken edges so that it is fairly hydrophobic.
Pure talc is the softest known mineral with a hardness of 1 on the Mohs hardness scale,
specific gravity is 2.8, and it has three indices of refraction, 1.539, 1.589 and 1.589,
according to crystal direction. Typical particles are shown in Figure 2.7.
70
Figure 2.7 Particles of a pure, fine talc
Talc is a secondary mineral, which is found characteristically in metamorphic rocks from the
degradation of minerals such as olivine, pyroxene and amphibole and also along faults in
magnesium rich rock. The designation talc covers a wide range of natural products because
the metamorphic changes that gave rise to talc also produced other magnesium minerals.
Impurities commonly encountered include magnesite (magnesium carbonate), chlorite (a
mixed magnesium silicate-magnesium hydroxide in which Fe2+, Fe3+ and Al3+ may substitute
for Mg2+ and Al3+ for Si4+) and tremolite (calcium magnesium silicate). In fact, commercial
talcs may contain the mineral talc only as a minor constituent or, in some (all chlorite) not at
all. The only two products of significance to the plastics industry are talc and chlorite.
Processable talc deposits are widespread, although not as extensive as those of calcium
carbonate or clay, with main production coming from north-east, south and west USA,
Norway, France, Italy, India, China and Australia. Some massive forms, known as steatite
or soapstone (after the characteristic soapy feel of talc) occur, but most of the talc is
found in veins.
It is produced by conventional selective opencast mining or by underground mining

followed by crushing, grinding, beneficiation and classification. After the crude rock is
crushed it is often subjected to a manual selection process, although automated techniques
are now being introduced (based on colour selection). It is then ground in a variety of
ball mills, hammer mills and fluid mills with air-classification systems included in a closed-
71
loop system to produce products with a range of particle-size distributions but with the
majority having top cuts of 100, 200, and 300 mesh, 20 and 10 m.
Some talcs may be subjected to beneficiation by froth flotation. The talc is ground,
dispersed in water, subjected to froth flotation in which the talc may be floated from the
impurities or vice versa using a surfactant, selective for the appropriate surface, to transfer
it to a foam and effect separation. The talc may then be subjected to grinding, classification
or both to achieve the desired particle size distribution.
2.2.9.3 Other Talcs
Although described as talcs, many commercial products can contain large quantities of
other minerals (as described above). These can markedly affect overall aspect ratio and
hardness, and care should be taken in choosing talc for a specific application. Some talcs
may contain fibrous minerals which pose health problems and the use of such talcs,
especially where the fibrous mineral is tremolite, is strictly controlled in many countries.
While normally lamellar or platy the aspect ratio of talc can vary considerably and is not
usually specified, although high aspect ratio is the most important property in its use.
Conventional surface treatments do not appear to be very effective on talc. This may be
due to the low concentration of reactive surface hydroxyls or to the weak nature of the
particles themselves.
2.2.9.5 Uses
Talc, because of its high aspect ratio, is used in a variety of applications. In rubber, it is
used as a partitioning agent and as a semi-reinforcing filler; in membranes, to reduce gas
and fluid permeability; and in electrical insulation and sheathing. In plastics it is used to
give rigidity to thermoplastics, mostly PP but also some PE and Nylon mouldings.
2.2.10 Montmorillonite (AlMg)8(Si4O10)3-(OH)10.12H2O
2.2.10.1 Properties and Occurence
The montmorillonite group, also known as bentonite, comprises a number of clay minerals
with dioctahedral (gibbsite) and trioctahedral (Si2O5) groups in three layer structures. They
72
have charge deficiencies partly due to isomorphous substitution of Al3+ and Si4+ in each
layer, which are balanced by cations (principally sodium and calcium). Water, other hydroxyl-
containing groups and amines readily break these ionic bonds. Once the sheets have been
parted, many layers can be adsorbed producing a marked expansion of the structure.
Bentonites treated with up to 40 wt% long chain fatty amines (such as octadecylamine),
often called organoclays, give structure or thixotropy to organic liquids and, for example
are widely used in solvent-based paints. Under certain conditions, separation of the platelets
into primary layers can occur giving very high aspect-ratio products.
Montmorillonite is monoclinic occurring in very thin, small platelets with specific gravity
2.5, Mohs hardness of 1-1.5 and refractive index of 1.50-1.64. It is the predominant
clay mineral in bentonite and is found with other clay minerals, such as kaolin, and
with silica. Commercial deposits are found in the Morocco, Spain, Turkey and USA.
2.2.10.2 Uses
The main uses of montmorillonite stem from its characteristic expansion, and it is used to
control viscosity or impart thixotropy to a variety of liquid polymers based on unsaturated
polyesters, PVC plastisols, polysulfides, alkyds, etc. It has also been reported to control the
melt rheology of thermoplastics and to reinforce polyamides. There has, over the last few
years, been enormous industrial and research interest, with many papers and patents,
published on montmorillonite, especially as an organoclay as the basis of polymer
nanocomposites. Because of the delamination process described above plastic-organoclay
nanocomposites have been reported to have very high rigidity, low permeability to fluids,
and fire resistance. This subject is covered in more detail in Chapter 10.
2.2.11 Barites (BaSO4)
2.2.11.1 Occurence and Properties
This is widespread usually as a gangue (impurity) mineral in hydrothermal veins associated

with metallic ores; some also occurs in limestone or clay. Its crystals are usually tabular
and often diamond shaped, but fairly symmetrical. It has two features of commercial
interest. Its specific gravity, 4.5, is the highest of the non-metallic minerals and it is
chemically inert. It has a Mohs hardness of 3.5, and a refractive index 1.64-1.65.
2.2.11.2 Uses
It is used in a variety of polymers to give a very high density, for example, for sound
deadening. It is also used in applications that require very high levels of chemical resistance.
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2.2.12 Calcium Sulfate Products
2.2.12.1 Occurence and Properties
Gypsum (CaSO22H2O), is a common mineral very widely distributed in sedimentary beds

throughout the world. It comprises monoclinic crystals with perfect cleavage yielding thin
folia. It is a soft mineral with a Mohs hardness of 2, specific gravity 2.32 and refractive index
1.52-1.53. It is slightly soluble in water and hydrochloric acid, but its principal chemical
reaction is that it starts to dehydrate between 65 and 140 C giving a hemi-hydrate known as
plaster of Paris, which further dehydrates up to 200 C giving anhydrite, which is also found
commercially. Gypsum can recrystallise from aqueous media to give a fibrous form, which
can be dehydrated to give plaster of Paris or anhydrite in fibrous form.
The hemi-hydrate will slowly rehydrate hardening and setting. Many millions of tonnes
of gypsum are used worldwide as a consequence of this dehydration - rehydration reaction
and are used in building boards, moulds, casts, plasters, etc.
There have been significant developments in recent years in the production of calcium
sulfate dihydrate, anhydrous and fibrous calcium sulfate, and their applications as flame-
retardants and as fillers for plastics. These are described fully by Socha and the reader is
referred to that paper [27].
2.2.13 Wollastonite (CaSiO3)
2.2.13.1 Properties
Wollastonite is a white, needle-like mineral with a specific gravity of 2.9, Mohs hardness
of 4.5 and refractive index between 1.63 and 1.67. It is triclinic and undergoes cleavage
along all three faces so it can be obtained in acicular forms with high aspect ratios.
However, these needles also readily fracture to give low aspect-ratio fragments. Their
aspect ratio is usually 1:8 but higher values can be obtained depending on production
route. Typical wollastonite particles are shown in Figure 2.8.
Although wollastonite is a constituent of many types of rock, it is rarely found in an

economically processable form. The majority of deposits are formed by contact
metamorphism of limestone and quartz. Extraction is concentrated on distinct, fairly pure,
layers of wollastonite-rich rock. Worldwide production is currently about 250,000 tonnes
per year, with China, Finland, India, Mexico and USA being the main producing countries.
74
Figure 2.8 Typical wollastonite particles
It is obtained by both opencast and underground mining. After extraction and crushing,
the material is beneficiated either magnetically to remove garnet and diopside, or by
flotation to remove quartz and calcite. The various wollastonite fractions are then blended,
dried and ground, either in a pebble or attrition mill. The latter mill produces the high
aspect ratio particles of most use in polymers. Finally, the products are classified and
bagged; surface treatments are also often added to grades intended for polymer uses.
Numerous surface treatments are used to improve dispersion, particle alignment and
particle to polymer adhesion. They can also aid in reducing the abrasiveness of the hard
particles to processing equipment, especially dies. Silane coupling agents are very effective
and are widely used. Stearate coatings have also been reported to have some applications,
but have not been specified by the wollastonite producers.
2.2.13.4 Applications
The polymer applications of wollastonite are mainly based on its combination of acicularity,
chemical inertness, whiteness and low water adsorption. Primary consuming polymers include
thermoplastics, such as polypropylenes and polyamides, and thermosets, such as polyester
dough and sheet-moulding compounds, epoxies and phenolics. Manufacturers are predicting
considerable growth in reinforced reaction injection moulding (RRIM) systems.
75
2.2.14 Crystalline Silicas
2.2.14.1 Properties, Occurrence and Extraction
Crystalline silica is the most ubiquitous mineral on earth, being found as a component in
almost all other mineral deposits. There are over 20 crystalline phases of silica, differing
only slightly in physical properties. Most of these occur naturally, but only a few find
any significant use in polymers, notably quartz, novacite and crystobalite. Quartz is the
most widely used and is usually found as prismatic crystals. Mohs hardness is 7, specific
gravity is 2.6 and refractive index 1.54-1.55.
Despite the widespread nature of crystalline silicas, high-purity deposits that are close
enough to the surface for economically feasible recovery are not numerous. For polymer
applications the purity normally has to be 99% or greater. Good-quality silica deposits
have been commercially developed in the US, Europe, India and Australia, although
processing methods are most developed and the widest range of grades are available in
the US and Europe. Japan has begun processing imported Australian and Indian silica,
and now has some grades available.
Naturally occurring silica is categorised as crystalline or microcrystalline according to

the size of the primary particles in the deposit. Some deposits contain mostly large primary
particles, well over 600 m in size, while others may contain primary particles of under
100 m. All deposits will contain mixtures of many primary particle sizes, either tightly
or loosely bonded together. High concentrations of small loosely bonded primary particles
usually characterise microcrystalline deposits and the matrix is thus usually quite friable.
Larger, more tightly bonded primary particles are usually referred to as crystalline silica.
Primary particle shape can range from round to angular, depending on the natural deposit,
but once the primary particle is broken by grinding, all crystalline silica particles become
angular in shape. Once ground, the performance of micrometre and submicrometre
crystalline silica particles in a polymer composite is influenced by both particle size
distribution and an acceptable topsize. Extraction is predominantly by crushing, removal
of major impurities, drying, grinding and classification. Typical silica particles are shown
in Figure 2.9.
2.2.14.2 Particle Size
Crystalline silicas as used for filler applications are generally low surface area, low-oil-
adsorption materials with angular particles graded by topsize. Identification is on the
basis of 98% passing a given spherical micrometre size. A 44 m product would
therefore have 98% by weight of particles below 44 m. (NB: This odd-looking
76
Figure 2.9 Typical particles of a crystalline silica used in polymers
definition is due to the inability of 100% passing to be precisely defined by practical

particle-size equipment. Passing 98% is more readily characterised and is still near
enough to 100% to be meaningful.)
Particle size distribution is as important as top size for many applications and can vary
due to the nature of the deposit or the processing conditions used. A major issue is
consistency of both top size and size distribution. In coatings and liquid composites with
relatively low loadings, a narrow particle size distribution is generally preferred. At high
loadings, a controlled, broad distribution is preferred for more efficient particle packing.
2.2.14.3 Uses in Polymer Composites
The uses of crystalline silica are a result of its high hardness, chemical inertness, heat
resistance, low coefficient of thermal expansion and good electrical insulation properties.
Crystalline silicas also respond readily to silane coupling agents and have useful optical
effects due to their lack of birefringence and low refractive index. Their major drawbacks
are their abrasivity (causing wear of machinery) and possible health hazards (see Section
2.2.14.4). The properties mentioned previously make silica a very good functional extender
for thermoset plastics, such as epoxy moulding and potting compounds for electrical
and electronic parts, and unsaturated polyester compounds for microwave dishware.
Crystalline silica has a natural affinity for silicone elastomers making it semi-reinforcing,
especially when a silane coupling agent is used.
77
2.2.14.4 Health Issues
Crystalline silica differs from the other minerals discussed previously in that there are
considerable concerns about its safety; while all the other minerals are currently regarded
as nuisance dusts, users and potential users are strongly advised to obtain specific advice
and information from individual suppliers.
The primary hazard with crystalline silica is the development of silicosis due to the
inhalation of fine particles (<10 m). There are reports that the exposure to silica (or the
existence of silicosis) is associated with an increase in the incidence of lung cancer; the
International Agency for Research on Cancer classifies silica in Group 2A probably
carcinogenic to humans. The applicable governmental regulations in various countries
should be consulted and followed. Also, various codes of practice, such as ASTME 1132
[28], Standard Practice for Health Requirements Relating to Occupational Exposure to
Silica, and ANSI Z 88.2 [29], Practices for Respiratory Protection, may be consulted.
The EU Scientific Committee on Occupational Exposure Limits (OEL) for Silica

(Crystalline) issued in July 2002, recommendations that its OEL should lie below 0.05
mg/m3 of respirable dust.
2.3 Synthetic Particulate Fillers
2.3.1 Carbon Black
Although synthetic and of relatively high cost, carbon blacks are produced in vast
quantities for use in polymers. This is mainly due to their widespread use as a reinforcing
agent for elastomers, especially in tyre applications. Worldwide production was estimated
to be 6.2 Mt in 1999, of which about 90% was used in rubber applications [30].
In addition to their economic importance, carbon blacks exhibit extreme forms of some of
the most difficult characterisation issues in the particulate fillers area, especially regarding
size and shape determinations, and surface chemistry. However, largely because of their
commercial value, more has been done to make advances in these fields than with most
other fillers and this pioneering work has much to teach us in a general sense.
In elastomers, carbon blacks are used at relatively high, filler, loadings, but function as
reinforcing agents, improving many properties of the composite, especially tensile strength,
tear strength, stiffness, abrasion resistance and dynamic properties. In thermoplastics,
they are used at lower loadings to improve weathering performance. A specialised
78
application is as an electrically conductive filler in the production of antistatic compounds

from both thermoplastics and thermosets. They are also widely used as pigments. Because
of their importance, carbon blacks have been studied extensively and have a voluminous
literature. Only a brief outline of their manufacture, properties and uses will be given
here. The reader is referred to specialist publications, such as that by Donnet and co-
workers, for more details [31].
2.3.1.2 Production
Carbon blacks are, in effect, soots produced by incomplete combustion of volatile

organic materials, principally oil and gas. As such they have been made and used as
pigments for well over a thousand years. Their production as fillers for polymers has
only been carried out since the early part of this century. During this time, there have
been four main processes resulting in products of different characteristics: furnace,
channel, thermal and lamp blacks.
Today, the furnace process dominates, accounting for well over 95% of all black
production, the rest being largely thermal black for specialised applications. The furnace
process, as its name implies, is based on combustion of gas or oil in a specially
constructed furnace. A carefully controlled air to fuel ratio is used. This, together with
the turbulence in the furnace, largely controls the particle shapes and sizes produced.
The nature of the feedstock also affects size, with the finest particles being produced
from natural gas rather than oil. Residence times in the furnace are very short and, on
leaving, the hot gases are quenched by a water spray. The carbon black is collected by
a combination of electrostatic precipitation, cyclones and bag filters.
As discussed in Chapter 1, the morphology or structure of carbon black is a very

important property. In addition to turbulence in the furnace, this is controlled by
introducing additives into the flame. Because blacks produced by this route are of very
low bulk density, they are difficult to transport and handle. They are therefore usually
formed into free-flowing pellets by a wet-pelletising process. This has to be controlled
carefully so that the pellets are strong enough to pass through solids handling equipment
without breaking down, but are readily dispersed to their primary particles when used
in polymers.
In the channel black process, diffusion flames burning natural-gas impinge on reciprocating
metal channels where carbon is deposited. Rotating drums may also be used. The carbon
is scraped off, collected, micro-pulverised and then usually pelletised. These blacks have
a much higher combined oxygen content than furnace blacks. This process is little used
now largely due to unfavourable economics and environmental problems.
79
The thermal process produces low-structure blacks of fairly large particle size. These
have certain niche applications and, hence, while not as economically attractive as the
furnace route, some thermal black continues to be made. The process is carried out
batch-wise by decomposing methane (from natural gas) into carbon and hydrogen in the
absence of air, in a furnace at about 1300 C. The furnace is preheated by burning an air-
fuel mixture, the fuel often being the hydrogen from the process itself.
A related process is used to produce acetylene blacks. Acetylene is decomposed to carbon

and hydrogen in a controlled manner. Being exothermic, this can be carried out in a
continuous fashion. The black produced has laminar or platy particles. Its primary use
in polymers is to impart electrical conductivity.
2.3.1.3 Properties
As the name implies, carbon black is largely composed of carbon, although considerable
quantities of hydrogen and oxygen can also be present. The particles are submicrometer in
size, with surface areas in the range of 5-150 m2 g-1. The thermal blacks are at the lower
end of the surface area range, and are approximately spherical; but the others have complex
three-dimensional shapes, which can be thought of as the partial fusing together of a number
of nanometre-sized spherical primary particles. This complex shape is known as structure
and is usually measured by a variant of the oil absorption procedure. Structure plays an
important role in determining many of the key properties of elastomer composites [32].
Because of this, much effort has been, and still is being, devoted to describing the shape of
carbon black particles and understanding how this affects composite properties. A further
discussion of shape measurement can be found in Chapter 1.
Carbon blacks have very chemically active surfaces resulting from their production process,
with hydrogen, oxygen and sulfur being the principal surface atoms combined with the
carbon. The species of most importance are acidic and basic oxides, active hydrogen
groups and highly reactive sulfur moieties. These lead to strong, covalent bonds with
many polymers, especially unsaturated elastomers. It is this strong bonding that helps
make carbon blacks such good reinforcing agents for elastomeric compounds. One
example of their high reactivity is the formation of bound (i.e., non-extractable), rubber
on simple compounding. This has also been discussed in Chapter 1.
Careful heat treatment can remove the reactive surface species. This process is known as
graphitisation as some limited crystalline growth is also observed, although, strictly speaking,
no three-dimensional graphitic order is produced. Such graphitised blacks show little, or
no, bound rubber formation and their elastomer reinforcing properties are severely reduced
[33]. Electron microscopy also reveals much earlier void formation on stretching than is
80
observed with normal blacks, confirming reduced polymer-particle interaction [34]. Because
of their large-scale use in very demanding applications, the measurement and effect of
particle characteristics has received much more study with carbon blacks than with any
other filler. As detailed previously, the principal factors are particle size, shape and surface
reactivity. Dispersion also plays a critical and often overlooked role, and excellent work on
this topic has been reported by Boonstra and Medalia [35, 36].
2.3.1.4 Uses
Carbon blacks are widely used in polymers. Principal applications are as reinforcing
agents for elastomers, especially in automotive tyres. Other applications include their
use as conductive fillers, pigments, and as stabilisers, especially in outdoor exposure.
2.3.2 Synthetic Silicas
Two forms of synthetic silica find significant use in filled polymers. These are both very
small particle, high specific surface area forms, and are known as precipitated and fumed
silicas. Long known as the white carbon black because of its reinforcing ability in
elastomers, the use of precipitated silica has increased markedly recently, due to its growing
use in low rolling resistance (energy or green) automotive tyres [37].
2.3.2.2 Precipitated Silica
a) Production
Precipitated silicas are normally made from solutions of sodium silicate (water glass).
The sodium silicate solution is usually made by digesting a massive form of silica,
such as sand, with sodium hydroxide solution. Precipitation is carried out by adjusting
the pH with acid (sulfuric is usually used). Like all precipitations, the process is
complex and governed by many variables, including: temperature, pH profile,
electrolyte concentration, agitation and time. Useful information can be found in Iler
[38], in Watson [39] and in manufacturers literature [40].
The conditions can be adjusted to give products with specific surface areas in the
range 25-700 m2/g-1. For filler applications, the range 25-250 m2/g-1 is the most
favoured. The products are usually isolated by filtering and washing on filter presses,
81
followed by drying, sieving and grinding. The products are often granulated to
reduce dusting and improve handling and to speed incorporation into polymers.
Precipitated silica technology has a long history and, until recently, it had all the
appearance of a mature technology. This changed with the advent of the large,
energy tyre application, which generated the resources for a fresh look at the product
and manufacturing processes. The result has been products with significant
improvements in dispersability, leading to similar improvements in vulcanisate
properties such as abrasion resistance [41]. The surface structure is also claimed to
have been improved, leading to products that need less silane coupling agent, a
significant cost factor [42].
Although frequently used with organo-silane treatments, these fillers have not
traditionally been pre-coated, the in situ method of addition being preferred (see
Chapter 4). Largely due to developments in tyre technology, some pre-coated
products are now becoming available.
b) Properties
Precipitated silicas are amorphous, and this has several advantages. Firstly, there is
no problem with varying refractive indices, which helps in formulating colourless
and transparent products. Most importantly, the health problems associated with
crystalline silicas should be absent.
In simplistic terms, the particles can be thought of as being similar to carbon blacks,
and to consist of very small primary particles that are aggregated into larger structures
and which are the effective particles. The primary particle size is in the range 5-100
nm and the aggregates can contain several hundred primary particles. The way in
which the primary particles are combined in the aggregates can vary from open,
chain-like structures, to denser, spherical structures and this will very much affect
both their physical properties and performance. As with the carbon blacks, structure
is a very important parameter and is usually measured by an oil absorption method.
One feature that surprises many people is the high water content of precipitated
silica. The actual silica content is only about 90%. The rest of the mass is made up of
three types of water: that combined as surface silanols, strongly hydrogen bonded
water and loosely held water. The latter is about 5% by mass of the filler and can be
removed by drying at 105 C. The effects of this water are not often considered, but
it can obviously be important, especially in reactions with surface modifiers, such as
organo-silanes. Normal products also contain significant amounts of sodium and
sulfate from the precipitation process.
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c) Surface Modification
The true particle surface is highly hydroxylated in the form of silanols, and hence
organo-silanes are very effective surface modifiers and widely used. As mentioned
previously, the real surface also has significant amounts of water present, which can
influence both the efficiency of the organo-silanes and the types of surface structure
formed. Three types of surface silanols can be distinguished, isolated, vicinal and
geminal and they have different reactivity towards silane coupling agents. More on
this topic can be found in Chapter 4. For tyre applications, sulfur-containing silanes
are used. Traditionally these have been added during compounding, but pre-coated
forms are now becoming available.
d) Polymer Applications
The main applications, by far, are as reinforcing fillers in hydrocarbon elastomers.

Organo-silanes, such as the mercapto, polysulfides, amino and vinyl are used to
improve filler to polymer interactions and reinforcement. Particularly important uses
are in tyres and in footwear. There is also significant use as a reinforcing filler in
silicone elastomers.
2.3.2.3 Fumed Silicas
a) Production
These silicas are produced by a gas phase, as opposed to a solution process. There
are a number of possible gas phase routes, but the predominant one is by hydration
of silicon tetra-chloride. This is carried out in a flame of hydrogen and oxygen at a
temperature of 1000 C or above, and is similar to the chloride route for the
manufacture of titanium dioxide pigments. Details of the process can be found in the
work by Watson [39] (see also Figure 2.10).
2H2 + O2 2H2O
SiCl4 + 2H2O SiO2 + 4HCl
2H2 + O2 + SiCl4 SiO2 + 4HCl
Figure 2.10 Process for manufacture of fumed silica fillers
83
The solid product is separated by cyclones or gas filters and contains some residual
absorbed hydrogen chloride. This is removed in a hot moist air stream, rather than
by washing. For the best economics, the hydrogen chloride should be recovered and
used to generate more silicon tetrachloride.
Particle formation is very similar to that for carbon black, with very small, primary
particles forming first and then fusing, while still mobile, into chain-like aggregates.
Properties like particle size, surface area and shape are controlled by factors such
as reactant ratio, temperature and turbulence. Because of the high temperature
formation process, the surface is less hydroxylated than that of the precipitated
silicas, and as a result adsorbs less water. The moisture loss at 105 C is usually less
than 1.5%.
b) Surface Modification
The presence of surface silanol groups makes these fillers very responsive to organo-
silanes and these are the main modifiers used. Many of the applications of fumed
silica require some degree of hydrophobicity. This is achieved by reacting the surface
with non-functional organo-silanes, such as dimethyldichlorosilane. Such hydrophobic
silicas contain less than 0.1% moisture.
c) Applications
The main polymer applications for fumed silicas are as reinforcing fillers for silicone
elastomers and as rheology control agents in coatings, sealants and adhesives.
2.3.3 Hydroxides and Basic Carbonates
Hydroxides and basic carbonates are classed together here, as their distinguishing feature
is a marked flame retarding effect when used in polymers at high loadings. This is because
they decompose endothermically, with evolution of inert gases, at temperatures at which
polymers pyrolyse. As a result, large quantities of these, predominantly synthetic, fillers
are used, with one in particular, alumina trihydrate (more properly aluminium hydroxide),
currently dominating the market.
The mechanisms by which such fillers reduce polymer flammability is discussed in depth
in Chapter 6. In this chapter, only the production of the fillers, and the properties relevant
to their use as fillers and flame retardants are discussed.
84
2.3.3.2 Aluminium Hydroxide
This is by far the most widely used flame-retardant filler, being available at relatively
modest cost and with a wide range of particle sizes, shapes and surface treatments to suit
various applications. Although its chemical structure is that of the hydroxide, it is often
referred to as alumina trihydrate (Al2O3.3H2O) or simply ATH. There is more than one
crystal form of aluminium hydroxide, but that used as a flame retardant is gibbsite. For
convenience the common acronym, ATH, will be used throughout this book.
a) General Properties
ATH is a white, non-toxic, material, which is soluble in strong acids and alkalies. It
has a specific gravity of 2.4, is relatively soft (Mohs hardness about 3) and non-
abrasive. It starts to decompose at about 200 C with the loss of 34.6% by weight of
water when fully decomposed.
b) Production
Gibbsite occurs naturally in many parts of the world but in an impure form in the
rock bauxite. This is the starting point for the manufacture of filler-grade ATH. The
principal source of ATH is associated with the conversion of bauxite into alumina
and aluminium metal by the Bayer process. In this process, the bauxite is extracted
with hot sodium hydroxide, resulting in a solution of sodium aluminate. After
filtration, the solution is seeded with fine gibbsite crystals and allowed to cool. This
results in crystal agglomerates of 60-80 m in diameter, which are separated, washed
and dried. They are then ground and classified to produce ATH fillers with a range
of particle sizes. Considerable purification takes place during the process, but some
organic matter (largely humate residues) from the bauxite remains, resulting in a
reduction in whiteness. These products also contain considerable quantities of sodium
ions trapped in the crystal lattice. These adversely affect water pick-up and electrical
performance. They are difficult to remove completely and appear to diffuse slowly to
the surface of the particles. Products obtained from the Bayer process are relatively
inexpensive and hence widely used, despite their colour limitations.
The Bayer process results in a waste stream known as red mud, which contains
considerable amounts of sodium aluminium silicates. These can be converted into
ATH if the red mud is mixed with limestone and sodium carbonate and calcined, to
form sodium aluminate. This is extracted into water and gibbsite then precipitated
as in the Bayer process. These products are known as sinter hydrates. They are whiter
than the Bayer products as the calcination destroys the organics, but they still contain
similar levels of sodium.
85
The main problem of the Bayer and sinter processes from a filler point of view, is the
relatively large size of the product. Although this can be ground to produce finer
grades, there is an economic limit to this. Also the grinding tends to produce platy
particles, due to preferential cleavage of the ATH along certain crystal planes.
It is becoming more common for ATH to be specially precipitated from purer feed
materials than the Bayer process, with the precipitation conditions (temperature,
concentration, seed contents) also being modified. This gives purer, finer and more
spherical products.
c) Thermal Decomposition
Starting at about 200 C, ATH dissociates into Al2O3 and H2O, but this apparently
simple reaction is actually quite complex. The first issue is stability. The onset of
decomposition is critical in determining the safe processing temperature in composites,
but is difficult to specify. Quoted values vary by as much as 50 C depending on the
method of measurement. The processing temperatures of some of the major polymers,
(e.g., PP) lie close to the decomposition temperature and hence a realistic assessment
is essential. Isothermal tests are probably the best guide and these suggest that 200
C is probably the upper limit for safe processing unless this is carried out under high
pressures. This decomposition makes ATH difficult to use with polymers such as
polypropylene and considerable effort has been expended in trying to overcome this
limitation. The main approach has been to use surface treatments that minimise
shear heating effects. Unlike magnesium hydroxide (see Section 2.3.3.3), there is no
evidence that surface treatments have any direct effect on stability.
The rate and extent of decomposition is complicated by the possibility of two pathways
being followed. Thus, in addition to direct decomposition to oxide, a hydroxy-oxide
intermediate (boehmite, AlO(OH)) can also be formed. This only decomposes to
oxide at relatively high temperatures (approximately 500 C). Decomposition by
this second route probably reduces flame-retardant effectiveness. Boehmite formation
is favoured by high partial pressures of water and the extent to which it occurs will
depend on heating conditions and the local environment of the ATH. It is well known,
for example, that the tendency to boehmite formation increases with ATH particle
size [43]. This is illustrated by the thermal analysis data for a coarse and a fine ATH
presented in Figure 2.11. It is also thought that polymer matrices may impede water
escape during pyrolysis and so favour boehmite formation. In support of this,
surprising levels of boehmite have been reported in the residue from pyrolised
polymethyl methacrylate/ATH composites [44]. This may be one of the reasons why
marked ATH particle size effects are observed for such composites in some
flammability tests [45].
86
Figure 2.11 The effect of particle size on the decomposition pathway of aluminium
hydroxide (ATH)
Even in the absence of boehmite formation, ATH decomposition requires high

temperatures to go to completion. This is probably due to the formation of some isolated
hydroxyls, which need to diffuse for relatively long distances before they can react.
The ATH flame retardant producers have long sought to develop products with
sufficiently increased thermal stability to enable wider use in polyolefins and similar
polymers. Some success in this area has recently been reported by Weber of
Martinswerk [46]. The more stable mono-hydrate, boehmite has also recently been
commercialised as a flame retardant filler [47].
d) Surface Modification
ATH responds well to organo-silanes and these appear to be the materials of choice
for modifying the surface, with the reactive organo-group being chosen to suit the
polymer matrix. Carboxylated polymers are also effective [48] and various organic
acids, both saturated and unsaturated are also utilised. Rothon and co-workers have
recently reported that some unsaturated acids can be give similar coupling efficiency
to the silanes in polymers such as ethylene vinylacetate [49].
e) Uses
ATH is widely used as a flame-retardant filler in elastomers, thermosets and some

thermoplastics. It is also used in significant quantities as a filler in other applications,
87
where flame retardancy is not the prime consideration. This is especially true in
thermosets; where good aesthetic qualities, (e.g., translucency), are often required
and the low hardness enables polishing out of scratches, etc., to be carried out.
2.3.3.3 Magnesium Hydroxide
a) Introduction
Magnesium hydroxide is a white crystalline material, with similar flame-retardant

properties to ATH but with superior thermal stability. Until recently, commercial
interest in its use as a flame-retardant filler was minimal outside Japan. This is because
the only products generally available were either of poor quality or expensive.
This picture has changed rapidly, as environmental concerns over halogen-containing

flame-retardant systems have developed, leading to attempts to replace them in
thermoplastic formulations, which process at too high a temperature for ATH to be
safely used. Progress has been made on many fronts. More economic routes to high-
quality product forms have been developed. Significant applications have also emerged
for the lower quality synthetic products, notably in the United States, where roofing
and decking applications are of growing importance. Success has also been achieved
in utilising natural sources for some applications. There is now every possibility that
magnesium hydroxide will become a significant flame retardant, complementing ATH.
b) General Properties
Magnesium hydroxide is a white crystalline material. Its specific gravity is 2.4. Like
ATH, it is soft and non-abrasive with a Mohs hardness about 3. It starts to decompose
at about 300 C. The naturally occurring mineral is known as brucite. The natural
crystal form is as a flat hexagonal shaped plate.
c) Production and Forms Available
Magnesium hydroxide is potentially available in a number of product forms, which

are all being developed and optimised for flame-retardant uses. Three distinct types
of magnesium hydroxide can be recognised: natural, synthetic seawater or brine, and
synthetic large crystal.
Although uncommon, workable deposits of magnesium hydroxide (known

mineralogically, as brucite) occur in several parts of the world, especially the United
States and China. Some of these are relatively pure, and after milling and beneficiation
processes, appear capable of producing material of filler-grade purity and size. Despite
88
the promise of the natural source, development of suitable products has taken a very
long time. Most of the problems now seem to have been resolved and significant
quantities of natural product are now being used in cable applications in Europe [50].
The commonest form of magnesium hydroxide in commercial production is generally

referred to as sea-water or brine type. This is composed of roughly spherical, somewhat
porous, aggregates of very small, platy magnesium hydroxide particles. The aggregates
are usually 3-10 m in diameter, are strong enough to resist breakdown during most
polymer processes, and are thus the effective particle form. This type of product is
produced by precipitation of the magnesium salts present in sea water or brine, by
adding lime or dolomitic lime. This type of precipitation produces very fine crystals,
and the conditions are deliberately chosen to lead to aggregate growth in order to
facilitate product isolation and handling. Many of the impurities in the lime can be
transferred to the magnesium hydroxide, and hence this has to be carefully selected
for best results.
Products of this type are produced on a large scale as an intermediate in the

manufacture of magnesium oxide refractories and thus, in principle, are available
fairly cheaply. As a result, considerable effort has been expended in trying to develop
filler-grade materials from them. The particle size, porosity, surface area and purity
can vary considerably according to the exact conditions used in the precipitation.
Even in the most favourable circumstances these products are far from ideal for
polymer applications and considerable further processing is usually required, especially
if low levels of soluble impurities are to be obtained. Most flame retardant applications
require very high loadings, and hence place severe demands on filler morphology
and have not been accessible to these products. Some, potentially large applications,
now appear to be emerging, where lower levels of flame retardancy are needed and
these products are beginning to take a significant part of the magnesium hydroxide
flame retardant market.
Leaving aside cost, the large-crystal synthetic products have the most desirable
physical form for filler applications. These are typified by crystals of the order of
0.5-2 m in size and particle sizes not very different (i.e., little aggregation). Surface
area is generally in the range of 1-10 m2 g -1. The aspect ratio of the crystals can
vary considerably but is often about 3:1. They can be produced by a number of
methods, including hydration of specially formed magnesium oxide [51],
precipitation from a magnesium salt solution by addition of ammonium, calcium
or sodium hydroxide [52] and by hydrothermal conversion of basic magnesium
chloride, itself produced by precipitation from a magnesium salt by addition of a
base [53]. In all cases, the conditions have to be controlled if the desired
morphologies are to be obtained. The hydration route has the advantage that no
89
soluble by-products have to be removed by washing, as is the case with the

precipitation routes, but morphology control tends to be more difficult. Among
recent developments, has been the commercial launch of nickel doped large crystal
magnesium hydroxide. The nickel is claimed to significantly improve the fire
retardancy, and allow lower filler loadings to be used [54].
d) Thermal Decomposition
The key property of magnesium hydroxide compared to ATH is its superior thermal
stability. This is illustrated by the isothermal data presented in Figure 2.12, which
suggests that decomposition only becomes significant at about 300 C. Unlike ATH
there is no evidence for two decomposition pathways and for formation of a stable
basic oxide intermediate. Even so, decomposition is slow to go to completion and
thermal gravimetric analysis (TGA) traces usually show two steps, the first making
up only about 85% of the theoretical weight loss. It is believed that the first step is
due to removal of bulk hydroxyls while the second slow step, is due to loss of
surface hydroxyls accompanied by oxide sintering [55]. Hornsby has reported that
the thermal decomposition varies with the form of the magnesium hydroxide [56].
Surprisingly some coatings do appear to modify the decomposition, as shown for a
stearate-coated material included in Figure 2.12. The reasons for this are not clear.
Metal impurity doping has also been claimed to alter the thermal stability, presumably
by introducing some strain into the crystal structure [57].
Figure 2.12 Decomposition of magnesium hydroxide under isothermal conditions
90
e) Surface Chemistry and Modification
Because these fillers are relatively new, this is an area where much still needs to be
done. There is little information concerning the surface chemistry of filler-type
magnesium hydroxide, but preliminary work by one of the present authors (RR)
suggests that this can be quite complicated and that surfaces of some forms may well
be highly carbonated. As would be expected, organic acids react readily with the
surface and both fatty acids and the unsaturated polymeric acids described in Chapter
4 bring about useful modifications. The latter have been shown to be effective coupling
agents in crosslinked elastomers and thermosets [58]. Silane coupling agents also
appear to be effective treatments. The situation is constantly evolving and other
coatings, especially phosphate esters, are beginning to appear [59]. The potential
effect of coatings on the thermal stability of the filler must always be bourne in mind,
as described earlier for fatty-acid coatings. Surprisingly, the carboxylated unsaturated
polymers appear to have no effect on stability.
Surface modification is likely to be a crucial area of development over the next few
years as producers attempt to differentiate their products and minimise the detrimental
effects on some composite properties. There is also an interest in use of surface
treatments to reduce the susceptibility of the filler to carbonation, which can even
lead to leaching from polymers by aqueous carbon dioxide [59].
f) Applications
Currently magnesium hydroxide is predominantly used in polyethylene and ethylene

vinyl acetate copolymers for electrical wire covering. The areas of greatest potential
are, however, in PP and polyamides for a wide variety of uses, and it is in these areas
where most development work is currently directed.
2.3.3.4 Basic Magnesium Carbonates
There are a number of basic magnesium carbonates, but the ones used for filler applications
approximate to the composition of the mineral hydromagnesite
[4MgCO3.Mg(OH)2.3H2O]. This material is insoluble, white and dissociates over a
temperature range suitable for observing flame retardant effects. It occurs naturally as
the mineral hydromagnesite and can be made synthetically, e.g., by the decomposition of
magnesium bicarbonate solutions. There is little exploitation of the natural material,
except where mixed with huntite as discussed in the next section.
Synthetic hydromagnesite normally has a very platy shape, with high oil absorption.
The platy nature gives useful properties in elastomers where it finds some use, but
91
limits the loadings obtainable, and also the flame-retardant properties. Thus, interest
in it as a flame retardant is minimal, although it is being promoted as a smoke
suppressant in PVC.
a) Thermal Stability
This is discussed here, despite the lack of interest in hydromagnesite itself, because of
the interest in mixtures with huntite. Thermal decomposition is quite complex with
release of water and carbon dioxide, following more than one pathway.
Thermal stability is not well established but is probably about 20 C higher than
ATH, indicating a safe processing temperature of about 220 C. This would seem
to make it suitable for PP but, in practice, the platy nature tends to cause greater
viscous heating and reduce this apparent advantage. The decomposition might be
expected to proceed in three distinct stages: loss of water of hydration, loss of
hydroxyls, and finally loss of carbonate. In practice, these overlap considerably
and one observes a broad decomposition over the range 200-500 C. Under ideal
conditions, with rapid removal of gaseous products, loss of CO2 occurs well before
the temperature one would expect for magnesium carbonate itself, but, in practice,
considerable magnesium carbonate can be formed on heating, delaying complete
decomposition.
b) Huntite/Basic Magnesium Carbonate Mixtures
These mixtures occur naturally in Greece, USA and possibly elsewhere, in the form
of a white, fairly pure, easily milled form suitable for filler use [60]. Although of
natural origin, the main polymer interest is in their flame-retardant nature and hence
they are discussed here.
c) General Properties
Hydromagnesite has already been discussed. Huntite is a rare, mixed magnesium

calcium carbonate with the formula 3MgCO3.CaCO3. The properties of huntite have
been reported in detail by Faust [61]. Specific gravity is 2.70. It is strongly bi-refringent.
It appears to decompose in two steps on heating. The first, at about 645 C, is believed
to be due to decomposition of the carbonate associated with the magnesium, while
the second, at about 900 C, is believed to be that associated with the calcium.
In the principal deposit in Greece, the ratio of huntite to hydromagnesite is about 1:1
and there are only traces of other minerals after milling and beneficiation. Other deposits
exist with higher hydromagnesite content, but have not been exploited to any extent to
date. The following information is based on material from the main deposit.
92
d) Filler Properties and Surface Treatments
The basic magnesium carbonate appears to occur in a more favourable morphology

in the natural mixture than when made synthetically. Nevertheless, it is still quite
platy, existing in the milled product as plates of about 4 m diameter and a thickness
of about 0.6 m. The huntite, unfortunately, is even more platy, having a mean
diameter of about 0.5 m and a thickness of only about 0.04 m. Because of the
presence of these two different particles, the mixture has a distinctly bimodal particle
size distribution. (NB: The mean sizes determined by standard particle-sizing
techniques tend to be distorted by the platy nature of the particles.)
The surface area is quite high (approximately 18 m2 g-1)) and so is its oil absorption.
This gives relatively high-viscosity compounds and dispersions making the achievement
of high loadings difficult. Little is known about the surface chemistry and the effect of
surface modification. Organic acids would be expected to react with both components
and a fatty-acid coated product is commercially available. Other coatings are also
offered, including silanes, but the nature of the surface reaction with these is unclear.
e) Fire Retardancy
When the mixture is examined by differential scanning calorimetry (DSC), four main
endothermic peaks are observed at 275, 440, 550 and 690 C. From information on
each separate component it seems reasonable to assume that the first two are due to
the basic magnesium carbonate and the last two are mainly due to the huntite, but
are lower than reported by Faust [61] for huntite itself (644, 901 C). The reasons
for this are not clear. Faust used a similar heating rate but used a fairly primitive
differential thermal analysis (DTA) technique and this may have affected the results.
Thus it would appear that the stability in use will be determined by the basic
magnesium carbonate and is likely to be around 220 C. Indeed, this is what the
producer claims. This is about 20 C higher than ATH, making it a more attractive
filler for PP, if flame retardancy and other properties are satisfactory. The effect of
the fine platy particles on viscosity may cause a greater heat rise during processing
than is observed with ATH and reduce the stability advantage somewhat.
Incorporation of the mixture into a polymer can also significantly modify its
decomposition behaviour. This is illustrated by the DSC data presented in Figure 2.13
for the filler itself and a PP compound containing 60 wt% filler. It is seen that the
first two peaks are considerably raised in temperature by incorporation into the
polymer, while the second two are relatively unaffected. Presumably, most of the
polymer will have disappeared by the time the huntite starts decomposing and thus
the latter will have no effect on the burning of the polymer. The weak shoulder on
the 550 C peak in the neat filler is more pronounced in the presence of polymer. It is
93
Figure 2.13 The effect of the prescence of a polypropylene matrix on the

decomposition of a huntite - basic magnesium carbonate filler
postulated that this is magnesium carbonate resulting from alteration of the basic
magnesium carbonate decomposition as discussed in subsection 2.3.3.4.
The fire-retardant effectiveness is a key question, which is particularly difficult to answer

in the light of present information. The difficulty lies in the presence of the huntite
fraction, which constitutes about half the material. As we have seen, this only appears
to decompose at about 500 C when most of the polymer has gone and its fire-retardant
effect must be in doubt, and this must apply in the mixed filler. However, the mixture
performs well in tests such as oxygen index. One of the present authors (RR) has
himself obtained excellent results with the mixed filler in oxygen-index testing in a
number of polymers and has shown by X-ray analysis that the huntite decomposes
under the test conditions. There are significant problems in oxygen-index testing as
discussed in Chapter 7. One of these is that the flame travels down through the filler
residue during the test, raising it to a high temperature. This would certainly be sufficient
to decompose huntite and significantly affect heat feedback to the underlying polymer.
Such conditions may not be observed in all flame tests, however, and oxygen index
may show the filler up in a particularly favourable manner. A detailed study of the
effect of the two filler phases and of their mixture on the flame retardancy of PP has
recently been reported by Doyle and co-workers [62].
94
f) Applications
Huntite/hydromagnesite mixtures are used as flame-retardant and smoke-suppressant

fillers in a variety of polymer types. Their utilisation very much depends on price
relative to ATH, prices of which have been quite low in recent years and this has
limited commercial utilisation.
2.3.3.5 Dawsonite
Dawsonite is the mineral name for sodium aluminium hydroxycarbonate, NaAl(OH)2CO3.

It can be produced synthetically in microfibre form, and decomposes at about 300 C
with release of water and carbon dioxide. There has been significant interest in its use as
a reinforcing flame-retardant filler but this seems to have waned recently, possibly due to
possible toxicity concerns. More information on the material and its performance can be
found in an article by Milewski [63].
2.3.3.6 Antimony Oxides
Both antimony trioxide (Sb2O3) and pentoxide (Sb2O5) are used in polymers because of
their high flame-retardant efficiency when used in conjunction with halogen compounds.
The trioxide is the preferred form for most applications and is used widely in the plastics
industry. The trioxide is white but the pentoxide is yellow and both have pigmenting
properties due to their high refractive indices. They have been used as pigments but have
now been largely replaced in this by titanium dioxide. Their pigmenting effect must be
allowed for in formulating compounds, but its strength can be controlled to a certain
extent by controlling particle size.
Antimony trioxide (Sb2O3) is a white crystalline powder. It occurs in nature in two crystalline
forms but deposits are impure and virtually all antimony trioxide used in polymers is
produced synthetically. Production is mainly by blowing air through molten sulfide ore or
metal, when the metal oxide sublimes, and is collected in relatively pure form simply by
cooling. Particle size is controlled by the temperature of volatilisation and cooling rate.
Nearly all the synthetic antimony oxide is in the senarmontite crystal form. This is of cubic
crystal habit with a specific gravity of 5.2 and refractive index of 2.087.
While antimony oxide itself has few flame-retardant effects it does, as mentioned above,
markedly improve the effectiveness of halogen compounds. This allows overall additive
levels to be reduced and lessens the loss in favourable polymer properties that generally
accompanies their use. The mechanisms by which the antimony-halogen combinations
95
produce enhanced flame retardancy are still the subject of debate. It seems clear that
much of the effect is due to the formation of volatile antimony halides, which operate in
the gas phase to interrupt flame propagation. Solid-state, char-forming processes may
also be significant. As one might expect, the ratio of antimony to halogen in the compound
is a critical factor as well as the overall level of additives. Further information on antimony
oxides can be found in the article by Touval [64].
2.3.4 Precipitated Calcium Carbonate (PCC)
Very small crystalline (<0.1 m) calcium carbonate can be produced by precipitation. All
three crystal forms, aragonite, calcite and vaterite, can, be produced this way, but calcite
is by far the most widely used in polymer applications.
The production of PCC has been described by Rothon [65]. A variety of precipitation
processes may be used, but today the most common involves blowing carbon dioxide
through a slurry of calcium hydroxide (milk of lime). The calcium hydroxide is itself
produced by calcination of limestone, followed by hydration. The ultimate crystal size,
the degree of aggregation and the aggregate strength are important factors in controlling
performance in polymer applications. These are, in turn, determined by many factors in
the precipitation process, many details of which are proprietary.
For polymer application, PCC is usually coated with a fatty acid during manufacture.
This not only improves polymer compatibility, but also aids filtration during production
and reduces aggregation effects during drying. Conventional coupling agents such as
silanes do not perform well with PCC but coupling may be brought about in many
instances by carboxylated unsaturated polymers [48]. These may be added during
manufacture, like fatty acids, or added during polymer compounding.
The traditional areas of use have been as fillers in elastomers and PVC. In elastomer
applications they give a unique combination of low modulus, high strength and low set.
Today they are widely used as rheological control agents in sealants, especially PVC plastisols.
Acknowledgements
The authors gratefully acknowledge the valuable contributions of Dr D R Brown (Croxton

& Garry Ltd, Curtis Road, Dorking, Surrey, RH4 1XA, UK) to the sections on calcium
sulfate and wollastonite, of Joseph L Scaries (US Silica Company, PO Box 187, Berkeley
Springs, WV 25411, USA) to the section on crystalline silica, and of Mrs Caryl Gould
(ECC International, Europe) for the SEM micrographs of mineral fillers.
96
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37. L. White, European Rubber Journal, 1998, 180, 1, 21.
38. R.K. Iler, The Chemistry of Silica, Solubility, Polymerization, Colloid and Surface
Properties and Biochemistry, Wiley Interscience, New York, NY, USA, 1979.
39. S.K. Watson in Handbook of Fillers for Plastics, Ed., H.S. Katz and J.V.
Milewski, Van Nostrand Reinhold, New York, NY, USA, 1987, Chapter 9.
40. Precipitated Silicas and Silicates for the Rubber Industry, Degussa AG, Frankfurt,
Germany, 1997.
41. P. Cochet, Tire Technology International, 2000, June, 43.
42. P. Cochet, Proceedings of the Functional Tire Fillers 2001 Conference, Intertech,
Fort Lauderdale, FL, USA, 2001.
43. I. Sobolev and E.A. Woycheshin in Handbook of Fillers for Plastics, Ed., H.S. Katz
and J.V. Milewski, Van Nostrand Reinhold, New York, NY, USA, 1987, Chapter 16.
44. G.V. Jackson, R.N. Rothon and G.A. Moorman, Proceedings of Filplas 92,
Manchester, UK, 1992, Paper No.10.
45. P. Hughes, G.V. Jackson and R.N. Rothon, Die Makromolekulare Chemie -
Makromolecular Symposia, 1993, 74, 179.
46. M.Weber, Proceedings of the Functional Effect Fillers 2000 Conference,

Intertech, Berlin, Germany, 2000, Session 2, Paper No.4.
47. R. Sauerwein, Proceedings of the Fire and Materials 2001 Conference,

Interscience, San Francisco, CA, USA, 2001, 395.
48. M.B. Evans, R.N. Rothon and T.A. Ryan, Plastics and Rubber Processing and
Applications, 1988, 9, 4, 215.
49. R.N. Rothon, J. Schofield, D. Thetford, P. Sunderland, G.C. Lees, C.M. Liauw
and F. Wild, Proceedings of the Functional Fillers for Plastics 2002 Conference,
Intertech, Toronto, Canada, 2002, Paper No.5.
99
50. E. Redondo Grizante, F. Peruzotti, D. Tirelli, A. Zaopo and E. Albizzati,

inventors; Pirelli Cavi E Sistemi SPA, assignee; WO 9905688A1, 1999.
51. R.N. Rothon, A.M. Ryder and A.G. Bourke, inventors; DEFPEO, assignee; EP
0,568,488A2, 1993.
52. A. Packter, Crystal Research and Technology, 1985, 20, 3, 329.
53. No inventors; Kyowa Chemical Industry, assignee; GB 1,514,081, 1978.
54. H. Kurisu, T. Kodani, A. Kawase and T. Oki, inventors; Tateho Chemical

Industries Co. Ltd., assignees; US 5,766,568, 1998.
55. J. Green, Journal of Materials Science, 1983, 18, 3, 637.
56. P.R. Hornsby and C.L. Watson, Proceedings of the Third Meeting on Fire
Retardant Polymers, Turin, Italy, 1989, p.66.
57. S. Miyata, inventor; Kabunshiki Kaisha Kaisui Kaguku Kenkyujo, assignee; EP

0498566A1, 1992.
58. R.N. Rothon, Proceedings of Moffis 91, Le Mans, France, 1991, p.37.
59. S. Miyata and M. Yoshii, inventors; Kyowa Chemical Industry Co. Ltd., assignee;
EP 0408285A1, 1990.
60. C.C. Briggs, Proceedings of Fillers and Additives in Plastics 91 Technical

Conference, Lund, Sweden, 1991.
61. G.T. Faust, American Mineralogy, 1953, 38, 4, 24.
62. M. Clemens, M. Doyle, G.C. Lees, C. Briggs and R. Day, Proceedings of Flame
Retardants 94, London, UK, 1994, p.193.
63. J.V. Milewski in Handbook of Fillers and Reinforcements for Plastics, Eds., H.S.
Katz and J.V. Milewski, Van Nostrand Reinhold, New York, NY, USA, 1978,
Chapter 24.
64. I. Touval in Handbook of Fillers for Plastics, Eds., H.S. Katz and J.V. Milewski,
Van Nostrand Reinhold, New York, NY, USA, 1987, Chapter 15.
65. R.N. Rothon, Advances in Polymer Science, Ed., J. Jancar, Springer Verlag,
Heidelberg, Germany, 1999, 139, 103.
100
3
Analytical Techniques for Characterising
Filler Surfaces
David P. Ashton, David Briggs and Christopher M. Liauw
3.1 Introduction
It is the constant theme throughout this volume that introducing fillers into polymers
can substantially modify the properties and cost of the material. However, in most
systems to achieve the full benefits of the effects offered by the filler, the interaction
between the filler and the polymer matrix must be optimised. Although, it should be
noted that optimising does not necessarily mean maximising the strength of adhesion
between filler and matrix, in some instances this causes embrittlement, and then a
lesser level of interaction is needed. To achieve the required effects a large range of
surface reactive chemicals have been developed. These may have a single functionality
which is reactive towards the filler surface, and used to improve the wetting by the
polymer, and hence the dispersion within the polymer. Alternatively, the surface-active
component may have dual functionality being capable of reaction with the filler surface,
and also crosslinking into the polymer matrix to form continuous chemical bonding
between the filler particles and the polymer matrix. Examples containing a single and
a dual functional reagent are described later in this section to illustrate these functions,
although a more comprehensive account of current surface coatings science and
technology is provided in Chapter 4.
The first example is of the single functionality reagent stearic acid that is commonly
used to surface modify calcium carbonate for improving the rheology when filling
thermoplastics such as polypropylene. In this system, the inorganic surface of the
carbonate particles is incompatible with the polymer matrix, i.e., it is not solvated,
and without surface modification would lead to very high viscosity melts. This in turn
would require higher mould filling pressures or lower filler concentrations to be used,
and the final component may, due to poor wetting, contain voids at the filler-matrix
interface with consequences for its mechanical integrity. Whereas, in surface
modification of the calcium carbonate with stearic acid, the acid groups react with the
surface carbonates to form the stearate salt leaving each filler particle with an outer
surface comprised essentially of hydrocarbon chains.
This is solvatable by the molten polypropylene and hence is fully wetted, leading to
low melt viscosities, low mould filling pressures and maximum filler loadings. In the
101
second example, the surface reactive chemical has dual functionality being capable of
interacting with the filler surface and crosslinking into the matrix to form continuous
chemical bonding from the filler particles through to the polymer matrix. The compound
chosen for this illustration is 3-(trimethoxysilyl)propyl methacrylate (MPS), which is
widely used as the coupling agent in filled thermoset systems, an example being silica
dispersed in methyl methacrylate which is commonly used for moulding into articles
such as kitchen sinks, baths and bathroom fitments. In this system the purpose of the
silane compound is to obtain strong chemical bonding between the filler and the matrix,
and to achieve the improved mechanical properties of the final component and not
necessarily to improve the rheology of the system. The methoxy groups attached to the
silicon atom in the silane molecule can be hydrolysed to silanols which can then form
hydrogen bonds with silanols on the silica surface, or more preferably undergo a
condensation reaction with the silanols to produce covalent siloxane bonds between
silane and the filler particle. The methacrylate group at the other end of the molecule
having a similar reactivity to methyl methacrylate reacts into the matrix during the
free radical polymerisation. However, in liquid dispersions such as these there is an
additional requirement: that of avoiding, during the pre-cured liquid state, flocculation
of the filler particles due to the Van der Waals forces acting between them.
Therefore, to achieve the necessary spacing between the silica particles, the coating
has a thickness requirement in addition to the solubility requirement. The thickness
of this steric barrier is dependent upon filler density and particle size, and for practical
systems the MPS molecule is too short to achieve a fully deflocculated dispersion of
silica in the uncured state. Therefore, to obtain the deflocculated state an additional
polymeric or oligomeric dispersant is required, although a similar short-term effect
can be obtained using thixotropes. To illustrate the importance of the bonding between
filler and matrix on the mechanical performance of the final composite, measurements
were carried out by one the authors (DPA) on silica filled polymethylmethacrylate
containing silica (50% by volume), and a mono functional polymeric dispersant,
with and without MPS. The composite containing the MPS had a flexural failure
stress of 115 MPa, whilst the composite with no coupling agent had a flexural failure
stress of 65 MPa.
The two examples described previously illustrate the importance of a number of factors
concerning the surface of the filler and the interface between the filler particles and the
matrix. These are summarised next:
The surface of the filler must be compatible with the molten polymer or, if a thermoset
system, with the uncured system, (i.e., the resin or elastomer), to achieve the optimum
rheology and filler dispersion.
102
Analytical Techniques for Characterising Filler Surfaces
The interface is critical to achieving the required mechanical properties from the
composite.
The thickness, which is usually related to the molecular mass, of the surface coating
is important for obtaining the required rheological properties. It may be necessary to
use more than one surface modifier to achieve all the effects required of the system.
An extremely important factor not implicitly obvious in the two examples described
previously is the specificity of the surface chemistry to each composite system. Of course
many surface reactive agents can be used in more than one system, and MPS and stearic
acid fall into this category. However, the MPS and stearic acid could not be interchanged
between the two examples, not only due to the mono functionality of the stearic acid,
but due to the relative lack of reactivity between silanes and calcium carbonate, and
stearic acid and silica. In the latter case, the hydroxyl groups, which are formed at the
silica crystal surfaces to satisfy valency demands, are acidic in nature and hence do not
form strong bonds with the carboxylic acid group. If the silica was substituted, for
example, with alumina then the stearic acid would interact with the surface of the filler,
as the hydroxyls formed at crystal discontinuities in alumina are basic in character.
Interactions between polymer additives such as stabilisers and filler surfaces are also an
important consideration as excessive interaction can lead to a loss of stabilisation. Whilst
an understanding of these interactions can lead to methods of preventing additive adsorption,
it is also important to appreciate that such interactions can be used to advantage in controlled
release of stabilisers from filler surfaces. Such an effect can result in improved retention of
the stabiliser and hence significantly enhanced stabilisation. This concept can be extended
to other functional additives such as biocides and perfumes, etc.
Any study of interfaces in filled polymer systems will show that this acid-base interactivity
is the constantly recurring driving force for the surface chemistry and its understanding
is crucial to predicting melt and composite properties. A theoretical approach to the
subject is discussed in some detail in Section 3.2 of this chapter.
It can be concluded from this introduction that to obtain the surface modification required
to achieve the optimum or desired composite properties an intimate understanding of
the chemical nature of the filler surface is required, and of the chemical reactivity of the
surface modifier. The ideal situation, of course, would be to have a comprehensive analysis
of all the chemical moieties at the filler surface and their precise spatial arrangement,
and then to design the surface modifier with functional groups that interact with the
surface moieties and which are correspondingly spaced. This ideal is a long way from
current scientific capabilities and may never be fully realisable, however, the target is
there and huge strides have been made on the road towards this ultimate goal.
103
Sophisticated techniques have now been developed for characterising and quantifying
the chemical nature of material surfaces, and the more important ones, listed below, are
discussed in some detail in this chapter:
Flow Microcalorimetry FMC

Inverse Gas Chromatography IGC
X-Ray Photoelectron Spectroscopy XPS
Secondary Ion Mass Spectroscopy SIMS
Fourier Transform Infrared Spectroscopy FTIR
In addition, with the use of fast powerful computers, there is significant activity in the
modelling of material surfaces. Much can be expected from this work over the coming
years, although the spatial characterisation of typical commercial fillers with the added
complications of surface contamination and inhomogeneity will remain a challenge for
many years to come.
However, despite the large chemical differences between even the most commonly used
fillers, such as alumina silicates, aluminium hydroxide, calcium carbonate, silica, titanium
dioxide, the most active groups at the surface and which dominate the surface chemistry
are more often than not hydroxyl groups. These form, as discussed previously, to satisfy
valence and electrostatic requirements at the fractured surfaces and discontinuities of the
crystal lattices, or amorphous particles. Furthermore, it is often the acidic or basic nature
of these hydroxyl groups that determine the chemical properties of the surface, and therefore,
which surface modifier is most suitable for the filler. Consequently, much of the
characterisation of filler surfaces is confined to measuring the relative acidity or basicity of
the active surface sites. It is worth commenting at this point that all superficially chemically
similar groups across any filler particle surface will not necessarily have the same acidic or
basic character due to variations in the immediate electronic environment of each moiety.
It will be more common for a spectrum of sites from acidic through to basic to be present;
therefore a simple pH measurement of an aqueous dispersion of the filler will only give a
mean value. It requires more sophisticated techniques to determine the spectrum.
3.2 Acid-Base Theory
3.2.1 Introduction
In the main introduction to this chapter the importance of acid-base interactions in

determining the interfacial chemistry between fillers and matrices in particulate composites
was emphasised. In this section, a summary of the more commonly used acid-base theories
will be presented.
104
There are two main types of molecular interaction: firstly, the non-polar dispersion forces
or London-Van der Waals forces caused by the fluctuations in the charge symmetry of
the molecules produced by their thermal energy. Few compounds exhibit only dispersion
forces, perhaps the most common examples are saturated hydrocarbons. Secondly, there
are polar interactions that are due to asymmetric charge distributions across individual
molecules, caused by the different electron affinities of the elements within the compound.
However, it has been shown that the strengths of these polar interactions are not simply
dependent upon the polarity of the molecules, but on their electron accepting or electron
donating, e.g., acidic or basic, character. In fact, Fowkes, [1-4] has shown that the strength
is independent of the dipole moments of the interacting molecules except when an acid
site is interacting with a basic site.
Lewis [5] was the first to describe acids and bases in terms of their electron accepting and
electron donating properties. Mulliken [6] further refined the understanding of the acid
base interactions for which he was awarded the Nobel Prize for Chemistry. His quantum
mechanical approach introduced the concept of two contributions, an electrostatic and a
covalent, to the total acid-base interaction. Pearson [7] introduced the concept of hard and
soft acids and bases, the HSAB principle, based on the relative contributions from the
covalent (soft) interaction and the electrostatic (hard) interaction. In his mathematical
treatment he defined the absolute hardness of any acid or base in terms of its ionisation
potential and electron affinity. Pearsons is probably the most robust approach, but the
approaches in most common use are those developed by Gutmann [8] and Drago [9], who
separately developed equations and methods to quantify the acid or basic strength of
compounds, from which their heats of interaction could be calculated.
3.2.2 Gutmann Approach
The Gutmann approach was to allocate a donor number (DN) for bases, and an acceptor
number (AN) for acids, corresponding to the definitions first proposed by Lewis. The DN
was determined by measuring in a calorimeter the heat of reaction between the base under
investigation and antimony pentachloride in a dilute 1,2 dichloroethane solution. The AN
was determined from the 31P NMR shift of triethylphosphine oxide (TEPO) when dissolved
in the acid under investigation. The number allocated was determined from a linear scale in
which n-hexane was designated as zero and antimony pentachloride was designated as 100.
Gutmann then proposed that the heat of reaction between acids and bases (Hab) could
be calculated using Equation (3.1):
AN DN
Hab = (3.1)
100
105
There are a number of weaknesses in the Gutmann donor-acceptor number approach.

Firstly, Riddle and Fowkes [10] showed that AN numbers determined from the 31P NMR
shift of TEPO using the technique disclosed by Gutmann contained a contribution due
to Van der Waals or dispersion interactions. They showed that even n-hexane, a compound
with no dipole, caused a shift in the 31P NMR spectra of the TEPO. An adjustment to the
AN numbers can be made to account for the contribution from the dispersion forces.
Fowkes has described [11] how the choice of a hard base, TEPO, and a soft acid, antimony
pentachloride, for the Gutmann test methods give higher values to hard acids and soft
bases than if the reverse was chosen; a soft base and a hard acid. This problem of the
order of basicity or acidity being dependent upon the test acid is a consequence of trying
to reconcile a single acid or base parameter with the two contributions, the ionic and
covalent, to acid-base interactions so elegantly presented by Mulliken.
3.2.3 Drago Approach
Drago [9] developed his theoretical approach for relating the enthalpy of interaction
with the acidity and basicity of the interacting species, by allocating two constants to
define the strength of acids and bases. These are the E and C constants which represent
the electrostatic and covalent, or hard and soft, contributions to the acidity or basicity of
the compound which loosely correspond to those determined by the quantum mechanics
treatment of Mulliken. The constants are determined from calorimetric measurements,
and are fitted empirically to the acids and bases and do not necessarily relate precisely to
the electrostatic and covalent contributions of the acid base interactions. However, this
has not prevented the Drago approach from being used with significant success. The
relationship is expressed in Equation (3.2):
Hab = CACB + EAEB (3.2)
Hab is the enthalpy of reaction between an acidic species A, and a basic species B. CA
and CB are the covalent constants for the acid and base, respectively, and EA and EB are
the electrostatic constants for the acid and base. This approach is also not without
limitation as it assumes that the two interacting species are purely acidic or basic, and
does not take into account any interactions due to acid sites on the basic species, or basic
sites on the acid.
3.2.4 Use in Characterising Fillers
The most significant work to use acid-base theory to understand the surface chemistry
of inorganic fillers has been carried out by Fowkes and his co-workers [1-4, 10-12].
106
They made use of the Drago Equation (3.2) to characterise a series of particulate
inorganic materials, e.g., ferric oxide, silica and titania, and ascribed E and C constants
to their surfaces.
The method adopted by Fowkes and co-workers was to determine the heat of interaction
between the fillers and probes with known Drago constants using calorimetric techniques.
Two techniques were adopted for measuring the heats of adsorption. The first used a
static Tronac calorimeter in which the filler surface was titrated with an excess of the
chosen probe, the integral heat of adsorption was determined from the calorimeter
response. Whilst the molar heat of adsorption was calculated by back titrating to quantify
the unreacted probe. The second was to use a flow microcalorimeter in conjunction with
a high pressure liquid chromatography (HPLC) detector, a technique described in detail
in Section 3.4.1.3, to determine the molar heat of adsorption (Hads) of the probes onto
the filler surfaces. These data were then used to produce plots derived from the rearranged
Drago Equation (3.3):
Hads C
EA = CA B (3.3)
EB EB
In this example of the rearranged equation the probe is a base with known constants CB
and EB and is being used to determine the EA and CA constants of the acid sites on the
filler surface. But clearly, the A and B subscripts could be interchanged and an acid probe
used to characterise the basic sites on the filler surface.
The plots of EA versus CA, of which an example from reference [12] is shown in Figure 3.1,
are constructed for each probe base by calculating the intercept on the EA-axis, i.e.,
Hads/EB when CA is zero, then drawing a line from it with gradient CB/EB. For any
given surface only one point on each plot is valid and that is at the EA and CA values
corresponding to those of the surface. This point is therefore where the plots produced
from the different probes intersect. The example given in Figure 3.1 is produced from
data collected from the adsorptions of ethylacetate, pyridine and triethylamine onto
silica, the EA and CA constants for the acid silanol sites were determined as 4.4 and 1.1;
the source of the silica was not disclosed.
This is an extremely powerful method for characterising the acidic and basic sites on filler
surfaces and produces data that corresponds, at least qualitatively, with the most
sophisticated quantum mechanics analyses of Mulliken. However, it is important to
appreciate that the method described [12] only gives an average value for the EA and CA
constants, as mentioned earlier different active sites may have quite different characteristics.
However, an adaptation to the FMC technique offers an opportunity to obtain a semi-
quantitative understanding of this surface heterogeneity, this is described in Section 3.4.1.3.
107
Figure 3.1 Determination of the Drago E and C parameters for the surface SiOH sites
of silica, using heats of adsorption of test bases determined by isothermal
microcalorimetry.
(Reproduced with permission from F.M. Fowkes, Journal of Adhesion Science and
Technology, 1987, 1, 1, 17. Copyright 1987, VSP.)
3.3 Analytical Techniques
The analytical techniques have been divided into three groups; the first group contains
those techniques that are used to characterise the surface of fillers by understanding their
reactivity with probe molecules. These are FMC and inverse gas chromatography (IGC)
and are discussed in Section 3.4.
The second group of techniques are the spectroscopic techniques that provide elemental
and chemical analysis. These are diffuse reflectance Fourier transform infrared spectroscopy
(DRIFTS), XPS, and SIMS. XPS and SIMS probe the first few nanometres of the surface
whereas DRIFTS probes an order of magnitude deeper. These techniques are discussed in
Section 3.5.
The third group of techniques [wide angle X-ray diffraction (WAXS) and differential scanning
calorimetry (DSC)] are those that are able to examine formation of structural order within
adsorbed layers of surface treatments on filler surfaces. These are discussed in Section 3.6.
108
3.4 Reactive Techniques
3.4.1 Flow Microcalorimetry
Probably the most notable feature associated with the adsorption (or desorption) of any
compound onto a solid surface is the change in enthalpy that occurs during the process;
and is captured in Dragos equation (see Equation 3.2).
For an adsorption process the enthalpy change is invariably an exotherm, and is a function
of the acidic and basic characters of the adsorbate and the adsorbent surface. With modern
calorimetric techniques this enthalpy change is relatively easily measured. Furthermore,
for adsorptions onto materials with low specific surface areas it can be more accurately
measured than the quantities of adsorbate. However, as will be described in more detail,
FMC in conjunction with frontal analysis using HPLC detectors offers the ability to
measure both the enthalpic changes and the quantities of adsorbate.
Many workers have used both static and flow calorimetry for measurement of the enthalpic
changes associated with adsorption and desorption processes. Two basic techniques are
used in static calorimetry. In the first, the adsorbent and adsorbate are placed in the
calorimeter, but in isolation from each other, the two are then mixed, for example by
breaking a membrane, and the heat of reaction is measured. In the second, the adsorbent
is charged to the calorimeter cell fully wetted with the solvent for the adsorbate, then a
solution of the adsorbate is injected into the calorimeter. Static calorimetry would appear
to have some advantages for studying batch systems, as the measured enthalpy change
would be the integral of all the surface and solution chemistry taking place within the
system. However, within the system there may be many interacting equilibria that a
single enthalpy change measurement can do little to elucidate.
In flow calorimetry the enthalpy change that is measured is that which occurs as the
adsorbant changes from being in equilibrium with a known fluid, e.g., pure solvent, to that
of a second known fluid, e.g., a solution of an adsorbate in solvent. Therefore, the initial
and final states are relatively well defined and the enthalpy can be more easily attributed to
known adsorption-desorption processes taking place at the surface of the adsorbent.
Further advantages of FMC over alternative techniques include the ability to measure
heats of interactions of polymers in solution with solids, i.e., filler surfaces: characterisation
of filler surfaces by IGC is limited to reversibly adsorbed volatile molecules. Also, HPLC
detectors can be connected in series with the calorimeter and used to determine quantities
adsorbed, and hence provide a measure of surface coverage.
The technique has been found by the authors to be most useful for gaining insight into
adsorption interactions between a range of probe molecules and filler surfaces. Probes
have included: polymers, filler surface treatments and polymer additives. In general FMC
is an underused technique in this field.
109
3.4.1.2 Flow Microcalorimeter
(a) Description. Almost any calorimeter can be adapted to operate in flow mode by
making a flow cell which fits into the standard calorimeter cell. However, the calorimeter
which will be described here is an instrument designed and produced by Microscal Ltd.
[(79 Southern Row, London, W10 5AL; (www.microscal.com)] as a dedicated flow
microcalorimeter, although the method of operation, data collection and interpretation
described in later sections would be valid for any flow calorimetry system. A line diagram
of the Microscal flow calorimeter and the flow system is presented in Figure 3.2.
The instrument contains four highly sensitive thermistors. In the more recent models
from Microscal, the two working thermistors are placed behind thin
polytetrafluoroethylene (PTFE) membranes that form the walls of the cell. These are
referenced, using a Wheatstone bridge arrangement to two thermistors, positioned about
Figure 3.2 Schematic diagram of a Microscal Flow microcalorimeter.

(Reproduced with kind permission from D.P. Ashton and R.N. Rothon in Controlled
Interfaces in Composite Materials, Ed., H. Ishida, Kluwer Academic Publishers, Dordrect,
The Netherlands, 1990, p.297. Copyright 1990, Kluwer Academic Publishers.)
110
half way into the thick PTFE walls of the cell. The circuit can respond to differences in
temperature of 1 x 10-5 C, the response is amplified for measurement with a simple
chart recorder, or can be fed into a chromatography data station (as used by the authors).
Microscal have produced their own PC based FMC control and data analysis system
called Calorimeter Digital Output and Sequencer (CALDOS). This removes the reliance
on chromatography data stations and software and hence provides the user with a system
designed especially for FMC.
(b) Method of Operation. The filler is charged to the calorimeter cell, where it can be
pretreated by heating under vacuum, or more usually by equilibrating in a flow of the
pure solvent chosen for the experiment. The cell of the Microscal flow microcalorimeter
has a volume of 0.15 cm2. As described previously the flow microcalorimeter is used to
measure the enthalpy change for the transition between the filler being in equilibrium
with fluid A and the filler being in equilibrium with fluid B. Fluid A is normally a pure
solvent, and fluid B is normally a dilute solution of the probe compound in the solvent.
Syringe No.1, see Figure 3.2, is filled with fluid A, and syringe No.2 is filled with fluid
B containing the probe. After completing any pretreatment of the filler, fluid A is
continuously passed through the filler in the calorimeter cell at a constant and preset
rate until equilibrium is achieved; this is indicated by a constant signal from the bridge
amplifier. The four-way valve is then switched to direct the flow of fluid B from syringe
No.2 to the calorimeter cell. The flow of fluid B is also constant and at the same pre-
set rate as fluid A during the initial equilibration. Flow is continued until the output
signal indicates equilibrium with the solution has been established. When this is achieved,
the flow may be switched back to that of the solvent, fluid A, to test for the reversibility
of the process.
More recently electrically actuated valves have become available and can be integrated
into the Microscal CALDOS PC based FMC control and analysis system. This allows
the user to leave the FMC unattended for the duration of the entire experiment, as there
is no need to return to the instrument and switch the valves over manually
(c) Output from Flow Microcalorimeter. As the solution of the probe, fluid B, passes
through the filler, the probe adsorbs onto the surface of the filler, the heat of adsorption
causes an increase in temperature which is detected by the thermistors and registered by
the recorder or data station. Conversely, after switching the flow from solution to solvent,
desorption of the probe species will cause a decrease in temperature. Therefore, the
output is the millivolt output from the amplifier, which is a linear function of the
temperature increase in the calorimeter cell, and this is plotted against time. Examples of
the outputs from the adsorption and desorption of methyl methacrylate onto alumina
trihydrate are presented in Figure 3.3.
111
Figure 3.3 Flow microcalorimeter response during adsorption and desorption of

methyl methacrylate onto ATH
The peak areas in the thermal data are proportional to the energy changes that have
occurred. The constant of proportionality is determined from calibration peaks that are
formed by passage of a known electric current for pre-selected time interval through a
coil of resistance wire that is integrated into some models of the FMC cell outlet connector.
Further insight into the nature of the interaction between irreversibly adsorbed species
and the filler surface can be gained from DRIFTS analysis of the filler sample taken from
the FMC cell after completion of the adsorption desorption cycle. DRIFTS is described
in more detail in Section 3.5.4, but in summary, it is an infrared spectroscopic technique,
that by virtue of a significant proportion of glancing angle reflections, affords enhanced
resolution of filler surface functional groups. The authors have found this technique
particularly useful when studying competitive adsorption of polymer stabilisers and
carboxylic acids onto silica and metal hydroxides, respectively.
(d) Choice of Reagents. In any single experiment there are essentially three reagents to be
considered, the filler charged to the calorimeter cell, the solvent, and the probe compound.
The filler under investigation will usually be determined by the composite system under
study. Sometimes, however, it is equally valid to use model fillers with properties chosen
to maximise the accuracy and reproducibility of the technique. The preferred filler
properties are good powder flow characteristics to avoid bridging and hence voiding
within cell, and a high surface area to maximise the signal and hence signal to noise
ratio. Certain very fine fillers such as fumed silica can create other practical problems
such as escape of filler though the outlet connector filter. This can be minimised by use of
a special purpose fine particle outlet connector featuring a polyvinylidene fluoride (PVDF)
112
membrane filter. In extreme cases very fine (colloidal) filler particles can pass though or
block the PVDF membrane, in such cases a static adsorption experiment can be carried
out with only minor modifications to the FMC.
The choice of solvent is also important, as the enthalpy measured is essentially that of
the displacement of the solvent from the filler surface by the probe molecule. For acid-
base characterisation a non-polar solvent such as n-heptane is ideal. However, poor
solubility of the desired probe molecule may demand the use of a polar solvent, when
this is the case the enthalpy of interaction of the solvent with the filler must be considered
when interpreting the results. If the probes in question are only capable of weak physical
adsorption, (i.e., not via hydrogen bonding), and are only soluble in highly polar solvents
such as tetrahydrofuran and dimethyl formamide, situations can arise where apparently
no adsorption occurs. This is due to the solvent having equal or stronger interaction
with the substrate than the probe. In such cases the value of performing FMC experiments
should be questioned and the use of more soluble model compounds considered. If
chemical adsorption of the probe occurs the polarity of the solvent is somewhat less
critical, provided the solubility of reaction products is not enhanced.
Of further importance is the need to use a consistently pure solvent, with special attention
paid to the water content. The authors have found drying of n-heptane over sodium metal
or freshly activated molecular sieves (3A or 4A) achieves low and consistent water levels in
the solvent. Another factor influencing solvent choice is the solubility of any products
formed as a result of chemical adsorption; for example, water and metal carboxylates in
the case of studies of adsorption of fatty acids onto metal hydroxides. Toluene is a much
better solvent for such salts, and the resulting water, than heptane. Generally it is the salts
of branched chain fatty acids that are more soluble due to their reduced ability to pack into
an ordered array. This is exemplified in Figure 3.4 [13] where the heat of adsorption of
isostearic acid (16-methyl heptadecanoic acid) onto magnesium hydroxide is reduced to a
far greater extent, when adsorbed from toluene, than stearic acid (octadecanoic acid).
Equivalent adsorption onto aluminium hydroxide shows that this is not merely a solvent
displacement effect. Formation of a fully neutralised, and hence potentially soluble
carboxylate, is far easier in the case of magnesium hydroxide than aluminium hydroxide.
This is due to the greater basicity of the former, and the 2+ charge on the magnesium ion:
this enables it to become more easily detached from the ionic lattice.
The probe compounds may be chosen as model acids (for example, carboxylic acids or
chloroform) and bases (for example, pyridine or ether), with which to measure the acid-
base character of the filler surface. However, the probes may be actual interfacial modifiers
used in the composite system under investigation, for example an organosilane coupling
agent or fatty acid dispersant. Furthermore other interesting interactions have been studied
by the authors and include stabiliser filler interactions during evaluation of controlled
release/displacement effects.
113
Figure 3.4 FMC data for adsorption of stearic acid and isostearic acid onto Mg(OH)2
and Al(OH)3 from heptane and toluene; adsorption data, desorption data. The
dashed lines represent vertically adsorbed theoretical monolayer levels. M: magnesium
hydroxide, A: aluminium hydroxide, hept: heptane, tol: toluene.
(Reproduced with permission from C.M. Liauw, R.N. Rothon, G.C Lees and Z. Iqbal,
Journal of Adhesion Science and Technology, 2001, 15, 8, 899. Copyright 2001, VSP.)
It is this ability to use these real components that is the main advantage of this technique.
The technique was used by Ashton and Rothon [14] to characterise the interaction between
3-trimethoxysilylpropyl methacrylate and aluminium hydroxide from n-heptane solution.
3.4.1.3 Use of HPLC Detectors
(a) Description. Whilst use of the flow microcalorimeter can generate important enthalpic
data, the power of the technique is substantially increased when it is used in conjunction
with one or more HPLC detectors in series with the calorimeter. These can be used
according to the method, described in (b) below, to determine the quantity of the probe
adsorbed, and therefore the molar heat of adsorption. In the study of the adsorption of
3-trimethoxysilyl-propyl methacrylate on to aluminium hydroxide from n-heptane
solution [14], refractive index (RI) and UV detectors were used, and found to be
114
Figure 3.5 Line diagram of flow microcalorimeter in series with HPLC detectors.
(Reproduced with kind permission from D.P. Ashton, R.N. Rothon in Controlled
Interfaces in Composite Materials, Ed., H. Ishida, Kluwer Academic Publishers, Dordrect,
The Netherlands, 1990, p.296. Copyright 1990, Kluwer Academic Publishers.)
complementary allowing different components in the eluent from the FMC to be

quantified. A line diagram showing the system containing these detectors is shown in
Figure 3.5.
(b) Output from HPLC Detectors. The eluant from the FMC is passed through the
HPLC detectors, the output from each detector correlates with the RI or UV absorbance
at the preset wavelength of the detector. Hence as the flow changes from solvent to
solution, a plot of response versus time gives a sigmoidal response as shown by line A in
Figure 3.6. However, if the probe is adsorbed onto the filler surface in the FMC, the
transition will be shifted to a longer time, as indicated by line B in Figure 3.6. The area
marked as C in Figure 3.6 is proportional to the mass of the adsorbed probe. To measure
this area requires subtracting the transition that occurs during adsorption of the probe,
from a transition when no adsorption takes place, but using the same flow and FMC
packing conditions. This subtraction can be handled by most standard chromatography
software packages and by the Microscal CALDOS system. The proportionality factor
can be determined by injecting pulses of solution, via the calibration loop, shown in
Figure 3.5, and measuring the area of the peaks produced in the output signal.
115
Figure 3.6 Typical response curves from the HPLC detectors during flow
microcalorimetry
In reactive adsorption studies such as that described previously, i.e., adsorption of 3-

trimethoxysilyl-propylmethacrylate on to aluminium hydroxide from n-heptane [14], or
reactions between fatty acids and basic filler surfaces [13], the small molecule split off as
a product of the chemisorption reaction, (i.e., methanol and water for the first and second
examples, respectively), can affect the differential refractometer response.
If the small molecule has a lower refractive index than the carrier solvent and the
probe a higher refractive index than the carrier solvent, the calculated level of amount
of probe adsorbed will be greater than it really is. If however, both the probe and the
small molecule have lower refractive index than the carrier solvent, the amount of
probe adsorbed will be smaller than it really is. The extent to which this problem
occurs also depends upon the solubility of the small molecule in the carrier solvent.
This effect has caused problems in a recent study [13] of adsorption of various carboxylic
acids on to metal hydroxides. Figure 3.4 shows both the heat of adsorption and amount
of carboxylic acid adsorbed. It is evident that adsorption of stearic acid (octadecanoic
acid) and isostearic acid (16-methyl heptadecanoic acid) from toluene affords apparently
reduced levels of adsorption, relative to when adsorbed from heptane. This is due to
both the probe and the water having lower refractive indices than toluene. DRIFTS
analysis of the respective filler samples retrieved from the FMC cell, however, indicates
similar levels of adsorption. Only in the case of adsorption from heptane is the level of
adsorption in concordance with theoretical values. This is due to reduced solubility of
water in heptane, relative to toluene.
A further treatment of the output data was used by Joslin and Fowkes [2], in which they
time sliced the outputs from the FMC detector and HPLC detector. This technique enables
116
the molar heat of adsorption to be calculated as a function of time through the adsorption
process, and gives an indication of the heterogeneity of strength of the acid or base
adsorption sites on the filler surface. Microscal Limited have developed a variation on
Joslin and Fowkes approach, using the latest Microscal system, controlled additions of
the probe solutions are injected into the cell and the reduction in the molar heat of
adsorption recorded as a function of amount adsorbed. The injections are carried out
under computer control via the Microscal CALDOS software.
3.4.1.4 Use of FMC in Competitive Adsorption Studies
Competitive adsorption of components of filler surface modifier systems, stabilisers

and lubricants, etc., is an inevitable event that occurs in the vast majority of filled
polymer formulations. Such phenomena can lead to inferior product performance in
terms of reduced coupling agent efficiency and poor stabilisation. Therefore an
understanding of such events is very beneficial if performance is to be optimised.
Studies have been carried out using combinations of acrylic acid and isostearic acid
in an attempt to produce surface modifier systems that combine effective coupling
with good dispersant characterisics [13]. In this study sequential adsorption of
isostearic acid and acrylic acid on to magnesium and aluminium hydroxides in the
FMC cell indicated that acrylic acid will displace isostearic acid from both fillers,
however, isostearic acid will adsorb onto a layer of adsorbed acrylic acid producing
a hybrid layer.
Combinations of stabilisers, (e.g., a hindered phenolic primary antioxidant, a phosphite

secondary antioxidant and a hindered amine light stabiliser) are frequently used.
Knowledge of the adsorption activity of a filler towards such additives can indicate
what additives can be avoided or how the filler surface may be modified, for example
with an epoxy resin or fatty acid, so that it no longer adsorbs the additive [15].
Conversely, it can be argued that the filler surface can be also be used as a reservoir of
stabiliser, provided it can be released from the surface in a controlled manner. Liauw and
co-workers have examined the effect of incorporation of gel silica (323 m2 g-1) at 0.1%
w/w, on the thermal stabilisation (melt and solid state) and UV stabilisation of linear low
density polyethylene [16, 17]. The adsorption characteristics of all the stabilisers
investigated were examined by FMC [17] and heat stabiliser/UV stabiliser combinations
were devised on the basis of relative strength of adsorption. The stabilisation performance
was found to be enhanced in the presence of silica only when the more active stabiliser
was weakly adsorbed relative to the less active one; this indicated a controlled release
mechanism that was associated with displacement of the weakly adsorbing stabiliser
117
[16]. This mechanism was confirmed by performing competitive adsorption experiments

using the FMC [17].
Figure 3.7 shows FMC data investigating the competitive adsorption of the hindered
phenolic antioxidant Irganox 1010 (I1010) and the polymeric hindered amine light
stabiliser Chimassorb 944 (C944). These probes are adsorbed from heptane on to silica.
Data are shown for adsorption of I1010 followed by C944 and for adsorption of C944
followed by I1010. It is evident that C944 is able to initially adsorb at sites not occupied
by I1010 as there is solvent released from the silica. DRIFTS studies on the silica isolated
from the cell clearly indicated that C944 totally displaced the I1010. It is evident from
Figure 3.7 that I1010 will not displace adsorbed C944 and that the latter will adsorb on
to all the sites receptive to I1010.
Figure 3.7 Raw FMC data showing (a) adsorption of Irganox 1010 followed by switch
over to Chimassorb 944, and (b) adsorption of Chimassorb 944 followed by switch
over to Irganox 1010.
(Replotted from C.M. Liauw, A. Childs N.S. Allen, M. Edge, K.R. Franklin and D.G. Callopy,
Polymer Degradation and Stability, 1999, 63, 3, 391, p.396. Copyright 1999, Elsevier)
118
3.4.2 Inverse Gas Chromatography
This technique [18] has now been in use for a number of years. In inverse gas
chromatography (IGC), a pulse of a small quantity of a probe is injected into a stream of
gas which passes over the filler which is packed into the separation column of the
chromatograph. The time taken for the probe to elute from the column, compared to
that of a non adsorbing compound, is a measure of the interaction between the probe
and the surface of the filler. A mathematical treatment can then relate this difference in
elution time to the free energy change in the adsorption process.
The technique can be considered as complementary to FMC, although it is constrained

by the need to use volatile probes, a number of experimental factors usually result in
more accurate thermodynamic data being obtained. The most important difference
between IGC and FMC is that in the former technique, the probe is at infinite dilution,
therefore, only the most active sites on the filler surfaces are likely to be probed. As
adsorption from the gas phase occurs during IGC, only weakly bound molecules of
carrier gas need to be displaced during the adsorption process, it is this aspect that may
lead to production of more accurate thermodynamic data.
In FMC the probe is at finite dilution and it is likely, in the case of some filler/solvent
combinations, that the most active sites will always be occupied by the solvent molecules,
therefore these sites may never be probed during the FMC experiment. This will almost
certainly be true in cases where the solvent and filler have strong hydrogen bonding
activity, i.e., alcohols with silica. However, it can be argued that in a polymer composite,
particularly when additive or filler surface modifier adsorption from the matrix melt (or
a liquid resin) is considered, the conditions of the FMC experiment are closer to reality.
IGC may on the other hand be more useful for analysis of filler-matrix interaction where
the matrix chains are essentially displacing nitrogen and oxygen molecules during
incorporation. Even in this situation, a question mark still hangs over IGC; in real systems,
adsorbed water will certainly be present on a filler surface before it comes into contact
with the matrix melt. A significant amount of this water will desorb due to the high
temperatures experienced in melt processing, though it is most unlikely that all of the
strongly adsorbed water will be totally removed. Under IGC conditions water is usually
considered to be completely absent; furthermore, the adsorption of the model compounds
may take place at temperatures that are far higher than normally encountered processing
temperatures. It is important to appreciate that probes used for IGC must not adsorb on
to the filler too strongly as they may take too long to elute from the column, or in
extreme cases, may not elute at all. Despite the reservations associated with FMC and
IGC these techniques are still valuable for gaining insight in to filler surface chemistry
and how this may influence product performance.
119
3.4.2.2 Thermodynamic Considerations
As described previously the important measurement that is made in this technique is the
elution time between injection and elution of the probe. Although more precisely, the
value used in the mathematical treatment is the net retention volume VN. VN is the
additional volume of carrier gas eluted from the chromatograph before elution of the
probe, compared to the volume eluted before elution of a non-adsorbing gas, for example
methane. VN is calculated using Equation (3.4):
VN = kF(tp-tn) (3.4)
Where, F is the carrier gas flow rate, tp is the retention time of the probe, tn is the retention
time of the non-adsorbing gas, and k is a factor which corrects for the drop in pressure of
the carrier gas as it passes through the chromatographic column. Equation (3.5) has
been used [19] for calculating this pressure change factor:
k=
( Pi / Po ) 1
2
(3.5)
(Pi / Po )3 1
where Pi is the gas pressure at injection, and Po is the gas pressure at the detector.
The net retention volume VN is related to the free energy of the acid-base interaction Gab
between the probe and the surface of the filler by Equation (3.6). This relationship is
valid only at infinite dilution when interactions between the probe molecules are zero, it
is therefore essential that very small volumes of the probe are injected into the carrier
stream to get as close to the ideal state as possible. Of course the detector sensitivity
dictates the minimum volume, it is usual to operate close to this limit of sensitivity:
o
Gab = RT ln VN + K (3.6)
where K is a constant which depends [20, 21] upon the chosen reference state. The
enthalpy change Hab for the adsorption process can be calculated using the Gibbs free
energy equation (3.7).
o
Gab = Hab TSab (3.7)
Although the entropy change (Sab) is an unknown quantity this can be determined by
conducting a series of adsorptions at different temperatures. The entropy change is then
calculated from the slope of the plot of Gab versus absolute temperature.
120
Therefore, by measuring the net retention volumes, over a range of temperatures, of a

series of acid and base probes with known Drago constants, then fitting the calculated
enthalpy data to the Drago Equation (3.2), the acid and base constants for the filler
surface are able to be determined. The method is described in Section 3.3 of this chapter
and uses plots (see Figure 3.1), derived from the rearranged Drago Equation (3.3).
A similar approach was adopted by Schultz and co-workers [22] but using Equation
(3.8) derived from the Gutmann Equation (3.1) to characterise the acid base characteristics
of carbon fibres using IGC:
Hab = AN f DN p + DN f AN p (3.8)
This method, based on the Gutmann equation, is also preferred by Panzer and Schreiber
[23] who believe that the dominant weakness of the Drago approach is its failure to
account for the amphoteric nature of the probe.
3.4.2.3 Inverse Gas Chromatography
(a) Description. IGC can be carried out on any modern gas chromatograph. The type of
detector used is not critical to the application, flame ionisation detectors (FID) and thermal
conductivity detectors (TCD) are the more commonly used. The FID is generally a more
sensitive detector and therefore permits experiments to be carried out at a greater degree
of dilution. However, on modern gas chromatographs the TCD also have high sensitivity
and are equally appropriate for IGC. The output can be measured on a traditional chart
recorder and retention volumes measured with a rule, or more conveniently using PC
based chromatography software that electronically measures the retention time, and can
be further programmed to calculate VN, see Equation (3.4).
The technique differs from the standard gas chromatography only in the material used
for the column packing and the processing of the data. The only additional hardware
required are pressure gauges at the injection point and detector, which enable the k
factor in Equation (3.4) to be calculated. A schematic diagram of an IGC is shown in
Figure 3.8.
The critical parameters are a constant and accurately measured gas flow rate, temperature,
and injection and detector pressures. A small injection volume of the probe molecule is
required, to ensure that the conditions of the thermodynamic treatment are met.
(b) Method of Operation. The filler under examination is packed into a standard gas
chromatograph column, typically a stainless steel tube 0.5 or 1 m in length, and ~5 mm
121
Figure 3.8 Schematic diagram of an inverse gas chromatograph system
internal diameter. The column may be packed with undiluted filler, or the filler may be
mixed with a non-interacting low surface area diluent. This would be used where a very
high surface area filler caused an excessively long retention time, or where filler packing
caused an excessively high pressure drop across the length of the column. The next stage
is to find the minimum detection limit of the detector and determine the minimum injection
volumes of the probes which still produce well defined peaks, with good signal to noise
ratio. Then an injection of a non interacting gas (for example, methane) is made, the
retention time of this gas gives the value tn for use in Equation (3.4).
The experiments can then be carried out by injecting the predetermined volumes of the
probes and measuring their retention times tp. If the enthalpies of the interactions are
required, then the injections need to be repeated at different column temperatures to
enable the entropy change to be calculated.
(c) Example of output. Figure 3.9 is a compilation of typical output plots obtained during
an IGC experiment. Time zero corresponds to the time of injection of the sample, a non-
adsorbing probe takes time tn to elute from the column, whilst the experimental probe
takes time tp to elute. The time difference between tp and tn relates to the strength of
adsorption of the probe onto the filler surface. By adsorbing a series of probes with
different acidic and basic nature a qualitative characterisation of the filler surface is
achieved. Although as described previously by inserting the experimental data into
Equations (3.4) to (3.7) it is possible to determine enthalpies of adsorption.
122
Figure 3.9 Typical response curves from an IGC experiment, with responses from non-
adsorbed control and adsorbed probe superimposed
3.4.2.4 Multiple Probe Temperature-Programmed IGC
This variation on traditional IGC has been developed from the McReynolds approach
[24], for characterisation of stationary phases, by McMahon and co-workers [25]. It is
particularly suited to rapid comparative screening of families of solid surfaces, for example
a range of carbon blacks with differing surface chemistry. However, it does not provide
quantitative measures of thermodynamic parameters. The multi-probe set includes those
specified by McReynolds together with several n-alkanes. Classified groups of these probes
can be injected into the column as mixtures. The temperature of the column is increased
at a constant rate and the temperature at which the probe elutes is recorded as the retention
temperature (TR).
The TR values of the probes can be plotted against probe boiling point. For n-alkane
probes this relationship is linear but data for other probes will not necessarily coincide
with this linear relationship. If the concentration of polar sites on the filler is higher than
that of non-polar sites then data for the other probes will fall above the n-alkane line. In
the reverse case, i.e., if the concentration of non-polar sites is higher than the concentration
of polar sites, the data for the other probes will fall below the n-alkane line. The retention
characteristics of the probes can be expressed as Kovats indices (KI), i.e., the carbon
number of the n-alkane that will co-elute with a given probe multiplied by 100. The
higher the KI, relative to the carbon number of the probe, the greater the strength of
interaction between the probe and the filler.
123
One of the filler samples can be selected as a reference column and the probe TR values
in the sample column can plotted as a function of respective TR values in the reference
column. The surface area of filler in each column must be identical. If the surface chemistry
of the samples is exactly equivalent a linear plot will result. The direction and magnitude
of deviation from linearity provides a measure of the relative strength of interaction. The
multiple probe temperature programmed approach to IGC certainly shows potential for
rapid screening of fillers and yields data that can be treated using chemometric
classification tools such as principle component analysis.
3.5 Spectroscopic Techniques
3.5.1 Introduction
Surface modification of filler particles is common and frequently mandatory in order to

achieve desirable properties such as dispersability, filler-matrix bonding and even stability.
Such modifications can range from the adsorption of less than one monomolecular layer of
a surfactant to the precipitation of a coating many nm thick. Surface composition analysis
therefore requires methods which posses sampling depths of order 1-10 nm to several m,
and that can characterise both inorganic and organic species, ideally in a fully quantitative
manner. Of the variety of ultra-high vacuum (UHV) based surface spectroscopic techniques
which have emerged since the late 1960s only two: X-ray photoelectron spectroscopy
(XPS) (also frequently referred to as ESCA), and secondary ion mass spectrometry (SIMS),
come close to meeting the nanometer sampling depth requirements and are discussed briefly
here. It is worth noting that Auger electron spectroscopy (AES), which has many of the
necessary attributes, fails in this context because of charging problems with highly insulating
powders and beam damage to organic materials.
For much more detailed descriptions of the techniques the interested reader should consult
references [26-28].
3.5.2 X-Ray Photoelectron Spectroscopy
3.5.2.1 Physical Basis
In XPS the sample, inside a high vacuum system (pressure <10-5 Pa), is irradiated with
soft X-rays, usually Mg K (1253.6 eV) or Al K (1486.6 eV). The primary event is
photoemission of a core (atomic) electron, but relaxation processes also lead to emission
of Auger electrons, as shown in Figure 3.10. The emitted electrons are collected by an
electrostatic energy analyser and detected as a function of kinetic energy (Ek), producing
a spectrum such as that shown in Figure 3.11. The intense, narrow peaks are due to
124
Figure 3.10 X-ray photoemission from a 1s core level and subsequent relaxation
processes leading to X-ray fluorescence and Auger electron emission
photoelectrons emitted from core orbitals, (e.g., carbon 1s). The binding energies (EB) of
these electrons, are obtained from the Einstein relationship (Equation 3.9):
EB = h Ek (3.9)
(where h is the X-ray photon energy and the sample work function) are highly characteristic
and allow the identification of all elements except hydrogen (and helium). The peak intensities
are proportional to the number of atoms sampled, and with the aid of appropriate sensitivity
factors, atomic compositions can be calculated, with typical detection limits of 0.1 atom%.
The much weaker series of peaks at very low binding energy is due to photoelectron emission
from the valence band (molecular orbitals). The other, broader peaks are due to Auger
electrons, for which the kinetic energy (Ek) is given by Equation (3.10):
Ek(ABC) = EA EB EC (3.10)
where A, B, and C are the photoionised level, the level of the electron that fills this
vacancy, and the level of the emitted Auger electron, respectively, (Figure 3.10). These
kinetic energy values are also element characteristic, although not all elements produce
strong Auger signals under typical XPS conditions, and are obviously independent of h.
The information from XPS is surface specific because the electrons that give rise to the
useful peaks in the spectrum have emerged from the material elastically, i.e., without loss
of energy. The inelastic mean free path (m) of electrons of energy E in an inorganic solid
is given, approximately, by Equation (3.11):
2170
+ ( aE) 2
1
m = 2 (3.11)
E
125
Figure 3.11(a) XPS survey spectra of uncoated commercial TiO2 pigment
where m is in monolayers and the monolayer thickness, a (nm), is given by Equation (3.12):
A
a3 = 1024 (3.12)
pnN
where A is the atomic or molecular weight, n is the number of atoms in the molecule,
126
Figure 3.11(b) XPS survey spectra of coated commercial TiO2 pigment. Note the
marked attenuation of Ti 2p signal relative to Figure 3.11(a) following coating.
N is the Avogadro number and p is the bulk density in kg m-3. From this universal curve
[29] typical values of m range from ~2 (100 eV) to ~11 (1500 eV) monolayers. Expressed
in nm (n = am) this range is from ~6 to ~40 nm. The vertical sampling depth,
corresponding to 95% of the measured electron intensity is given by 3 sin where is
the electron detection angle with respect to the surface (the take-off angle).
127
3.5.2.2 Instrumental Aspects
The photon sources commonly used are Mg K1,2 and Al K1,2; the doublet nature of the
X-ray line is not resolved and the line widths are 0.7 and 0.85 eV, respectively. Mg K
therefore has the advantage for spectral resolution but Al K covers a greater energy
range (see section 3.5.2.1). Al K can also be monochromated using Bragg diffraction
from quartz crystals, reducing the line width to ~0.3 eV. In the past this was at the
expense of intensity/sensitivity but modern instruments have overcome this problem
through more efficient collection of the photoelectrons.
Electron energy analysis is achieved by means of an electrostatic concentric hemispherical

analyser operating in the fixed analyser transmission mode. All the photoelectrons are
retarded to a constant pass energy through the analyser; the higher this energy the
greater the sensitivity but the lower the energy resolution.
Insulating samples charge up under X-ray bombardment due to secondary election

emission. With conventional sources, this is counterbalanced by the flood of low-energy
electrons emanating from the front face of the window separating the X-ray source from
the analysis chamber. With monochromated sources this mechanism is not available and
a discrete source of electrons needs to be provided from a low-energy flood gun.
3.5.2.3 Information Levels
The main source of information is the core levels. With Mg or Al K sources at least one
core level electron is excited from all atoms in the periodic table except hydrogen. The
peak positions are highly element specific with relatively few overlap problems allowing
straightforward elemental analysis. As noted previously the peak intensity data is
inherently quantitative. The appropriate sensitivity factors can be calculated from
theoretical cross-sections and known instrumental factors, but are often best determined
empirically using pure stoichiometric standards. Core level binding energies (BE) vary
slightly (typically over a range of few eV) depending on oxidation state, electronegativity
of attached ligands/chemical environment, etc., (chemical shift effect). This allows more
detailed structural interpretation. Thus in the example shown in Figure 3.11, from the
BE of the appropriate core levels the oxidation states of the elements aluminium,
phosphorus, titanium and zirconium could be established.
For organic systems the C ls, etc., chemical shifts reveal information about functionality
as illustrated in Figure 3.12. Often this information can be augmented via use of the
Auger peaks (from the same element) to give a number, the Auger Parameter, independent
of charging effects, that is characteristic of that chemical state (the Auger peaks also
suffer chemical shifts as a consequence of Equation 3.10). These data can be very material
128
specific and large tabulations of chemical shift and Auger Parameter data are available
[30]. By using higher energy X-ray sources, (e.g., Ag L at ~3 keV) to excite deeper core
levels more Auger Parameters can be measured.
Figure 3.12 C 1s spectra from filler surfaces following interaction with MPS.
(a) Alumina after treatment (solid line), alumina before treatment multiplied by (1x),
where x is the calculated coverage by MPS, subtraction (broken line);
(b) Subtraction spectrum obtained as in (a) for MPS on quartz and fitted with three
components representing C-C/C-H, C-O and C(-O)= functionalities (increasing order
of binding energy). These components have relative intensities of ~5:1:1 in agreement
with the structure of MPS.
(Reproduced with permission from F. Garbassi, E. Occhiello, C. Bastioli, G.

Romano, Journal of Colloid and Interface Science, 1987, 117, 1, 266.
Copyright 1997, Elsevier.)
129
Bonding electrons are also photoemitted and these appear in the valence band between,
say 0-30 eV BE. Emission from many closely spaced levels with different cross-sections
gives rise to a complex spectrum, often rich in structure, which in principle contains
more direct structural information than the core level peaks. The spectrum is rather low
in intensity (typically only a few percent that of major core lines) but with higher power
instruments it is routinely accessible. The fingerprint utility of the valence band is
increasingly being augmented by full interpretations based on theoretical calculations.
A range of carbon black samples of varying degree of oxidation and sulfur content were
examined using XPS by Pena and co-workers [31]. In this study the O 1s spectra (543-
523 eV) and S 2p spectra (177-157 eV) were used to determine the relative amounts and
the nature of oxygen and sulfur containing functional groups, respectively. The surface
chemistry of the carbon black samples was very well resolved by XPS and was related to
FMC data for adsorption of a wide variety of polymer stabilisers and relevant model
compounds [31-34]. The multi-probe temperature programmed IGC study by McMahon
[25] used two of the same carbon black samples as in [31-34]. The latter IGC data fitted
in well with the XPS and FMC data obtained (note CB-1 and CB-2 in [25] are CB-B and
CB-A, respectively in [31]).
3.5.3 Secondary Ion Mass Spectrometry
3.5.3.1 Physical Basis
In SIMS the sample, inside an ultra-high vacuum system (pressure <10-7 Pa) is bombarded
with a primary ion beam, (e.g., Ar+, Cs+, Ga+, O2+) of energy 1-30 keV. Of the fragments
of material ejected (sputtered) from the surface a few percent are charged either positively
or negatively. These are extracted into a mass analyser to yield, separately, positive or
negative secondary ion mass spectra. The fragments can be single elemental ions or clusters
of atoms with a collective, usually single, charge.
An immediate distinction needs to be made between dynamic and static SIMS experiments.
In the former, a primary ion current density of typically > 10 A cm-2 is used and this leads
to rapid sputtering of material. The surface is eroded at a rate of order nm s-1 and by
following the intensity of chosen peaks in the mass spectrum as a function of time, a
concentration depth profile can be constructed. In this mode SIMS can be very sensitive,
with trace element detection limits in the ppm-ppb range. However, quantification is not
straightforward. Secondary ion intensities are strongly matrix-dependent and extensive
calibration procedures involving closely related standards of known composition and under
identical experimental conditions must be used to extract quantitative concentrations.
In static SIMS, on the other hand, the aim is to reduce sputtering to the absolute minimum
whilst obtaining a spectrum of adequate intensity. For inorganic systems a primary ion
130
dose of ~1014 ions cm-2 may be tolerated, resulting in the sputtering of ~10% of the
uppermost monolayer. For organic systems, ion-induced damage leads to loss of spectral
integrity more quickly and so a maximum dose of 1012-1013 ions cm-2 is permissible. The
spectra obtained under these static conditions provide a molecular fragmentation pattern
representative of the surface molecular structure. Figure 3.13 shows the positive and
negative ion mass spectra from the same pigment examined by XPS in Figure 3.11(b).
The negative ion spectrum is dominated by fragments from one or more organic species on
the surface - either contamination from sample handling/storage or preparation for analysis
(powder deposited onto glass from methanol slurry). The pattern of intensities represents a
fingerprint as in conventional gas phase mass spectrometry (but the ionisation/fragmentation
processes are different). The sampling depth in SIMS is only 1-2 monolayers (~10 ).
Figure 3.13(a) ToF SIMS spectra from coated pigment giving XPS spectrum of
Figure 3.9(b): positive ion spectrum; annotated peaks are due to Na+ (m/z 23), Al+
(27), Ti+ (48), TiO+ (64), TiO(OH)+ (81), ZrO+ (106) and ZrO(OH)+ (123).
See next page for Figure 3.13(b)
131
Figure 3.13(b) ToF SIMS spectra from coated pigment giving XPS spectrum of
Figure 3.9(b): negative ion spectrum; annotated peaks are due to PO2- (63), PO3- (79),
H2PO4- (97) all other peaks are molecular fragments from organic species.
132
3.5.3.2 Instrumental Aspects
Since dynamic SIMS is principally a tool for trace element analysis and depth profiling it
will not be considered further here. In static SIMS the major instrumental differences are
related to ion sources and mass analysis. Early experiments involved the combination of a
noble gas (electron impact) ion source with a quadrupole mass spectrometer. Typically
4 keV Ar+ or Xe+ ions in either a raster-scanned focussed spot or a broad stationary spot
would be used. Either way a current density in the 1 nA cm-2 regime is the prerequisite for
static SIMS analysis. The quadrupole mass spectrometer (QMS) is a compact device with
the advantage of a large collection area, suited to the above ion bombardment conditions.
A good QMS will have a mass range of 0-1000 atomic mass units (amu) and a transmission
of ~0.1% (ions detected:ions ejected). However, transmission decreases with mass (T M-1
to M-2) and mass resolution is poor (typically, close to 1 amu over the mass range covered).
During the last decade time-of-flight (ToF) mass analysers have completely eclipsed the
QMS to the extent that the terms static SIMS and ToF - SIMS have become synonymous
[28]. ToF analysers give much greater transmission (>10%, mass independent) and
extended mass range (up to 10,000 amu). In ToF - SIMS the primary ion beam is pulsed
and all the secondary ions are detected in parallel between each pulse. In contrast the
QMS is a serial device, the mass range being scanned. Thus ToF - SIMS instruments are
~104 times more sensitive than QMS instruments and this allows them to perform static
SIMS analysis of much smaller areas. Liquid metal ion sources (Ga+) giving small probe
diameters (~400 ) are ideal for imaging at high spatial resolution. ToF instruments also
give high mass resolution (of the order of 10,000) which greatly enhances the analytical
power of the technique through the resolution of ions with the same nominal mass (a
trivial case is a metal ion having the same nominal mass as an organic fragment). Intense
Cs+ sources, but with spot sizes of order 30 m, are used to increase data acquisition
rates when high spatial resolution is not required.
Insulating samples charge up under ion bombardment and this effect must be prevented
during SIMS analysis. With QMS systems a stationary flood of relatively low energy
electrons is used to charge neutralise. In ToF systems where the primary ion beam is
pulsed at high frequency the electron flood takes place between individual ion pulses
when the secondary ion flight times are being measured. Because the pulse averaged
current density is also much lower than with a QMS system, this is a much more effective
solution to the problem.
3.5.3.3 Comparison of XPS and SIMS
The fingerprint quality of static SIMS spectra has already been noted. Identification of
surface species is aided by the existence of an expanding library of static SIMS spectra
133
with a search engine [35] and the use of accurate mass measurement to assign empirical
formulae to chosen peaks. Because of the high surface sensitivity, surface coverage of the
substrate by organic molecules is somewhat easier to judge than by XPS. The cluster ion
spectra of inorganics are similarly reflective of structure but much less work has been
done in this area. SIMS can be much more sensitive to elemental species than XPS,
particularly to highly electro-positive or -negative elements. The two techniques are very
complementary in respect of quantification, structural insight and sampling depth. In
situations such as filler surface analysis, where layered systems involving both organic
and inorganic components are involved, SIMS is a valuable adjunct to XPS.
3.5.3.4 Examples
There are relatively few detailed studies of particulate fillers by surface analysis and
space limitations preclude a review. The interested reader is encouraged to study a series
of papers by Johansson and co-workers [36-39] that address the characterisation of
coated TiO2 pigments. These discuss in considerable detail the relationship between data
from XPS, SIMS and X-ray fluorescence as well as relating surface analytical information
to other methods of pigment surface characterisation and to pigment behaviour.
3.5.4 Diffuse Reflectance Fourier Transform Infrared Spectroscopy
3.5.4.1 Background
Infrared spectroscopy is a technique that gives intimate structural detail of the molecules
under examination. The infrared radiation is absorbed by changes in the vibrational
state of the molecule, that is the bending or stretching of the bonds within the molecule.
Consequently, the interpretation of the spectra not only gives the chemical groupings
present in the molecule but information about the environment of each of the groupings
and hence the structure of the molecule. The reader should refer to [40] and [41] to gain
a more fundamental understanding of the science.
The basic transmission infrared spectroscopy technique has been a workhorse for chemical
analysis for many years. As computers and computing techniques became more advanced
(FTIR) spectrometers were developed. The introduction of FTIR revolutionised infrared
(IR) spectroscopy because for the first time weak signals could be cleared of noise thanks
to co-addition and Fourier analysis of many scans.
The ability to produce high quality spectra from weak signals led to new sampling
techniques, such as diffuse reflectance and microscopy, that simply could not be used
with the older dispersive IR spectrometers. The advent of FTIR therefore brought about
134
a step change in the resolution and ease of use of IR spectroscopy. FTIR is now no longer
the preserve of prestigious university and industrial research laboratories, now quality
instruments can be purchased for as little as 12,000.
This enhanced sensitivity and ability to subtract spectra with precision led to many
adaptations of the technique. One of these adaptations was DRIFTS. This technique was
designed to enable spectra of powders to be analysed without the need for grinding and
elaborate preparation that can of course modify the chemical nature of the material.
The added benefit of DRIFTS is that it is also far more surface specific than transmission
IR due to a significant proportion of low and glancing angle reflections though filler
surface layers. This effect was effectively demonstrated by Gilbert and co-workers [42]
who showed that stearic acid in physical mixtures with various fillers gave very weak IR
absorbance in DRIFTS spectra, relative to equivalent amounts of stearic acid that had
been adsorbed on the filler surface.
FTIR data analysis software enables spectral data for the uncoated filler to be subtracted
from that of the coated specimen, thus creating a difference spectrum that enhances
absorption bands associated only with the surface treatment. It is important to point out
that subtraction does not always yield additional information, especially when a small
absorption associated with a surface treatment is obscured by a large absorption associated
with the filler. Spectral changes relative to the unbound surface treatment/additive provide
insight into the nature of interaction with the surface. Examples of use of DRIFTS are
described in Section 3.5.4.4. DRIFTS spectra can be quantified provided sample
preparation/presentation and representation of the data is correct.
3.5.4.2 Comparison of DRIFTS and XPS
It is important to appreciate that whilst DRIFTS is an IR spectroscopy method that has

significant surface specificity, it is by no means an exclusively surface analytical technique
as is the case with XPS and SIMS, which have penetration depths in the order of
nanometres. The penetration depth in DRIFTS is an order of magnitude higher, i.e.,
micrometres. However, the high proportion of low and glancing angles of incidence
afford the high degree of surface specificity that is the key advantage of the technique.
Sutherland [43] has found that with a 20 m2 g-1 calcium carbonate filler, detection limits
of less than 0.05 monolayers can be achieved. Rather surprisingly this level of sensitivity
was higher than that achievable using XPS on the same series of samples. This can be
explained, however, by the greater sampling depth of DRIFTS that enables resolution of
surface modifier within pores in the filler surface. The different sampling depths available
using these techniques have been exploited by Gilbert and co-workers in more recent
studies of fatty acid treated fillers [44].
135
3.5.4.3 Sample Preparation
It is possible to analyse the filler in an undiluted state using DRIFTS, however, specular
reflection and excessively strong absorption can lead to poor quality spectra featuring
negative peaks. It is now widely accepted that the filler sample must be diluted with an
IR transparent powder such as KBr or KF. The latter must be finely ground and ideally
the same batch of ground diluent must be used for a whole sample series. The level of
dilution should be such that there is no compression or saturation of the spectrum. This
can be observed by comparison of the DRIFTS spectrum with a transmission spectrum
of the untreated filler in a KBr disk. Usually 1-10% w/w filler in the diluent will give
uncompressed spectra.
It is also very important that the ground KBr and filler are not mixed roughly, i.e., by
grinding, as the surface layers will be disrupted and non-representative data will be generated;
the two components should be mixed by a gentle folding motion with a micro-spatula.
3.5.4.4 Description of DRIFTS Cell
A simplified line diagram of a cell is shown in Figure 3.14. The essential features of the
cell are mirrors and optics to focus the incident infra-red beam onto the surface of the
powdered filler which is held in the sample holder. The reflected radiation that is now
scattered across a wide angle, due to the random orientation of the surfaces of the filler
Figure 3.14 Schematic diagram of a typical DRIFTS cell
136
Figure 3.15 Schematic diagram of DRIFTS sample holder with specular reflection blocker
particles from which it is reflecting, is captured by the elliptical output mirror. The mirror
refocuses the radiation back into a beam that is further corrected by the output optics
before passing through to the detector.
A further refinement of the sample holder has been the introduction of a specular
reflection blocker. Specular reflection is the radiation that is reflected from the front
surface of the sample and has not penetrated the powder. This can occur if the filler
sample is not sufficiently diluted with KBr or KF. Specularly reflected radiation can
render some data transformations invalid and can therefore potentially reduce the
accuracy of any quantitative measurements. To overcome this problem blocker devices
have been developed that are adaptations of the sample holder. The most basic type is
illustrated in Figure 3.15, this simply introduces a physical barrier to the specularly
reflected radiation.
Correct dilution of the filler powder with finely ground KBr or KF can, however, eliminate
the vast majority of specular reflection components without recourse to the blocker. The
authors have found that the blocker also removes a significant fraction of the diffuse
reflection components and can therefore needlessly weaken the signal.
3.5.4.5 Treatment of Data for Quantitative Analysis
Treatment of diffuse reflectance IR data normally involves the Kubelka-Munk (KM)

Equation (3.13) that takes account of scattering and absorption characteristics [45]. The
constants s and k are used to describe the scattering and absorption properties, respectively,
and R is the reflectivity of an infinitely thick sample:
137
k (1 R )
2
= (3.13)
s 2R
This relationship is only valid if there are no specular reflection components. Sutherland
[43], however, has compared plotting of ratioed data both in absorbance and in KM
units as a function of added surface treatment level. As linear relationships were obtained
in both cases it was therefore considered that there was no advantage to be gained in
using the KM equation.
In transmission IR spectroscopy, using a constant path length, absorbance is proportional

to concentration; this relationship (the Beer-Lambert law) will only be true for DRIFTS
if the nature of dispersion of filler particles in the diluent does not change with the level
of surface treatment. Such an ideal condition will rarely be realised. Therefore it is essential
to use internal standards within spectra and ratio variable absorptions to these internal
standards. Use of absorbance peak area is preferable to the absolute absorbance value
(peak height) as area takes the overall energy of the absorbance into account and thus
accounts for changes in peak width.
The internal standard should be selected carefully as it should not be affected by treatment
level. For example with metal hydroxide fillers the OH stretching bands at 3750-3070 cm-1,
(depending on actual hydroxide) are a convenient internal standard. This may at first seem
surprising considering the fact that many surface modifiers react with the OH groups/ions
of the filler, but the reasoning behind use of these bands is clear when the micrometre
penetration depth of DRIFTS sampling is considered. The surface area of most mineral
fillers for polymers is relatively low (< 30 m2 g-1) therefore the reactive groups on the filler
surface are insignificant in number relative to those in the bulk of the filler particles. Hence
under such circumstances it can be considered valid to use the IR absorbance of surface
treatment reactive groups as internal standards. However, in the case of filler with high
surface area, i.e., some grades of silica, the latter argument is not valid. This therefore
requires the use of a truly non-reactive IR absorbing group as the internal standard, for
example the siloxane related adsorption of silica, centred at 800 cm-1.
3.5.4.6 Examples
The following examples illustrate the power of the DRIFTS technique for analysis of
interaction between fillers and surface treatments or polymer additives.
The first example examines the adsorption of maleanised polybutadiene (MPBD) onto
aluminium hydroxide (ATH) and magnesium hydroxide. These are two very effective
flame retardant fillers, ATH is the most commonly used, but magnesium hydroxide with
138
its higher decomposition temperature has become established in some sectors of the
market. MPBD is an effective dispersant and coupling agent, both in thermoset composites
or rubber compounding.
The spectra (Figures 3.16, 3.17 and 3.18) are presented in transmittance mode and not
Kubelka-Munk units as discussed previously. However, the purpose of this investigation
was to understand the chemical reactions taking place at the filler surface and not to
make any quantitative measurements.
Figure 3.16 shows the spectrum of MPBD. The sample was prepared by coating a film
onto a sodium chloride disc and the spectrum was measured in transmission mode. The
key features are the peaks at 1860 cm-1 and 1781 cm-1 corresponding to the symmetric
and asymmetric carbonyl stretching frequencies.
Figure 3.17 contains the difference spectrum between ATH and ATH which had been
coated, from solution, with the same grade of MPBD. In this spectrum relatively weak
adsorptions at 1860 cm-1 and 1781 cm-1 are present indicating some unreacted MPBD,
but in addition a strong peak at 1700 cm-1 exists which corresponds to the absorption
frequency of the carbonyl stretch in the carboxylic acid. Clear evidence that the anhydride
has hydrolysed, but the lack of a strong peak at 1580 cm-1, the carbonyl stretching
frequency of the salt, shows that the acid had not reacted with the surface of the ATH to
form salt bridging between the polybutadiene backbone and the filler surface.
Figure 3.16 Transmission infra-red spectrum of MPBD
139
Figure 3.17 DRIFTS difference spectrum of ATH subtracted from ATH coated
with MPBD
Figure 3.18 DRIFTS infra-red difference spectrum of magnesium hydroxide subtracted

from magnesium hydroxide coated with MPBD
Figure 3.18 is also a difference plot, but between magnesium hydroxide and
magnesium hydroxide coated in MPBD by the same solution coating procedure used
for the ATH. In this spectrum there are again relatively weak absorptions at 1860 cm-1
140
and 1781 cm -1 from unreacted MPBD, but now only a very weak absorption at
1700 cm-1 from carboxylic acid. However, a strong absorption at 1580 cm-1 shows
that the MPBD had reacted with the magnesium hydroxide to form the salt, to fully
couple the butadiene backbone with the filler surface.
The second example shows how DRIFTS can give insight into the environment in
which adsorbed species reside and how this environment changes with addition level
[46]. Figure 3.19 shows the carbonyl region of substrate subtracted DRIFTS spectra
of magnesium hydroxide that has been treated with varying levels of stearate (from
ammonium stearate).
Figure 3.19 Substrate subtracted DRIFTS spectra for the carbonyl region of
magnesium hydroxide treated with increasing amounts of ammonium stearate.
(a) 10 mg g-1, (b) 20 mg g-1, (c) 30 mg g-1, (d) 45 mg g-1, (e) 60 mg g-1, (f) 90 mg g-1,
(g) magnesium stearate and (h) stearic acid.
(Reproduced with permission from C.M. Liauw, R.N. Rothon, G.C Lees and W.C.E.
Schofield, Journal of Adhesion, 2002, 78, 7, 603. Copyright 2002, Taylor & Francis).
141
Interesting changes are evident in both the asymmetric and symmetric carboxylate
carbonyl stretching frequencies (1580-1550 cm-1 and 1420-1360 cm-1, respectively). It
is evident that the asymmetric stretching frequency increases to a limiting value
somewhere between 30 mg g-1 (the monolayer coverage) and 45 mg g-1. Changes in the
symmetric stretching vibration frequency relative to the asymmetric vibration can
provide insight in to the degree of coordination of the magnesium ion [47]. At a stearate
level of 10 mg g-1 adsorption is via the monocarboxylate (C17H35COOMgOH) (here
the wavenumber difference between the symmetric and asymmetric stretching
frequencies are greater than in pure magnesium stearate). Increasing the addition level
to 20 mg g-1 led to to mixed adsorption via the monocarboxylate and dicarboxylate
(the symmetric stretching vibration is now split in two). Increasing the level to 30 mg
g-1 and beyond indicated exclusive production of the dicarboxylate.
Formation of the dicarboxylate on top of the first monolayer is manifested as attainment

of a limiting value of the asymmetric stretching frequency at an addition level greater
than the monolayer level, i.e., between 30 and 45 mg g-1. The fact that the limiting
value of the asymmetric stretching vibration frequency is identical to that in pure
magnesium stearate indicates that the adsorbed layers are only weakly associated with
the filler surface.
Figure 3.20 Infrared absorption peak area ratio (C-H stretch [from AS] (A(C-H)s)/O-H
stretch [from Mg(OH)2] (A(O-H)s), obtained from DRIFTS spectra of ammonium
stearate treated magnesium hydroxide.
(Reproduced with permission from C.M. Liauw, R.N. Rothon, G.C Lees and W.C.E.
Schofield, Journal of Adhesion, 2002, 78, 7, 603, Figure 3. Copyright 2002, Taylor & Francis)
142
Continual adsorption beyond the monolayer level is confirmed by plotting the C-H
deformation band to OH deformation band area ratio versus the addition level. Whilst
there is a linear increase in the peak area ratio up to the monolayer level, there is still a
progressive increase beyond it.
The ability of IR spectroscopy to probe the environment in which bonds vibrate allows
it to be used to examine structural ordering of surface modifier molecules. If alkyl
chains for example are in a liquid-like state of disorder the dispersion forces of attraction
between chains are not maximised and vibration of the C-H bonds is influenced almost
solely by the bond stiffness. If on the other hand the chains are in an ordered crystalline
array, dispersion forces are maximised. This causes the C-H bonds to become very
slightly longer (and therefore weaker) than when in the liquid state. This reduction in
stiffness causes the asymmetric C-H stretching vibration frequency of a C18 alkyl chain
to reduce by 3-5 cm-1. Such frequency shifts have been used by Kellar and co-workers
[48] to investigate ordering of oleic acid monolayers and by Liauw and co-workers
[13, 49]. Vaia and co-workers [50] have also used this approach to examine the order
of alkyl chains of quaternary alkyl ammonium intercalants in organo-clays for
nanocomposite applications.
The third example shows how DRIFTS can be used to gain further insight into what
interactions occur in the FMC cell. A study of the adsorption of isostearic and acrylic acids
on to aluminium and magnesium hydroxide, was carried out with the intention of evaluating
mixed surface modifier systems that possess dispersant and coupling capabilities.
Figure 3.21(a) shows a DRIFTS spectrum of a sample of magnesium hydroxide recovered

from the FMC cell (and air-dried) after adsorption and desorption of isostearic acid
followed by adsorption and desorption of acrylic acid. Figure 3.21(c) shows a DRIFTS
spectrum of filler obtained after the reverse experiment, i.e., adsorption and desorption
of acrylic acid followed by adsorption and desorption of isostearic acid. Figures 3.21(b)
and 3.21(d) shows DRIFTS spectra after adsorption and desorption of acrylic and
isostearic acids, respectively. It is evident that acrylic acid will completely displace
isostearic acid, however, isostearic acid will adsorb onto a layer of adsorbed acrylic
acid. It is envisaged that mixed isostearate and acrylate binary salts may form during
the latter adsorption process but not when adsorption of isostearic acid is followed by
adsorption of acrylic acid. This is likely to be due to the higher acidity of acrylic acid
and magnesium isostearate being more soluble in the toluene carrier solvent than
magnesium acrylate.
Further examples of application of DRIFTS, and other surface analytical techniques, to

organosilane treated fillers and interphase characterisation in organosilane modified
composite, have been reviewed by Suzuki and Ishida [51].
143
Figure 3.21 DRIFTS spectra of magnesium hydroxide recovered from the FMC cell
after adsorption from toluene of: (a) isostearic acid followed by acrylic acid, (b) acrylic
acid, (c) acrylic acid followed by isostearic acid and (d) isostearic acid.
(Reproduced with permission from C.M. Liauw, R.N. Rothon, G.C Lees and Z. Iqbal,
Journal of Adhesion Science and Technology, 2001, 15, 8, 908. Copyright 2001, VSP)
3.6 Methods for Examining Structural Order in Filler Coatings
Whilst structural order within adsorbed layers of surface modifier molecules is usually
considered to be confined to linear chain fatty acids, it is important to appreciate that
silane-based treatments can also undergo a degree of structural ordering under certain
conditions. Ghde [52] may have indirectly observed such structural ordering with MPS
adsorbed on glass, as the latter gave rise to preferred orientation of polyethylene chains.
In a study of adsorption of MPS on to lead oxide, Miller and Ishida [53] attributed a
shift in the SiOSi asymmetric stretching band (in DRIFTS spectra (see Section 3.5.4))
144
to structural ordering as polysilsesquioxane ladder polymers absorb in the same region.

In this last section, brief details of other suitable analysis methods that may confirm the
presence of structural order are given.
3.6.1 Wide Angle X-Ray Diffraction
By virtue of the conveniently sized wavelength diffraction/scattering of X-rays is a long

established tool for probing the structure of materials. X-ray diffraction (or WAXS) can
be used to measure distances between planes in crystalline structures. For a review of the
concepts and methods of WAXS the reader is referred to Cullitys book [54]. The authors
[13, 49] have found WAXS useful for establishing if any structural order is present in
fatty acid coatings on filler surfaces. Gilbert and co-workers [55] have also found the
technique useful for analysis of fillers treated with fatty acids and fatty acid salts.
Stearic acid adsorbed from heptane solution on to magnesium hydroxide (as magnesium
stearate) was shown to exhibit structural order [49]. This was manifested as a reflection
that became apparent at coverage levels at and beyond monolayer. The d-spacing of the
reflection corresponded to the short spacing of magnesium stearate. Isostearic acid and
oleic acid adsorbed under the same or similar conditions as the stearic acid showed no
evidence of structural order due to the inability of the alkyl/alkenyl chains to pack into
an ordered structure [13].
WAXS has become the one of the main techniques for analysis of organoclays and
polymer layered silicate nanocomposites. These aspects have been thoroughly reviewed
by Vaia [56].
3.6.2 Differential Scanning Calorimetry
DSC can be used to observe phase transitions in materials such as melting behaviour
(first order transitions) and second order transitions that are associated with the glass
transitions of polymers [57]. In essence DSC measures the energy required to maintain a
constant temperature in the sample relative to an inert reference. Therefore processes
that lead to a change in heat capacity, i.e., melting and glass transitions can be observed,
as can endothermic or exothermic chemical reactions. DSC instruments are now extremely
sensitive and are quite capable of resolving phase transitions of adsorbed surface modifiers.
For analysis of fillers dynamic DSC is most useful. In this mode, the difference in electric
power input required to keep the reference pan at the same temperature as the sample
pan (i.e., the heat flow), is recorded as a function of steadily increasing (or decreasing)
temperature. A typical dynamic DSC analysis may consist of a heat-cool-heat cycle.
145
The same stearic acid treated magnesium hydroxide samples, discussed in Section 3.6.1
showed evidence of melting of stearic acid and/or magnesium stearate even at the
monolayer level. Use of heat-cool-heat cycles can indicate structural changes that occur
as a result of further reaction of a surface modifier with the substrate. This effect
occurred with magnesium hydroxide that had been treated with 2.5 monolayers of
stearic acid [13]. DSC data from the first heat segment of the cycle showed evidence of
free stearic acid but data from the second heat segment showed that this may have
become magnesium stearate (Figure 3.22) [58]. Coatings derived from oleic and
isostearic acids showed no melting endotherm peaks and were thus considered
amorphous, in concordance with the WAXS data.
Figure 3.22 First heat (upper) and second heat (lower) DSC data (from a heatcool-
heat cycle) showing the change in structure within adsorbed layers of (a) stearic acid
and (b) isostearic acid on magnesium hydroxide, together with untreated magnesium
hydroxide (c). Note change in heat flow scale from first to second heat.
(Reproduced with data from C.M. Liauw, R.N. Rothon, G.C Lees and Z. Iqbal, Journal
of Adhesion Science and Technology, VSP, 2001, 15, 8, 896. Copyright 2001, VSP.)
146
3.7 Summary
This chapter has described how the most important property of a particulate filler,
with regard to its reactivity, is the acidic or basic character of its surface sites.
Furthermore, that the surface of a single filler particle can have sites ranging from
strongly acidic to strongly basic. It has been shown that techniques for characterising
filler surfaces can be broadly divided into three groups.
In the first, the reactivity of the filler surface to well defined probe molecules is
observed. Of these, FMC is perhaps the more powerful, giving the ability to measure
heat of adsorption directly and using the polymers, coupling agents or additives of
interest. IGC is more instrumentally developed, but generally requires the use of
model probes because of the need for them to be volatile and reversibly adsorbed.
The second group, XPS and SIMS, are the analytical techniques that are capable of
determining the chemical composition of filler surfaces, as opposed to the bulk.
DRIFTS has a greater penetration depth than XPS or SIMS but in many cases, such
as when the filler has a porous surface, this is advantageous. The DRIFTS examples
clearly demonstrated how insight into the nature of interactions between surface
modifiers and filler surfaces could be acquired.
The third group of techniques (WAXS and DSC) can be used to establish the existence
of structural order in adsorbed layers of surface modifiers. DSC in particular can be
linked to FTIR if a suitable DSC hot stage is used on an infrared microscope, this
combination has exciting potential for following the reactions between fillers and
surface modifiers.
The fact that certain fillers are now valuable functional additives for polymers is a
testament to the ever-increasing importance of surface characterisation. Insight into
the surface chemistry of fillers opens the door to surface modification; a technology
that in-turn leads to high added value products. The emergence of nanocomposite
technology places even more emphasis on the filler surface by default due to the fact
that the interfacial region in a fully exfoliated nanocomposite forms a very significant
fraction of the composite volume. In such systems there is huge potential for
modification of the interfacial region by modification of the platelet surfaces.
Therefore improvements on the techniques described here will be inevitable and will
be driven by an ever-increasing quest to use filler surfaces to promote unique composite
properties. It is highly likely that data from these improved techniques may help in
creation of improved computer models of surfaces, leading to advanced modelling of
adsorption interactions.
147
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152
4
Surface Modification and Surface Modifiers
Roger N. Rothon
4.1 Introduction
As described in the earlier chapters, the filler surface plays a vital role in determining the
processing behaviour and properties of composites. The main methods for characterising
filler surfaces were discussed in the previous chapter. This chapter covers the use of
additives to beneficially modify the surface of fillers, and thus optimise composite
processing and properties.
A wide range of such surface modifiers are offered and used commercially, ranging
from the inexpensive fatty acids, to silanes, titanates and zirconates and all are
discussed. Reference is also made to non-commercial treatments, such as borates
and phosphates.
4.2 Reasons for Using Surface Modifiers
With the notable exception of carbon blacks, the natural surfaces of most particulate
fillers are less than optimum for dispersion into, and interaction with, polymers. Surface
modifiers can frequently improve this, and other filler properties. Sometimes materials
which are effective surface modifiers will be found to have been added for filler
manufacturing reasons. The main reasons for finding surface modifiers present are:
Improved filler production. Thus, they can be used as milling aids and to improve
filtration and reduce hardness development during drying.
Protection of the filler in storage and in the end application. Thus, they can reduce
water pick up and protect fillers such as magnesium hydroxide from attack by
atmospheric carbon dioxide.
Improved processing. Surface modification often improves the rate of incorporation

into the polymer and reduces the viscosity of the mix. This can lead to significant
savings in energy, or to faster throughput. Indeed, some form of surface modification
is often essential when high filler loadings are used.
153
Reduced adsorption of expensive additives, notably curatives and anti-oxidants.

Resulting improvements in curing can also lead to improved properties.
Improved composite properties. These can include: increased strength and stiffness,
better impact strength, increased abrasion resistance, reduced adsorption and less
swelling in the presence of water and other fluids.
It should also be noted that the presence of surface modifiers can also influence other
properties. This includes properties such as bulk density, powder flow and dustiness.
They can also have unexpected effects on properties such as thermal stability, fire
retardancy and ageing. These effects may be positive or negative.
4.3 General Principles of Surface Modification
Virtually all treatments in commercial use are chosen to chemically bond an organic
species to the filler surface, thus improving compatibility with organic polymers.
The most common functionalities used for this are acids or acid precursors, such as
anhydrides (for basic or amphoteric fillers) and alkoxy-silanes (for fillers with metal
hydroxyls present, especially siliceous fillers). Organo-titanates and related
compounds are also proposed for use with a wide variety of fillers.
Two distinct types of surface modifier can be recognised: non-coupling and coupling.
The non-coupling types have a chemical bond to the filler surface, but no strong
bonding to the polymer matrix. The widely used saturated fatty acids are typical of
this class.
The coupling types, usually described as coupling agents, have both a chemical bond
with the filler surface, and some means of strong interaction with the polymer matrix.
This interaction with the polymer is usually due to some chemical functionality, which
can react with it. In some instances, it is due to the anchored species having long
enough chains to entangle, or co-crystallise, with the matrix.
Where the matrix polymer undergoes a polymerisation, or crosslinking process, during

composite formation; then it is fairly simple to choose a suitable polymer reactive
group (e.g., a carbon=carbon double bond). However, with polymers such as the
polyolefins, this can be difficult. Highly reactive functionalities, such as azides, are
sometimes used in this case. It is also possible to pre-functionalise a part of the
polymer matrix, by grafting on a species such as an acid, anhydride or alkoxy-silane,
in a separate process.
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4.4 Methods of Using Surface Modifiers
Modification of the surface of fillers may be brought about in a variety of ways. The
most appropriate will depend on many factors, including: the nature of the filler and the
process used in producing it, the nature of the additive, and of the polymer and the
composite processing conditions.
The first differentiation is into pre-coating and in situ methods. In the latter, the coating
agent is added during compounding, making its way to, and reacting with, the filler
surface during this process. The main advantages and disadvantages of the two procedures
are summarised in Table 4.1. The relative importance of the various factors will vary
depending on the nature of the coating and filler and on the composite processing
conditions. In some cases, especially where some new surface may be generated during
processing, a combination of the two approaches may give optimum results.
Table 4.1 A comparison of the pre-coating and in situ methods of filler treatment
Pre-coating In situ
Usually requires an expensive additional Usually less expensive, but may require
step, but is claimed to give more efficient higher additive levels.
use of the additive.
Volatile by-products such as alcohols are Volatile by-products can be a problem.
easily dealt with.
Essential where improved filler
processing and stability are sought.
Surface reaction and coverage can be Surface reaction is very much at the
strictly controlled. Interference from mercy of processing conditions, including
other compounding additives can be competition from other additives.
minimised. Residual, unreacted, additive more likely
to be present and may cause problems.
Unable to treat fresh surface generated Opportunity to treat fresh surface
during compounding. generated during compounding.
Interpenetration of coating and matrix Greater opportunity for coating/matrix
may be limited. interpenetration.
Limited flexibility for adjusting the Greater formulation freedom, although
formulation. the additive must have some degree of
solubility in the polymer.
155
Where the filler is pre-coated, various methods may be used, depending on the nature of
the filler, the coating, and the filler preparation procedure. When the filler is produced
from aqueous solution, such as by precipitation, it is often advantageous to add a water
dispersible or soluble, form of the coating, prior to filtration and drying. If the coating is
carefully chosen, it can actually aid filtration and reduce caking during drying. Fatty
acid treatments fulfil such a role on precipitated calcium carbonates. In most cases however,
the cost of solvent removal makes solution coating uneconomic, and dry coating is
favoured wherever possible.
Dry coating is often achieved during a milling process, or by use of a suitable mixer. In
the dry milling procedures, the conditions must be carefully chosen to ensure complete
coverage and surface reaction. The best form of mixer will depend on the filler. In most
instances, a high shear mixer is used to ensure rapid de-agglomeration and coating. Such
mixers usually generate a significant amount of heat, which can be useful, especially
where the additive has to be melted, or a reaction product like water or alcohol has to be
removed. With shear sensitive fillers, such as acicular grades of wollastonite, low shear
mixers are necessary to avoid excessive degradation of the filler. In such cases, coating
times are longer and external heating may be needed with some types of additive.
Coating methods are returned to in the sections dealing with specific additive types.
4.5 Choice of Coating Level
After deciding on the types of modifier to use, one has to decide on the amount that is
needed. Many modifiers are relatively expensive, so it is important not to waste any.
Moreover, excess amounts can sometimes lead to deleterious effects.
The optimum level will depend on the effects that are being sought, as well as factors
such as: how the modifier reacts with the surface, how well it covers that surface, what
the thickness and structure of the coating layer are, and how it interacts with the matrix.
Some useful guidelines exist to enable an approximate level to be decided on, but final
optimisation usually requires trial and error.
The most important theoretical concept is probably that of the mono-layer. By this is
meant the amount of additive required to just produce a surface layer, one coating molecule
in thickness. This appears to be a straightforward concept, but there are quite a few
complications in practice. Theoretical mono-layer amounts can be calculated using factors
such as the density of reactive sites and the area occupied by a molecule of coating. The
smoothness and accessibility of the surface also has to be taken into account. Some of
the main issues that can arise are summarised in Figure 4.1.
156
Figure 4.1 Different idealised structures for surface mono-layers on a filler surface
Figure 4.1c shows the ideal situation: where the surface is smooth and its reactive sites
are spaced at just the right distance for a tightly packed surface layer to be formed.
While this situation may be thought unlikely, it seems that stearic acid coatings on calcium
carbonate come very close to it, which may explain their great success with this filler.
Figure 4.1a shows a situation where the surface sites are widely spaced. Only part of the
surface layer can now be strongly bound and the layer is unable to pack so tightly. Small
molecules such as water could easily penetrate to the surface. Figure 4.1b shows the
reverse case: the reactive sites are too closely spaced for complete reaction. Again, small
molecules could reach the surface and possibly destabilise the bonding.
A further area of confusion is in assessing molecular orientation at the surface. Most

molecules have a number of possible orientations, which makes calculation of geometric
coverage difficult. This is especially true of some organo-silane coupling agents, where
the functionality intended to react with the matrix may in some circumstances be strongly
adsorbed onto the filler surface, resulting in flat, or bridged, rather than vertical orientation
(see Section 4.7). Even long chain carboxylic acids may adsorb flat rather than vertically
at low coverages. This situation is illustrated in Figure 4.1d. Loopy adsorption such as is
illustrated in Figure 4.1e is possible when multifunctional adsorbates are used.
157
A further factor not usually taken into account is the surface topography. Thus, while
good packing of adsorbed species may well be achieved on a molecularly flat surface
such as glass or mica, most particulate mineral fillers will have a rough surface which
may prevent such densely packed layers forming. Ishida and Koenig have reported on
the effects of surface topography on the structure of some silane coupling agents [1].
Finally, it must be realised that adsorption onto a surface may not be uniform. There
may be patches, several molecules thick, in some places and bare surface in others.
While the issues discussed previously may seem academic, they are of great practical
importance. This is particularly so with regard to the durability of coating effects under
humid conditions, where the ability of the surface to adsorb water, which may hydrolyse
surface bonds, is a key issue.
In general, properties start to change well before complete surface coverage is reached
and in some applications, full coverage may not be essential. In many cases, the maximum
effect is often found at about the mono-layer level, but multi-layers are found to be
beneficial in some instances, particularly where they are able to interpenetrate with the
matrix polymer.
A good example of the effect of additive level on a wide number of properties of a magnesium
hydroxide filled ethylene vinyl acetate (EVA) co-polymer can be found in work by Rothon
and co-workers [2]. This includes effects on flame retardant properties and on ageing. The
latter is particularly interesting, as it was found that excess of the fatty acid led to a significant
decrease in ageing resistance. This was most marked when a commercial blend of fatty
acid was used, but was still very significant with pure stearic acid.
4.6 Techniques for Determining the Amount of Coating Present, and

Assessing the Amount Needed for Mono-layer Coverage
The main techniques for characterising the structure of filler surfaces have been covered
in detail in the previous chapter. This section deals with methods for determining the
amount present on a filler surface and for obtaining an indication of the amount of
additive needed for mono-layer coverage.
4.6.1 Determination of Amount of Additive and its Distribution
A number of analytical methods are possible, depending on the chemical nature of the
filler and additive, and the techniques available. Some of the main ones are described
158
next. One of the problems with many techniques is in differentiating between additive
that is actually on the filler surface, and that which is merely present as a physical mixture
with the filler.
4.6.1.1 Chemical Analysis Methods
These can be used where the additive has an element that is clearly different from the
filler, and where the amount of additive is sufficient for the sensitivity of the technique
being employed. Thus, carbon analysis can be used for many additives on silica surfaces,
and titanium analysis is possible for organo-titanates on many fillers. This approach
does not distinguish between surface and admixed additive though.
4.6.1.2 Pyrolysis
This can also be used with success in many cases providing any weight loss from the filler
itself is corrected for. Again, it does not distinguish between surface and admixed amounts.
4.6.1.3 Infra-red Methods
These are particularly useful where, as often happens, the additive has at least one
characteristic spectral band that is clearly different from the filler. The hydrocarbon
bands present in many additives usually provide a good marker. Pre-calibration is
necessary, using fillers with known amounts of additive, and it helps if it is possible to
use a strong filler peak as an internal standard. Transmission methods will detect both
surface and admixed additive, while reflectance methods such as diffuse reflectance
Fourier transform infra-red spectroscopy (DRIFTS) [3] are surface sensitive, and thus
provide a method for assessing how much additive is actually on the filler surface. As
described in the previous chapter, these techniques can also often give information
concerning the way in which the additive has reacted with the filler surface. High
quality equipment is relatively inexpensive and infra-red methods are well worth
considering for quality control.
4.6.1.4 Adsorption Methods
Various adsorption methods, including dye adsorption (see Section 4.6.2.3), can be used
to determine the amount of uncoated surface remaining. This provides an indirect estimate
of the amount of coated surface present.
159
4.6.2 The Monolayer and its Determination
A number of relatively simple methods are used to find out what the apparent mono-
layer level is. The most common ones are described in the rest of this section.
4.6.2.1 Theoretical Calculation
The amount of additive needed to cover unit area of surface has been determined
experimentally, or calculated from molecular models, for many common additives.
This enables the theoretical mono-layer amount to be calculated, if the specific surface
area of the filler is known. As described previously, factors such as surface irregularity
and additive orientation have to be taken into account. The reported coverage for a
number of common surface modifiers is given in Table 4.2. As demonstrated by the
data for the two vinyl silanes, the nature of the alcohol has a major effect on the
covering power of these additives.
Table 4.2 Approximate surface coverage of some modifiers

Coverage (m2 of available surface, per
Modifier gram of additive)
-Aminopropyltriethoxysilane 360
-Mercaptopropyl trimethoxysilane 350
Vinyltrimethoxysilane 525
Vinyltrimethoxyethoxy silane 280
-Methacryloxypropyltrimethoxysilane 315
Lauric acid (C12) 690 vertical
Stearic acid (C18) 420 vertical, 1,800 horizontal
Oleic acid (unsaturated C18) 940 vertical, 1,800 horizontal
4.6.2.2 Viscosity Reduction or Settling Volume of a Suspension of the Filler in

a Simple Organic Liquid
It is frequently observed that a minimum viscosity or settling volume is reached at about

the mono-layer level.
160
4.6.2.3 Dye Adsorption
This is an old fashioned technique, cheap and easy to perform, and not given the attention
it warrants in determining levels of geometric coverage. The principle is simple, and
adapted from that used to determine surface area [4, 5]. A dye is used which strongly
adsorbs on the uncoated filler surface, but not onto coated areas, and the level of
adsorption relative to uncoated filler is then used to assess the amount of untreated
surface.
An example of the use of this method follows, and also shows the potential for combining
ultrasonics with adsorption techniques in studies related to the use of coated fillers in
composites. Dye adsorption curves for congo red (CI: 22120) on various precipitated
calcium carbonates are presented in Figure 4.2.
The carboxylated polybutadiene coated sample is seen to give a much lower dye adsorption
than the uncoated filler, as would be expected. When subjected to an ultrasonic probe
treatment, slurries of both the coated and uncoated fillers show a marked rise in dye
adsorption. This is assumed to be due to break up of filler aggregates exposing fresh
uncoated surface. Similar results were obtained with a stearate coated filler. Such
generation of uncoated surface might also be expected when fillers of this type are subjected
to high shear mixing processes.
Figure 4.2 Use of the dye adsorption technique to follow the effect of ultrasonic
treatment on the amount of bare surface in both uncoated and coated precipitated
calcium carbonates (congo red dye adsorbed from aqueous solution)
161
4.6.2.4 Adsorption Isotherms
Simple adsorption isotherm studies are widely used to assess the amount of coating that
is needed to fully treat a filler surface. The isotherms may be determined by a number of
techniques; for example following either the reduction in solution concentration
(gravimetrically, spectroscopically, titrimetrically, etc.), or the build up on the filler after
isolation and washing. Reversibility of adsorption may also be studied.
The main use of the technique has been to assess the amount of coating needed for full
coverage without necessarily understanding how the coating is adsorbed, whether it
reacts with the surface, and what full coverage means. In some instances, the shape of
the adsorption isotherm and reversibility studies can provide information concerning
the degree of surface reaction as opposed to physical adsorption. Combination of
adsorption studies with calorimetry can be more informative, as in the flow micro-
calorimeter methods discussed in the previous chapter.
Typical isotherms for the adsorption of a carboxylated polybutadiene onto an aluminium

and a magnesium hydroxide filler of similar surface areas are presented in Figure 4.3.
The isotherms were determined by using infra-red to follow the decrease in solution
Figure 4.3 Adsorption isotherms for a carboxylated unsaturated polymer on to

aluminium and magnesium hydroxides. Determined by the change in toluene solution
concentration method and normalised to the specific surface area of the aluminium
hydroxide (7 m2g-1)
162
concentration of the additive in the presence of filler. The isotherm for magnesium
hydroxide is typical of very strong filler polymer interaction, with the filler initially
removing virtually all of the polymer from solution. With aluminium hydroxide, the
interaction appears less strong, but the equilibrium adsorption level is about twice that
for magnesium hydroxide. When adsorption levels were determined gravimetrically, by
recovering and washing the filler, then the value for the magnesium hydroxide was
unchanged but that for aluminium hydroxide was reduced to a similar level, confirming
that considerable reversible adsorption appeared to occur with this filler.
4.6.3 Effects of Processing on the Coating Structure
Before leaving this section it is essential to remind the reader that, while studies on
coated fillers give useful information, great caution must be taken when extrapolating to
real coating layers in composites. Marked changes in these layers may well occur due to
the processing conditions and the presence of polymer and other additives. Unfortunately
in situ characterisation of polymer/filler interfaces is still in its infancy. Some progress is
currently being made in instrumental techniques and considerable advances can be
expected in this area.
4.7 Surface Modifier Types
4.7.1 Monomeric Organic Acids and their Salts
Acidic groups provide a convenient method for anchoring organic species to basic and
amphoteric fillers, and have been widely studied for filler surface modification. Both
non-coupling and coupling structures can be envisaged, depending on the organic group
used. Saturated fatty acids are examples of non-coupling types, while unsaturated and
amino-acids can be thought of as possible coupling types.
Some comment on terminology is needed here, as it is particularly difficult and potentially

misleading in this area. The treating agent is usually the free acid, but its bonding to the
filler surface is thought to be through the formation of a partial salt, which is bound to the
filler. The literature often refers to coatings as, for example, stearic acid or stearate, when
it more properly means the product of the reaction of the acid with the filler surface. It
would, on the other hand, be inappropriate, to simply refer to salt coatings, as this implies
that the salt has been used to carry out the coating. This may be possible, but may also lead
to weakly bound material with no partial salt link to the filler surface. To further complicate
matters, the actual structure of the coating on the surface has frequently not been elucidated
and could be a mixture of free acid, part salt and free salt. In the following discussions,
163
acid refers to the species used to produce the filler treatment, with the coating being the
product of the reaction of this with the surface, whatever form this may take.
4.7.1.1 Saturated Fatty Acids
Saturated fatty acids are the classic non-coupling additive, and are the workhorse surface
treatment used on calcium carbonate and other basic fillers, with which the acid group can
give strong surface interaction. This type of coating is easily applied, inexpensive and can
give a range of useful effects, including easier processing and reduced water adsorption.
Under favourable circumstances, dispersion can also be improved, but under other
conditions, this may actually be made worse due to the decreased shear during compounding.
The fatty acids most used consist mainly of straight, saturated, hydrocarbon chains 16-
18 carbon atoms long, and with even numbers of carbon atoms. (For reasons associated
with their natural product origin, fatty acids with odd numbers of carbon atoms are
rare, and there has been little or no study of their effects). The chain lengths used are too
short to entangle with a polymer matrix. They also have no means of chemically reacting,
and so coatings are generally weakly interacting, and produce low bond strengths between
filler and matrix. This results in filler de-bonding at relatively low stress levels. The
consequences of this are usually marked stress whitening and a decrease in ultimate
strength, although there can sometimes be significant improvements in properties such
as elongation and toughness. Indeed fatty acid coated calcium carbonate is widely used
in polypropylene because of the excellent impact strength obtainable.
While there has doubtless been a great deal of industrial study of the effect of hydrocarbon
chain length and structure, there is very little useful work reported in the scientific
literature. The work of Ivanishchenko and Gladkikh, referred to again later, indicated
that maximum hydrophobicity is obtained at about 14 carbon atoms [6]. Similar results
were obtained by Cave and Kinloch for straight chain hydrocarbon derivatives of alkoxy-
silanes [7]. There is good evidence that, at least on smooth surfaces, chain lengths of
about 14 carbon atoms are needed if a tightly packed, crystalline, layer is to be obtained
and this is probably important for hydrophobic effects. Liauw and co-workers have
reported evidence for crystalline order in stearic acid coatings on magnesium hydroxide
[8]. Haworth and Raymond [9] reported no differences in the processing behaviour and
property improvements obtained in polypropylene homo-polymer filled with calcium
carbonate, whether they used C10 or C22 fatty acid treatment at the mono-layer level. On
the other hand, Haworth and Birchenough [10] reported significant differences related
to chain length in the same range, when working with magnesium hydroxide in
polypropylene. Strength and stiffness were found to increase, but toughness to decrease,
with increasing chain length. The work of Tabtaing and Venables [11] discussed in the
164
section on unsaturated acids, indicates that a chain length of C10 is sufficient to lead to
significant improvements in ductility of a calcium carbonate/polypropylene composite,
as determined by elongation and impact properties. They found no marked additional
effect up to chain lengths of C20.
Fatty acids are most economically derived from natural sources, where they occur as
complex mixtures in both animal and vegetable matter. In practice, economics rules, and
fatty acids with about 18 carbons are used, as they are the most readily available and of
lowest cost. Some of the shorter chain acids also have extremely unpleasant odours,
which is not desirable. Fortunately, it does seem that the C18 chain length is somewhere
near the optimum in terms of building a stable, hydrophobic layer. Economics also dictates
that blends of acids are normally used industrially, as separating out pure components
can be quite costly. These blends can be very complex, containing a number of different
chain lengths, and even small amounts of unsaturated chains and non-acid material. The
composition of the fatty acids used in pre-coating fillers is rarely specified and can vary
markedly, making accurate scientific comparisons very difficult.
Fatty acids are usually pre-coated onto fillers and two methods of coating are generally
used: wet coating and dry blending.
In the wet coating process, a hot concentrated aqueous solution of a salt of the fatty acid
is added to an aqueous slurry (usually also hot) of the filler. Under these conditions,
rapid reaction with the surface of fillers such as calcium carbonate occurs. (Note, there is
some evidence that precipitation may occur first). As mentioned earlier, this procedure
can aid product isolation and handling. While sodium salts are often used for convenience,
this can lead to undesirable levels of sodium in the final product, unless extensive washing
is carried out. Ammonium salts are used to overcome this problem.
In the dry coating procedure, filler and fatty acid are usually reacted together in a high
shear mixer. The conditions have to be carefully selected and controlled if complete
surface coverage and reaction is to be achieved. Most fatty acids are solids, and unless a
solvent is used, they have to be melted before coating can take place. In some cases the
mixer generates enough heat, but it is often necessary to supply external heating.
It is also possible to coat from organic solutions of the fatty acid but, although sometimes
used in laboratory work, this is usually too expensive for commercial use. It can also
give false results, especially where the salt of the acid is soluble in the organic solvent.
The chemistry of fatty acids is far more complex than might be imagined from this
brief description, with features such as micellisation in aqueous solution and
dimerisation in organic solvent being important factors likely to affect coating behaviour.
Unfortunately these aspects have largely been overlooked in this context. For a
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comprehensive treatment of the properties of fatty acids, the reader is referred to

textbooks such as that edited by Markley [12]. It should also be noted that, while the
hydrocarbon chain has been thought of as inert, it is now beginning to be realised that
this can have a significant hydro-peroxide content, depending on the exact nature of
the blend and the way in which it has been handled [13]. This could have significant
consequences in some polymer applications.
Careful thought has to be given to the way in which the fatty acid reacts, if strong
attachment to the filler surface is to be obtained. Thus, it is necessary to only achieve the
formation of a partial salt with the metal cation of the filler. If a full salt is produced,
then the metal atom will no longer be a part of the filler structure, and may be readily
removed from the surface. While it has received little recognition until recently, this
aspect is most important with fillers such as calcium carbonate and magnesium hydroxides
and may explain a lack of consistency in fatty acid treatment on these fillers.
4.7.2 Stearic Acid (CH3(CH2)16COOH
As mentioned earlier, this is the most widely used fatty acid for filler treatment. However,
the reader must bear in mind that most commercial grades of stearic acid, as used in
pre-coating fillers, are actually complex blends containing both saturated and
unsaturated acids, with the stearic content often under 60%. Pure stearic acid is at
least twice the price of common blends, with other acids generally being more expensive
still. The compositions of some typical fatty acid blends used for filler treatment are
given in Table 4.3. The iodine value is a guide to the total amount of unsaturation
Table 4.3 Composition of some fatty acid grades used for filler surface treatment
% w/w in
Component
A B C
C12/14 saturated 2 2 3
C14 monounsaturated - - -
C16 saturated 48 48 45
C16 monounsaturated - - -
C18 saturated 34 48 52
C18 unsaturated 13 2 -
C20/22 saturated 3 - -
Iodine Value g/100 g 13 4 0.5
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present. The minor components can have an importance influence in some applications
and hence the blend has to be carefully chosen. Some of the unwanted effects of minor
components include poor colour, odour and reduced composite stability. This section
will deal with studies where pure stearic acid has been used.
The adsorption and conformation of stearic acid at surfaces has been widely studied,
especially using the Langmuir Trough procedure [14]. This has clearly shown that stearic
acid adsorbs onto polar surfaces through the carboxylate group and with the hydrocarbon
chain perpendicular to the surface. Under these conditions, the surface area occupied per
molecule is approximately 0.21 nm2 [15] and this is often used for calculating theoretical
surface coverages.
4.7.2.1 Stearic Acid and Calcium Carbonate
As mentioned earlier, stearic acid is most widely used on calcium carbonate fillers. This
section therefore concentrates on the interaction between these two materials.
The adsorption isotherm of organic solutions of stearic acid onto the calcite form of
calcium carbonate has been determined by workers such as Suess [16]. This work has
shown that mono-layer coverage is obtained when the area occupied per molecule is
around 0.21 nm2, which implies that orientation is in this case again perpendicular to
the surface. It has also been calculated by Suess that this coverage level corresponds well
with the density of calcium atoms in the surface of the inorganic substrate. Thus it is
seen that fatty acids, like stearic acid, provide a very good match for the surface of
calcite, thereby probably explaining the widespread use of such treatments with calcium
carbonate fillers.
Ivanishchenko and Gladkikh have studied the adsorption of stearic and other fatty acids
onto chalk, using isopropyl alcohol solutions [6]. This work demonstrated that multi-
layer adsorption is possible. On measuring the water adsorption and ohmic resistance of
the coated chalk they found this to vary in a cyclic manner with the level of coating as
shown in Figure 4.4. This behaviour was interpreted in terms of the layers orienting
oppositely, thus alternately exposing hydrocarbon and carboxylated surfaces. As we shall
see later (see Section 4.7.3), by comparing the behaviour of acids of different chain
lengths they were also able to draw other interesting conclusions. This work has not
perhaps received the attention it deserves.
Papirer and co-workers used tritium labelled stearic acid to study adsorption, from a
solvent onto a high surface area precipitated calcium carbonate [17]. They found that
adsorption (presumably at room temperature) was very slow with up to 24 hours being
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Figure 4.4 Effect of lauric acid coating (from iso-propyl alcohol) on the water
adsorption and resistivity of a chalk powder.
(G.P. Ivanishchenko and Y.P. Gladkikh. Reproduced with permission from Colloid
Journal USSR, 1979, 41, 3, 661. Copyright 1979, Kluwer/Plenum.)
required to reach equilibrium. (This could be due to the stearic acid being present as a
dimer in the solvent). They found that a monolayer coverage was obtained at 8% w/w
for the 32 m2g-1 surface area filler, a value which again is in excellent agreement with the
0.21 nm2 value for perpendicularly oriented molecules.
The previous adsorption studies have been carried out at room temperature, where the
adsorption may be physical, rather than due to salt formation. This must be borne in
mind when relating this work to commercial coating processes, where conditions probably
ensure chemical reaction with the surface.
There has been very little work on adsorption of stearic acid from aqueous solution,
probably due to the low solubility of the acid. Suess has however made some measurements
using carbon-14 labelled acid [16]. As with adsorption from organic solvent, a Langmuir
type isotherm showing mono-layer adsorption was observed, however this was at a much
lower level than for solvent adsorption. The reasons for this are not clear but were
postulated to be due to adsorption as a hydrated complex salt. Presumably, this is converted
to the stable coating layer during drying.
Commercially, aqueous coating is carried out using hot dispersions of fatty acid salts.
Very little information has been published about these processes where precipitation,
rather than surface adsorption and reaction, is probably the controlling mechanism.
168
Dry coating techniques have also received little scientific study. There has however been
some good work by Fekete and co-workers [18]. They showed that in high shear coating,
the adsorption is very dependent on the type of mixer and the exact conditions used.
Under optimised conditions, they found they were able to define an addition level up to
which complete reaction with the filler was obtained (as shown by no solvent extractable
material). Above this level, some further reacted material was generated, but accompanied
by residual extractable acid and finally a plateau was reached above which all further
stearic acid was extractable. They define a value C100 where extractable material is first
observed. This value was found, as expected, to be proportional to surface area for a
range of calcium carbonates. More interestingly, calculations based on their data show
an area per molecule at the C100 point of about 0.21 nm2. This again suggests vertical
alignment and provides some evidence for the dry-coating process giving layers of a
similar nature to solvent coating. It does not, however, explain how further reaction
seems possible in the dry coating process.
There has been a great deal of work on the characterisation of stearic acid coated calcium
carbonate using a variety of techniques. The work of Ivanishchenko using electrical
conductivity and water adsorption has been referred to earlier [6]. Fekete and co-workers
[18] examined fractional coating levels up to their C100 value on a high shear coated
calcium carbonate. Using inverse gas chromatography (IGC) they found both the dispersive
and polar components of the surface energy to fall with stearic acid addition. Surprisingly,
perhaps, the majority of the effect on both components was observed when only a quarter
of the C100 monolayer value was obtained. This may be interpreted to mean that while
perpendicular orientation is observed at a true mono-layer, the stearic acid lays flat at
lower coverages. It could also be interpreted as resulting from a non-uniform distribution
of energetic sites.
Papirer and co-workers have also used IGC to study stearic acid coated calcium carbonates
[17]. In their work, a high surface area precipitated filler was used, and coating was
from toluene solution. They also prepared fractional coating levels based on solution
adsorption isotherms. Stearic acid treatment was again found to decrease both the
dispersive and polar contributions of surface energy to values typical of a hydrocarbon.
Both acidic and basic probes were used in this work and interestingly, the uncoated filler
was found to contain sites capable of interaction with both.
In further work, Schmitt and co-workers studied the adsorption of hydrocarbons with
varying chain length on the stearate coated filler [19]. Short probes (< 8 carbon atoms)
appeared to completely insert into the coating layer, but only partial insertion occurred
with higher chain lengths. Ahsan and co-workers have used gas chromatography to study
the effect of coating an especially pure precipitated calcium carbonate with stearic acid
[20]. The stearic acid was deposited from aqueous solution of the ammonium salt and at
significantly less than a mono-layer coverage. They found the calcium carbonate to have
169
a heterogeneous surface, with exposed polar cationic sites capable of strong interaction
with unsaturated hydrocarbons. The stearic acid coating appeared to preferentially block
these sites producing a lower energy surface.
4.7.2.2 Stearic Acid and other Fillers
Among the other fillers where stearic acid could be used are aluminium and magnesium
hydroxide, basic magnesium carbonates, dolomite (CaCO3.MgCO3) and magnesite
(MgCO3).
There is little published information concerning the adsorption of stearic acid on the
carbonates, although in several cases commercial products exist. Suess studied the
adsorption of stearic acid onto dolomite from organic and aqueous solutions at room
temperature [16]. In both cases, monolayer coverage was observed at almost exactly half
the quantity of stearic acid required by calcite. It was concluded that the magnesium
sites were inactive for adsorption under the conditions of the experiment. They may
however react at higher temperatures.
Rothon and co-workers have reported on the coating of a magnesium hydroxide filler
with stearic acid deposited from aqueous solution of the ammonium salt. Mono-layer
coverage was determined by a number of techniques and found to correlate well with the
amount to be expected for a vertically adsorbed, close packed mono-layer [2].
Liauw and co-workers have studied the adsorption of stearic acid onto magnesium
hydroxide, using a variety of techniques, including DRIFTS and flow micro-calorimetry
[8, 21]. The mono-layer level was again found to correspond well with a close packed
vertical mono-layer. Evidence for order in the adsorbed layer was obtained by a number
of techniques, including X-ray and differential scanning calorimetry.
4.7.3 Other Saturated Fatty Acids and Related Substances
There has inevitably been a great deal of industrial interest in examining the effect of
fatty acids other than stearic acid. However little of this work has been published. Pure
fatty acids are all considerably more expensive than the blends generally described as
stearic acid and dramatic effects would be needed to make their use worthwhile. This
probably explains why there are very few commercial examples of other acids being
used. Iso-stearic acid is sometimes used, probably because it is a liquid and easier to use
in dry coating processes. The branched structure may also improve the dispersion effects
obtainable, but would be expected to reduce the mono-layer amount and prevent a tightly
170
packed surface layer being formed. Liauw and co-workers have reported that the mono-
layer coverage on magnesium hydroxide is less than for stearic acid and that no ordered
structure is formed [8].
The study of the adsorption of stearic acid onto calcium carbonate from alcohol solution
by Ivanishchenko and Gladkikh [6] has already been mentioned. They also determined
adsorption isotherms and the variation of ohmic resistance and water adsorption with
coating level for shorter chain acids. Acids with ten and twelve carbon atoms appeared
to form mono-layers on chalk with 1.5 x 10-5 moles g-1 of filler while longer chain acids
only required 0.9 x 10-5 moles g-1 (unfortunately the surface area of the filler was not
specified). With the shortest chain acid (C10), about three molecular layers were required
to maximise hydrophobicity, but when more than 14 carbon atoms were present then
only one mono-layer was needed. Their results also indicated that, for the shorter acids
at least, the first molecular layer was packed differently from subsequent layers.
4.7.4 Effects of Stearic Acid Coating in Composites
As already alluded to, stearic acid is often added to aid filler handling during production.
It is especially useful with very fine precipitated materials, such as calcium carbonate,
where it reduces shrinkage on drying and thus improves dispersability. It also makes
the filler hydrophobic, and reduces water adsorption, but can make some fillers
considerably dustier.
Most interest revolves around the effects that the stearic acid generates when the coated
fillers are used in composites. Much is written in general terms claiming improved
incorporation, better dispersion and improved physical properties. There have however
been few comprehensive studies and several conflicting reports in the literature, which
suggests that the effects may be system specific, even possibly depending on filler particle
size and loading. As more comprehensive details will be found in later chapters, only a
brief account will be given here.
In thermoplastics it is generally held that fatty acid treatments reduce melt viscosity, improve
filler dispersion, decrease modulus, reduce tensile strength but improve elongation and
impact resistance. While generally true, there are a significant number of exceptions reported.
Fulmer and co-workers [22] have shown clear evidence of faster incorporation and lower
melt viscosity in calcium carbonate filled polypropylene homo-polymer. However, despite
the widespread use of fatty acids for improving processability, melt viscosity reductions
are not always obtained. Bohlin and co-workers have published an interesting paper on
the effect of stearic acid treatment of a dolomite filler in polypropylene [23]. They found
171
no effect on viscosity as measured by a capillary rheometer over a wide range of shear

rates. A small strain rheological technique showed much lower storage modulus for the
coated filler however, which was mainly attributed to improved dispersion. In a fairly
comprehensive study of the effect of stearic acid treatment of calcium carbonate in
polypropylene, Hancock and co-workers confirmed most of the mechanical property
effects mentioned previously, but again observed no improvement in melt viscosity [24].
On the other hand Miyata and co-workers found a marked reduction in melt viscosity
when stearic acid was used on a magnesium hydroxide filler in polypropylene [25]. Rothon
and co-workers found only small improvements in melt flow index of EVA filled with
magnesium hydroxide treated with varying amounts of stearic acid [2].
As mentioned earlier, Rothon and co-workers have also reported on the effect of stearic
acid on many properties of the magnesium hydroxide filled EVA [2]. They confirmed the
general picture of decreasing tensile strength, and increasing elongation. They also found
a small benefit in flame retardant performance. Levels of stearic acid above a mono-
layer were found to be quite detrimental to ageing. The ageing effect was significant with
a pure stearic acid, but even more so with a commercial blend, even though it was a high
quality type, often used for treating fillers. Fulmer and co-workers have also reported
ageing effects in a calcium carbonate filled polypropylene [22]. Pukansky and co-workers
have also carried out a comprehensive study of stearic acid treatment of calcium carbonate
in polypropylene. The coating was found to decrease tensile strength and modulus and
to increase elongation at break [26].
In the authors experience, correctly chosen fatty acid treatments can improve the colour
of some filled polymers. Fulmer and co-workers have also reported this effect [22].
The role of treatments such as fatty acids in altering thermoplastic composite properties
may be quite complex. Thus Hutley and Darlington found that high loadings of most
fillers could affect the crystallisation behaviour of polypropylene, leading to reduced
impact strength [27]. Treatments such as stearic acid could to some extent overcome this
(this is also referred to in Chapter 8). Raymond and Gilbert also found that stearic acid
treatment of a platy magnesium hydroxide led to increased modulus in polypropylene,
which was found to be due to increased particle alignment [28]. Among other factors of
possible significance is the presence of variable amounts of hydroperoxide in many fatty
acids, as mentioned earlier.
In elastomers the effects of stearic acid coating of fillers appear much more dramatic in
solution polymerised polymers than in emulsion ones. As shown by Rothon, this is due
to the presence of large amounts of residual surfactants in the emulsion polymerised
polymer [29]. These probably adsorb on the filler surface, producing effects similar to
stearic acid. In the absence of these competing effects, stearic acid reduces viscosity but
also reduces the filler polymer interaction, resulting in decreased bound rubber and
172
reinforcement. Even in emulsion polymers stearic acid coating can be detrimental to

some properties however, especially tensile strength.
Fatty acid treatments do not seem to have much use in thermoset applications.
4.7.5 Fatty Acid Salts
It has to be admitted that the situation regarding fatty acid salts is not well established.
Indeed there is much ambiguity in the literature with the terms stearic acid and stearates
often being used interchangeably. As discussed earlier, some form of salt is the effective
coating material after a fatty acid has reacted with the surface of fillers, but a part salt
has to be involved if the acid is to be thought of as reacted onto the filler surface. A full
salt will only be weakly attached.
Full fatty acid salts themselves, are frequently used as polymer additives, usually as
processing aids and acid scavengers. Both Gilbert and co-workers [30] and Hornsby and
Watson [31] have indicated that such fatty acid salts can be used to beneficially pre-treat
fillers, with the effectiveness depending on the metal present in the salt and the filler.
Fatty acids and their salts when used as additives may adsorb onto the surface of untreated
fillers and this has to be taken into account when developing formulations [32]. Fulmer
and co-workers, also claim that using fatty acid salts as additives can be as effective as
pre-coating fillers [22]. More work is needed to clarify this area.
4.7.6 Unsaturated and other Functional Organic Acids in Composites
By analogy with the vinyl and methacryl silane discussed later, unsaturated organic acids
such as acrylic, fumaric, maleic, methacrylic and oleic might be expected to give a coupling
agent effect in appropriate systems. Amino-acids might also be considered as potentially
having similar effects to amino-silanes. Results have, however, been quite mixed, and
there isnt much commercial use of such additives.
There have been few academic studies of the adsorption of unsaturated acids onto fillers.
Ottewill and Tiffany studied the adsorption from heptane solution of acids with 18
carbon atoms and various levels of unsaturation, onto uncoated rutile titanium dioxide
[33]. As with calcium carbonate, stearic acid was found to give monolayer coverage at a
concentration suggesting vertical orientation. With all the unsaturated acids, stepped
isotherms were obtained, which were interpreted as multipoint attachment through both
acid and unsaturated groups at low concentrations, but with re-orientation to a
conventional vertical orientation at higher concentrations.
173
In the work mentioned previously, Liauw and co-workers also examined the adsorption of
acrylic, linoleic, linolenic and oleic, acids from organic solution onto a magnesium hydroxide
filler [8]. Salt formation was observed for all the acids. All the unsaturated long chain acids
gave lower apparent mono-layer levels than stearic acid, which was thought to be due to
steric effects and even multi-point adsorption through the unsaturation.
Miyata and co-workers have compared stearic and oleic acid derived coatings on
magnesium hydroxide fillers in polypropylene and found better impact strength for the
oleic acid treatment [25]. The reason for this is unclear and the results do not appear to
have been confirmed by others. Nevertheless, some commercial magnesium hydroxides
are coated with unsaturated acids similar to oleic, suggesting that there may be a real
benefit from its use in some circumstances.
In the past, there has been significant interest in acids with especially reactive unsaturation,
such as acrylic and maleic acid (or its anhydride) [34]. More recently, pre-grafting of
these species onto a polymer backbone has become the preferred method of use. This is
discussed in Section 4.7.7.
Another interesting material, which is used commercially to some extent is rosin. This
contains unsaturated structures and is claimed to give better performance than stearic
acid in some elastomers. This is demonstrated by the data for precipitated calcium
carbonate given in Table 4.4.
Table 4.4 A comparison of a rosin and a fatty acid coated precipitated calcium
carbonate in a sulfur cured styrene-butadiene rubber (SBR) elastomer
(100 phr filler)
Fatty acid treatment Rosin acid treatment
Elastomer property
(2.6% w/w) (2.6% w/w)
Tensile Strength, MNm-2 5.5 6.7
Elongation to break, % 560 600
-2
300% modulus, MNm 1.6 1.9
-1
Tear strength, Ncm 1.6 2.4
Hardness, IRHD 66 67
IRHD: International Rubber Hardness Degrees
Furukawa and Yamashita have reported on the effect of various functional organic acids
as coatings on precipitated calcium carbonate. Unfortunately the acids were added prior
174
to the precipitation, and most of the effects observed seem to be due to modification of
the crystallisation reaction rather than any effect on filler polymer interaction [35].
Related to the functional acids, dimaleimides have also been attracting attention, mainly
for use in filled polypropylene [36].
There is currently considerable interest in nano-clays as reinforcing fillers for polymers.

One of the most successful combinations is in polyamides, where amino-acid treatments
can be thought of as effective coupling agents. This is discussed in Chapter 10.
4.7.7 Polymeric Acids and Anhydrides
These are an interesting class of surface modifiers, now finding significant commercial
uses and capable of being used as dispersants and coupling agents with a wide range of
filler types. With these products, the unsaturated acid, or pre-cursor such as anhydride,
is pre-reacted onto a suitable polymer backbone. Two main classes of product are available,
one with a saturated hydrocarbon backbone, the other with an unsaturated one.
4.7.7.1 Acid Functional Saturated Polymers
These are based on polyolefin homo- and co-polymers. Acid functionality is usually
introduced by use of acrylic acid or maleic anhydride. Peroxide induced grafting is usually
used, but co-polymerisation can also be used. One of the problems with peroxide grafting
is that extensive chain scission and loss in molecular weight can occur with some polymers,
notably polypropylene. When acrylic acid grafting is used there can be significant homo-
polymerisation, leading to quite long chains between the acid group and the polymer
backbone. This doesnt occur with the maleic anhydride, which is highly resistant to
homo-polymerisation.
These additives are intended for use in filled polyolefins, where coupling to the polymer
matrix is thought to be due to processes such as chain entanglement and co-crystallisation
[37]. The acid levels are usually not high enough to provide solubility and enable fillers
to be pre-treated and they are usually used as formulation additives. In some instances,
emulsions can be prepared and these may be used for pre-treatment. Where the filler is
responsive to silanes, but not acid functionality, then coupling can be achieved by using
an amino-silane on the filler and this is now one of the main ways of coupling glass fibre
into polypropylene. There has been little scientific study of the effect of molecular weight
and acid content, but Pukansky has reported that a molecular weight of about 10,000
was necessary in a wood fibre/polypropylene system [38].
175
4.7.7.2 Acid Functional Unsaturated Polymers
The use of such materials was prompted by the need to find coupling agents for calcium
carbonate, as silanes were largely ineffective with this filler. Simple unsaturated acids
also appeared to have little effect, but Hutchinson and Birchall found unsaturated
polymeric acids to be excellent treatments for precipitated calcium carbonate [39]. The
concept was developed and extended by Evans and co-workers [40, 41].
The structure of a typical unsaturated polymeric acid anhydride surface modifier based
on maleanised polybutadiene (MPBD) is shown in Figure 4.5 together with its postulated
mode of action. The anhydride groups are believed to lead to reaction with the filler
surface, probably by salt formation, while the residual unsaturation is available for
participation in various curing or crosslinking processes.
Figure 4.5 Typical structural features of a maleanised polybutadiene surface modifier
Sufficiently high levels of acid can be introduced to allow water soluble products to be
produced, and so this type of additive can be used either pre-coated onto a filler, or
added separately during compounding. The relative merits of the two processes have
been discussed earlier.
The effectiveness of an MPBD type additive when pre-coated onto precipitated calcium
carbonate is demonstrated in Table 4.5. This compares uncoated, fatty acid coated, and
MPBD coated fillers in a crosslinked ethylene-propylene-diene terpolymer (EPDM)
elastomer and clearly shows the benefits arising from the use of the latter coating.
176
Table 4.5 A comparison of fatty acid and MPBD coating of precipitated calcium
carbonate on performance in a sulfur cured EPDM elastomer
(100 phr filler, both coatings at 2.6% w/w on filler)
Property Untreated filler Fatty acid coated MPBD coated
-2
Tensile strength, MNm 10.0 4.5 13.3
-2
300% modulus, MN m 2.3 1.4 3.7
-1
Tear strength, Ncm 1.6 1.0 2.4
While originally developed for calcium carbonate, these additives have since been found
to be effective on a wide range of fillers including aluminium and magnesium hydroxides,
clays and talcs.
Rothon has reported work by Carey, which investigated the effect of molecular weight and
anhydride content of MPBD additives on the properties of a precipitated calcium carbonate
filled emulsion SBR elastomer [42]. This work showed that properties in this system generally
improved with increasing anhydride content and molecular weight, but began to plateau
at a molecular weight of about 10,000 and 20-25% by weight of anhydride.
Unpublished work by the present author has since found that the molecular weight effect
is not as marked in solution polymerised elastomers. It is postulated that the difference is
due to the need for the MPBD to compete for the filler surface with residual surfactants
in the emulsion polymerised polymer.
Ashton and co-workers have studied MPBD adsorption onto magnesium hydroxide using
Fourier Transform Infrared (FTIR) spectroscopy, flow microcalorimetry and classical
adsorption techniques [43]. They confirmed the formation of a carboxylate salt at the
filler surface and found the chemisorbed layer to be only about 15 thick. This implies
loopy adsorption and multiple point attachment.
The MPBD type additives have also been shown to be effective dispersants and coupling
agents for fillers in peroxide cured methacrylate resins [44].
4.7.8 Organo-silicon Compounds
4.7.8.1 General
Organosilicon compounds are in widespread use for modifying the surface of mineral
fillers. The compounds used have the general formula:
177
(R)4-n Si Xn where n = 1 to 3
The group X is an hydrolysable group chosen to react with surface hydroxyls of the filler
to produce a stable bond, and is usually halogen or alkoxy. The group R is attached
through a hydrolytically stable carbon silicon bond and may be inert or contain a reactive
organic functionality such as vinyl, amino, etc. In the latter case strong bonds can be
produced with the polymer matrix as well as with the filler surface and these materials
are known as silane coupling agents or often simply as silanes. The silane coupling agents
in commercial use are generally alkoxy based and only contain one organic group (OR)
attached to silicon, the general formula being:
R Si (OR)3
Both non-reactive and reactive organo-silanes are important filler treatments and will be
discussed here.
4.7.8.2 Filler Types Susceptible to Silane Treatment
As mentioned in the previous section, organo-silanes rely on reaction with surface

hydroxyls to produce a stable layer. They are thus most effective on fillers with high
concentrations of reactive hydroxyls. Materials such as silica, silicates (including glass),
oxides and hydroxides are most receptive. Even with these surfaces, problems can arise
if the surface has a high pH, as under exposure to moisture the attachment of the silane
to the surface may slowly degrade.
Silanes have little effect on carbon blacks. They are also not generally effective on surfaces
such as sulfates and carbonates, although attempts have been made to improve silane
effectiveness on such surfaces by pre-coating them with silica [45] or by phosphate layers
[46]. It has been reported that some organo-silanes, notably, amino-silanes, can produce
an effect on calcium carbonate by some form of encapsulation [47].
4.7.8.3 Coating Techniques
Organosilanes are complex species, which often have the potential of reacting with
themselves in the presence of moisture as well as with filler surfaces. The nature of the
surface layer and its reaction with the filler will thus vary markedly according to the
method of coating. Some early discussion of the coating techniques in use is thus necessary
as there is a great deal of confusion in this area.
178
The non-coupling silanes in use are generally quite volatile, and filler coating is often
carried out in the gas phase by exposing the filler to their vapours. This ensures maximum
reaction with the surface and minimum self-condensation. The silane coupling agents,
on the other hand, are less volatile and are usually coated in liquid form, either as neat
additives, or from a suitable solvent.
Silane coupling agents have been most used for coating glass fibres. In this application
pre-hydrolysis and partial self-condensation have been found to aid the coating process
and this is the usual procedure used.
Similar solution coating procedures have been widely used in much of the scientific work
on silane treatment of particulate fillers. Unfortunately such procedures do not lend
themselves readily to most commercial filler production processes, where some form of
direct reaction between the silane and filler powder is frequently used. In many instances
the filler coating is actually carried out in situ during the compounding process, essentially
utilising the polymer matrix as the solvent. These distinctions must be borne in mind
when trying to relate laboratory studies to results achieved with commercial products.
4.7.8.4 Reaction of Organo-silanes with Filler Surfaces
Two distinct processes can be recognised for the reaction of the SiX group with surface
hydroxyls. Thus there can be direct reaction with the surface, producing a siloxane bond
and eliminating HX (Equation 4.1) or there can be prehydrolysis with surface moisture
followed by silanol condensation and release of water (Equations 4.2, 4.3).
SiX + HO-M SiOM + HX Equation (4.1)
or SiX + H2O SiOH + HX Equation (4.2)
SiOH + HOM SiOM + H2O Equation (4.3)
In addition, the organo-silanes can react with themselves to produce complex three-
dimensional networks. For this part of the discussion we will however concentrate on
the surface reactions.
The simplest case to consider is the reaction of molecules such as (CH3)3SiX with an
amorphous silica surface under dry conditions where direct reaction with the surface
is experienced.
179
The structure of such a silica surface has been extensively studied and the work has been
reviewed by Iler [48]. It is generally accepted that, in the absence of surface moisture, a
fully annealed surface has about 4.6 surface silanol groups (SiOH) per nm2. It might
then be thought that surface coverage would require an equivalent number of organo-
silane molecules. This proves not to be the case, however, as not all the silanols are
reactive, the bulk of the organo-silane is too great to allow such coverage and the hydrolysis
product of the group X can itself react with and block some of the surface.
Under anhydrous conditions, the surface silanols are of two types: isolated and freely
vibrating, and hydrogen bonded, with the former being about 30% of the total.
Workers such as Armistead and Hockey [49], Hertl [50], and Hair and Hertl [51] have
found, using spectroscopic methods, that reaction only seems to occur with the isolated
silanols even at high temperature and where a very reactive group X such as halogen is
used. Eakins has also reported that because of packing considerations only about 2.45
(CH3)3SiO groups per nm2 would be obtainable [52].
Information such as this is very important in understanding hydrophobic effects. Thus

Zettlemoyer and Hsing found that water was still able to penetrate through a fully
trimethylsilylated layer and form a hydrogen bonded monolayer with unreacted surface
silanols [53]. The trimethylsilylation was, however, effective in preventing subsequent
multi-layer development.
The situation becomes much more complex when one moves to compounds such as
(CH3)2SiX2 and CH3SiX3. They can now react with more than one surface site and with
each other. Various surface structures can then be produced. As an example the compound
(CH3)2SiX2 can lead to the surface structures shown in Figure 4.6.
Under essentially anhydrous conditions, the self-condensation will be very limited and
surface reactions will predominate. Such reactions have been studied by Hertl [50, 54]
who found that surface reaction is still predominately with the isolated silanols, although
some reaction with the hydrogen bonded ones can occur, especially where X is an halogen.
A particularly interesting part of Hertls work is concerned with the molecule

methyltrimethoxy silane CH3Si(OCH3)3, which can be taken as a model for the silane
coupling agents. Again it was found that reaction was only through the free surface
silanols and, from an analysis of the kinetic data and the amount of methanol released,
he deduced that about 40% of the silane molecules react mono-functionally with the
surface and 60% di-functionally. (On steric grounds it is very unlikely that tri-functional
reaction will occur). A considerable proportion of the methanol by-product was found
to form surface ester groups reducing silanol availability. He also showed that partial
dehydration of the silica surface by heating increased the number of available silanols
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Figure 4.6 Some structures possible after the reaction of dimethyldihalogenosilane

with a silica surface
and allowed more silane to react. This principle is reported as having been applied to
enhance silane coupling agent treatment of clays [55].
When moisture is present, then the picture becomes far more complex with hydrolysis
and condensation reactions between both silane and the surface and with itself the main
processes.
The most studied case is where a tri-alkoxy silane is deliberately pre-hydrolysed before
coating the filler, as is common practice in glass-fibre treatment. Plueddemann has given
a particularly good description of the processes involved [56] and only a brief outline
will be given here.
It is believed that best results are obtained if treatment is carried out with a dilute aqueous
solution in which the additive is predominately present in silanol form and the pH is
such as to minimise self condensation. With cationic silanes pH control is also necessary
to produce good surface alignment.
Coating solutions are prepared by dissolving the tri-alkoxysilane in an acidic water alcohol
mixture. The alcohol is used to enhance solubility of the starting material and the acidic
pH is used to produce rapid hydrolysis and relatively stable silanols.
Coating then relies on adsorption of the hydrolysed species onto the filler surface followed
by silanol condensation both with other silanols in the coating and with surface hydroxyls.
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The trick is to produce conditions at the surface that favour these reactions even though
the solution pH is chosen to minimise it. In the case of glass fibre and some fillers, the
surface may be sufficiently alkaline to accomplish this. In other cases a two-step process
has to be resorted to in which a filler slurry is first produced in the acidic solution which
is then made alkaline before the filler is filtered and dried. Thermal treatment is also
used to drive the condensation reaction.
As might be envisaged, coatings produced by these processes are extremely complex and
poorly characterised in terms of structure and surface bonding. (As one is working in an
aqueous environment the earlier discussions regarding preferential reaction with non-
hydrogen bonded silanols are now irrelevant). Current views regarding the structure of
these coatings will be discussed in Section 4.7.8.5.
Finally some mention must be made of organo-silane reaction when applied without
pre-hydrolysis from organic solvent. This could be thought of as a model for in situ
coating processes where the solvent is a polymer or polymer precursor. In this type of
process, hydrolysis is assumed to take place with surface moisture followed by
condensation reactions.
Bascom and Timmons have studied the hydrolysis of triethylethoxysilane with an

amorphous silica surface using carbon tetrachloride as the solvent [57]. They found that
no hydrolysis occurred in wet solvent or in the presence of dry filler, but proceeded
rapidly at room temperature when water was present on the filler surface. The reaction
rate increased abruptly at a water level corresponding to a 1:1 ratio of water to surface
silanols, implying that a certain specific arrangement of water molecules is necessary.
They believed this to be due to the establishment of a hydrogen bonded network allowing
the acidic surface silanol species to catalyse the hydrolysis reaction.
A surprising feature of their results was the discovery of a maximum hydrolysis rate at
about 25 C and a sharp decrease above this. This was put down to disruption of the
hydrogen bonded network at the higher temperatures.
Unfortunately, silanol condensation reactions were not studied in Bascom and Timmons
work. It is widely reported however that the reaction can be slow on many mineral surfaces
unless a catalyst or heat is used. Amines are effective catalysts and the amino-silanes are
self-catalytic in this respect. Alkoxy-titanium compounds are also useful condensation
catalysts and this may explain synergistic effects claimed for silane/titanate mixtures [58].
Overall, the in situ method remains very poorly characterised. Relying as it does on
diffusion through polymer to the filler surface, where conditions must be right for
hydrolysis and condensation. It sounds very haphazard, but seems to work remarkably
well in practice.
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While the surface of silica fillers is generally well understood and models for their reaction
with organosilanes can be developed as described previously, this is not true for most
other filler types. Thus while the general principles will still apply, great care must be
taken in attempting to extrapolate to the surface of fillers such as clays and hydroxides
which are less well characterised.
4.7.8.5 Structure of Coatings Produced with Reactive Organo-silanes
The ability of tri-alkoxy silanes to condense with themselves to produce various three-
dimensional networks makes the concept of monolayer coverage based on simple surface
reaction of restricted value when considering this type of molecule. This is especially true
of the silane coupling agents, where the picture is often further complicated by the tendency
of some of the functional groups present to also interact with the surface. As will be
discussed later, it has also been demonstrated that optimum results are sometimes obtained
with coating levels well in excess of a notional monolayer.
Elucidation of the exact nature of the surface layers, and their relationship to the coating
conditions has proved difficult. This has been made more so by marked differences in
behaviour imposed by the different functional groups present in the reactive silanes,
which have severely inhibited the development of a generalised picture.
More recently, the advent and application of modern analytical techniques [especially
FTIR, X-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS)]
have allowed considerable advances to be made, especially in relation to coatings produced
from aqueous solution. A brief outline of the current views follows. The reader is referred
to some excellent reviews by Ishida [59] and Plueddemann [60, 61] for more details.
Much of the work has been on silane treatments deposited from dilute aqueous solution
onto glass fibres. Here, the current view is that coupling agent layers need to be much
thicker than a nominal monolayer for optimum reinforcement to be obtained. It is also
believed that patchy adsorption often occurs, especially at low treatment levels. These
thick layers are very complex and depend sensitively on the nature of the coating
conditions, the surface being treated and the chemistry of the reactive functionalities
present. In general terms it is believed that coatings as normally produced (and before
use of the coated material in a composite) consist of a mixture of chemisorbed and
physisorbed material. The physisorbed material is readily removable by solvent washing
and consists of silane oligomers. The chemisorbed material can be further subdivided
into a surface monolayer, the structure of which depends critically on the surface of the
substrate and the nature of the organo-functional group, (i.e., its ability to interact with
the surface). Above this there is a layer of tightly bound material and further out more
loosely bound structures.
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The picture is less clear for particulate mineral fillers. The same general concepts appear
to apply, although there seems to be less benefit from using multi-layers.
Ishida and Miller have carried out a detailed study of the structure of coatings produced
from a water/butanol solution of [-(methacryloxy)propyl] trimethoxy silane ( -MPS)
on a variety of fillers [62]. This work confirmed the existence of physisorbed and
chemisorbed layers, the relative proportions of which depended on the acid-base balance
of the surface, as well as surface chemical nature and silane loading. Fillers with a near
neutral surface (assessed by slurry pH) gave the greatest proportion of chemisorbed silane.
The physisorbed silane was found to be composed of unhydrolysed and partly hydrolysed
monomers and polysiloxane oligomers and polymers. The molecular weight of this fraction
was again greatest on a neutral surface. Interestingly, similar products could be produced
in the absence of filler by adjusting the solution pH to that of the filler surface.
While the previous picture has largely been worked out for silane coatings produced
from aqueous solution, it seems that it probably applies, in very general terms at least, to
other coating methods. The relative proportion of physisorbed and chemisorbed material
and their detailed structure will however probably vary markedly. Among the important
factors will be the concentration of suitable surface hydroxyls, the surface pH and the
amount of water present.
In one of the few relevant studies, Nakatsuka and co-workers [46] examined calcium
carbonate and clay fillers coated with -MPS by dry blending (from water/alcohol solution,
however). They found that a considerable proportion of silane was actually lost from the
calcium carbonate system, due to evaporation during drying. Physisorbed material was
found on both fillers, but while that on calcium carbonate was of very low molecular
weight, that on clay was of much higher molecular weight.
They also found that pre-treating the calcium carbonate with phosphoric acid resulted in
the formation of higher molecular weight physisorbed material and enhanced the coupling
agent effect, as assessed in a vulcanised elastomer.
Ishida has reported that dry coating, as often used in particulate filler treatment, results
in an approximate monolayer of chemi-sorbed silane, giving imperfect coverage with the
rest of the silane being weakly physisorbed [59]. Unlike the situation with solution coating
of glass fibre, it is unusual to use more than a monolayer. Hence, the interphase concepts
are less important in this case.
It is now generally recognised that the exact nature of the chemisorbed and physisorbed
layers plays a significant part in the effectiveness of silane coated fillers in polymers. This
aspect is also very complex but beginning to be elucidated by the use of modern techniques.
The relevance of these structures to polymer properties will be dealt with later (Section 4.7.8.8).
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4.7.8.6 Applications of Non-Coupling Compounds
These additives are used for making filler surfaces hydrophobic and oleophilic. The trimethyl
compounds are most widely used for this purpose, with both the chloro- and methoxy-
derivatives being used. The most useful compound for introducing the trimethylsilyl group
is however, hexamethyldisilazane [HMDS; (CH3)3SiNHSi(CH3)3]. This reacts with surface
moisture to form only volatile by-products, and with surface silanols to release only
ammonia, so the reaction is particularly clean. More recently, long chain hydrocarbon tri-
alkoxy silanes, such as CH3(CH2)n,Si(OCH3)3 have been made available.
Fillers, especially high surface area silicas, are commercially available with such
hydrophobic surface coatings. They are expensive and seem to be mainly used in sealant
and adhesive applications rather than in polymer composites, where they produce low
particle matrix adhesion similar to fatty acid and other cheaper additives.
Typical effects obtained by use of these treatments on fillers in elastomer systems can be
found in the work of Dannenberg and Cotten [63]. They examined trimethylsilane
treatment of a fumed silica and found effects consistent with reduced filler rubber
interaction. Thus rebound resilience, modulus, tear strength and bound rubber were all
reduced. Surprisingly, the treatment gave a considerable improvement in abrasion
resistance, which it was believed resulted from the increased hysteresis.
4.7.8.7 Application of Reactive Compounds (Silane Coupling Agents)
Silane coupling agents are much more widely used in particulate filled composites than
the non-coupling analogues. This is because of their ability to improve filler polymer
adhesion, as well as improving dispersion and reducing hydrophilicity. In the simple
model, a monolayer is envisaged in which one end of the silane coupling agent bonds to
the filler, and the other end reacts with the polymer matrix. Unfortunately the real situation
is much more complex. The complexity of the reaction at the filler surface and of the
coating structure has already been described. The complexity of the coupling agent layer
interaction with the polymer must now be considered.
4.7.8.8 Current Views on Silane Coupling Agent-Polymer Interaction
With the advent of modern analytical techniques, especially FTIR, XPS, SIMS and solid
state nuclear magnetic resonance (NMR), the true nature of the interaction between
silane coupling agent layers and polymers is beginning to be unravelled. We have already
seen (Section 4.7.8.5) how silane coupling agent layers on fillers are believed to consist
185
of a mixture of chemisorbed and physisorbed material. This idea has been extended into
the filled polymer itself, leading to the concept of the existence of an interphase of graded
structure between the filler and polymer matrix, the exact properties of which control
polymer reinforcement. The nature of this interphase will depend on the structure of the
silane, the coating conditions, the nature of the filler surface, the nature of the matrix
polymer and the compounding conditions. Hence one has a very complex picture, which
can only be covered in outline here. Again the reader is referred to the excellent reviews
by Ishida [59] and Plueddemann [60, 61] for more details.
The first issue to be addressed is the importance of the physisorbed silane. There are
mixed views on this and very little data. Two different aspects have to be considered,
processing and reinforcement. Of these, processing is easiest to understand. The
physisorbed material will be similar to a silicone oil, and hence should be a good lubricant
and aid processing of mineral filled polymer melts. This probably explains the beneficial
effects of silanes on rheology of such systems. Han and co-workers have reported on the
effect of reactive and non-reactive silanes (amino-, propyl- and octyl-) on the viscosity of
calcium carbonate and glass bead filled polypropylene [64]. Both silanes markedly reduced
the viscosity of the calcium carbonate system, but not of the glass bead one. As proposed
by Ishida this can be explained by the existence of considerable low molecular weight
oligomers able to act as a lubricant on the calcium carbonate, but not present on the
more reactive glass beads [60].
The effect of the physisorbed material on reinforcement is much more difficult to predict
and will probably depend very much on the system. In some cases this material will
dissolve in the matrix and play little role in the interphase. In other cases it may penetrate
a little way only and during processing and cure may react with the chemisorbed silane
(through silane condensation or its reactive functionality), with itself, and with the matrix
polymer. Under favourable circumstances then it could lead to an extensive interphase of
an interpenetrating network type, with bonding to both filler and matrix. More often,
however, reaction may only occur with the matrix and not with the chemisorbed layers.
This will give poor results. In the few studies where the physisorbed material has been
removed before use, properties have indeed been improved [65, 66].
We now come to the nature of the chemisorbed layers. It is well known (in glass fibre
systems at least) that considerably more than a notional monolayer of silane is required for
optimum composite mechanical strength. This is in conflict with the simple chemical bonding
theory and has usually been explained by surface contamination, incomplete coverage, etc.
As reported by Ishida, several observations suggest that there is a more fundamental cause
[59]. Firstly, the optimum thickness is found to be very reproducible for a given system.
More importantly the vinyl functional silane is frequently found to be less effective then
the methacryl version, even where both should be able to copolymerise with the matrix.
186
In order to explain these observations, Plueddemann suggested that interpenetration of

matrix and coating may be an essential requirement [67]. This is believed to be partly
due to the layer of silane at the mineral surface being relatively unreactive, which itself is
probably due to deactivation of the organo-functional group by adsorption onto the
surface. Such adsorption has been observed with methacryl and amino functional silanes
[60]. The outer layers do not suffer from this problem and hence are free to react with
the matrix. A certain looseness of the structure of these layers will allow very good
mixing between polymer matrix and coating and promote bonding (especially where the
polymer is initially present in low molecular weight, liquid form, as in many thermoset
systems). This is proposed as the reason for the better performance of methacryl- as
opposed to vinyl-silane [59]. The latter is believed to be very prone to molecular ordering,
leading to a tight packed network, while the former gives a very loose, open structure.
Interestingly, Ishida [59] also reported that the effectiveness of both silanes was similar
on powdered, as opposed to fibre glass, indicating that the ability to form tightly packed
films, also depends on the smoothness of the surface.
Despite the recent advances in analytical methods we do not as yet know how well the
first silane layer is bonded to the remainder of the chemisorbed material or, more
importantly, the detailed structure of the interphase region once polymer processing has
been carried out. Hopefully, this will become clearer as techniques are further developed.
4.7.8.9 Principle Silane Coupling Agent Types and their Use
A considerable range of silane coupling agent types are available commercially, or have
been reported in the literature. A vast literature detailing their characteristics and
performance also exists. A number of excellent reviews of these subjects are available
[61, 68] and hence only the silane types most commonly met will be covered here together
with limited examples of the effects they can produce.
Three parts of the silane need to be considered, the alkoxy end, the spacer group and the
polymer reactive end.
The silanes are almost always tri-alkoxy derivatives. While the alkoxy group is lost during
the filler treating process, its nature plays an important role and needs to be carefully
selected. It controls volatility and flash point, affects toxicity, and plays an important
role in determining the rate of hydrolysis. The most common groups used are, methoxy-,
ethoxy-, and methoxy-ethoxy.
Economics dictate that there is little scope for varying the length of the hydrocarbon
spacer group between the silicon and reactive functionality. Jang and co-workers have
examined the effect of the length of this group in the methacrylic functional silanes, and
found only minor differences in performance [69].
187
The functional groups most used commercially in particulate filled composites are: amino,
epoxy, vinyl, mercapto, methacryl and polysulfide. The principle features of each of
these and their utility will now be discussed briefly.
a) Vinyl
This is the workhorse silane coupling agent, and commercial products generally have the
vinyl directly attached to the silicon atom. The hydrolysable groups are usually methoxy,
ethoxy, methoxy-ethoxy or acetoxy. This type of functionality is mainly used in polymers
that cure or are crosslinked by a free radical process such as peroxide. Gent and Hsu
have shown, using infra-red spectroscopy, that the vinyl group does react during peroxide
curing [70]. The vinyl group is however not sufficiently reactive for all systems, and
methacryl functionality is sometimes preferred. The tendency for this silane to form close
packed structures due to molecular orientation has been referred to previously.
b) Methacryl
This is a more reactive form of unsaturation than vinyl, and is used extensively in
free radical curing formulations, where the extra reactivity is of benefit, e.g., acrylics,
some polyesters. Commercial products usually contain -methacryloxy propyl groups,
and hence the double bond is further away from the silicon than is the case with the
vinyl silane. As mentioned previously, Jang and co-workers have studied the effect of
the length of the spacer group [69].
The presence of a carbonyl group in the molecule leads to a tendency for it to lie flat
on filler surfaces under some conditions [59, 60]. This is thought to lead to a reduction
in its ability to copolymerise with matrix polymer. Garbassi and co-workers have
also reported that some filler surfaces, (e.g., quartz), appear to cause self-
polymerisation of the methacryl groups [71].
c) Epoxy
Commercial products are based on 3-glycidoxy propyl trimethoxy silane. While they
can perform well in a number of systems, they are relatively expensive and are mainly
used in epoxies for which they are generally superior to other silane types. The epoxy
products have received less scientific study than some of the other silanes but as with
methacryl and amino, there is a strong possibility for deactivation of the epoxy group
on a filler surface.
d) Amino
Amino functional silanes are fairly widely used. The commercial ones are usually based
on the -aminopropyl functionality. They have a wide versatility, being used in epoxies,
phenolics, urethanes, polyamides, some thermoplastic polyesters and elastomers.
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Unlike most silanes they give aqueous solutions of great stability. This is believed
to be due to hydrogen bonding between the silanol groups resulting from hydrolysis,
and the primary amine. It is most marked when the amine is in the 3 position, as it
is in the standard commercial products, and can form an internal 5 or 6 membered
ring [56].
The reactivity of the amine group has made structural characterisation of the nature
of surface layers resulting from its adsorption on fillers very difficult. The amine
itself may absorb strongly on a variety of surfaces and has also been shown to be
very prone to bicarbonate salt formation with atmospheric carbon dioxide. Modern
analytical procedures are beginning to elucidate some of the important features of
these coatings and Ishida has given a very good account of the current state of
knowledge [59].
e) Sulfur Functional
These are specialist coupling agents, specifically designed for sulfur curing elastomer
systems, but nevertheless are used in considerable amounts. Two principal forms
are available, -mercapto propyl silane and various polysulfidic silanes (especially
tetrasulfide). Both types are very effective, the mercaptosilane is probably the most
efficient, but tends to be more scorchy than the polysulfides. There has been a
remarkable growth in the use of the tetrasulfide over the last decade, due to its key
role with precipitated silica in the development of low rolling resistance, or green
tyres [72]. Largely as a result of this success, other polysulfides, especially the
disulfide, are becoming of commercial interest [73].
f) Mixed Silane Systems
While not often described in the scientific literature, the use of mixed silane layers
is becoming of significant industrial importance. As described by Pape and
Plueddemann [74] mixtures of reactive and non-coupling silanes can still give high
property levels with improved hydrolytic stability. Mixtures of two different reactive
silanes are also reported as being beneficial.
g) Oligomeric Silanes
Another recent development is the use of oligomerised silanes. These are partly
self-condensed products and have the advantage of reduced volatility and decreased
alcohol release [75].
189
4.7.9 Examples of Silane Coupling Agent Effects in Filled Polymers
A brief account of the use of silanes in various polymer systems follows, more details
will be found in the appropriate chapters later in the book.
4.7.9.2 Elastomers
Silane coupling agents are widely used to improve the performance of mineral fillers in
elastomer systems. The silanes most commonly used are the various sulfur-based ones
and the vinyl and amino functional. The sulfides are generally used both pre-coated and
in situ. The fillers most often used in conjunction with silane coupling agents are
precipitated silicas and clays. The primary objective of the treatment is to improve polymer
to filler bonding, although other benefits such as lower viscosity, better dispersion and
reduced water adsorption are also observed.
The main benefits to be observed from the improved adhesion are higher modulus, higher
tear strength, better fatigue resistance and higher abrasion resistance. More complete
details can be found in the chapter on elastomers.
It should also be recorded here that Schwaber and Rodriguez used dilatometry to provide
direct evidence for improved adhesion resulting from the use of silane coupling agents in
silica and clay filled elastomers [76].
4.7.9.3 Thermosets
Silane coupling agents are widely used in thermoset systems, especially unsaturated
polyesters, acrylics and epoxies. The silanes most commonly used are vinyl, methacryl,
epoxy and amino. Among the fillers commonly treated are various silicas and silicates
and aluminium hydroxide. The latter is particularly widely used for its flame retardancy.
The in situ treatment method is frequently used with thermosets.
The coupling agents are again predominantly used to produce stronger filler to matrix
adhesion, especially after exposure to moisture, though other benefits, especially better
dispersion, may also be observed. In addition to leading to better strength retention in
wet conditions, the improved adhesion results in improved impact strength. Specialised
dispersants are often also used in thermoset systems and have to be carefully chosen to
minimise competition with the silane for the filler surface. More details will be found in
the chapter on thermosets.
190
4.7.9.4 Thermoplastics
In discussing thermoplastics we have to distinguish between condensation polymers (like

polyamides and polyesters), and polyolefins (such as polyethylene and polypropylene).
The condensation polymers are fairly reactive under melt processing conditions and can
react with silane functionalities such as primary amine. Such silanes are thus widely used
with this class of polymers.
Standard silane coupling agents are generally less effective in polyolefins, due to their
chemical inertness. A very reactive azido silane was developed specifically for use in such
polymers [67], but has now been withdrawn, as other technologies appear to have replaced
it. One of the alternative approaches, originally developed by Union Carbide and now
marketed by Crompton OSi Specialties is based on the use of organo-silicon chemicals
which are of a proprietary nature. Details of the performance of this approach have been
given by Godlewski [77, 78]. The use of silane coupling agents as additives for
thermoplastics has also been reviewed by Godlewski and Heggs [79]. More recently, the
use of acid functional polyolefins appears to have become the dominant technology.
These can be used directly with some fillers (such as calcium carbonate and aluminium
hydroxide), but in other cases, the filler has to be treated with an amino-silane, which
then forms an amide linkage with the acid functional polymer.
The fillers most commonly treated are silicas, clays and other silicates and flame retardants
such as aluminium and magnesium hydroxides. While both in situ and pre-coating
methods are utilised, pre-coating is most popular. This is in part at least due to the
problems that can be encountered due to alcohol release in compounding machinery
when the in situ process is used.
4.7.10 Organo-Titanates and Zirconates
Organo-titanates are a very interesting class of surface modifier, which have aroused
great interest in recent years. They can all be regarded as derivatives of ortho-titanic
acid, Ti(OH)4, and hence are commonly known as organo-titanates rather than by their
systematic names. This convention will be adopted here, in order to be consistent with
existing literature.
While several companies produce organo-titanates for a variety of uses, one group of
workers (Monte and Sugerman) have specialised in producing compounds for filler
modification, which they refer to as coupling agents. As well as producing an enormous
191
range of potential modifiers they have devised a methodology for describing the action
of the organo-titanates, and a system for classifying the various types available in the
light of this methodology. Most of the scientific and trade literature follows this approach.
As we shall see later, some scientific studies have thrown doubt on the validity of this
approach. Nevertheless it will be followed in the early part of this article, for simplicity
and compatibility with the existing literature.
As well as arousing interest, the organo-titanates have also aroused a great deal of
controversy. This is mainly related to their mode of action, and in particular, whether
they act as true coupling agents, or merely as very effective dispersants.
Unfortunately while there is an extensive literature, most of this is of a commercial or

purely effect describing nature and there have been virtually no useful basic scientific
studies. This has combined with the bewildering range of available products to create
confusion and some distrust of the products.
The natural chemistry of titanium causes problems with organo-titanates in some

applications. To overcome this, organo-zirconate products have been recently introduced.
The structure and general principles of the zirconates are similar to the titanates and no
separate discussion of them will be made, except to point out reasons why zirconates are
preferred in some applications.
4.7.10.2 General Principles
Conceptually, the organo-titanates are similar to silanes. Thus, they are designed to have
groups (generally alkoxy) that readily hydrolyse to titanium hydroxy groups which can
condense with surface hydroxyls and to also carry other organic groups, which are more
hydrolytically stable, and may also provide some reactive functionality. Depending on
their chemical nature, organo-titanates can be pre-coated from organic or aqueous
solution, dry blended or used in situ.
As discussed next, the chemistry of titanium causes some difficulties in producing suitable
structures, and partly accounts for the complex nature of the products that are available.
The most important factor is that, unlike the silicon to carbon bond, the titanium to
carbon bond is very unstable and cannot be used to permanently attach organic groups
for surface treatment applications. The organo-titanates are thus generally based on
tetra-substituted titanium, where all the substituents are linked by titanium-oxygen-carbon
bonds, and their chemistry is dominated by the hydrolytic sensitivity of these. Alkoxy
radicals are rapidly hydrolysed, with the rate in water decreasing as the chain length
increases, due to reduced solubility. Acyloxy derivatives are also fairly readily hydrolysed,
192
again with a chain length effect. They are generally thought to be somewhat more stable
than the alkoxides. Fairly good hydrolysis resistance can be obtained with chelate groups
attached to titanium, particularly where a five or six membered ring is formed.
Alkanolamines, diketones, keto esters, hydroxy acids and certain glycols are useful
chelating agents. In some instances inorganic acids such as phosphates are used to attach
organic groups to titanium, the titanium-oxygen-phosphorus bond being fairly
hydrolytically stable.
It must also be borne in mind that titanates are very active chemicals and can exhibit a
variety of crosslinking and catalytic effects in polymeric systems, which may in part
contribute to their effectiveness as filler treatments. Crosslinking occurs through
alcoholysis reactions with polymers containing active hydrogen atoms. A wide variety of
catalytic effects are also observed. The most important ones in the present context are
esterification, trans-esterification, polyamide formation and olefin polymerisation. Finally
the sensitivity of titanium IV compounds to photo-reduction must be mentioned as,
under certain circumstances this can lead to undesirable colour effects, which limit the
usefulness of organo-titanates in some applications. Very useful articles on the chemistry
and application of organo-titanates are available from some of the manufacturers [80]
and are worth consulting by anyone interested in more detail.
4.7.10.3 Organo-Titanate Types Proposed for Surface Modification
Monte and Sugermans basic approach is to use alkoxy groups as the hydrolysable group
on the titanium and acid groups (carboxylate, phosphate, sulfonate) to give stable
attachment of other organic groups. Initially single isopropoxy groups were used as the
hydrolysable group and these products are described as monoalkoxytitanates. More
recently neopentyl (diallyl) oxy groups have also been used. These are claimed to have
better thermal stability and be more suited to in situ use in thermoplastics compounding.
Derivatives of this type are known as neoalkoxytitanates. Chelate, co-ordinate and
quaternary types based on pyrophosphates are also available. The reader is referred to
the manufacturers literature for more details [81] and to the extensive publications by
Monte and Sugerman [82].
4.7.10.4 Types of Filler Susceptible to Organo-Titanate Treatment
While no comprehensive study has been made, it is generally claimed that organo-titanates
are effective on a wide variety of particulate mineral surfaces, including calcium carbonates
and carbon black. This claim is however often based on dispersant action in simple tests,
where adsorption rather than strong surface bonding is often sufficient to produce an
193
effect. Based on the proposed mode of action, one would expect best performance on
heavily hydroxylated surfaces such as silica, silicates and hydroxides. Organo-titanates
seem especially effective on calcium carbonate, however, even though this surface has
few hydroxyls and ortho-titanic acid is too weak to displace carbonate. Some other
bonding mechanism must thus be involved. It must be borne in mind that considerable
free carboxylic acid is potentially present and may play a significant role on this particular
surface (see Section 4.7.10.5).
4.7.10.5 Monoalkoxy Types
The simplest organo-titanates in general use as filler modifiers are nominally triacyloxy
isopropoxy derivatives. As mentioned earlier, the supposed mode of action is hydrolysis
and surface condensation through the isopropoxy group and stable bonding of the acyloxy
groups to the titanium. Where these acyloxy groups are long chain fatty acids, then
simple hydrophobing and dispersion effects should be observed. If however they contain
some reactive functionality, then chemical coupling to the matrix polymer is theoretically
possible. Typical compounds of these types are:
Non-reactive:
[CH3 (CH2)16COO] 3TiOR
Reactive:
CH3(CH2)16COO
TiOR
[CH2=C(CH3)COO]2
The sort of structure claimed to be formed on filler surfaces is shown in Figure 4.7a.
Several points need to be made about this structure. Firstly, the molecule is very bulky
and in this scheme only has one attachment point to the surface. Thus it is unlikely to
be able to react with more than a small fraction of the surface hydroxyls present on
many fillers. Secondly these idealised structures differ from the silane coupling agents
in having no bonding between adjacent coating molecules. One would expect that
such a coating may exhibit poor hydrolytic stability. Finally the acylate groups
themselves are also of doubtful hydrolytic stability. It could well be then that some of
these hydrolyse leading to further surface reaction and condensation similar to that
observed with the silanes.
194
Figure 4.7 Some structures proposed for the reaction of monoalkoxytitanates with
filler surfaces. a) Monofunctional reaction; b) bifunctional reaction; c) complex, partly
hydrolysed and condensed layer
While basic scientific work is relatively scarce, there have been some useful studies which
tend to confirm that the simple idealised picture is indeed far from correct. Perhaps the
most important of these has been by Cans and co-workers [83]. They worked with a
commercial organo-titanate (KR TTS from Kenrich) claimed to be
isopropyltriisostearoyltitanate, containing a small amount of free alcohol. This is probably
the most widely used titanate for filler modification and features in much of the scientific
and commercial literature. The usual method of coating is from an isopropanol solution.
Cans and co-workers used proton and 13C NMR to establish the structure of this material
and were surprised to find that it appeared to be a mixture of diisopropyldiisostearoyl
titanate and free isostearic acid. It would thus appear that the excess alcohol present has
solvolysed one of the acyloxy groups. They also found that further solvolysis readily
195
occurred if the titanate was dissolved in alcohol (as is often the case when coating fillers)
and that both solvolysis and hydrolysis could be catalysed by filler surfaces. Similar
results were also obtained with another commercial titanate (said to be
isopropyldimethacryl isostearoyl titanate with free isopropanol but analysed as diisopropyl
methacryl isostearoyl titanate and free methacrylic acid).
It would thus seem that, in practice, the titanates most commonly used are probably
diacyloxydialkoxy compounds with free acid present. This means that, even if the residual
acyloxy groups are stable, multiple surface attachment and self condensation more
analogous to silane chemisty can take place. If, as seems probable, some of the remaining
acyloxy groups are also hydrolysed, then these effects will be further enhanced.
The nature of the surface layer will then depend markedly on the method of surface
treatment used. If coating is carried out from an aprotic solvent and the filler is relatively
dry, then one may approach simple difunctional reaction with two remaining acyloxy
groups still attached (Figure 4.7b). However where further solvolysis and hydrolysis is
possible then in the extreme case one can envisage a partially formed titanium dioxide
network with some random surface attachment and some remaining chemically bound
organic groups (Figure 4.7c). In addition, the role of the free organic acid must be
considered, both that apparently present in some commercial titanates and that formed
by further hydrolysis.
These complications have not been recognised in the vast majority of the available
literature, especially that concerned with relating structure to performance effects. One
group has however recognised that in some applications the organic acid alone may
achieve the same results as the titanate [84].
A few papers relating to adsorption onto particle surfaces and the structure of coating
layers are worth a brief mention at this point. Landham and co-workers synthesised a
disopropoxy diacyl titanate using 12-stearoyloxystearic acid to give a branched, long chain
hydrophobic group and studied its adsorption on to alumina and barium titanate [85].
The solvent was hexane and the particles well dried, so this should have approached the
simple difunctional situation outlined previously. This additive was found to be an effective
dispersant for both particles but to require considerably in excess of the calculated monolayer
coverage for maximum effect. The stability of the adsorbed coating on alumina was assessed
by soxhlet extraction of the filler with ethyl acetate. Very little was removed while under
the same conditions up to 90% of a carboxylic acid (unspecified) was removed.
Golander and Sultan used infra-red and XPS techniques to study titanate coatings (applied
from isopropanol!) on an aluminium surface [86]. They found a coating thicker than the
XPS sampling depth but with a higher titanium to carbon ratio than expected, indicating
hydrolysis had occurred. Tsuchiya and Iwatsuki have examined the reaction between
196
titanates and a silica powder using FTIR spectroscopy, thermal analysis and gas
chromatography, and claimed to find evidence for reaction with the surface silanols
[87]. Finally Abu-Zeid and co-workers have used photoacoustic spectroscopy to examine
the interaction between KR-TTS and calcium carbonate [88]. Coating was from mineral
oil. The results were interpreted as showing the existence of chemical bonding beneath
rather than at the surface of the particles. These conclusions need further investigation.
4.7.10.6 Other Organo-Titanates
Despite the wide range of organo-titanate types available there have been virtually no
scientific studies with types other than the monoalkoxytitanates.
4.7.10.7 Effects produced by Organo-Titanates
Irrespective of the controversy over the structure of the organo-titanates and their mode
of action, they do appear to give useful effects and this is after all what matters.
Their main use appears to be in giving excellent dispersion of particles and hence low
viscosity, easily processable, formulations with good end properties. In this respect they
must then be judged against other materials used to achieve the same effects, notably
surfactants and fatty acids. The latter are especially relevant as the organotitanates in
use are largely based on these and, as we have seen, may indeed contain or form
considerable quantities of the free acids. Unfortunately very little data exists on which
one can properly judge the relative merits of the organo-titanates and other treatments.
As mentioned earlier, Kenrich KR-TTS is probably the most widely studied organo-titanate
at present and serves as a good example of the utility of organo-titanates. Several examples
of its use to produce low viscosity dispersions of fillers such as calcium carbonate and
aluminium hydroxide in organic liquids can be found in the manufacturers literature
[81] and the paper by Monte and Sugerman [82].
It is claimed that a significant part of their effectiveness is due to chemical removal of the
surface water layer on the particles, which significantly improves dispersion. Such an
effect is not present with other common types of dispersant. Unfortunately no good
comparison between organo-titanate and other dispersants has been made, although
Landham and co-workers did report that organo-titanates formed more stable layers on
alumina particles than fatty acids [85].
A great deal of interest has been focussed on calcium carbonate filled polypropylene
where materials such as KR-TTS are claimed to give excellent results. The work of Sharma
197
and co-workers is typical [89]. They coated ground calcium carbonate with KR-TTS
from toluene solution in a high speed mixer. The filler was dry blended with polypropylene
powder and compounded in a Buss Ko-Kneader. Test specimens were produced by both
compression and injection moulding. The coating was found to improve melt flow index,
tensile elongation and notched Izod impact strength relative to the uncoated filler. Scanning
electron microscopy indicated better dispersion of the filler due to the presence of the
titanate, but gave no evidence of a chemical bond between filler and matrix. Unfortunately,
no comparison with a simple fatty acid treatment, which would be expected to give
some, at least, of these benefits was carried out.
Unfortunately there have been no useful scientific studies with organo-titanates containing
unsaturated acyloxy groups to show whether they provide true coupling ability.
4.7.10.8 Limitations of Organo-Titanates and use of Organo-Zirconates
In addition to the tendency to colour formation due to photo-reduction already mentioned,

organo-titanates can also give undesirable colour effects in the presence of phenolic
functionality such as often encountered in antioxidants and light stabilisers. The ready
reduction of titanium IV also causes problems in peroxide cures where deactivation of
the free radicals and reduction in cure efficiency can occur.
These problems are largely eliminated if titanium is replaced by zirconium and hence
organo-zirconates analogous to the organo-titanates have been developed. They are
considerably more expensive to produce than the titanates and hence are unlikely to
completely replace them. The same questions over hydrolytic stability of the attachment
of the organic functionalities apply as for the titanates.
4.7.11 Aluminates and Zircoaluminates
Use of aluminates is in its infancy and there is very little information available concerning
the nature of the products and their effects other than that they are chemically modified
alkoxy aluminium chelates. Their use is being pioneered by Kenrich Petrochemicals [81].
Zirco-aluminates have been available for several years, but do not seem to have made
much headway in the particulate fillers area. Again structural details and useful scientific
data is scarce. They are said to be based on a low molecular weight zirco-aluminate
backbone carrying two ligand types. One type confers hydrolytic stability to the backbone,
while the other contributes organo-functionality. A number of functionalities are possible
including methacryloxy, mercapto, and amino.
198
While described as coupling agents, the main benefits illustrated appear to be in dispersion
and especially in producing low viscosity filler dispersions of excellent stability in liquid
systems such as unsaturated polyester resin. Among the advantages claimed are the ability
to produce hydrolytically stable coatings easily and rapidly with aqueous slurries of
particulate fillers including calcium carbonate. The reader is referred to publications by
Cohen [90-92] for more details.
4.7.12 Phosphates and Borates
Organic derivatives of both boric acid and phosphoric acid have been proposed as filler
treatments especially for use on calcium carbonate.
Borates have been proposed in a patent assigned to Dart Industries [93]. The standard
principle of having a readily hydrolysable group for surface attachment and more stably
attached groups for retained organo-functionality is followed. In the patent, the
hydrolysable group is isopropoxy and the other groups are long chain alkoxy groups
such as stearoyl. Calcium carbonate was coated with these additives by dry blending in
a high speed mixer and found to give improved properties (melt flow, impact strength,
elongation) in polypropylene homo and copolymer compared to untreated filler. As in so
much of this work, one has to ask whether these effects are better than could be achieved
with fatty acid alone and thus justify the higher cost of such treatment. This information
is not available but as this method of treatment has not become generally adopted it
would appear that it offers little real benefit. A more interesting case would be where the
retained groups had polymer reactive functionality and were able to give a true coupling
effect. This is hinted at, but not exemplified in the patent. The hydrolytic stability of the
attachment points would then become critical and might be found wanting.
Organophosphates are more interesting, and their use as surface modifiers for calcium
carbonate has been the subject of a number of papers by Nakatsuka and co-workers (46,
94, 95]. They have concentrated on organofunctional dihydrogen phosphates (RO-PO3H2)
obtained by phosphorylation of organic hydroxy compounds using phosphorus
trichloride. By this method they obtained compounds where the R group was a simple
hydrocarbon (ethyl, butyl, hexyl, octyl) or contained additional functionality such as
olefinic double bonds, methacryloxy, chloro or mercapto groups. In addition to simple
functional alcohols they also used a low molecular weight hydroxyterminated
polybutadiene.
These organophosphates were used to coat both precipitated and ground calcium
carbonates, and the coated fillers were assessed in SBR and EPDM elastomers. Coating
was by adding an aqueous or organic solution of the phosphate modifier to an aqueous
199
slurry of the calcium carbonate, filtering and drying. Microscopy showed evidence for
surface reaction and precipitation of calcium salts of the additives. The non-functional
alcohols were found to improve wetting and dispersion in the polymers but not to increase
reinforcement. The unsaturated additives on the other hand gave marked improvements
in peroxide cures typical of increased filler to elastomer adhesion. The unsaturated
additives were found to be less effective in sulfur cures where as might be expected, a
mercapto derivative gave the best performance.
Despite the apparent promise of this approach, there seems to be little or no commercial
use of this type of coating. The additives are probably expensive to prepare and the
benefits obtainable may not then warrant their use.
4.7.13 Organic Amines and Amino-acids
Until recently this has been a minor topic, with a small use of organic amines to treat
clays and related materials. The growing interest in the use of organo-clays as nano-
fillers is creating what may become a significant market opportunity for this type of
modifier. More details will be found in Chapter 10.
4.8 Conclusions
It can be seen that modification of filler surfaces both to aid processing and improve
composite properties is an important and active area of research. While there are a
considerable number of treatments proposed, they all follow the principle of a filler surface
reactive group linked to an organic backbone, which may carry further functionality. The
main variation is in the group used to achieve surface reaction. As we have seen this may
be an acid or acid precursor, an aluminate, borate, phosphate, silane, titanate or zirconate.
There is little difference in the organic groupings available in the different coating types; with
long chain alkanes, vinyl and methacryl unsaturation and amines predominating. By and
large, these groupings produce similar effects irrespective of the method of filler attachment
and hence the cheapest, easiest to use forms, with best hydrolytic stability are used.
More recently, greater sophistication is being brought to bear with ever increasing
performance of the surface treatments being required. The concept of a thick interphase
region is being developed with control of its microstructure seen as crucial to maximising
performance. Newer coating types are being developed to achieve this control, especially
polymeric modifiers and the organosilicon chemical mixtures. We can expect to see this
trend continue.
200
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Institute Conference, New York, NY, USA, 1984, Section 19E.
92. L.B. Cohen, Proceedings of the 41st Annual SPI Reinforced Plastics/Composites
Institute Conference, Atlanta, GA, USA, 1986, Section 26A.
93. M.M. Fein, B.K. Patnaik and F.K.Y. Chu, inventors; Dart Industries, assignee;
US4,073,766, 1978.
94. T. Nakatsuka, H. Kawasaki, K. Itadani and S. Yamashita, Journal of Applied

Polymer Science, 1982, 27, 259.
95. T. Nakatsuka, H. Kawasaki and S. Yamashita, Rubber Chemistry and

Technology, 1985, 58, 107.
206
5
Compound Preparation, Mixture
Characterisation and Process Enhancement of
Particulate-Filled Polymer Compounds
Peter R. Hornsby
5.1 Introduction
The term polymer compounding, as it applies to plastics and rubbers, normally describes
operations undertaken once the polymer leaves the polymerisation reactor and up to the
point where conversion to a finished product takes place, for example, using moulding
techniques or die-forming operations based on extrusion. Frequently, compounding is
associated with methods for combining polymer with additives, such as fillers, pigments
or reinforcements, which may aim to influence its end-performance, appearance,
processibility, or simply to reduce overall cost.
However, many variations exist to this generalised description of polymer compounding

technology, which may also include procedures for alloying and blending together of
different polymer types, or reactive modification of polymers, to induce chain grafting,
or adjust the polymer molecular weight. Materials separation processes, concerned, for
example, with removal of moisture or other volatiles and monomer polymerisation, can
also be considered as forms of compounding technology.
Whilst many of these areas fall outside the scope of this chapter, particulate polymer
composites are becoming increasingly complex and commonly require more than just
inclusion of a filler or particle additive in order to achieve optimum properties. For
example, rubber modification of mineral-filled thermoplastics to yield a balance of
enhanced toughness and stiffness, is an area of commercial importance. In these ternary-
phase systems, there is not only a requirement to attain good dispersion of the filler
component, but also a need for breakdown of the rubbery inclusion to yield the most
effective size and spatial location within the composition. Whilst this may depend to a
large extent on characteristics of the materials formulation, it can also be influenced by
the materials compounding route.
Reactive modification of polymers is also highly relevant to the preparation of

particulate-polymer composites, since the incorporation of functional groups onto
an otherwise non-reactive polymer chain, can promote adhesion to the particulate
phase, with attendant improvements to physical properties. Adjustments to polymer
207
reactivity or polarity in this way, has been exploited in filled polymer composite
technology, for example, using carboxylated polybutadiene, and polypropylene
functionalised with maleic anhydride (MA) or acrylic acid. This system is also used
for the preparation of silicate layer nanocomposites in polypropylene and as a means
for enhancing interfacial bonding in natural fibre-filled thermoplastics composites.
Historically there has been a clear distinction between the objectives of compounding
to achieve well-mixed polymer formulations, usually in pellet form, and conversion
processes, where the compound pellets are reformed into finished products. More
recently however, through developments in machinery design, combined compounding
and end-forming is possible on one machine, with resulting economic and quality
benefits, since the material experiences reduced overall shear and heat history. This
may take the form of direct compounding extrusion into a profile such as sheet, or
combined compounding and injection moulding on the same machine.
Further factors, which can have an important bearing on the approach adopted to
compounding, are the nature of the particulate additive and its level of addition.
Thermally sensitive fillers, such as starch, natural fibres, or organic pigments, have
limited heat stability, beyond which they may undergo decomposition, depending on
the temperature and time of exposure experienced. Some additives are highly shear
sensitive and may readily fracture in the severe environment of a high-intensity
compounding machine. Such attrition is commonly encountered in the preparation
of fibre-reinforced polymeric composites, but can also be evident with brittle
particulate additives like hollow glass microspheres, which may collapse under high
pressure, or from application of a critical shear stress.
Conversely, finely divided particles, such as carbon black, tend to aggregate into
larger agglomerates, sometimes with significant inter-particle attraction, requiring
generation of a high shear stress during compounding to ensure effective dispersion
in the polymeric phase.
An increasing number of polymer formulations contain high levels of filler to meet

certain property or processing requirements. Mineral fillers, for example, calcium
carbonate and talc, may be added at loadings of 40% by weight to enhance stiffness
and heat distortion resistance of thermoplastics. Pigment masterbatches may contain
well-dispersed additives of around 60% and simulated wood products up to 80% by
weight of woodflour filler. Even higher filler loadings are encountered in ceramics
and metal injection moulding compositions, where additions of 80-90% by weight
of the particulate species is bound within an organic binder, typically comprising a
high polymer and other components, such as waxes and process aids. In these systems,
after compounding and subsequent moulding of the composition, the minor organic
208
Compound Preparation, Mixture Characterisation and Process Enhancement of
phase is removed in a controlled burn-off procedure, and the ceramic or metallic

residue densified by sintering at high temperature.
Additional demands may be placed on compounding methods when using high filler
loadings, such as the need to convey large amounts of powdered species through the
machinery, exacerbated if additives are heat or shear sensitive, or are especially difficult
to disperse.
It will be evident from the previous discussion that the design and effective operation
of compounding plant to achieve optimum end-performance of a filled polymeric
composition, is a matter requiring close attention. Criteria used to assess the quality
of the compound produced, poses a further complication, since frequently this is
non-quantitative and often highly subjective.
This chapter will review current practice in the preparation of particulate polymer
compositions, with emphasis on the basic processing steps demanded from polymer
compounding operations in relation to feedstock characteristics, the application of
these principles in the design of both batch, and continuous compounding machinery
and quality assessment of the compound produced. The discussion will focus
extensively on the preparation and analysis of high-viscosity filled polymer
compositions, although it should be noted that particulate fillers are also widely
used in low-viscosity systems, such as polyvinyl chloride (PVC) pastes and thermoset
moulding compounds. The interrelationship between compounding route and material
properties will also be considered using examples of recent developments, which
have resulted in refinements or variations to established compounding methods and
means for enhancing end product performance through modified processing
technology.
5.2 Functional Characteristics of Compounding Machinery
In order to prepare polymeric composites containing particulate additives to meet

acceptable quality criteria, it is necessary to perform a series of well-defined and
sometimes overlapping steps during the compounding operation. The precise
requirements will depend on the form of polymer being processed, for example,
whether it is thermoplastic, thermosetting, or elastomeric in character, together with
the nature of the additive present. Further distinction can be made between batch
and continuous processes and the form of ancillary equipment needed. The
characteristics of these stages will be reviewed from a fundamental viewpoint and
then in a subsequent section, their practical application in the design of polymer-
compounding machinery considered.
209
5.2.1 Transport of Feedstock
Feedstock characteristics can have a profound effect on the ease of handling prior to
introduction into the compounder, on conveying behaviour during processing and on
their tendency to agglomerate. Polymers are used in many forms, including granules of
different size and shape, powders and flake, liquid resins and with many rubbery materials,
crumb and bales. An equally wide variety of forms are available with particulate additives,
differing greatly in shape (spherical, plates, fibres and related variants), and size
(submicrometre to tens or even hundreds of micrometres in diameter). Further
characteristics relevant to handling of both polymeric and particulate feedstocks are
their ability to deform under pressure, their tendency to absorb water and surface-
interactive forces promoting attraction.
Particle size and shape influence packing characteristics and hence material bulk density,
an important factor determining throughput, particularly in continuous compounding
operations. The ability of polymeric or additive particles to compact and occupy less
volume under load is also relevant to the early stages of compounding, since material
may be under pressure inside a hopper and to a much greater extent during processing
prior to and during melting. Compaction may occur in two broadly different ways,
through a particle rearrangement mechanism and from compressibility effects, if the
solid is deformable.
With powder systems, including polymer additives, compaction behaviour is determined

by particle size and shape, surface characteristics and the presence of adsorbed water.
On compression, applied forces are transmitted through the material at the points of
contact, generating an internal stress field. During the early stages, consolidation and
particle rearrangement occurs, which is greatly influenced by inter-particle friction [1].
As pressures are raised and further rearrangement becomes more difficult, deformation
of the particle will occur by elastic, plastic or even destructive mechanisms, depending
on the magnitude and rate of application of the applied stress. For example, the compaction
behaviour of a range of pigment powders has been studied using an instrumented tableting
machine [2, 3]. A wide variation in elasticity was found, with the pigments tested all
showing evidence of yielding and deformation beyond their elastic limit. In general,
organic pigments tested were more elastic than inorganic ones.
This observation has important implications on the mechanism of agglomerate formation,

since, during compaction, points of surface contact will increase together with inter-
particle attractive forces, and supports practical experience that more elastic agglomerates,
such as those formed from phthalocyanines, are usually more difficult to disperse [3].
Powder compaction is relevant to many processing industries and has been considered
with other material forms such as coal [4].
210
As mentioned earlier, surface interaction and the extent of particle combination is

closely related to compaction behaviour, together with the physical and chemical nature
of the material. Pigment powders, for example, may contain three basic types of particle
differing in strength and size [3]. Primary particles or crystallites (usually between
0.01 and 5 m) can unite to form larger strongly bound aggregates. These may then
cluster to produce more loosely associated agglomerates, which may be several hundreds
of micrometres in size. When added to polymers, the last mentioned structural form is
generally of most concern, necessitating effective dispersion procedures, which will be
discussed in Section 5.2.3.
Agglomeration will occur naturally in fine powders due to attractive forces existing at
the surface, which vary enormously in magnitude, creating particle associations of differing
strength. The principal bonding mechanisms in operation increase agglomerate strength
in the following order [5]: electrostatic forces < van der Waals forces << liquid bridge
forces << solid bridges.
Solid bridges are formed by crystallising salts or by sintering and are generally too strong
to overcome through generation of shear stresses prevalent during polymer compounding
processes. The presence of even small amounts of moisture can result in the formation of
strong liquid-bridge forces between fine particles, being about four times greater than
van der Waals interactive forces, which in turn are an order of magnitude greater than
electrostatic adhesion forces arising from contact potential. The magnitude of adhesion
forces may also depend on the surface roughness of particles and, as mentioned earlier,
the extent of elastic or plastic deformation induced during compaction. Estimation of
the strength of agglomerates has been determined both theoretically, through consideration
of the adhesion forces prevailing [5] and also by direct measurement of the mechanical
strength of compacted powders [3, 6, 7].
Regular flow of feedstock into compounding machinery is an important consideration,

if fluctuations of feed rate are to be avoided, and with multi-component compositions
prepared from separate feed sources, if uniform concentration of the components is to
be achieved. Such considerations have a bearing on the design of hoppers, for example,
to avoid bridging and ensure uniform mass transport, output consistency of metering
feeders, and also the early stages of movement in single-screw extruders, where
Archimedean screw conveying predominates.
In response to external forces, particulate solids have characteristics of solid- and liquid-
like behaviour, capable of resisting flow until a limiting shear stress is exceeded, after
which infinite flow will occur. Unlike liquids, however, shear stress is proportional to the
normal load applied rather than the rate of deformation and, unlike solids, the magnitude
of shear stress is generally indeterminate, depending on the inter-particle static coefficient
211
of friction. In this context, the internal cohesiveness of the powder (its tendency to
agglomerate) and its coefficient of friction against a containing external surface, are
important considerations, particularly in the optimum design of containers and hoppers,
where gravitational flow predominates and flow disturbances, (e.g., powder bridging)
must be minimised [8].
Conveying in polymer-processing equipment, including most continuous forms of

compounding plant, generally results from frictional effects between polymer and metal
surfaces, resulting in so-called drag flow, or through positive displacement created,
typically, by intermeshing screws. The former mechanism is evident in most forms of
single-screw extruders, although some important differences are apparent in extruders
modified to achieve enhanced mixing capability, such as ko-kneaders.
Polymer conveying in the feed zone of a single-screw extruder has been analysed with
varying degrees of rigour. Full details are beyond the scope of this review, but can be
found in the literature [9]. It is generally assumed, however, that material, present in the
feed zone before melting occurs, exists as a solid plug capable of behaving elastically and
generating pressure internally. For effective transport, a higher coefficient of friction
should exist between the material and barrel than between the material and screw.
Complications arise in predicting conveying performance for a given polymer type due
to effects from the many variables that may influence values of frictional coefficient,
including material temperature and pressure, the geometry of the screw (in particular
helix angle) and the surface finish of both screw and barrel. Reduced sensitivity to frictional
coefficient and increased material throughout is possible using longitudinal tapered
grooves in the feed section of the barrel, which increase the relative friction of material
to the barrel [9].
Further uncertainties are apparent when processing multiphase polymeric compositions,

due to the possible effect of the minor phase(s) on frictional behaviour. Indeed, with
many filled polymer formulations containing appreciable additive levels, material transport
through a drag-flow mechanism may be seriously hindered, resulting in limited, or no
material movement through the extruder. Under these circumstances the positive
displacement action, which arises in many forms of intermeshing twin-screw extruder
can be particularly effective in overcoming this difficulty. In such designs, material
contained in the screw channels is propelled forward axially due to penetration by the
adjacent screw flight.
Displacement efficiency in twin-screw extruders depends on the flight geometry, the

extent of conjugation (intermesh) between the screw flights (generally greatest for
trapezoidal screws and channels) and the number of thread starts. Screw design and
positive-displacement action will also be influenced by the direction of screw rotation,
212
i.e., in the same or opposite directions [10]. So-called self-wiping screw geometries
have limited flight penetration into adjacent screw channels and therefore exert reduced
positive transport, showing greater dependency on frictional effects and hence drag
flow. Non-intermeshing twin-screw extruders generally behave more like two single-
screw extruders arranged side by side depending almost entirely on drag flow for
material conveyance.
5.2.2 Melting and Shear Heating
During melt compounding, uniform and rapid melting of polymer is necessary in order
to maximise production rates, and when fillers are present, to ensure that the particles
are effectively coated by polymer. The heat required to melt the polymer may be derived
from a number of sources, in particular thermal conduction from surrounding hot
metal surfaces and from viscous dissipation of mechanical energy through repeated
shear deformation of the material. Reliance solely on the former, however, would result
in unacceptably low rates of heating due to the low thermal conductivity of the melt.
Shearing of polymers provides a much more efficient and uniform method of heating,
but can sometimes result in excessive temperature generation necessitating application
of cooling measures.
Since dissipation of mechanical energy into heat is strongly dependent on the rheology
of the polymer medium, the presence of fillers will increase viscosity and exacerbate
shear heating.
Generally, in continuous compounding operations based on extrusion, the early stage

of melting occurs through the formation of a melt film at the heated wall of the barrel
or process chamber. This heat is derived from external sources such as electrical
resistance heater bands or circulating oil. As mentioned earlier, melting by conduction
only, is a relatively inefficient means for heating polymers, which would result in
prohibitively long production times. In extrusion-based compounding processes, the
so-called mechanism of conductive melting with forced (drag-induced) melt removal
has been well studied, particularly with respect to single-screw extruders and variations
may be found in other compounding procedures [9].
In a common version of this mechanism, the melt film produced at the barrel wall is
wiped by the traversing screw flight, causing polymer to collect and circulate at the
rear of the channel. The solid bed of polymer granules or powder further forward in
the channel is pressurised against the barrel surface. Extensive shear deformation of
polymer occurs at the solid-melt interface generating considerable heat and making a
substantial contribution to the overall melting process.
213
In other forms of compounding plant, such as internal mixers, dissipation of mechanical

energy is normally the dominating factor determining the rate of heating, both for
material in solid form, from inter-particle frictional effects and subsequently as the
polymer melts [8].
The influence of fillers on melting mechanism has not been considered in detail. However,
at low or modest filler levels it is unlikely to be changed much. Increased rates of heating
are likely from particle attrition and increases in polymer melt viscosity. Set against this
will be the additional heat required to compensate for heat absorption by the filler
component depending on its specific heat capacity.
5.2.3 Mixing
A requirement central to most compounding situations is intimate blending of the

components, both at the micro and macro level. This is strongly influenced by machinery
design and to a large degree by material formulation.
Dispersive mixing involves the breakdown of agglomerates or clumps of solid particles,

generally in a deforming viscous polymer melt, by forcing the mixture to pass through
high shear zones generated between narrow clearances evident in polymer compounding
equipment. Agglomerate rupture occurs when hydrodynamic forces exerted on the
particles exceed the cohesive surface attraction within the agglomerate. As mentioned
earlier, particles may be bound together by forces of physical or physiochemical origin
enhanced by the presence of moisture or by applied pressure.
The overall process of dispersion can be considered as a number of stages:
(i) encapsulation and wetting of solids by the melt;
(ii) repeated rupture of agglomerates when internal forces generated by viscous drag on
the agglomerate exceed a critical threshold value; and
(iii) separation and distribution of the resulting fragments in the polymer matrix, so that
re-agglomeration will not occur.
Various models have been proposed describing the dispersion process, which can be
categorised into two general types, depending on the physical characteristics of the
agglomerate and the dynamics of the flow field [11]. Models for the dispersion of cohesive
agglomerates, in which the nature of the flow field is important, involve abruptly yielding
rupture, where fragmentation into relatively large pieces occurs at discrete time intervals.
214
In slowly yielding agglomerate breakdown models, break-up of cohesionless agglomerates

occurs over finite intervals, more gradual erosion taking place through detachment of
small fragments from the outer surface of the agglomerate over an extended period of
time. At present it is not possible to generalise on the breakdown mechanism for all
particulate agglomerates. Carbon black, for example, appears to disperse predominantly
by rupture, whereas titanium dioxide agglomerates are thought to gradually erode.
It is useful to analyse the forces developed during the dispersion process leading to
agglomerate rupture. These can be estimated by considering a single agglomerate in the
form of a rigid dumb-bell consisting of two unequal beads of radii, r1 and r2, connected
together and placed in a homogeneous velocity field of an incompressible Newtonian
fluid [12]. A force is developed in the connector, tending to separate the beads, which
depends on the dumb-bell orientation and the degree of viscous drag from the surrounding
fluid. The maximum separating force (Fmax) acting between the beads in simple shear,
occurs at a dumb-bell orientation of 45 to the direction of shear and is given by:
rr
Fmax = 3 1 2 L (5.1)
r1 + r2
where is the viscosity of the surrounding fluid, the applied shear rate and L, the
length of the connector joining the beads.
For elongational flow, the maximum separating force occurs when the dumb-bell is aligned
in the direction of flow as follows:
rr
Fmax = 6 1 2 L (5.2)
r1 + r2
where is the rate of elongation.
It is apparent from this analysis that it is easier to rupture combinations of larger beads
than smaller ones and that dispersive mixing is favoured by conditions of high shear
stress or elongational flow. In practice, however, most forms of dispersive mixer operate
under conditions of high shear obtained by flow through narrow clearances.
Models have also been developed to analyse the dispersibility of ellipsoidal clusters [13]
and the relative effects of different flow geometries, from which biaxial extension was
found to be most efficient in influencing particle rupture [14, 15]. Furthermore, although
it is generally assumed that in the agglomerate rupture process the parent agglomerate
produces two identical fragments, controlled experimental studies have also been
215
undertaken using carbon black, which cast doubt on this assumption [11]. It has also
been shown, again using carbon black and a specially constructed test rig that the number
of passes through the high shear zone has a dominant role in influencing dispersive
mixing [16].
Surface treatment of fillers is common to minimise particle interaction and to facilitate

dispersion. Additionally, appropriate treatment will lower the filler surface energy, thereby
increasing compatibility with the polymer phase. This will aid wet-out by the melt and
may result in enhanced physical properties depending on the relative interaction between
surface modifier, filler and polymer. It will be evident from the previous discussion that
dispersion will be determined by the level of shear stress experienced by the filler particles,
which in turn is dependent on process-operating conditions and above all, by compounding
machinery design (Figure 5.1).
In addition to breaking down particle structures into their smallest physical components,
a further goal during mixing is to randomise their spatial location within the polymer.
Convective mixing is a general term often used to describe this process of rearrangement
from a less to a more probable order. Redistribution of solid components in a mixture
Figure 5.1 Materials and processing parameters influencing dispersion of particulate

fillers in polymers
216
may be undertaken in low intensity compounding operations, for example, by tumble

mixing, or in solid/melt combinations, where the convective mixing results from laminar
shear flow. Some additives may deform, however, leading to a reduction in distance
between rows of particles (or striations) and an associated increase in interfacial surface
area, as mixing progresses. The total shear strain experienced by the mixture during
compounding is therefore indicative of the degree of mixing. This quantity is difficult to
calculate, however, except in processes where the rheology of melt flow is well understood,
for example, in two-roll mills, or in flow through a single-screw melt pump. In the
conventional design of a single-screw extruder, where melt mixing is relatively poor, the
weighted average total strain (WATS) can be defined as the product of shear-rate and
residence time for fluid elements at different channel depths, then integrated across the
entire channel, namely:

WATS = ( ) = tf ( t ) dt (5.3)
t0
where is the shear rate, t0 is the minimum residence time in the extruder, and f(t) is
the residence time distribution function. Using this analytical approach, mixing
effectiveness can be determined in an extruder using different screw geometries or
operating conditions [17].
It should be noted, however, that in plasticating extruders WATS defines mixing only in
the melt-conveying zone of the extruder and neglects the very substantial contribution to
overall mixing evident during polymer melting [18].
Distribution of components in a mixture through laminar shear mixing frequently occurs

in a disordered manner, although motionless mixers are designed to blend in a more
regular way through a process of repeated stream splitting and material combination.
5.2.4 Melt Devolatilisation
There are several reasons why it may be important during compounding to devolatilise
polymer melts containing particulate additives. Firstly, there may simply be a need to
remove entrapped air introduced into the compounder together with the feedstock. In
single-screw extruders this should pass back through a solid bed of partially or unfused
plastic as melting progresses and escape through the hopper. However, in some single-
screw variants of more complex design and in closely intermeshing twin-screw extruders,
this process may be hindered by the closed nature of the screw channels preventing
escape of the air. In such cases, downstream melt venting is very common through the
combination of a low-pressure decompression screw profile and an open port on the
217
barrel, often aided by vacuum extraction. Under different circumstances, however, this
form of screw and barrel design may serve as a convenient point for downstream filler
addition into the compounder.
Volatile removal may also be necessary in polymer compositions containing moisture,

for example, with hygroscopic polymers and additives, such as wood flour, or where
residual quantities of monomers or reactive by-products must be removed. Generally, in
these situations, amounts of volatiles extracted are small, typically less than 3% by weight.
Polymer melt devolatilisation has been the subject of extensive theoretical analysis [19],
resulting in important practical implications for the preparation of filled polymer
composites, with optimum particle wet-out and freedom from volatile matter.
Hence, in order to enhance efficiency of volatile removal during compounding, it is

advantageous to generate large surface areas per unit mass of material, with frequent
renewal of the mass interface. In this way diffusion distances through the polymer can be
minimised and steep concentration gradients achieved within the melt. Diffusion and
volatile extraction is improved with increasing melt temperature, a decrease in equilibrium
volatile concentration at the interface between polymer and volatile using reduced
environmental pressure, and long material residence times in the devolatilisation zone.
With polymer melts, devolatilisation is normally diffusion controlled. Within the bulk of
the polymer melt, diffusion rate depends on a volatile concentration gradient existing
towards the polymer-free surface.
Through diffusional mass transport, volatiles are moved to the interface between the
melt and surrounding environment. Differences in volatile concentration at this surface
and in the surrounding medium, determine the rate of volatile removal by convective
mass transport. Normally, however, mass transport through the melt is the rate-
determining step.
Under some circumstances, creation of bubbles in the melt phase can help convect volatiles
at increased rates, with subsequent release into the environment. This may be achieved
by injection of a carrier substance, such as water, into polymer causing foaming and
diffusion of volatiles to the melt-cell interface [20].
5.2.5 Melt Pumping and Pressurisation
In most compounding procedures there is a requirement to generate sufficient melt pressure

in order to convey material through defined geometrical configurations, such as extrusion
dies, clearances between roll mills or specially designed mixing devices. Pressures generated
218
tend to be large due to the high viscosity of polymer melts, which is further increased by
the presence of particulate additives, and the need to pump molten polymer through
small flow channels at high production rates, thereby generating sufficiently large shear
stresses to effect filler dispersion.
Of particular relevance to the design of polymer-compounding plant are drag-induced

flow fields caused by one or more moving external surfaces and positive displacement
flow, resulting from external mechanical pressurisation [8]. The former mechanism, also
termed viscous dynamic pressurisation, is applicable to the design of single-screw extruders
and roll mills, for example, whereas twin-screw compounding extruders generally behave
as positive melt-displacement pumps, depending on the direction of screw rotation, the
clearances between the screws and the extent to which they intermesh. Detailed analysis
of these pressurisation methods has been reported for various flow situations, forming a
basis for design of processing machinery [21].
5.3 Constructional Design of Compounding Plant
Machinery used to prepare particulate-filled polymer composites may be classified in

terms of the applied shear intensity and whether the operation is of a batch or continuous
nature. Furthermore, most compounding processes are critically dependent on the
efficiency of ancillary equipment to undertake various functions, including additive and
polymer feeding, melt filtration and pelletising procedures.
The form of the product may also differ, depending on the type of polymer and components
used in the formulation. Most particulate-filled polymer compounds based on
thermoplastics matrices are made in pellet form, although it should be noted that granule
shape may differ from a cubical to lenticular or rod-like geometry, depending on the
method of pelletisation used. Some thermoplastics formulations, notably PVC-containing
particulate additives, are compounded to give a so-called dry-blend powder. Compounds
made from thermosetting polymers often require rather different preparation methods.
For example, polyester-based dough-moulding compounds (DMC) require appropriate
measures to combine solid inclusions uniformly into the viscous resin phase. Rubber
mixes may leave the compounding stage as a strip or sheet, to be subsequently shaped
and vulcanised into the final product form.
With this wide range of material types and approaches to compounding, incorporation
of particulate additives into polymers can vary greatly from one compound to another.
Attention will therefore be directed only on the main types of compounding plant used
industrially, highlighting their principles of design and operation specifically for the
preparation of particulate-filled polymeric compositions.
219
5.3.1 Low and Medium Intensity Premixing Procedures
Frequently the compounding process entails preliminary combination of polymer and

additive(s) through an initial blending stage, to pre-distribute the formulation, prior to
high shear mixing with polymer in a molten state.
During premixing, the components are randomly interspersed with each other and levels
of developed shear are generally low. Formulations include solid/solid mixtures of polymer
and additive particles, where temperatures are maintained below the polymer melting point,
or low-viscosity liquid/solid formulations, as is found with PVC pastes and DMC premixes.
For this requirement, various forms of machinery are available, including tumble mixers, V-
blenders and double-cone blenders, where powders and particulate components of a mixture
are gently moved from end to end through a tumbling action as the mixer revolves (Figure 5.2).
Differences in mixing efficiency may be apparent depending on the ability of the blender to
divide repeatedly and combine the contents during operation. Some pre-mixers such as ribbon
blenders, incorporate impellers, often with complex geometry, which rotate at speeds up to
60 rpm, transporting the components back and forward along a trough-shaped horizontal
mixing chamber, as well as creating movement from top to bottom. Differences in ribbon
design are possible, which can vary the intensity of end to end flow, in addition to double
trough arrangements with improved cross-flow characteristics.
Figure 5.2 Low-intensity mixer designs (a) double-cone blender; (b) twin-shell (V)
blender; (c) conical screw mixer; (d) conical screw mixer
220
Conical screw mixers also contain a screw for conveying and mixing, but this is located
inside an inverted conical-shaped mixing chamber. The screw is angled from the base of
the mixer to the outside of the top. It may revolve on its own axis at about 60 rpm, whilst
slowly orbiting the cone at around 3 rpm. Pelletised or powdered polymer, and additives
are transferred from bottom to top by the rotating screw, from the walls to the centre of
the chamber as the screw circulates, to fall on to material being carried upwards.
5.3.2 High-Intensity Compounding Machinery
Mixers that impart high shear to the components may differ according to whether the
polymer melts or not, and if the process is of a batch or continuous nature.
5.3.2.1 Non-Fluxing Mixers
High-intensity non-fluxing batch mixers are frequently used in the preparation of PVC
dry-blends, which may contain appreciable quantities of particulate additives and liquid
plasticisers [22].
The equipment comprises a revolving impeller, capable of high rotational speeds (up to
about 4000 rpm located in the bottom of a jacketed mixing chamber. During blending
the components are thrown out radially by the rotor, travel up the walls of the mixer and
fall down through the central zone forming a vortex. A baffle may also be introduced to
create additional turbulence to this fluid-like flow. The process of producing a PVC dry-
blend involves the generation of heat, which can be applied externally, but arises principally
from inter-particle frictional and shear effects.
Mixing times and procedures, for example, the sequence of addition of the various
components, depend on the formulation, but may vary from 20 s to 20 min, resulting in
material temperatures up to 140 C. Hence, to ensure rapid and uniform cooling, after
blending, the batch of powdered compound is fed from a high-speed mixer to a low-
intensity cooling unit, where it is gently agitated until cool.
It is important to note that the particle morphology and resulting processing characteristics
of the powder blend produced depend strongly on the mixing regime adopted and may
have a substantial effect on material flow and gelation during subsequent melt conversion
by extrusion or injection moulding [23].
High-speed mixers can also be an extremely effective means of pre-blending powder

forms of polymer (other than PVC), with particulate additives, such as pigments or mineral
fillers. The action is essentially one of inter-particle randomisation. It is questionable
221
whether high-speed mixing in this manner aids the dispersion of all but loosely aggregated
particle structures, and may even contribute to agglomerate formation by compacting
particles together, particularly near the chamber walls and mixing impeller [24].
Mixers of this type provide a convenient method for surface application of treatments to
fillers, in order to modify their interfacial properties. Since filler is in a fluidised state and
may be cold or heated, surface treatment can be introduced through an opening on the
mixer lid to achieve rapid and uniform coating.
Special forms of high speed mixer have been developed which produce agglomerated
mixtures of thermoplastics and fillers in compacted form, thereby enhancing feeding
capability into extruders, reducing dust and moisture content associated with hygroscopic
materials, such as organic fillers [25].
5.3.2.2 Two-Roll Mills
Two-roll milling is a well-established and widely practised melt-mixing process, which

can be used for blending particulate additives into rubbers, thermoplastics and
thermosetting polymer compositions. Although most frequently encountered in
laboratories, due to the highly effective mixing action created, it is still used in some
large-scale industrial plants.
The machine comprises two contra-rotating rolls, which may be heated or cooled, and
can often run at differential speeds. Softened polymer adheres to one of the rolls, forming
a continuous band passing through an adjustable gap between the rolls. In this region it
experiences high levels of localised shear, which, together with manual (or sometimes
automated) lateral mixing across the rolls, provides a highly effective means for both
dispersion and distribution of additives into the polymer. Additional, but relatively low
levels of laminar shear occurs within a rolling bank of excess polymer situated on the
upstream side of the rolls. The estimation of shear imposed on fluid elements passing
through the nip of a two-roll mixer can be made for power-law fluids, such as polymer
melts, which have highly shear-dependent viscosities. The reader is referred elsewhere
for details [21].
5.3.2.3 Internal Mixers
High-intensity internal mixers are used for incorporating particulate additives into most
polymer types, including thermoplastics, thermosets and rubbers. Limitations, such as
the manual intervention generally encountered with two-roll mills, can be overcome,
whilst maintaining a significant dispersive and distributive mixing capability.
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Batch designs of internal mixer comprise a temperature-controlled mixing chamber

containing two fluted mixing rotors, which commonly revolve in opposite directions
and sometimes at different speeds. Materials introduced into the chamber are pressurised
using a floating ram, which is lowered onto the feedstock, causing intensive mixing
within the chamber. This action is strongly dependent on features of the rotor design,
such as clearances between the chamber wall and helical projections on the rotors, together
with prevailing operating conditions, notably temperature, rotor speed and ram pressure.
The mechanism of mixing is complex, since material is sheared both at the walls of the
mixing chamber and between the rotors, in addition to being repeatedly transferred
from one side of the chamber to the other. Considerable levels of frictional heat may be
generated during the mixing cycle, arising from viscous dissipation of mechanical energy
from the rotor drive, as the material is sheared.
The widespread use of internal mixers for polymer compounding over many decades,
has resulted in many refinements to mixer, and particularly rotor design, together with
optimisation of mixing procedures.
Despite the wealth of practical experience gained from the application of internal mixers
to a wide range of polymer compounding tasks, it is only in recent years that more
fundamental studies have been undertaken to analyse and model their mixing action.
These include flow visualisation experiments to monitor different flow fields and levels
of mixing, created by various rotor designs [26], and process parameters [27], such as
mixing times and thermal boundary conditions. Several workers have applied finite
element analysis techniques to predict flow behaviour of polymers and in particular their
mixing efficiency [28-30]. For example, using a fluid-dynamics package, a three-
dimensional analysis has been carried out for the whole mixing chamber, providing
information on the effects of processing conditions and design parameters on velocity
profiles, pressure contours, the development of shear stress and elongational flow
behaviour [31].
On completion of the mixing cycle, compound is discharged from the underside of the
mixing chamber, often on to a two-roll mill to undergo further homogenisation, or into
a pump-extruder equipped with a pelletising facility.
Continuous forms of internal mixer are also available, in which polymer and additive
feedstock are continuously starve-fed on to twin counter-rotating screws, before
progressing into a mixing zone, housing two rotors, similar in design to those used in
batch-internal mixers described previously [32]. Compound moves forward and discharges
continuously through an adjustable orifice gate, or into an extruder pelletiser. Mixing
intensity can be varied through control of temperature, rotor speed, feed rate and discharge
orifice opening. Of particular relevance to the preparation of polymer compounds
223
containing heat- or shear-sensitive particulate fillers, is the availability of special continuous

mixer designs with provision for the introduction of the additive component after the
melt has been formed.
5.3.2.4 Extrusion Compounding
Continuous forms of compounding plant engineered for the preparation of particulate-

filled polymer composites are frequently based on variants of the extrusion machine,
modified to impart increased mixing capability.
The application of single-screw extruders for conversion of plastics and rubbers into
finished products by die forming is widespread, and the reader is referred to specialist
texts, which consider their design, operation and fundamental analysis [9, 21]. As
mentioned earlier, their use as mixing devices is less successful, due to an inability of the
basic helical screw form to generate sufficiently high levels of shear strain or localised
shear stress within the polymer melt. Hence, single-screw extruders (and single-screw
reciprocating injection moulding machines) are frequently fed with pre-compounded
material, or pre-dispersed additive masterbatch.
Common means of enhancing the mixing efficiency of single-screw extruders include use
of modified screw forms containing special mixing devices, or static mixers, which are
located between the extruder and die. The various forms of mixing screw design available
may function in either a dispersive and/or distributive manner.
The latter type frequently operate in the melt phase to randomise the position of the
minor component, by interrupting the laminar flow path of the polymer melt, causing
repeated stream splitting and recombination of fluid elements, and generating substantially
increased shear strain in the melt. Static mixers are normally introduced between the
extruder and die, containing helical or other forms of element design, which divide and
reunite flow streams in a controlled manner.
A further alternative is the cavity transfer distributive mixer, which comprises a rotor
with hemispherical depressions located within a closefitting stator, also configured with
hemispheres. Polymer melt continuously transfers between rotor and stator cavities, and
experiences substantially increased shear strain, resulting in increased mixing.
Screw designs created to improve dispersive mixing impose the polymer melt and additive
components, to high levels of shear stress by intensive flow through narrow clearances,
often located between the screw tips and barrel wall. Variants using this principle include
Union Carbide and Egan mixers. These, and other forms of mixer design for single-
screw extruders, have been reviewed [33].
224
The inadequacies of single-screw extruders, such as melt compounders, are overcome in

the ko-kneader [33, 34]. This incorporates a single screw with gaps between the screw
flights contained within a barrel, having rows of teeth projecting from and running axially
along its length. The screw can both rotate and reciprocate, such that the teeth on the
barrel pass forwards and backwards between the gaps on the screw. The rotation and
axial oscillation of the kneading screw produces a relative motion between kneading
teeth and screw flights providing combined axial and radial mixing. Such movement
also creates a self-wiping action against the barrel and screw surfaces, and generates a
positive pumping movement on the material, reducing its reliance on frictional and drag
flow as the primary means of material conveyance. This unique operating concept has
established ko-kneader mixers as a widely accepted means of preparing polymer
composites containing many different forms of particulate additive, including masterbatch
formulations with high levels of pigments or mineral fillers.
Many other specialised forms of single-screw compounding extruder have been

commercialised, such as Transfermix, EVK and pin-barrel extruders [9]. The design of
the latter has some similarities to the ko-kneader, in that adjustable pins protrude from
the barrel into the screw channel, which contains slots at various pin locations. During
rotation of the screw (which does not reciprocate), the pins pass through the gaps on the
screw flight enhancing mixing capability and providing good melt temperature uniformity.
This is found to be particularly useful for rubber applications.
An increasing number of compounding tasks are being undertaken on twin-screw

extruders, due to their continuous operation at high throughput rates, their highly effective
mixing action and provision for interchangeable screw and barrel geometries. This enables
machine configuration and process optimisation for a wide variety of compounding tasks,
such as preparation of thermoset powder-coating compounds, heat-sensitive flame
retardant formulations, or very heavily loaded ceramic- or metal-injection moulding
compositions. Versatility in screw and barrel assembly also facilitates application in
multifunctional compounding situations, for example, requiring downstream or split
feeding of particulate additives, introduction of liquid reactants into the melt and melt
devolatilisation. Extremes in mixing intensity are readily achievable, through the use of
various forms of mixing elements and helical screw types.
In view of the complexity of these systems and the numerous design permutations
available, it is not easy to generalise on their mode of operation. However, several in-
depth accounts have been published, which detail their design principles and theoretical
treatment [35, 36]. An overview of pertinent features is presented below.
In classifying twin-screw extruders, distinction must first be made between the direction of
screw rotation (co- or counter-) within a figure-of-eight screw barrel, whether or not the
225
Figure 5.3 Screw configurations used in twin-screw extruders
barrel is conical (as can be found in some counter-rotating designs) and the extent to which
the screws intermesh, if at all. Further differences can be found in the form of screw flight.
Co-rotating designs, for example, may have rounded or so-called self-wiping screw flights,
which have large channel clearances across the intermeshing zone, or trapezoidal-shaped
channels and flights with more restricted interchannel flow (Figure 5.3).
This can have important implications with regard to their positive conveying efficiency
and the nature of mixing between the screws. Trapezoidal-shaped screws are generally
more effective in both these respects. Furthermore, with these designs, controlled material
stream splitting and combination can occur across the intermeshing zone [37].
Industrially, co-rotating, rather than counter-rotating intermeshing twin-screw extruders

are widely, but not exclusively, used for compounding a wide variety of polymer-based
formulations to specified quality standards. Counter-rotating twin-screw extruders with
tightly intermeshing screws have an established role in the extrusion of unplasticised
PVC dry-blends into pipe or other profile, on account of their exceptional conveying
efficiency using powdered feedstock and close temperature control. In conical form these
designs are ideally suited to the preparation of highly loaded woodflour-filled
thermoplastics composites, as discussed in Section 5.4. Non-intermeshing counter-rotating
designs have limited positive displacement action but, due to effective surface renewal of
melt, are especially helpful for efficient polymer devolatilisation.
226
An essential feature in most co-rotating twin-screw extruders used for preparing

particulate-filled polymer compounds, is the incorporation of special mixing elements
and screw designs, which enhance mixing or melting capability, depending on their location
in the screw profile. These frequently take the form of reverse-flighted screws, segmented
discs and, very frequently, bilobal or trilobal kneading elements. An alternative approach
to the same end is to use so-called barrel valves, which regulate material flow through
clearances of variable size.
With kneading elements, shear and mixing intensity is determined by the frequency of
lobes (two or three), the width and number of elements, their relative configuration,
(i.e., degree of stagger in a forward or reverse helical pattern), and the clearances
existing between the element tips and barrel wall. The action of kneading discs has
been analysed theoretically demonstrating the influence of element design and
configuration on mixture quality [35]. This treatment is particularly relevant to the
blending of particulate fillers into polymers and can provide useful pointers to the
optimisation of kneading-element assembly.
Under some circumstances, for instance during melt compounding of PVC formulations,
it can be beneficial to separate mixing and pumping functions of the extruder to minimise
shear heat input. This can be achieved by mixing material on a co-rotating twin-screw
extruder, before delivering the compound under low pressure into a cross-head single-
screw extruder running at low-speed, to pressurise material gently through a strand die
for pelletisation.
5.3.2.5 Ancillary Equipment
Ancillary equipment has an essential role to play in the preparation of filled polymer
compounds with reproducible quality. Firstly, delivery of the polymer plus additives into
the compounder must be accurately controlled. Often this involves weighing and pre-
mixing the ingredients, or sequential addition in batch processes, such as internal mixing.
Most twin-screw compounding extruders are starve-fed, where individual components
of the compound may be metered independently using volumetric or weigh-feeding devices.
The former rely on the use of dosing screws, hence output is highly sensitive to feedstock
bulk density. Weigh belt feeders deliver material on a mass basis and are therefore capable
of a much higher degree of accuracy. Loss-in-weight gravimetric feeders also use a
weighbridge principle but control the rate of weight change of the feeder hopper plus its
contents, relative to previously set parameters.
Melt filtration is commonly used during continuous melt compounding operations to

enhance product quality, by reducing adverse effects from contaminants or unwanted
227
material residues, which may be detrimental to visual appearance or adversely influence

material end-performance. This includes, for example, screening of polymer gel particles,
degraded polymer and poorly dispersed additive particles, such as pigment agglomerates.
This aspect will be discussed again (see Section 5.5.1) in relation to the effects of compound
quality on physical properties.
Many different melt filtration systems are available commercially ranging from simple
screen pack and breaker plate assemblies, which require the process line to be halted
every time the screen is replaced, to more sophisticated continuous screen changers,
where contaminated filter mesh is automatically moved away from the melt flow path
when the pressure drop across the filter exceeds a set level.
Particulate-filled polymer compounds generally leave the compounding stage in granular

or pellet form. Several routes are available for the conversion of polymer compound
from melt to solidified granule, for example, using a dicer for material produced as sheet
or strip, a pelletiser for compound made into continuous strands then cooled, or a die-
face cutter, where melt extrudate is cut by rapidly rotating knives at the die exit, then
cooled in circulating air or water. Die-face cutting is a particularly effective means of
compound pelletisation, when processing polymer compositions of limited melt strength,
(e.g., at significant filler loadings), and when throughput rates are very high, causing
possible difficulties in strand extrusion stability, as may be the case with large twin-
screw extrusion compounding lines.
5.4 Characterisation of Filled Compounds
5.4.1 Introduction
To obtain optimum additive efficiency in polymers, it is necessary to compound the materials

in the most appropriate manner to achieve defined property requirements, depending on
the end-application for the material. Thus for example, a pigmented compound may only
need to satisfy arbitrary and often non-quantifiable visual criteria, perhaps in terms of
colour uniformity and the absence of poorly dispersed additive, evident as streaks or regions
of high pigment concentration. However, electrically conducting compounds made from
polymers filled with conductive additives, such as forms of carbon black, must achieve a
much more stringent level of quality performance, defined in terms of the required electrical
properties. Polymers containing flame-retardant fillers are formulated to pass specified
testing procedures, which rate the material in terms of its ability to inhibit combustion.
Frequently, fillers such as hard minerals or soft rubbers are combined with polymers to
modify mechanical properties, such as elastic modulus or resistance to crack propagation
228
under impact loads. In these circumstances, the quality of the compound is assessed by
determination of specific mechanical properties. It is evident, therefore, that necessary
property measurements depend on the functional role of the additive, being strongly
influenced by the method of combination in the polymer and, in particular, by the form
of microstructure produced.
Of great relevance to filled polymer formulations, is the uniformity of particle distribution,

the degree of dispersion achieved and the interaction between the filler and matrix phases.
Other influencing factors include the presence of micro-porosity, reductions in the molecular
mass of the polymer, and changes to the form and level of crystallinity in semi-crystalline
thermoplastics. It can be beneficial to consider the measurement of quality in filled polymers
in terms of characterising these structural parameters, since, as will be considered later,
often an identifiable relationship exists with the compounding route used.
Measurement of mixture uniformity and, in particular, the level of filler dispersion is

generally considered of utmost importance. To this end, information can be obtained
from analysing the operating performance of compounding machinery through
measurement of residence time distribution, machine power input and pressure
development. Additionally, rheological analysis may be undertaken on filled polymer
melts, or solid specimens may be characterised using a variety of microstructural
identification techniques. There is an increasing interest in the development of quality
assessment techniques at the compounding stage, either in-line with the compound
produced, or on-line, through discontinuous measurement of diverted process flow stream.
Direct and indirect approaches more commonly used for determination of filler
compound quality are summarised in Table 5.1, together with pertinent measured
parameters and influencing factors. Further discussion of characterisation procedures
follows in Section 5.4.2.
5.4.2 Residence Time Distribution
Polymer feedstock and modifying additives entering continuous compounding machinery

at the same time will generally exit it at different times, depending on the extent of
longitudinal mixing experienced. This can be quantified using an appropriate tracer,
which is added to the feed stream (generally as a pulse) then measuring its concentration
in the output as a function of time [38, 39]. Subsequently, a residence time distribution
curve can be constructed, providing a record of the heat and shear history of material
passing through the compounder. This will be a function of the material composition,
the operating conditions used and, most importantly, the design of the compounder, in
particular clearances between screw flights in intermeshing twin-screw extruders, or the
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Table 5.1 Methods for the characterisation of filled polymer compounds

Characterisation method Measured parameter
Ashing
Dissolution Filler concentration
Ultrasonics
Screen pack analysis (pressure filter test) Filler dispersion
Light/electron microscopy Filler dispersion/distribution
X-ray radiography Wet-out
Image analysis Interfacial bonding (qualitative)
Filler dispersion
Rheometry (capillary/dynamic/melt- Polymer molecular mass changes
flow index) Effects of surface treatment on melt-flow
behaviour
Gel-permeation chromatography
Molecular mass changes
Solution viscometry
Infrared spectroscopy Chemical effects from polymer degradation
Physical property measurements
Filler dispersion/distribution
(mechanical, electrical, optical, colour, etc).
configuration of mixing elements present. Optimisation of residence time is most important

when processing heat-sensitive filler compositions or in reactive formulations, where
chemical activity can be influenced by the uniformity of heat exposure.
The residence time distribution of polypropylene-containing barium sulfate has been

determined through a co-rotating twin-screw extruder [40]. Filler was added as a pulse
into the feed stream, and its concentration in the extrudate determined by ashing and
weighing material collected at different time intervals. Results were expressed as an internal
age distribution (or 1-F()) function representing the quantity of filler remaining in the
compounder at increasing times, actual time being normalised against the mean residence
time (). More accurate determination of residence time was achieved by neutron
activation analysis using a radioactive tracer.
Residence time distribution measurements not only generate information about the
processing history of a polymer, but have also been used to characterise the conveying
and self-cleaning efficiency of compounding machinery.
230
Table 5.2 Specific energy consumption values for pigment concentrates

produced on co-rotating intermeshing twin-screw extruders (adapted from [42])
Specific energy
Polymer Pigment* consumption
(kWh kg-1)
LD polyethylene 75% TiO2 + 12.5% wax 0.11
LD polyethylene 60% TiO2 0.17
LD polyethylene 40% carbon black 0.31
Polypropylene 30% organic blue pigment + 10% TiO2 0.70
Polypropylene 20% inorganic yellow pigment 0.80
Polystyrene 50% TiO2 + lubricant 0.10
Polyester 20% organic blue pigment 0.18
Polyamide 6 35% TiO2 0.22
*Additive additions in % by weight.
5.4.3 Specific Energy Input
Specific energy consumption may be expressed as the ratio of the required power input
to the effective material throughput and is expressed in kWh.kg-1 [41]. Since mixture
uniformity is sensitive to specific energy input, measurement of this parameter can provide
an indirect indication of overall product quality for a particular compounding process.
With filled polymer formulations, specific energy input depends on the melt rheology
during compounding, in addition to machinery design and operating conditions, such as
temperature, screw, rotor speed, and degree of fill. Table 5.2 lists specific energy input
values for various pigment masterbatch formulations prepared on co-rotating intermeshing
twin-screw extruders.
5.4.4 Screen Pack Analysis
A direct approach for the assessment of additive dispersion, is to analyse pressure

development in polymer melt flowing through a screen pack of defined restriction. This
so-called pressure filter test has been specifically applied to pigment-containing
compositions, where a premix of pigment masterbatch and virgin polymer (with total
pigment content of 4% by weight) is melted in an extruder then metered through a
screen pack using a gear pump. Pressure developed in front of the screen is monitored
231
and plotted as a function of time. The test is completed either when a pressure of 12 MPa
is reached or after 90 minutes [42]. A pressure filter value (DF) can be calculated from:
(Pmax P0 )F 100
DF =
tKG
(Pa cm 2
g 1 ) (5.4)
where Pmax is the final pressure (Pa), P0 the pressure using unpigmented polymer (Pa),
F the screen area (cm2), t the measuring time (min), K the pigment concentration (%)
and G the mass throughput (g. mm-1). A low value of DF is indicative of good dispersion.
A similar approach has also been considered for on-line measurement of dispersion in
a 40% by weight-pigment masterbatch, by analysing the side-stream output from a co-
rotating twin-screw extruder [43]. Although emphasis has been given to the use of this
technique in analysing pigment dispersion, it may also be suitable for use with other
filled polymer compositions.
5.4.5 Rheological Analysis
Rheological data can provide useful information about the influence of filler type, content
and surface treatment on the overall melt viscosity of polymer containing particulate
additive. Many reports exist describing these effects [44-46].
At high shear rates, changes in shear viscosity may correlate with variations in filler content.
However, often these become most evident at very low shear rates, as do apparent differences
in the level of structure formation within the filled composition. Low shear viscosity is
conveniently undertaken using a parallel plate rheometer oscillating at low angular
frequencies. When applied to a study of polypropylene containing calcium carbonate fillers,
using particles of 4 m mean diameter, dynamic storage modulus (G) was found to increase
with filler loading up to 30% by weight, although little difference was seen in the value of
G at low frequencies [47]. However, with finer (0.25 m mean diameter) calcium carbonate
particles at a filler loading of 30% by weight, a noticeable increase in G was observed,
which was attributed to increased filler agglomeration in this composition.
Similarly, with polypropylene containing different forms of magnesium hydroxide filler, but
at the same level of addition, their behaviour at low shear amplitudes can be distinguished,
resulting from the relative interaction between the particles (Figure 5.4). Beyond a critical
level of shear, dependent on the filler type and whether or not the filler is surface treated,
structural changes occur, which are attributed to reduced particle agglomeration.
On-line rheometers are also available, suitable for use with continuous compounding
lines, such as co-rotating twin-screw extrusion processes. Exploratory work has been
232
Figure 5.4 The relationship between dynamic storage modulus and angular frequency
for polypropylene containing uncoated magnesium hydroxide fillers
(60% by weight filler)
reported using this approach with thermoplastics pigment concentrates where on-line
rheological measurements have demonstrated that changes in additive concentration can
be accurately determined [43].
5.4.6 Ultrasonic Measurement
Ultrasonic methods have been considered for non-destructive evaluation of compositional

changes and mixture uniformity in filled polymers. In principle, it is feasible to determine
the size, shape and distribution of filler particles, to detect agglomeration and to assess
the extent of filler-matrix interaction, through appropriate application of ultrasonic
procedures [48]. The method involves determination of the elastic behaviour of solids by
measurement of ultrasonic wave velocity. Propagation of a plane wave in a linear elastic
material can be related to its elastic modulus (E) and density () according to:
12
E
V= (5.5)

where V is the ultrasonic wave velocity. It also follows that the wave transit time through
the material (ts) can be determined from:
233
ls
ts = (5.6)
V
with ls , being the transit distance.
Off-line ultrasonic studies have been undertaken on calcium-carbonate-filled

polypropylene injection mouldings at a frequency of 5 MHz [49]. Over filler levels between
0% and 40% by volume, correlation was observed between the compression velocity of
the ultrasound and filler loading (Figure 5.5). The non-linear behaviour shown was
attributed to the relative effects of calcium carbonate filler on the density and elastic
properties of the composite. Compressional wave velocity appears to be influenced more
by density changes at low concentrations and by changes to elastic properties above a
threshold concentration value [50]. From this study it was also concluded, using ultrasound
and microfocus radiography, that the filler particles were uniformly dispersed, mostly
with dimensions much less than /4 ( being the wavelength of the compressional waves),
i.e., agglomerates or voids above 100 m were largely absent.
Earlier attempts to apply ultrasonic wave-velocity measurements to in-line determination

of filler concentration during compounding met with mixed success, however. In one
study [51], measurements were undertaken by measuring ultrasonic transit times across
Figure 5.5 The influence of calcium carbonate filler loading on ultrasonic

compressional velocity through polypropylene injection mouldings
234
polymer melt passing through a rod-die. In contrast to off-line measurements on solid

materials, fluctuations in ultrasonic velocity increased substantially with increasing filler
concentration. Inaccuracies in the in-line results were attributed to two causes, instrument-
and process-related errors. These included limitations due to triggering of the electronic
timing circuit of the particular instrument used and a lack of resolution of real transit
time measurements. Further contributing factors to the lack of reproducibility were the
sensitivity of ultrasonic transit time measurements to changes in melt temperature and
pressure (no attempt was made to compensate for such fluctuations) and real changes in
filler concentration observed, particularly at higher filler loadings.
In another study, in-line measurements of polyethylene melt containing 20% by weight of

glass beads of different sizes, were undertaken. Focused ultrasound was used to detect the
presence of particles with diameter greater than 50 m [52]. More recently, using magnesium
hydroxide filled low density polyethylene (LDPE) and high density polyethylene (HDPE)
polymer melts, in-line ultrasonic measurements have been made to determine the effect of
melt temperature, pressure and filler concentration on ultrasonic velocity through the melt
[53]. Tests were also carried out on static samples of melt under conditions of no flow and
used in combination with extrusion processing data to predict filler concentration. It was
found that ultrasonic velocity was most sensitive to changes in temperature, least affected
by pressure and decreased with increasing filler concentration.
5.4.7 Microstructural Analysis
The most common approach to the assessment of quality in particulate-filled polymer

composites is by direct observation of microstructure, using a variety of analytical techniques,
including light, electron-optic and X-ray methods. For example, BS2782 (Methods 823A
and 823B) [54] describes the determination of carbon-black dispersion in polyethylene
using transmitted light microscopy, however, the procedure is highly subjective.
The choice of techniques and their application is complicated by the aims of the analysis
and whether or not this is quantitative. Scanning electron microscopy (SEM), for example,
is widely applied to assess the extent of interfacial adhesion in filled polymer composites,
usually through examination of fracture surfaces. However, the information obtained is
generally non-quantitative, although estimates of interfacial shear strength are possible
from fibre pull-out measurements in short-fibre reinforced polymer composites [55].
In semi-crystalline thermoplastics, it is well known that particulate additives can strongly

influence polymer morphology and hence physical properties [56]. Indeed, some particulate
additives, such as sodium benzoate, are deliberately added to polymers to improve
mechanical properties or clarity, through controlled nucleation of the melt during cooling.
235
Morphology of the polymer at and away from the surface of the additive particles, is
conveniently determined by polarised light microscopy and, where higher resolution is
required, by electron microscopy. More detailed consideration of the effects of
particulate additives on polymer crystallinity is presented elsewhere in this book.
Since the state of additive distribution and dispersion is generally of prime concern in
the preparation of filled polymer compositions, attention will be focused on this aspect
of characterisation.
An initial requirement is to select a portion of the material that is representative of the

sample as a whole. Macroscopic examination, perhaps at low magnification, can
establish whether unusual features, such as voids or regions depleted in additive, are
present. Of crucial importance then is the method of specimen preparation in relation
to the chosen characterisation technique, in order to highlight contrast between the
phases present. This requires specialised expertise, for example using staining or selective
etching procedures to achieve satisfactory results, depending on the components present
in the system. Examples are presented below, to illustrate some possibilities available
for the characterisation of dispersion in filled polymer composites, with specific reference
to polypropylene containing 40% by weight of calcium carbonate filler [57].
Specimen preparation techniques include isolation of the filler through removal of the
polymer by ashing or dissolution. However, this introduces the probability of changes
in particle structure. Microtomy (at room or preferably at sub-ambient temperatures),
pressing at elevated temperature, or controlled deformation of thin sheet using
compressed air (bubble blowing), are all possible methods for producing thin specimens
(5-10 m thick), suitable for examination by transmission techniques. Frequently the
former approach is the preferred option, although with materials containing high levels
of poorly bonded filler, particle pull-out is a common problem.
Specimen polishing, for example, using successively finer grades of diamond paste,
provides an alternative preparation method for surface examination. Filler particles
may be subsequently etched, however, this can complicate interpretation of the image
produced, since air voids contained in the structure may be indistinguishable from
extracted filler.
From the array of microstructural analytical methods available, light microscopy may
be conveniently applied in transmission or reflection modes to identify the presence of
particle agglomerates. In transmission, errors due to particle overlap through the
specimen thickness must also be considered. SEM and transmission electron microscopy
(TEM) give a much greater degree of resolution, which is useful when working with
very finely divided fillers, or when details of agglomerate structure are required, e.g.,
236
with pigments. When combined with elemental analysis, the compositional identity of
unusual features or structures can be confirmed. X-ray microradiography has been
widely applied to assess orientation distributions in short glass fibre-reinforced
thermoplastic mouldings [58, 59], titanium dioxide filler dispersion in polymers [60]
and is equally applicable to the study of mixture quality in other particulate-filled
thermoplastics compositions, including the presence of calcium carbonate. It should
be appreciated from this overview of microstructural characterisation methods, that
many variations of these techniques exist, which can be applied to enhance additive
contrast or yield greater information on structural hierarchy.
Whilst the qualitative analysis of filler dispersion in polymer composites poses its own
difficulties, quantitative evaluation of mixing in these systems creates further challenges.
Firstly, to establish the spatial location or size distribution of the additive, a statistically
representative number of particles must be examined, preferably from various fields of
view within the specimen. Providing there is sufficient contrast between the phases, as
is discussed later, automatic image analysis techniques can be applied to rapidly
assimilate and process data. Secondly, additive particles frequently have an irregular
geometry and may also be exposed in a two-dimensional array at sections other than
their mid-point, (i.e., only the tips of the particles may be on view). Thirdly, there is
the question of how to define mixing and express this numerically.
With reference to the last mentioned point, extensive literature exists on the theoretical
representation of mixture quality [38]. With polymer-based systems containing
particulate fillers, diffusive mixing is generally absent and it is necessary to consider
the relative positioning of the components, together with their clumpiness in the mixture.
The intensity of segregation defines the extent to which the composition at each point
differs from the average concentration in the mixture and may be determined through
measurement of the variance:
(C )
1 2
S2 = i C (5.7)
N 1 i =1
where
N
1
C=
N C
i =1
i (5.8)
i.e., from a randomly sampled mixture, N measurements of concentration Ci are made,

giving C as the average concentration.
237
Intensity of mixing (I) is then represented as:
S2
I= (5.9)
S20
where S02 is the variance for total segregation of the components, given by:
(
S20 = C 1 C ) (5.10)
Scale of segregation also has statistical origins and relates to the size of clumps in a
mixture. It is based on the idea of correlation of concentrations between nearby points in
a mixture. The correlation coefficient R(r) can be determined as a function of r (a chosen
distance between pairs of points in the mixture), namely:
( C ( x ) C )( C ( x + r ) C )
1
R( r ) = i i (5.11)
S2 N i= 1
The graphical representation of the relationship between R(r) and r is termed a correlogram
and the linear scale of segregation (SL) representing the average size of the clumps, defined
as the area under the correlogram:

SL = R(r ) dr
0
(5.12)
A related volume scale of segregation can also be written.
Polymer mixtures containing deformable components tend to contain streaky or layered

structures resulting from laminar shear flow. In such cases, the striation thickness (the
distance between the streaks) can be measured to provide an indication of degree of
mixing. As mixing progresses, a decrease in striation thickness is accompanied by an
increase in interfacial area between the components. Reductions in striation thickness
will depend on the level of imposed shear strain and the orientation of the components
relative to the direction of shear [38].
Returning to the quantitative analysis of mixture quality using image analysis, a digital
representation of the mixture can be obtained by direct attachment of a video camera to
a microscope containing the sample under investigation or, if necessary, by viewing
previously prepared micrographs of the specimen. The camera signal is transferred to a
video digitiser, which divides the picture into many thousands of small rectangular units
238
(called pixels) and numerically measures the light intensity in each area, according to a
defined scale of grey levels. The image can then be processed by relating the light intensity
at each pixel to the mixture composition at that position. The digital image obtained is
stored in a computer and may be conveniently analysed using appropriate software to
generate numerical quantities, which describe the quality of the mixture.
The technique can be applied to the study of mixing (and specifically the degree of
dispersion) in polymer compositions containing particulate fillers. For example, reflected
light images of polypropylene containing 40% by weight of calcium carbonate filler
have been examined to assess the level of additive dispersion [57]. To overcome the
difficulties mentioned earlier of irregular particle shapes, recorded particle areas obtained
from the raw count data were converted to equivalent spherical areas (expressed as the
number of particles per unit area) and plotted as a function of particle diameter. These
data were transformed into the number of particles per unit volume and accounting for
sectioning errors by applying the Schwartz-Saltykov diameter analysis, which assumes
that the view in two dimensions is statistically repeated in the third dimension [61].
Since it was the small number of larger particles and agglomerated structures, which
were of interest in this study, results were then expressed as a distribution of the volume
of particles per unit volume. A mean volume diameter from this distribution can provide
a single number to describe average level of dispersion. Analysis of the data can also
provide information about concentration fluctuations of the minor component within
and between different fields of view, and hence the variance of the mixture.
Other approaches have been reported for mixture analysis of digital images including
the use of fast Fourier transform algorithms as a means of determining correlation
coefficients [62].
5.4.8 Miscellaneous Methods of Analysis
A variety of other analytical techniques have been considered for the assessment of mixture
quality in filled polymer compositions following compounding, in both off-line and in-
line situations. It has been suggested, for example, that nuclear magnetic resonance (NMR)
imaging could provide a non-destructive three-dimensional technique, which might be
used to determine the spatial distribution, chemical nature and physical characteristics
of components in highly filled polymer mixtures [63]. Using high loadings (60-70% by
volume) of ammonium sulfate powder in an acrylonitrile-terminated polybutadiene
matrix, proton NMR images were obtained, which together with measurements of the
relative incidence of grey levels within the image, provided a means for assessing the
spatial location and degree of dispersion of the additive phase.
239
Radiometric density measurements using specially developed sensors have been proposed
for on-line monitoring of pigment or filler additive levels, which together with feedback to
additive and polymer dosing units, could enable accurate control of additive concentrations
[64]. The technique does not provide spatially resolved information, however, and may be
less applicable when blending together several components of similar densities.
In-line Fourier transform infrared spectrophotometers can provide both qualitative and
quantitative information about additives during continuous processing, in addition to
determining possible structural transformations occurring. This may be particularly useful
during reactive compounding operations, for example, to assess degree of grafting of
vinyl methoxysilane to polyethylene chains [64].
Details of an on-line procedure for colour control during compounding have been given
[65]. Pigmented pellets from a twin-screw extrusion compounding line are diverted to an
adjacent injection moulding machine to prepare test plaques. These are transported
automatically by robot to a spectral photometer, where colour intensity is measured and,
if necessary, to maintain consistent quality, subsequent automatic adjustments are made
to the rate of colourant addition at the compounder. The whole system is centrally
computer controlled.
Instrumentation for direct on-line analysis of particulates in polymers is in commercial

use, for detection and sizing of additive agglomerates and impurities, such as polymer
gels [66]. Intense light is transmitted through a stream of polymer melt and, using a
shadowgraph principle, particle images detected on the other side. These are then analysed
by a real-time high-speed computer, enabling the particles to be counted and classified
according to their size range. Particles as low as 5 m in size can be resolved by this
method.
5.5 Process Enhancement of Particulate Polymer Composites
The interrelationship between compounding route, compound micro-structure and

properties is less well documented, due in part to a limited understanding of what is
happening inside the compounder and, in many instances, to incomplete characterisation
of the processed materials. With particulate-filled polymer compositions, however, the
effects of poor compounding practice can be profound. For example, mechanical
properties, such as fracture toughness and strain to failure under tensile deformation,
are very sensitive to the state of filler dispersion and the size of additive inclusions. The
aesthetic qualities of pigmented polymers are also dependent on the level of mixing
experienced, which may result in specks or streaks in unfavourable cases. Electrical
conduction pathways in polymer compounds containing conductive fillers, such as carbon
240
black or metal powders, critically depend on the relative association of the additive
particles and their level of dispersion.
The effectiveness of functional fillers, such as flame retardants, heat and light stabilisers,
can be markedly enhanced through optimisation of mixing procedures during
compounding. This may even allow additive content to be reduced, whilst maintaining
an acceptable level of performance.
In most of the situations outlined previously, there is a need to ensure high levels of
additive dispersion together with uniform spatial distribution within the polymeric phase.
The conditions needed to achieve this state may result in excessive degradation of the
polymer, however, resulting in a loss in properties of the composite as a whole. Similarly,
hollow glass microspheres used in the preparation of syntactic foams and brittle reinforcing
additives of high aspect ratio, such as glass fibres and platey minerals, may experience
severe damage during compounding, again leading to inferior product quality.
Examples of filled polymer compositions are discussed, where the role of the preparation
method has been clearly identified in relation to compound structure and end properties.
Particular attention is also given to recent developments in the field of natural fibre-filled
composites, supercritical fluid assisted processing of filled polymers, re-use of thermoset
recyclate fillers and silicate layer polymer nanocomposites.
5.5.1 Addition of Rigid Particulate Fillers
Mineral fillers can change the physical properties of polymers in several ways. Firstly,
the particle characteristics (size, shape and modulus) can have a significant effect on
mechanical properties. Whilst most minerals have a large modulus relative to the polymer,
a wide range of sizes and aspect ratios may be encountered. Secondly, the filler may
cause a change in the micromorphology of the polymer by acting as a nucleant, thereby
altering the amount or type of crystallinity. Both of these effects can be influenced by
compounding route.
It is well known that to achieve good impact strength in mineral-filled thermoplastics

composites, effective dispersion of the filler is of overriding importance.
For a linearly elastic material the fracture stress (F) for a plate containing a sharp crack
of length a is given by [67]:
12
2E
F = (5.13)
a
241
where E is the Youngs modulus, is the surface energy and a the crack length. A large
aggregate will constitute a flaw, which will reduce the stress needed to cause the
composite to fracture and fail. For a material subjected to a uniform tensile stress, the
calculated values of stress introduced in the region of an elliptical flaw in an otherwise
homogeneous matrix, can be described as a function of the major:minor axis ratio of
the ellipse [68].
From this analysis, it is clear that high aspect ratio filler particles, which are needed to
achieve stiffness in a composite will inevitably cause increased stresses in the polymer
matrix near the particle edges, which will facilitate failure under impact loads.
A systematic investigation has been given detailing the effects of filler dispersion on the
mechanical properties of calcium-carbonate-filled polypropylene composites prepared
using different mixing conditions [69]. Dispersion index, expressed in terms of the size
and number of agglomerates, was found to have no effect on tensile modulus, tensile
yield strength and notched Izod impact strength over the specified levels of dispersion
achieved. However, ultimate tensile strength and, most dramatically, falling weight impact
strength increased with improved filler dispersion. With the latter mentioned property,
extensive toughening of the composite was found when the particles were well dispersed
but, significantly, a transition to brittle failure occurred as dispersion deteriorated.
Filler dispersion is influenced by many factors, including polarity of the matrix, surface
treatment applied and the magnitude of shear stress experienced during compounding.
For example, differences have been reported in impact strength of polypropylene filled
with calcium carbonate subjected to low-intensity single-screw compounder and a high-
intensity twin-screw extruder. In this work there was clear evidence of filler agglomeration
present in the former sample [67].
The change in filler dispersion at different positions along the screws of a co-rotating
twin-screw extruder, has been determined by image analysis on polished specimens. A
marked increase in dispersion was observed in the region of polymer melting, where
intense shear is generated at the solid-melt interface [70]. Factors found to be detrimental
to filler dispersion include the presence of moisture and applied pressure, causing an
increase in inter-particle adhesion.
In cases where elimination of agglomerates is essential to ensure that optimum compound

properties are achieved, melt filtration can be used. This is important in pigment
masterbatch production or in coloured compounds to be spun into fibres, where
agglomerates can lead to fibre breakage. Removal of impurities or large defect particles
by melt filtration can also increase the fatigue life of HDPE pipe and the resistance to
breakdown of polymer subjected to an electrical stress [71, 72].
242
More subtle differences in the properties of filled polymer compounds result from changes to
the micromorphology of polymer surrounding the filler particles. For calcium carbonate-
filled polypropylene a correlation has been observed between falling weight impact strength
and onset temperature of crystallisation when cooled from the melt. High onset crystallisation
temperatures were associated with composites having poor impact strength [73]. The origin
of this effect is not fully understood but may be related to the capacity of the filler to nucleate
crystals, and has been shown to be sensitive to the method of compounding adopted.
Blending together thermoplastics and rubber modifiers is an established means for

enhancing toughness. Whilst the properties of the blend depend on the nature, amount
and distribution of each phase present, the compounding procedure used can also have
an important influencing role. In the following example, polypropylene modified with
30% by weight of ethylene-propylene diene terpolymer rubber was prepared on single-
and twin-screw extruders under conditions of differing mixing intensity [74]. Compounds
made from this formulation exhibit phase separation, with rubber particles dispersed in
the polypropylene matrix. However, the extent of this dispersion and the effect of the
rubber on properties was found to be sensitive to the compounding conditions adopted.
Notched impact strength of the polypropylene increases significantly when rubber particles
are present, however, dramatic differences were apparent between materials made on the
different types of extruder, results being superior using the twin-screw compounder. In
the case of the single-screw extruder, perhaps surprisingly, filler dispersion decreased
with increasing screw speed, however, this was attributed to the much greater viscosity
of the rubber relative to the polypropylene (it was noted that improved rubber dispersion
was possible using an optimum viscosity ratio, i.e., close to 1).
Properties of a compound, made on the twin-screw extruder showed some sensitivity to

screw speed, screw profile (shear intensity) and mass output rate, with the best results
obtained using a high screw speed and low material throughput. Blend homogeneity and
impact resistance were closely related to the energy input through the compounder drive.
It was also recorded, however, that examination of impact strength after injection moulding
revealed much less difference between the various forms of compounding procedure used.
5.5.2 Effects on Polymer Molecular Weight
Frequently, during compounding, the attention given to achieving good dispersion or

distribution of a filler phase within a polymer matrix can result in generation of high
melt temperatures and excessive shear. Whilst these conditions may be beneficial in
obtaining compositional uniformity, they may also be detrimental to the polymer structure,
243
resulting in chain scission and a consequent reduction in mechanical properties. This

may be particularly evident if the material is processed more than once, as is the case
with recycled compounds.
The sensitivity of molecular weight changes in polystyrene and polypropylene to

compounding procedure using a co-rotating twin-screw extruder have been reported
[75]. Variables considered were melt temperature, screw speed (hence shear rate) and
screw profile. Polystyrene was considered to degrade more by mechanical degradation at
lower melt temperatures and by thermal means at high values, whereas polypropylene
showed a much greater tendency to degrade during compounding, with thermo-oxidative
degradation being the dominant mechanism.
5.5.3 Short Fibre-Reinforced Thermoplastics Composites
To maximise the mechanical properties of short fibre-reinforced thermoplastic composites,

it is necessary to achieve effective stress transfer between fibre and polymer matrix and
appropriate fibre alignment in the finished component relative to the direction of applied
stress. The former requirement is governed primarily by the method of compounding,
whilst fibre orientation is very dependent on moulding conditions [76].
Hence, during compounding, it is generally desirable to obtain the longest possible well-
wetted fibres in the polymer. However, common fibre reinforcements (glass and carbon)
are very brittle, showing a marked tendency to break during melt blending. This problem
is exacerbated as the fibre loading is increased and under intense mixing conditions
needed to achieve good fibre wet-out. Thus, fibres entering the machine with 6 mm
lengths will generally end up no longer than about 500 m in the final compound.
Steps can be taken to minimise this problem through attention to screw profile (in extrusion
compounders), the location of addition (preferably by feeding through a downstream
port into the melt in extruders and continuous internal mixers), and the melt temperature
and shear rate experienced.
With aramid fibres (Kevlar), similar considerations are necessary. Although these fibres
are not brittle in the same way as glass or carbon, they can suffer serious damage during
over-intensive compounding, manifested by fibrillation (or fibre splitting) and kink (or
shear) bands formed along the fibre length (Figure 5.6).
Whereas qualitative information about the level of interaction between fibre and matrix
can be obtained by electron microscopy, various methods are available for quantitative
evaluation of fibre-matrix interfacial shear strength in thermoplastics and thermoset
polymers [55]. Table 5.3 shows interfacial shear strength and critical fibre length values
244
Figure 5.6 Scanning electron micrograph of aramid fibre-reinforced polyamide 6,6

fracture surface. Compound was prepared in a co-rotating twin-screw extruder.
Table 5.3 Critical fibre length and interfacial shear strength values for glass-fibre
reinforced polypropylene compositions determined by a single-fibre
fragmentation technique (adapted from [78])
Fibre diameter Silane surface Critical fibre Interfacial shear
Fibre
(m) treatment length (m) strength (MPa)
A 13 Type 1 650 34.0
B 18 Type 2 (1%) 950 31.9
C 18 Type 2 (1.75%) 860 35.6
D 18 Type 2 (2.5%) 660 46.4
E 9 Type 2 (2.5%) 760 20.1
F 10 No treatment* 750 22.7
**
G 10 No treatment 650 26.2
*
Transcrystallinity present at fibre-polymer interface.
**
No transcrystallinity.
Ultimate tensile strength of fibres assumed to be 3.4 GPa.
245
Table 5.4 The effect of compounding route in the average fibre-matrix

interfacial shear strength of glass-fibre-reinforced polyamide 6,6 mouldings
Compounding route Interfacial shear strength
(MPa)
Co-rotating twin-screw extruder (high-intensity profile) 33
Co-rotating twin-screw extruder (low-intensity profile) 26
Pultruded compound (long fibre material) 22
Notes:
1. Direct measurement of interfacial shear strength by single fibre fragmentation
technique 46 MPa.
2. Shear yield strength of matrix 48 MPa.
for different fibre forms, surface treatments and microstructural effects in a polypropylene
matrix, when determined by a single fibre fragmentation technique [77].
Average values for interfacial shear strength can also be obtained by analysis of stress-
strain curves determined from compounded materials [78]. This approach can distinguish
between the effects of compound preparation method on interfacial shear strength and
hence degree of fibre-matrix interaction (Table 5.4).
5.6 Woodflour and Natural Fibre-Filled Thermoplastics
There is currently widespread commercial interest in the use of natural fibres as reinforcing
additives for thermoplastics. Within Europe, flax and hemp reinforced polypropylene are
being increasingly used for automotive applications, normally as mats interwoven with
polypropylene fibres, then compression moulded into products such as door liners and
parcel shelves [79]. Shorter forms of these fibres have also been developed as reinforcements
in injection moulding compositions [80, 81]. The driver for these applications stems from
the high specific mechanical properties of the natural fibres, yielding weight savings in
parts, and the fact that they are derived from renewable resources.
In the USA, and to an increasing extent in Europe, woodflour filled thermoplastics are being
used as wood substitutes, in areas such as decking and window frames [82]. Although still
fibrous in character, their aspect ratio is generally no greater than 4:1, hence their reinforcing
potential is limited. In these compositions, filler loadings may be as high as 80% by weight,
necessitating special processing measures and inclusion of processing aids to facilitate flow.
246
Common to the preparation of natural fibre-reinforced thermoplastics made by melt

processing, is the need to maximise fibre-matrix interfacial bonding, minimise the moisture
content and heat history of the organic filler and reduce odour arising from exposure to
processing temperatures of around 200 C.
Frequently, MA modified polypropylene is introduced into polypropylene compositions

to aid fibre bonding to the matrix [83], which also gives these composites greater resistance
to moisture pick-up in processed composites. For outdoor applications, polyethylene is
the preferred matrix due to its greater ultraviolet stability than polypropylene. Other
methods reported for enhancing fibre-matrix bonding include the use of silane treatments,
fatty acids (which also assist processibility) and modification of the fibres by corona
discharge, or more speculatively, by acetylation [84, 85].
Pre-treatment of natural fibre-reinforcements can be difficult and often inappropriate,

due to their variable physical nature and the fact that new fibre surfaces are exposed
during transport through high intensity polymer processing equipment. In situ treatment
of fibres can therefore be more effective, either using maleinised polypropylene or
polyethylene as mentioned above, or with liquid surface treatments, by drip feeding
these into the melt during processing or by using porous carriers added in granular form
containing absorbed surface modifying additive.
Since the presence of moisture can result in porosity in processed material, this can be
removed by pre-drying the additive before processing, downstream melt devolatilisation,
for example during extrusion of profile, or by use of low moisture content filler, available
from some manufacturers.
There have also been technological developments, which facilitate processing of natural
fibre-filled thermoplastics. Figure 5.7 demonstrates an integrated extrusion compounding
procedure, which enables pulping of natural fibres during the first part of the process,
where moisture can also be extracted and surface treatment added. Polymer melt is then
introduced through a downstream feed port, using a secondary extruder, for combination
with the fibres before die-forming into profile or pellets [86]. Conical twin-screw extruders
are also being used to perform a similar function, with the advantage that the high volumetric
capacity of their feedthroat assists in the introduction of low bulk density organic filler.
Direct compounding injection moulding technology (Figure 5.8), which combines the
stages of twin-screw extrusion compounding and injection moulding into a unified process
unit, offers the advantage of reduced heat input to thermally sensitive fillers. Although
proposed originally in the 1960s, then developed commercially for injection moulding
of ceramics and highly filled polymer formulations [87, 88], this concept has recently
been proposed for moulding natural fibre-filled thermoplastics [89].
247
Figure 5.7 Integrated polymer compounding procedure
Figure 5.8 Direct compounding injection moulding machine
For automotive use, natural fibre-filled thermoplastics must meet odour and emission
standards specified by car manufacturers [90]. These requirements can be achieved
248
using proprietary odour suppressants, use of purer natural fibres (with reduced lignin
and pectin content) and most importantly, by minimising thermal exposure of the fibres
during processing.
5.7 Supercritical Fluid Assisted Processing of Filled Compounds
Supercritical fluids are neither in the gaseous or liquid state and can be formed above a
critical temperature and pressure. For example CO2 becomes supercritical above a temperature
of 31 C and a pressure of 7.3 MPa. Under these conditions supercritical fluids can provide
a more environmentally acceptable alternative to organic solvents and have consequently
found widespread application in a range of process industries, such as extraction aids in
both pharmaceutical and food preparation [91-93].
There is also much potential for the application of supercritical fluids in polymer processing
due to the unique ability of supercritical CO2 (scCO2) to impregnate, extract from, and
modify the behaviour of polymers [94]. The use of scCO2 is particularly well established
for the preparation of microcellular foams from polyolefins and other commodity plastics
[95, 96]. Additionally, dissolution of scCO2 in polymer melts can strongly plasticise the
material, yielding significantly reduced viscosities [97-99] The likely explanation for this
effect is a shift of the glass transition temperature to lower temperatures.. It has also been
reported that addition of supercritical fluids during melt processing can improve the
miscibility of polymer blends. For example, the viscosity reduction of polystyrene
containing scCO2 was found to be greater than that measured for polyethylene, enabling
greater similarity in the viscosity of these polymers when combined as a mixture [100].
The implications of these effects to the processing of filled thermoplastics is profound,

since by reducing the melt viscosity, processing temperatures and/or pressures can be
lowered, providing faster throughput rates, less thermal damage to heat sensitive fillers,
or allowing increased filler levels without compromising processibility. Although at a
preliminary stage, these benefits have been demonstrated using in-line extrusion rheometry
using polymers containing glass beads and ceramics injection moulding compositions,
containing high levels of filler dispersed in a sacrificial polymer binder [101]. Figure 5.9
demonstrates this effect using silicon carbide/polyethylene mixtures. It was also found
that under certain process conditions and using low scCO2 addition levels, foaming could
be prevented as the mixture emerged into a lower pressure environment at the exit of the
die. Furthermore, this approach has also been adapted to the injection moulding process
with, for example, highly filled particulate biomedical composites and melt processible
ceramics formulations [101, 102]. Products were moulded in either a foamed or
unexpanded state as required, by judicious control of processing parameters, in particular
the mould cavity pressure.
249
Figure 5.9 Supercritical fluid assisted processing of filled polymer compositions. Blend
of 50% by volume silicon nitride/polyethylene extruded at 180 C
5.8 Processing of Thermoset Recyclate Waste Materials
Whereas thermoplastics can be mechanically recycled at end of product life, thermosetting

plastics are infusible and cannot be reprocessed by this means. Apart from landfill, which
is becoming increasingly expensive and environmentally unacceptable, strategies for
disposing or reusing these materials are mostly limited to incineration or comminution, for
subsequent application as a low cost filler. Polyester, epoxy or phenolic resin based
compositions generally contain high levels of non-combustible fillers, reinforcing fibres
and often, fire retardants, hence the calorific value of these materials is generally low.
Nevertheless, their incorporation in cement kilns is one option, which has been considered,
where fuel costs are reduced by combustion of the polymer phase and inorganic components
are incorporated into the cement mixture. Using specially designed fluidised bed reactors
combustion of the polymer and recovery of reinforcing glass fibres is also feasible [103].
The reduction in glass fibre strength during combustion limits their reuse as a reinforcement
for polymers however. Preliminary work on the combustion of carbon fibre containing
thermosets shows greater potential, since these fibres are inherently stronger, stiffer and
more valuable. Oxidation and loss of strength is small at temperatures and low exposure
times around 500 C, resulting in fibre properties similar to virgin glass [104, 105].
250
Controlled comminution of thermoset waste, for example using a hammer mill, can
yield so-called microcomposite particles, containing a mixture of glass fibres, mineral
fillers and thermoset resin. With appropriate surface treatment technology, they can be
applied as low cost reinforcing additives for thermoplastics [106-108]. Table 5.5 compares
mechanical properties of polypropylene, with various filled compositions, in each case
containing 30% by weight of filler. Polyester and phenolic recylates used in this study
included 5% and 24% of glass fibres, respectively, which is reflected in the different
reinforcing efficiencies of these systems.
Table 5.5 Mechanical properties of PP-thermoset recyclate composites at 23 C

Glass in Tensile Tensile Notched Charpy
Composition* composite, strength, modulus, impact strength,
wt% MPa GPa J mm-2
PP - 26.5 (0.3)** 1.8 (0.1) 7.7 (0.7)
PP-CaCO3 - 20.4 (0.1) 2.1 (0.2) 3.2 (0.5)
PP-Glass fibre 30 72.3 (0.6) 7.7 (0.4) 5.4 (0.20)
PP-DMC untreated 5 18.4 (0.9) 2.7 (0.3) 2.4 (0.2)
PP-DMC treated 5 29.1 (0.1) 3.1 (0.1) 2.4 (0.2)
PP-GWP untreated 24 28.9 (0.2) 5.2 (0.6) 4.7 (0.2)
PP-GWP treated 24 62.1 (0.4) 5.1 (0.2) 7.4 (0.2)
*
30 wt-% filler; GWP = glass (woven fabric) phenolic recyclate.
**
Figures in parentheses show standard deviations.
5.9 Preparation of Silicate Layer Polymer Nanocomposites
Silicate layer polymer nanocomposites consist of delaminated clay platelets with ultimate
dimensions around 1 nm x 500 nm, that are well dispersed in a continuous polymer
matrix. It is the small size and uniquely high aspect ratio of these inorganic particles that
distinguishes them from conventional mineral fillers and reinforcing glass fibres, conferring
a significant enhancement in properties to the host polymer even at very low filler loadings,
typically between 2% and 5% by weight. In this regard, it is significant that a single
8 m montmorillonite particle contains over 3000 platelets [109].
251
Even at these small addition levels, marked increases in mechanical properties, heat
distortion resistance, gas barrier properties and flame retardancy are apparent, stimulating
extensive academic research and commercial interest in these materials [110]. Of central
importance to achieving this enhanced performance, however, is the extent of polymer
penetration between the silicate layers and the resulting inter-layer spacing achieved.
When this distance is relatively small the polymer is said to be intercalcated within the
silicate galleries, producing a well ordered multilayer structure with alternating polymer/
inorganic layers and a repeat distance of only a few nanometers. However, delamination
and dispersion of these particles creates a so-called exfoliated structure [111]. It is often
assumed that the most desirable properties are achieved in the exfoliated condition,
although there are notable exceptions to this generalisation. For example, it has been
shown the reduced toughness of some exfoliated systems can be alleviated in an
intercalcated morphology, although at the expense of modulus [112].
The ultimate microstructure formed, critically depends on a number of factors, including:
(i) the nature of clay pre-treatment used to make it organophilic, for example using
alkyl ammonium cationic surfactants,
(ii) whether or not the polymer is in a melt state, in solution, or made by in situ
polymerisation of monomer in the presence of the filler;
(iii) the polarity of the polymer;
(iv) the inclusion of functionalised polymer, such as MA modified polypropylene; and
(v) the processing conditions and technology used to effect filler dispersion.
A more extensive account of the formation, structural characterisation and physical

properties of silicate layer nanocompsites can be found in Chapter 10. The discussion
below focuses on nanocomposite preparation by melt processing, since this provides the
most promising route for more widespread acceptance and subsequent commercial
exploitation of these materials.
To achieve delamination and exfoliation of organically modified clays (organoclays) during

processing, high shear intensity melt mixing technology is usually recommended, as
considered earlier in this chapter. However, a number of issues are known to affect the
degree of delamination and dispersion, in particular the compatibilty of the chemical
treatment on the clay with the resin matrix and the specific compounding conditions
used. The following mechanism has been proposed for this process [109]:
(i) Particles of montmorillonite (MMT) clay shear apart giving tactoids, or polymer
intercalated MMT, in stacks around 100-150 nm high.
252
(ii) Polymer entering the galleries of the MMT clay pushes the platelets further apart
eventually causing them to peel off the intercalated stacks. This peeling process is
time-dependent and does not require intense shear. Hence increased residence time
increases delamination and dispersion, whereas this may be limited under high
shear conditions.
(iii) The more compatible the organoclay and polymer the faster this process occurs.
With polar polymers, in particular polyamides, the task of achieving exfoliation is relatively
easy and can even be achieved using a single-screw extruder configured with an appropriate
mixing head or screw profile [113]. For example, exfoliated polyamide-12 nanocomposites
have been successfully prepared by melt compounding in a conventional single screw
extruder fitted with a barrier screw design. In this work, a surface modified fluoromica
was used at 4% by weight loading.
However, this task becomes more challenging with polyolefins, and it is generally necessary
to have some polar functionality present, most commonly by inclusion of MA grafted
polymer in the composition (typically at a 5% polymer addition level) [114]. A co-rotating
twin-screw extruder is frequently recommended for this purpose, however the form of
screw profile used and feed location of the components, can influence the structure and
properties of compounds produced [115]. For example, it was reported that combined
dosing of polymer and filler at the feed end of the extruder gave better intercalation than
downstream addition of the clay.
It has also been shown that a pre-dispersed organoclay/polypropylene masterbatch

concentrate also containing MA-grafted polypropylene compatibiliser, can be successfully
let-down to 6% by weight using a single screw extruder [116]. In this work, the following
screw designs were compared: standard flights, a Union Carbide dispersive mixer, a
distributive mixer and a newly developed dispersionary mixing section. The last
mentioned variant gave comparable composite properties to material let down within a
twin-screw extruder.
Reactive extrusion provides an alternative approach to melt compounding, for the

preparation of polyamide-6 nanocomposites [117]. In this study, a co-rotating twin-
screw extruder was used to anionically polymerise -caprolactam in the presence of
organically modified montmorillonite clay. Hence, intercalcation and delamination occur
concurrently with polymer formation.
To assist in the production of silicate layer nanocomposites scCO2 has also been used.
Intercalcated poly(methyl methacrylate) clay nanocomposites, containing 25-50% by
weight of clay, have been made by polymerisation of methyl methacrylate in a scCO2
pressure vessel [112]. This overcame previous melt processing difficulties caused by the
253
increased viscosity from inclusion of large amounts of filler. Polystyrene nanocomposites

containing 10% of organoclay filler have also been prepared in a twin-screw extruder in
the presence of scCO2. The principal objective here was to minimise surfactant degradation
on the clay by processing at lower temperatures. Using this approach, it was also
demonstrated, using TEM, that improved clay dispersion could be obtained [118].
5.10 Conclusions
The principal objective of this chapter has been to demonstrate that the preparation of
polymer compounds containing particulate additives to meet specific performance criteria
requires attention to not only the design of the compounding machinery, but also an
understanding of how the process influences components within the composition and
ultimately its structure. Hence, there is a need for a basic knowledge of the functional
stages of the compounding process to aid optimum machine design and the development
of appropriate (and preferably quantitative) characterisation procedures to identify
relevant structural parameters in the composition under examination. It has also been
shown that the performance of the composite can critically depend on the material and
process technology applied during compound or end-product manufacture.
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262
6
Effects of Particulate Fillers on Flame
Retardant Properties of Composites
Roger N. Rothon
6.1 Introduction
Particulate fillers play a very significant role in flame retardant technologies for polymers.
The main focus of this chapter is on those particulate fillers which function by endothermic
decomposition and act as primary flame-retardants in their own right. They have the
advantage of a low environmental impact, being of low toxicity themselves, and with
much lower smoke and toxic fume generation than some of the more traditional
approaches. As a result, the use of this type of filler is now well established, and is
continuing to expand as environmental awareness grows.
Nano-clays are also discussed, as they are starting to show commercial promise. For
completeness, fillers like antimony oxide, which work in combination with other additives,
such as halogens, are also briefly discussed. This chapter concentrates on fire retardant
effects, the synthesis and general properties of the various fire retardant fillers having
already been described in Chapter 2.
6.2 General Effects of Fillers on Polymer Flammability
Before discussing the special effects of fillers that are active fire retardants, it is useful to
recognise that the addition of any particulate, non-combustible, filler to polymers can
considerably affect their thermal stability, resistance to ignition and combustion, and the
amount and nature of the combustion gases in terms of smoke, corrosion and toxicity.
The main general effects are:
i) Simple dilution, reducing the amount of fuel available for combustion.
ii) Changing the heat capacity and thermal conductivity, thus altering the rate of heating
and heat distribution.
iii) Various thermal effects, such as reflectivity and emissivity.
iv) Formation of a solid residue (ash). This may possibly strengthen any polymer char.
263
v) Slowing down the rate of diffusion of oxygen and pyrolysis products.
vi) Effects on polymer melt rheology (especially where dripping is a significant factor).
The relative importance of these different effects is likely to vary with the polymer type,
and its mode of degradation, and also with the type of flammability test.
On their own, the above effects are not usually sufficient to pass fire resistance tests and
additional features are required. The main effects of this type are:
i) Various solid state effects due to the chemistry of the additive, or its surface, or
shape, which promote polymer charring and the formation of a strong char.
ii) Heat adsorption due to endothermic decompositions.
iii) Release of gases such as water, which can affect solid state processes, provide a
significant dilution and cooling of the pyrolysis products, and possibly insulate the
substrate from radiative energy transfer.
Phosphorus and phosphates, notably ammonium polyphosphate (APP), are an example

of the first effect. Nano-clays also appear to enhance char properties, although the
mechanisms are not fully understood at present.
The main focus of this chapter is on fillers, generally known as fire retardant fillers, which
have an endothermic decomposition, coupled with the release of inert gases. These two
processes are always found together, principally in some carbonates, hydrates and
hydroxides. For these effects to be important, they must occur above the polymer processing
temperature, and near to the polymer pyrolysis temperature. Thus, calcium carbonate is
not effective, although it decomposes, with a large endotherm and release of carbon dioxide,
as this occurs well above the pyrolysis temperatures of common polymers. As described in
Chapter 2, there is some commercial interest in doping the surface of endothermic fillers
with metals such as nickel, to add char promotion to their other effects. Doping has also
been claimed to be able to alter the decomposition temperature to some extent [1].
6.3 Fire Retardant Testing
Tests play a vital and somewhat controversial role in determining the effect of fillers on
polymer flammability and some discussion is essential before examining the fire retardant
performance of fillers.
Large scale tests are used for assessing the real fire resistance of articles containing polymers.
The construction of the article and even its method of mounting can be important, and
264
Effects of Particulate Fillers on Flame Retardant Properties of Composites
these tests are usually carried out on complete items. They are also usually designed to
replicate the fire hazard situation the article is likely to experience. Thus, the appropriate
test for a cable jacketing will be different to that for chair upholstery or a wall covering.
Various smaller scale tests are used for product development and quality control purposes.
These are usually carried out on flat specimens, and are more related to material properties.
The main characteristics one is trying to assess in small scale tests are:
Ignitability: How readily a material will catch fire under certain conditions.
Propagation: How rapidly fire will travel once ignition is achieved.
Heat Release: How much the fire will raise the temperature of the surroundings, thus
causing the problem to spread.
Afterglow and smouldering: This is an important, but often ignored factor, as it can
cause re-ignition after a fire has apparently been extinguished.
Dripping: Dripping can reduce the apparent flammability by removing heat from the
specimen. On the other hand, it can also lead to propagation, if the drops themselves
are burning.
Smoke and toxic and corrosive gases.
Char integrity: This is becoming of some importance for building products.
Unfortunately, all of these parameters are very dependent on the test conditions, especially
the amount of radiant heat from an external source. Indeed, the rating of materials can
be reversed in some tests merely by changing the radiant heat conditions.
Virtually all the basic work has been carried out using these small scale tests. The main
ones being the oxygen index test, the Underwriters Laboratory UL94 test [2] and the
ASTM D635-88 [3] horizontal burn test. More recently great interest has been expressed
in the cone calorimeter test [4], which appears to have significant potential for basic
studies under more realistic conditions. The equipment is expensive, but it is becoming
more widely used.
A brief description of the main small scale tests follows. A useful description of some of
the larger scale tests, and attempts to correlate them with the oxygen index can be found
in the paper by Wharton [5]. It must be borne in mind that Whartons work did not
include filled polymers, and hence any correlations found may not be applicable to such
composite products.
265
6.3.1 Oxygen Index Test (ASTM D2863-87) [6]
This measures the minimum concentration of oxygen in a flowing mixture of oxygen

and nitrogen that will just support flaming combustion of a material initially at room
temperature. The sample is ignited and burns from the top downwards. The rating or
oxygen index is expressed in terms of this volume percent oxygen concentration.
There is no external heat provided once the sample has ignited and the heat required to
keep the sample burning comes from the flame itself. A useful description of the test and
factors affecting results has been published by Wharton [7]. As discussed later, this test
has been successfully modelled. The oxygen index itself does not measure ignitability,
afterglow, smoke or dripping. It is possible to observe whether afterglow occurs and
how much smoke is formed, but it must be remembered that this is under unrealistically
high oxygen concentrations.
There is an upwards burning variant of the test, which is sometimes used. There is also a
temperature index variant, in which radiant heat is used, and the temperature variation
of the oxygen index is determined. The temperature index is quoted as the temperature
at which the oxygen index is 20.8 (corresponding to the oxygen content of air). The
temperature index is regarded by some as more relevant, especially as the oxygen
concentration is more realistic, but it is more time consuming to determine and has been
little used to date.
6.3.2 Underwriters Laboratory Vertical Burn Test (UL94 -1980) [2]
A strip of the test material is held vertically in air and ignited from the bottom with a
Tirrell burner using a set procedure.
The material receives a rating according to its burning characteristics. The top rating in
the test is Vo. To achieve this, the material must extinguish very rapidly after removal of
the flame, show very little afterglow, and not have burning drips. The test is very dependent
on sample thickness and this must always be taken into account when comparing results
from different workers. While more comprehensive than the oxygen index test, it does
not measure smoke.
There is some component of ignitability in this test, and Ashley and Rothon have adapted
it to give a direct measure of ignitability [8]. The same burner, sample size and
configuration are used, but instead of a fixed application time, the burner is applied for
varying times until the time to achieve lasting ignition is found. While crude, this can
give good reproducibility and is a very cheap way of assessing ignitability.
266
6.3.3 Horizontal Burn Test (ASTM D635-98) [3]
The sample material is tested in air in the form of strips held with their longitudinal axis
horizontal and their transverse axis at 45 to the horizontal. The sample is ignited at one
end with a Tirrell burner and the rate and extent of burning is reported.
6.3.4 Ignitability Test (ISO 5657 1997) [9]
This measures the susceptibility of a material to be ignited by an external flame and

when exposed to a radiant heat source. The radiant energy is applied from a conical
heater, thus giving a uniform heat flux over the sample. The severity of the test can be
varied by varying the energy output from the radiant heater.
The pyrolysis gases are allowed to build up in the cone heater and a small pilot flame is
intermittently applied. The time to ignition is determined visually and quoted together
with the heat output of the radiant heater.
6.3.5 Cone Calorimeter (ASTM E1354 [10], ISO 5660 [11])
This is a much more complex test than those described previously, and is thought to
come closer to real fire conditions. The method is based on what is known as oxygen
depletion (or consumption) calorimetry. The development of the method has been
described by Babrauskas [4].
It has been found empirically that the amount of heat produced during combustion of
most types of material is equal to 13.1 MJ for each kg of oxygen consumed from air. The
rate of heat release can thus be determined from the rate at which oxygen is consumed.
This allows heat release to be followed under typical combustion conditions, rather than
in some artificial set-up.
In the commercial equipment, the sample is heated by radiant heat from an electrically
heated truncated cone. This ensures an even heat flux, which can be controlled in the range
0 100 kW/m2. Ignition is by a spark igniter. The sample is mounted on a load cell, which
allows the rate of mass loss to be followed. The combustion gases pass though an exhaust
hood into a pipe-work system, where measurements are made that allow the oxygen
depletion and hence heat release, to be automatically computed. Obscuration (smoke) is
measured in the exhaust gases using a laser method. Carbon monoxide and dioxide are
also determined in the exhaust gases, and corrosivity and toxicity tests may also be made.
A large number of parameters may be derived from the data. The most important are:
267
Time to ignition
Peak heat release rate
Time to peak heat release
Total heat release
Peak smoke production rate
Time to peak smoke production
Total smoke production
Fire growth rate index (FIGRA)
Smoke growth rate index (SMOGRA)
FIGRA is now believed to be one of the most relevant parameters and is related to the
size and growth rate of a fire. FIGRA is calculated from the peak heat release rate divided
by the time to peak. Similarly, SMOGRA is the peak smoke production rate divided by
the time to peak.
6.3.6 Smoke and Corrosive Gas Tests
As with flammability, tests play a key role in studies of smoke formation from burning
polymers. A wide variety of tests have been used, often in conjunction with flammability
tests. Hirschler has given a brief description of most of the main tests [12].
Until recently, one of the main tests was the National Bureau of Standards (NBS) smoke
chamber (ASTM E662) [13]. In this test, a vertical sample is decomposed under radiant
heat in a sealed cabinet and the build up of optical density is monitored. The test can be
run under both smouldering and flaming conditions, depending on whether a pilot ignition
flame is present.
Various parameters can be obtained from the NBS test. Those usually quoted are:
maximum optical density, time to maximum density, the time to reach an optical density
of 16 (the critical observation time) and the optical density after 4 minutes. The critical
observation time is an indication of how long before visibility would become too bad to
allow one to find a way out of a room, while the density at four minutes is relevant to
whether smoke would affect escape from, say an aircraft, before other life threatening
aspects of a fire became important.
Today, smoke measurements are more and more being obtained by cone calorimetry as
described in Section 6.3.5.
268
Various corrosion tests are in use, often based on absorbing combustion or pyrolysis
gases in water and determining the pH. In one test the effect of combustion gases on the
electrical resistance of a printed circuit board is determined. Again, corrosion data can
be obtained from the cone calorimeter.
6.4 Fire Retardant Fillers that Rely on Endothermic Decomposition
These fillers are of great industrial importance, and are the main subject of this chapter.
They owe their fire retardant effectiveness to their ability to decompose endothermically
at polymer pyrolysis temperatures, with the release of inert gases such as water. Thus,
unlike some other flame retardants, they are able to combine a high level of flame
retardancy, with low smoke and low toxic and corrosive gas emissions, and are thus
becoming of increasing importance. One of the simplest such materials is aluminium
hydroxide (also known as alumina trihydrate, ATH).
6.4.1 Historical Background
The ability of ATH to flame-retard cellulose was recognised almost a century ago. A
patent on its use as a flame retardant for elastomers appeared in 1921 [14] and a further
patent on its use to improve arc resistance of various polymers in 1956 [15]. There
appears to have been little or no commercial exploitation of these effects at that time,
however. Significant commercial use of ATH as a flame retardant seems to have started
in unsaturated polyesters in the mid-1960s, following work by Connolly and Thornton
[16]. Interest in elastomer systems followed in the early 1970s when workers such as
Lawson and co-workers [17] and Nelson [18] recognised the low smoke benefits associated
with the use of ATH as a flame retardant. The effectiveness of other fillers, especially
magnesium hydroxide, was also recognised by them.
The commercial use of hydrated fillers was given a great boost in the mid-1970s, by
legislation in the USA requiring carpet backing to be flame retarded, an application for
which aluminium hydroxide was ideally suited.
Today ATH is a well established flame-retardant additive, especially for unsaturated

polyesters, elastomers and some thermoplastics.
Growing concerns over the problems (real or imagined) associated with organo-halogen
flame retardants is now creating further opportunities, especially in other polymers,
notably polyolefins and polyamides, where ATH is not ideally suited because of its
relatively low decomposition temperature. This has led to a surge of interest in other
269
more thermally stable materials, notably magnesium hydroxide. Concurrently with this,
the demands on the performance of ATH have become more sophisticated requiring the
development of new grades to maximise performance. Thus, the area is one of considerable
activity and development at the present time.
6.4.2 Potential Endothermic Flame Retardant Fillers
At first glance, there seem to be many materials that decompose endothermically and
might be thought of as potentially useful, but there are other important criteria to consider.
In particular, the material must be inexpensive, freely available in quantity, non-toxic, non-
coloured, of low solubility and with a morphology suitable for filler use. A significant
decomposition (by experience at least 25% weight loss) is needed, if the endothermic process
is to have a useful effect. Furthermore, the decomposition temperature must be high enough
to survive polymer processing, but low enough to exhibit a fire retarding effect.
Only a few materials meet some, if not all of these criteria. The main candidates are
summarised in Table 6.1. This list excludes other, well known materials, which have
significant endotherms, but where they are not sufficient to make the additive a primary
flame retardant. These include, some clays and talc, and some stannates and borates. The
materials in Table 6.1 are seen to cover a wide range of decomposition temperatures, and
to include release of carbon dioxide as well as water. With such a range of materials available,
it would be thought that a clear ranking of their performance would allow conclusions to
be drawn, regarding the relative importance of the different parameters. Unfortunately,
this is not the case at present. This is partly because, as we shall see in Section 6.4.3,
particle morphology can play a significant role, leading to marked variations between
different forms of the same material. A proper comparison would thus have to use forms
of the different materials with the same morphology and this has not been possible. More
importantly, most comparative work has been carried out using the simplistic oxygen index
test to assess flame retardant performance. As we shall also see in Section 6.4.3.2, this test
has its limitations and may not accurately predict the relative performance of fillers in
other tests, or indeed in real fire situations. Clearly more could be done in this area.
Despite these reservations, the presently available data suggests that, with the possible exception
of nesquehonite, none of the candidate materials is a significantly more effective flame retardant
than aluminium hydroxide (also known as alumina trihydrate or ATH), although as will be
shown later, magnesium hydroxide may have some advantages in terms of smoke production.
ATH also comes closest to meeting all of the criteria mentioned previously, and this explains
its current pre-eminence. It owes its relatively low cost and wide availability to its production
on a vast scale as an intermediate in alumina manufacture. The main limitation of ATH is
270
Table 6.1 Principle candidate flame-retardant fillers

Approximate Approximate Volatile content
Candidate material
onset of enthalpy of % w/w
(common names and
decomposition decomposition
formula) H2O CO2 Total
(C)* (kJ kg-1)
Nesquehonite
70-00 1750 39 32 71
MgCO3.3H2O
Calcium sulfate dihydrate,
Gypsum 60-130 Not available 21 0 21
CaSO4.2H2O
Magnesium phosphate
octahydrate, 140-150 Not available 35.5 0 35.5
Mg3(PO4)2.8H2O
Alumina trihydrate,
Aluminium hydroxide 180 -200 1,300 34.5 0 34.5
Al(OH)3
Basic magnesium carbonate,
Hydromagnesite 220-240 1,300 19 38 57
4.MgCO3.Mg(OH)2.4H2O
Dawsonite (sodium form)
240-260 Not available 12.5 30.5 43
NaAl(OH)2CO3
Magnesium hydroxide
300-320 1,450 31 0 31
Mg(OH)2
Magnesium carbonate
sub-hydrate (MCS) 340-350 Not available 9 47 56
MgO.CO2(0.96)H2O(0.30)
Boehemite
340-350 560 15 0 15
AlO(OH)
Calcium hydroxide
430-450 1,150 24 0 24
Ca(OH)2
* The decomposition temperatures are only approximate, as they are usually determined
under dynamic conditions and depend on heating rate and sample conditions.
its relatively low decomposition temperature (about 180 C) which has restricted its use
in applications where processing temperatures are above this, notably many thermoplastics.
ATH also loses some of its cost advantages when the morphology or purity available from
the alumina processes is not sufficient and special grades are required.
271
A brief discussion of the other materials follows. More complete details, including aspects
other than flame retardancy, will be found for most of these and for ATH in Chapter 2.
Nesquehonite (MgCO3.3H2O) is an effective flame retardant, as is to be expected from

its large volatile content and endotherm, but suffers from a very low decomposition
temperature, and is not produced commercially with attractive morphology or price. Its
effect in unsaturated polyester is illustrated later in Figure 6.3 (Section 6.3.4.2).
Calcium sulfate dihydrate is a low cost material with significant fire retardant effectiveness.
It is restricted by its low thermal stability, but is reported to have some applications in
thermosets, such as unsaturated polyesters [19].
Magnesium phosphate octahydrate appears to have interesting properties, although of

limited thermal stability, and the present author has obtained excellent results with it in
some thermosets. It has received little scientific or commercial interest to date. It has a
relatively low specific gravity, which could be attractive in some applications. There are
other magnesium phosphates with similar properties.
Basic magnesium carbonate (hydromagnesite, 4MgCO3.Mg(OH)2.4H2O) is also an

effective flame retardant, and can be formed from nesquehonite, although it is usually
synthesised directly. It is more stable than nesquehonite and used on a small scale as a
flame retardant and smoke suppressant, principally in elastomers. It is generally more
expensive than ATH, and its readily available forms tend to consist of high surface area,
platy particles, not ideally suited for highly filled polymer applications. This has probably
limited its use.
Significant workable deposits containing natural basic magnesium carbonate exist, notably
in Greece. These are usually associated with the mineral huntite (3MgCO3.CaCO3). Flame
retardant fillers based on these deposits have been commercially developed. Unfortunately,
it is not economic to remove the huntite. The present author has found (by x-ray analysis
of the ash) clear evidence that the huntite decomposes under oxygen index test conditions
(see Chapter 2 for further details). Even so, it does not appear to be such a good flame
retardant as the basic salt and this reduces the effectiveness of the mixture [20].
Various forms of synthetic hydrated alkali alumino-carbonates such as dawsonite (the

sodium form) have been proposed and indeed marketed as flame retardant fillers [21].
Such materials are of proven effectiveness, but have made little commercial progress.
They are relatively expensive, have some water solubility problems and there have also
been toxicity concerns over the acicular nature of some of the products.
Magnesium carbonate sub-hydrate is included here to illustrate the problems that can be
encountered in this area. Like basic magnesium carbonate, it can be produced from
272
nesquehonite, but it is more stable and can be used at processing temperatures up to at

least 300 C. Initial work by the present author showed oxygen index results equivalent
to ATH, suggesting a good flame retardant performance, but other tests subsequently
showed virtually no flame retardant effect (see Section 6.4.3.2 for more detail).
Currently great interest is being shown in magnesium hydroxide. On the basis of present
information, its flame retarding effects are similar to ATH: it appears to have better
smoke suppression effects under some conditions. On the other hand it may be more
prone to afterglow problems (see Section 6.4.4.3). Like ATH it is the intermediate in
large scale refractory manufacture (MgO) and should in principle be relatively inexpensive.
However, the morphology and purity available from this process is not usually ideal for
filler use and more expensive, specially prepared, forms are generally utilised. The
attraction of magnesium hydroxide compared to ATH lies in the much higher
decomposition temperature (~300 C). This allows use in applications such as
thermoplastics, which are processed at too high a temperature for ATH. Workable deposits
of natural magnesium hydroxide (brucite) exist, principally in the United States and
China and after much unsuccessful work, these are now beginning to make a significant
commercial impact [229].
Boehmite is a partly dehydrated form of ATH. It is appreciably more stable, but would
be expected to have less fire retarding effect, due to the lower endotherm and water
content. Nevertheless, it appears to be of some commercial interest [23].
Calcium hydroxide is an interesting material as, although appearing to have suitable

properties, both Nishimoto and co-workers [24] and Ashley and Rothon [8] have found
it to exhibit relatively poor flame retardant properties in the oxygen index and other
tests. Ashley and Rothon showed that, in some polymers at least, the final product from
the oxygen index test was calcium carbonate rather than the oxide. As carbonate formation
is exothermic, they associated this with the poor performance. More recently, Miyata
has claimed that doping with certain metals significantly improves the performance of
calcium hydroxide [25], but this has not been verified.
6.4.3 Performance of Endothermic Flame Retardant Fillers
While descriptive papers on the performance in various tests abound, scientific

understanding is only partly developed at present. This is due to a number of factors,
especially the notorious difficulty is defining and assessing the fire performance of materials
using laboratory tests. A great deal of the available literature is also in a patent or product
promotional form, and of limited scientific use. The inability to find fillers where the
273
endothermic and gas release effects are separated also makes mechanistic studies difficult.
Nevertheless, some progress is being made and details of the most useful work in the
area follow. For clarity the issues of flammability and smoke generation, while closely
related, are dealt with separately.
6 4.3.2 Effects of Fillers in Various Tests
a) Oxygen Index
As mentioned earlier, this test has been the most widely used, despite its limitations.
The popularity of the test is due to its simplicity, use of relatively inexpensive equipment
and small samples and good reproducibility. Nevertheless there is considerable
controversy over its relevance. Ashley and Rothon [8] and Hornsby and Watson
[26] have shown how it fails to correlate with other tests when applied to filled
systems. As described later in this Section, this is probably due to the dominant role
filler ash structures can play in the heat balance so important in this test.
The general effects of fillers on the oxygen index of a polymer are illustrated in
Figure 6.1 taken from work by Case and Jackson [27]. An inert filler such as calcium
carbonate is seen to have given a small but significant increase in oxygen index,
becoming more pronounced at high loadings. An endothermic flame retardant filler
such as ATH is seen to have much greater effect. The oxygen index values increase
rapidly and non-linearly with filler loading, but high levels of ATH are needed before
the oxygen index reaches values, which by experience would be regarded as giving
good flame retardancy (about 30%). This need to use high filler levels is the main
drawback of endothermic fillers, and makes control of their effects on other factors,
such as processability and mechanical properties, a vital concern.
A further feature of flame retardant fillers in this test is that different grades of the
same filler can give widely differing results, despite no change in their endotherm or
inert gas release. Such effects usually become noticeable as enhanced performance of
very fine fillers and are generally described as a particle size effect, although other
factors such as shape may also be important. Typical results of this type for ATH in
polymethylmethacrylate (PMMA) are presented in Figure 6.2, taken from work by
Hughes, Jackson and Rothon [28].
The enhanced performance of fine fillers in this test has created considerable interest
as, if reflected in larger scale tests, it may point the way to allowing reduced filler
loadings to be employed. Unfortunately, fine fillers also generally have a more detrimental
effect on processing and physical properties so there may be no overall gain.
274
Figure 6.1 A comparison of the effect of calcium carbonate and aluminium hydroxide
fillers on the oxygen index of a filled polyethylene
Figure 6.2 The effect of filler particle size on the oxygen index of PMMA filled with
aluminium hydroxide
275
Some of the problems of trying to relate the oxygen index test on filled polymers to
other flammability tests have been described by Ashley and Rothon [8] They found
that materials such as calcium carbonate were able to give oxygen indices in crosslinked
ethylene vinyl acetate (EVA), far higher than glass beads and approaching those of
ATH. Furthermore, dilution of magnesium hydroxide with up to 75% w/w of calcium
carbonate had little effect on its oxygen index in the same polymer. Nevertheless,
both calcium carbonate and diluted magnesium hydroxide hardly improved the
ignitability characteristics under UL94 conditions, relative to the unfilled polymer.
The same workers also found that additives such as coupling agents could dramatically
reduce the oxygen index of certain filled systems, again without any apparent effect
in other tests. This effect was put down to increased spalling (thermal cracking),
resulting in weakening of the ash structure.
The interpretation problems outlined previously and the so far unexplained effects
of particle size, make comparisons of the performance of various potential flame
retardant fillers reported in the literature very questionable. This is graphically
illustrated by the case of MCS referred to earlier (Section 6.4.2).
MCS is a synthetic material that showed great promise when assessed by the oxygen
index test in a number of polymers, giving values as good as, if not better than ATH.
However, when other tests, such as ignition time or the UL94 test, were carried out
the performance was little or no better than the base polymer. Typical results
illustrating this point are presented in Table 6.2.
Table 6.2 A comparison of the flame retardant performance of aluminium

hydroxide (ATH) and MCS [125 phr in crosslinked EVA]
Result with
Test No Filler Glass Beads ATH MCS
Oxygen index (%) 18.5 21.5 30.5 33.0
Ignition time (seconds)
<2 <2 20 5
(UL 94 method)
Ashley and Rothon used X-ray methods to analyse the ash from the oxygen index
tests performed on MCS filled polymers, and found virtually complete decomposition
to magnesium oxide [8]. However, when the ash was continuously removed during
the test they found that the oxygen index fell markedly. Thus it would seem that the
relatively stable MCS is given time to decompose under oxygen index conditions,
276
probably as the flame travels down through the ash layer, but decomposes too slowly
to be effective in ignitability tests.
Just as the oxygen index test has been the one most widely used in research, so it has
been the one test that people have attempted to model.
Bolodyan and co-workers have modelled the test in terms of a heat balance equation
[29]. They have used this to account for the effect of inert fillers in terms of their heat
capacity and found reasonable agreement with experiment. More recently, the heat
balance approach has been extended by Case and Jackson [27] and by Khalturinskii
and Berlin [30] to include the thermal properties of flame retardant fillers. The Case
and Jackson work has taken the analysis further than Khalturinskii and Berlin, and
is reproduced in detail here.
Case and Jackson consider the heat balance over the whole combustion sequence.
This heat balance is applied to combustion of unit weight of polymer having a
gasification endotherm Q, forming fuel gases with heat of combustion H and oxygen
requirement, r parts by weight of oxygen. The polymer is loaded with l parts by
weight of filler, with a decomposition endotherm, E, evolving a fraction of its
weight as non-combustible gas, (i.e., CO2 and/or H2O in the present work). The
weight fraction oxygen indices for the filled and unfilled polymers are Y and YO,
respectively, and it is assumed that the oxygen containing gas stream and the unburnt
polymer system have the same initial temperature, TO . The temperature at which the
gaseous products and solid filler residues exit from the combustion cycle are TE and
TS, respectively. The constant pressure heat capacity terms, c, are identified by
subscripts referring to the filler residue (S), filler generated inert gas (I), diluent nitrogen
(N) and combustion products (p). The heat balance leads to the Equation 6.1, in
which an energy term R has been included to allow for all heat losses:
cN (TE TO ) (H Q) R cp
= cp cN + (TE TO ) (6.1)
YO r r r
To take account of the enthalpy absorbed by endothermic breakdown of the filler

and raising the temperature of its decomposition products, an extra term directly
proportional to the loading must be subtracted from the right hand side of this
equation. Assuming that all the terms in Equation 6.1 are not significantly affected
by filler incorporation, the reciprocal of the oxygen index can be directly related to
filler loading l as shown in Equation 6.2:
1 1
= l (6.2)
YO Y
277
E + (1 )cS (TS TO ) + cI (TE TO )

Where: = rc N (TE TO )
Equations 6.1 and 6.2 thus provide a basis for analysing the way in which the oxygen
index of a filled polymer is determined by (a) the known thermochemical properties of
the components and (b) the unknown parameters TE, and TS, and the heat loss term R.
Case and Jacksons analysis predicts that a plot of the reciprocal of the weight fraction
oxygen index against filler loading (on a parts by weight per hundred of polymer
basis) should be a straight line of slope . They examined the effect on the oxygen
index of various loadings of aluminium hydroxide and nesquehonite (MgCO3.3H2O)
in PMMA, polystyrene, polyethylene, unsaturated polyester resin and phenol
formaldehyde and of calcium carbonate in polyethylene only. Providing the fillers
were not too fine, good agreement between experimental and theoretical predictions
were obtained. Typical results are presented in Figure 6.3 for nesquehonite and alumina
hydroxide in unsaturated polyester.
On the basis of this work they concluded that the thermal effects of the fillers were
sufficient to account for their effects on the oxygen index. They were also able to
Figure 6.3 Linearity of the reciprocal of oxygen index versus filler loading plots, as
predicted by the model of Case and Jackson for two fillers (aluminium hydroxide and
nesquehonite) in PMMA
278
conclude that for a given filler/polymer system, TE, TS and R do not change significantly
over the range of filler loadings studied.
Case and Jackson also showed by analysis of the combustion gases produced just
above the oxygen index value, that the fillers had little effect on their composition
and thus on the heat release per unit of polymer consumed. They were then able to
derive values for TE and TS of about 900 and 600 C, respectively. These were largely
independent of filler and polymer type.
Finally, by using these derived values and the known filler decompositon endotherms,
they were able to calculate the contribution to the overall heat balance of the different
filler effects. This is summarised for two of the fillers in Table 6.3.
Table 6.3 Contribution of various factors to the oxygen index effect

(using the analysis of Case and Jackson)
% Contribution to heat balance effects
Enthalpy of Heat capacity of Heat capacity of
Filler
decomposition residue the evolved gases
Al(OH)3 51.4 18.5 30.1
MgCO3.3H2O 56.9 7.6 35.5
While clearly demonstrating the importance of the endotherm in the heat balance, it
is interesting to note that the heat capacity effects, especially of the evolved gases, are
also significant contributors.
The success of Case and Jacksons analysis is demonstrated by the fact that they were
able to show that the previously published endotherm for ATH decomposition could
not be correct. This led to a redetermination of the value by Jackson and Jones who
obtained a value in keeping with the predictions of the model and with theoretical
consideration [31].
Case and Jackson also carried out studies on upward burning oxygen index values
and again found good agreement with their model, the lower oxygen index values in
this configuration being due to reduced heat losses.
The one condition where the model does break down is with very fine fillers. These
do not give straight line plots when the data is treated as described, the oxygen index
279
value increasing faster with loading than predicted. This is in keeping with the particle
size effect noted earlier.
As the decomposition endotherm is not affected by particle size and complete

decomposition is already assumed in the analysis, then the effect must be due to a
change in one or more of TE, TS and R.
Case and Jackson were able to show that anomalously high values were always
associated with a fine grained ash structure and that continuous removal of this
ash residue gave values in keeping with prediction. These observations suggest
that the main effect may be on TS and R rather than on T E. Indeed the present
authors own observations are that the flame actually enters this fine ash structure,
and raises it to incandescence. Thus TS may approach 900 C, increasing the
contribution from the heat capacity of the residue and possibly also increasing
radiative heat losses.
Unfortunately, while the oxygen index test appears fairly well understood, its relevance
to other tests is not well founded, and these other tests are themselves poorly
understood in terms of filler effects.
As seen previously, the endotherm and heat adsorbing effects can contribute markedly
to the heat balance in the conventional oxygen index test, where only a small fraction
of the heat of combustion is fed back. In other tests such as UL94 and particularly
radiant heat tests, these effects probably become less significant and other factors
may become dominant.
Thus, Hornsby and Watson have highlighted insulation by a robust ash layer and
solid state stabilisation effects as possible important factors [32]. They have also
drawn attention to the high surface area of the oxides produced from decomposition
of fire retardant fillers as possibly playing an important role. These may well undergo
sintering reactions leading to strong ash structures being developed. This is an aspect
not often recognised and might explain some of the differences observed between
different grades of the same material.
b) Other Tests
Unfortunately, there has been little scientific work using tests other than oxygen
index. Probably the most comprehensive is that by Hughes, Jackson and Rothon on
the effect of ATH on PMMA. They have investigated the effect of filler loading and
particle size using the oxygen index, ignitability (ISO 5657) [9], UL94 vertical burn
[2] and ASTM horizontal burn tests [3, 28].
280
The oxygen index results have already been presented in Figure 6.2. Results for the
same fillers in the ISO ignitability test are presented in Figure 6.4. This shows the
coarsest fillers to have very little effect in this test, while the finest has a very dramatic
effect.
In the UL94 vertical burn test, the finest fillers achieved a Vo rating at 50% by weight,
while 60% was required for the intermediate sizes, and the coarsest was still
unclassifiable at 60%. The effect of filler loading and size in this test configuration is
illustrated by time to ignition data determined by the procedure developed by Ashley
and Rothon [8]. This is presented in Figure 6.5. Data for the ASTM horizontal burn
test are presented in Table 6.4 and again show a particle size effect.
Figure 6.4 The effect of filler particle size on the ignitability (ISO 5657 [9]) of PMMA
filled with aluminium hydroxide. Test carried out at 20 kWm-2
Table 6.4 The effect of ATH particle size on the horizontal burn performance
(ASTM D635) [3] of 50% w/w filled PMMA composites
Filler specific surface area (m2 g-1) Burn time (s) Extent burnt (mm)
~0.1 654 72
0.5 20 9.1
2.2 6.5 6.7
281
Figure 6.5 The effect of filler particle size on the ignition times (UL 94 configuration)
of PMMA filled with alumina hydroxide
Thus, the beneficial effect seen in oxygen index has been shown, in this system at least,
to be mirrored in a range of other tests. Furthermore, the particle size effect is also
observed in all of the tests, although it appears more marked in some than in others. In
an attempt to explain the particle size effect, the fillers were all examined by differential
scanning calorimetry (DSC) but only minor differences, insufficient to account for the
observed variation in performance, were found (see the section on ATH in Chapter 2
for a detailed discussion of particle size effect on kinetics of decomposition).
Miyata and co-workers have examined the effect of magnesium hydroxide on the
flammability of polypropylene, using the UL94 vertical burn test [33]. They found
that the performance again increased with decreasing effective particle size and that
levels of about 58% w/w were needed to achieve Vo rating at 0.3 cm thickness. The
rate of change was very steep below this filler level.
Hornsby and Watson have also investigated the effect of various magnesium
hydroxides on polypropylene. They found some effect of filler type on UL94 vertical
burn rating, but were unable to correlate this with particle morphology [26].
Herbert has carried out a comprehensive study of the effect of ATH on the fire
resistance of a peroxide crosslinked EVA (18% vinyl acetate), using the cone
calorimeter [34]. This work showed that ATH was an effective fire retardant in this
test, with significant reductions in most parameters, notably reduced peak heat release
rate and smoke level.
282
Figure 6.6 A comparison of the effect of aluminium hydroxide and calcium carbonate
fillers on the heat release rate from an EVA copolymer using cone calorimetry. Filler
loading 60% w/w, irradiance 35 kW m2. (After Herbert [34])
Typical results are shown in Figure 6.6. ATH is seen to be much more effective than
an inert filler, such as calcium carbonate, thus confirming that any effects are more
than simple dilution.
Somewhat surprisingly, given the results of some of the other studies referred to
previously, no significant particle size effect was observed. Although a considerable
size range was used in the study, they were all fairly fine and it may be that an effect
would still be seen with coarser material.
In work not yet published, the present author and co-workers used cone calorimetry
to examine the effects of various magnesium hydroxides on the fire resistance of a
polypropylene copolymer. The fillers were all fatty acid coated, and compounds were
prepared using a Buss ko-kneader, followed by injection moulding. Magnesium
hydroxide was found to increase the time to ignition, and to reduce the rate of heat
release, peak heat release rate and smoke formation. They found significant differences
in performance among magnesium hydroxides from different suppliers, but no
significant effect of particle size (over a limited range) or of coating level, for a given
magnesium hydroxide type. Typical results demonstrating the differences in
performance are presented in Figures 6.7 and 6.8. The heat release rate curves are
283
Figure 6.7 A comparison of the effect of two similar magnesium hydroxide fillers on
the heat release rate from polypropylene using cone calorimetry.
Filler loading 65% w/w, irradiance 50 kWm-2
Figure 6.8 A comparison of the effect of two similar magnesium hydroxide fillers on
the smoke level from polypropylene using cone calorimetry. Filler loading 65% w/w,
irradiance 50 kWm-2
284
particularly interesting as, while one shows twin peaks, the other does not. This
finding was confirmed by repeat compounding and testing. In the work referred to
previously, Herbert often found similar twin peaks for ATH filled composites and
speculated that the first peak was the point at which the fire retardant filler first
became effective, while the second occurred once it had all been used up.
The results of Hughes and co-workers, referred to in the preceding section, are worthy
of further comment here. Thus, while a particle size effect is apparent in all the tests
investigated, its magnitude appears to vary considerably from one test to another. A
poor correlation is also often observed if one attempts to plot results from one test
against another, even for the coarser fillers. This implies that the various factors that
govern filler performance are varying in relative importance according to the nature
of the test.
By analogy with halogenated flame retardants, most workers put great emphasis
on the importance of the filler decomposition closely matching that of the polymer.
While this is undoubtedly true for the halogens, which by their mechanism of action
must accompany the volatile pyrolysis products, it is unproved for flame retardant
fillers, which function by different mechanisms. While too high a decomposition
temperature is almost certainly undesirable, more rapid decomposition than the
polymer may well give excellent results in some tests (try lighting wet wood!). One
can imagine that a combination of fillers, to achieve a broad decomposition range
could be beneficial in some tests, (e.g., cone calorimetry), and this is sometimes
used in practice.
6.4.3.3 Application of Thermal Analysis
Various thermo-analytical procedures are frequently used for assessing the temperature
and rate of decomposition of fillers, polymers and composites. While these undoubtedly
have an important part to play, great care must be taken in carrying out and interpreting
such analysis.
Thus, as found by Jackson, the results can vary markedly according to the exact nature
of the sample (powder, chip, etc.) [35]. Also as reported by Rychly and co-workers, the
decomposition of both the filler and polymer may be different in the composite to those
of the separate components [36]. Jackson and Rothon have observed that elevated pressure
can delay the decomposition of hydroxides and hydrates [37] and such an effect may
well be observed in a polymer matrix. Of particular interest is the tendency of ATH to
form boehmite, rather than undergoing complete dehydration. This may well be favoured
by the presence of polymer and has been discussed in Chapter 2.
285
Other factors that have to be considered are:
i) the faster rate of heating in flammability tests than is possible in most thermal analysis.
ii) the concentration on solid state effects in thermal analysis, while gas phase processes
are also important in flammability.
iii) both surface and bulk effects have to be taken into account.
iv) the nature of the heating source: conductive, radiative, etc., can be important.
The application of thermal analysis is illustrated in Figures 6.9-6.12 based on unpublished

work by Ashley and Rothon.
Figure 6.9 shows DSC traces for the effect of magnesium hydroxide on Nylon 6 under
nitrogen. The endotherm for the filler is clearly seen and occurs well before that for
polymer pyrolysis, which in this case is apparently unaffected in position by the filler.
Figure 6.10 shows similar DSC traces in air. These are much more complex. The early
decomposition of the filler is still apparent as an endotherm, but now may be overlapping
the start of the polymer exotherm. The shape of the exotherm also seems to have been
much affected by the presence of the filler.
Figure 6.9 DSC traces (in nitrogen) showing the effect of magnesium hydroxide
in Nylon 6
286
Figure 6.10 DSC traces (in air) showing the effect of magnesium hydroxide in Nylon 6
The dramatic effect of magnesium hydroxide on the solid state processes involved in
polypropylene air pyrolysis is illustrated by the DSC data in Figure 6.11. The presence of
the filler is seen to cause both a delay in the exotherm, and a marked sharpening when it
does occur. This is in keeping with increased char formation, followed by sudden oxidation
of the char, as mentioned elsewhere. Surprisingly a very similar trace is observed with
calcium carbonate as the filler. While not as dramatic, this effect is also demonstrated by
the thermo-gravimetric analysis (TGA) data presented in Figure 6.12. This shows the
weight loss to be delayed but to go very rapidly once it does occur.
Rychly and Pavlinec have developed a method for analysing thermo-gravimetric data
for multi-step processes obtained under non-isothermal conditions to provide kinetic
data for each step [38]. Rychly and co-workers have applied this and other methods to
a detailed study of the flame retardant effects of fillers [36]. In addition to the oxygen
index, they used an ignition test based on an adapted thermal analysis method to
assess flammability.
Rychly and Pavlinec [38] put particular emphasis on the effect of fillers on the
activation energy for polymer pyrolysis determined in air. Movement of this value
287
Figure 6.11 DSC traces (in air) showing the effect of magnesium hydroxide
in polypropylene
from that determined on the neat polymer in air towards that for the same polymer
in nitrogen is interpreted as indicating efficient surface blanketing by filler
decomposition gases.
Their work is particularly interesting as it attempts to understand the effects of fillers

on ignition. Increased polymer thermal stability in air as shown by a move of the
associated weight loss in TGA or by higher activation energy gave good correlation
with longer ignition times. The most pronounced effect on ignition time they found
was for magnesium hydroxide in polypropylene and this correlated well with increased
polymer stability. In polyethylene, the magnesium hydroxide they used had a much
more marked effect on activation energy than did the aluminium hydroxide and was
also found to produce a higher ignition time.
These workers also observed that in EVA copolymer they only obtained two steps in
the TGA trace, while summation of independent filler and polymer traces would indicate
288
Figure 6.12 Thermogravimetric traces (in air) showing the effect of magnesium
hydroxide in polypropylene
that three should be obtained. It appears that in this polymer water release is delayed
from aluminium hydroxide but accelerated from magnesium hydroxide. This is probably
due, at least in part, to the effects of acetic acid released from the polymer.
They also observed that carbon retention and subsequent oxidation could be very
important and was particularly noticeable with magnesium hydroxide in polypropylene
leading to a sharp exotherm of the type already illustrated in Figure 6.11. They also
claimed that this could lead to greater heat feedback in the oxygen index test, thus
reducing fire retardant filler effects.
In separate work aimed at elucidating filler effects on surface, oxidation Vesely and co-
workers [39] have examined the oxidation of polyethylene and polypropylene containing
high levels of calcium carbonate. The grade of filler used was found to decrease polymer
thermal stability, an effect they associated with transition metal impurities. They also
believe that, in the presence of fillers, heteregeneous oxidation reactions become more
important. They observed black polyenes to be formed above about 320 C and
postulated that these could be acting as photo-sensitisers.
289
Finally Baillet and Delfosse have developed an apparatus for determining the temperatures
of ignition and incandescence of filled polymers [40]. They have applied this to an EVA
copolymer filled with either aluminium or magnesium hydroxide. Both fillers were found
to increase the self-ignition temperature with the particular magnesium hydroxide used
being the more efficient at low loadings [41]. In the same work they used TGA to examine
filler effects on polymer decomposition, and concluded that the main solid state effect in
EVA is the oxidation of carbonaceous residues. Their work is discussed in more detail in
Section 6.4.4.3.
6.4.4 Smoke and Corrosive and Toxic Gases
Conventional methods for flame retarding polymers are usually halogen-based and
rely on interruption of gas phase combustion processes for their efficiency.
Consequently, these additives generally give rise to relatively high smoke levels
compared to non-flame retarded polymers. The combustion gases are also usually
rich in hydrogen halides, which can pose hazards to both humans and equipment in
a fire scenario. Furthermore, although not proven, there is a concern that toxic organo-
halogen compounds may be evolved during the processing and use of such flame
retardant polymers as well as in a fire.
As mentioned earlier in Section 6.1, one of the driving forces behind the growth in the
use of hydrated fillers is their low level of smoke generation, coupled with the lack of
evolution of corrosive and toxic off-gases. This is because they do not function by
interrupting the combustion process and only add water and in some cases carbon
dioxide to the combustion products. In addition to producing less smoke than
halogenated flame retardants, there is also some evidence that hydrated fillers can
reduce smoke levels compared to the unfilled, non-flame retarded, host polymer, and
that some fillers are more effective than others in this respect. Because of the importance
of smoke, this topic is worthy of further examination.
Unfortunately, the present state of knowledge in this area is even less developed than
with flame retardancy. This is due in part at least to the complexity of the smoke issue
in flammability studies and the difficulties in carrying out meaningful measurements
under laboratory conditions. Smoke generation is known to vary according to whether
the sample is smouldering, or burning, and to depend on the oxygen level which can
fall considerably in some types of fire situation. Furthermore, the effects of hydrated
fillers on smoke generation will probably vary considerably according to the nature of
the host polymer, thus making generalisations very difficult.
290
The whole issue of smoke formation and measurement in burning polymer systems has
been extensively reviewed by Hirschler [12, 42, 43] and this provides a very useful
background.
6.4.4.2 Endothermic Fire Retardant Filler Effects
An important early study on the effect of fillers on smoke formation was carried out by
Lawson and co-workers [17]. They studied the effects of aluminium hydroxide, calcium
carbonate and magnesium hydroxide fillers on soot and smoke formation from styrene-
butadiene rubber (SBR) foams.
While their results for smoke were obtained under unrealistically high oxygen
concentrations and must be treated with caution, soot was measured under ambient air
combustion and some useful observations were made.
i) All the fillers reduced soot formation compared to unfilled foam. The order of
effectiveness was CaCO3 < Al(OH)3 < Mg(OH)2. The calcium carbonate effect was
attributed to dilution, that of the other fillers to a combination of dilution and
promotion of solid state crosslinking and charring.
ii) Soot particle size distribution and CO:CO2 ratio in the combustion gases was very
similar for both calcium carbonate and aluminium hydroxide fillers. This was taken as
evidence for the relative unimportance of the water released from the hydrated filler in
reducing smoke levels (by carbon oxidation via the water gas reaction for instance).
iii) Although obscured by the unrealistic experimental conditions, both hydrated fillers
gave less smoke under flaming conditions than calcium carbonate, with magnesium
hydroxide being the more effective.
iv) The increased char formation observed with the hydrated fillers was attributed to
their endothermic cooling effect, causing slower heating and favouring crosslinking
as opposed to pyrolytic degradation processes. The difference in effectiveness between
aluminium and magnesium hydroxides was further attributed to the higher
decomposition temperature of the latter better favouring the crosslinking processes
in the SBR foam.
v) The possible synergy of aluminium/magnesium hydroxide mixtures was briefly explored.
vii) The occurrence of afterglow, possibly due to slow burn-off of carbon residues, was
also noted with magnesium hydroxide.
291
Mosesman and Ingham examined the effect of various fillers on smoke generation from
ethylene-propylene-diene monomer (EPDM) elastomers under both flaming and non-
flaming conditions, using the NBS smoke chamber [44]. The fillers used were calcium
carbonate, soft clay, ATH and magnesium hydroxide.
Very little difference was noted between the fillers under non-flaming conditions. Under
flaming conditions, both hydrated fillers performed better than the soft clay with
magnesium hydroxide being far superior to ATH. Surprisingly, calcium carbonate gave
results almost as good as the magnesium hydroxide. Unfortunately, no mechanistic studies
were carried out.
Keating, Petrie and Beekman compared magnesium hydroxide and calcium carbonate in
polypropylene using the NBS smoke chamber [45]. Magnesium hydroxide gave some
smoke reduction compared to the inert filler under flaming conditions and also under
non-flaming conditions at high heat fluxes. They also compared magnesium and ATH in
polyethylene, where the magnesium compound again gave better results under flaming
and higher heat flux, non-flaming conditions.
In both polymers, magnesium hydroxide was observed to promote char formation compared
to the other fillers; as determined by the carbon content of the residue from pyrolysis
experiments. This was thought to be the origin of the reduced smoke levels observed.
Hornsby and Watson have examined the effect of fillers on smoke generation from a
number of polymers [26, 32, 46]. Magnesium hydroxide was found to give marked
smoke reductions (more than expected from dilution effects) under both flaming and
non-flaming NBS smoke chamber conditions when added to acrylonitrile-butadiene-
styrene (ABS), polypropylene oxide (PPO) and polybutylene terephthalate polymers. All
these polymers give very high levels of smoke when unfilled. Polypropylene was examined
using the UITPE4 test (International Union of Public Transport Method E4, also known
as the 3 metre cube test from the size of the test chamber). The expected dilution effect
on smoke was observed with calcium carbonate, with significantly lower smoke levels
being observed with both aluminium and magnesium hydroxides. In this case, the ATH
gave slightly better results. Magnesium oxide was found to give similar smoke reduction
levels to the hydroxide, indicating again that the water release does not play a significant
role in smoke reduction.
The levels of carbon monoxide evolution were also found to be reduced from ABS and
PPO containing both magnesium hydroxide and oxide, again indicating that the water
gas reaction has little effect.
They also noted a reduced effect from magnesium hydroxide under non-flaming
conditions, which they associated with incomplete filler decomposition.
292
Overall, their conclusions were that the smoke reducing effect is predominately a
consequence of the high surface area oxides resulting from filler decomposition. They
adsorb soot precursors leading to solid state coking processes and also promote subsequent
oxidation of the carbon to non-obscuring oxides. The reduced combustion rates may
also play a part in improving oxygen to fuel ratios, thus further reducing smoke.
These workers also draw attention to the afterglow phenomenon associated with slow
carbon burn-off.
Hirschler and Thevaranjan investigated the effect of magnesium oxide and hydroxide on
smoke formation from polystyrene [47]. Both additives were found to produce marked
reductions in smoke, again showing that the endotherm and water release are unimportant
in this effect. In other work, Hirschler found that very small quantities of high surface
area silica were an effective smoke suppressant for polystyrene [48]. This was thought to
function by sintering to form a glassy surface layer.
Herbert has reported on the effect of ATH in a peroxide crosslinked EVA [34]. Using the
cone calorimeter with an irradiation of 35 kW/m2, the ATH was found to give much lower
smoke levels than calcium carbonate and aluminium oxide fillers.
In addition to their use in non-halogenated systems, fillers, especially of the hydrate type,
have been extensively studied for use in halogenated polymers such as polyvinyl chloride, or
in conjunction with halogenated flame retardants. The aim is to combine their effects and
produce a composite with high flame retardancy, low smoke and low corrosive gas emission.
One of the problems of using fillers to adsorb hydrogen halides is that this prevents them
functioning as gas-phase flame retardants and hence can reduce the flame retarding effect,
although this can to some extent be offset if hydrated fillers are used.
This approach appears to have had reasonable success but has received little fundamental
study. One of the earliest studies was by Stewart and co-workers who demonstrated the
benefit of ATH in reducing smoke from polychloroprene foam [49].
6.4.4.3 Afterglow
The afterglow phenomenon is a recurring theme in the work described previously. This
effect can seriously reduce the effectiveness of flame-retardants in certain applications
and hence must be taken seriously.
A detailed study of this effect in filled ethylene-vinyl acetate copolymer has been made by
Delfosse and co-workers [41]. Using a heated quartz reactor purged with air, they were
293
able to follow self-ignition and incandescence effects both visually as well as by monitoring
the temperature of the sample and of the gas phase just above it. Depending on the reactor
temperature a polymer sample will slowly oxidise, incandesce or burst into flame.
The unfilled polymer was found to have a self-ignition temperature of about 456 C.
Below this, it slowly oxidised with weak exothermicity and no incandescence. Fillers
such as aluminium and magnesium hydroxide were found to progressively raise the ignition
temperature, with magnesium hydroxide being the more effective at low loadings. At the
same time, however, incandescence appeared at lower temperatures. The onset temperature
of incandescence decreased with filler loading and the magnesium hydroxide used was
found to have a greater effect than the aluminium hydroxide at all loadings. These effects
are summarised in Figure 6.13.
It was also observed that the residue from the experiments under incandescent conditions
was a white ash with no carbonaceous matter. By contrast, a kaolin filled sample showed
no incandescence and a black residue below the self ignition temperature. Thermal analysis
Figure 6.13 The effect of aluminium and magnesium hydroxide fillers on the self-
ignition and incandescence temperatures of an EVA coplymer.
(Reproduced with permission from L. Delfosse, C. Baillet, A. Brault and D. Brault,
Polymer Degradation and Stability, 1989, 23, 4, 337, Figure 1 [41]. Copyright,
1989, Elsevier Science)
294
studies showed that both flame retardant fillers affected the pyrolysis of the polymer
with more complete oxidation observed in the final stages.
Overall they concluded that the afterglow or incandescence was, like smoke reduction,
due to catalytic oxidation of carbonaceous residues by the oxides resulting from filler
decomposition. The greater effect of magnesium hydroxide was then assigned to the
known greater catalytic effects of its oxide.
In later work Baillet and Delfosse examined the effect of the flame retardant fillers on
the formation of carbon oxides during pyrolysis of an EVA polymer and tested various
additives for incandescence suppression effects [50]. Using the same quartz reactor
described previously, they demonstrated that below the self-ignition temperature, the
filled systems gave much more complete oxidation (higher CO2:CO levels) than the unfilled
polymer. This supports the greater degree of char combustion referred to previously.
In their search for incandescence inhibitors, they screened a number of known organic catalyst
poisons but without success, probably due to insufficient thermal stability. Inorganic additives
proved more promising. Ammonium polyphosphate (APP) was found to be very effective
but suffers from water sensitivity problems and was rejected on this basis. Surprisingly
antimony trioxide, which is often regarded as an incandescence promoter itself, was found
to be very effective and was their preferred material. Unfortunately, the effectiveness of
antimony trioxide on flame retardancy and smoke formation was not reported on.
6.4.4.4 Summary
While the results are far from conclusive, and the danger of generalising must be borne
in mind, the following picture is emerging:
i) Fire retardant fillers such as aluminium and magnesium hydroxide generally reduce
the smoke from burning polymers, especially under flaming as opposed to non-
flaming conditions.
ii) The mechanism of their action seems independent from their endothermic and water
releasing characteristics. It seems to be composed of a simple dilution effect exhibited
by all fillers, plus solid state carbon formation and oxidation capabilities associated
with the catalytic nature of the oxide formed and the high surface area resulting
from the filler decomposition process. Improved oxygen to fuel ratios due to slower
burning may also play a part.
iii) There is some evidence that magnesium hydroxide is a more effective smoke suppressant,
probably due to greater catalytic activity of the oxide formed. However, this also manifests
itself in an afterglow phenomenon, which may be a problem in some applications.
295
6.5 Nano-Clays
Currently there is much interest in the use of nano-clays as flame retardant additives for
polymers. The topic has recently been reviewed by Porter and co-workers [51]. Present
understanding is not well developed, but Gilman and co-workers at NIST are carrying
out an extensive study of the area [52, 53]. Commercial applications are also starting to
appear [54].
The production and characteristics of nano-clays are covered in Chapter 2 of the present
work. Their uses in polymers, including further discussion of fire retardant effects, are the
subject of Chapter 10. Some aspects of their compounding are dealt with in Chapter 5.
Nano-clay composites contain very thin, high aspect ratio, alumino-silicate platelets, derived
from the stacks present in the parent clay. Two types of structure can be recognised, intercalated
and delaminated. In the intercalated form, the stacks of platelets are still present, but with
polymer chains present between clay platelets, pushing them apart. In the delaminated form,
the original stacks are no longer present, and the platelets are fully dispersed.
Due to their nature, nano-clay loadings are usually restricted to about 10% w/w because
of processing difficulties. At these levels, they show little benefit in the traditional small
scale tests, such as oxygen index and UL94 and this probably led to a lack of interest in
them until recently. It has now been found that very good results can be obtained with
filler loadings of 2-10% in some fire retardant test parameters, particularly using the
cone calorimeter, and they are now receiving serious study.
The principal effects observed in cone calorimeter tests are a marked reduction in peak
and average rate of mass loss and in heat release. There appears to be little reduction in
total heat of combustion or in smoke levels. The workers at NIST report that there seems
to be little difference between intercalated and delaminated forms of nano-clay, despite
evidence that polymer thermal stability can be more improved by the intercalated structure.
As an example, Gilman and co-workers [52] reported a reduction of over 60% in peak
heat release rate for a 5% w/w loading of a nanoclay in polystyrene. There was little
benefit from increasing the loading beyond 5%. They also found that the processing
conditions were critical to obtaining good fire retardant effects. Similar reductions in
peak heat release rate have been reported for other polymers, including polyamides and
polypropylene [55]. Alexandre and co-workers [56], reported similar results for an EVA
composite. They found a 47% reduction in the peak heat release rate at 5% w/w of a
nano-clay and no further benefit by increasing the loading. The effect on ignition time is
not clear, but the workers at NIST have reported that the ignition time can sometimes be
reduced, an effect that they think may be due to instability of the surface treatment
present on the clay that was used.
296
The primary effect of the nano-clays seems to be related to char formation. The workers
at NIST have found that a reduction in mass loss and heat release rate only starts once
the surface of the polymer is at least partly covered by char. Beyer reported that, while
no char was produced by burning unfilled EVA, the filled composite formed a strong
char early in the process [54]. Once the amount of clay is taken into account, final char
levels are often similar to unfilled polymer, indicating that while a stronger, more insulating,
char may form and retard combustion, it is eventually consumed in this test.
Currently, nano-clays are of most interest as admixtures with flame retardant fillers such
as ATH, rather than as primary flame-retardants. Beyer [57] has reported that replacement
of a small amount of ATH can significantly improve fire retardancy and increase char
integrity at the normal filler loadings used. Alternatively, the overall filler loading can be
significantly reduced, while maintaining the existing level of fire retardancy.
This work is still in its infancy, and further developments in understanding, products
and applications can be expected.
6.6 Ammonium Polyphosphate (APP)
Although not strictly a filler, this additive deserves a brief mention. Its mode of action is
predominately by the promotion of char formation, resulting from high acidity phosphoric
acids produced on pyrolysis. The polyphosphate is used, as it is less water soluble and
hygroscopic than the orthophosphate. APP is effective on its own in polymers with suitable
chemistry for char formation to occur by this mechanism. In other polymers, it is used in
conjunction with a charring agent, such as a melamine derivative [58].
6.7 Fillers for Use in Conjunction with Halogens
Organo-halides, especially bromides, are very effective fire retardants for most polymers.
They work mainly by interruption of the gas phase combustion processes. This leads to
incomplete combustion and high levels of smoke formation.
It has been known for a long time that the efficiency of the halogenated flame retardants
can be much increased by the use of certain additives, usually known as synergists. Most
of these synergists are particulate inorganic fillers. Their main mode of action is believed
to be the result of the formation of volatile metal halides.
The main synergist in commercial use is antimony trioxide, which is believed to

function by forming volatile antimony halides, which interfere with the gas phase
297
combustion processes. Antimony oxide appears to have little solid phase activity,
with most of the antimony being lost to the gas phase during combustion. High
levels of smoke result from the gas phase action. Maximum efficiency is generally
found at an antimony to available halogen molar ratio of 3:1. Touval has provided a
good review of this additive [59].
Alternative synergists include borates, molybdates and stannates. The borates and
stannates are often in the form of zinc salts. Cook and Musselman have recently reviewed
the performance of these materials [60]. Cusack and co-workers have also carried out
extensive studies of the zinc stannates [61, 62]. Briefly, it appears that, in addition to gas
phase effects similar to antimony trioxide, these additives show significant solid state
activity, increasing char formation, with considerable amounts of the metal remaining in
the solid phase. It appears that most of the solid state effects are due to halide salts and
so require the presence of halogen. The borates may also give a stronger, glassy char.
There may also be some endotherm and inert gas contribution from some of the materials.
Higher addition levels tend to be needed than with antimony oxide, but smoke levels are
lower. These additives are usually used in combination with antimony oxide for best
overall effect. Cusack and co-workers have reported that the efficiency of the zinc stannates
can be markedly improved if they are finely divided and carried on a filler such as ATH
to improve dispersion.
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302
7
Particulate Fillers in Elastomers
David Skelhorn
7.1 Introduction
This chapter is devoted to the use of particulate fillers in elastomers, which make greater
use of fillers than do most other polymers, largely because fillers are able to improve
greatly many of their properties to an extent not found in other composites. This is
particularly true of their use in automobile tyres where the high performance levels taken
for granted today would not be possible without very sophisticated carbon blacks and
silicas. Because of the value of fillers to the elastomer industry, it is not surprising that
the most advanced work on filler characterisation and links with composite properties
have been carried out in this area. Many of the filler characterisation aspects have been
covered elsewhere. This chapter concentrates on the basic principles of elastomer
formulation and the role of fillers in this.
7.2 Uses of Elastomers
Elastomers are used in a wide range of industrial, transportation, domestic, construction

and aerospace end-applications. The major consumer of both natural and synthetic rubber
is the tyre industry. Five types: natural rubber (NR), styrene butadiene rubber (SBR),
polybutadiene, polyisoprene and the butyl (and halobutyl) rubbers are used in massive
quantities around the world. Smaller applications for rubbers include: conveyor belting,
footwear, pharmaceutical closures, plant lining, hoses, extruded goods, flooring, power
cables, gaskets and seals, and many, many other applications.
7.3 Elasticity of Rubber
Rubber as an engineering material is unique in its physical behaviour. It exhibits

physical properties that lie mid-way between a solid and liquid, giving the appearance
of solidity, while possessing the ability to deform substantially. Most solid materials
have an extensibility of only a few percent strain and only a portion of that is elastic,
being typically Hookean in character, exhibiting a linear stress-strain relationship.
Rubbers, however, may be extensible up to over 1000% strain, most of which is
303
elastic and non-Hookean. This is true of rubbery materials that have been vulcanised.
Rubber in the unvulcanised state exhibits substantial flow in addition to elasticity
and should be regarded as a high-viscosity fluid, a factor that is vital to the
manufacturing operations. Like all polymers, rubber is a viscoelastic material with
complex flow behaviour [1].
Rubbers exhibit these properties because unlike conventional solids, which are
comprised of atoms that occupy fixed positions relative to each other, they are formed
from molecules that are arranged to form a flexible, long-chain macromolecule or
polymer. While not all polymers are rubber-like, all rubbers are polymeric. The
characteristic that makes a polymer rubber-like is its ability to undergo rapid molecular
movement, allowing it to deform readily, and the ability of the molecule to return to
its original configuration after the deforming forces have been removed. A number
of qualities are necessary for attainment of rubber-like properties.
Polymers may exhibit a number of different properties, which are dependent on

temperature. Heat is a major source of the energy required for molecular mobility
(Figure 7.1). Under low-energy conditions (cold), molecular rotation is slow so the
polymer behaves as a rigid solid. As energy availability increases, the polymer
progressively becomes leathery, then rubbery, followed by a transition to a rubbery
fluid and ultimately total fluidity is achieved. A rubber, therefore, is a polymer whose
rubbery region coincides with ambient temperature. It also follows that, on cooling,
the rubbery behaviour will be lost (below the glass transition temperature) and, on
heating, the rubber will ultimately become more fluid and flexible.
Figure 7.1 Variation of stiffness with temperature for polymers.
304
It is also essential that the polymer be of sufficient length, otherwise the molecule will
behave essentially as a fluid and will possess little elasticity. Relative molecular masses
in the range 100,000-2,000,000 are typical for rubbers, which ensures that a significant
amount of chain entanglement occurs.
Only a relatively small number of polymers have sufficient mobility to be rubbery at

room temperature. The molecular mobility depends heavily on the composition of the
polymer backbone, which often contains a significant proportion of simple hydrocarbon
species, such as those derived from ethylene, butadiene or isoprene. These species are
small and are able to undergo bond rotation with relative ease, since they do not suffer
problems due to steric hindrance [2] or the presence of strong dipoles. The rubber
molecule is also able to undergo extension easily because the forces acting on the material
are relatively weak secondary intermolecular forces, i.e., those acting between molecules,
and not the primary inter-atomic forces, i.e., those existing within a molecule [3].
A further requirement, that of recovery of shape after deformation, is also provided by

high molecular mobility and the fact that long-chain polymers have a preference to
exist as a randomly coiled chain, which represents a minimum energy-state condition
for the polymer. A move away from this state, such as occurs during mechanical
deformation of the polymer, is only achieved by the input of energy, which creates a
state of higher order in the thermodynamic sense, i.e., a reduction in the entropy
(disorder) of the system. The return to maximum entropy is one of the key elements of
a high elastic recovery [4, 5].
Another important element for rubbery behaviour is the fixation of the polymer
molecules relative to each other, since flow would occur as a result of a deforming
force, if this were not achieved. This state is conventionally achieved in rubber by a
crosslinking or curing process, where chemical reactions are initiated with the specific
intention of joining adjacent polymer molecules via a small number of chemical bonds
or bridges. The frequency of bond formation must be carefully controlled, since too
few would result in excessive fluid behaviour, while too many results in loss of flexibility.
This is an area of great complexity for the rubber chemist.
Other materials that achieve rubbery behaviour may achieve this state by physical
processes, such as when a copolymer contains one element that has elastic properties
and another that is glassy or crystalline. In this case, the glassy or crystalline portion
may exist as a separate rigid phase, binding the polymer spatially. Such materials are
generally described as thermoplastic elastomers, since on heating to a temperature
above the melting point of the glassy or crystalline element, the polymer attains fluidity
and may be processed as a thermoplastic. This class of material is not considered further
in this chapter.
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7.4 Formulation of Elastomers
7.4.1 General
Elastomers are complex mixtures of a large number of different materials. Essential

additives for elastic behaviour would include crosslinking agents and anti-degradants.
These are often complex blends of a number of chemicals designed to achieve a balance
of process and end-use performance at minimum cost. Many other specialised additives
are used according to the needs of the product being considered. A rubber produced
using only the additives described thus far would have physical properties which are
totally unsuitable for most engineering applications. The modulus (resistance to
deformation) is very low and the product highly extensible. For many polymers physical
properties, such as tensile or tear strength, may also be very poor. One of the main ways
of modifying elastomers, so that acceptable engineering properties are obtained, is by
the incorporation of fillers. The filler system may be composed of one or more of a wide
variety of materials, but the main classifications used are carbon blacks, silicas and mineral
products such as kaolin (china clay) or calcium carbonate. Each filler imparts a particular
balance of properties, and selection, therefore, is made based on the property requirements
of the end product.
Typically, carbon blacks would be used to enhance strength characteristics, while minerals
provide a more modest strength enhancement at significantly reduced cost. All modify
processing performance and allow the production of articles that could not otherwise be
fabricated.
A rubber formulation may be broken down into a number of component groups, which
has a specific function. These are listed in Table 7.1 and discussed by class below.
7.4.2 Selection of Polymer
The first decision in the design of a rubber formulation is the selection of the base polymer
to be used. This choice will be determined principally by the end-product specification
and/or service conditions. This will stipulate such conditions as upper and lower operating
temperatures, type and level of chemical or fluid resistance, mechanical or electrical
properties, etc. This task requires a comparison of the basic properties of the polymer
types and grades available with a view to making a selection on a cost-effective basis.
There are few areas of ambiguity about the choice of polymer to be used as most polymers
have a specific profile of chemical and physical properties. Where a single polymer cannot
provide the requisite properties, then a blend of two or more may often be used. The
performance aspects of the polymer are discussed further in Section 7.5.
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Table 7.1 The rubber formulation

Addition
Ingredient Function
range (phr)
Polymer 100 Determines the base properties of the end
product, (e.g., elasticity, resistance to
oxidation, fluids and chemicals; low-
temperature, dynamic and electrical properties)
Curing system 5-15 Determines the rate of cure to an elastic material.
Influences the mechanical properties and stability
of the rubber
Antioxidants/ 0-7 Inhibit attack by oxygen and ozone. Improve
antiozonants flex fatigue and inhibit the degradation effects
of metal impurities
Coupling agents 0-2 Modify the polymer-filler interface
Oils/plasticisers 0-250 Modify mechanical and processing properties
and low-temperature flexibility
Fillers 20-400 Modify mechanical properties, processing
characteristics and cost
Examples of specialised additives
Process aids 0-20 Influence the processing behaviour of the
rubber compound
Peptisers 0-3 Reduce compound viscosity
Mill release 0-10 Prevent sticking to processing equipment
Fire retardants 0-300 Inhibit the rubber's ability to burn
Smoke suppressants 0-20 Inhibit smoke evolution on burning
Tackifiers 0-30 Promote building tack
Pigments and dyes 0-20 Used to colour the compound
Bonding agents 0-6 Allow direct bonding of the rubber to a variety
of substrates, (e.g. metals, textiles)
Antistatic agents 0-4 Prevent build-up of surface charges
Odourants 0-2 Mask or modify the odour of rubber
Blowing agents, etc. 0-20 Generate gas during cure to form expanded
open- or closed-cell foamed products
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7.4.3 The Curing System
The selection of chemicals used for crosslinking the rubber has to be made based on the
chemical reactivity of the polymer, and the stability and type of crosslink that will perform
best in the end product. A number of basic types are used but within these categories the
complexity of chemicals in use may be high.
7.4.3.1 Sulfur-based Systems
This type of curing system is used for those rubbers containing unsaturation, which is
either along the polymer backbone or, as in the case of ethylene propylene diene elastomer
(EPDM), it is pendant to the backbone.
Sulfur-based systems are the most frequently used system for several reasons:
1. The polymers using this system form the bulk of rubbers in use.
2. The systems are relatively inexpensive.
3. The system is extremely flexible due to the diversity of materials available for use.
This allows considerable scope for engineering the system to the needs of both
production and performance requirements.
Sulfur-curing systems are comprised of several components, which are listed next [6].
(a) Activators. The materials normally used are zinc oxide and stearic acid. Other oxides
of cadmium or lead may be used for specific properties, and other fatty acids may be
used. Zinc carbonate or stearate may be used where translucency is required.
(b) Elemental sulfur or a sulfur donor. Several grades of sulfur are available and a number
of organic accelerators are capable of generating free sulfur during the curing reaction.
Sulfur forms the interchain crosslinks.
(c) Organic accelerator(s). These materials are often used in combination to gain improved
efficiency or to ensure solubility of the system in the polymer. They control the rate
of crosslink formation and influence the type and stability of the crosslink.
(d) Retarders and prevulcanisation inhibitors. Retarders may be added to delay and
slow down the rate of crosslink formation. Prevulcanisation inhibitors delay the onset
of cure but do not reduce rate of cure. These are not essential components of the
sulfur-curing system but provide additional control of the cure process.
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Figure 7.2 Sulfur vulcanisation of diene rubbers
The chemistry of the sulfur system is extremely complex, but the generally accepted
mechanism involves the formation of zinc-accelerator complexes, which interact with
sulfur to form a zinc perthio salt [7].
This salt reacts with a rubber hydrocarbon to form a rubber-bound intermediate. This
intermediate extracts hydrogen from another rubber hydrocarbon (which is most frequently
in the alpha position relative to the double bond) to form a crosslink. Accelerator is regenerated
during the process to continue the reaction with sulfur and zinc oxide (Figure 7.2).
7.4.3.2 Metal Oxides
Several rubbers may be crosslinked using divalent metal oxides, usually zinc oxide. There
are a limited number of polymers that utilise this method, which is used with halogenated
polymers such as polychloroprene [8], chloro- and bromobutyl, and chlorosulfonated
polyethylene and carboxylated nitrile rubbers. The system may utilise the metal oxide
alone or in combination with the organic accelerators used with sulfur-curing systems. In
the case of halogenated polymers, magnesium oxide may be added to act as an acid scavenger.
7.4.3.3 Peroxides
Peroxide-curing agents are effective at crosslinking most rubbers. Exceptions to this

are butyl and chlorobutyl rubber, some polyacrylates and some fluoropolymers (these
being grade dependent). Peroxides form direct carbon-carbon crosslinks, which are
309
inherently, more stable than many other crosslink types. The short length of the
crosslink, however, results in reduced extensibility and mechanical strength. The use
of co-agents, such as acrylates or cyanurates, enhances the efficacy of the peroxide
crosslinking reaction by reducing the losses resulting from chain scission and results
in a modified crosslink structure in which the co-agent is substituted for the direct
carbon to carbon bond.
7.4.3.4 Other Curing Systems
Many other chemicals are available for crosslinking rubbers. Some of these materials have
broad applicability while others are specific to certain polymer grades. Examples are:
Resin-curing systems Silane crosslinking

Soap/sulfur systems Isocyanates
Urethane crosslinking agents Poly-functional amines
Bisphenol curing agents High-energy radiation
7.4.4 Antioxidants and Antiozonants
Most of the rubbers used commercially require addition of an antioxidant whose function
is to protect against high temperature or long-term oxidative degradation. Only the
more thermally stable polymers may have sufficient stability not to require antioxidant
protection. There are many classes of antioxidant but for simplification these can be
categorised as staining types (amine based) or non-staining (phenol based). Antioxidants
often have secondary protective properties such as protection against light, flex fatigue
and inhibition of heavy-metal catalysis.
Antiozonant protection is required for most rubber products, which are based on diene
rubbers. Ozone attack is different to oxidative ageing in that specific conditions are
required for it to occur. These conditions are:
(1) presence of ozone;

(2) unsaturation in the polymer backbone; and
(3) a specific strain level must be exceeded (critical strain).
Many of the chemical antiozonants also provide powerful antioxidant protection. The
most important of these are the paraphenylene diamines but other products also have
commercial importance.
310
Wax blends are also widely utilised for static ozone protection. The wax migrates to the
rubber surface where it forms a protective film. This film cracks, however, when the
product is flexed. The most comprehensive system uses a combination of both materials.
The wax enhances the chemical system by carrying it to the surface more efficiently
where it is required.
7.4.5 Coupling Agents
Coupling agents are chemicals, which are able to form a strong, physical or chemical
bond between a filler and the polymer in which it is used. By so doing, the properties
of the composite can be significantly modified. Coupling agents are important
technically, as they allow composite materials to be produced with enhanced
performance characteristics.
Coupling agents are discussed in detail in Chapter 4. In rubber systems, coupling agents
can improve a wide range of properties, so much so that they are indispensible for high
performance products such as power cable [9] and tyres [10, 11].
One point of fundamental importance when selecting a coupling agent is to ensure

that it is able to react with both the filler and the polymer, which is being used. The
level of addition must also be determined experimentally, if the desired results are to
be achieved.
With most coupling agents it is possible to either pre-treat the filler in advance of
mixing the compound, or to add the coupling agent directly to the mixer where reaction
takes place in situ. In many applications, either method can be used to achieve similar
results. In some cases, both methods of treatment must be used together to achieve
optimum performance [12]. A number of coupling agent types are available
commercially and include organo-silanes [13], organo-titanates and carboxylated
polybutadienes [14].
7.4.6 Process Oils and Plasticisers
Plasticisers used in rubbers are materials, which have the effect of reducing compound
viscosity, thus making the material more plastic during processing. These materials also
function to control physical properties such as hardness and low-temperature flexibility.
Plasticisers have an influence on many other properties and thus must be selected in
order to provide the overall property profile for the end product. Basic types available
are as described in the following sections.
311
7.4.6.1 Mineral Oils
(a) Paraffinic oils. Composed of mixed hydrocarbons but containing, predominantly,

non-cyclic linear or branched hydrocarbon species. These are used in non-polar
rubbers such as EPDM and butyl rubber.
(b) Naphthenic oils. Composed of mixed hydrocarbons but containing, predominantly,

unsaturated cyclic hydrocarbon species. These are used as general-purpose
plasticisers in many rubbers because of their relatively low cost and broad
compatibility with non-polar and moderately polar rubbers.
(c) Aromatic oils. Composed of mixed hydrocarbons but containing, predominantly,

unsaturated cyclic aromatic species. These are used in general-purpose rubbers
such as NR and SBR because of their low cost and efficacy. These materials are
dark coloured and cause staining, which limits their use.
The composition of the oils may be inferred from several of the key properties
measured [15] which includes the viscosity-gravity constant, refractive index, density
and aniline point. Other properties measured include viscosity, flash point, volatility
and colour.
7.4.6.2 Ester Plasticisers
A wide range of products fall into this category based on monomeric and polymeric
types. Used with polar polymers for compatibility reasons. Selection of type used must
be made according to properties required [16]. These may be classified as general-
purpose, low-temperature, high temperature, flame-retardant or permanent plasticisers.
7.4.6.3 Other Types
Many other classes of material are used as plasticisers for rubber for specific property
enhancement. Examples are:
Chlorinated paraffins Low-cost flame retardant

Reactive monomers Polymerise during cure
Thermoplastic polymers High-temperature plasticisers
Resinous materials High-temperature plasticisers
Liquid polymers Co-vulcanise with the rubber
312
7.4.7 Fillers
Fillers of many types are used in rubber formulations. A filler may be considered to be
any particulate material, which is added for one or more of the following reasons:
1. Modification of physical properties.

2. Modification of processing performance.
3. Reduction in cost.
7.4.7.1 Modification of Physical Properties
Fillers influence the whole spectrum of physical characteristics of a rubber, including

hardness, strength, extensibility, heat build-up, vibration damping, electrical insulation
or conductivity, colour, long-term ageing performance, permeability to fluids, swelling
in and absorption of fluids, and adhesion to substrates.
7.4.7.2 Modification of Processing Performance
It is true to say that, of the many materials used in the rubber formulation, it is the
polymer that is the cause of poor processing behaviour. This is to be expected, because it
is the very quality of possessing elastic behaviour that confers poor processing
performance. For ease of processing the compound must often be formulated to behave
as a non-elastic (plastic) material for the purposes of shaping and shape retention. This
must be followed by conversion to an elastic material for the end product (vulcanisation).
These conflicting requirements must be rationalised in the formulation of the compound.
The main method of achieving a formulation with good processing performance is to

replace a portion of the polymer with materials, which do not exhibit elastic behaviour.
Most compounding ingredients are non-elastic and addition of fillers provides one
important means of influencing this property by direct replacement of polymer, by physical
interaction with the polymer and by permitting increased levels of liquid plasticisers to
be used without sacrificing other valuable properties.
7.4.7.3 Reduced Cost
The volume cost of fillers used in the rubber industry is usually below that of the
polymers in which they are used. The extremes of cost vary from approximately one-
twentieth of the polymer cost to costs that are similar in magnitude to the lower cost,
general-purpose rubber grades.
313
Selection of filler type must be made with careful consideration of materials available
and their cost-performance characteristics. It is quite common for a multiplicity of products
to be used to gain specific benefits in one area or another. The use of fillers is discussed
in detail in Section 7.6.
7.4.8 Specialty Additives
A wide variety of chemicals may be added to impart specific properties to a rubber.

These include the following types:
7.4.8.1 Process Aids
The term process aid is a general description for any material that will improve one or
more aspects of the processing behaviour of rubber. These materials generally improve
the flow behaviour, providing smooth surface finish to calendared or extruded products.
Typical process aids include the following material types:
Paraffin wax Fatty acids

Soaps Emulsified esters
Polyethylene waxes Polyethylenes
Polyoctenamer Liquid polymers
7.4.8.2 Peptisers
Peptisers are materials that reduce the viscosity of rubber. They fall into two classes, chemical
peptisers and physical peptisers. Chemical peptisers are materials that are added to a rubber
compound and cause a reduction in the molecular weight of the polymer, reducing viscosity.
Physical peptisers reduce viscosity by functioning as internal lubricants for the polymer,
allowing polymer chains or localised polymer domains to slip easily past each other during
processing. The molecular weight of the polymer remains relatively little changed [17].
7.4.8.3 Mill and Mould-Release Agents
Many additives aid the release of rubber compound from the steel processing equipment
used for processing. The materials used are often chosen for their effectiveness in specific
polymer types and include the following:
314
Cis-polybutadiene Fatty acids and soaps

Waxes (paraffin and polyethylene) Emulsified fatty-acid esters
Factices
7.4.8.4 Fire Retardants
A wide range of materials are available that will inhibit combustion. Many may be
classified in other ways, e.g., fillers or plasticisers. Examples are:
Aluminium trihydrate (ATH) Fine calcium carbonates

Antimony trioxide Chloroparaffin plasticisers
Magnesium hydroxide Zinc borate
Phosphate ester plasticisers Halogenated hydrocarbons
7.4.8.5 Smoke Suppressants
A number of materials may inhibit smoke generation during burning such as ATH and
magnesium hydroxide.
7.4.8.6 Tackifiers
Many resinous products increase building tack, which is important for the construction
of many rubber products. Examples of these are:
Coumarone-indene resins Terpene resins

Petroleum hydrocarbon resins Phenol-formaldehyde resins
7.4.8.7 Pigments and Dyes
For coloured products, it is necessary to use a colouring agent (pigment) in conjunction

with a white base. This is normally achieved by addition of titanium dioxide (or
alternatively lithopone or zinc oxide) plus a pigment, which may be either organic or
inorganic in nature.
Soluble dyes may be used in some systems to allow compound identification to be made
easily by rubbing of the final product with solvent wipe to reveal the dye, giving positive
identification of the composition.
315
7.4.8.8 Bonding Agents
Many rubber composites require that the rubber adheres permanently to a substrate
such as steel, brass, textiles or other media. There are a number of established
proprietary additives, which may be added to the rubber compound, which function
in this capacity. The resorcinol-formaldehyde-silica (RFS) system is commonly used
to achieve adhesion to metals. This system relies on the interaction of resorcinol (or
a resorcinol donor), a methylene donor such as hexamethylene tetramine and
precipitated silica. Other systems that may rely on cobalt complexes or blocked
isocyanates may also be used.
7.4.8.9 Antistatic Agents
These are usually highly polar liquids, which form a surface film that is antistatic in
character. This prevents the build-up of electrostatic charges on the surface of the product.
This type of additive is normally added to light-coloured compounds, as most carbon-
black-filled composites are inherently antistatic. Many of these proprietary additives are
quaternary amines.
7.4.8.10 Odourants
A number of products are available to mask the characteristic odours of rubber products.
This may be desired for domestic products.
7.4.8.11 Blowing Agents
Foamed products may be produced by adding a chemical, which decomposes, usually

during curing, to generate gas (usually nitrogen or carbon dioxide). This gas remains
dissolved in the rubber under high pressure during cure but expands immediately on
release of the moulding forces applied during cure, forming a micro-cellular or open
cell foam.
7.4.8.12 Other Additives
This list is not by any means exhaustive but does give some idea of the complexities
involved in formulating rubber products. Many other specialty additives may be added
according to the requirements of the application.
316
7.5 The Performance of the Polymer
7.5.1 Specification of the Polymer
The properties used to describe a polymer are many and varied, but depend to a degree
on the special characteristics of the individual products. The basic properties that describe
the polymer, such as composition or rheology, are required in order to select the
appropriate polymer for any application. These properties, which indicate such
performance characteristics as upper and lower temperature resistance or oil resistance,
are usually described in general terms, partly because the values obtained depend on the
method of measurement and partly because the exact properties are formulation
dependent. These do allow the chemist to select from a narrow range of polymers those,
which are likely to conform to performance criteria. Data of this type are often presented
in graphical or tabular form (Figure 7.3 and Table 7.2).
Figure 7.3 Performance characteristics of various polymers.
317
Table 7.2 Polymer characteristics
318
Working temperature (C) Resistance to: Gas Electrical
Rubber type
Minimum Maximum Ozone Light Oil permeability insulation
Natural rubber -50 100 P P P H VG

Butadiene rubber -80 100 P P P H G
Styrene butadiene rubber -50 120 P P P H G
Polynorbornene -50 70 P P P H P
Ethylene propylene rubbers -40 150 E P M H E
Polyolefin elastomers -60 175 E P P M E
Butyl rubber -50 130 VG M M VL VG

Chloroprene rubber -50 100 VG M G H P
Polysulfide rubber -50 70 VG VG E VL P
Chlorosulfonated polyethylene -50 140 E E G H M
Nitrile rubber -50 125 P P VG M-L P
PVC-nitrile -40 100 E G E L P
Poly(ether)urethane -50 100 E G E H G
Poly(ester)urethane -50 100 E G E H P
Epichlorhydrin copolymer -40 130 E G G M P
Epichlorhydrin homopolymer -10 150 E E L H M
Chlorinated polyethylene -40 150 E G VG H M
Table 7.2 Continued
Working temperature (C) Resistance to: Gas Electrical
Rubber type
Minimum Maximum Ozone Light Oil permeability insulation
Polypropylene oxide -50 135 E E G H M

Ethylene vinyl acetate -50 180 E G VG H P
Hydrogenated nitrile rubber -50 175 E G VG M- L P
Acrylic rubbers -40 180 E G E M P
Silicone rubber -100 250 E E P H E
Fluoroelastomers -40 250 E E E L E
Perfluoroelastomer -50 300 E E E L E
Polyfluorophosphazene -40 170 E E VG - -
Ethylene acrylic elastomer -30 170 E VG G H P
P = poor; M = moderate; G = good; VG = very good; E = excellent; VL = very low; L = low; H = high
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Cost considerations also have a strong influence on selection. When a specific polymer
type has been selected for use, it then becomes necessary to look in detail at the
differences between grades. Firstly, if the polymer is a copolymer, the level and
regularity of the two monomers in the polymer must be examined. In the case of
nitrile rubber, for instance, the level of acrylonitrile influences most of the properties
of the polymer. High acrylonitrile materials are tough, highly oil-resistant, relatively
thermoplastic elastomers with high brittle point and low gas permeability. Low-
acrylonitrile-content polymers, however, are elastic, moderately oil resistant polymers
with low brittle point and high gas permeability. Intermediate substitution levels of
acrylonitrile provide intermediate properties. Similarly, the styrene level in SBR, or
chlorination or chlorosulfonation level in chlorinated or chlorosulfonated
polyethylenes provide significant property variation [18, 19].
The next basic property that must be fixed is the viscosity of the grade to be used.
This will require some knowledge of the viscosity limitations of the processes to be
used. Viscosity is normally given in Mooney degrees determined on a Mooney
viscometer (ASTM D1646-03) [20] using one of several test temperatures (usually
l00 C or 120 C) and measured after a set period of time. Mooney viscosity influences
such properties as processability, and the ability for extension with fillers and
plasticisers.
NR, as a specific example is often selected according to its oxidation resistance. This
may be assessed by measurement of its plasticity retention index (where Wallace
rapid plasticity is measured before and after heat ageing at 140 C, e.g., ASTM D3194-
99 [21]). The drop in plasticity found after ageing is an indicator of this polymers
oxidation resistance.
For general purpose rubbers, the quantity and type of monomer incorporated for
cure may be of vital importance. This will determine the method and rate of cure
that is possible. Several of the more exotic polymers have recently become available
with termonomers incorporated to allow crosslinking by peroxides rather than by
the use of more exotic chemicals. This has provided a greater degree of latitude to
the chemist in polymer choice.
Stereoregularity is of importance in some cases. Polyisoprenes are available with cis-

isoprene contents between 92% and 98%. This influences the processing and
mechanical properties of the compound substantially. Similarly, SBR are available as
random or block copolymers with different configurations. These influence strength,
rolling resistance and wet skid properties of tyres. In emulsion polymers, the type of
coagulation system and stabiliser added influences the end-application. Similarly,
the type and level of oil and/or carbon black extension of specific grades of polymer
must be controlled.
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7.5.2 Processing Considerations
The term processability describes the ease with which a rubber may be processed. There
are a multitude of processing operations in use within the industry so the term has a very
broad applicability. In general terms, it describes the ease with which the rubber is able
to flow during mixing and shaping processes such as extrusion, calendaring or moulding.
The processability of a compound is influenced by many of the ingredients used in its
manufacture. Indeed, many are added specifically to modify process behaviour. The effect
of fillers is discussed in Section 7.6.2.
The polymer influences processing performance through a number of parameters. Viscosity

is dictated by molecular weight and weight distribution of the polymer. The rate of
change of viscosity with processing temperature varies considerably from polymer to
polymer. A high molecular weight polymer, indicated by a high Mooney viscosity, will be
more difficult to process than its low molecular weight equivalent. However, it may be
possible to incorporate higher loadings of filler and plasticisers to obtain a lower cost
than would be possible with the lower viscosity grade. High-viscosity grades will usually
disperse fillers more readily through the higher shear forces applied during mixing. They
will be less prone to flow at high temperatures, e.g., exhibit good collapse resistance on
extrusion, and cause fewer problems with porosity during low-pressure cure. Heat build-
up during processing, however, will be greater.
Many polymers have their own process characteristics. NR and SBR process very easily
on a two-roll mill. Other polymers process differently. Nitrile rubbers are well known
for bagging (non-adherence to the rolls), while other polymers, especially those that are
chlorinated, tend to stick firmly to the mill roll. Consequently, specific solutions have
been found for each polymers processing idiosyncrasies.
The requirement for ease of processing demands that the rubber behave as a plastic
material. While the effect of heating will aid in converting the tough elastic polymer into
a plastic, the process is far from complete. Many grades of polymer are available in a
pre-crosslinked form to assist in this respect. These polymers have usually been crosslinked
prior to coagulation of the emulsion from which they were derived. The three-dimensional
network helps to reduce the elastic component of the compound but at the expense,
usually, of mechanical strength. Reclaimed rubbers form a supply of polymer with similar
properties because of the residual crosslink structure from the parent material.
7.5.3 Strength Characteristics of Polymers
The strength of rubbers is influenced strongly by the effect of filler type and loading.
This is discussed further in Section 7.6.1. The addition of plasticisers is known to reduce
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strength substantially. The elastomers may be classified into three distinct types
according to their strength properties:
1. Those elastomers that exhibit low modulus plus high strength in the unfilled gum
state because they undergo stress-induced crystallisation.
2. Those with a high modulus and high strength.
3. Amorphous polymers, which have low modulus plus low strength.
Other factors are known to influence strength. If the molecular weight of the polymer
can be maintained at a high level, then strength characteristics will be maintained.
This may be achieved by selection of high-molecular-weight (high Mooney) polymer
initially and/or by using processing procedures that do not cause molecular weight
reduction, (e.g., short mixing cycles and physical rather than chemical peptising).
7.5.4 Compounding Considerations
The principal properties that the formulator attempts to optimise are discussed next.
7.5.4.1 Strength Characteristics and Hardness
The strength characteristics of a rubber, such as tensile stress-strain properties, tear

strength, abrasion resistance and hardness are influenced by the interacting effects of
polymer, additives, vulcanisation conditions and reinforcing characteristics of the
filler(s) used in the formulation. The strength aspects of rubbery polymers were
discussed briefly in Section 7.5.3. The influence of additives may be significant but is
generally deleterious to strength enhancement, especially if the additives themselves
are inherently weak, e.g., if they are liquids or waxes.
Vulcanisation conditions vary enormously according to the process used and chemistry
selected, but may be optimised to provide limited control over product strength. A
full discussion of these parameters is outside the scope of this chapter.
The influence of fillers is generally described under the topic of reinforcement, since
this term describes the influence of particulate materials over strength of the resultant
composite.
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7.5.4.2 Permanent Set
Permanent set measurements provide a means of assessing the longer-term stability of

the crosslink structure under the influence of deforming forces, heat, oxidation, etc. This
type of test may be carried out either in tension (tension set) or, more commonly, under
compression (compression set) by application of fixed stress or fixed strain conditions
applied for controlled time and temperature. Permanent deformation occurs as a result
of a variety of processes (see below), which result in a net permanent deformation of the
article. This is obviously undesirable as it leads to both changes in dimensions and,
where sealing properties are required, a reduction or loss of the sealing forces.
Processes influencing permanent set are:
1. Slippage and flow of polymer chains.

2. Chain disentanglement.
3. Chain scission/chain extension.
4. Crosslink modification.
5. Crosslink formation.
6. Oxidation of the polymer.
7. Effects from the use of fillers.
These are discussed further in Section 7.6.3.1. No doubt, there are other agents that may
also lead to permanent set in rubber products but, whatever the cause, it is an aspect of
product design to which much attention is devoted.
7.5.4.3 Gas Permeability
The permeation rate of fluids (gases and liquids) through rubber is of particular importance
in applications where the rubbers function is to contain a fluid, such as a tyre inner liner,
fuel and liquid petroleum gas hoses, diaphragms, etc. Permeability is the product of a
pressure gradient across a membrane and the diffusivity (the rate at which fluids will enter
and leave a polymer) [22]. Solubility determines the amount of fluid held in the polymer.
These are all influenced by temperature, which results in increased permeability with
increasing temperature through increased polymer mobility. Permeability is determined
partly by polymer structure and by compounding considerations. If the structure contains
polar groups, then permeability is reduced, e.g., nitrile rubbers [23]. Likewise, the presence
of methyl groups reduces permeability (butyl rubber). Permeability is also influenced
strongly by the amount and type of filler used in the rubber (see Section 7.6.3.2).
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7.5.4.4 Electrical Properties
The electrical properties of rubbers may be varied enormously but can be considered to
fall into one of three classes, dependent on the resistivity of the end product. Testing for
electrical performance of rubber is not entirely consistent and may involve testing of an
article or composite, or determination of the fundamental performance characteristics.
Three types of product may be identified based on the resistivity requirements of the end
product. These are conductive, antistatic and insulating. The three material types fall
approximately into the resistivity ranges shown in Table 7.3.
Table 7.3 Classification of elastomers by electrical properties

Classification Volume resistivity
Conductive < 104 ohm cm
Antistatic 104 - 109 ohm cm
Insulating > 109 ohm cm
Most commercial polymers may be classified as insulating, having volume resistivities of

109 ohm cm or above. However, their properties are extensively modified by compounding,
with fillers having the largest effect on properties. These are discussed in Section 7.6.3.3.
7.5.4.5 Dynamic Properties
One of the main reasons for manufacturing a product from rubber is the need for the
product to accommodate movement of some description. This requirement may be
minimal as in the case of static sealing where the movement may be single cycle
compression or it may be more extreme as in the case of a tyre, which undergoes repeated
high-frequency cycling under load. Cyclic movement requires that a number of properties
are considered [24]:
Fatigue resistance crack initiation and growth.

Dynamic mechanical properties.
Vibration damping.
Repeated stressing of any product will eventually lead to failure through crack formation.
The action of oxygen, ozone, heat, light and other agencies result in crack formation and
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crack growth on flexing. Formulation for fatigue resistance normally involves attainment
of stability towards the agents responsible for degradation. This normally requires that
the polymer be stabilised towards oxidation and ozone attack especially. Low modulus
is also desirable for best fatigue resistance in many applications. This may be achieved
by control of the crosslink type, density and stability. It is known that short mono- and
disulfidic crosslinks perform poorly on repeated flexing. Polysulfidic crosslinks perform
much better, presumably because of the increased polymer mobility. These crosslinks are
thermally less stable and on ageing may give poor long-term performance. A low crosslink
density is also known to give good fatigue resistance. The effects of filler are discussed in
Section 7.6.3.4.
During repeated flexing of a viscoelastic material, such as rubber, heat is produced internally.
This results from the fact that the rubber is not perfectly elastic but is a viscoelastic material.
The viscous element of the rubber leads to internal frictional heating on repeated cycling.
This is influenced strongly by the nature of the polymer and its crosslink structure. It is
also affected by the filler system in use and the polymer-filler interface.
Many rubber applications involve use of the rubber for vibration damping purposes. For
this, the response of the filled polymer to cyclic deformation through a frequency spectrum
must be determined as must the way in which this changes with temperature. The damping
characteristics are primarily determined by the viscoelastic behaviour of the polymer,
but is influenced also by the filler and filler loading used [25, 26].
7.5.4.6 Resistance to Liquids
Many rubber products must operate in contact with fluids of various types. An important
part of compound design is formulation for resistance to fluids. Selection of suitable
polymer is important, (e.g., use of a polar rubber for oil resistance), while for minimal
swelling it is desirable to have a high crosslink density. Other design considerations are
also important, such as the effect of the liquid on the filler and plasticiser systems.
Plasticisers will often be extracted by fluids and occasionally replaced by the fluid within
the compound. Filler effects are discussed in Section 7.6.3.5.
7.5.4.7 Burning Behaviour
The requirement for fire retardance in many applications has never been greater. Not
only is the requirement for flame retardance increasing, but the control of airborne by-
products has become more important. In small-scale fires, it may be sufficient for a
product to be self-extinguishing. There are, however, in the modern building, ship, train
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or factory an increasing number of computers or microprocessors. It has been found that

conventional flame-retardant rubbers, which are halogen containing, may do far more
damage from acid gas evolution than the damage caused by the primary fire. There is
also an increasing requirement for low-smoke or smoke-free rubber products (for cables,
flooring, etc.), which will permit easier evacuation in a fire situation than older systems,
which generate smoke on combustion. As a result, recent attention has centred on those
polymers that are both halogen free and burn cleanly. There are, of course, applications
where the more conventional systems may be used.
The polymer may be modified significantly by the use of fire-retardant additives, which
may act as fillers, plasticisers, and so on [27]. The combustion behaviour of fillers is
discussed in Section 7.6.3.6
7.6 The Performance of Fillers
7.6.1 Reinforcement of Rubber by Fillers
The phenomenon of reinforcement by fillers is unique to rubbery materials. The relative

order of reinforcement by fillers appears to be the same for all dry rubber polymers but
the relative magnitude of the effect is influenced strongly by the inherent strength
characteristics of the unfilled elastomer. Those elastomers that exhibit high strength in
the gum state, (i.e., those which may undergo stress-induced crystallisation and those
with a high modulus), are influenced to a lesser degree than those which are amorphous
and exhibit low modulus. Several definitions of reinforcement have been proposed over
the years [28, 29]. These include measurement of the tensile product (the product of
tensile strength and elongation at break) or energy of rupture; but the definition preferred
by the author is based upon the influence of the filler on a high-quality natural rubber
gumstock. This convention classifies the spectrum of fillers into three types: reinforcing,
semi-reinforcing and non-reinforcing. As with most systems of classification, there are
grey areas, especially in the regions between types.
A reinforcing filler is a particulate material that is able to increase:
(1) the tensile strength;

(2) the tear strength; and
(3) the abrasion resistance of NR.
A semi-reinforcing filler is a particulate material that is able to:
(1) increase tensile strength; and

(2) tear strength, but does not improve abrasion resistance.
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A non-reinforcing filler is unable to provide any increase in these properties and functions
only as a diluent.
7.6.1.1 Factors that Influence Reinforcement of Rubber by Fillers
The reinforcing ability of fillers is influenced by three primary characteristics of the

filler: particle size, polymer-filler bonding, and particle shape complexity [30].
Particle size. The primary particle size of the filler has the most significant influence on
reinforcement. This assumes, of course, that the filler in question is adequately dispersed.
Particle size has a direct influence on the specific surface area of the filler and it is the
increase in surface area that is in contact with the rubber phase that probably leads to
the increase in reinforcement. It can be argued that reducing particle size simply leads to
a greater influence of polymer-filler interactions. One area of great importance to
reinforcement is the presence (or absence) of large particles or agglomerates in the rubber
[31, 32]. These detract from strength, not only because of the reduced surface contact,
but through localisation of stresses which would thus lead to premature failure by
functioning as failure initiation sites.
Polymer-filler bonding. The ability of the filler to react with the polymer resulting in
adhesion, increases strength significantly. This process may be physical or chemical,
although in the case of carbon blacks it is considered to be physical adsorption by the
filler that is primarily responsible for reinforcement [33]. Polymer-filler bonding,
particularly in the case of carbon black, develops naturally between filler and rubber
through active sites on the filler surface resulting in bound rubber attached to the filler
surface. The effect of these surface interactions has been clearly demonstrated by
comparing the effect of using carbon black before and after graphitisation [34, 35].
Adhesion may also be induced by addition of a coupling agent, which participates in the
vulcanisation reaction to form polymer-filler crosslinks. Inorganic fillers in particular
often respond to use of coupling agents to create polymer-filler crosslinks, which would
not be formed in their absence. On the other hand, fillers with active surfaces, such as
carbon black, develop a high level of polymer-filler bonding in the absence of coupling
agents through formation of physical and chemical bonding. Both mechanisms lead to
the formation of high modulus compounds, which is a very clear indicator that polymer-
filler bonding has taken place. The increased modulus occurs as a direct result of
attachment of the rubber to the filler, which has the effect of reducing polymer mobility.
The particle complexity. Particle shape may provide further changes in reinforcement.
This is especially true for carbon blacks where products with differing structures are
327
produced. Increasing carbon black structure has the effect of reducing tensile strength
and increasing abrasion resistance, but has little effect on tear strength [35]. Overall, the
effect on reinforcement is relatively small. Particle complexity has a more pronounced
effect on processing behaviour than on reinforcement and provides important benefits in
this area. It can also significantly increase modulus due to occlusion or shielding of some
of the rubber phase [34].
Table 7.4 provides a list of commonly used fillers, categorised according to their ability
to reinforce elastomers.
7.6.1.2 General Properties of Fillers
The reinforcement of rubber may be illustrated by examining the response of two dissimilar
general-purpose polymers to the increase in filler loading (Figure 7.4).
NR, which can stress crystallise, exhibits very high mechanical strength in the absence of
filler and is used in a number of applications (rubber bands, baby feeders, etc.), because
of this fact. SBR offers no such properties, and must be filled in order to achieve even
modest strength. The bulky benzene rings along the rubber molecule prevent approach
of the polymer chains on extension, which is necessary for crystal growth to occur. As a
result, its gum strength is low. When compounded with fillers, however, the two materials
may exhibit similar mechanical strengths.
Figure 7.4 Reinforcement of rubber by fillers. Filler type versus strength.
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Table 7.4 Classification of fillers by reinforcement

Primary particle Polymer-filler
Filler Particle shape
size (m) adhesion
Reinforcing fillers
Fumed silicas 0.005-0.025 Very high Structured
Precipitated silicas 0.015-0.060 Very high Structured
Precipitated silicates 0.015-0.060 Very high Structured
N100 carbon blacks 0.011-0.019 Very high Structured
S300 carbon blacks 0.026-0.030 Very high Structured
Semi-reinforcing fillers
Precipitated calcium carbonate 0.050-0.100 Low Spherical
N900 carbon blacks 0.201-0.500 Very high Spherical
Silane treated fine kaolin 0.200-1.000 Very high Platy
Fine kaolins 0.200-1.000 Low Platy
Zinc oxide 0.090-0.150 Low Spherical
Synthetic aluminium trihydrate 0.500-1.000 Low Particulate
Calcined clays (fine) 0.600-1.000 Low Complex
Micronised talcs 1.000-2.000 Very low Platy
Non-reinforcing fillers
Calcined clays 1.5-2.5 Low Complex
Coarse kaolins 1.0-5.0 Low Platy
Neuburger chalk 1.0-5.0 Low Semi-platy
Coarse talcs 2.0-50.0 Very low Platy
Ultrafine chalks and marbles 0.7-2.0 Very low Particulate
Natural aluminium trihydrate 5.0-1000 Very low Particulate
Barytes 20.0-1000 Very low Particulate
Chalk/limestone/marble 2.0-1000 Very low Particulate
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7.6.2 Processing Considerations
Fillers have a major influence on most aspects of the processing behaviour of rubbers.
It is true to say that many of the products manufactured from rubber could not be
produced effectively without the addition of fillers to control processing behaviour.
It may be considered that the component of the formulation that provides poor
processing is the polymer. By virtue of being an elastic material its flow (plastic
component) performance is poor and it will always exhibit some tendency to recover
after deformation (a property often described as nerve or extrusion shrinkage in
the industry). Obviously, if the rubber component is replaced by other additives,
which result in dilution, the elasticity of the component will be reduced. This is only
part of the story, however, as many fillers have an extraordinary effect on this aspect
of processability. There is a useful (but not total) relationship between control of
nerve and reinforcement, in that the fillers that exhibit the greatest influence are
those that are the most reinforcing because the parameters that influence reinforcement
also influence processability. Fine carbon blacks, and synthetic silicas and silicates
exhibit an extraordinary influence on nerve and extrusion shrinkage, while natural
platy minerals have a limited effect, and the particulate fillers have a minor effect.
The anomaly in this model is precipitated calcium carbonate, which is a semi-
reinforcing filler, and yet exhibits very poor control of nerve. The phenomenon is
probably influenced by polymer-filler bonding brought about during mixing and is
influenced by the surface area of the filler. Processing aspects where this property is
important are die swell during extrusion and dimensional stability during calendaring.
Compound viscosity, green strength and heat build-up follows the same pattern with
the fine surface-active fillers having highest viscosity and generating greatest heat
build-up during processing. This is primarily due to the increased viscosity, which
correlates with the formation of bound rubber. Bound rubber content is influenced
by surface area, surface activity and particle-shape factors in much the same way as
reinforcement.
Platy minerals such as clays and talcs, are useful for providing stiffness to hot, semi-
processed rubber products. This is particularly useful for thin-walled extrusions,
which emerge from the die at high temperatures. The stiffening effect is usually
sufficient to prevent collapse under the products own weight immediately prior to
and during cure.
Low moisture contents are required for many processes as temperatures often exceed
the boiling point of water, resulting in the potential for porosity. For most rubber
processes, fillers with less than 2% moisture are satisfactory, although it should be
330
noted that many of the fine, high surface-area fillers, (e.g., precipitated silicas), may
have a moisture content above 5%. This is often unavoidable and therefore
accommodated by compound adjustment with moisture scavengers. For particularly
sensitive applications, (e.g., low-pressure curing media), low moisture content fillers
such as calcined clays or calcium carbonates may be preferred.
Cure rate is strongly influenced by the nature of the filler surface and the amount of
filler used. Generally speaking, fillers are preferred with a high surface pH, as this
will usually provide positive benefits for the cure reaction. This rule of thumb,
however, may not always be satisfactory, as fast-curing formulations may be prepared
from acidic china clays without the need for specific compound adjustments. The
complexity of interactions available within commercial rubber formulations is such
that prediction may not be possible with any certainty.
Mill sticking and bagging are problems that most rubber processors encounter with
annoying frequency when processing on a two-roll mill. High green-strength and
stiff compounds tend to release from the roll easily and may fail to adhere to the roll
surface (bagging). Low-stiffness compounds with poor green strength or adhesive
qualities may stick strongly to the rolls (mill sticking). Both conditions make it difficult
to process rubber, but mill sticking is the more serious of the two conditions. Extremes
are relatively easy to predict but subtle changes to compound design may result in
significant effects on these properties. Specific additives are usually added to control
these phenomena.
The effects of mill sticking are often most serious with halogenated polymers, where
mild corrosion of process equipment may provide a clean steel surface, thus promoting
high bond strengths. Heat build-up exacerbates the problem severely. Within the
clay minerals it is known that the total surface hydroxyl content (which is the product
of surface area and hydroxyl concentration) influences mill sticking and other
properties markedly [36]. Other aspects of processability are also known to be
influenced by this (Table 7.5).
Although the effect of filler on some properties has been discussed, their use in rubber
has an effect on almost every property of the end product. The final choice of filler
as with all ingredients of the compound, will be made based on an overall assessment
of the performance of the end product.
331
332
Table 7.5 Typical properties of clays
Calcined clays
Clay type Finer Kaolins Coarser Kaolins
Metakaolin Amorphous
Surface area BET (m2g-1) 30 16 13 10 7.5 12 8. 5

Surface hydroxyl concentration (nm-2) 8 8 8 8 8 1 1
Total surface hydroxyls (1018 g-l) 240 128 114 80 60 12 85

Equilibrium moisture content (%) 2.0 1.4 1.2 1.0 0.7 0.3 02
Water absorption Very high High Moderate Low Low Very low Very low
Accelerator and peroxide adsorption Very high High High Moderate Moderate Very low Zero
Ease of dispersion Difficult Moderate Moderate Easy Easy Very easy Very easy
Mill-sticking
General purpose rubbers High Moderate Moderate Low Low Zero Zero
Chlorinated polymers Very high Very high High High Moderate Moderate Very low
7.6.3 Compounding Considerations
7.6.3.1 Permanent Set
Permanent set is a complicated phenomenon discussed further in Section 7.5.4.2.

The choice and nature of any filler used, however, may play a significant role in
attaining low values. Several general statements may be made relating to filler effects:
1. As filler becomes finer, permanent set increases. With most types of filler it is known
that the permanent set performance is poorer for finer particle sizes. It may be
necessary to sacrifice reinforcement in order to achieve lowest permanent set.
2. High polymer-filler adhesion reduces compression set. The ability for the polymer
to be immobilised at the filler surface limits the ability for the polymer to flow to
a different configuration when stressed. This effect may be demonstrated readily
by examining the effect of silane coupling agents on the set performance of silicate-
mineral-filled rubber. The resultant compression set may be as low as 50% of the
value without coupling agent.
3. High aspect ratio fillers give high permanent set, (e.g., talcs). It is thought that
increases in aspect ratio have the effect of increasing the stresses generated
internally between filler particles when a compound is stressed. This in turn leads
to increased flow rates between the filler particles, which results in increased
permanent set
4. Fillers with polar surfaces may give poor permanent set as a result of curative
adsorption, (e.g., silicas and fine clays). Silicas and clays have surfaces that contain
polar hydroxyl groups. These are able to attract polar materials, (e.g., curing
agents and accelerators), by hydrogen bonding and thus remove them from
solution within the polymer phase. The effect of this is similar to addition of a
lower level of curing agent, i.e., reduced crosslink density. This is obviously a
costly waste of curing agent. The mechanism proposed for this cure retardation
is through reaction with fatty-acid-solubilised zinc formed during sulfur
vulcanisation. The zinc reacts by replacement of the surface hydroxyl group on
the silica surface. The effect is proportional to the total surface area of silica
available, hence it is surface area and loading dependent [37].
This problem is relatively easy to deal with as the curing agents adsorbed may be
displaced by addition of a polar additive, such as diethylene or polyethylene glycol,
triethanolamine, etc. These materials are preferentially adsorbed on to the filler
surfaces and thus inhibit accelerator adsorption [38].
333
7.6.3.2 Gas Permeability
Fillers reduce permeability as a consequence of their own impermeability. Replacement

of the polymer by filler naturally results in a reduced permeation rate. Some fillers,
notably those with a platy shape (fine clays and talcs) have a considerable influence on
permeability [39]. These fillers work by forcing the fluid to take a longer path around
the plates to escape from the opposite side of the membrane. In addition, the plates
reduce the effective area through which the fluid may pass. Thus, the net result is the
same as if a thicker membrane of smaller area were used (Figure 7.5).
Figure 7.5 Permeation paths through unfilled and filled rubber
7.6.3.3 Electrical Properties
The effect of fillers on the electrical properties of rubber is substantial. Varying the filler type
and loading can result in compounds that fall anywhere into the range of volume resistivities
from <10 to >1016 ohm cm, i.e., from conductive to insulating. Electrical behaviour of
networked and filled composites may be described by percolation theory [40]. Both the
polymer, and filled polymer composites may be considered to be networks of connecting
material. In such networks, the ability for electrons to flow requires the formation of a
conductive pathway through the material. The pathway requires a critical density of
connections for effective passage of current. Highly structured carbon blacks, in particular,
are effective in forming interconnecting, percolation, networks which permit passage of current.
Because the system is elastomeric, and subject to deformation, these networks often weaken
during periods of deformation but usually re-build after a period of rest. Simple concept
models of low and high density percolation systems are shown in Figure 7.6.
Conductive rubbers are normally produced by incorporation of specific grades of

conductive carbon black having a high surface area and a high structure. These systems
334
Figure 7.6 Examples of weak and strong percolation network structures
may be considered to be efficient, disordered electrical percolation networks. Values

as low as single figures (< 9 ohm.cm) are obtainable with these fillers.
Semi-conductive materials may be produced by addition of conventional carbon

blacks. Resistivity is lowest for those grades with the highest structure and highest
surface areas. Non-black products generally rely on the use of antistatic additives,
which reduce the surface resistivity of the product, since most non-black fillers are
insulating in nature.
Insulating properties require careful selection of polymer and additives in order to

achieve the specific properties sought. Many of the more polar polymers have volume
resistivities, which restrict their application in this area. The major application
requiring insulating properties is, of course, in power cable insulations. The
requirements are such that the insulation properties must be maintained under
operating conditions, which may involve high working temperatures and exposure
to water, and yet the product is expected to perform satisfactorily for many years.
Achieving this level of performance requires careful selection of polymer and raw
materials used.
Other aspects of dielectric performance, such as dissipation factor, relative permittivity

or breakdown strength, may become important in power cable technology. The
intricacies of this sector of the rubber industry are beyond the scope of this chapter.
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7.6.3.4 Dynamic Properties
There are many aspects to consider when formulating for dynamic performance,
where the elastomer experiences repeated cyclic deformation during service. The key
properties include fatigue resistance, dynamic heat build up and adhesion to other
components of the composite product.
Selection of filler can play an important role in achieving good fatigue resistance. Of
paramount importance is the selection of grades that contain minimal levels of coarse
particles, which may initiate cracking [30, 31]. In addition, finer particle sized fillers
are known to improve flex cracking resistance, presumably due to the improvements
in tear strength that results. In fixed-strain deformations, low-modulus compounds
are known to perform better than those with a high modulus. This favours the use of
finer, non-black, fillers. High levels of filler are not favoured because of the increase
in modulus that results. The increased modulus increases stress on the material when
it is deformed, reducing the critical strain at which ozone attack may take place.
Increased filler loadings also reduce the volume fraction of polymer in the composite.
This often increases the rate of property degradation from oxidation and/or ozone
attack of the reduced polymer phase as a result of the increased gas:polymer ratio at
the surface, particularly in general purpose elastomers which are more easily degraded.
One of the major recent changes in filled elastomer technology has been the
introduction of green, or energy saving tyres. These first came into use to provide
lower rolling resistance, and so better fuel economy. This was achieved by utilisation
of precipitated silicas in combination with high levels of silane coupling agent in
order to achieve reduced heat build-up during service of the tyre tread. This was
achieved somewhat at the expense of abrasion resistance and ease of processing of
these tyres and considerable research continues in order to optimise the contradictory
properties required of this application, not just with silicas but also with new
generation carbon blacks. It is desirable to formulate, not just for mechanical and
construction parameters, but also around minimum cyclical energy losses at different
temperatures or frequencies [41-43].
7.6.3.5 Resistance to Liquids
The effect of fillers on the resistance to change or deterioration in the presence of liquids
is quite marked. Fillers influence the degree of swelling by replacement of polymers that
swells by filler that does not, resulting in reduced swelling through reduction of the
volume fraction of polymer in the compound. Some fillers are obviously not suited to
specific applications, e.g., carbonate fillers decompose in the presence of acids.
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Filler surface effects may be important. Silicas and silicates that contain hydroxyl groups
on their surfaces may result in increased water attraction. Attainment of high filler-polymer
bonding may reduce or eliminate this type of effect by eliminating the interface. Hydrophobic
treatments may have a similar effect, but increased crosslink density, resulting from strong
filler-polymer interactions, can be an additional advantage of coupling agents.
7.6.3.6 Burning Behaviour
A number of fillers are produced specifically to reduce the rubbers ability to burn, generate
smoke or liberate corrosive gases. These are often used in combination with each other
and with careful selection of other compounding ingredients. Examples of these fillers
are shown in Table 7.6.
Table 7.6 Fillers which influence burning behaviour

Filler Function
Antimony trioxide (+ halogen donor) Flame retardant
Precipitated calcium carbonate Acid absorber
Acid absorber, flame retardant and
Magnesium hydroxide
smoke suppressant
ATH Flame retardant and smoke suppressant
Zinc borate Flame retardant and intumescent
These materials have different effects on the way in which the composite burns.
Precipitated calcium carbonates reduce acid gas emissions by reaction and neutralisation
during combustion. This may in turn increase the ease of combustion, as the halogen has
a gas-phase quenching effect.
Magnesium hydroxide and ATH decompose endothermically, thus removing energy from
the combustion source, and generate quenching gases, which dilute the oxygen availability.
When added in sufficient quantities they can be highly effective at inhibiting combustion.
Zinc borate decomposes endothermically to generate a porous glassy material that acts as
a physical insulating barrier to inhibit combustion.
Antimony trioxide requires the presence of a small quantity of a halogen containing material.
During combustion antimony pentahalides are formed, which are extremely powerful free-
radical scavengers. They remove the active species from the combustion source, and so
inhibit combustion effectively.
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Many of these materials may be considered to be specialty additives but the volume of
material required for efficacy requires that their properties as fillers (especially the effect
on reinforcement) be given significant attention.
7.6.3.7 Colour
Most rubber products are black because of the supremacy of carbon black as a reinforcing
agent, so colour does not play an important role in most industrial applications. For
those applications where colour is important, the selection of filler is restricted to those
non-black fillers, which are able to provide the properties required. The effect of these
materials on colour is readily predictable from the whiteness of the filler. It is important,
however, not to rely too heavily on the optical qualities of fillers as they are not produced
for primary pigmentation purposes.
7.7 Filler Types
7.7.1 Specification of Fillers for Elastomers
The specification for fillers for rubber varies considerably according to the nature of the
product. Users of fillers must also be quite clear of the fact that no two fillers are exactly
the same. Conventions that categorise fillers such as the American Society for Testing
and Materials (ASTM) system for blacks provide only a system for grouping products
with similar characteristics. If two fillers with identical specification values are compared
in critical products, significant differences in performance will still often be found. Filler
interchangeability must be approached with a certain degree of caution.
Fillers vary in particle size by many orders of magnitude, their production and processing
methods vary enormously, and the chemical nature of the types available varies
considerably. Probably the most important single requirement of any product is batch to
batch uniformity. Properties most usually described are:
Moisture content Sieve residue

Mean particle size Particle size distribution
Colour (for non-blacks) Impurity levels
Surface area Iodine number (blacks)
Oil absorption Chemical composition
pH Density
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Moisture content should be controlled to be as low as possible, bearing in mind the

surface area and chemistry of the filler. Low surface area fillers with hydrophobic surfaces
will naturally maintain a low moisture content once dried. High surface area fillers with
hydrophilic surfaces, such as precipitated silica, will regain moisture from the atmosphere
rapidly and relatively high levels of moisture (5-7%) are unavoidable. Other minerals
such as kaolin are also sensitive to moisture regain, but to more acceptable levels of
moisture (0.5-2.0%). Total absence of moisture, however, should be avoided as water
plays a subtle role in many crosslinking reactions.
Low sieve residues are important for all but the most undemanding of rubber applications.
Coarse impurities may result in die blockage on extrusion, pinholes in calendared sheet
and abrasive wear to processing equipment generally. In application they may act as
failure sites in tension or on flexing, may cause failure electrically in cables, and cause
leakage of gas or fluid through membranes.
Mean particle size, particle size distribution, surface area and oil absorption are all indicators,
directly or indirectly, of particle size. For coarse fillers, particle size measurements are
easily performed, while for fillers with mean particle sizes below 0.1 m, size may be
measured by microscopy (very time consuming) or by indirect measurement techniques
such as surface area (BET), iodine absorption, oil absorption, etc.
While most fillers are not produced for their primary pigmenting properties, consistency
of colour may be of concern for non-black applications. Most non-black fillers are
produced to a basic colour or whiteness specification. Carbon blacks, too, may be
categorised by their colour or tinting strength. While this is useful to know, it is often of
little value to the end-user who rarely possesses the equipment necessary for colour
determination. There are also a large number of measurement methods in use, which
leads to some confusion in this area. Most processors must content themselves with
making visual comparison with an established reference sample.
A number of impurities found in compounding ingredients are known to influence the ageing
behaviour of rubbers, especially NR. High iron oxide impurity levels, and some forms of
copper and manganese impurities are known to be the cause of rapid oxidative degradation.
There is little literature available that relates either the active form of impurities or that
identifies the level of impurities found in fillers to specific effects on polymer degradation.
Nonetheless, it is occasionally an area of concern. It should be noted that every source of
filler will be different in its level and type of impurities, so each material must be considered
in isolation. Specification values may not be an indicator of performance in polymer.
The chemical composition of fillers is often provided with the specification. This will
often provide information about chemical purity, which may be important. With
naturally derived fillers, however, this is likely to provide typical information only,
339
since the composition is substantially fixed by the nature of the materials source. The
chemical composition of many minerals expresses the main components, by convention,
as their oxides.
Most fillers, when produced, have a pH that arises as a consequence of their origins. The
pH is rarely controlled by the production process unless a surface treatment of some sort
has been applied to the filler. Nonetheless, it is useful to have information of the fillers
pH as this is one of the simplest methods of characterising the filler surface.
Likewise, the density of a filler is a property that is rarely influenced by the filler production
process and therefore should not form part of a production specification. It is of great
importance, however, to know the density, if for no other reason than for costing purposes.
This description of specification parameters is not meant to be at all exhaustive. Many

other properties may be provided by individual filler producers on the composition and
characterisation of their fillers. These are often directed specifically at one application
where this type of filler is commonly used. These should be considered on their own
merits and discussed with the supplier.
The importance of the relevance of specification parameters to applicability should be

borne in mind at all times. As we have seen, fillers play a vital role in the formulation of
most rubber products. They are produced using a wide variety of processes and may
have either natural or synthetic origins. Hence, fillers vary enormously in their chemical
characteristics and in particle size, which, in turn, influences the fillers overall behaviour
in rubber. Fillers provide the formulator with a range of materials that can modify
processing behaviour, and physical and chemical properties of the polymer. Details of
the production routes used and the characteristics of the individual filler types are shown
in greater detail in Chapter 2. This chapter will concentrate on those aspects of particular
importance to elastomers.
7.7.2 Carbon Black
Carbon blacks [44] are a form of carbon produced by controlled pyrolysis of hydrocarbon
oil or gas. They are the most important filler type for use in rubber as they are the main
agents for providing high-strength compounds. These materials also have a pronounced
effect on the processing behaviour of rubbers.
Two main production routes are used for the manufacture of carbon black, the thermal
process and furnace process. The furnace process is used for the bulk (approximately
98%) of carbon black production today.
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The most important properties used to characterise carbon blacks are:
(1) Particle size or surface area

(2) Structure
(3) Surface chemistry [45]
As a material, carbon blacks are available with primary particle sizes between 15 nm
and 450 nm. Surface area is usually used for characterisation. Surface area measurements
may be made using nitrogen BET [46] (Brunauer, Emmett and Teller) surface area or by
iodine adsorption. A technique is also used based on cetyl trimethyl ammonium bromide
(CTAB), which more directly relates to rubber reinforcement.
The primary particles exist in an aggregated form where they are fused together in a
randomly branched, chain-like form described as structure. The structure is formed
during the production process and is not broken down by subsequent processing
operations. A secondary structure also exists, which is formed by loose attraction of
black particles. This structure is easily destroyed during processing and is not described
by the term structure. Structure is normally measured using dibutyl phthalate (DBP)
absorption, which fills the voids between the particles. This method is also used in a
modified form where the black is initially crushed to breakdown any secondary structure
prior to DBP absorption. The crushed DBP is claimed to relate more closely to the way in
which carbon black is found in a rubber mix [47].
The chemical and physical nature of the carbon-black surface is known to influence
reinforcement strongly. There is no doubt that polymer interacts very strongly with the
surface of carbon black to form a layer of bound rubber that cannot easily be removed.
The attraction forces are considered to be primarily physical in character but many reactive
chemical sites [33] are also present on the surface. These may play an important role on
vulcanisation behaviour. The surface of carbon blacks are also known to contain varying
degrees of porosity (from surface area measurements) [48].
The most universal system for categorising carbon blacks is ASTM 1765 [49]. This system
classifies blacks according to particle size and cure rate.
7.7.2.1 Furnace Blacks
The furnace process is based on incomplete combustion of oil fractions in purpose-designed

furnaces. The product is removed from the air stream by cyclone and bag filters. It then
passes to a pelletising unit (either wet or dry). Dry-pelletising is carried out by tumbling
the black in large rotating drums. Wet-pelletisation is carried out by mixing with water
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followed by drying in heated rotating horizontal drums. The particle sizes produced are
between 14 and 90 nm.
The range of products available is diverse in both particle size and structure available,
allowing this class of blacks to be tailored to a broad range of end-uses. For this reason,
furnace blacks have become the dominant filler for highly reinforced systems, and
particularly in tyres. However, with the recent introduction of precipitated silica in tyres
for low rolling resistance, the furnace blacks have come under threat. As a result, new
grades of furnace blacks are under development. New products based on modified reactor
conditions are described as nano-structure blacks [50], having increased surface
roughness, providing enhanced filler-polymer interaction. Other approaches include
physical modification of the blacks and development of hybrid black/silica systems [41].
The key strength of carbon black is in its processability and ability to confer high abrasion
resistance to the tyre tread.
7.7.2.2 Thermal Blacks
The thermal process involves thermal decomposition of natural gas at 1300 C in the
absence of air. The process involves heating one of two kilns with a mixture of hydrogen
and air. At 1300 C, gas is introduced. This breaks down to form hydrogen and carbon
black. The hydrogen is used to heat the second kiln. When the second kiln reaches
temperature, production is switched to this kiln where the cycle recommences.
A second variant (the Jones process) exists where oil is used to heat the kiln. A mixture
of steam and oil is then introduced. The oil cracks to form a medium thermal black plus
a mixture of gases.
7.7.2.3 Special Grades
A number of specialised carbon blacks are used in rubbers. Acetylene black is produced
using a variation of the thermal process but, with acetylene decomposing exothermically,
heat is only required to start the process. This black is primarily used for its electrical
conductivity. Lampblack is produced by burning oil residues in shallow pans. The smoke
is directed to chambers where the black flocculates. Lampblack replacements are now
manufactured by the furnace process.
Channel blacks are made by the impingement process where natural gas (or natural gas
enriched with oil) flames impinge on either steel channel irons or a rotating drum. The
black is collected by scraping. Very fine products may be made by this process with
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particle size ranging from 10 to 30 nm. Only one plant remains in production (in Germany)
manufacturing this type of product.
7.7.3 Synthetic Silicas and Silicates
Synthetic silicas and silicates are powerful reinforcing agents for rubber. These materials
may be classified according to their method of production, thermally produced (pyrogenic
or fumed) silicas and wet-produced (precipitated) silicas [51].
7.7.3.1 Fumed Silica
Fumed silicas used in rubber are made by flame hydrolysis of silicon tetrachloride. The
products that result have a primary particle size in the range of 5-50 nm. The product is
found in the form of agglomerates. The surface is highly active and contains silanol
groups, which make the unmodified product hydrophilic. Modified hydrophobic forms
are available. As a product, fumed silicas have limited use in rubbers but they are used as
a reinforcing filler for silicone rubbers.
7.7.3.2 Precipitated Silica and Silicates
Precipitated silicas and silicates have widespread applications in rubber. They have two
distinct functions in rubber: (1) as a reinforcing filler; and (2) as an integral part of
proprietary bonding systems. The products are produced by precipitation from sodium
silicate (water glass) by reaction with acids. Replacement of the acid, in part or in total,
by metal salts (of calcium or aluminium) results in the production of metal silicates.
Because of the purity of the water glass used, the products are free from contaminants.
The precipitate is filtered and dried using a variety of techniques.
The products available have primary particle sizes in the range of 5-100 nm. They have
a structured or agglomerated form similar to that of carbon black. Precipitated silicas
contain approximately 12% water, 6% as chemically bound silanol groups plus 6% as
free water, physically adsorbed on the surface [30]. The high level of silanol groups at
the surface provides this filler with an extremely polar surface, which will readily attract
polar additives. The problem of accelerator adsorption can be eliminated through addition
of polar activators such as polyethylene glycol, ethylene glycol or triethanolamine, which
are attracted in preference to organic accelerators. This high surface activity is also
responsible, with the fine particle size, for the high level of reinforcement achieved. One
of the outstanding qualities of precipitated silica is the very high tear strength. Silica is
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the only significant competitor to carbon black for reinforcement in tyres and recently
become a significant filler in tread reinforcement because of its inherent low rolling
resistance [50, 52, 53].
The silica manufacturers are improving the processability performance of traditional

precipitated silica by developing modified products to meet the demands of the tyre
community. Three new generation sub-groups have become available, these being classified
as (a) Easy Dispersing Silicas (EDS), (b) Highly Dispersible Silicas (HDS) [53] and, (c)
Highly Dispersible and Reactive Silicas [54] (HDRS). These grades are produced under
modified conditions to improve dispersion characteristics in an attempt to improve
abrasion resistance. Surface treatment with coupling agents, usually of the organo-silane
class, is also offered to further improve dispersability and processability.
Precipitated silica has wide applications in integral bonding systems based on resorcinol
and methylene donor (the RFS system) or for systems based on cobalt complexes [55].
High levels of adhesion to steel, zinc plate, brass and a variety of textile substrates can be
achieved with these systems.
7.7.4 Clay Minerals
Clay minerals are widely used in rubbers because of their cost effectiveness in terms of
providing beneficial reinforcing and processing properties at a modest cost. The main
clay mineral of importance is kaolin (china clay) and the derivatives produced by chemical
treatment and/or heating (calcining). These clays may be classified in many ways. The
method most commonly used by the rubber industry is to classify clays into one of two
types, hard clays and soft clays. This terminology dates back to the early part of the last
century when only two basic grades of clay were produced, these being very fine (secondary
clays) with mean particle sizes between 0.2 and 1 m and coarser grades (primary clays)
having a mean diameter of 1.5-5 m. The two types clearly provided very different
performance characteristics being semi-reinforcing and non-reinforcing, respectively. This
classification system is totally unrealistic today but nonetheless persists, even though the
types available and the processes used have changed substantially. The following
classifications are more useful [56].
7.7.4.1 Primary Clays
The term primary clay refers to those clays that are found in the 1ocation in which they
were geologically formed. They are found in deposits that contain substantial quantities
of other minerals. The kaolin is processed in an aqueous slurry and must be separated
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from the impurities using a number of processes, which are followed by de-watering,
drying and pulverising. It is possible to apply a number of techniques to the slurry to
produce many different particle-size fractions ranging in size from 5 to 0.4 m. These
products may be either semi-reinforcing or non-reinforcing in rubber.
7.7.4.2 Secondary Clays
Secondary clays are those clays, which have been transported away from their primary
source to another location, where they have been deposited as a sediment. The
transportation process was usually effective at both mineral separation and at particle
size selection, in that only the finer particles remained in suspension long enough to
reach the final deposit. Important secondary deposits are found in the kaolin belt of
south-eastern United States (Alabama, through Georgia into South Carolina) and south-
western England. These clays are very fine with mean particle sizes from 0.1 to 2.0 m.
These are all semi-reinforcing fillers.
Secondary clays may be processed hydraulically (water washed) or by dry processing (air
classification or air flotation). Wet-processed products are recognised as having lower
levels of coarse contaminants, and are often whiter and purer because of the opportunity
of applying purification processes such as flotation or magnetic separation. A number of
grades are also available from a fraction of the deposit in which the clay exists in stacks
(rather like a pack of cards). These clay platelets may be separated for use in applications
where the higher aspect ratio of the delaminated clay can be utilised. The costs of wet
processing are, however, substantially higher than dry processing. Dry processing involves
very simple blending of feedstocks, dry milling, and passing through an air classifier or
separator to remove oversize particles. The product is then packaged for use in rubber.
The dry route provides very low-cost semi-reinforcing fillers, which are extremely cost
effective in rubber.
7.7.4.3 Calcined Clays
When kaolin is heated, it undergoes chemical and physical changes. Between approximately
450 C and 700 C, dehydroxylation occurs (often described as loss of water of
crystallisation) to form a product called metakaolin. This is accompanied by approximately
13% loss of mass as water. At higher temperatures, between 950 C and 1030 C, metakaolin
undergoes an internal rearrangement to form an amorphous product described as a defect
spinel. For rubber applications, products are manufactured at temperatures just above
these transitions. Metakaolin is produced primarily for use in flexible polyvinyl chloride
wire and cable insulations, but is also used in EPDM cable insulations.
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The defect spinel form is used extensively in rubber applications. The primary application is
in low- and medium-voltage power-cable insulations where it provides both excellent insulation
stability under wet conditions and useful extrusion performance. Pharmaceutical closures
form another important application due to the need for a chemically inert, white, filler.
It is also used in a variety of extruded products, especially those vulcanised under low-
pressure conditions because of its very low moisture content.
7.7.4.4 Treated Clays
Both kaolin and calcined clays are available with surface treatments. Many treatments
may be applied but few have any commercial importance. Kaolins are available treated
with surfactants and pH adjusters, which produce kaolins that may be dispersed directly
into water, (e.g., rubber latices), or with amines to enhance cure performance. Stearic acid
treated products may provide ease of dispersion. The most important treatments, technically,
are the organo-silanes.
(a) Silane-treated kaolins. Fine kaolins are produced in the USA for use in rubber
applications such as white sidewalls, tyre inner-liner, footwear, flooring, and so on [57,
58]. Materials available range in particle size from 0.2 to 1.0 m and are usually
treated with either a mercapto-silane, amino-silane or other coatings.
(b) Silane-treated calcined clays. Silane-treated calcined clays are produced specifically for
use in high-voltage power-cable insulations where they provide the processing
performance necessary for production and provide the low water absorption
characteristics required of the insulation in service. These grades are usually produced
to minimise dissipation factor which imparts energy losses to the cable, which is critical
in high performance applications [9]. No other fillers offer such a high level of
performance for this type of product [59].
7.7.5 Calcium Carbonates
Calcium carbonates have a number of characteristics of particular importance to rubber.

Products used in rubber are all based on the crystalline form of calcium carbonate, calcite
(although some precipitated grades of aragonite are available, they are not generally used
in rubber). As a group of products, they provide low hardness at a given loading, and have
the advantage of low compression set and low inherent moisture content. Disadvantages
associated with calcium carbonates are mainly concerned with limited reinforcement and
poor processing performance and sensitivity towards acids. They must be subdivided into
naturally derived and precipitated products to describe their applicability to rubbers.
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7.7.5.1 Precipitated Calcium Carbonate
Precipitated calcium carbonates are produced by controlled precipitation from calcium

hydroxide solution by carbonation. The products of these processes are fine particles
(0.05-0.2 m) and are often coated with a fatty acid (stearic) or a reactive resin
(carboxylated polybutadiene). Uncoated grades are also available.
Some precipitated calcium carbonate is also available as a by-product of water-softening

plants. These grades are generally coarser with poorer control of properties and, naturally,
less costly. Other precipitated calcium carbonate grades are available from 0.2 to 5 m
but do not find general applicability in rubber.
The ultrafine materials are all semi-reinforcing in character, as a consequence of their fine
particle size. The uncoated and fatty-acid-coated grades exhibit very poor interaction with
polymer, so the modulus (a function of polymer-filler interaction) is very low, thus soft
compounds are readily obtained. The high purity ensures that these fillers are very white
and heat-ageing performance is superior to naturally derived calcium carbonates. One of
the outstanding features of these fillers is their good high-temperature tear resistance [60].
Precipitated calcium carbonate with a reactive coating is available and exhibits increased
modulus and fatigue properties compared with stearate coated grades. This product is
competitive with coarse carbon blacks [61, 62].
7.7.5.2 Natural Calcium Carbonates
Natural calcium carbonates are produced from three types of rock: chalk, limestone and
marble [63]. All are forms of the mineral calcite. Chalk and limestone are very similar
and differ only in the degree of compaction (initial hardness of the source mineral) and
are most usually formed from the skeletal remains of micro-organisms such as coccoliths.
Chalk is less compacted than limestone but in practice there is a gradual transition from
one form to the other, the principle difference being degree of compaction and cementation,
which reflects the geologic history of the source. Marble, the metamorphic form, has
been re-crystallised under pressure and is usually produced commercially from sources
with high whiteness and purity. Calcium carbonate is abundant throughout the world,
thus the cost of the product is very low and this forms the basis for much of its use.
Stearic acid coated grades are also readily available. The products obtained may be divided
into six types according to particle size and coating (Table 7.7).
Those products with a mean diameter of 1 m or finer do provide superior properties

than those that are coarser [64, 65]. This is especially important where hot tear strength
is a requirement and the ultrafine products may compete with precipitated grades in less
critical applications.
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Calcium carbonate
types
Table 7.7 Ground calcium carbonate types

Mean diameter Uncoated Coated Production route and sources
Wet ground. Chalk, limestone
Below 1 m Yes Yes
and marbles.
Wet or dry ground available.
1-4 m Yes Yes
Chalk, limestone and marble.
Wet or dry ground available.
5-12 m Yes -
Generally limestone and marble.
Above 12 m Yes - Dry ground. Generally marble.
Stearate coating provides products with superior water resistance and a significant
improvement in dispersability, providing shorter mixing cycles and improvements in
consistency. The water resistance is of particular value in cable applications, where wet electrical
properties are important and in extruded products, which are cured under low-pressure
conditions (salt bath, fluidised bed, microwave or hot air) or in steam (cables or hoses).
7.7.6 Aluminium Trihydrate
The most important feature of ATH is its function as a flame retardant and smoke suppressant.
Its flame retardancy is due to the fact that the product decomposes endothermically at
temperatures at or below the temperatures required for combustion of most polymers. This
strong endotherm (Equation 7.1) removes heat from the ignition source. On decomposition,
inert gases are produced (water), which reduces oxygen availability. Smoke suppression [66]
is thought to be due to heat dissipation effects that occur during burning, favouring the
formation of polymeric char rather than soot particles. To be effective, high loadings are
necessary, thus in rubber the filler qualities must be considered as well as combustion behaviour.
These fillers are available in a wide range of sizes with mean particle diameters from
100 m (non-reinforcing) to 0.5 m (semi-reinforcing) and with a variety of surface
treatments available on demand.
Equation 7.1 Endothermic decomposition of aluminium trihydrate
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7.7.7 Talcs
Talc is a hydrated magnesium silicate, which has a platy shape, similar to clays. Unlike
clays, the mineral does not possess a significant level of surface hydroxyl groups, which
is the primary reason for the application differences between the two minerals. Talcs
have a surface that interacts poorly with rubber (it has a characteristic slippery feel), is
basic in character, and is relatively hydrophobic. Good sources of talc are relatively
scarce. This has ensured that the cost of talc is relatively high.
Talcs are used in rubber applications for one of two reasons: (1) as a dusting agent to
prevent rubber from sticking to itself, and (2) as a compounding ingredient in specific
applications. The former category utilises large quantities of coarse, often relatively impure
talcs. As a compounding ingredient, however, the finer, micronised products are used
because of their specific qualities. The micronised talcs are useful semi-reinforcing minerals.
The platy shape is useful in extruded or calendared applications. The lubricating effect
of the surface provides a lower processing viscosity than clays with similar aspect ratio
and size, plus better mill-release behaviour. The basic nature of the surface is often
advantageous in acid-sensitive polymers such as polychloroprene and will often provide
improved heat stability to filled products. The finer grades are used to provide low gas
permeability in many membrane applications. Electrical insulation properties are good,
especially under wet conditions in low-voltage applications.
Specific drawbacks of talcs include poor wetting by the polymer, resulting in longer
mixing cycles. The platy shape and poor polymer-filler interaction leads to very poor
compression-set performance in most applications. This can be reduced by using a silane-
treated grade. Airborne cross-contamination is another hazard associated with talc, which
can cause problems, especially of poor part-to-part adhesion, with manufacturing
operations that are remote from the location in which it is being used.
7.7.8 Natural Silicas
Natural silicas have some application in rubbers. One cause for concern with these products
is the presence of high levels of free crystalline silica. The most frequently used types are
based on deposits found in Bavaria [67], known as Neuburger silicas. These products are
mixed minerals being typically 70% silica and 30% kaolin in the form of an intimate blend.
The major application is in extruded products where they are able to combine excellent
surface finish with reasonable mechanical properties and low compression set. They are also
used in a wide range of products, including low-voltage cable insulations. A wide range of
surface-treated products is also available. Other grades of silicas are available, particularly in
North America, which are of a high purity. These are often used in silicone elastomers.
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7.7.9 Barites and Blanc Fixe
Barites and blanc fixe are both forms of barium sulfate. Barites is found as a naturally
occurring product and is processed to provide a range of relatively coarse products for
use in rubber. Blanc fixe is a precipitated form of the mineral and is used in more technically
demanding applications.
These materials have several useful qualities:
1. They have a high specific gravity, SG = 4.3.

2. They are chemically inert.
3. They are thermally stable to very high temperatures.
The high SG provides a useful filler for sound-deadening applications. Chemical inertness
allows the filler to be used in chemical plant lining and industrial gaskets of different
types, which also require high thermal stability. Blanc fixe has some application in
pharmaceutical compounds for its chemical inertness and purity.
7.7.10 Miscellaneous
The fillers described previously form the bulk of materials used in rubber applications.
The list is by no means exhaustive but those that are not covered are more specialised
in use. Other fillers known to be used in rubber include: calcium sulphate, cork,
dolomites, feldspar, graphite, lead, lithopone, magnesium carbonate, molybdenum
disulphide, rubber crumbs, textile fibres (flocks), wollastonite, wood flour, zinc oxide
and many others.
Acknowledgement
The author would like to thank Imerys for encouragement and permission to publish.
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355
356
8
Filled Thermoplastics
Chris DeArmitt and Michael Hancock
8.1 Introduction
8.1.1 Thermoplastics and Typical Applications
Thermoplastics have become an essential part of our everyday lives. Our cars and appliances
contain more and more plastics every year. Even our clothes are often made from synthetic
thermoplastics. They are a very important class of material for many reasons. They combine
good mechanical and electrical properties with low density and high formability. Clearly,
the driving force for their success has been that they can often provide an overall solution
that is less expensive than that achievable with other materials such as glass, wood, metal,
thermosetting polymers or ceramics. Thermoplastics, as implied by their name, are materials
that flow upon heating, and harden when cooled. They can be formed using a wide variety
of techniques, such as injection moulding, thermoforming, blow moulding and rotational
moulding. Injection moulding in particular allows complex shapes, so it is possible to
integrate several smaller parts into one larger part, thus saving on assembly costs. As well
as being easily processed when molten, they also have the potential to be recycled by re-
melting them to form new articles, or burnt and used to generate electrical energy. New
legislation is being introduced to encourage recycling of used products; this is expected to
favour thermoplastics over other materials, which are not as easy to reprocess.
Thermoplastic demand in Western Europe is 37 x 106 tonnes compared to 10 x 106 tonnes

for thermosetting polymers. A breakdown of thermoplastics by application area is given in
Figure 8.1.
Some of the main properties and applications are given next for the five main thermoplastics,
which together account for 75% of the total thermoplastics market.
Polyethylene (low density) LDPE, (linear low density) LLDPE: 7.6 x 106
tonnes
Properties: Flexible, translucent, very tough, weatherproof, good chemical
resistance, low water absorption, easily processed by most methods, low cost.
357
Figure 8.1 Use of thermoplastics in Western Europe
Applications: Squeeze bottles, toys, carrier bags, high frequency insulation,

chemical tank linings, heavy-duty sacks, general packaging, gas and water pipes.
Polyethylene (high density) HDPE: 5.0 x 106 tonnes
Properties: Semi-rigid, translucent, weatherproof, good low temperature toughness

(to 60 C), easy to process by most methods, low cost, good chemical resistance.
Applications: Chemical drums, jerricans, carboys, toys, picnic ware, household and
kitchenware, cable insulation, carrier bags, food wrapping material.
Polypropylene PP: 7.0 x 106 tonnes
Properties: Semi-rigid, translucent, good chemical resistance, tough, good fatigue

resistance, integral hinge property, steam sterilisable, good heat resistance.
Applications: Sterilisable hospital ware, ropes, car battery cases, chair shells, integral
moulded hinges, packaging films, electrical kettles, car bumpers and interior trim
components, video cassette cases.
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Polyvinyl chloride PVC: 5.8 x 106 tonnes
Properties: Rigid or flexible, clear or opaque, durable, weatherproof, flame resistant,

good impact strength, good electrical insulation properties, limited low temperature
performance.
Applications: Window frames, drain pipes, sewage and soil pipes, roofing sheets,
cable and wire insulation, floor tiles, hose and pipes, stationary covers, fashion
footwear, leathercloth.
Polystyrene (general purpose) GPPS: 3.1 x 106 tonnes combined with high
impact polystyrene (HIPS)
Properties: Brittle, rigid, transparent, low shrinkage, low cost, excellent X-ray
resistance, free from odour and taste, easy to process.
Applications: Toys and novelties, rigid packaging, refrigerator trays and boxes, cosmetic
packs and costume jewellery, lighting diffusers, audio cassette and CD cases.
Polystyrene (high impact) HIPS
Properties: Hard, rigid, translucent, impact strength up to seven times that of GPPS,
other properties similar.
Applications: Yoghurt pots, refrigerator linings, vending cups, bathroom cabinets,

toilet seats and tanks, closures, instrument control knobs.
Polyesters (thermoplastic) PET: 3.1 x 106 tonnes
Properties: Rigid, clear, extremely tough, good creep and fatigue resistance, wide range
of temperature resistance (40 C to 200 C).
Applications: Carbonated drink bottles, synthetic fibres, video and audio tape,
microwave utensils.
8.1.2 Thermoplastic Composites
One disadvantage of thermoplastics is that they soften appreciably as they are heated. As
this happens, their modulus decreases and they begin to creep (slowly deform over time)
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and at higher temperatures they progressively lose their shape, and then melt. There has
been a great deal of effort spent in trying to overcome this limitation. Filling PP with talc
is an early example of this. In fact, addition of mineral fillers increases the modulus of all
thermoplastics, and increases their heat distortion temperature (HDT) [1].
It is commonly thought that the primary goal of adding fillers is to lower the overall
materials cost of the composite compared to the unfilled polymer. This is, however, rarely
the case. Polyethylene (PE) and PP are the worlds number one and two highest volume
polymers, respectively, and they are also the least expensive per unit volume. Addition of
any common filler, with the exception of calcium carbonate, increases the material cost
of these polymers. Even in cases where the main goal is to decrease cost, the addition of
filler changes nearly every property of the polymer. It is therefore now common to use
the term functional fillers to emphasise that the fillers change the polymer, giving many
advantages, and naturally, some disadvantages. Making good composites is all about
knowing how to find a good balance of properties at the lowest cost. In order to make
the right decision, one needs to know about polymers, engineering, fillers and surface
science. That is what makes the study and application of composites so challenging,
fascinating and rewarding. In this chapter, we will discuss the main polymer properties
and how they are influenced by the addition of various common fillers. The global fillers
market is estimated as between 5-10 million tons per year, with over 90% of the filler
going into rubbers, PVC and polyolefins, e.g., PE and PP. PP is the one of the most
commercially important filled polymers [2] and it will therefore be used to illustrate
some of the main points. Similar trends are seen when fillers are compounded into other
semi-crystalline thermoplastics such as PE PVC [3] and the polyamides. The amorphous
polymers such as polystyrene and polycarbonate also respond similarly to filler addition.
Incorporation of fillers into thermoplastics alters all the properties of the material. Some
of the changes will be beneficial and some will be detrimental. It should be noted that
these are not absolutes and the determination of pros and cons is only meaningful to the
proposed end-use of the material. Burditt listed 21 reasons why filler may be added to a
polymer [4]. In addition to those intentional changes, there are a multitude of unintentional
effects that must also be considered. In this chapter the main properties of composites
and how they vary with filler type and level of addition will be discussed.
An essential point to note, is that the properties of the composite depend upon the volume
percentage of filler added [5, 6]. Often in the literature, one sees properties plotted versus
the weight percentage of filler, which is not particularly useful and may even be misleading.
It is more meaningful to plot properties versus the volume percentage of filler [7]. In
many cases, this latter approach gives straight lines, allowing simple, accurate
extrapolation and prediction of properties [8, 9]. The properties of a composite are
usually in between those of the component materials. Several of the properties such as
360
density, modulus and yield strength can be predicted by the rule of mixtures, according
to the volume fraction of each component. In other cases, there are more complex
mathematical models that can be used to describe and predict properties as the volume
fraction of the ingredients is varied.
Sometimes, the inclusion of filler can chemically or physically modify the polymer phase
to such as extent that it becomes more difficult to apply simple models. It is important to
realise that these complications may occur, and to look for them when characterising
composites. This will help in the understanding and design of new composite materials.
One example of this behaviour is changes in crystallisation, such as nucleation of crystal
growth [10-14] and changing of the crystal phase of the polymer [15, 16]. Chemical
degradation of the polymer may be catalysed by the filler, or impurities in the filler,
especially transition metals [17, 18]. Another common example is where the filler surface
adsorbs stabilisers and antioxidants, which are then unable to protect the polymer during
processing and during its service life [19-21]. Alternatively, mechanical degradation may
occur when high levels of filler cause unduly high viscosity, thereby inducing chain scission
due to the excessive shear needed to process the material.
In this chapter, an attempt has been made to mention each of the factors that influence
composite design and performance. For a given application, one must identify the key
properties that are important and concentrate on those. It will be seen that there are
many different parameters to consider and that in some cases, optimisation of one
precipitates an inevitable worsening of some other property. There is no one optimal
composite; rather the goal is to seek the best balance of properties through compromise
and an awareness of the entire picture in terms of economics and performance. In cases
where the filler is less expensive than the polymer, then the goal is to increase the filler
loading as much as possible, while still retaining sufficient processability and properties.
Conversely, when the filler is more expensive than the polymer on a volume basis, then
one seeks to identify the minimum filler loading that gives sufficient properties.
8.2 Bulk and Process Related Properties
8.2.1 Specific Gravity or Relative Density
The common fillers used in plastics are minerals (densities from 2.4-2.8 g/cm3), which
give a composite of higher density than that of the unfilled polymer (densities of 0.8-1.9
g/cm3). The density of a composite of known composition can be calculated according to
the linear rule of mixtures (Equation 8.1), where c, f and p are the densities of the
composite, filler and matrix, respectively, and mf is the mass fraction of filler.
361
f p
c =
pm f + f (1 m f )
Equation 8.1 Composite density
Such calculations usually agree well with measured values. A lower than expected density
may be due to inclusions of air resulting from poor mixing or poor wetting of the filler
surface by the polymer. Higher than expected density occurs when the filler nucleates
crystal growth in the polymer. The increased crystallinity increases the density of the
composite because crystals are of higher density than amorphous regions in the polymer.
The expected density of the composite can be calculated using Equation 8.1, assuming
no air inclusions and that the filler does not influence density of the polymer phase by
nucleation of crystal growth for example. The filler loading mf is usually determined by
ashing, namely burning away the polymer from a known mass of composite and weighing
the amount of residual filler. This method is simplest if the filler has enough thermal
stability so that it does not lose mass at the high temperatures needed to burn off common
polymers ( 300 C). For fillers that are somewhat thermally unstable, such as aluminium
trihydrate, it is necessary to correct the ashing result using the mass loss for the filler
alone under the same ashing conditions. Recently ovens based on microwave ashing
have been introduced. These operate at low temperatures, removing the polymer while
leaving the filler unaffected. Density can also be determined by measuring the volume of
liquid displaced by a known mass of composite or using a density gradient column.
Increased density is usually undesirable because products must inevitably be transported

to be sold, or installed. This may result in increased transportation costs. Weight increases
are undesirable when the material is to be used to make cars, trucks, trains, aeroplanes
or spacecraft. Recent European legislation on packaging will also penalise by weight.
Decreased density is possible through use of fillers such as wood flour (or fibre), hollow glass
microspheres, hollow polymer microspheres [22] (e.g., Expancel) or hollow spheres from
fly ash. Low-density thermoplastic composites are useful for products that must float.
8.2.2 Acoustic Properties
It is appropriate to mention acoustic properties here, as they are affected by density.

Adding filler usually increases the density compared to the host polymer, and this is
usually an unwanted side effect. However, it is common to make sound deadening
composites by using high-density fillers such as barium sulfate (BaSO4, 4.5 g/cm3) or
magnetite (Fe3O4, 5.1 g/cm3) [23].
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In order to dampen sound, a material must be able to absorb vibrational energy (sound)
and transform the energy into thermal energy (heat). The loss factor, tan , is the parameter
that best describes the sound damping ability of materials [5]. It is the inelastic component
of the materials response to deformation. The loss factor can be measured by dynamic
mechanical thermal analysis (DMTA), which shows its behaviour with changes in
frequency and temperature. It is common to select a matrix with a high tan in the
frequency range to be damped. Then, high-density filler can be added in order to further
improve performance. Mica is also used, as the platy particles cause multiple reflection
of the sound waves so they may be absorbed in the composite instead of passing straight
through [5]. Adding too much filler should be avoided however, because this leads to
particle-particle interactions, and eventually percolation, where a continuous path exists
from particle to particle. Under those conditions, the acoustic energy can pass through
the interparticle contacts, largely avoiding interaction with the matrix.
8.2.3 Melt Viscosity (MFI)
The melt viscosity of polymers is usually measured as the melt flow index (MFI), also
known as melt viscosity index (MVI) and melt flow rate (MFR). A pressure is applied to
force the molten polymer through a hole at a controlled temperature [24]. All three
parameters are set out in standards appropriate to the polymer being measured [24]. The
measured value is in grams of polymer extruded through the hole in a set period of time,
e.g., ten minutes. This of course, is actually the reciprocal of the viscosity, so a high MFI
means low viscosity and vice versa.
There are some caveats when using MFI as a measure of viscosity. Firstly, MFI
measurements are performed in the medium shear rate range [24], whereas polymer
processing is often performed at higher shear rates. Therefore, the MFI may not correspond
well to the flowability of the polymer melt during compounding and processing. A further
point is that raw MFI data should not be used to compare viscosities of polymer melts
containing different filler loadings. This is because adding filler increases the density of
the melt, and therefore the MFI will increase because more mass of polymer melt flows
in a given time, even if the volume of material flowing remains constant. Therefore, the
MFI data must be adjusted by dividing by the density. This gives the volume of material
flowing in unit time and allows fair comparison of samples with differing filler amounts
[8]. A detailed description of filled polymer melt rheology can be found in a book by
Shenoy [24]. Of particular interest is Shenoys method for extrapolating MFI data to
give an idea of the expected rheology of the polymer melt at the higher shear rates
encountered during polymer processing. Another good review has been made by Hornsby
[25]. This latter work includes an investigation of the degree of filler dispersion at various
points as it passes through a twin-screw extruder.
363
An inevitable consequence of adding filler is that the viscosity of the polymer melt increases
[8, 24-26]. This is exacerbated at high volume fractions of filler, and when the filler
particles are smaller, especially for nano-sized fillers such as carbon black [27]. In fact,
the increase in viscosity often limits the amount of filler in the compound. At low filler
addition levels, this effect is very low and is masked by the high inherent viscosity of the
polymer melt. As the filler addition increases, the viscosity begins to rise more sharply,
until eventually it approaches infinity at some critical filler level, which depends upon
particle size, shape and amount of agglomeration. High melt viscosity is to be avoided,
as it lessens the throughput during extrusion, increasing production costs. It may also
prevent complete filling of the mould, leading to high reject levels.
The viscosity of a very dilute dispersion of rigid spherical particles in a Newtonian fluid
is described by the Einstein equation (Equation 8.2) [26]. Where is the viscosity of the
dispersion, l is the viscosity of the fluid alone, is the volume fraction of particles and
kE is the Einstein coefficient, which is 2.5 for spherical particles. kE depends upon both
particle shape and orientation.
= l (1 + kE )
Equation 8.2 Einstein equation of dispersion viscosity
Although it is a starting point for understanding the effect of filler on viscosity, the
Einstein equation is not applicable to filled polymer melts. Polymer melts are non-
Newtonian, and the filler concentrations are often too high to ignore particle-particle
interactions. A plethora of equations exist for modelling dispersions of particles. However,
the best approach is to make the desired formulation and test it under real conditions,
such as measuring the torque and volume throughput during extrusion, plus mould filling
when injection moulding.
8.2.4 Compounding and Extrusion
Extruders are used to mix ingredients into thermoplastics [28]. The polymer is fed into a
hopper and is then forced into the barrel, either by gravity, or by mechanical means, such
as a feeder screw. The barrel is heated to melt the polymer and a rotating single or twin-
screw arrangement transports the polymer melt down the barrel and out of the die (hole)
at the end. There are usually ports at various points along the barrel to allow for the
introduction of additives such as lubricants, antioxidants, pigments and fillers. These
additives may be added individually, but more commonly they are fed in together as a
364
concentrate known as a masterbatch. After it emerges from the die, the molten polymer
string is usually cooled rapidly by running it through a water bath. The polymer is then
dried and lastly, the cooled polymer strand is chopped into small granules using a pelletising
machine. If the material is to be stored before use, then it is common to seal the pellets to
protect them from contamination and water pick-up.
The extrusion step is not particularly costly in comparison with the price of the raw materials,
but the cost is still significant and impacts on the overall economics of the final material. It
is therefore worthwhile to devote effort to optimisation of the extrusion process in terms
of increased throughput (productivity) and decreasing energy consumption and machine
wear. In the authors opinion, the subject of throughput does not receive the attention it
deserves. There are countless reports of the mechanical properties of thermoplastic
composites but no mention of the extrusion characteristics of the materials. For a meaningful
comparison of different composites, one must consider not only their mechanical and
aesthetic properties, but also the relative economics of extrusion.
8.2.4.2 Volume Throughput
As with all of the other properties of a composite, when considering extruder output one
must think in volume terms, not in terms of weight. If one is making a certain amount of
composite, that material must be of sufficient volume to create a certain number of parts,
each of which has a fixed volume determined by the size of the mould to be filled. Therefore,
the mass of material produced is, in itself, of no interest. There have been various reports
that filler increases extruder throughput. These claims are often erroneous, or at least
greatly exaggerated, because the throughput is given in units of mass per unit time. That is
not a valid way to compare throughput, for the same reasons mentioned previously for
MFI. Namely, that the addition of mineral fillers increases the density of the filled polymer
compared to its unfilled counterpart. Naturally, this elevates the mass throughput of the
extruder, giving a false impression of improved productivity. One possible cause for the
confusion over throughput, may be the way in which extruders are rated by the manufacturer.
Usually, the capacity of the extruder is given in terms of kilograms of polymer extruded per
hour. This value conjures up an image that the maximum throughput of the extruder is
limited to a given mass of polymer, as shown on the side of the machine. In reality, that
value is valid only in the case of a standardised grade of unfilled polymer, and is merely a
convenient means for the extruder manufacturer to show the relative capacities of different
machines. Perhaps in the future, the extruder manufacturers will consider expressing the
maximum throughput in volume terms to avoid confusion.
There are two classes of extruder, single-screw and twin-screw. The primary drawback
of single-screw extruders is that they give poor dispersion of fillers compared to the
365
more expensive twin-screw variants. Thus, twin-screw extruders are used almost
exclusively when good filler or pigment dispersion is required. Recently, it has been
suggested that the lack of dispersion associated with single-screw extruders is not an
intrinsic limitation [29]. It is argued that single-screw extruders had not been optimised,
as all of the attention and R&D has been on the more lucrative twin-screw machines.
Furthermore, it is claimed that the newly designed single-screw extruders can now give
sufficient dispersion for filled systems along with advantages such as being simpler, less
expensive, easier to maintain and giving higher volume throughput compared to twin-
screw machines. It will be interesting to see whether single-screw extruders do indeed
gain acceptance for the manufacture of thermoplastic composites.
The volume throughput and the quality of filler dispersion are the main parameters to
consider. One might assume that it would be a simple matter to measure the volume
MFI, as described previously, and then correlate that to extruder throughput. However,
it has been shown that the transport of the polymer melt in an extruder is more complicated
than the simple flow used in measuring MFI. In fact, the mechanism is different for melt
transportation through a single-screw compared to a twin-screw machine [28]. The best
approach is to extrude the proposed formulations in the production extruder that will be
used. The volume throughput can be measured as well as the torque on the screw and the
energy input to the motor. However, production extruders can have outputs of well over
one thousand kilos (litres) per hour, which means a lot of filler and polymer is needed to
run a test. Even more problematic is the loss of productivity when a production extruder
is used for testing purposes. Usually, the test material made will not conform to existing
specifications and may have to be scrapped/discarded. More commonly an instrumented
laboratory extruder is used for initial testing. The feeding and screws of the laboratory
machine should be set up to mimic the configuration of the production extruder. When
this is done, one can obtain good correlations between the properties of compounds
made in the laboratory and production material. A more detailed treatment of
compounding is given in Chapter 5.
8.2.4.3 Dispersion
Good dispersion is nearly always beneficial for the properties of a composite so one tries
to optimise the dispersion of filler. The level of dispersion can be measured directly or
indirectly. The most common direct measurement is to perform scanning electron
microscopy (SEM) on a cross-section. It is advisable to use two different magnifications
to examine the filler distribution on a macroscopic and dispersion on a microscopic
scale. An indirect measurement is to measure the unnotched impact strength of the
composites, as that property is sensitive to agglomerates. In a rather insightful study,
Hornsby showed the degree of dispersion of filler as it passed through a twin-screw
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extruder [25]. This was achieved by using a clamshell extruder that could be stopped
and opened so that samples of compound could be removed for analysis. It was found
that the greater part of the dispersion was imparted in the melt zone where the pellets of
polymer are just melting. The high viscosity in that region requires a high energy input
and encourages deagglomeration. Feeding the filler into the unmelted polymer may give
good dispersion, but it also results in higher wear of the extruder so that this approach is
only advisable for soft, surface treated fillers. It is more usual to add the filler when the
polymer is already molten although a multitude of feeding possibilities exist [25].
8.2.4.4 Machine Wear
Machine wear is a concern, partly because it costs money to replace a worn barrel or
screw. The main problem though, is the loss of productivity when the machines must be
shut down for maintenance. Potentially, wear may lead to significant metal contamination
levels with accompanying polymer stability problems. Although machine wear is an issue,
it is not a subject that has received much attention.
There are a few studies that have investigated the effect of filler properties on wear
[17, 30]. One simple method is to extrude through a plate of soft metal and measure
weight loss from the perforated plate at regular intervals. It was concluded that hard,
large irregular particles cause most wear. Surface treatment with a lubricating additive
such as stearic acid helps alleviate wear because the additive forms a protective layer
around the particles.
8.2.5 Thermal Conductivity and Specific Heat Capacity
It is not only the final properties of the composite that matter, processability and
economy of manufacture are also important. If the part can be cooled more quickly,
then money can be saved through improved productivity. Mineral fillers typically have
thermal conductivities in the range 0.023 WK-1m-1 [5, 22, 31] that are an order of
magnitude higher than those of polymers [2, 32-34]. The volume specific heat capacity
of mineral fillers (~1900-2000 J litre-1K-1) [5, 22, 31] are very similar to those of polymer

melts (~1500-3000 J litre-1K-1) [2, 33-35]. An equation has been proposed for calculating

the heat capacity of composites based on the composition and the heat capacities of
the components [36]. The result is that the filler speeds heating and cooling of the
filled polymer melt through improved conduction. Therefore, filling a polymer often
allows for reduced cycle times in injection moulding [30] and thermoforming [34]
because the part cools and hardens more quickly, allowing it to be removed from the
mould earlier. In the literature, there have been some contradictory statements about
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the relative specific heat capacities of mineral fillers and polymers. This confusion may
have arisen because the specific heat capacity is usually given in terms of mass with
units of Jkg-1K-1, whereas to compare fairly, these values must be converted into volume
terms, i.e., JL-1K-1.
There is a niche market for thermoplastics with very high thermal conductivity. These
are marketed for CPU cooling in laptop computers and other high performance
applications. An interesting point to note is that thermal and electrical conductivity actually
benefit from poor filler dispersion. Agglomeration and network formation (percolation)
allows better heat conduction due to the network of particle particle contacts.
8.2.6 Thermal Expansion
The thermal expansion coefficients (CTE) for polymers (~10 x 10-5 mm mm-1 C-1) [2,

36, 34] are approximately an order of magnitude higher than those for mineral fillers
(~10 x 10-6 mm mm-1 C-1) [31] or for metals (~20 x 10-5 mm mm-1 C-1) [31]. This may

lead to problems in applications where plastics and metals are in contact, as differential
expansion and contraction can cause such parts to warp. It is possible to estimate the
CTE of a composite based on the composition and knowledge of the CTE for each
component [37]. The polymer chains can become oriented during flow of the polymer
melt and this can give rise to a difference in the amount of shrinkage parallel and
perpendicular to the flow direction. Addition of particulate fillers such as calcium
carbonate, silica and talc tend to lessen the amount of polymer chain orientation, and
thereby reduce not only shrinkage, but also shrinkage differentials, with a corresponding
decrease in warpage [22, 34]. In contrast, fibrous fillers and other highly anisotropic
fillers, tend to partially align in the flow direction, leading to an increased shrinkage
differential and a tendency for the part to warp during cooling. Warpage is not easy to
predict, and so it is common to use low aspect ratio fillers for parts where warpage must
be avoided. Another approach is to use a mixture of low aspect ratio filler and fibres
[38], which can ameliorate the high warpage observed when fibres alone are used, whilst
maintaining sufficiently good mechanical properties.
It is often not possible to use the same mould for filled and unfilled polymer because the
change in shrinkage gives parts that are out of specification. On the other hand, adding
filler to a polymer allows its shrinkage to be systematically tuned. This tuning method is
useful for example, if one is attempting to use an existing mould with a different polymer.
Filler may be added to the newly chosen polymer to achieve similar shrinkage to that of
the previously used polymer. Injection moulding tools (moulds) are very expensive and it
is preferable to keep using the same mould rather than purchasing a new one specifically
made to accommodate the new polymer.
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8.2.7 Electrical Properties
The high tonnage, commercially important polymers are, in general, excellent insulators
with resistivities in the range 1012 1018 cm [22]. The top three polymers in volume

terms (in descending order) PE, PP and PVC are all used extensively as cable insulation.
There are some intrinsically conductive polymers [39-41] such as polyaniline [42, 43]
polythiophene and polypyrrole [43], but these are relatively expensive, intractable, niche
materials, that must be modified to impart processability [44-46].
Most fillers, while having good dielectric properties and resistivities, are in general worse
than a plastic. Also, incorporation of a filler will introduce flaws and interfaces, charged
ions and traces of water (all fine particles adsorb some water from their environment) and
hence reduce electrical properties. Usually, however, because of the good electrical properties
of the plastic, fillers may be used simply as an extender, the composite still giving good
properties. Calcined clay (produced at just above 1000 C) and other calcined silicates, do
not degrade electrical performance as severely as other fillers, because of low water pick-
up, and immobilisation of matrix ions. Conversely, metakaolin, because of its highly reactive
surface absorbs ions and thus improves the electrical performance of polymers such as
plasticised PVC and ethylene vinyl acetate (EVA) copolymers [47]. Due to their good
insulation characteristics thermoplastics can suffer from tracking, i.e., the build-up of surface
charge which then discharges across the surface, because that path has less resistance than
passage through the plastic. Filler particles can reduce this problem by acting as a physical
barrier and by distributing the charge before critical build-up occurs [48, 49].
In many cases, it is beneficial to introduce some level of electrical conductivity into a

polymeric material [5, 22]. The highly insulating polymers are susceptible to static build
up. This may be a nuisance, attracting dust to the surface, or it may lead to damage of
sensitive electronic parts, when manufacturing integrated circuits, for example. Even
very low levels of surface conductivity will resolve this problem [6]. Organic based
antistatic additives are available or alternatively conductive fillers such as carbon black,
graphite, or metals may be added [6].
Sometimes, a material of much higher conductivity is required. One example is for

electromagnetic interference (EMI) shielding [22]. This is achieved by adding a sufficient
level of conductive filler. Initially, as one adds more conductive filler, the conductivity does
not rise appreciably, because the conductive particles remain isolated from one another. As
the filler loading is gradually increased, the conductivity suddenly rises sharply, by many
orders of magnitude, approaching the conductivity of the conductive filler itself, and then
levels off [50]. This discontinuity is known as the percolation threshold and it signifies the
volume percentage of filler required to attain a continuous network of interconnected
particles throughout the matrix [22]. Usually, 10-30 volume percent of filler is needed to
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achieve percolation, depending upon particle size, shape and the level of dispersion. Smaller,
more anisotropic particles show lower percolation thresholds [39]. As with thermal
conductivity, good dispersion is detrimental to electrical conductivity [22, 51]. On the
contrary, the aim is to achieve percolation by inducing an agglomerated network of particles.
8.2.8 Barrier Properties
Thermoplastics are widely used as packaging materials due to their low cost, excellent
chemical resistance, good barrier properties and the potential for recycling. In fact, over
35% of all thermoplastic is used in packaging. They are also used in a variety of other
applications where barrier properties are required. These include water and gas pipes, as
well as car petrol tanks.
Permeability of a material to small molecule penetrants, such as oxygen and water,

increases with the solubility of the small molecule in the matrix [52] and with the diffusion
coefficient in that material [53]. Polymers are very sensitive to plasticisation by small
molecules. Thus, the presence of small molecules may greatly increase the diffusion
coefficient. Based on these observations, one can envision ways to decrease permeability
by reducing the solubility and/or the diffusion coefficient.
Molecules can neither dissolve in, nor diffuse through, mineral fillers to any appreciable
extent. Therefore the presence of filler reduces the solubility of the diffusant in the composite
material, and thereby the permeability, in proportion to the volume fraction of filler.
In addition, the presence of impermeable filler in a polymer forces the diffusant molecule
to travel further around the filler particles. This physical blocking effect is known as
tortuosity, because the filler forces the diffusant to take a more indirect, or tortuous,
path through the material. The degree of tortuosity imposed is dependent upon the
anisotropy and orientation of the filler particles with respect to the direction of diffusion.
For example, platy particles oriented perpendicularly to the diffusion vector will be
particularly effective in retarding diffusion. The permeability of a composite can be
calculated using an equation that allows for the reduction in permeant solubility and for
the tortuosity (Equation 8.3). Where Pc and Pp are the permeability of the composite and
the unfilled polymer, respectively. The terms w and t refer to the width and thickness of
the filler and p and f represent the volume fraction of polymer and filler.
Pc p
=
Pp 1 + (w / 2t ) f
Equation 8.3 Composite permeability
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As mentioned previously, the addition of filler may also change the amount of crystallinity
in the polymer. As polymer crystals are impermeable even to low molecular weight species,
an increase in crystallinity also results in improved barrier properties, through increased
tortuosity [54]. This effect is expected to be especially prevalent for fillers that induce a
high degree of transcrystallinity.
Dispersion and wetting of the filler can also affect the permeability of the composite. It
has been shown that PE filled with 25 volume percent calcium carbonate was actually
four times more permeable to oxygen compared to the unfilled reference PE. This was
attributed to poor wetting of the filler, so that the diffusant was able to travel unimpeded
along the polymer/filler interface. In contrast, stearic acid coated calcium carbonate at
the same loading resulted in three times lower oxygen permeability than the unfilled PE
[55]. Similarly, Tiburcio and Manson showed that the water vapour permeability of
glass-bead filled phenoxy films decreased sharply as the degree of adhesion between the
filler and the matrix was increased [56].
In some cases, it is desirable to increase the permeability of a polymeric material. One

example is breathable films. For example, calcium carbonate filled PP films are first
made by solvent casting, or extrusion casting or as blown film and subsequently stretched
to delaminate the filler polymer interface [57]. High filler loadings are used to ensure
interconnecting voids, giving unimpeded diffusion [58].
8.3 Mechanical Properties
8.3.1 Introduction
For any given application, certain mechanical properties will be of more importance than
others. It is therefore, essential to identify and rank the most relevant properties and formulate
or purchase the least expensive composite material that satisfies the requirements. The key
mechanical properties for most applications are modulus (tensile or flexural), yield strength,
impact strength and possibly HDT. A distinction is often made between reinforcing and non-
reinforcing fillers, but unfortunately, the term reinforcement is rarely defined explicitly. Fibres
are usually considered to reinforce and isotropic fillers are not, with platy fillers somewhere
in between. As shown later, it is not appropriate to define reinforcement in terms of particle
shape, because that definition breaks down with variations in anisotropy and particle size. In
agreement with Ram [59], the definition of reinforcement as the simultaneous improvement
of both modulus and yield strength will be used in this chapter.
Polymer mechanics is a broad subject and the interested reader is directed to specialised
texts [60]. Each of the main properties is described here, along with a consideration of
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how it changes with filler type and level of addition. The effect of surface treatments
such as dispersants and coupling agents are also mentioned, where applicable. A more
detailed description of surface treatments is given in Chapter 4.
8.3.2 Modulus Tensile and Flexural
One of the main reasons for adding mineral fillers to thermoplastics is to increase the
modulus (stiffness). Tensile (under tension) modulus is the ratio of stress to strain, at some
low amount of strain, below the elastic limit. Flexural (bending) modulus is also often
measured. The most relevant modulus to measure depends upon the expected deformation
mode of the part that will be made from the material. Often, the flexural modulus and
tensile modulus are rather similar. The exception is the case of anisotropic fillers, which
can become aligned in the flow direction when the test specimens are moulded.
There is a good understanding of how addition of filler affects the modulus of a polymer.
Chow has done an extensive review of the area, and the interested reader can consult
that work for a more detailed description [61]. In fact, the simple rule of mixtures is
fairly accurate at low strain levels (Equation 8.4). Ec, Ep and Ef are the moduli of the
composite, polymer and filler, respectively, and f is the volume fraction of filler. The
moduli of thermoplastics are in the range 1-3 GPa [1, 32, 35, 34] whereas common
fillers have much higher moduli [5, 22, 31] (calcium carbonate and dolomite ~ 35 GPa,
mica ~ 17.2 GPa and wood flour ~10 GPa).
Ec = (1 f )E p + E f
Equation 8.4 The dependence of composite modulus on volume fraction of filler
The modulus increases with increasing volume percentage of filler [62]. In most cases,
this relationship is linear for filler concentrations up to approximately 20 volume percent.
Filler orientation strongly affects modulus [63]. This is important because injection
moulded ASTM standard dog-bone shaped test specimens give high filler orientation.
The moduli measured on such specimens may be far higher than those attained in a real
injection moulded part where the orientation is usually not optimal. Increasing crystallinity
in the polymer phase can also lead to a higher modulus because the crystal phase is
stiffer than amorphous regions [64, 65]. Various attempts have been made to account
for other factors such as polymer-filler interaction and interparticle interactions. One
such semi-empirical model is known as the Nielsen equation, also known as the Lewis-
Nielsen or modified Kerner equation [66, 67].
In these theories, modulus is independent of particle size. However, Heikens [68] has
found that when the polymer is strongly bonded to the plastic composite, modulus is
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affected by the filler particle size. Particle size effects are allowed for to some extent in
the modified Kerner equation by the introduction of an effective filler volume fraction.
The most important filler parameter affecting modulus is its shape. Unfortunately, when
the filler is non-spherical theories become much more complicated and the reader is
advised to refer to Chows review [61]. Shape factors can be incorporated in the models
mentioned previously but are only useful when applied to very high aspect ratio materials,
e.g., fibres. There is also an almost insurmountable problem with particulate fillers: the
difficulty and effort to measure aspect ratios of micrometre sized particles. Pukansky
examined the effects of 11 different fillers in polypropylene [69] and concluded that
Youngs modulus is affected by the amount of bonded polymer, which is in turn related
to surface area, and therefore to both particle size and shape. That observation helps to
explain the strong effect that nano-fillers have on the modulus of a composite. Schreiber
and Germain showed that modulus depends on the strength of interaction between the
polymer and the filler surface [62].
To exemplify the effect of fillers on a thermoplastic, PP homopolymer filled with differing

filler types and consequently very different shapes is shown in Figure 8.2. It can be seen
that a linear fit can be used successfully for most of the fillers. The exception is mica,
which deviates from linearity at high filler levels where interparticle interactions become
important. The modulus values also reflect the expected shapes of each of the fillers.
Similar trends are reported for other common polymers [22].
Figure 8.2 The effect of common fillers on the tensile modulus of PP homopolymer
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In conclusion, it can be stated that the effect of fillers on modulus is relatively well
understood and may be predicted. The other properties are less easy to predict as they
are measured under conditions where the composite is deformed to a greater extent.
This means that other factors such as particle debonding, particle re-orientation and
polymer orientation, must be considered.
8.3.3 Heat Deflection Temperature (HDT)
The HDT is the temperature at which a beam of polymer deflects by a given amount
under a specified load. The HDT is a complex function of the composites modulus and
polymer properties such as glass transition temperature (Tg), melting temperature (Tm),
degree of crystallinity and amount of bonded polymer in the filler-polymer interphase.
Examining the effect of fillers on the HDT of PP homopolymer (Figure 8.3) shows that
the trends are similar to those for modulus. There are two common standard conditions
for testing the HDT of PP; one uses a force of 0.46 MPa, whereas the other uses 1.8
MPa. Care must be taken when comparing results for different composites to ensure that
the same test conditions were used.
The greatest enhancement of HDT is seen with semi-crystalline thermoplastics such as

PE, PP, polyamides and PET, with only minor enhancements achieved for filled amorphous
Figure 8.3 The effect of common fillers on the HDT of PP homopolymer
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polymers like polystyrene, acrylonitrile-butadiene-styrene (ABS), polycarbonate and

polysulfone [1]. Addition of glass fibre to semi-crystalline polymers gives an HDT
approaching the melting point of the matrix. In the case of amorphous polymers,
incorporation of glass fibre gives an HDT (at 1.8 MPa stress), which is close to the Tg of
the matrix. For this reason, filler is most commonly used in semi-crystalline polymers
where the HDT is improved most because the crystalline regions help transfer stress to
the filler under load [70].
8.3.4 Yield Strength
Yield strength is a measure of the force that a material can withstand before it suffers
macroscopic plastic deformation. For most materials, e.g., metal, it is taken as the
point on the stress-strain curve when the line becomes non-linear (the elastic limit).
However, for plastics, it is taken as the peak of the stress-strain curve, as that is
simpler to measure. In practice, most parts are designed so that they never experience
a force approaching the yield stress because yielding represents failure of the material.
Yield strength is a key property when designing parts. Fillers are often added because
they increase the yield strength of the polymer, this effect is known as reinforcement
if the modulus is also improved [59]. The explanation for reinforcement lies in the
fact that adding filler actually changes the polymer phase. It has been shown that
polymers interact with the filler surface, forming an interphase of adsorbed polymer
[71-74]. The thickness of the interphase can vary widely from system to system.
That is to be expected; for example polar polymers such as polyamides are capable of
strong, specific interactions with groups on the filler surface. In contrast, non-polar
polymers such as PE and PP have weaker interactions with fillers. The apparent
thickness of the interphase also depends strongly upon the measurement method.
Lower values of around 0.004 m are reported from extraction experiments, whereby
all non-adsorbed polymer is solvent extracted [75, 76]. Values deduced from
mechanical data such as by dynamic mechanical analysis or modulus tend to be much
larger, in the range 0.012 to 1.4 m [77]. This interphase has mechanical properties
intermediate between those of the polymer and the filler [78, 79], thereby allowing
an increased yield strength for the composite.
Several factors determine the level of reinforcement attained by adding filler. These include,
the volume fraction of filler added, the surface area of the filler (related to particle size),
particle shape, the level of adhesion between the filler and polymer [80], as well as the
thickness and nature of the interphase between the two phases. A linear correlation
between yield strength and heat of crystallisation has also been reported in the case of PP
filled with calcium carbonate [81]. It is well known that spherical fillers give least
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Figure 8.4 The effect of common fillers on the yield strength of PP homopolymer
reinforcement, platy fillers are better and fibrous fillers are best of all [5, 30]. Usually, it
is considered that spherical fillers such as calcium carbonate and dolomite do not reinforce
at all, and in fact they usually reduce the yield strength of the material (Figure 8.4).
However, that is not necessarily true, as it has been shown that it is possible to increase
the yield strength of PP by using very fine spherical filler with a mean diameter of 0.01
m [78, 79]. This improvement must be due to the high surface area of the filler as the
filler is isotropic. The high surface area increases overall polymer-filler adhesion and
thereby improves yield strength.
It is observed that spherical fillers do not reinforce whereas platy fillers like mica may do,
and glass fibres are most effective (Figure 8.4). In this particular example, talc does not
reinforce, probably because the talc grade used did not have sufficient anisotropy. As with
yield strength, the data shown is for PP homopolymer, but similar trends are seen for a
wide range of other thermoplastics [3, 22]. The filler creates an additional complication
especially for injection moulded parts. Namely, during mould filling, the filler distribution
becomes non-homogeneous due to the flow. One consequence is flow lines and weld lines.
These are created when two fronts of molten polymer meet. For an unfilled polymer the
melt can easily mix when two melt fronts meet and so the mechanical properties are normally
unchanged (except for the special case of liquid crystalline polymers). The uneven distribution
of filler at the weld lines creates a weak point, so for example, the measured yield strength
and elongation to break are reduced. This effect is not as great for isotropic fillers but for
more anisotropic fillers the yield strength may be reduced by more than fifty percent. It is
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therefore essential to design with this in mind. This can be done by designing parts to avoid
weld lines and by judicious placement of injection points. Additionally, it should be
remembered that the reported mechanical properties for composites are for ideal specimens
with no weld lines, whereas the actual yield strength in the part may be far lower.
8.3.5 Impact Strength (Toughness)
The impact strength of polymers and composites is another key property. In contrast to the
other mechanical properties, it is not possible to predict the impact strength of a
thermoplastic composite. The reason is that there are too many factors to be considered.
One of the major complications is that adding hard filler can change the mode of failure
from ductile to brittle [2, 7], or vice versa for rubbery fillers [7]. The filler may act as a
flaw, if there are large particles or agglomerates [82, 83]. Alternatively, well dispersed,
small particles can improve the impact strength by a crack-pinning mechanism. Another
problem in predicting impact strength of composites is that mechanical properties of
polymers are very dependent upon the rate at which the testing is performed. Most
mechanical data are acquired at low speeds; for example, tensile testing is often performed
at a strain rate of 0.110 mmmm-1min-1. In contrast, impact testing is a very rapid event
(>10 000 mmmm-1min-1) and the polymer often responds very differently. For example, a
polymer that fails in a ductile way during tensile testing may become brittle under impact
test conditions because when the deformation is fast, the polymer chains have insufficient
time to move and accommodate the deformation. It is well known that the response of
polymers is dependent upon testing rate [60, 84-86]. The WLF (Williams, Landel and
Ferry) equation [87] can be used to account for this effect at temperatures near to the Tg.
The WLF equation predicts that the effective Tg of a polymer changes by about 6.9 C for
every decade of change in the rate of testing [84]. That means that a polymer which has a
Tg below room temperature under tensile testing conditions, may have a Tg well above
room temperature under impact test conditions. Therefore, the polymer may behave in a
ductile manner, with high strength, under tensile testing but it may be brittle under impact,
giving low impact strength. In cases where the mode of fracture does not change with
testing speed, then it is expected that the energy to break determined by tensile testing (the
area under the stress-strain curve) will correlate with the impact strength.
Similar complications exist when it comes to measuring impact strength. Many methods
are available, the most common of which involve either a pendulum striking the sample
(Izod and Charpy), tensile impact testing, or a falling dart. In general, impact tests do not
correlate well with each other, although it has been shown that there is a correlation between
Izod and Charpy values [88]. Impact tests may be performed on unnotched (as moulded)
samples or pre-notched samples, whereby a well-defined flaw is introduced to ensure that
the sample fails at the desired point. Adding a notch improves the reproducibly noticeably,
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but it may not be realistic as parts in actual use are not notched, at least not intentionally.
Unnotched testing is best for detecting agglomerates and flaws because the crack initiates
at such imperfections. Notched impact testing is comparatively insensitive to agglomerates
and large particles because the sample fails preferentially at the large, introduced flaw.
Reverse notched testing such as Izod E is especially suitable for composites. This sample is
struck on the opposite side to the notch. In this way the stress is concentrated opposite the
notch but the introduced notch is not the site where crack growth occurs. The notch
encourages reproducibility by localising the stress on the opposite side of the sample, but
the crack initiation occurs at some imperfection in the composite and so the method is still
sensitive to agglomerates.
In the final analysis though, the lab scale impact tests are of limited value. They may be
used to compare materials qualitatively, but the ultimate test is to make the part or
prototype and perform impact tests on that, in a manner that closely simulates the way
in which the part is to be handled during manufacture, or used.
There are many reports describing the effect of fillers on the impact strength of polymers.
These are however, hard to compare as they often use different polymers, test methods
and filler particle size distributions. It is therefore difficult to make any general
comments. One study showed that increased filler anisotropy (aspect ratio) resulted in
reduced falling weight impact strength [89]. That is particularly interesting because
increased filler anisotropy is known to improve modulus. This is therefore an excellent
illustration that one must be prepared to sacrifice some property for the sake of
improving another, more important one. There has been some success in creating high
modulus composites with good impact strength. This was done using ternary composites
where a dispersed, stiff filler is encapsulated in a rubbery layer dispersed in the matrix
polymer [90]. It can be stated that fillers can either decrease or increase the impact
strength compared to the unfilled polymer. A common technique for increasing impact
strength is to disperse a soft, or rubbery, filler in a harder polymer to increase its
impact resistance. This method is used to make HIPS and to improve the impact
resistance of PP, especially at low temperatures [91].
Hard fillers on the other hand may either increase or decrease impact strength [92].
For example, fine calcium carbonate or talc can increase the impact strength of PP
homopolymer by more than a factor of two [93, 94]. This only holds if there is good
dispersion to avoid agglomerates, if there are no large particles, above about 10-20 m
in diameter, the calcium carbonate is stearate coated and the particle size distribution
has been optimised [94]. There seems to be a definite interaction or synergy between
particle size and coating level, and the highest impact strengths are found with calcium
carbonates with 1% stearate coating and a mean particle size 1-2 m, depending on
the type of polymer and the nature of the impact test (se Figure 8.5).
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(a)
(b)
Figure 8.5
(a) Effect of stearate coating level on a ultrafine calcium carbonate (d50: 0.8 m) on
the properties of polypropylene
(b) Effect of particle size of stearate coated calcium carbonate on the properties
of polypropylene
379
In the case of PP copolymer and impact modified PP, the effect of filler is very different;
impact strength is lowered significantly by hard particulate fillers. This is because the
filler interacts with the soft or rubbery component and nullifies its ability to adsorb
energy during impact.
In conclusion, it seems that soft rubbery fillers improve impact strength by helping to
dissipate the energy of impact. Hard fillers decrease the impact strength of ductile
materials, which already have high impact strength. On the other hand, well dispersed,
hard particles of the correct particle size may improve the impact strength of brittle
materials like PP homopolymer or polystyrene [22] by promoting crazing.
8.4 Effects of Filler on the Polymer Phase
8.4.1 Introduction
To understand and predict the properties of composites, it is necessary to realise that

adding filler may affect the polymer phase, both chemically and physically. Chemical
changes may occur if the filler, or impurities on the filler surface, catalyse degradation of
the polymer. Alternatively, various physical changes may result from the incorporation
of filler. Some fillers nucleate crystal growth in certain polymers, which in turn influences
manufacturing and mechanical properties.
In the literature, the possibility that the filler may have altered the polymer phase is
rarely considered. It is important to realise that the polymer may be altered by the filler,
especially in the case of semi-crystalline polymers [95] like PE, PP, PVC, PET and the
polyamides. Therefore, these effects are mentioned here to allow a better understanding
of the factors affecting the performance of a composite.
8.4.2 Nucleation
It is widely recognised that fillers may affect the crystallisation of polymers [96]. The
filler may increase the rate of cooling, as mentioned previously, and may thereby affect
crystallisation. Some polymers have more that one type of crystal phase, which occur
preferentially when cooling within a certain temperature range [97, 98]. These crystal
types have different mechanical properties [99, 100] and therefore, the relative amount
of each phase will influence to the properties of the thermoplastic composite.
In other instances, the filler may nucleate crystal growth. This is often beneficial, as it
causes the material to harden more rapidly on cooling, giving the possibility of faster
production. In fact, it is common practice to add a small amount of fine talc to nucleate
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Figure 8.6 The effect of some common fillers on the impact strength
of PP homopolymer
crystallisation of PP, especially in thin-walled parts. Interestingly, dolomite is also rather

effective, and calcium carbonate and mica have a slight effect on crystallisation onset
temperature (Figure 8.6). In some cases surface treatment of the filler affected nucleation
and in other cases no effect was seen.
As well as the crystallisation onset temperature, the peak of the crystallisation endotherm
may also be used as a measure of nucleating effectiveness. The two methods show the
same qualitative trends.
Another important parameter is the proportion of crystallinity in the composite. The

crystalline phase has a higher modulus than the amorphous phase, and it has been reported
that the yield strength is linearly proportional to the heat of crystallisation [81]. Clearly,
the mechanical properties of the composite are influenced by the degree of crystallinity.
For a given PP copolymer grade, the degree of crystallinity was 43 weight%, whereas
this was 45-48 weight% when 60 weight% of magnesium hydroxide, dolomite or talc
was added. When measuring the degree of crystallinity one must correct for the amount
of filler added. For example adding 50 volume % filler will reduce the apparent crystallinity
[as measured by differential scanning calorimetry (DSC)] by 50%. The explanation is
quite simply that 50% of the polymer has been removed. It is quite common that this
dilution effect is not accounted for, or it is not stated whether it has been corrected for.
This leads to some confusion in the literature.
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Unfortunately, it is not possible to predict whether a particular filler type will nucleate
crystal growth. For some time it was thought that high energy surfaces nucleated, but this
has since been proven incorrect [95]. Instead, Hobbs has shown that surface microtopology
influences nucleating ability [101]. In that work, Hobbs made a replica of a nucleating
surface using a non-nucleating material, to produce a surface that was strongly nucleating.
It can be concluded that any thorough study of filled polymers must also consider the
possibility of nucleation and changes in the degree of crystallinity.
8.4.3 Transcrystallinity
Transcrystallinity may occur when a polymer is cooled in contact with a highly nucleating
filler or surface [95, 102]. Usually, polymer crystals are spherulitic, growing out radially
from the nucleation site [2, 85, 86]. In contrast, when crystals are nucleated very close
together, they impinge on each other almost immediately, and are forced to grow in one
direction, away from the nucleating surface [95]. For a polymer where only one crystal
form occurs, it has been shown that the microstructure of the transcrystalline phase is
the same as that for the spherulites [103]. The transcrystalline layer is typically 10-30
m thick, which means that for higher filler loadings, the whole matrix may be composed
of transcrystalline material [95]. Transcrystallinity has been reported in several systems
including glass [104], PET [105, 106] and some types of carbon fibre in PP [107], as well
as Kevlar fibres in Nylon 6,6 and even in Nylon-PP blends.
Sheets of transcrystalline PP have been prepared by cooling PP from the melt in between
PET (Melinex) sheets and the properties studied [108]. This rather elegant work by Fowkes
and Hardwick showed that the transcrystalline sheet had a much higher Youngs modulus
(1.09 GPa) compared to the control PP sample that was quenched to give a fine spherulitic
sheet (0.67 GPa). The tensile yield strength of the transcrystalline material was also higher
at 25.0 MPa, compared to 18.6 MPa for the spherulitic sheet. Some of the properties were
much worse compared to normal, spherulitic PP. For example, the transcrystalline sheet
showed just 4% elongation to break and an energy to failure of just 28.0 kJm-2, compared
to >300% and 48.5 kJm-2, respectively, for the fine spherulitic analogue.
Clearly then, the filler can greatly influence the type and level of crystallinity, leading to
profound changes in the properties of the resultant composite material.
8.4.4 Interphase
Aside from changes in crystallinity, there is another way in which the presence of filler may
alter the host polymer. It has been shown that polymer adsorbs onto the filler and that this
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adsorbed material has different properties compared to those of the bulk matrix [68, 71,
109, 110]. Pukansky and Fekete have written a review of the importance of the interphase
in thermoplastics [9]. The relevance of the interphase to adhesion at planar interfaces, and
in composites, has been discussed by Berg [109]. As expected, the thickness of the interphase
varies depending upon the extent of interaction between the polymer and filler. It has been
shown that the thickness of the interphase is proportional to the reversible work of adhesion
[8]. Reported thicknesses are usually in the range 0.0040.15 m, depending upon the
polymer filler combination and the method used to estimate the thickness [9, 22]. It is
anticipated that the interphase thickness should be influenced by the ubiquitous van der
Waals forces plus any specific chemical interactions such as Lewis acid-base or hydrogen
bonding or covalent bonding [22]. Therefore it should be affected by surface treatment of
the filler. The degree to which the interphase affects the properties of the composite should
also therefore depend on the total surface area of the filler [22] and is therefore especially
important for nano-composites.
8.5 Surface Science Aspects
8.5.1 Introduction
The importance of surface interactions in composites is widely recognised, and yet, it is

probably the one that leads to most confusion. This is partly because it is difficult to
characterise the interphase, but also because the composites field is interdisciplinary,
requiring not only surface science and adhesion science but also an understanding of
polymer science. This section will briefly mention some of the relevant points, but surface
and colloid science is a wide area and specialist texts should be consulted if more detail
is required [111-114]. Pugh has reviewed the wetting and dispersion of ceramic powders
in liquids, which is highly informative and relevant to the case of mineral particles dispersed
in a polymer [115]. The interfacial interactions in particulate filled composites have been
reviewed by Puknsky and Fekete [9]. Most recently, Berg has written an excellent review
on the subject of wetting and adhesion [109].
8.5.2 Surface Energy and Surface Tension
Surface energy must be introduced in order to be able to understand the forces that
drive wetting and adhesion. If one imagines an atom or molecule located in the bulk
of a material, the forces acting upon that entity are symmetrical. Each unit is attracted
to its neighbours equally. If one then cleaves the material, then the forces acting on
the units (atoms or molecules) at the newly formed surface are no longer symmetrical.
Those surface units are still attracted towards their neighbours, but they lack attractive
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interaction in the direction of the new interface. Because these units at the interface
are in a new environment, energetically speaking, there must be a change in the total
free energy. This change in energy relative to the bulk is termed the surface free
energy, with units of mJm-2. For liquids, the net force towards the bulk manifests
itself as a tension at the interface. This gives rise to the concept of surface tension in
liquids, with units of mNm-1. There are various old and new units of surface energy
and surface tension, but fortuitously, it turns out that they are numerically equivalent,
i.e., 1 mNm-1 = 1 mJm-2 = 1 dyne cm-1 = 1 erg cm-2. So, in summary, the surface

energy is the energy required per unit area to form a new surface of that material in
a vacuum. The symbol for surface tension and surface energy is , where S, L and SL
refer to the surface energies of the solid, the liquid and the interfacial surface energy
between the solid and the liquid, respectively.
The surface tension of liquids is easily measured by a wide variety of methods, whereas
it is much more difficult to measure the surface energy of solids. A comprehensive overview
covering methods applicable for liquids and solids is presented by Adamson [111].
8.5.3 Wetting and Spreading
When the filler is mixed with the polymer melt, it is important that the polymer wets the
filler. It is desirable for the polymer to penetrate in between the particles, displacing the air
and giving intimate contact between the polymer and filler surface. This will prevent trapped
air bubbles and aid adhesion between the filler and polymer. Wetting, and more specifically,
immersional wetting, is the term used to describe this process [112, 115]. The driving force
for wetting to occur is related to the surface energies of the wetting fluid and the solid [8,
109, 111-115]. The surface energy of solids is usually determined using static contact
angle measurements. This is a useful method, although the results are affected by surface
roughness, drop size and contaminants [116]. Furthermore, contact angle measurements
are only valid when the liquid does not penetrate into the solid under analysis [116], which
is of particular importance for polymers, as they are often swollen by liquids.
Theoretically, under equilibrium conditions, a low surface energy liquid, such as a polymer
melt, should completely wet the high energy mineral filler surface [112, 115]. However,
this view is overly simplistic, and does not apply in reality for several reasons. One
reason is that high energy surfaces attract contaminants and are usually covered in a
layer of hydrocarbon material spontaneously adsorbed from the atmosphere [112]. This
means that the high energy surface no longer behaves as such. Another, more fundamental
problem is that polymer processing is a dynamic process and so kinetic aspects of wetting
are more important than thermodynamics. Dynamic wetting has been studied as it is of
great industrial importance. It can be shown that the low surface energy and the high
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viscosity of the polymer melt both disfavour wetting of the filler [111, 112]. Dynamic
wetting in composites is an area that deserves further study in order to understand and
optimise wetting under real processing conditions. Some studies have been performed, in
particular for fibre reinforced composites [117].
The spreading coefficient represents the thermodynamic driving force for the liquid to
spread onto and wet the solid (Equation 8.5). For spontaneous spreading to occur, the
spreading coefficient must be positive, implying a contact angle of zero.
S L / S = S ( L + SL )
Equation 8.5 The spreading coefficient
8.5.4 Adhesion
The degree of adhesion between the filler and polymer is expected to influence the mechanical
properties of the composite. This can be predicted theoretically, although it is much more
difficult to prove experimentally. It is a major challenge to change the adhesion between
the polymer and the filler without invalidating the experiment by unintentionally altering
other parameters [109] such as filler dispersion level or polymer crystallinity.
Even so, many workers have tried to correlate the calculated reversible work of adhesion
with the mechanical properties of composites. Studies on planar surfaces have shown
that measured adhesive bond strengths are, at best, only one tenth of the calculated
value based on van der Waals interactions alone. It might therefore be assumed that the
reversible work of adhesion would have rather limited utility as an indicator of adhesion
at the interface. Despite that, it has been shown numerous times that the reversible work
of adhesion often does correlate rather well with the mechanical properties of composites,
in particular yield strength [8, 109]. Berg addressed the question of whether it was
worthwhile to use concepts such as reversible work of adhesion to predict and tune
adhesion [109]. The conclusion was that the approach is reasonably effective already
and will improve in the future.
The first criterion for good adhesion is intimate contact, that is good wetting of the
surface. Wetting is a necessary, but not sufficient, condition for good adhesion [109]. In
addition, one should seek to maximise the work of adhesion. The simplest case is to
consider the work of adhesion to be attributable solely to non polar (London) forces
between the materials. This is indeed the case when at least the adhesive (polymer melt)
or adherand (filler surface) is non-polar. So, for thermoplastics such as PE, PP and
polytetrafluoroethylene (PTFE) this simple case should apply.
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The work of adhesion is given by Equation 8.6. This implies that the work of adhesion
can be maximised for a given adherand by increasing the surface energy of the adhesive.
However, we also know that wetting is required and so the surface tension of the adhesive
must not exceed that of the adherand. So, the ideal case is when the surface tension of
the polymer melt is as high as possible, but without exceeding that of the filler surface,
so that spontaneous spreading still occurs. This has been verified experimentally for a
range of polymeric adhesives on a set of surfaces with controlled surface energy [109].
WA = 2 S L
Equation 8.6 Work of adhesion (WA) for the non-polar case
Later, it was realised that polar interactions could also play a role in wetting and
adhesion. The surface energy was divided into non-polar and polar components and
new equations were then proposed to allow for the possibility of polar interactions
across the interface (Equation 8.7). From that equation it can be expected that maximal
adhesion will occur when the ratio of polar to non-polar surface energy is the same for
the adhesive and the adherand.
WA = WAd + WAp = 2 dS Ld + 2 Sp Lp
Equation 8.7 Work of adhesion for the polar case
Wu proposed another equation using an harmonic mean approach to estimate the non-
polar and polar interactions across the interface [8, 109, 116]. This approach gives the
same criterion for maximising adhesion.
Folkes went a step further by arguing the importance of Lewis acid and base interactions.
This leads to a new elaboration of the equation for calculating the work of adhesion
(Equation 8.8).
WA = WAd + WAp + WAAB
Equation 8.8 Work of adhesion in Lewis acid-base terms
The premise is that each component can only interact with its corresponding component
in the other material. Intuitively, it seems reasonable that this should be the case, although
again, it is not clear whether the geometric or harmonic mean, or some other method, is
best for estimating the magnitude of the Lewis acid-base interactions across the interface.
Fowkes proposal has been widely accepted and verified experimentally. For example
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Sinicki and Berg varied the Lewis acid-base interactions systematically and found a
correlation between adhesion measured by peel testing and the calculated thermodynamic
work of adhesion [118].
Schreiber and Germain used plasma treatment to alter the Lewis acid-base balance of
three fillers [62]. These were then compounded into two different matrix polymers. Firstly,
polyethylene (LLDPE), which is completely apolar and cannot form Lewis acid-base
interactions. The other polymer was poly(ethylene-vinyl acetate) [EVA], which is based
on polyethylene, but contains some (28 mole%) acetate groups, which they found to be
Lewis acidic (although acetate groups are also reported to be Lewis basic [109]). They
then measured tensile modulus and elongation at break to assess the affect of adhesion
on mechanical performance of the composites. In LLDPE, a fluoropolymer (PTFE-like)
coating on the filler gave lowest modulus and highest elongation to break, attributed to
poor adhesion. An ammonia plasma was used to give a polar, Lewis basic surface. For
this combination, the modulus was lower and the elongation to break higher than for
the untreated filler. This was consistent with reduced adhesion compared to the untreated
filler, but better than for the fluoropolymer coated filler. The modulus and adhesion
were maximised when the filler was plasma treated with methane to make the surface
non-polar like the polymer.
When the matrix polymer was changed to EVA, the results were quite different. In that
case, the highest modulus and least elongation to break were recorded for the ammonia
plasma treated filler. This was interpreted as being due to enhanced adhesion from the
bonding between the Lewis acidic groups in the polymer and the Lewis basic sites
introduced on the filler surface through ammonia treatment.
8.5.5 Dispersion and Agglomeration
Good dispersion of fillers and pigments is a prerequisite for good mechanical and
aesthetic properties. For example, multiple studies have shown that filler agglomerates
act as stress concentrators, reducing tensile and impact strength [82]. Similarly, good
dispersion results in a smoother surface, with a concomitant increase in specular gloss
[119]. Shenoy [24] and Hornsby [25] have each given detailed descriptions of the factors
influencing dispersion of particulates in polymers. In the case of pigments, good
dispersion results in a higher tinting strength so that less pigment is needed to attain a
given level of pigmentation. The principal exceptions are thermal and electrical
conductivity, which are improved by particle agglomeration to form a percolated
(continuous) network [22].
The ubiquitous van der Waals forces ensure that particles attract each other, thus favouring
agglomeration. The magnitude of this attractive force can be calculated if the Hamaker
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constants for the disperse phase (filler particles in this instance) and the dispersion medium,
i.e., the polymer melt are known. The Hamaker constants for several inorganic materials,
including fillers such as calcium carbonate, muscovite mica, silica and titania have been
calculated by Bergstrm and co-workers using Lifshitz theory [120, 121]. In a subsequent
study, it was possible to directly measure the van der Waals forces between materials using
atomic force microscopy (AFM). The results were found to be in good agreement with the
magnitude of the attractive force predicted from the calculated Hamaker constants [122].
Once the particles have agglomerated, the surfaces come into intimate contact and other,
short-range forces can become important. Thus, the force required to separate the particles
will depend on the van der Waals force plus any specific surface interactions that have
occurred such as water bridging, hydrogen bonding or Lewis acid-base interactions. The
polymer melt competes to interact with the surface so that the overall energetics depend
on whether it is more favourable for the filler surface to interact with another particle, or
with the polymer phase.
In order to separate the particles, mechanical energy must be added [25]. Then, once
separated, the particles must be kept from reagglomerating. This can be achieved by
reducing the attractive forces between the particles (by adding a dispersant), or by
increasing the affinity of the polymer phase for the filler surface (by adding some polymer
modified to interact with the filler). These two approaches are well understood and are
described in texts on surface and colloid science [111-115]. A brief description of
dispersants and coupling agents is given below, but is dealt with more thoroughly in
Chapter 4. A theoretical model has been developed to help in optimising dispersion in
twin-screw extruders [123].
8.5.6 Surface Treatments Dispersants and Coupling Agents
Surface treatments for fillers have been extensively reviewed [124]. Ernstsson and Larsson
studied a range of mineral fillers in terms of the Lewis acid-base character [125, 126]. It
was found that each one had a different surface chemistry and they were all amphoteric
(possessing both Lewis acid and basic sites). Another point was that trace impurities of
iron on the filler surface, presumably picked up during processing, significantly changed
the surface chemistry of silica.
In unpublished work, DeArmitt and Breese used a novel rheological method to characterise
a wide variety of mineral fillers. The method was especially attractive in that it allowed
investigation of the surface chemistry of the fillers, while at the same time showing which
types of organic probe molecules were most effective as dispersants. This work confirmed
the findings of Ernstsson and Larsson [125, 126]. Each mineral displayed a unique affinity
for the probe molecules and each was appreciably amphoteric, adsorbing Lewis acid and
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Lewis basic probes. This shows that the dispersant should be chosen to optimise its
affinity for the filler or pigment.
It is important to ensure that the chosen surface treatment agent does in fact bind to the
filler. If the additive does not bond to the surface then it cannot fulfil its function. Excess
additive is, at best, a waste of money, but in some cases it may have worse consequences
such as destabilising the polymer. For example, it has been shown that calcium stearate,
a common dispersant, can destabilise polyolefins and cause yellowing, by interacting
with the antioxidant [127].
8.5.6.1 Dispersants
As mentioned, dispersant design and mode of action are well understood by surface
and colloid scientists [43, 112-115]. In that field, the term dispersant refers to any
additive that reduces the interparticle interactions, thereby encouraging dispersion of
the particles. This is achievable via a number of mechanisms using low molecular weight,
oligomeric, or polymeric additives [128]. Steric stabilisation is most relevant to mineral
fillers in polymers because it is the main way to achieve colloidal stability in low polarity
solvents. This stabilisation mechanism operates by strong adsorption of a layer of
organic additive that physically prevents close interparticle approach.
Stearic acid and metal stearates are widely used as dispersants, especially in cases where
high filler loadings are required. Examples are polyolefins filled with aluminium hydroxide
or magnesium hydroxide where 60 weight percent of filler or more may be needed to
achieve sufficient flame retardancy [129, 130]. Of course the correct level of addition
depends upon the amount of filler surface to be covered, and therefore upon the amount
of filler, and its specific surface area. Excess additive is to be avoided as it can seriously
destabilise some polymers and give yellowing problems [127].
8.5.6.2 Coupling Agents
Dispersants need only adhere to the filler, and help reduce particle particle interactions.
Whereas for coupling agents, as implied by the name, the additive must be bi-functional,
adhering both to the filler and to the polymer. It is therefore found that the best choice of
coupling agent varies depending on the filler and polymer. In some instances, the so-
called coupling agent may not couple to either phase, or may only adhere to the filler.
In the latter case it may act solely as a dispersant, rather than as a coupling agent. It is
therefore important to note that an additive marketed as a coupling agent will only
provide coupling for certain combinations of filler and polymer.
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Particulate-Filled Polymer Composites Filled Thermoplastics
It is often assumed that coupling (adhesion) is good, but that is not always the case. For
example, good coupling is undesirable during extrusion, because it would dramatically
increase the torque (and energy) needed for extrusion. This would reduce extruder
throughput and that would result in a significantly more expensive material. Coupling is
advantageous when high yield strength is required, but it is often detrimental to the
elongation at break. Impact strength is more difficult to predict, it may increase or decrease
depending on the filler polymer combination. The effect of coupling agents on modulus
is less clear. The equation for describing modulus has no term for adhesion between filler
and polymer, so coupling agents should not affect modulus (Equation 8.4). However,
there are reports that they do affect modulus. This may be due to increased orientation
of the filler or due to the way that the modulus was determined. The modulus should be
determined at low stress, in the linear part of the stress-strain curve, where filler debonding
has not yet occurred, and should therefore be insensitive to adhesion.
8.6 Aesthetics
8.6.1 Introduction
Often thermoplastic composites are used in applications where the consumer will see the
part [131]. In those instances, it is vital to consider the aesthetic aspects of the material
as well as the mechanical, electrical and other properties. Fillers affect the surface finish,
colour and scratch-resistance of the composite and these factors should be optimised to
give a marketable product.
8.6.2 Colour/Pigmentation
Pigments may be either organic or inorganic particles that are added to give colour to a
plastic, as opposed to dyes, which dissolve in the plastic. Pigments can be considered as a
special class of filler, and they influence the polymer in much the same way as any other
filler would. So, for example, they can lower the thermal stability of the polymer matrix
[18], adsorb antioxidant and nucleate crystallisation of the polymer. They also affect the
mechanical properties in the same way as any other filler, but usually pigments are used at
concentrations that are too low to significantly affect modulus, yield strength or HDT. It is
essential to disperse pigments thoroughly in order to achieve the maximum tinting strength,
and to avoid agglomerates, which would lower the impact strength, as discussed previously.
As dry powders, several common fillers appear white, because they scatter light strongly,
and it might therefore be supposed that they would make good pigments for polymers.
This is usually not the case however, because the amount of scattering is determined by
the difference in refractive index between the particulate and continuous phases. This
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refractive index difference is small for common fillers and thermoplastics and so scattering
is limited. In fact, in some cases the filler is invisible in the polymer because the refractive
indices match very closely. An example is glass beads in PVC. Calcium carbonate is
available in high whiteness and gives a mild pigmentary effect, but if high whiteness is
required, then a pigment of higher refractive index, such as titanium dioxide, must be
used. Titanium dioxide and carbon black are used to protect against UV radiation as
they scatter and adsorb it, respectively. It should be noted that commercial titanium
dioxide is always has an inorganic coating, e.g., aluminosilicate, plus an organic additive
such as a polyol or silicone [132]. This is necessary because naked titania can oxidatively
degrade polymers when exposed to UV light.
8.6.3 Surface Finish and Gloss
Surface finish is important to the end-user. It can be altered to be glossy or matte, as

fashion dictates, and similarly, textures can be used to convey the right feel when handling
the product. The surface may also be tuned for more functional reasons. For example,
smoother surfaces are generally more hygienic and easier to clean, whereas a rough
surface can prevent blocking (self adhesion) of films or increase the coefficient of friction.
It is well known that fillers can affect the surface finish of the host polymer [133]. Coarse
particles tend to give a rough surface finish, whereas fine particles decrease roughness
with a concomitant increase in gloss [119]. Surface treated filler can give better gloss by
aiding dispersion. For a given filler type the gloss is steadily reduced as more filler is
added. However factors such as the mould surface and processing parameters can have
a very large effect on the final gloss. For low shear situations like gas-assisted injection
moulding even 10 weight% of filler may decrease the gloss to unacceptable levels. For a
normal injection moulded part the gloss may still be high at filler levels as high as
40 weight%. At low filler loadings it is possible to retain much of the gloss of the unfilled
polymer, but above a certain filler level (depending on filler type, size and treatment),
there is a sharp reduction in gloss. Special surface treatment of the filler has been shown
to decrease scratch visibility.
8.6.4 Scratch and Abrasion Resistance
Scratch and abrasion resistance is very important, especially in the home appliance
and automotive industries [134]. The manufacturer may be forced to use a more
expensive polymer or an unfilled polymer in order to maximise scratch resistance.
There are two different aspects of scratch resistance. One is the actual size of the
physical scratch, but the more important aspect is usually the visibility of the scratch,
because that is what the user sees. Often filler increases the visibility of scratches. A
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commercially important example is talc-filled polypropylene where the talc particles

become exposed by scratching, giving an undesirable white mark. Other fillers suffer
the same problem and a great deal of work has been devoted to lessening the scratch
depth and visibility of thermoplastic composites.
Attempts to correlate the mechanical properties of polymers to their scratch-resistance

have been largely unsuccessful. This is partly because the response of polymers to
deformation is very dependent on the speed of testing. The mechanical properties of polymers
and composites are usually determined at much lower rates than those encountered during
scratching. Evans and Fogel used the WLF equation to correct tensile testing results and
were then able to correlate the energy to break to the scratch resistance [135]. Another
complication is that there is a wide variety of scratch-testing methods. These vary from
scratching the surface using pencils of varying hardness (B, HB, H, 2H, etc.), through
scratching with hard styli whilst incrementally increasing the load, (e.g., Erichsen pen), all
the way to fully instrumented methods that examine the scratch profile and its dependence
on load [136, 137]. Many polymeric materials display some recovery over time and this
too must be allowed for if the true scratch performance is to be established [138]. Krupicka
has reviewed methods and factors affecting scratch performance of organic coatings [138].
One can say that scratch resistance may be improved by one, or some combination of three
methods. Lowering the coefficient of friction may make it more difficult to scratch the surface.
This can be achieved for example by adding a lubricant that migrates to the surface [136,
137]. Another method is to increase the hardness of the surface, although this is only effective
if the scratching medium is not too hard. For example, this method might protect against
scratching by another polymer, but not against sand, grit or metal objects. By far the best
method is to make the surface elastic using a soft, rubbery coating for example. One prime
example is in the plastic flooring industry, where the flooring is usually coated in a polyurethane
layer optimised to give scratch-resistance, the desired gloss level and the right level of friction.
8.7 Stabilisation and Recycleability
8.7.1 Introduction
Contrary to popular public perception, polymers are not very stable and are readily
attacked by atmospheric oxygen, heat and UV light [132, 139, 140]. Most of the high
volume polymers require additives that stabilise them during processing at high
temperatures, during their service life, and during any subsequent recycling operations.
In fact, polypropylene is so unstable that all commercial grades must be stabilised [18]
and the same is true of PVC. Once properly stabilised, these polymers can have a useful
service life of tens or even hundreds of years.
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Fillers often affect the stability of polymers via a variety of mechanisms. Although this is
recognised, at least to some extent, it has not been studied as thoroughly as the stability
of unfilled polymers. As the stability and recycleability can be critical issues, hopefully
this subject will receive more attention in the future.
Thermoplastics are usually processed in the molten state, at temperatures in the range
150-350 C depending on the melting point and viscosity of the polymer. There are
many standard stabilisation packages on the market, often containing a process stabiliser
and a long-term stabiliser. Most of the stabilisers are synthetic, although recently, a natural
hindered phenol, -tocopherol (vitamin E) was found to be effective in polyolefins [141-
143] and has been commercialised. For further information, the reader can consult books
explicitly dedicated to stabilisation of polymers [132, 144].
During service, most polymers experience mean temperatures in the range 20-40 C,
whereas peak temperatures may be much higher for short periods. The mechanical
properties of polymers depend upon molecular weight, and it takes relatively little
degradation to seriously impair mechanical performance. The degradation may result in
crosslinking or chain scission depending on the chemistry of the polymer and the
conditions the polymer is exposed to.
By far the most important stabilisers are the hindered phenols, which are used in a wide
range of polymers including the polyolefins, (e.g., PE and PP), polyamides, polycarbonate
and PET. These stabilisers are effective both during processing at high temperature and
for long-term use under ambient conditions. For increased effectiveness, they are usually
combined with other stabilisers to attain an optimised combination of stabilisation and
other properties such as discoloration. Often, the antioxidant is physically lost, primarily
by extraction or volatilisation, rather than by chemical consumption [145]. The trend is
therefore to use higher molecular mass antioxidants [132, 139, 146].
Fillers may affect the stability of polymers via a number of mechanisms. The two most
important ones are discussed here. Those are the catalysis of degradation by the fillers
surface and the indirect lowering of stability that occurs when the filler surface adsorbs,
and thereby deactivates, the antioxidants.
8.7.2 The Effect of Filler Chemistry and Impurities on Stability
It is well documented that transition metals such as chromium, copper, iron and vanadium
can catalyse the degradation of polymers [132, 139, 144]. These metals promote the
decomposition of hydroperoxides, which are important in the degradation mechanism
of most polymers.
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Most common fillers are not based on these elements, but they may be present as impurities
in the filler, or they may be picked up by the filler during processing operations such as
milling. Talc and mica commonly contain traces of iron. In fact, talc grades with low
iron content command a price premium over less pure grades because it is assumed that
iron content correlates to polymer stability. In fact, that assumption is completely
erroneous. For example, iron oxide (Fe2O3) is used as a pigment, but it does not cause
polymer degradation because it is not the total iron concentration that is important, but
more the chemical form of the iron, or other metal [5]. It would be more accurate to
measure the actual destabilisation caused by each talc grade and then adjust the price of
the talc accordingly. However, this has not been done, probably because it would be
rather labour intensive and therefore expensive. There is a fast, inexpensive alternative
and that to measure the effect of filler on the stability (oxidation induction time) of a low
molecular weight model liquid. For example, instead of compounding the filler into PE
or PP, one can mix in a small amount of filler into squalane and measure the effect on
stability [147]. It has been shown that squalane degrades by the same mechanism as PP
[148]. This approach requires only very small samples and the procedure can be automated
so it is very rapid to perform. Other model liquids may be used to simulate other polymers.
8.7.3 The Effect of Antioxidant Adsorption on Stability
Antioxidants often contain functional groups that are capable of interaction with
the filler surface. This can result in antioxidant adsorption depending upon the surface
chemistry of the filler and the type of antioxidant. Once adsorbed, the antioxidant
becomes ineffective because it is unable to diffuse to, and react with, the radicals
that cause polymer degradation. The amount of deactivated antioxidant can be
significant, and the usual response in industry is to add more antioxidant to attain
the required level of stability. However, that approach raises the cost of the compound
significantly. Another commercial approach is to use an epoxy additive that
preferentially adsorbs onto the filler surface, physically blocking antioxidant
adsorption. That helps to reduce cost, but the epoxy additive is itself still a relatively
expensive chemical.
DeArmitt, Breese and Lamthe [149] studied the propensity of calcium carbonate to
adsorb Irganox 1010 using squalane as a model liquid to simulate PP (Figure 8.7).
Oxidation induction time (OIT) is a well-accepted method for measuring antioxidant
concentration [145]. First a calibration curve of Irganox 1010 in squalane was made.
Then increasing amounts of Irganox 1010 were added to a 20 weight percent
dispersion of calcium carbonate in squalane. This was mixed and left for some time
to allow the antioxidant to adsorb. The dispersion was then centrifuged to give a
clear supernatant solution, which was analysed by OIT to determine the residual
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Figure 8.7 Effect of fillers on the nucleation of PP
Figure 8.8 The effect of calcium carbonate on the stability of squalane
antioxidant concentration in the squalane. The results showed that the Irganox 1010
was completely ineffective until enough had been added to saturate the filler surface.
The 20 weight percent dispersion of calcium carbonate (specific surface area 5 m2g-1)
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adsorbed and deactivated 300 ppm of Irganox 1010. The same results were found
when the calcium carbonate was not removed by centrifugation. The OIT
measurements were performed at 190 C, so the antioxidant must have been strongly
bound to the filler, otherwise it would have desorbed and raised the OIT of the
squalane. Interestingly, calcium carbonate surface treated with stearic acid did not
adsorb any antioxidant. Stearic acid treated calcium carbonate is more expensive
than untreated grades, but the cost differential is largely compensated for by the
reduction in antioxidant required. If this were more widely recognised, it might
promote the use of surface treated calcium carbonate.
8.7.4 Recycleability
Thermoplastics may be recycled in a variety of ways such as mechanical recycling (collection,

sorting, and reprocessing), burning to give energy, or biological recycling [150, 151]. There
is a public perception that synthetic polymers are less friendly to the environment than
natural polymers such as cellulose, poly(lactic acid) and poly(hydroxyalkanoates). That
view is not supported by the facts. Life cycle analysis reveals a very different picture,
favouring the synthetic polymers, especially polyolefins [150].
Although thermoplastics and thermoplastic composites are potentially easy and

economical to recycle, in practice there are some impediments to the implementation of
widespread recycling. The main one is that the used materials must be collected, separated
and cleaned economically. This is feasible in some instances but often it is not. In general,
polymers are immiscible with one another, and, if melt processed as a mixture, the result
is phase separation to give domains of one polymer in the other. This morphology leads
to rather poor mechanical properties. Therefore, there are efforts to find better separation
techniques in order to avoid the problem or to use compatibilisers [152] that lower the
interfacial tension, improve the adhesion of the two phases, and encourage smaller
domains of the disperse phase.
8.8 Uses of Filled Thermoplastics
8.8.1 Uses of Fillers
As shown in Table 8.1 more than 80% of the filler used in thermoplastic is based on
calcium carbonate minerals. Most is used in PVC, with major sectors being cables, flooring,
hose, plastisols, pipe, profiles and fittings. The main reason for this is firstly due to the
fact that PVC has to be compounded in order for it to be used. The incorporation of
stabilisers is an essential prerequisite for its successful use and therefore fillers can be
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Fillers European
consumption
Table 8.1 Estimated European consumption (in kilotonnes) of fillers

in plastics, 1998
PVC PP PE Thermoset ETP Total
Calcium carbonate 850 75 50 100 1 1076
Talc 120 10 1 131
Calcined kaolin 7 small 2 6 15
Mica small Small
Wollastonite 4 4 8
Kaolin 5 1 6
Total 862 199 52 111 12 1236
ETP: engineering thermoplastics
included without increasing processing costs substantially. Secondly, PVC is compatible

with both organic and inorganic substances so that changes in properties due to the filler
can be more readily controlled than the other thermoplastics.
Not withstanding the previous statement, the use of fillers in polypropylene, polyethylene
and polyamide is of considerable commercial importance and seeing greatest growth
and most research and development. The main fillers used are talc, ground calcium
carbonate and calcined kaolin.
The bulk of the filler comprises low-cost products for which price is the main specification
requirement but in all applications, certain criteria are important. The filler should not
greatly worsen the colour either directly by increasing light absorption (K) or indirectly by
reducing heat stability or by degrading other additives in the plastic. However, in several
applications the functionalities shape, size, size distribution and coating, are very important.
In unplasticised PVC (uPVC), extrusions and mouldings, PP mouldings, PP film and PE

film, the particle size, size distribution and surface coating play an important role in
determining processing, mechanical and aesthetic properties.
Talc is used principally in PP, and to a lesser extent polyamide and PE, to give rigidity, a
consequence of its (usually) high aspect ratio. In PP it is also used as a nucleating agent.
Calcined kaolin is used in film as an anti-blocking agent, in thermal barrier agricultural
film, and to allow for carbon dioxide laser printing. Aminosilane treated calcined clay is
used principally in polyamide to give rigidity, toughness with low anisotropy. Wollastonite
is also used in polyamide to give rigidity.
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8.8.2 Fillers in PVC
PVC is produced by the free-radical polymerisation of vinyl chloride in suspension, emulsion,

solution and mass, with the first two being the most important. Its fundamental unit is:
CH2 CH
Cl
and commercial polymers have molecular weights between 50,000 and 120,000. They
have approximately 5% crystallinity. All PVC polymers are unstable to heat and light
with hydrogen chloride being evolved in an unzipping mechanism. The resulting polymer
chains are highly coloured, rigid and infusible. Stabilisers must be added to the PVC for
it to be processed and used satisfactorily. These are added in a compounding operation
at which time other additives can be added with little cost penalty. Density, refractive
index, Tg, melt viscosity and other properties are dependent on the additives used.
PVC is produced as a powder containing irregular grains with diameters between 65 and
170 m (for suspension grades, other types are different). These grains are quite complex
structures with a strawberry looking surface, because they are composites with very small
domains of 10-30 nm diameter which have agglomerated to form spherical primary
particles of 0.21.5 m in diameter. The surface of the PVC grain (except for the mass
polymer) is a skin of surfactants, polymerisation aids and other additives. During processing
lubricants, processing aids and plasticisers penetrate this structure aiding melting and
homogenisation. This process is known as gelation or fusion and fillers affect it significantly.
The level of fusion determines many of the properties of the final PVC article.
As a consequence of its complex chemistry and formulations, PVC is used in a very wide
range of applications, making it the plastic with the third largest tonnage. However, the
last few years have seen a very strong movement against PVC as a material because of its
chlorine content and the possibility that, during its production, converting and disposal,
chlorinated organic compounds known as dioxins may be formed. Possible formation of
dioxins is also of concern during burning and disposal. As a consequence of this converters
of PVC have made determined efforts to replace it with non-halogenated polymers. This
has led to some changes in the uses of fillers. There are also moves occurring to replace
the most commonly used lead-based stabilisers with organic and heavy metal free
stabilisers because of concerns over its toxicity. These changes impose more stringent
requirements on the purity of the filler. One of the most obvious changes is in colour
because lead stabilisers give much greater opacity than the alternatives.
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Table 8.2 Estimated use of calcium carbonate in thermoplastics in Europe

Application Grade of calcium carbonate kilo tonnes
Medium and fine coated and
PVC Cables 250
uncoated
uPVC Extrusions Ultrafine and fine coated 110
uPVC Windows and Profiles Ultrafine coated 80
Precipitated, ultrafine coated, fine
PVC Plastisols 25
and coarse
PVC Flooring Ultrafine coated, fine and very fine 177
PVC Flexibles (general) Fine, coated and uncoated 133
PE Compound and
100
Masterbatch
PP Compounds 70
8.8.1.1 Fillers in Plasticised PVC
Calcium carbonate is used in virtually all plasticised (flexible) PVC applications as an

extender as seen in Table 8.2.
The effects that the filler has on mechanical properties, colour and stability, are similar
to those reported in Section 8.8.1.2 for cables, and will not be discussed in detail, although
the formulations are far more variable.
8.8.1.2 Cable Coverings
Most of the calcium carbonate used in plasticised PVC cable (insulation, sheathing and
filling) in Europe is fine, good-quality chalk whiting often with a stearate coating, although
where non-lead stabilisers are being used white marble based products are being used
because of higher colour needs. In North America, Italy, Spain and other countries where
relatively pure ground limestone or marble is abundant, then these are already being
used. The use of stearate is not necessary as it can be added as extra lubricant in the
formulation. In this case allowance must be made for the reaction that will occur between
stearic acid and calcium carbonate. Even so, many users prefer a stearate coated filler as
the coating improves the powder flow and general handling of the filler.
The main type has a high purity usually 94-98% CaCO3, good whiteness 80-95 ISO, a
mean particle size of 2-3 m and low levels of coarse particles 1-10% above 10 m. The
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Figure 8.9 The effects of calcium carbonate fillers in plasticised PVC
Table 8.3 PVC Cable Sheathing Formulation

Compound ph r
PVC (suspension grade K67) 100
Di-2-ethylhexylphthalate 50
Tribasic lead sulfate 5
Coated calcium carbonate 10 0
properties of the calcium carbonate have little effect on the mechanical and electrical
properties of a PVC compound. This is shown in Figure 8.9 for the cable-sheathing
compound given in Table 8.3, in which the calcium carbonate filler is based on chalk
whiting that has been ground to different particle size distributions, and the compounds
were extruded as a flat strip. Gloss values show a significant particle size effect increasing
markedly with finer fillers. Many high-gloss cable covers are produced using ultrafine
fillers. Particle size also effects stress whitening and scratch marking.
As a generalisation, it may be said that insulation compounds will be filled with 40-70
parts per hundred resin (phr) and sheathing with 20-100 phr; filler loading, plasticiser
level and lubricants are used to control properties of the cable covering. In some
applications, such as high temperature resistant or high voltage compounds the electrical
properties obtained using calcium carbonate as filler are not good enough. In these cases
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metakaolinite (calcined clay produced at around 700 C) is used at between 5 and 15

phr, although loadings as high as 20 phr are sometimes encountered.
8.8.1.3 Floor Tiles and Homogeneous Flooring
Coarse calcium carbonate with a broad particle size distribution, based on chalk, limestone
or marble, or dolomite with an average particle size of approximately 15 m, is the main
filler used in PVC floor tiles. Price is the main specification but control of colour and of
levels of coarse particles is needed. It is used as an extender at 200-450 phr. To give extra
dimensional stability, reduced water pick-up, and green or hot strength during calendering
and extrusion of the carpet high aspect ratio platy particles are used with the calcium
carbonate. Stabilisation systems have to be modified to allow for the extra reactivity of
the silicate surface.
In homogeneous flooring all types of calcium carbonate are used but finer products are
more common at loadings between 25 and 250 phr. Sometimes stearate coated grades
are used. The biggest developments in PVC flooring are, unfortunately, its replacement
with other types of floor coverings such as wood and carpet due to fashion, or the
replacement of PVC with other polymers such as polypropylene and polyethylene. These
can be heavily filled but because the developments are new and ongoing little can be said
concerning the filler requirements.
8.8.1.4 Wall Coverings/Leather Cloth/Spread Coatings/Calendered Sheet
Fine calcium carbonates (average particle size 2-5 m) is used as an extender at loadings
between 25 and 50 phr; precipitated calcium carbonate is sometimes used as a rheological
control, although whatever filler is used there will be a significant effect on rheology,
which is of great importance in these applications. Filler dispersion is also important.
8.8.1.5 Hose and Profiles
Most grades of calcium carbonate are used, except very coarse, (i.e., above 10 m average
particle size), as extenders at levels of 20-50 phr.
8.8.1.6 Footwear
Precipitated and 1-3 m grades are used for rheological control in rotational moulded
products and as extenders in injection moulded products.
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8.8.1.7 Plastisol/Sealants
Mostly precipitated grades are used as rheological control additives in combination

with medium (2-5 m) or fine (1 m) grades as extenders, the latter at levels of
40-200 phr.
8.8.2 Uses of Fillers in Unplasticised PVC
As with plasticised PVC applications, most uPVC uses natural calcium carbonate as
a filler. Loadings, however, are usually lower, in the range 3-30 phr. Low levels of
impact modifier and processing aids are frequently used with the higher loadings to
achieve desired mechanical and processing properties. Often non-specification
products will use higher loadings with levels up to 100 phr being encountered,
especially in pipe in China, Indonesia and the Indian sub-continent.
Another quite significant difference with plasticised products is that in uPVC the
filler affects processing and end-properties significantly. Usually fine and ultrafine
products with top cuts of 10 m and average particle sizes of 1-2 m are used, but in
lower specification products 3 m grades are being used. The filler affects processing
by affecting fusion of the PVC particles. This is a consequence of the interaction and
reaction of the lubricants used in the compound with the surface of the calcium
carbonate changing the balance of internal and external lubrication. This, of course,
depends on the surface coating used on the filler and the fillers surface area [153].
The speed and level of fusion or gelation play significant roles on efficiency of
processing, and in determining mechanical properties, especially impact strength [154].
The particle size of the filler, especially levels of coarse particles, also affects tensile
and impact strengths either positively by the fine particles acting as stress diffusers
or crack stoppers or adversely with the coarse particles acting as flaws or stress
concentrators.
Filler loading has a significant effect on processing and on properties, especially on

impact strength, which can reach a maximum often higher than the unfilled. The
optimum loading is determined by particle size, coating levels and by other additives
in the formulation. For coated ground calcium carbonates with a top cut of 10 m
and a d50 of about 0.8 m, maxima have been found at between 15 and 20 phr for
lead stabilised compositions without any impact modifier [153], with acrylic modifier
[153] chlorinated PE [155], and with tin stabiliser and styrenics [156].
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8.8.2.2 Pipes, Conduit and Fittings
The fillers used are mostly 1-3 m grades based on chalk in Europe, limestone and
marble in the rest of the world principally to reduce costs. The finer grades also act as
impact modifiers and processing aids and are preferred to coarser grades in more
demanding applications, and in decorative areas where gloss becomes important. In
pressure pipes and fittings levels are usually between 1 and 5 phr; in rainwater goods,
sewage, soil and agricultural drainage levels are 8-20 phr; and in conduit and ducting
levels are 3-40 phr. In non-specification pipes, loadings can be as high as 100 phr but
most national and international specifications are now including limit values for fillers,
either directly or indirectly by specifying the maximum specific gravity permissible.
This differs from application to application but typically will be around 1.46 g/cm3.
This equates to a stabiliser plus filler content of around 20 phr.
8.8.2.3 Window and Other Profiles
Technical properties supplied by the filler are as described previously for pipes,
although in most 4-5 phr TiO2 is added to give whiteness, light and some heat stability.
Stearate-coated ultrafine (0.7-0.8 m) produced from chalk, white limestone and
white marbles are most widely used. Growth in the whiter fillers is being spurred by
changes in aesthetic requirements; by the move from lead stabilisers to calcium-zinc
or tin-based which do not give the same levels of opacity as lead composites; and by
developments in coloured profiles.
Filler levels for window and other building profiles have been creeping higher in the
last few years from 3-5 phr to 5-15 phr with the limiting factors being cold impact
strength, extrudate gloss and corner weld-strength. In various non-critical applications
such as blinds and roller blinds coarser grades (1-3 m) are used with levels up to 75
phr being encountered. In these cases, small amounts of plasticisers (7.5 phr) are
added to aid processing and properties.
8.8.2.4 Film
The market for uPVC film is diminishing under environmental pressure and
consequently the use of particulate fillers is also diminishing. Most of the film is
transparent for food packaging, display, blister packs and so on, and kaolins and
other silicate minerals are used as antiblocking additives, without detriment to colour
and transparency of the film.
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8.8.3 Uses of Fillers in Polypropylene
Polypropylene has the general formula:
CH2 CH n
CH3
with n being about 2000. It is a linear polymer, essentially a hydrocarbon with many
similarities to PE, being chemically inert, flexible, tough and having fairly low softening
and melting points. The presence of the methyl groups, however, introduces several
significant differences. Tacticity is introduced due to the various spatial arrangements of
the methyl groups that are possible. Commercial polymers are 90-95% isotactic; that is
the methyl groups occur on one side of the polymer chains. This introduces some
crystallinity (approximately 50%), and higher softening points. However, the methyl
groups also induce greater susceptibility to oxidation and chemical attack (usually at the
hydrogen atom to the methyl group). It is the lightest common plastic with a specific
gravity of about 0.9. Ethylene can be polymerised at levels of 4-15% with propylene,
either randomly or as blocks to give copolymers that are more flexible and tougher than
the homopolymer. Alternatively the polypropylene may be compounded with ethylene-
propylene rubber to give copolymers as a physical mixture or rubber-modified-grades
(depending on the level of the rubber). All suffer from oxidative instability and are always
stabilised in service. Particulate fillers and coupled glass fibres are used in all these polymers
for many applications to increase rigidity and heat distortion.
8.8.3.2 The Uses of Filled Polypropylene
As mentioned previously, the principle reason why fillers are used in PP is to increase
rigidity, especially at higher than ambient operating temperatures. The rigidity or modulus
of a composite is affected by the modulus of the inorganic component, its loading and by
its aspect ratio, that is the ratio of its length (or largest dimension of a particle) to its
thickness (or smallest dimension). The modulus of any inorganic filler is very much
higher than that of a plastic, and thus differences between types of fillers are not so
important in determining modulus as the other two factors. As volume loading of filler
increases, the modulus of a composite increases almost linearly at low to moderate filler
levels. The higher the aspect ratio the higher the modulus. Thus, where rigidity of the
final product is the most important single parameter, high-aspect-ratio fillers such as talc
404
or glass fibre are preferred. Mica and wollastonite are available with high aspect ratios
but their main use is in North America where their cost-performance ratio is advantageous;
in Europe, talc is most widely used.
Original developments in filled PP were compounds with much higher stiffness than the
unfilled, especially at higher than ambient temperatures, but which would be low cost to
match the styrenics, especially ABS. Talc, being widely available, low cost and usually
having a high aspect ratio is the preferred filler type, and all polypropylene compounders
have several talc-filled grades available. Typical uses are in: automotive components
such as air-filter covers, timing chain covers, heater boxes, and battery box tops, domestic
appliances, such as washing machine soap dispensers, and in some disposable food
packaging such as skeletal fruit packages. New initiatives on recycling, particularly in
the automotive industry, are tending to limit polymer types used. Polypropylene is strongly
favoured and this is helping drive the market for filled grades.
Crudely, the talcs that are used can be divided into five types: three based on pure talc
(less than 10% impurities) with top cuts of 300 BS mesh, 20 and 10 m; and two based
on less pure minerals with top cuts of 300 BS mesh and 20 m. Particle size has no effect
per se on rigidity but, depending on the method of processing, finer types may have
higher aspect ratios and therefore will give higher rigidities. Particle size does affect
composite impact and tensile strength with smaller particle size products giving higher
strengths [157], although the results are not unambiguous because methods of producing
fine talcs also produce higher aspect ratio particles [158].
Virtually all applications for talc-filled PP are those that do not require toughness or
high strains because the rigidity imparted by talc is accompanied by brittleness. The
toughness can be improved by changing the base polymer to a copolymer with ethylene
as comonomer, by incorporating ethylene-propylene rubber, or by changing the mineral
to stearate coated calcium carbonate. All methods, however, reduce the rigidity of the
composite compared with the talc filled equivalent. As discussed in [94], particle size
and coating of the calcium carbonate affect impact strength and toughness, while other
properties are not affected greatly. Loading of the coated calcium carbonate also affects
properties. Rigidity increases, and tensile strength decreases virtually linearly with loading
but impact strength can go through a maximum at between 20 and 40 wt%.
This high level of toughness coupled with a rigidity which is higher than the unfilled,
good flow in mouldings, good light and temperature stability means that calcium carbonate
filled PP is regarded as a separate material, with major uses in injection moulded garden
furniture, automotive components, food packaging, fibres, tapes and blown oriented PP
(BOPP) packaging film. A very rapidly growing market for fine coated calcium carbonate
is in breathable films, in which micropores form around the calcium carbonate particles
during film orientation (mostly oriented PP). In fibres and tapes, the stearate-coated
405
calcium carbonate is used at around 8 wt% and acts as a delustering agent and also
reduces fibrillation. Another large and growing market is in BOPP film used in packaging.
Loadings up to 70 wt% are used in the central layer of a three-layer film, produced by
co-extrusion, with the outer layers unfilled.
Mineral filled polypropylene often replaces ABS, polyamide and other engineering plastics,
although their mechanical, processing and optical properties are different. However, by
experimenting with the large number of permutations and combinations of type of filler,
type of polypropylene and rubber toughening agent, satisfactory matching of cost-property
performance is achievable. Reductions in cycle time, shrinkage, sink marking and improved
noise reduction are among the benefits resulting from mineral filling, but detrimental
effects have usually been observed in the aesthetic properties. Gloss is normally reduced
but the surface can be tailored by choice of filler. For example, a high gloss moulding can
be obtained by using a blend of talc and calcium carbonate [159].
Colour is also changed by the mineral filler: pure talc gives translucent, almost colourless
compounds while high quality calcium carbonate gives a white colour with some opacity.
Increasing levels of impurities in both minerals causes colour degradation. Colour will
also be caused by any instability introduced into the polypropylene by the mineral.
One problem from which all particulate filled plastics, and in particular filled PP, suffer
is that of scratch marking and marring; as the plastic is scratched, light scattering occurs
at exposed filler particles. This has been overcome to some extent by choosing the correct
filler and by modifying the filler plastic interface. Calcined talc is being used in automotive
compounds for its improved resistance to scratching. Filled PP sheet is also being used
extensively as thermoformed packaging materials because the filler confers good sheet
extrudability and thermoforming characteristics [160].
8.8.4 Uses of Fillers in Polyethylene
Polyethylene (CH2CH2)n is essentially a high-molecular-weight paraffin, which as a

consequence, is inert to most chemicals, flexible with low softening and melting points.
Three types are now commercialised: LDPE, produced by polymerisation over a free-
radical source at high pressures; HDPE, produced by polymerisation over Ziegler catalysts
(complex catalysts based on metallic co-ordination compounds); and LLDPE, produced
by a variety of techniques designed to give chains with limited short-chain branching
and incorporating low levels of other olefins butene, hexene and octene. All grades are
semi-crystalline with levels of about 60% for low density, and up to 90% for high density,
406
but these can be lowered by branching. There is much argument about the Tg with values
from 20 C to 130 C being reported. They have softening points from about 77 C to
124 C. The main applications for filled polyethylene, film and bags, blow moulding and
electrical insulation dictate the required properties and limit the potential for fillers.
8.8.4.2 The Uses of Filled Polyethylene
A considerable amount of calcium carbonate is used in LDPE, LLDPE and HDPE. Medium
particle-size grades (with d50 of between 2 and 3 m) are used in masterbatch either
alone or to extend pigments, principally white TiO2 and carbon black. These in fact
dominate the masterbatch market, with film and bags being the final destination for
most. In natural masterbatch, the filler level will usually be 70-75 wt%; in pigmented
products it is used to dilute the prime pigment by amounts dictated by the requirements
(opacity, colour and gloss) of the end application. Mostly dilution at 10-20 wt% is used
but some masterbatches can be formulated with 10% prime pigment and 60 wt% calcium
carbonate. Levels of course are also dictated by any other additives (stabilisers, lubricants,
etc.), in the masterbatch.
Cost is naturally very important, but the filler does play an important role in several film
properties [161]. For example, in LLDPE extruded film, ground calcium carbonate
improves efficiency by both increasing the cooling rate of the bubble and the level of
fusion; it improves printability; primary pigment dispersion can be improved; it reduces
the coefficient of friction by increasing the surface hardness of the film; and it acts as an
anti-blocking agent.
Other minerals are used to give specific properties. Medium and coarse china clays (average
particle size 2 and 5 m) are used at 5-10 wt% to reduce stretch, to reduce slip, act as
anti-blocking additives and to give thermal barrier properties (see below). A variety of
minerals are used to anti-block all types of film (although HDPE film is not so prone to
blocking because it is much stiffer, so anti-blocking needs are less). Talc, silica (natural
and synthetic), aluminosilicates, zeolites and calcined kaolin are all used at levels of 0.1-
1.0 wt%, the loading depending on the stickiness of the film and the temperatures at
which it may be used. The surface chemistry, shape, purity and refractive index of the
mineral determine the blocking, friction, clarity, haze and colour of the film. A major use
for calcined clay is in agricultural film. Because of its very strong absorption bands in the
far infrared (IR), it renders the plastic opaque to heat (and consequently more like a
flexible glass) [162]. Other minerals absorb IR radiation in lesser amounts but are still
used by some film producers. All of course are added via masterbatch, which will also
include stabilisers and lubricants the levels of which being dictated by the intended service
length of the agricultural film.
407
Linear low-density polyethylene is principally used in film and bags, with similar criteria
applying as in LDPE. There is some interest in using it (because of its toughness) in
engineering and automotive applications, but its stiffness has to be increased by using
fillers. In recent years there has been a rapidly growing and very large market for ground
calcium carbonates in LLDPE in the production of microporous films, where holes have
been incorporated into a plastic sheet or film through de-bonding of the polymer from
filler particles dispersed in the matrix. The most common plastic used is LLDPE (often in
blends) and the most common filler is coated ground calcium carbonate with average
particle size 1-3 m. The de-bonding is achieved by stretching and orienting the film.
Loading levels of the calcium carbonate are around 55-60 wt%, and the particle size and
efficiency of coating are key to producing film with controlled pore size. The principal
uses are in the production of controlled atmosphere or breathable films and in white
opaque films. The former has various uses hygiene, medical and industrial garments,
building membranes, house wrap but the biggest single use is in the production of babies
nappies. The latter includes food packaging, labels and paper replacement.
High-density polyethylene finds its major outlets in blow-moulded bottles and containers,
film and carrier bags and pipes (the last often used with LDPE and the blends are known
as medium density polyethylene (MDPE)). Although fillers have been and are still being
looked at periodically in blow mouldings, processing imposes severe restrictions before
costs and product properties are considered. Film and bags will have some ground calcium
carbonate included via masterbatch as an extender for the prime pigment. The main pipe
sectors are for gas and water transportation, and end-users have imposed very strict
regulations on additives and properties; potential use of fillers is very low. There has
been some interest in using HDPE in ducting, competing against uPVC, and a filler, at
high loadings, will be essential to achieve the required stiffness and cost balance, if this
replacement is to be successful.
8.8.5 The Use of Fillers in Polyamides
Nylon is the generic name for the family of polyamides (PA) with PA6 and PA6, 6 being
the most common. They are named after the chemical group:
O H
C N
formed during the condensation polymerisation which occurs when an organic acid is
heated with an organic amine. The numbers which always occur with the name Nylon or
408
polyamide refer to the types of acid or amine used in the production. The regular spacing
of the amide groups means that the polymers crystallise with a high intermolecular
attraction leading to high-strength polymers with high melting points. Levels of
crystallinity depend on thermal history and can vary from 15% to 50%. Nylon is fairly
hygroscopic and its Tg (temperature below which the polymer become brittle) and
mechanical properties depend on the amount of absorbed water.
8.8.5.2 Properties of Filled Nylon
All polyamides are tough, rigid plastics with high heat distortion temperatures but
they are thermoplastic, that is, they exhibit plastic flow (high creep) and soften at
elevated temperatures. Mostly they are used unfilled but there is a significant application
sector in which higher rigidities and higher heat distortion temperatures are required
than can be achieved from unfilled polyamide. Glass fibre (with a size or a silane
coating) fills most requirements giving very high rigidity, etc. Other mechanical
properties of a properly coupled glass-fibre filled Nylon are also good. Some 200,000
tonnes per year of glass-filled Nylon is now used, and it is regarded as a separate
engineering material. However these fibre filled composites suffer from anisotropy
due to fibre orientation during processing; that is, the properties of the composite vary
depending on the direction in which they are measured. Fibre orientation also causes
uneven shrinkage that can lead to unpredictable warpage (bending and distorting),
which is not acceptable in products that require good dimensional stability. Anisotropy
and warpage are proportional to the aspect ratio of the filler used and can be reduced
to zero by using glass spheres [163]. Calcined kaolins give good, low, anisotropy and
when treated with a bifunctional aminosilane, give very good mechanical properties
and tend to dominate the European and Pacific filled Nylon market. Both particle size
and coating level affect impact strengths. Pre-treatment gives much better properties
than when calcined clay and silane are added separately to the compounding operation
[164]. Some talc and wollastonite is also used giving high rigidity (although this depends
on the grade and its aspect ratio), although impact properties are worse. In the case of
talc, this has been related to its inability to couple through silanes with the polyamide.
Calcined talc is being developed to improve the interaction [154].
8.8.5.3 Uses of Filled Nylon
Mineral-filled Nylon is widely used: in automotive applications, such as wheel discs,

headlamps, water pumps, air inlets and grills; in electrical engineering; in electronics;
appliances and consumer goods [165]. Significant recent developments have seen its use
in the production of automotive engine covers. The mineral, as mentioned previously, is
409
frequently used in combination with glass fibre. Loading levels have, in the automotive
industry, dropped to around 20 wt% under pressures to reduce vehicle weight but in
some cases are still as high as 40 wt%.
8.8.6 Polybutylene Terephthalate
Polybutylene terephthalate (PBT) is a fairly tough, rigid thermoplastic which has a

very good gloss in mouldings. It is less susceptible than Nylon to moisture when moulded
but otherwise most of its mechanical properties are not so good. Many glass-fibre-
filled compounds are available from specialty compounders and polymer producers
and some mineral filled grades are also widely used. Talc, aminosilane-treated calcined
clay, ultrafine calcium carbonate, ultrafine china clays, glass beads and glass flakes
have all been encountered. Benefits from the particulate fillers have been reported to
be rigidity with good dimensional stability, high impact strength and exceptional surface
finish [166].
8.8.7 Polyethylene Terephthalate
One of the most important uses of PET is in producing many types of film and tapes.
In these a variety of speciality fine grades of china clays, calcined clays, calcium
carbonates (natural and precipitated), synthetic silicas and silicates are used at levels
of about 0.1 wt% as anti-blocking agents; they may also nucleate crystallite formation.
Fillers seem to be precluded from the largest single market for PET bottles, not
only because of the difficulties in successfully blow moulding filled products in general,
but also their application properties such as optical clarity and burst strength will be
adversely affected by fillers. Many bottles are now being recycled into a variety of
plastic and fibre applications; fibres and particulate fillers are being looked at to
extend the range of applications. The high HDT and softening temperature of PET
have recently led to developments in its use in food cook-in applications. However,
its HDT is not quite high enough for conventional oven use and fillers are being
looked at to improve this.
8.8.7.1 Polystyrene, High-Impact Polystyrene and ABS
The styrenics are a family of low to medium price, rigid, easily processed plastics with
good gloss and optical properties. ABS and HIPS are more tough, due to the acrylonitrile
rubber content, which has either been incorporated into the plastic or copolymerised
with the styrene monomer, respectively. Fillers have been looked at by several producers
410
and compounders but do not give good enough properties to allow them to be used in
any significant amounts, although products containing kaolin, calcium carbonate and
talc have been reported. These may have the filler incorporated as a diluent in colour
masterbatches used in the plastic. Some very old patents cover the incorporation of china
clays and ultrafine calcium carbonates into the rubber before compounding this into the
polystyrene but again no noticeable commercial success has been achieved. Talc is used
in expanded polystyrene as a nucleating agent.
8.8.7.2 Polyphenylene Oxide (or Ether)
Polyphenylene oxide is an engineering plastic that is commonly blended with polystyrene,

with the blend having significantly better properties than the separate plastics. Modified
polyphenylene oxide has been available now for approximately 30 years and its uses are
widespread including automotive components, business machines, domestic appliances,
wire covers and water treatment. Other blends with PBT and PA are in the market place
offering different property balances. These composites (and other polymer blends) are
being trialed for automotive body parts, and particulate fillers are needed to give the
correct coefficient of thermal expansion. This type of filler is also needed to give rigidity
without affecting impact properties. Very fine kaolins (with mean equivalent spherical
diameter (esd) of about 0.3 m) with and without silane coupling agent give good impact
strength [167].
8.8.7.3 Polyphenylene Sulfide (PPS)
Polyphenylene sulfide is a high temperature, stiff, fire-resistant, chemically resistant plastic,

which has a very low melt viscosity and accepts fillers and reinforcing agents very well.
Talc, china clay, dolomite, quartz and glass fibre filled grades are all available but volumes
are very small and the situation changes very rapidly.
8.8.7.4 Polyformaldehyde or Polyoxymethylene Polymers
These plastics are characterised by high stiffness, good impact resistance, high HDT,
good chemical resistance and have the best fatigue resistance of any plastic. Glass fibre-
and mineral-filled grades are used to increase stiffness, hardness and resistance to
distortion. The type of filler that can be used is important as the polymers are badly
depolymerised by acids, the unzipping of the polymer chain giving gaseous formaldehyde.
Minerals with acid surfaces, such as china and calcined clays, can cause this
depolymerisation. Calcium carbonate reduces some mechanical properties but one calcium
carbonate filled grade is claimed to have better abrasion resistance.
411
8.8.7.5 Others
The properties of particulate fillers in a number of other thermoplastics are being investigated
by plastics producers and academic institutions but usually with a low priority rating. This
activity has been growing less and less in recent years as companies, in particular, have
been reducing the staffing levels in the research and development departments.
8.9 Conclusions
Thermoplastic composites are all around us and their use is increasing every year. The
reason for this is that thermoplastics have an excellent combination of cost and
performance. The performance can often be further enhanced by addition of fillers while
maintaining a favourable cost. The recycleability of thermoplastic composites is an
advantage compared to rubbers and thermosetting polymers because the latter two types
cannot be melted and reshaped. This favours the continued growth of the thermoplastics
and their composites at the expense of other polymeric materials.
To understand and optimise composites, one must have an overview of all the different
economic, chemical, surface and physical aspects. Furthermore, one must have a clear
goal, and be able to correctly prioritise the properties of most import for the intended
application. The best composite is the one that makes the best compromise between the
multitude of properties, at the lowest cost.
The use of fillers has been increasing incrementally for many years and that trend is
expected to continue as the use of traditional fillers is optimised and as new nano-fillers
eventually become economically attractive.
What can we expect in the future? In the near future, composites must be designed with
re-use in mind. That means proper stabilisation so that the polymer can be recycled with
sufficient retention of mechanical and aesthetic properties. There will be an increased
tendency to use fewer, standard materials to reduce cost and to reduce the need for
extensive separation of materials for recycling. It can also be anticipated that products
will be designed for easy disassembly.
It seems probable that surface treated filler will become more popular. Although the
treatment adds cost it gives many advantages and when these are summed, the overall
cost and performance of the material may be better for the surface treated type. For
example, stearic acid coated calcium carbonate in PP homopolymer gives higher extruder
throughput, better gloss, better impact strength and improved stability (because it prevents
antioxidant from adsorbing onto the filler and becoming inactive). Any one of these
412
benefits may not justify the extra cost of pre-treated filler, but taken together they give a
very attractive combination of price and performance.
Another trend for the future may be the increased use of single-screw extruders to make
composites. At the moment twin-screw extruders are used almost exclusively, because
they are able to achieve better dispersion. However, recent developments have improved
mixing in single-screw extruders. Therefore, it may become common to use single-screw
extruders because they are cheaper, easier to maintain and give higher throughput. Again,
surface treatment of the filler also helps here to give good filler dispersion even for a
single-screw extruder.
Progress in polymer composites has been held back because it is expensive and time-
consuming to prepare multiple formulations and then perform thorough mechanical testing.
It is possible to save time and money by screening new fillers, antioxidants, dispersants
and coupling agents in a model liquid instead of the polymer. The screening can then be
followed up by full testing, using the polymeric matrix. Hopefully, this method will be
used to help develop new filler grades and surface treatments, more quickly and cheaply.
Acknowledgements
We would like to thank several people for their assistance in writing this chapter. Firstly,
the editor Professor Rothon who has been a great help in making suggestions, proof-
reading and for general discussions. Professor John Berg (who deserves a special thanks
for being such a help with the section on adhesion), Professor Ulf Gedde, Professor
Aubrey Jenkins, Kevin Breese, Massimo Sanit, Carlo Tomaselli, Roy Goodman, Chris
Paynter, Richard Day, Anna Kron and Werner Posch are all warmly thanked for making
significant contributions by reading draft versions and for making valuable comments
that improved the quality of the chapter.
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424
9
Filled Thermosets
Graham V. Jackson, Michael L. Orton and Howard Taylor
9.1 Introduction
Thermosets is the term used to describe those polymers produced by polymerisation of

relatively low-molecular-weight precursors either within a mould cavity or in some other
in situ situation. Thus, the part shape is set by chemical reaction within the mould cavity
and this distinguishes thermosets from thermoplastics for which shape is set by the cooling
of a melt. Most polymers processed as thermosets are crosslinked and therefore undergo
an irreversible liquid to solid transition unlike thermoplastics, which show a reversible
liquid to solid transition. Consequently, thermoplastics may, in principle, be directly
reprocessed, while thermosets cannot, though they can be reused by granulating and
using as a filler. In this chapter the term resins is used to describe the relatively low-
molecular-weight precursors of thermosets and polymer is used for the high-molecular-
weight cured product.
During the curing or polymerisation of a crosslinked polymer, two phenomenological steps

occur - gelation and vitrification. Gelation occurs when conversion of the reactive groups
on resin/monomer has proceeded to such an extent that the amount of branching ensuing
is sufficient to generate a global network of essentially infinite molecular weight [1-4]. A
physical picture of gelation is that of a giant molecule swollen by unreacted resin/monomer.
The conversion at which gelation occurs depends upon the mechanistic type of the
polymerisation, but for free-radical addition polymerisations, can be as low as a few per
cent (see Sections 9.2.1-9.2.3). Clearly, mould filling has to be complete before the gel
point. As conversion proceeds, the glass transition temperature (Tg) of the resin swollen gel
increases and, when it corresponds to the temperature at which the resin is polymerising,
vitrification occurs, i.e., the swollen gel is hardened to a glass. The significance of the point
of vitrification is that, after vitrification, the mobility of the reactive groups within the
glass is severely inhibited and the rate of further reaction falls sharply, eventually becoming
zero. Thus, in moulding thermosets, it is important that the mould temperature or the
maximum exotherm temperature be close to the Tg of the fully cured polymer, i.e.,
vitrification occurs as late as possible in the conversion process, otherwise undercure will
result [5]. If a resin is initially undercured, it can be postcured to achieve full cure, though
if too much time elapses before postcure, full cure and mechanical strength cannot be
achieved due to loss of mobility of reactive groups within the resin.
425
Crosslinked polymers can be characterised conveniently by defining their crosslink

density as branch points per unit volume or average molecular weight between
crosslinks. This parameter in conjunction with the molecular nature of the polymer
defines whether the material will behave as an elastomer or as a rigid material, which
shows either ductile or brittle failure behaviour. Fillers can be used to modify properties
further across the whole range of polymer behaviour. Because inorganic fillers are,
compared to most polymers, much stiffer and less extensible materials, their
incorporation into a polymer will usually produce a composite material of reduced
strain to failure and increased stiffness relative to the polymer, i.e., the composite
will be less elastomeric or less ductile. Nevertheless, large quantities of fillers are
used in polymers that already have low strains to failure and show brittle failure
behaviour. This chapter will confine itself to a discussion of the use of fillers in ductile
and brittle crosslinked polymers.
The function of the filler in a thermoset can be to offer material cost reduction, since
most fillers are of low cost relative to polymers or to confer property modification.
Highly crosslinked polymers are generated in their final shape by in situ processing
of lower molecular weight monomeric or oligomeric precursors. Since the low-
molecular-weight precursors are usually low-viscosity liquids at their moulding
temperatures, an important use for fillers is for rheology control both before and
during the polymerisation or curing step. Other features to be considered in the
processing of crosslinked polymers are:
(1) the polymerisations are exothermic and, if rapid cure is required, exotherm
temperatures can be high (as high as 200 C); and
(2) the polymerisations often occur with a significant reduction in volume since the
polymer, with extremely few exceptions, has higher density than the precursors
from which it has been derived.
Fillers, through their essentially volumetric and thermal inertness at typical thermoset
resin-processing temperatures, offer a valuable means of exotherm and shrinkage
control.
Fillers can modify the properties of the cured polymer in a wide variety of ways.
Some examples of properties readily modified by incorporation of fillers are
mechanical properties such as stiffness, hardness, strength and toughness, and thermal
properties such as expansion, conductivity or thermal decomposition. The latter can
have a considerable effect on flammability and smoke generation. Fillers are also an
important way of varying and enhancing aesthetics.
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Filled Thermosets
9.2 Brief Chemistry of Thermoset Polymers
Many highly crosslinked polymers have been synthesised and reported since the emergence
of Bakelite as a synthetic moulding material [6, 7]. However, to keep the subject matter
of this chapter within reasonable bounds, we have restricted our discussions of filled
polymers to examples of the more common crosslinked matrices, unsaturated polyesters,
epoxies, methacrylics and phenolics. The resins are cured by different mechanisms:
free-radical chain growth (unsaturated polyesters and acrylics);
step addition (epoxies, although occasionally epoxies are cured by ionic mechanisms);
and
condensation (phenolics).
9.2.1 Free-Radical Chain-Growth Curing Resins
9.2.1.1 Unsaturated Polyester Resins
An unsaturated polyester resin has two primary components, a polyester containing

polymerisable double bonds and a copolymerisable solvent monomer, of which the most
commonly used is styrene. Unsaturated polyesters are made by esterification of glycols
with mixtures of maleic anhydride and saturated diacids (Structure 9.1). The term alkyd
is used to describe low-molecular-weight polyesters, where molecular weight is broadly
Structure 9.1 Preparation of unsaturated polyester resins
427
controlled by reacting polyhydroxy and polycarboxylic compounds in non-stoichiometric

amounts, or by modification with monocarboxylic acids. Thus unsaturated polyester
resins are often referred to as comprising unsaturated alkyds in styrene.
The other resins, which cure by a free-radical chain-growth mechanism, also have a low-
molecular-weight double-bond functional species dissolved in a solvent comonomer but,
since these species are not polyesters, they cannot be termed alkyds. The term oligomers
is used to describe them instead, although it is not a strictly correct use of this term, since
the species are not always a multiplicity of repeat units.
The properties of the polyester resin and the final polymer after curing can be varied by
choice of diacid and glycol, and by the molar ratio of maleic anhydride to saturated
diacid. This ratio is typically from 1:1 to 3:1 m/m and is particularly important in
determining reactivity during cure and crosslink density after cure. High maleic anhydride
to diacid ratios give high-reactivity resins with fast gelation and cure characteristics, and
final polymers having high heat distortion temperatures (HDT) but which show the
most brittle failure behaviour due to their high crosslink density. The higher double
bond content also leads to high-volume shrinkage on curing. Conversely, reducing maleate
ratios reduces reactivity and crosslink density with the consequences of long gel times
and low heat distortion temperatures, but lower volume contraction on curing and a less
brittle polymer. It is very rare to find an unsaturated polyester with a maleate to phthalate
ratio less than 0.5:1 m/m.
The most common diacids are the phthalic acids, orthophthalic acid (phthalic anhydride is
actually used) giving general purpose resins and isophthalic acid giving resins of improved
corrosion resistance. Adipic acid is also used, but on a smaller scale and where chain
flexibility is particularly required. The most commonly used glycol is propylene glycol
because it does not lead to branching in the polyester chain and has no tendency to crystallise.
Other diols are used to achieve special properties, e.g., propoxylated bis-phenols to confer
corrosion resistance. Typically, the resin would incorporate the three components in the
molar ratio, maleic anhydride:phthalic anhydride:propylene glycol (5:5:11).
A typical unsaturated polyester is shown in Structure 9.1. Esterification of the three

components would produce a distribution of species [1, 8, 9] and the previous ratio
would produce a polyester alkyd with a number average molecular weight (Mn) of about
2000 and a weight average molecular weight (Mw) of about 4500, but with a spread of
molecular species ranging from, say 500 to 10,000 molecular weight. The bulk of the
material has from 3 to 15 unsaturated groups per polyester chain and the unsaturation is
predominantly in-chain with only a statistical terminal unsaturation. Although maleic
anhydride is the starting material, esterification isomerises much of this to fumarate and
the resulting polyesters probably contain some 70-90% of unsaturation as fumarate.
428
Filled Thermosets
Properties of the unsaturated polyester resin and cured polymer are also influenced strongly
by the nature and amount of solvent comonomer used. The solvent comonomer
polymerises with the polyester unsaturation and with itself to form bridges or crosslinks
between the polyester chains. The following discussion is restricted to the use of styrene
as comonomer, it being by far the commonest, with some reference to methyl methacrylate
for speciality uses. Full discussion of other comonomers can be found in [10].
High styrene contents lead to low-viscosity resins and this is desirable if high filler
loadings are required, but there are tight limits on the polyester/styrene ratio, if an
acceptable cure is to be achieved. If the styrene:maleate/fumarate ratio is too low (<
1:1 m/m), inadequate cure results because there is insufficient styrene to bridge the
maleate/fumarate units in an alternating manner, or the resin vitrifies at too low a
conversion under the moulding conditions used. The result is that, although all the
styrene would be polymerised, only about 75% of the maleate/fumarate would be
reacted. Conversely, if the styrene:maleate/fumarate ratio is too high (> 3:1 m/m), cure
is slow and inadequate due to the relatively slow rate of the styrene homopropagation
step. Under the typical initiation conditions used, the rate of decomposition of the
initiator becomes fast relative to the styrene homopropagation step leading to an
increased tendency for primary radical termination, and consequent undercure and
high residual styrene. Thus, the preferred styrene:maleate/fumarate ratio is usually
around 2:1 m/m, i.e., the average length of crosslink between polyester chains is 1-2
styrene units, and this ratio under good-practice cure conditions would be expected
to lead to > 95% of both styrene and maleate/fumarate unsaturation being reacted.
These boundary conditions imposed by the reactivities in polymerisation lead to styrene
contents typically limited to the range 30-40 wt% which puts a lower viscosity limit of
around 0.2 Pa-s on unsaturated polyester resins. The 2:1 m/m ratio produces resins
with a double bond concentration of about 6 mol litre-1 and a volume contraction on
curing of about 8.5% (see Section 9.4.4).
With compositions close to the preferred styrene:polyester ratio, the overall rate of
conversion depends on the reactivity of styrene with maleate and fumarate, the ratio
of maleate to fumarate in the polyester, and the reactivity of styrene with itself. Data
from the literature on relevant reactivity ratios are conflicting, but the consensus of
evidence is that styrene is more reactive with fumarate than with maleate and is
more reactive with either than with itself. Similarly, maleate/fumarate is more reactive
with styrene than with itself, hence the tendency to form alternating copolymers
from styrene and maleate/fumarate unsaturation. Methyl methacrylate is sometimes
used as a component in unsaturated polyesters to reduce refractive index and thereby
derive aesthetic variations when the polymers are filled with particulates or glass.
However, methyl methacrylate could not wholly replace styrene in polyester resins
because, unlike styrene, methyl methacrylate is much more reactive with itself than
429
with maleate/fumarate and would, therefore, tend to homopolymerise in unsaturated

polyester/methyl methacrylate compositions. Nevertheless, styrene and methyl
methacrylate do copolymerise readily and the upper limit of methacrylate
incorporation is that sufficient styrene be present to act as the necessary link between
maleate/fumarate and methacrylate.
9.2.1.2 Vinyl Ester and Vinyl Urethane Resins
A second group of thermosets curing by free-radical chain addition are those that
use methacrylate, or acrylate-derived double bonds, in the oligomer component of
the resin. It is a feature of these resins that the unsaturation is thus always terminal,
although some members of this class do contain in-chain maleate/fumarate
unsaturation as well. The group comprises vinyl esters, vinyl urethanes and urethane
acrylics/methacrylics, the resins being differentiated by the specific molecular nature
of the oligomer backbone and the choice of solvent comonomer. Those resins that
have entirely acrylic functional oligomers are reactive with styrene or methyl
methacrylate, and either monomer can be used alone or in a mixture of any proportion.
Those that do contain some in-chain maleate/fumarate unsaturation must have an
appropriate amount of styrene if full cure is to be achieved. When styrene is used as
the solvent comonomer, then, because of the relatively slow homopropagation of
styrene, composition limits still have to be applied if undercure is to be avoided (see
discussion of unsaturated polyester alkyds in Section 9.1.2.3). Again, the ratio of
styrene:oligomer unsaturation is typically < 3:1 m/m, the average crosslink between
oligomers being 2-3 styrene units.
The vinyl esters are derived from epoxy resins, adducts of bis-phenol A and
epichlorhydrin, by reaction of the terminal epoxide groups with methacrylic acid
(Structure 9.2) [11, 12]. Thus, these resins have only terminal unsaturation, but do
have hydroxy functionality on the oligomer.
The vinyl urethanes are normally derived from hydroxyl-terminated unsaturated polyester
alkyds, e.g., propoxylated bisphenol A fumarate, which have been end-capped with a
polyisocyanate and then subsequently end-capped with an hydroxy alkyl methacrylate.
Thus, these resins have both terminal acrylic and in-chain maleate/fumarate unsaturation,
the ratio depending on the oligomer molecular weight and the functionality of the
polyisocyanate. High molecular weight results in a lower terminal: in-chain unsaturation
ratio, while a polyisocyanate functionality > 2 increases the ratio. A typical oligomer
structure is shown in Structure 9.3 [13, 14].
430
Structure 9.2 Preparation of vinyl ester resins
Structure 9.3 Preparation of vinyl urethane resins

Filled Thermosets
431
9.2.1.3 Urethane Methacrylate Resins
Urethane methacrylates are made by end-capping isocyanate-terminated, low molecular

weight urethanes with hydroxyalkyl methacrylates [15]. The synthesis is illustrated in
Structure 9.4. Although Structure 9.4 implies that a single molecular species will result
from reaction of the diisocyanate, diol and hydroxyalkyl methacrylate, in practice the
oligomers will consist of a mixture of species of type ABA, ABCBA, ABCBCBA and
higher, where A is hydroxyalkyl methacrylate, B is diisocyanate and C is diol. In
commercial resins, the structures may be further complicated by the use of isocyanates
and polyols of functionality > 2, which introduce branching into the oligomer. In the
production of these urethane oligomers, it is common practice to use mixtures of polyols
of low molecular weight, e.g., propylene glycol, and of molecular weights > 2000, e.g.,
polypropylene ether diol. In such cases, the oligomer molecular weight distribution
becomes bimodal (or multimodal) in nature because some oligomers contain high
molecular weight diol and some contain only low molecular weight diol or no diol. In
such distributions, Mn and Mw have little meaning.
Unsaturated polyester alkyds and vinyl urethanes rarely contain high molecular weight
diols, as incorporation of these would lead to lower reactivity and even higher viscosity.
Therefore, polyesters generally have a single peak distribution of molecular weights.
Vinyl esters also have a single distribution of molecular weights.
The incorporation of unsaturated diols in urethane methacrylate resin oligomers is

reported but is very rare, and it can be reasonably assumed that commercial resins contain
urethane oligomers having unsaturation only in terminal positions. The actual average
functionality of the oligomer depends on the average functionalities of the polyol and
isocyanates as indicated in Structure 9.4. As with other acrylic functional oligomers, the
resin can be formulated in either styrene or methyl methacrylate, but the same arguments
still hold requiring the ratio of styrene: oligomer unsaturation to be < 3:1 m/m.
In contrast, oligomers with acrylic unsaturation can be copolymerised with, and

therefore formulated with, methyl methacrylate in any proportion and high conversion
is still achieved in reasonably short times. This high-dilution feature of urethane
methacrylate oligomers in methyl methacrylate renders such resins particularly suitable
for filling to high volume fraction, because the resin viscosity can be tailored to meet
specific volume fraction and rheological requirements without the cure being impaired.
Dilution does increase gel times but gel to peak times are less sensitive to dilution, and
snappy cures still result, even at methyl methacrylate:oligomer unsaturation ratios of
10:1 m/m [16]. The reason for the excellent cure, even at high methyl methacrylate
contents, lies in the auto-acceleration phenomenon that occurs in the
homopolymerisation of methyl methacrylate. This does not occur in styrene
homopolymerisation [17-19].
432
Filled Thermosets
Structure 9.4 Preparation of urethane methacrylate resins
433
Figure 9.1 Cure exotherms for urethane methacrylate/methyl methacrylate resins (a),
compared with unsaturated polyester/styrene resins (b)
The practical consequences of an auto-acceleration effect on exotherm and conversion

are illustrated by the exotherm curves in Figure 9.1. The urethane methacrylate/methyl
methacrylate resin that shows auto-acceleration at all oligomer/monomer ratios is
compared with an unsaturated polyester/styrene resin, which only shows an auto-
acceleration (or gel effect) at high alkyd/styrene ratios. The urethane methacrylate
oligomer copolymerised with styrene shows virtually the same exotherm behaviour as
the unsaturated polyester for equivalent styrene/oligomer unsaturation ratios.
The freedom in monomer/oligomer unsaturation ratio in the all-acrylic functional resins

allows crosslink density and hardness/softness properties of the cured polymer to be varied
434
Filled Thermosets
over a wide range by changing the nature and amount of the urethane segment. The hard
properties derive from the methacrylate and associated isocyanate and the soft properties
from the polyol segments. Thus, the urethane methacrylates can range from all hard, i.e.,
no polyol used, to increasingly soft as the polyol content increases. Indeed, the properties
of the increasingly soft urethane methacrylates polymerised by free-radical chain growth
overlap with those of high-modulus polyurethanes made by step addition [20].
9.2.2 Step Addition Curing Resins
9.2.2.1 Epoxy Resins
Epoxy resin is a term that covers a diverse range of molecular types, the common
feature being the presence of epoxide groups through which curing the crosslinking occurs.
Also included within the general descriptive term are the hardeners or co-reactants, which
are used in conjunction with the actual epoxy resin and which again are of diverse
molecular type related only through possession of functional groups reactive with epoxide.
Only the more common types of epoxy resin are discussed here.
The common epoxide resins fall into four molecular types:
(1) bisphenol A-derived resins;

(2) epoxy novolacs;
(3) glycidyl amines; and
(4) cycloaliphatic epoxides.
In (1) and (2), epichlorhydrin is reacted with a di- or polyphenol, in (3) with a di- or
polyamine, and (4) is made by peroxidation of a bis cyclic olefin. A characteristic
parameter, which depends on functionality and molecular weight, is the epoxide
equivalent weight; the weight of resin that contains one epoxide group (also sometimes
expressed as number of epoxide groups per kilogram). This parameter has to be known
when considering the curing reaction. The majority of epoxy resins are in categories (1)-
(3), derived from epichlorhydrin, and thus have epoxide groups present as the glycidyl
entity. Epichlorhydrin reacts, in the presence of alkali, with compounds containing active
hydrogen atoms by a two-step reaction, initial formation of a chlorhydrin and generation
of a new epoxide by ring closure with sodium hydroxide.
9.2.2.2 Bisphenol A Diepoxides
The most common epoxy resins are the reaction products of bisphenol A with excess
epichlorhydrin and have the structure shown in Structure 9.5. Because the simple diepoxide
435
Structure 9.5 Preparation of bisphenol epoxy resins
(n = 0) is reactive with the phenolic groups of bisphenol A (see later), chain extension or
advancement occurs and higher molecular weight species are generated (n = 1, 2, 3, ),
each chain extension reaction generating a hydroxyl group. For n < 1, resins are
supercooled liquids at ambient temperature; as molecular weight increases n > 2, resins
are solids with softening points in excess of about 70 C. The control of reactant ratios
and the addition rate of NaOH can be used to keep molecular weights low if required,
but typically n = 0.1-0.2 even for the lowest molecular weight resins. A gel-permeation
chromatograph of a typical low molecular weight resin could show n = 0 (84%), n = 1
(11%), n = 2 (4%) and n = 3 (1%) (parts by weight), giving an average of n = 0.12.
Because of side reactions in the preparation, epoxide functionalities are slightly less
than 2, being typically 1.95. However, as n increases, the hydroxyl to epoxide ratio
increases and for very high molecular weight resins, reactions through the hydroxyl
groups may be more dominant in the curing process than ring opening of the epoxides.
Chain extension of the notional diepoxide with tetrabromo bisphenol A gives fire-
retardant resins.
9.2.2.3 Epoxy Novolacs
Epoxy novolacs are made by glycidylation of phenol formaldehyde novolacs, the latter
being the low molecular weight thermoplastic condensation products from phenol and
formaldehyde that are formed under conditions of excess phenol and acidic catalysis (see
Section 9.2.3.1). The resins are of the structural type shown in Structure 9.6, the methylene
Structure 9.6 Epoxy novolac resins
436
Filled Thermosets
bridges being a mixture of ortho and para. The molecular weight of the epoxy novolac
clearly depends on the molecular weight of the starting novolac and, similar to the
bisphenol diepoxides, the low members are liquids at room temperature (n < 2) but
become solid as molecular weight increases (n > 2). The simplest species present in the
novolac (n = 0.15) is the diepoxide of bisphenol F. In contrast to the bisphenol A
diepoxides, the epoxide functionality of the novolacs increases with increasing molecular
weight, and also novolacs do not possess aliphatic hydroxyl groups and have a mixture
of o-o, o-p and p-p linkages.
9.2.2.4 Glycidyl Amines
Glycidyl amine resins are prepared by reaction of epichlorhydrin with either primary
diamines, monoamines or aminophenols. Each primary amine gives rise to two epoxide
substituents. The reaction again involves two steps: reaction of the epichlorhydrin with
an active hydrogen to form the chlorohydrin, followed by ring closure with sodium
hydroxide to generate the new epoxide. The common glycidyl amines are the reaction
products of epichlorhydrin with diamino diphenyl methane and with p-aminophenol.
As with bisphenol A diepoxides, reaction of the diepoxide with the amine still present
generates higher molecular weight species but, in the case of the glycidyl amines, chain
extension leads to an increase in epoxide functionality and branching, as well as generation
of hydroxyl groups. Furthermore, the combination of high functionality and the presence
of tertiary amine and hydroxyl groups, both of which catalyse epoxide
homopolymerisation, can lead to problems of short pot lives with glycidyl amine resins.
Thus, particular commercial activity is directed to keeping molecular weights low in
these resins. Typical epoxide equivalent weights for diaminodiphenyl-methane based resins
are 115-130 compared with a theoretical weight of 105 for the simple non-extended
tetraepoxide and, for p-aminophenol-based resins, 105-115 compared with 92 for the
simple triepoxide.
9.2.2.5 Reactive Diluents
Reactive diluents are often added to epoxy resins to lower viscosity and ease processing.
They are normally low molecular weight glycidyl compounds and either monofunctional,
e.g., n-butyl glycidyl ether and C12-C14 aliphatic glycidyl ethers, or difunctional, e.g.,
butane diol diglycidyl ether, neopentyl glycol diglycidyl ether. When amine curing agents
are used, multifunctional acrylates are sometimes used as diluents and curing of the
diluent is achieved by Michael addition to the primary or secondary amine.
437
9.2.2.6 Curing of Epoxy Resins
Epoxide groups may homopolymerise or react with active hydrogen atoms in other
molecules, usually termed hardeners or co-reactants, to produce copolymers. Cure of an
epoxy resin may involve either or both of these reactions, and can be very complex, since
reaction of an epoxide with one functional group can produce new functional groups for
additional reaction with epoxides, and so on.
Homopolymerisation is promoted by tertiary amines and certain Lewis acids, which do

not contain acidic hydrogen. The amines promote a mechanism in which an anion is the
propagating species; the Lewis acids promote a cationic propagation mechanism. In
polyepoxide resins, both mechanisms lead to polymers that are essentially highly
crosslinked polyvinylene ethers in which each vinylene unit carries a crosslink.
Copolymerisation is typically with polyfunctional primary or secondary amines, or with

polycarboxylic acids or anhydrides. Diepoxides plus primary diamines give the step-
addition polymer (Structure 9.7), a linear polymer containing both hydroxyl and secondary
amine groups. These both provide sites where further reaction with epoxide groups can
occur to generate crosslinked polymers. The reaction with the secondary amine generates
further hydroxyl groups and also a tertiary amine, which can promote the etherification
reaction of epoxides discussed previously. For the special case of a primary monoamine,
a linear polymer is still generated if reactions of the hydroxyl groups are ignored, because
both hydrogens are active. Secondary amines have to be at least difunctional to continue
polymerisation. Typical amine curing agents are linear polyamines, cyclo-aliphatic amines
and polyamide polyamines. Examples of the linear amines are diethylene triamine,
triethylene tetramine and higher homologues, these being liquids that contain both primary
and secondary amine groups. For high temperature use, diaminodiphenyl sulfone is
commonly used and for latent cure, dicyandiamide. The cycloaliphatics are typically
isophorone diamine, 1, 2-diamino cyclohexane and N-methyl piperazine. To reduce vapour
pressure and odour, the low boiling polyamines are often adducted with diepoxides,
Structure 9.7 Curing of bis-epoxides with primary diamines
438
Filled Thermosets
which increases molecular weight. The polyamide curing agents are widely used and are
typically the reaction products of stoichiometric excess of diethylene triamine with dimer
acid, the latter being the Diels-Alder adduct of 9,11- and 9,12-linoleic acids.
Because of the diversity of amines and polyepoxide resins, it is necessary to determine

an appropriate stoichiometry for each resin/co-reactant pair if good cure is to be
obtained. Provided etherification side reactions are not considered, the stoichiometry
can be derived by equating the weight of polyamine containing one active hydrogen to
the weight of resin containing one epoxide group. Where commercial mixtures are
supplied, these values are normally given by the manufacturer.
Species containing acidic hydrogen, polyfunctional carboxylic acids and phenols are
commonly used, and these will react with epoxide groups. A difunctional carboxylic
acid reacting with a diepoxide produces a linear hydroxy functional polyester.
Crosslinking is through the independent etherification reaction, itself catalysed by
acid. In the absence of etherification, monofunctional acids would only produce
trimers with diepoxide. In acid conditions, protonation of the epoxide facilitates
etherification through reaction, either with hydroxyl groups or a second epoxide
(Structure 9.8). If the desire is to suppress etherification, basic catalysts can be used,
which promote only the esterification reaction. With bisphenol A diepoxides
containing hydroxyl groups, cyclic anhydrides from difunctional acids can be used
as co-reactants. These produce crosslinked polymers directly without the need for
independent etherification reactions, because the initial reaction is the opening of
the anhydride group by the pendant hydroxyl group, which produces a carboxylic
functional ester. This then reacts with an epoxide group to generate another hydroxyl
group and so on (Structure 9.9).
Curing by the reaction of epoxide with phenolic OH is usually done using a phenolic
novolac. These are high-temperature cures and produce very highly crosslinked polymers
due to the frequency of OH groups on the novolac.
Structure 9.8 Protonation of epoxide leading to etherification
439
Structure 9.9 Curing of bis-epoxides with anhydrides
Thus, the family of epoxy resins, depending on how and by what they are cured, can
generate polymers containing a variety of linking groups, ether, ester and secondary
and tertiary amine, in addition to any functional linkages present in the initial resin
and co-reactant. The reader will therefore appreciate that the cured polymers are
certainly not polyepoxides.
9.2.3 Condensation Resins
9.2.3.1 Phenolic Resins
Phenolic resins are the reaction products of formaldehyde (usually in the form of aqueous
formaldehyde), with phenol. Sometimes alkyl phenols, such as cresol and xylenol, are
incorporated to reduce crosslink density and brittleness, although reactivity is also
reduced. Phenolic resins are offered in two forms, novolacs and resols, characterised
by their different methods of manufacture and curing.
440
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(a) Novolacs
These are prepared using excess phenol and strong acid catalysts, and are essentially linear
or lightly branched, low molecular weight thermoplastic resins. Formaldehyde:phenol molar
ratios are typically 0.6-0.85:1. Aqueous formaldehyde can be considered to exist as
methylene glycol and, in the presence of strong acid, the phenol nucleus undergoes
electrophilic substitution at the 2 or 4 position by the protonated form of this glycol
according to Structure 9.10. Other phenol nuclei can then undergo electrophilic substitution
by the protonated methylol phenol and so on, the average molecular weight being determined
by the starting formaldehyde to phenol ratio. A broad range of molecular weight
distributions are obtained in this way. The low formaldehyde ratios give average molecular
weights of a few hundred and n about 1 in Structure 9.10. The higher formaldehyde
ratios give average molecular weights of around 1000, with an average n about 6-9 in
Structure 9.10. At low molecular weights, branching is small because of the lower reactivity
of the doubly substituted phenol units but, as molecular weight increases, branching does
likewise. Strong acid catalysis gives a predominance of 2,4 linkages, and weaker acids,
such as divalent metal acetates, give a preponderance of 2,2 coupling.
Structure 9.10 Preparation of novolac resins
441
(b) Resols
Resols are produced using alkaline catalysts (typically sodium hydroxide) and an excess
of formaldehyde, typical formaldehyde:phenol molar ratios being 1.2 to 3:1. The first
step in the reaction sequence is the production of a mixture of methylolated phenols.
These then undergo partial condensation to higher molecular weight structures, which
possess either dimethylene ether links, via elimination of water, or methylene links, via
further elimination of formaldehyde at higher temperatures. Liquid resols have a low
level of condensation and average less than two benzene rings per molecule; solid resols
are more condensed and average 3-4 benzene rings.
(c) Curing of phenolic resins
Resols possess a plurality of methylol groups through which crosslinking during curing
primarily occurs. In contrast, novolacs are cured through reaction of the vacant ortho
and para positions on the phenolic nuclei and require a co-reactant.
Resols are the true thermosets and cure is effected by heat, which causes a continuation
of the manufacturing process. Heating at about 180 C at alkaline pH condenses the
remaining methylol groups to form initially ether links, followed by elimination of
formaldehyde and generation of methylene links (Structure 9.11a). Room-temperature
curing of liquid resols is carried out with strong acid catalysts, e.g., p-toluene sulfonic
acid. Cure then effectively mimics novolac formation, i.e., protonated methylols substitute
at free ortho and para positions on phenol nuclei (Structure 9.11b). Thus, either cure
mechanism involves elimination of water but further methylol condensation can also
involve formaldehyde elimination, although the liberated formaldehyde can itself then
enter into crosslinking reactions. This elimination of volatiles can be a problem in closed
mould processing, as it could be as high as 14 wt% and formulations have to be chosen
to minimise it. So the final crosslinked polymer could look something like Structure
9.12, a mixture of methylene links, ether links and some unreacted methylol groups.
Structure 9.11(a) Heat cure of resol
442
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Structure 9.12 Cured crosslinked resol
Structure 9.11(b) Acid cure of resol
Novolacs are cured by reaction with a co-reactant to supply latent methylene links.
Hexamethylene tetramine, the reaction product of formaldehyde with ammonia,
(CH2)6 . N4, at about 5-15 wt% is normally used. Curing occurs via a reaction at free
443
ortho and para positions on phenolic nuclei with elimination of ammonia and the
cured polymer is a mixture of methylene and secondary amine links.
Because of their high crosslink density and very brittle behaviour, phenolic moulding
compounds are invariably filled with reinforcing fillers such as wood flour, wollastonite,
mica, mineral wool flour and glass fibres. Solid moulding compounds are normally novolac
based; resins for transfer moulding (RTM) and other liquid laminating processes are resols.
9.3 Mechanical Properties
While many different mechanical properties may be measured for polymer composites,
the description of the mechanical behaviour is afforded by the critical stress intensity
factor, Kc, the fracture energy, Gc, Youngs modulus, E, yield stress, y , together with a
knowledge of failure stress and fatigue behaviour. These properties are explained further
in this section.
9.3.1 Modulus
It was observed empirically by Hooke that, for many materials under low strain, stress is
proportional to strain. Youngs modulus may then be defined as the ratio of stress to strain
for a material under uniaxial tension or compression, but it should be noted that not all
materials (and this includes polymers) obey Hookes law rigorously. This is particularly so
at high values of strain but this section only considers the linear portion of the stress-strain
curve. Clearly, reality is more complicated than described previously because the application
of stress in one direction on a body results in a strain, not only in that direction, but in the
two orthogonal directions also. Thus, a sample subjected to uniaxial tension increases in
length, but it also becomes narrower and thinner. This quickly leads the student into tensors
and is beyond the scope of this chapter. The subject is discussed elsewhere [21-23]. There
are four elastic constants usually used to describe a macroscopically isotropic material.
These are Youngs modulus, E, shear modulus, G, bulk modulus, K, and Poissons ratio, v.
They are defined in Figure 9.2 and they are related by Equations 9.1-9.3.
E = 2G(1 + ) (9.1)
E = 3K(1 2) (9.2)
(3K 2G)
= (9.3)
2(3K + G)
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Figure 9.2 Definition of E, G, K and v
It must also be remembered that, because polymers are viscoelastic materials, the measured
value of modulus is dependent on strain rate. The following discussion concentrates on
Youngs modulus (often measured under three-point bend), but is equally applicable to
any of the other elastic constants.
The introduction of a rigid particulate filler into a polymer matrix results in an increase in
Youngs modulus. This is shown in Figure 9.3 for (i) a urethane methacrylate polymer
containing no polyol soft-block and (ii) a copolymer of methyl methacrylate (60 wt%) and
an ethoxylated bisphenol A dimethacrylate (40 wt%). Both polymers are filled with silica
sand. Note that the gradient of the curve increases as filler volume fraction increases. This
behaviour is typical of that seen for many other systems, for example various epoxies filled
with silica sand [24], glass spheres [25-28] and polyester resins filled with glass spheres
[25]. For unidirectional, continuous fibre composites, relationships are well developed
which predict modulus from a knowledge of the fibre modulus and volume fraction and
matrix modulus. However, the situation for particulate composites is more complex, because
variations in the stress and strain fields are introduced by the discontinuous nature of the
445
Figure 9.3 Graph of Youngs modulus against filler volume fraction for two
acrylic polymers
reinforcement. Several models have been reviewed in detail by McGee and McCullough
[29]. The modulus of a composite can, in principle, be determined from the corresponding
volume fraction and modulus of the components. In practice, either assumption must be
made to simplify the analysis, or else the analysis must carried out for a special case. The
authors categorise the various approaches by the nature of the assumptions made:
1. Mechanics of materials approach

2. Embedding or self-consistent field approach
3. Bounding approach
All the approaches assume that the phases are in direct contact (but not necessarily
chemically bonded) to allow stress transfer and attention is directed towards overall
response of the material to loads or deformation.
The mechanics of materials approach is the simplest and least useful. It assumes that
each phase is subjected either to the same strain (the Voigt model; Equation 9.4) or the
same stress (the Reuss model; Equation 9.5). This yields the relationships:
Pc = VmPm + Vf Pf Voigt (9.4)
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where P = K or G (E may then be calculated from Equations 9.1 or 9.2)
1 Vm Vf
= + Reuss (9.5)
E c E m Ef
The Voigt model results in a linear relationship between Ec and Vf and gives a gross
over-estimate of Ec while the Reuss model gives a reasonably accurate estimate of Ec
for Vf < 0.3. The Voigt and Reuss models are given in Figure 9.4 with data for a
urethane methacrylate polymer (containing no soft-block) filled with silica sand.
Figure 9.4 Comparison of Voigt and Reuss models with experimental data for a
urethane methacrylate polymer (no polyol soft-block) filled with silica sand
The self-consistent field approach models the microstructure of the composite in order
to deal more realistically with the internal distribution of stress and strain. The various
treatments in this category have been brought together by Wu and McCullough [30].
The treatment relates to an arbitrary reference material and encompasses a bounding
approach. The lower bound of calculated modulus refers to a dispersion of filler particles
in a continuous matrix of polymer and the upper bound refers to inclusions of polymer
in a continuous phase that has the properties of the filler. The approach is further
modified in reference [29] and the derived equations which relate modulus to Vf are
shown next:
(1 + pl plVf )
Pc = Pm where P = K or G and
(1 plVf )
447
(Pf Pm )
where pl = (P + P )
f pl m
VfVm (1 Vm )(Pf Pm )( pu pl )
= 1+
Pf + pu (Vf Pf + VmPm )
2v c 1
=
vc
vc is a critical volume fraction at which there is a sharp change in phase continuity

between continuous matrix phase and continuous filler phase.
pu and pl are given by:
property pu pl
2(1 2f )Kf 2(1 2 m )

K (1 + f )Km (1 + m )
and and
(7 5f )Gf (7 5 m )
G (8 10f )Gm (8 10 m )
where vf and vm are the Poissons ratios for the filler and matrix, respectively. E may then
be calculated from the calculated values of K and G for the composite. Despite the
complexity of this model and the difficulty in readily assigning physical significance to
all the parameters, it does nevertheless model well the relationship between E and Vf, as
is shown in Figure 9.5, where our data for the urethane methacrylate polymer (containing
no soft-block) filled with silica sand are plotted together with the predicted curve.
Guild and Young [31] have developed a finite element model to predict the modulus of
an epoxy resin filled with glass spheres. Monodisperse spherical particles are assumed
to be dispersed randomly in an infinite matrix and the authors consider a cylinder of
resin containing a single particle. The cylinder is represented by a plane with one corner
at the centre of the spherical particle and of sides equal to the half height of the cylinder
and to its radius. Finite element analysis is carried out on a one-radian segment which
is considered to be deformed along two edges so that the deformed segment retains
parallel sides. The analysis was repeated for various ratios of cylinder radius to particle
radius. In order to relate the result to a specific filler volume fraction, the analysis must
be carried out on a grid, the dimensions of which relate to that volume fraction. This
448
Filled Thermosets
Figure 9.5 Comparison of data for a urethane methacrylate polymer (no polyol soft-
block) filled with silica sand, with the model of McGee and McCullough
takes into account the fact that interparticle distances are variable in a real material.
The model gives rise to two values of modulus, an upper bound that assumes equal
strain in the cylinders and a lower bound that assumes equal stress. These bounds are
much closer together than those in the previously described models. Modulus was
calculated by the authors for a range of Vf from zero to 50% and the theoretical
predictions compared very favourably with the experimental data. In order to determine
the modulus of composites with different values of Em and f, the whole analysis has to
be repeated and therefore, regrettably, the predictive value of this approach is limited.
9.3.1.1 The Effect of Strain Rate
This was studied by Spanoudakis and Young [28] for an epoxy resin (Epikote 828)
hardened with tetraethylene pentamine and filled with glass ballotini. These authors
found that for the unfilled polymer, Youngs modulus (measured in flexure) increased
by 9% from 3.5 GPa to 3.8 GPa over two decades of strain rate. As Vf was increased
then the strain rate dependence increased so that for Vf = 0.46, Youngs modulus
increased from 10.8 GPa to 12.4 GPa over the same two decades of strain rate. This
increase is 15%. The authors found the same trend for all the filler particle sizes studied.
No explanation of this behaviour was offered, but it was noted that this was an area
warranting further investigation. It is not expected that the presence of a large area of
bonded filler surface should reduce segmental mobility within the polymer matrix,
449
9.3.1.2 The Effect of Particle Size
The same authors studied the effect of filler particle size on Youngs modulus (again
measured in flexure) for the same epoxy resin filled with monodispersed glass ballotini.
It was found that, particularly at high Vf (> 0.2), E decreased linearly with increasing
filler particle size, d. Thus at Vf = 0.46, E was 11.3 GPa for a particle size of 4.5 m
and E fell to 10.1 GPa for a particle size of 62 m. The authors attribute this fall to a
skin effect, which was first described by Lewis and Nielsen [32]. In flexural
measurements, the properties of the surface dominate the magnitude of the property
that is measured. For large particles it is argued that the skin is more depleted of filler
than is the case for small particles. If this is the case, then composites containing the
smaller particles will have a higher modulus than those containing larger particles, at
the same volume fraction. If this explanation is correct then the particle size effect is,
in truth, merely an artefact of the flexural experiment and would not be observed
either for specimens where the surface layer had been abraded away prior to
measurement or for modulus measured in a tensile experiment.
9.3.2 Fracture Toughness and Fracture Energy
The failure stress of a material depends not only upon its structure, but also on the size
of the largest flaw it contains. Failure stress is, thus, not a material property and it is not
valid therefore to compare the inherent integrity of materials on this basis. Such a
comparison is provided by fracture mechanics with the parameters Kc and Gc. The stress
intensity factor, K, was introduced by Irwin [33] who derived a model for the stress field
round a crack tip. In this model, K relates the magnitude of the stress at a point near the
crack tip to the applied stress and the geometry of the sample. K thus characterises the
intensity of the stress field around the crack tip. As applied stress is increased, so K
increases until it reaches a critical value, Kc, at which crack propagation begins. Kc is the
critical stress intensity factor or fracture toughness and is a measure of a materials ability
to resist crack propagation. Clearly, the stress field depends on the direction of the applied
stress relative to the crack. For the case where the stress is pulling the crack open (that is
in a tensile experiment), the loading is termed mode I, the critical stress intensity factor is
given this subscript and is written KIC. Kc is a material property and the units of Kc are
MPa.m1/2. The bigger its value then the more resistant is the material to crack propagation.
The value of KIC for poly(methyl methacrylate) (PMMA) is about 1 MPa.m1/2 while
brittle thermosets, for example some epoxies, may have values of KIC below 0.5 MPa.m1/2.
Polycarbonate has a value of KIC of about 2 MPa.m1/2.
Gc is defined as the energy required to form 1 m2 of new surface. It is related approximately

to Kc through the equation:
450
Filled Thermosets
K2c
Gc =
E
where E is Youngs modulus.
The value of GIC for PMMA is 500 J/m2, that of a brittle thermoset is typically 100 J/m2
and GIC for polycarbonate is 1100 J/m2. Note that, just because a material has a high
value of KIC, it does not follow that GIC is also high. Certain ceramics have high values of
KIC but low values of GIC. For example, partially stabilised zirconia has a KIC of 6 MPa.m1/
2
but a GIC of only 180 J/m2 [34]. In order to derive a meaningful comparison between
materials it is necessary to consider both KIC and GIC (in addition to y and E).
There are many methods available for measuring KIC and GIC of which the more popular
are three point bend [35], compact tension [36] and double torsion [37-39]. The three-
point bend method is a European standard. It is relatively straightforward to carry out
and requires only small samples. This geometry does not, however, allow crack
propagation to be studied, because once the crack starts to propagate, it accelerates to
the end of the sample. Compact tension and double torsion geometries allow crack
propagation and the effect of crack propagation rate to be investigated. In order to
measure a meaningful value of KIC it is essential to have a sharp crack and the dimensions
of the specimen are also important. A more detailed discussion of the principles of fracture
mechanics is beyond the scope of this chapter, but the reader is directed to [21, 22, 40].
9.3.2.1 Observations
The addition of a rigid particulate filler to a brittle thermoset matrix significantly affects
KIC and GIC. While general statements may be made regarding these effects exceptions
will be found and the theories to explain the effects are still being developed.
(1) As filler volume fraction, Vf , increases, then KIC increases, see Figure 9.6. Thus,
perhaps contrary to expectation, the addition of a rigid filler to a thermoset makes it
more resistant to crack growth.
(2) As Vf increases, then GIC passes through a maximum, see Figure 9.7. Note that this
statement is not in contradiction to (1) because GIC is related to KIC by E, which also
increases with filler volume fraction, (G = K2Ic /E). Once again, contrary to expectation,
the addition of a rigid filler results in a composite that is usually tougher than the
thermoset matrix.
(3) The maximum in the plot of GIC against Vf moves to higher Vf as mean filler particle
size decreases.
451
Figure 9.6 Effect of filler volume fraction on KIc
Figure 9.7 Effect of filler volume fraction on GIc
(4) For Vf in a broad range around the GIC maximum, crack growth is not continuous in
samples that are subjected to a continuous cross-head displacement test, but instead
propagation is observed, see Figure 9.8. This behaviour is usually observed in unfilled
polymers of low yield stress and therefore in materials where plastic flow may account
for crack-tip blunting. While the mechanism may be different, crack-tip blunting is
also believed to be responsible for stick-slip propagation in particulate composites,
see Section 9.3.2.5. Briefly, in the arrest condition, the crack tip is blunt relative to
that during propagation and so the crack overloads until the stress is high enough to
initiate propagation. Once this occurs the crack tip becomes sharper and a rapid
release in strain energy occurs as the crack propagates rapidly. The applied stress
soon falls below the value critical for crack propagation however, at which point the
crack arrests and the tip then blunts by whatever blunting mechanism is operating.
This condition remains until the stress once more builds up to a value at which the
452
Filled Thermosets
Figure 9.8 Slip-stick propagation
blunted crack will propagate and the cycle is then repeated. Consequently, a saw-
tooth curve of load against crosshead displacement is observed. This behaviour is
known as stick-slip propagation, see Figure 9.8.
(5) The degree of adhesion between filler and matrix affects GIC and KIC, but improving
adhesion may increase these parameters or decrease them depending on the matrix
and the rigid filler.
(6) The incorporation of a rigid filler into a tougher matrix leads to a smaller percentage
increase in KIC than is observed when a less tough matrix is filled.
9.3.2.2 Effect of Vf on KIC and GIC
Figure 9.9 is a plot of KIC against Vf for two composites:
a copolymer of methyl methacrylate (60 wt%) and an ethoxylated bisphenol A

dimethacrylate (40 wt%) filled with silica.
a urethane methacrylate polymer, which contains no soft-block, filled with silica.
The silica is well bonded to the matrix using 0.3 wt% (on filler) of a silane coupling
agent (-methacryloxypropyl (trimethoxy) silane) for both sets of composites.
Figure 9.10 is a plot of GIC against Vf for the same composites. In both cases there is a
maximum in GIC at about a Vf of 0.1, but for all filled samples GIC is as high, or higher,
than the value for the unfilled matrix. It was also found that for samples with Vf of 0.1,
453
Figure 9.9 Plot of KIc against Vf for two acrylic composites
Figure 9.10 Plot of GIc against Vf for two acrylic composites
stick-slip crack propagation occurred, whereas for all other volume fractions of filler
and for the unfilled polymers, crack propagation was continuous.
These observations have been observed for composites of several other thermosets and
fillers. Lange and Radford [41] studied an epoxy (ERL 2774; Union Carbide Co.) filled
with aluminium hydroxide and, indeed, were the first to report the toughening effect of a
rigid particulate filler in a polymer matrix. Brown [42] investigated an unsaturated polyester
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Filled Thermosets
(Crystic 191MV; Monsanto) and a range of fillers. Mallick and Broutman [26] studied an
epoxy resin (Epon 828; Shell Chemicals) cured with 14 phr m-phenylene diamine) and
Broutman and Sahu [43] studied this system and an unsaturated polyester (Co Rezyn-
1808-2; Interplastic Corp.); both thermosets were filled with 45 m diameter glass beads.
All the composites in these studies exhibited the type of behaviour shown for the acrylic
composites in Figures 9.9 and 9.10. Perhaps the most comprehensive study to date is that
of Spanoudakis and Young [28, 44]. These authors also used an epoxy resin (Epikote 828
cured with tetraethylene pentamine) filled with glass beads and they too observed a
maximum in the plot of GIC against Vf. More recent work on both thermoplastic and
epoxy matrices by Pukansky and Maurer [45] and epoxy materials by Kim and Khamis
[46], Hussain and co-workers [47] and Lee and Yee [48] all show the same trend.
Thus a wide variety of thermosets filled with rigid particulates of different morphology,
size and chemistry all show the same general behaviour.
9.3.2.3 The Crack Pinning Model
The increase in fracture energy of a brittle matrix by a rigid particulate filler was first
discussed by Lange [49] and his theory was later developed by Evans [50] and by Green
[51, 52]. The theory and its developments have been reviewed [22, 28]. From a study of
the fracture surfaces of magnesium oxide crystals containing small voids, Lange observed
that the crack front became pinned when it met these voids. In order to propagate further,
he proposed that the crack must bow out between the voids, while remaining pinned,
until eventually it is able to break away and continue. This bowing increases the length
of the crack (Figure 9.11) and, Lange proposed that there was an extra energy term
associated with this increase in crack length.
He derived the expression:
T
Gc (c ) = Gc (m) + 2
D
where: Gc(c) is the fracture energy of the composite

Gc(m) is the fracture energy of the matrix
T is the line energy per unit length of crack
D is the interparticle spacing
Lange considered several other possible mechanisms to account for the increase in GIC:
(1) The fracture surfaces are not smooth and so an increase in fracture energy associated
with increased roughness should be taken into account.
455
Figure 9.11 Crack pinning in a particulate composite
(2) Energy may be absorbed by the particles through plastic deformation.
(3) Friction between the parting fracture surfaces can absorb energy.
The contributions from (1) and (3) were calculated to be extremely small, while (2) is
extremely unlikely for inorganic particles. Spanoudakis and Young [28] and Green and
co-workers [52] have also considered crack-tip blunting as a mechanism of increasing
fracture energy and, as will be shown later, this does occur. Nevertheless, it is generally
agreed that the major contribution to the increase in fracture energy, in particulate
composites, is from crack pinning.
Langes model correctly predicts that Gc(c) increases with filler volume fraction (that is
as D decreases), but it does not explain why Gc(c) is often observed to pass through a
maximum at higher values of Vf.
9.3.2.4 The Effect of Filler Particle Size
Further limitations to Langes model are revealed when the effect of filler particle size on
Gc(c) is considered. Lange himself [53] measured Gc(c) against Vf for three series of
sodium borosilicate glass/alumina composites in which the average alumina particle size
was 3.5 m, 11 m and 44 m, respectively. For any given value of Vf, Gc(c) increased
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Filled Thermosets
with particle size, as predicted by the model (D decreases as particle size decreases).
However, Lange then plotted Gc(c) against 1/D. Each series gave the expected linear
relationship, but the slopes were different (the larger the particle size then the larger the
gradient), implying that each particle had its own associated line energy. Mallick and
Broutman [26] observed similar behaviour in their epoxy/glass bead composites as have
Spanoudakis and Young [28] for low values of 1/D. Similarly, Lange and Radford [41]
reported this behaviour for epoxy/alumina trihydrate composites. Lange introduced a
dimensionless parameter F(D) to account for these experimental results:
T
Gc (c ) = Gc (m) + 2
D
but this parameter has dubious physical significance. Building on this work Evans [50]
and Green and co-workers [51, 52] carried out extensive theoretical analyses of crack
pinning, taking into account particle shape, particle penetration by the crack front,
secondary crack shape and secondary crack interactions. These studies have proven that
the contribution of the line energy to Gc(c) is indeed dependent, not only on interparticle
spacing, but also on particle size. Using Langes results [53], Evans showed that data for
the different composites all fell on a theoretically derived curve of Gc(c) against r/D,
where r is the particle radius. Furthermore, a similar treatment of Lange and Radfords
data for alumina trihydrate/epoxy composites [41] also showed that the data fitted the
theoretically derived curve at low values of r/D. However, Gc(c) fell below the theoretical
line at higher r/D values. Penetration of filler particles by the crack front was the
explanation of this phenomenon and alumina trihydrate is susceptible to cleavage (see
later discussion in Section 9.3.3). Thus, toughening by crack pinning is much less effective
when the filler particles can be penetrated or cleaved by the advancing crack front.
What can be concluded is that the major factors in determining the fracture toughness
and fracture energy are the properties of the matrix material, the decrease in volume of
matrix material due to the introduction of particulates and the interaction between the
matrix and particulate. In the case of rigid particulates, the stress field ahead of a crack
generally results in debonding, which leads to significant plastic deformation of the matrix
material. A model proposed by Pukansky and Maurer [45] assumes that property changes
due to interaction are proportional to the actual value of the given property and arrived
at a relationship in the form:
Gc0 1
Gc = . exp(Bf )
E / E0 1 + 2.5
They got very good correlations with experimental data from a range of composites,
including some reanalysis of earlier data from Spanoudakis and Young [28, 44].
457
In summary, the crack pinning model, as described so far, explains why fracture energy
increases with filler volume fraction and it accounts for the particle size effect. In the
next section a rationalisation of the maxima in the plots of GIC (c) against Vf is presented.
9.3.2.5 Extensions to the Crack Pinning Model and the Effect of Particle
Matrix Adhesion
To date, the most comprehensive and systematic experimental study of rigid particulate
composites is that of Spanoudakis and Young [28, 44]. These authors have studied the
effect of crack propagation rate, particle volume fraction, particle size and particle matrix
adhesion on KIC, Youngs modulus and fracture energy. They point out that previous studies
have concentrated on the dependence of GIC (c) rather than KIC (c) on Vf and the maxima
observed have been ascribed to changes in failure mechanism. This can be misleading,
however, because Gc(c) is a function of both KIC(c) and composite modulus, Ec. Using
values of KIC (c)/KIC (m) predicted from Greens analysis [52] and values of Ec from Ishai
and Cohen [24], Spanoudakis and Young were able to show that maxima in GIC (c) versus
Vf could be demonstrated solely from the crack pinning model, without invoking a change
in crack propagation mechanism. The crack pinning model would now appear to explain
all of the phenomena observed for the behaviour of particulate filled composites.
Not surprisingly, reality is a little more complicated than this. For many samples
Spanoudakis and Young observed stick-slip propagation, as was described for the acrylic
composites previously and where this occurred the KIC of initiation was greater than
the arrest value, or the continuous propagation value usually seen at the highest
measured crack propagation rates. The authors point out that stick-slip propagation is
associated with crack-tip blunting in certain polymers and their analysis concluded
that it was probably occurring in this case. Thus, a secondary toughening mechanism
may also operate in certain ranges of Vf. Particle-matrix adhesion further complicated
the situation. While KIC (c) was relatively unaffected by the degree of adhesion, Ec was
smaller in composites where adhesion was poor compared with composites where
adhesion was good. This then generally resulted in GIC (c) being higher in composites
where poor particle-matrix bonding occurred. Nevertheless, scrutiny of the authors
data does reveal compositions where the reverse is true and, once again, the secondary
toughening mechanism of crack-tip blunting is superimposed on all of these data. Lastly,
Spanoudakis and Young also observed that, as adhesion improved between filler particle
and matrix, then the position of maximum stress moves from the particles equator (no
bonding) towards its poles. The result is that fracture surfaces of well-bonded composites
show less evidence of filler particles because the crack front is deflected towards the
poles and often remains within the polymer. This too may reduce the effectiveness of
the crack pinning mechanism.
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Filled Thermosets
Figure 9.12 Graph of KIC against coupling agent concentration for an

acrylic composite
Figure 9.13 Graph of GIC against coupling agent concentration for an

acrylic composite
Thus, while the basic mechanism of toughening of thermosets by rigid particles is well
established, it is clear that further work is required before a comprehensive
understanding of the subject is gained. As further illustration of this consider Figures
9.12 and 9.13, which are plots of KIC (c) and GIC (c) against coupling agent concentration
for composites of silica filled (60 wt%) PMMA made in our laboratory. Good adhesion
results in a 50% increase in KIC and a 100% increase in GIC. These results are different
from those reported by Spanoudakis and Young and suggest that good adhesion is
extremely beneficial for these composites. All of these samples exhibited continuous
crack propagation.
It is not clear from the foregoing arguments if good adhesion merely promotes
debonding at a higher stress thus resulting in massive shear yielding. The same
behaviour has been observed in rubber-toughened epoxies, where the common
argument centres on the role of cavitation as detailed in a review by Bagheri and
Pearson [54]. Some argue that cavitation within rubber particles precedes localised
459
shear banding and is the cause of the localised deformation. Huang and Kinloch [55,
56] have found from finite element analysis that cavitation can occur before or after
shear banding particularly if particles have a high modulus and low Poissons ratio.
It seems reasonable to suppose that once a critical strain is reached in the matrix
then localised shear banding will occur regardless of cavitation in the rubber particles.
Bagheri and Pearson [57] in a study comparing rubber modifiers and hollow particles,
showed however that cavitation resistance of the rubbery phase does not increase
toughness in the epoxy matrix.
9.3.2.6 The Effect of Polymer Fracture Toughness
We have found that the ratio KIC(c)/KIC(m), for a given value of Vf, is dependent on the
inherent matrix brittleness. For example consider the data for three sets of acrylic
composites each containing 40 volume per cent silica sand (mean particle size 10 m).
These data are summarised in Table 9.1.
Table 9.1 Effect of polymer fracture toughness on composite fracture toughness

KIC(m) KIC(c)
Polymer matrix KIC(c)/KIc(m)
(MPa.m1/2) (MPa.m1/2)
Urethane methacrylate (no soft-block) 0.55 1.15 2.10
Ethoxylated bisphenol A/MMA copolymer 0.65 1.30 2.00
Urethane methacrylate (soft-block) 1.05 1.50 1.30
The urethane methacrylate polymer which contains no soft-block and the ethoxylated
bisphenol A/MMA copolymer both have relatively low values of KIC and their composites
have fracture toughnesses approximately double that of the respective polymer. The urethane
methacrylate polymer which contains a polyol soft-block, on the other hand, has a fracture
toughness which is approximately twice that of the other polymers, but for the composite
KIC is increased only modestly. Thus, the higher the fracture toughness of the polymer then
the less is the fracture toughness of the particulate composite enhanced relative to it.
Recently we have begun a programme of work on similar urethane methacrylate polymers,

but have used glass ballotini coupled into the matrix with -methacryloxypropyl (trimethoxy)
silane. Values of KIC were measured by double torsion for composites of Vf = 0.4. The
results are shown in Figure 9.14. For the urethane methacrylate polymer (containing no
soft-block) filled with ballotini of mean particle size 10 m, KIC(c)/KIC(m) is 2.1, the same
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Filled Thermosets
Figure 9.14 Plot of KIC against crosshead speed for various acrylic composites
value as that obtained for composites of the same polymer and silica sand of mean particle
size 10 m. For the less notch sensitive urethane methacrylate polymer which contains a
polyol soft block and is filled with the same ballotini, KIC(c)/KIC(m) is only 1.1. When a
grade of ballotini with a larger particle size range (50-100 m) was used then stick-slip
propagation occurred and high values of KIC at the initiation of crack growth (KICi) were
461
observed. However, if the methodology of Spanoudakis and Young is followed and if the
extrapolated continuous crack propagation value of KIC(c) (1.15 MPa.m1/2) is taken, then
once again KIC(c)/KIC(m) is 1.1, but clearly the larger filler particles are hindering crack
growth. Our preliminary observation is that when the filler particles are smaller than the
calculated critical crack opening displacement of the polymer, then KIC(c)/KIC (m) is unity
or slightly greater. When the filler particles are larger than the critical crack opening
displacement, however, KIC(c)/KIC(m) may be significantly increased (> 2), if KICi is used.
One of the major problems associated with much of the work carried out to show the
effect of polymer matrix toughness on the composite toughness, is that the polymers
used often have very different chemical structures, which may lead to differences in
fracture behaviour. One study by Lee and Yee [48] used a series of glass bead filled
epoxies to investigate the effect of inherent matrix toughness on fracture behaviour. The
matrix toughness was varied by increasing the molecular weight of epoxides, which in
turn decreased the crosslink density, increasing the inherent matrix toughness. As expected
the fracture toughness of the filled epoxies increased as the inherent matrix toughness
increased. However, the toughening effect was also seen to increase and the effect of
glass beads was therefore more effective in tougher epoxide matrices. From microscopy
studies of the fractures they found that a number of micro-deformation mechanisms
occurred during the fracture of the filled epoxies. These were classified as step formation,
debonding, diffuse matrix shear yielding and micro shear banding. At the higher inherent
matrix toughness, diffuse matrix shear yielding and micro shear banding were found to
be the most prevalent toughening mechanism. It was also concluded that localised shear
yielding is the major energy absorption mechanism for both filled and unfilled epoxies.
9.3.2.7 Ductile to Brittle Transition
It is generally accepted that as the thickness of a fracture specimen is increased, the

measured toughness will reduce. This effect can be seen both in toughened and un-
toughened blends and is generally considered to be due to a change in dominant stress
state from plane stress at small thickness to plane strain at larger thickness. A similar
transition has been observed by Bagheri and Pearson in rubber-modified and micro-void
toughened epoxies where the toughness reduces with increasing inter-particle distance
[57]. They studied the effect of a wide range of particle size and spacings and concluded
that the occurrence of particle cavitation relieves plane strain constraint from the matrix
allowing plastic deformation to occur locally. Reducing the interparticle distance on a
range of particle sizes from 0.2 to 40 m increased the measured toughness in the epoxy,
the effect being consistent for both rubber and micro-void toughening spacings of 0.2 to
50 m. These spacings are all comfortably less than the plane strain plastic zone sizes at
these toughnesses (1 to 2 MPa.m1/2) which are in the range 20 to 80 m. The effect of
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Filled Thermosets
particle size was found to induce the same amount of deformation in the matrix at larger
interparticle distances. The work showed clearly that the transition in toughened epoxies
does not occur at a critical interparticle spacing and that increasing the particle size
shifts the transition to larger interparticle spacings.
9.3.3 Failure Stress
Failure in polymers may occur in a brittle or a ductile manner. Let us illustrate this using
PMMA as an example, for which the tensile yield stress is about 90 MPa and KIC is
about 1.0 MPa.m1/2. For a specimen containing a through crack, failure stress, um, is
related to KIC by the equation based on Griffiths theory:
1
K2 2
um = IC (strictly this is only true for an infinite plate)
a
If um is calculated for different values of a, we obtain the plot shown in Figure 9.15.
Figure 9.15 Plot illustrating the concept of inherent flaw size
463
Note that this intersects the yield stress at a value of 3 x 10-5 m or 30 m and this point is
termed the inherent flaw size. For cracks above 30 m in size, PMMA breaks in a brittle
manner, because the overall stress in the polymer is too low to cause significant bulk yielding
during the timescale of the experiment. However, if the flaws present in the sample (naturally
occurring or deliberately introduced) are below 30 m, then a sufficiently high stress may
be applied to the sample that yielding will occur and any further applied strain will result
in plastic flow and not in an increase in stress. In thermosets, brittle failure is usually
observed because yield stresses are usually high (> 120 MPa). There are exceptions though,
an example being the urethane methacrylate polymer which contains a polyol soft-block,
for which the tensile yield stress is 56 MPa and the inherent flaw size is about 1 mm. In
particulate composites the situation is considerably more complicated because there are
two phases present, each with very different mechanical properties and, in addition, the
interface between them may also be critical in determining the magnitude of the failure
stress. Failure occurs almost exclusively in a brittle manner. It is usually observed that:
(1) For composites with poorly bonded filler particles, where either no coupling agent
has been employed, or indeed the filler has been pre-treated with a mould release
agent, then failure stress decreases very significantly with filler volume fraction.
(2) For composites with well-bonded filler particles the variation of failure stress on
filler volume fraction depends greatly on the system concerned. For example stress
may be independent of filler volume fraction, increase slightly with filler volume
fraction or, more usually, exhibit a slight or moderate decrease followed by a recovery.
These statements are illustrated in Figures 9.16 and 9.17 for two acrylic matrices one
filled with silica and one with aluminium hydroxide. It has also been shown that epoxy
composites [25, 58] and polyester composites [59] exhibit similar behaviour. These are
the observations that require explanation.
As a starting point, let it be assumed that failure is not initiated within a filler particle. This
should usually be true because the failure stress of most mineral fillers is considerably larger
than the polymer matrix. Exceptions may occur, however. For example, many layer minerals,
including the fire retardant filler aluminium hydroxide, may be mechanically weak in the
[001] direction and strongly aggregated particles may also be relatively mechanically weak.
Figure 9.18 is a scanning electron micrograph of the two fracture surfaces of a mica-containing
acrylic composite which has undergone tensile failure. The locus of failure is seen to be a
mica particle and, since the particle appears on both failure surfaces, it may be inferred that
its fracture initiated the failure of the composite. More usually, though, it is either the matrix
or, in particular, the filler-matrix interface, from which failure initiates.
The most comprehensive description of the failure of particulate composites is that of Leidner
and Woodhams [59]. These authors consider a specimen of a particulate composite containing
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Filled Thermosets
Figure 9.16 Graph of tensile failure stress against filler volume fraction for an
acrylic composite
Figure 9.17 Graph of tensile failure stress against filler volume fraction for an
acrylic composite
465
Figure 9.18 Scanning electron micrograph of the two fracture surfaces of a mica-
containing acrylic thermoset that has undergone tensile failure. The mica particle
appears on both fracture surfaces and is at the locus of failure
spherical filler particles under load. They base their approach on the theory for fibre-reinforced
composites developed by Kelly [60] and Outwater [61] by treating the spherical filler particle
as a series of cylinders. Where there is no adhesion between filler particles and the matrix it
is argued that stress is transferred from the matrix to a filler particle by frictional forces only.
The authors thus derive an expression for the average stress (av) in a particle:
av = 0.83p
where: p is the pressure exerted by the matrix on the particle and is the coefficient
of friction.
In our experience however, polymerisation shrinkage at high filler volume fractions will
occur away from filler particles to leave voids around them and in this case no stress
transfer from matrix to filler can occur.
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Filled Thermosets
The maximum load carried by the filler phase at composite failure is then:
av = 0.83pVf
where: Vf is the volume fraction of filler.
Since the filler particles are themselves stress concentrators, the load carried by the matrix
(m) at the failure point of the specimen is not simply the product of the failure stress of
the unfilled polymer (um) and its volume fraction (1 - Vf). Instead, the authors use the
expression:
m = Kum(1 - Vf)
where K is the relative change in strength of the matrix due to the presence of the filler.
Thus, their final expression for the ultimate strength of the composite (uc), for the case
of no filler-matrix adhesion, is:
uc = b + m = 0.83pVf + Kum(1 - Vf)
This equation predicts:
(1) uc is a linear function of Vf.
(2) uc (as Vf approaches unity) is 0.83 p and is independent of d.
If we also consider Griffiths theory then:
(3) for constant Vf, uc is a linear function of d-1/2 where d is the filler particle diameter.
(4) uc (for Vf = 0) is equal to Kum and depends on d.
In this case as Vf approaches zero, the failure of the polymer is governed, not by the
inherent flaws it contains, but by the size of an isolated filler particle, if this acts as a
larger flaw. As filler size decreases then f increases according to the proportionality:
f 1 d1 2
However, once d is smaller than the size of the inherent flaws in the polymer, f becomes
independent of filler particle size (Figure 9.15), which is not made clear in reference
[59]. Over the range of Vf studied, Leidner and Woodhams confirmed predictions (1)
and (2), above, for a polyester resin filled with spherical glass beads, although there
467
was considerable scatter in their data. It is found that for acrylic composites (Figures
9.16 and 9.17) uc is not necessarily a linear function of Vf and this is also the case for
epoxies [25, 58]. Leidner and Woodhams treatment assumes that um is constant,
independent of Vf and related, through Griffiths equation, to the diameter of the largest
filler particle. However, the flaw size, even in a well dispersed composite, may be much
larger than the size of the individual filler particles, because of the finite probability
that two or more particles will find themselves in close proximity to one another. On
this basis, the size of the largest flaw increases with increasing Vf and this yields the
concave plot shown in Figure 9.17. This behaviour was fitted mathematically by Nicolais
and Nicodemo [58].
Leidner and Woodhams also considered the case of good adhesion between filler and
matrix. Stress is transferred from matrix to filler in two ways:
(1) through shear stresses at the matrix-filler interface (s).
(2) through the tensile stress at the matrix-filler interface (a).
When the filler loading is small they argue that the extra load placed on the matrix,
when the matrix-filler bond fails, is small and so b approximates to the case for no
filler-matrix adhesion. At high filler loadings the authors derive the following expression
for the load carried by the filler at composite failure:
b = a + s = (a + 0.83m)Vf
where: m is the shear stress of the matrix.
The load carried by the matrix at failure is given by:
m = aS(1 Vf )
where: S is a stress concentration factor.
The stress concentration around the filler particle means that the average tensile stress in
the matrix is lower than the stress at the filler/matrix interface. Thus, the ultimate strength
of the composite is given by:
uc = (a + 0.83m)Vf + aS(1 - Vf) high Vf
uc = 0.83pVb + Km(1 - Vf) low Vf
This treatment predicts behaviour as shown in Figure 9.19 and this is indeed the behaviour
shown in Figures 9.16 and 9.17 for acrylic composites and in [25, 58, 59].
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Filled Thermosets
Figure 9.19 Prediction of tensile strength against filler volume fraction

(after Leidner and Woodhams)
9.3.4 Fatigue
A material subjected to an applied stress, well below its failure stress under monotonic
loading at conventional strain rates, is nevertheless often observed to fail after a certain
period of time. This process is known as fatigue; if the loading has been constant, it is
termed static fatigue or creep rupture and if the loading has been cyclical, it is termed
dynamic fatigue. Note that there is no demarcation between monotonic loading and static
fatigue experiments, hence the use of the term conventional strain rates in the first sentence.
There are many variables to be considered in the design of fatigue experiments and
particularly so for dynamic fatigue experiments. The principal ones are:
Specimen geometry
Specimen preparation
Wave-form, e.g., sine, square, saw-tooth
Maximum applied stress or strain
Minimum applied stress or strain (it does not have to be zero)
Frequency
Temperature
Environment
469
For brittle thermosets, parallel-sided dumb-bell or waisted dumb-bell specimens are

preferred; simple parallel-sided specimens often fail in the jaws of the testing instrument.
Moreover, in our experience, sample preparation is absolutely critical. Even minor
imperfections and scratches on the surface of the specimen can lead to failure occurring
in times several orders of magnitude earlier than expected.
The result of a typical dynamic fatigue experiment is a plot of maximum applied stress
or stress amplitude against the number of cycles to failure (an S-N curve) and these have
been generated for many polymers for a wide range of the variables listed previously. For
static fatigue experiments results are usually plotted in the form of applied stress against
the logarithm of time to failure. Such plots are often, but not always, linear for unfilled
polymers and once again a large body of data exists from work done on them. In all
fatigue experiments, the relative importance of crack initiation and crack propagation to
fatigue life is often unknown and indeed the former is often ignored. Crack growth is
usually found to obey the Paris equation [62, 63]:
da
= A.K n
dN
where:da/dN is the crack growth per cycle

K is the applied stress intensity factor
A and n are constants
Experiments are usually conducted on specimens in a double-cantilever beam geometry.

K is calculated from a knowledge of specimen dimensions, maximum and minimum
applied load and crack length. Crack growth rate may be measured with a travelling
microscope or from the change in resistance of a thin metal film attached to one face of
the specimen. A typical plot is shown in Figure 9.20 where it may be seen that crack
growth rate is linear for a wide range of K. Once again such curves have been generated
for many unfilled polymers and for a wide range of experimental conditions.
In static fatigue experiments the time to failure is also governed by the time required for a
crack to initiate from a flaw, ti, and the time for the crack to propagate through the specimen
tp. Once again, if initiation is ignored a specimen failure time may be derived from the Paris
equation and this has been applied successfully by several authors. We may speculate on
the physical transition from a flaw into a crack. For example a urethane methacrylate
polymer containing sufficient polyol soft-block undergoes yield prior to failure in a tensile
experiment. The fracture surface of these tensile specimens usually show no evidence that
particulate inclusions are the flaws responsible for failure. Polymerisation of thermosets
rarely occurs uniformly and we hypothesise that even in post-cured specimens microscopic
regions will have different crosslink densities and therefore have different yield stresses.
The regions of low yield stress, it is argued, will undergo yield first and thus lead to the
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Filled Thermosets
Figure 9.20 Typical Paris plot
formation of a crack. In particulate composites, even well bonded ones, the filler-matrix
interface is usually the weakest feature and it may be envisaged that a poorly bonded area
on a filler particle is the flaw which, under stress, leads to the generation of a crack.
An extensive review of this broad area is beyond the scope of this chapter and the reader
is referred to Kinloch and Young [22] and McCrum [40] for a fuller review.
In the case of filled thermosets, relatively little work has been reported in the literature and
of that which has, none has been carried out on identical compositions or under identical
conditions. Examples are given in references [64-72] (dynamic fatigue) and references [27,
73, 74] (static fatigue). In the authors view it is too early for a robust model which describes
fatigue in particulate filled thermosets to be presented from the existing literature. Individual
studies give insight into specific aspects of one specific type of composite, but the area
lacks a comprehensive and systematic study that will enable the individual pieces of the
jigsaw to be assembled into a coherent whole and we are no exception! However, two
aspects of fatigue in particulate composites from our work, which illustrate that this is
indeed a challenging and rewarding area for study will be discussed next.
9.3.4.1 The Effect of Filler Particle Size on Dynamic Fatigue
From the foregoing discussions it would be expected that any changes to the composite
structure, apart from having an effect on static properties would also have some effect on
471
static properties Silica filled
PMMA
Table 9.2 Static properties of silica filled PMMA

SiO2 Particle Volume Tensile Modulus, E KIC
Size (m) Fraction (MPa) (MPa) (MPa.m1/2)
10 0.44 65 8875 1.5
350 0.48 38 8056 2.4
590 0.64 22 13449 1.9
the fatigue life of a particulate composite. A recent study by Antunes and co-workers [75]
has looked at both fatigue crack growth rates and total fatigue life in silica filled PMMA.
Table 9.2 shows some static properties which were measured. The fatigue tests resulted in
much lower fatigue crack growth rates in the composite materials compared to the bulk
PMMA. The bigger particles gave a bigger improvement (reduction) in fatigue crack growth
rate. The same was not true for the total fatigue life, with the bigger filler particles reducing
the total fatigue life. This can be explained when considering that the total life is made up
of both the crack growth and the number of cycles to initiate a crack. When compared
with the static results a trend may be observed. The larger particles result in larger potential
initial defect sizes, from flaws in the silica particles, which then grow to form cracks. In a
tensile test these initiate failure at a lower applied stress. The fracture toughness is measured
from a pre-notched specimen where the notch is much larger than the particle size and this
shows a rising toughness with increasing particle size.
9.3.4.2 The Effect of Filler-Matrix Adhesion on Dynamic Fatigue
It might also be expected that an improvement in bonding between filler and matrix would
lead to an increase in the fatigue life of a particulate composite. Indeed this may be true as
shown in Figure 9.21, where S-N curves obtained in flexural geometry are plotted for a
methyl methacrylate/ethylene glycol dimethacrylate copolymer filled with 60 wt%. The data
for curve (a) are derived from samples in which no coupling agent has been added to the
formulation and those for curve (b) are for specimens prepared from a formulation containing
0.4 wt% (on filler) -methacryloxypropyl (trimethoxy) silane. Clearly, the addition of coupling
agent has increased the failure stress of the composite and therefore at any specific value of
stress, the fatigue life has also been increased. However, now consider the data plotted as
applied stress as a fraction of failure stress against log cycles to failure (Figure 9.22). This plot
contains data for four different coupling agent concentrations (including zero) and it may be
seen that they all fall on the same master curve. Thus, in absolute terms, fatigue life is improved,
but this improvement is only the result of an increase in failure stress. Better coupling for
these composites does not affect the S-N curve in any fundamental way.
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Filled Thermosets
Figure 9.21 S-N curves for two acrylic composites, one containing coupling agent and
one without coupling agent
Figure 9.22 Dry flexural fatigue of silica-filled methacrylate composites containing

different concentrations of coupling agent
473
9.3.4.3 The Effect of Water on Dynamic Fatigue
Water and organic liquids can have a catastrophic effect on the fatigue life of polymers
and particulate composites, with specimens failing several orders of magnitude earlier
than for equivalent specimens tested dry. For example, consider the silica filled
methacrylate composite containing no coupling agent, which was described in the previous
section. Figure 9.23 shows two sets of data obtained from a flexural dynamic fatigue
experiment, one set for the composite tested dry and the other for the composite tested
under water at 20 C. Clearly the effect of water is profound, for example at 50 MPa,
fatigue life is reduced by three orders of magnitude. Now let us consider the effect of
filler-matrix adhesion on dynamic fatigue life in an aqueous environment.
Figure 9.24 is a plot of applied stress as a fraction of failure stress against number of
cycles to failure for the four composites described above that contain 0-0.4 wt% -
methacryloxypropyl (trimethoxy) silane. The upper curve is the master curve for the dry
specimens already shown in Figure 9.23. It may be seen that the fatigue life is moderately
improved by the presence of > 0.1 wt% coupling agent and this improvement is genuine
and not just related to an increase in failure stress over the uncoupled case. It is, however,
only a modest one and still does not compare with the fatigue life of the dry specimens.
Filler-matrix bonding with silane coupling agents is susceptible to hydrolysis [76] and
therefore it is perhaps not surprising that such coupling chemistry is only so modestly
effective in improving fatigue life. In the case of methacrylic thermosets, the filler-matrix
Figure 9.23 Wet and dry flexural fatigue for an acrylic composite
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Filled Thermosets
Figure 9.24 Wet flexural fatigue for silica-filled methacrylate composites containing
different amounts of coupling agent
interface is but one factor, the matrix itself is also sensitive to water. This is illustrated in
Figure 9.25, which shows the S-N curve obtained from a flexural geometry for an
ethoxylated bisphenol A/MMA copolymer. It may be seen that even the unfilled polymer
shows a catastrophic response to water.
It should be emphasised that this discussion is specific to methacrylic thermosets and

need not apply generally. As an example consider the S-N curves in Figure 9.26 for an
epoxy matrix containing 50 wt% silica. These two sets of data were obtained for specimens
in flexural fatigue, one set under dry conditions and the other set under water. It may be
seen that for this system water has no measurable effect on fatigue life.
This phenomenon may be explained by considering the action of a fluid on the surface of
the specimen under water. If the wetting angle of the composite is large then the water will
be able to enter the growing fatigue crack. The action of the water in the growing crack
will cause hydraulic jacking of the crack flanks as the flanks try to close during the unloading
part of the fatigue cycle. This action will result in an increased fatigue crack growth rate. If
however the wetting angle of the composite is small then water will not penetrate down
the fatigue crack to the same degree and the additional hydraulic jacking will not occur.
475
Figure 9.25 S-N curve for MMA/ethoxylated bisphenol A dimethacrylate co-polymer
Figure 9.26 Dynamic fatigue of an epoxy polymer filled with 50 wt% silica
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Filled Thermosets
9.4 Applications
9.4.1 Cost Reduction
Reduced cost is a reason often quoted for adding filler to thermoset resins. However, the
shape and size of a moulding, together with requirements for strength and stiffness dictate
that the moulding should have a certain volume rather than a certain weight. So, although
fillers are typically much cheaper by weight than resins, their higher density means that
volume costs are not reduced by as great an extent.
For example, let resin cost = x kg -1, density = 1.1 g ml-1 then volume cost = 1.1x litre-1.
Let filler cost = 0.1x kg-1, density = 2.6 g ml-1, volume cost = 0.26x litre-1. Thus, a 50/50
w/w mixture would cost 0.55x kg-1 or 0.86x litre-1, i.e., a volume-cost reduction over the
resin of only 22% compared with a weight-cost reduction of 45%.
9.4.2 Modified Mechanical Properties
The modification of mechanical properties by incorporation of fillers has been extensively

discussed in Section 9.3 and, even where this is not the primary aim, the filler being incorporated
for some other purpose, the effect on mechanical performance is always of importance.
Probably the two physical property changes for which fillers are commonly added are to
increase modulus and reduce coefficient of thermal expansion. The increased modulus allows
a thinner part, for example, for equivalent centre span deflection of a rectangular beam:
3
d E 1
= =
d E 2
where d and E are the thickness and modulus of the filled polymer, d and E those of the
unfilled polymer. If at a filler loading of 50/50 w/w an approximate doubling of modulus
is assumed (from Section 9.3), then d = 0.79d, i.e., the volume of material falls to about
80%. So, if a criterion were equivalent deflection and other aspects of the design of the
moulding permitted it, use of filler could permit a volume reduction with an attendant
further cost reduction. Thus, cost in unfilled resin = 1.1x, cost in filled resin = 0.79 x
0.86x = 0.68x, i.e., a 38% cost reduction over unfilled resin. The potential for cost
reduction therefore exists, but it is by no means universal and each resin/filler combination
and each application has to be worked through separately.
Coefficients of linear thermal expansion a, for typical crosslinked thermoset polymers

over the temperature range 10-70 C, (i.e., below the Tg), are in the range 60-100 ppm K-1.
(Coefficients of volume expansion approximate to 3a.) This range of values is high
477
relative to metals, 12-28 ppm K-1 and to ceramics, 0.3-5 ppm K-1. If used to make large
parts, the high a of polymers can lead to excessive dimensional changes in normal use
and, if polymers are used in conjunction with other materials in fabricating assemblies,
differential stresses can be set up as a result of temperature changes. Fillers, having low
expansion coefficients, typically < 6 ppm K-1, can be used to offset the high polymer
values but, because their effect is dependent on volume rather than weight fraction, the
magnitude of the decrease is modest. For example, on a rule of mixtures basis, 33 vol%
of filler (50 wt%) would bring the linear expansion coefficient down to 40-68 ppm K-1,
still considerably higher than that of steel (15 ppm K-1) or aluminium (25 ppm K-1).
The incorporation of filler does reduce the expansion anisotropy in glass-fibre laminates.
The latter use either continuous or very high-aspect-ratio fibre, l/d > 1000 and the simple
rule of mixtures for thermal expansion does not apply, as the expansion is governed
principally by the fibre in the plane of the laminate (x-y direction). The consequence is that
with an increase in temperature, the matrix, because it is coupled to the fibre, is constrained
from expanding in the plane of the laminate and is thus put under compression. In this
state, some stress relaxation by creep can occur. In the direction perpendicular to the plane
(the z direction), the aspect ratio of the fibre is clearly one and the rule of mixtures can be
applied. Thus, for a random chopped-strand laminate of fibre volume fraction 0.2, coefficient
of thermal expansion in the plane of the laminate might be 25-35 ppm K-1, whereas in the
perpendicular direction it would be 50-80 ppm K-1. Incorporation of 50 wt% filler in the
matrix polymer could reduce this to 35-55 ppm K-1.
9.4.3 Exotherm Control
Fillers are also useful for moderating exotherms during the cure of thermoset resins.
High exotherms can occur in thick parts or in mouldings which are polymerised rapidly.
The actual temperature reached depends on the balance between the rate of heat release
(heat of polymerisation, part thickness and rate of polymerisation) and the rate of heat
transfer, the latter depending on the thermal conductivity and thermal capacity of the
mould and to some extent of the curing resin. Lowest exotherms are for slow-cured thin
parts in metal tooling, where the high thermal conductivity and usually high mass of the
latter can lead to approximately isothermal conditions, and the part temperature then
remains essentially that of the tool. Conversely, for rapidly cured thick parts in fibre-
reinforced plastic tooling, where the thermal conductivity is very much lower, near
adiabatic conditions might pertain in the centre of the part. For example, the upper limit
of adiabatic temperature rise for unsaturated polyester or urethane methacrylate resins,
assuming 100% conversion, could be as high as 200-220 C. A special and extreme case
is the foaming of thermosets, where the very low thermal conductivity of the foamed
curing resin itself promotes the development of an adiabatic condition.
478
Filled Thermosets
Thus, in particular circumstances, high exotherms can be generated and these can be
damaging in a number of ways. They are most likely to occur when plastic or soft
tooling is being used. Subjecting the tool to temperatures, which might be in the region
of the glass-transition temperature of the tooling gel coat, can lead to creep in the tooling
polymer with print through of the backing fibre pattern on to the gel coat. It may also
lead to delamination of the tooling gel coat due to differential thermal expansion. Reduced
tool life is the consequence in both cases. If the resin is being used for encapsulation, a
high exotherm can cause damage to the encapsulated component. High exotherms can
also cause distortion in the moulded part, particularly if the part is of non-uniform
thickness. Local hotspots during curing can lead to stress gradients in the final part. In
extreme cases and where volatile comonomers such as methyl methacrylate are used in
free radically cured resins, monomer evaporation and even boiling can occur, leading to
very poor surface finish on the moulding. Exotherm cracking is another consequence of
high exotherms and occurs in highly crosslinked polymers and particularly in thick
sections. If the crosslinked networks are developed to high conversion at high temperature,
then, on cooling, the thermal contraction is sufficient to generate stresses, which in the
presence of stress-concentrating flaws, cause rupture of the polymer.
Fillers can be used to reduce exotherms and moderate some of these extremes of behaviour.
They work by reducing the amount of polymerisable material in the mould and by
providing a heat sink. However, because of their low thermal capacity relative to the
resin/polymer, the effect is moderated, although still very significant.
For example, let resin exotherm = 90 cal g-1 (typical of unsaturated polyester), resin
specific heat 0.45 cal g-1 C-1 and filler specific heat = 0.2 cal g-1 C-1, for a 50/50 w/w
resin/filler mix; exotherm of mix = 45 cal g-1 and specific heat of mix = (0.5 x 0.45 + 0.5
x 0.2) = 0.325 cal g-1 C-1. Thus, the adiabatic temperature rise of mix = 139 C compared
with 200 C for resin alone.
Whilst fillers are beneficial in moderating exotherms and taking out hotspots, it is
important that exotherms are not over-suppressed, otherwise the extent of cure will be
inadequate and will result in the part having poor green strength out of the mould.
This in turn will necessitate post-curing at elevated temperature. It is necessary for the
exotherm to attain the region of the polymer Tg to allow sufficient molecular mobility
for the crosslinking reactions to proceed to upwards of 95% conversion. Undercuring
leads to low polymer modulus and strength, depression of the Tg/HDT and a tendency
subsequently to warp.
Although the moderating effect of fillers can reduce the extent of cure at the high-
conversion final stage, their presence can enhance gelation in the early stages of cure.
The filler surface, through adsorption and reactive coupling of resin components,
effectively participates in the branching and network generation such that the gel point
479
(where an infinite network exists) occurs at a lower conversion and in a shorter time. For
free radically cured resins exhibiting auto-acceleration or the gel effect (unsaturated
polyesters, methacrylates), the fast conversion stage of the cure is then triggered.
9.4.4 Shrinkage Control
Fillers are also used to counteract excessive shrinkage in some thermoset resins. Shrinkage
occurs on curing thermoset resins because the polymers have higher densities than the
low-molecular-weight monomers or precursors. This is a consequence of the Van der
Waals distances separating the reactive groups of the low molecular weight species being
replaced by chemical bonds of shorter length as curing proceeds. Thus, the overall
shrinkage is dependent on the molecular interactions in the liquid uncured state and on
the number of functional groups that react to form new chemical bonds in the cured
polymer. Shrinkage can be expressed in absolute terms as the percentage change in volume
going from uncured resin to cured polymer at the same temperature, thus:
Shrinkage = 100(Vp Vr)/Vr = 100(1(Pr/Pp))
where: V is the volume

P the density
r the uncured resin and
p the cured polymer.
Polymerisation shrinkages range from values of 3-6.5% for epoxies, 6-9% for unsaturated
polyesters to 10-12.5% for urethane methacrylates. The actual volume-change profile
shown by a curing thermoset is quite complex. The absolute polymerisation shrinkage as
a function of conversion is offset in the early stages by the thermal expansion of the resin
due to any elevated initial mould temperature and expansion of the resin/curing polymer
mixture due to the polymerisation exotherm itself. After the exotherm maximum has
passed, the polymer then undergoes a cooling contraction. This behaviour is quite distinct
from that of thermoplastics, where mould shrinkage is due to the melt being cooled by
contact with a cooler mould.
The consequences of the polymerisation shrinkage of thermosets depends on the moulding

technology being employed but are most severe in closed-mould technologies such as
casting, compression moulding (sheet moulding compound, dough moulding compound),
RTM and structural-reaction injection moulding, and less so in open-mould processes
such as hand-lay and filament winding. In developing formulations for closed-mould
processing, shrinkage is often measured as a linear shrinkage, cold mould to cold part,
in which the distance between two etched lines on the mould is compared with that
480
Filled Thermosets
transferred to the moulding. This is convenient for thin essentially planar mouldings but
it does not take into account any shrinkage in the perpendicular z direction, and it is
the latter that has a marked effect on the surface finish.
A small amount (1-2%) of shrinkage in a moulding can be desirable as it aids demoulding,

but excessive amounts have increasingly deleterious effects. For example, loss of
dimensional accuracy, sink marks over ribs or in thick sections, cracking in thick parts,
fibre print-through in laminates and undesirable surface finish effects due to separation
of the moulded part from the mould surface before full conversion is reached are all
potential consequences of high polymerisation shrinkage. The shrinkage can be
counteracted by incorporation of thermoplastic or inorganic fillers. Thermoplastic
additives are widely used in the free radically cured styrene or methacrylate-based resins,
and offset the shrinkage by the generation of voids in the thermoplastic phase during
polymerisation [77-81].
Fillers work by either simply providing inert bulk but again their relatively poor volumetric
efficiency moderates the benefit achievable, or by expanding during the exotherm through
liberation of water, for example. In the latter case zero shrink can be attained as with
the thermoplastic additives [82]. Used for their inertness, fillers at 50/50 w/w will only
reduce the shrinkage of the mix to about 70-75% of that of the unfilled resin and, even
increasing filler to 60/40 w/w, which is about the limit for viscosity reasons, will only
drop it to 60-65% of the neat resin. Thus, 50/50 w/w filled compositions of urethane
methacrylates will still show shrinkages of about 8.5% and of unsaturated polyesters
about 5%. At these loadings of filler, the interparticle spacing is such that, if the interface
is perfectly bonded, the interface and polymer are in a state of hydrostatic tension. If the
interfacial adhesion is poor, void formation can occur due to polymer shrinkage away
from the filler-particle surface. Only if filler volume fractions are low is the interface in a
state of compression due to polymerisation shrinkage.
9.4.5 Processing Aids
Fillers can help to reduce air entrainment when processing fibre composites by reaction
injection moulding (RIM) or pultrusion. Low-viscosity resins (< 0.05 Pa-s) have the
advantage of rapid penetration of fibre rovings and wetting of individual filaments.
However, the attendant disadvantage is that, in RIM, as resin is injected into the preplaced
fibre mat, resin wicks along the rovings ahead of the main resin front, and can result in
air bubbles being bypassed and thus entrained at the interstices where rovings cross one
another. Low resin viscosity also means that the resin pressure in the tool is essentially
atmospheric and there is no driving force for displacement of the bubbles. Incorporation
of filler provides competing surface, reduces wicking and gives a more stable flow front.
481
The increased viscosity from filler addition also raises resin pressure within the tool
cavity further aiding elimination of air.
The same effect is seen in pultrusion using the wet-bath process. Resin-impregnated fibre
rovings are pulled through a heated shaping die where the curing takes place. If resin
viscosity or fibre volume fraction is too low, resin can run back down the fibre rovings
and the entrance to the die does not then act as a tight restrictor to squeeze out air fully.
Increased viscosity through addition of filler to the resin, reduces resin backflow and
increases the packing in the front end of the die. Air is then effectively squeezed out as
the rovings are pulled into the die and a high-quality profile is produced. If high filler
loadings are used to fill the front end of the die in pultrusion, a good profile can still be
made out at lower glass loadings. If the reduced stiffness and strength resulting from
lower glass is acceptable, this provides a means of lowering costs.
9.4.6 Flame Retardants
Lastly, a major use of fillers is for flame-retardant applications, with aluminium hydroxide
being extensively used, especially in unsaturated polyesters. This is dealt with in depth in
Chapter 6.
9.4.7 Metal Fillers
The use of semi-metallic soft tooling has increased in recent years due to an increased
demand for more complex dies, reduced costs and increased use of rapid prototyping.
Chung and co-workers [83] have looked at the effect of adding aluminium short fibres
and cast iron chips to a heat-cured epoxy casting resin. The short aluminium fibres
were around 5 mm in length and the cast iron flakes of more random size up to around
150 m and they looked at the effect on the tensile strength, wear resistance, shrinkage
and thermal conductivity. They found that the tensile strength was generally lower
with aluminium flakes than that of the epoxy due to voids or bubbles thought to have
been introduced during the mixing process. The tensile strength increased quite markedly
with the cast iron flakes however and this was thought to be a result of the high density
of the mixture eliminating such bubbles. It is also possible that the high reactivity of
aluminium could react with components in the epoxy to cause foaming during cure at
high temperature. The wear resistance showed a clear increase as more aluminium
flakes were added; the maximum wear resistance though was found in the cast iron
flake filled material. Shrinkage was also found to decrease as the filler content was
increased though the metal fillers could not be added easily at more than 50% by
volume as the high viscosity made mixing very difficult. Not unexpectedly, the thermal
482
Filled Thermosets
conductivity increased as more aluminium fibres were added with the epoxy having a
conductivity of around 0.23 W/mK and the filled composite around 1.82 W/mK at
50% aluminium fibre content. Tools were successfully tested using the aluminium fibre
composite to mould wax patterns for investment casting. This was done with a metal
mould tool having an aluminium fibre/epoxy soft tool insert.
More work is being done on metallic fillers to investigate the filler/matrix adhesion, as
other workers have found that additions of copper, zinc and aluminium produce quite
varied results when tested in tension. Indeed the authors have also found that zinc will
react readily with dicyandiamide, which is commonly used as a hardener in epoxies.
The reaction can cause severe foaming and a change in the structure of the cured
epoxy at the interface with the zinc.
9.4.8 Structural Adhesives
The use of structural adhesives in the automotive sector for bonding bodyshell
structures has often been highlighted as a major growth area [84-86]. These high
strength adhesives are a group of adhesives that play a truly structural role in the
construction of the bodyshell. The adhesive is the major connector between panels
and has to be capable of supporting high loads throughout the life of the vehicle. The
most common structural adhesive in this type of application is high toughness mineral
filled epoxy. They have the ability to bond directly to oil contaminated steel and the
toughened variants can provide the necessary impact performance for many
applications. To date however, their use has been very limited due to the lack of the
information about their long-term durability. While the strength of bonded joints, as
measured in a simple lap shear test, is equal to or greater than that of their spotwelded
counterparts, when loaded in warm, humid environment the performance can be
significantly poorer.
The improvements in performance have been largely due to the addition of fillers,
often wollastonite and talc in combination with rubber toughening additions. This has
produced a family of adhesives which have excellent toughness up to 50 C and down
to 40 C.
Acknowledgements
The authors would like to thank ICI for permission to publish and W.S. Balch and S.H.
Rogers for allowing us to present some of their work and for many useful discussions.
483
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10
Composites Using Nano-Fillers
Roger N. Rothon and Chris DeArmitt
10.1 Introduction
Although they have been known for a long time, composites using extremely small (nano-
particle) fillers have until recently been of minor commercial interest. This is now changing,
and nano-filler technology is currently experiencing a period of intense activity, mainly
focussed on plate shaped particles derived from layer silicates. Although present
commercial use is small, it is forecast to grow rapidly. One estimate puts the demands for
layer mineral based nano-composites as several million tons by 2010 [1]. Even with the
low filler levels involved, this would mean tens of thousands of tons of nano-filler. There
are, however, many challenges to be overcome if this is to be achieved.
Some aspects of the technology are covered in other chapters of this work, but it was
considered that the topic was of sufficient current interest to warrant its own chapter.
However, it must be stressed that what is presented here is only a snap-shot in what is
a rapidly changing and developing technology.
10.2 Scope
The term nano-fillers is vague and often abused in the literature. For the purposes of this
chapter, it is restricted to particles which can reasonably be described by the adjective nano-
and which are also of low enough cost to be considered for conventional polymer applications.
While there is no precise definition, nano-fillers can be considered as particles which,

when dispersed in polymers, are very small in at least one dimension. This concept is
pushed quite far in some of the literature, with particles of up to at least a hundred
nanometers being described as nano-particles. A reasonable working definition would
seem to be that at least one dimension of the effective particle, when dispersed in a
polymer matrix, should be no more than 20 nm, or 200 . As a result, the specific
surface area, which plays a significant role in the effects observed, will be at least 150
m2/g. The term effective particle is used to eliminate fillers, such as carbon blacks, where
the primary particle could be in the specified range, but are strongly aggregated into
larger structures, that become the effective particles.
489
10.3 General Comments
Extremely small particles are not that difficult to prepare, and have been known for a very
long time, usually prepared in the forms of sols or smokes (fumes). The challenge is to
isolate them in a form that is easily handled and readily dispersible. Some type of
agglomeration/aggregation is generally used to isolate the particles, but this is usually partly
irreversible, resulting in products that cannot be redispersed into a polymer in their nano-
particle form. Carbon blacks and most fumed and precipitated silicas are examples of such
products. One way around this is to form the particles directly in the polymer, or in a
liquid monomer, but this has restricted applicability, partly because there are usually co-
products from the particle formation process to deal with. It is only recently that sufficient
commercial incentive has been identified to focus real attention on this problem.
Because of their nano-dimensions, the surface is particularly important for nano-fillers.

Their specific surface area is one to two orders of magnitude higher than for conventional
fillers. For example, while most minerals fillers would have specific surface areas in the
range 1-10 m2g-1, a spherical silica nano-filler, with a diameter of 10 nm, would have a
specific surface area of about 250 m2g-1, and a nano-clay can have a specific surface area
of 1,000 m2g-1 or more. Although nano-fillers are used at significantly lower volume
fractions, the total surface present in a composite is still much higher than for most
conventional fillers. Thus, the silica nano-filler at 5% filler level would contribute about
1,250 m2 of surface to 100 g of a composite, compared to about 200 m2 for a fine
calcium carbonate used at 40% w/w. The amount of surface modifier present is also a
very significant factor. It can easily be 30-40% by weight of the nano-particle, which
even at 5% filler level, can be over 1% of the total composite.
This high surface area can have profound effects on the composite, as the presence of a
mineral surface can significantly modify the properties of the polymer in its near vicinity.
The amount of modified polymer is small with most conventional fillers, but can be
quite significant with nano-particles (up to about 20% of the polymer can be affected)
and its presence has to be considered in calculating composite properties. Finally, the
high surface area can have deleterious effects on polymer stabilisers and composite stability.
This is often overlooked, but it is becoming apparent that new stabiliser systems may be
needed if optimum composite performance is to be achieved [2]. The influence of the
filler surface on thermoplastic composites is covered in some detail in Chapter 8.
10.4 Nano-Filler Forms
Three potential forms of nano-particle can be distinguished, depending on how many

dimensions are in the nano-range. These are regular, rod-like and platy and are illustrated
in Figure 10.1.
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Figure 10.1 Three basic types of nano-particle
All three types have some current interest as fillers. The platy ones (mainly in the form of
layered silicates) are receiving by far the most attention, and will be focussed on in this
work. The various forms are briefly discussed next.
10.4.1 Regular Shapes
The most commonly met regular nano-fillers are silicas and titanias. These are generally
made by controlled precipitation in the presence of surfactants, to prevent agglomeration
and fusion of particles. Sol-gel processes starting from metal alkoxides are often utilised.
Some very fine particles produced by more conventional gas phase processes are just
within the definition used for this discussion. For example, fumed silicas, with diameters
of under 10 nm are available.
With the precipitation methods, organosilanes can be added during the precipitation, so
that they become built into the surface layers. In order to obtain good dispersion, the
precipitation is sometimes carried out in the host polymer, or its pre-cursor, such as a
monomer. Another method of achieving the same result is to directly transfer (flush) a
stabilised suspension, resulting from precipitation, into a liquid monomer. By the use of
such methods, high loadings can be achieved in some polymers, such as poly(methyl
methacrylate (PMMA). More details can be found in various publications [3-6].
In principle, similar things can be achieved with other materials that can be precipitated
in fine form, such as calcium carbonate (PCC), although little seems to have been done
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with them so far. In the case of PCC, acid-based surface modifiers would probably need
to be used in place of the organosilanes.
One of the notable features of composites produced with such fillers is high transparency,
as the particles are too small to scatter visible light. On present information, the
applications for this type of nano-composite seem to be specialised, and they have not,
so far, become of widespread interest.
Part of the reason for their relative unimportance is their high cost. Their main potential
applications to date seem to be at conventional (relatively high) loadings, where the
amount of expensive surface modifier needed is very significant. Systems, such as the
PCC-based ones, have the potential for significant cost reductions and could repay
further investigation.
In a particularly interesting recent study, Nelson and co-workers examined the use of
surface modified spherical silica particles of various sizes in PMMA and in polystyrene
(PS) [7]. They found significant strength and modulus increases at low loadings of the
smallest sizes (under 10 nm). This suggests that there may be more scope for these materials
than realised to date. Low levels of PCC have also been reported to give significant
improvements in modulus and impact strength of polypropylene (PP) [8]
There are some other products, which fall into the size definition, but are currently too
expensive to be considered as fillers for other than very specialised applications.
The ultimate regular nano-particles are probably the carbon fullerenes [9] and the
polyhedral oligomeric silsesquioxanes, or POSS [10-12]. The fullerenes, usually known
as buckyballs, are soccer-ball shaped 60 or 70 carbon atom clusters, under 1 nm in
diameter. The POSS materials are similar, extremely small, silica cages, carrying reactive
and/or non-reactive organic groups. The cost of the POSS products are predicted to fall
to levels where they can be considered for large-scale polymer applications as production
is scaled up and this could be a very interesting development.
10.4.2 Rods, Fibres, etc.
There are a number of products which are described as nano-fibres or nano-tubes. These
are mainly carbon or metallic in nature and principally intended for electrical applications,
where they produce conductivity at significantly lower volume fractions than more
conventional conductive fillers. Most of these products are several tens of nanometers in
diameter and so are outside of the definition of nano-particles adopted for this discussion.
Pyro-graphitic fibres are a typical example. Their diameter is from 60-200 nm, with
specific surface areas of 100-20 m2/g, respectively [13].
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The finer products are usually too expensive to be considered as commercially viable fillers
and are generally produced in a tangled, or birds nest, form making dispersion difficult.
The nearest products to true nano-fibres are probably fullerene derived single and multi-
wall carbon tubes, which can have diameters as small as 10 nm and aspect ratios of several
hundred. They have excellent theoretical reinforcement potential, but problems of dispersion,
maintenance of aspect ratio and control of surface chemistry have to be overcome for this
to be realised [14]. One important feature of this type of filler is its electrical conductivity
and exceptionally high thermal conductivity. The high aspect ratio gives percolation at
much lower volume fractions than observed for conventional fillers. Currently, these are
niche products produced in small quantities at high price.
10.4.3 Platy Nano-Fillers (Nano-Clays and Related Materials)
The main commercial interest is currently in composites based on platy nano-particles

[15]. This is due to a combination of several factors. The first is that they can be obtained
from relatively inexpensive raw materials, especially certain clays. The second is that the
combination of shape and high specific surface area gives rise to some useful effects at
relatively low loadings (below 10% w/w). This not only reduces the overall cost, it allows
products to be made with lower density and better surface finish. The useful effects that
can be obtained include: gas barrier properties, fire retardancy, increased stiffness and
increased heat distortion temperature (HDT). Finally, it seems to be easier to overcome the
isolation, handling and redispersion issues with platy particles than with the other types.
Conventional platy fillers, such as mica and talc, are well known, but the plates are quite
thick and the aspect ratios accessible are limited, if the other dimensions are to be kept to
reasonable levels. The plate thickness also means that quite high filler loadings are still
required. Certain layer silicates, both natural and synthetic, allow very thin plates, with a
high aspect ratio to be produced, while keeping the other dimensions to a reasonable level.
The materials of most interest are made up of alumino-silicate layers which are imperfect
and so carry a negative charge, neutralised by various cations, usually sodium and calcium,
intercalated between them. The layers themselves are nano-sized in thickness, with the
other two dimensions being such that plates of aspect ratio in the range 50-1,000 can be
obtained, without the other dimensions being so large as to pose problems.
Montmorillonite clay, with a plate thickness of about 1 nm, is particularly useful.
The challenge is to both separate these plates and make them compatible with (wetted by)
a polymeric matrix. Various swelling agents can enter into the space (gallery) between the
clay layers, pushing them apart. These agents include water and polar organic species such
as alcohols and glycols. The swelling agents can also carry soluble species, which can react
with the clay surface, or monomers that can be subsequently polymerised. The spaces
between the plates are known as galleries and materials that penetrate them as intercalants.
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There are a number of potential ways of incorporating and dispersing swollen layer
silicates into polymer matrices. Some of these are outlined in the scheme in Figure 10.2.
Some make direct use of the dispersion in which the swelling took place, but these are of
restricted applicability. In many practical situations, it is desirable to isolate a dry solid
for use in subsequent compounding procedures and this type of processing will be
concentrated upon here.
Figure 10.2 Some processing strategies for making nano-clay polymer composites
There are several important factors in producing a suitable dry clay. The most important
are that it should not collapse back into its original state on drying, and that the plate
surfaces are converted into an organophilic state to make them compatible with the intended
polymers. Fortunately, an established technology can be used for this purpose. This is
organo-clay thickener technology, in which suitable clays are swollen in aqueous solutions
of organic amines and their derivatives. These additives ion-exchange with, and displace,
the gallery cations. The basics of this procedure are illustrated in Figure 10.3.
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Figure 10.3 Much simplified view of the expansion of the layer silicate gallery
resulting from ion exchange with a long chain organic cation
Two other factors have to be considered. Firstly, the clay needs to have a suitable
purity and plate diameter. This is achieved by careful selection and processing of the
raw material but can add considerably to the costs. Secondly, any salts produced from
the cations by the ion-exchange process usually have to be removed from the product
by extensive washing.
The key to the performance of nano-clays is how well they can be dispersed into a
polymer matrix. Before discussing this, the types of dispersion that can be achieved
need to be considered. Three extreme types of structure are usually recognised. These
are: normal clay stacks (sometimes known as micro-composites), intercalates, where
there is some polymer between the plates, but the stack morphology is preserved,
and exfoliates with completely delaminated and dispersed nano-particles. (In practice,
dispersed structures known as tactoids are also frequently observed. These are small
stacks of intercalated plates). The three main types of structure are illustrated in
Figure 10.4. The fully dispersed form is most useful for the majority of commercial
applications, and is the one that is normally aimed for, although conventional
processing methods often give mixed structures. A further sub-division of the fully
dispersed state should also be made, this is into oriented and randomly aligned states,
as also shown in Figure 10.4. For many applications, it is the oriented form that
gives the best results.
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Figure 10.4 Different states of dispersion for a layered silicate in a polymer composite
Some brief description of the methods used to characterise the type of dispersion is also
needed. Two approaches are commonly used, X-ray diffraction and electron microscopy.
The X-ray method relies on the fact that the layer silicate diffraction pattern contains a
readily identified peak, the position of which is directly related to the inter-plate spacing.
When intercalation takes place (as with the organic amines), this peak moves in response
to the increasing spacing. When complete delamination and dispersion (exfoliation) take
place, this peak is lost. These concepts are illustrated in Figure 10.5. While apparently
very simple, this method is far from perfect and must be used with caution.
Electron microscopy data can be more informative, but also needs to be treated with
care. Some structures seen by this method are shown in Figure 10.6. It is worth noting
that while most of the literature, especially theoretical treatments, implies flat plates,
curved structures are often seen in real composites.
Intercalation of polymer and subsequent delamination is a difficult process, and the best
results obtained to date have been where the organo-clay has been dispersed into a
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Figure 10.5 Schematic illustration of the use of wide angle x-ray diffraction for
studying the dispersion of montmorillonite clay plates. (a) sodium form, (b)
quaternary ammonium form and (c) quaternary ammonium form dispersed in polymer
monomer prior to polymerisation. This was the basis of the first commercial applications
by Toyota [16], who developed nano-clay/polyamide composites. A very neat approach
is possible here, with the introduced organic moiety becoming an integral part of the
polymer matrix. In the first step, an amino-acid is ion-exchanged into the clay galleries.
The treated clay is then dispersed into monomer prior to polymerisation. The chemistry
of this process is illustrated in Figure 10.7, where it can be seen that the organo-treatment
is acting as a coupling agent. (Coupling agents are discussed in detail in Chapter 4). The
polymer is sometimes said to be tethered to the clay plate in this type of structure and the
process is sometimes called polymerisation filling.
Unfortunately, the polymerisation filling processes are not so easy with many polymer
types, although they are apparently being used for some polyolefins, with polymerisation
catalysts being carried on the surface of the clay plates [17]. They also tend to put the
technology into the hands of the polymer producers and other, more complex, processing
methods are needed for general application. Most interest has been with what is known
as melt intercalation. In this process, an organo-clay is added to a polymer melt during
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Figure 10.6 High resolution electron micrograph of a cross-section of a nano-clay/

polypropylene composite illustrating some intercalated, partly dispersed clay stacks (tactoids)
(Micrograph kindly supplied by Monica Celotto)
Figure 10.7 Illustration of how in situ polymerisation can lead to grafted polyamide
chains (one plate surface only shown for clarity)
498
the compounding process. If the correct organic treatment is present and the compounding
conditions are carefully controlled, a significant amount of intercalation and delamination
can be achieved. It is rare for complete delamination to result from this process however.
As a result, somewhat more organo-clay is required to achieve the same level of
performance as compared to the polymerisation method.
This melt processing area is one where a considerable amount of effort is currently being
expended and where the situation could be significantly different in a few years time.
Among the avenues being explored are:
Optimisation of the compounding equipment and procedure [18]

Use of ultrasonics to enhance dispersion [19]
Use of a supercritical fluid, such as carbon dioxide, to aid processing [20]
Use of co-agents to improve incorporation and dispersion [21]
Freeze drying [1]
There is also some interest in what is known as one-pot compounding, in which the clay
is ion-exchanged, delaminated and dispersed during the compounding process itself [22].
One of the problems with this approach is the formation of metal salts arising from the
ion-exchange. Alternative intercalants are being examined and may offer a possible way
of overcoming this [23]. A further refinement is the addition of water, or solvent, swollen
clay direct into the polymer matrix [24].
10.4.3.1 Particle surfaces and the organic intercalant.
As discussed in detail in Chapter 4, the level of interaction between a particle and polymer
matrix has a big impact on the processing, dispersion and final properties of filled
composites and various organic treatments are used to obtain optimum results. These
treatments have to be carefully designed to suit the filler surface and application.
The same situation exists for nano-clays, but is complicated by the presence of surface-
active species used in their preparation. These organic treatments comprise a significant
part of most nano-clays, and fulfil a number of very important functions. Thus, they
increase the gallery spacing, making it easier for other species, such as monomers or
polymers, to intercalate. The increased spacing also makes it easier to disperse, or
delaminate the structure. In the simplest cases, these intercalants would also provide the
compatibility and interaction with the polymer matrix described previously. It is thus
obvious that the nature and amount of intercalant have to be chosen carefully and
controlled. For ease of treatment, it is also helpful for the intercalant to be water soluble.
499
These competing demands are difficult to reconcile and it is by no means clear that
optimum surface treatments have yet been developed. Indeed there are reports that some
conventional intercalants can degrade during processing and even initiate degradation
of the matrix polymer [25].
Virtually all of the reported work to date has been with organic species such as amines
and amino-acids, which can be dissolved in the form of salts and then form onium
compounds by ion-exchange with cations on the clay surfaces. The main variables are:
the number of chains attached to the nitrogen of the amine, (i.e., is it a primary, secondary,
tertiary or quaternary amine?), the length distribution and branching of these chains,
whether they are simple hydrocarbons or carry some other functionality such as carboxylic
acid or unsaturation and finally, their concentration on the filler surface.
Some general comments can be made. First is the level of treatment. The current approach
relies on ion-exchange with the clay surface to anchor the additives. The amount of
exchangeable cation varies with the clay source, but is usually 100 milli-equivalents per
gram (meq/g) or less. This will result in a much lower density of surface attachment and
less tightly packed chains than is normal with filler treatments. Thus a fully delaminated
and dispersed clay will have a specific surface area of over 1,000 m2/g and would need an
ion exchange capacity of up to 750 meq/g to form a fully packed surface layer (depending
on the bulkiness of the organic intercalant). At a level of 100 meq/g, there is likely to be a
considerable amount of free surface. On the other hand, the levels of additive needed for
such a packed layer would be very high (up to about 200% w/w on clay).
It seems that patchy coverage, with some available plate surface is helpful in getting
intercalation and dispersion. The intercalation of polymeric species between the silicate
plates seems at first sight to be unlikely, due to extra constraints imposed on the polymer
chains. Close analysis suggests that intercalation can become thermodynamically
favourable under certain conditions. In melt processing the main driving force appears
to be interaction between the polymer and the filler surface. It also seems that having too
strongly packed an interlayer of surfactant can actually impede polymer penetration and
be detrimental.
Secondly, we need to consider the position of the modifier. The clay chemistry dictates
that conventional onium ions will only become firmly attached to the basal plate surfaces,
leaving the edges and other faces untreated. These untreated surfaces will probably have
sites amenable to treatment with more conventional additives, such as organo-silanes.
Thus, mixed surface treatments may be most effective in covering all active surface sites.
Indeed, it has been reported that all common mineral fillers are amphoteric to some
extent and therefore have sites for adsorbing both acidic and basic surface treatment
additives [26].
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There is also the question of the method of attachment. Currently this is by onium ion,
resulting from the ion-exchange process. As mentioned previously, there is some concern
over the thermal and hydrolytic stability of this type of attachment and alternatives are
being sought.
Finally, the role of added coupling agents needs to be considered. For nano-clays in
polypropylene, it is common practice to add maleated PP to aid delamination and enhance
adhesion and thereby improve some properties [27]. The full consequences of adding
materials such as maleated PP are almost always overlooked. For example, the amount
of maleated PP must be adjusted depending upon the surface area of the filler. Even more
importantly, it is not generally recognised that the maleated PP reduces the thermo-
oxidative stability of nano-composites. This is probably due to a combination of two
factors. Firstly, carboxylic acids such as stearic acid destabilise PP, as seen by a reduction
in oven ageing time for PP containing a standard hindered phenolic antioxidant package.
Secondly, maleated PP is made by grafting maleic anhydride onto PP using peroxide
initiators. These peroxides may not be fully consumed in the grafting process and residual
peroxides are expected to have a very deleterious effect on the oxidative stability of the
material. One recent unpublished study by Sanit in the Electolux laboratories in Italy
showed that unfilled PP with normal stabilisation levels had an oven ageing time of
820 hours at 150 C, whereas the same PP had an oven ageing time of only 250 hours
once 22 weight% of maleated PP had been added.
One can expect that clay-based nano-composites may show three modes of destabilisation.
That due to transition metal impurities in the filler, that due to the organic intercalant
and that due to maleated PP (if present). This may necessitate the addition of significant
extra antioxidant, adding to the overall composite cost.
10.4.3.2 Alternatives to Natural Clay-Based Particles
While attractive on cost grounds, products from natural clay sources have some
limitations. First, extensive purification is needed, removing some of the cost advantage.
Secondly, the clay will usually have some colour, which will be apparent at high loadings,
or in thick articles. Thirdly, the surface chemistry may be sub-optimum for some purposes.
This is especially true of the use of ionic bonding of the intercalant. Finally, the plate
aspect ratios and concentration of ion-exchangeable sites are quite limited.
Synthetic layer silicates, particularly fluoro-micas, are starting to be exploited where

these issues are a real concern. There is also interest in other layered inorganics: especially
magnesium salts like hydrotalcite, which can be synthesised as very thin plates and for
which other forms of modifier attachment are possible.
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10.4.3.3 Composite Effects and Applications
The principal exploitable properties that nano-plates can bring to a polymer composite
are shape related, with the main ones being:
Increased stiffness
Increased HDT
Reduced gas and fluid permeability
Reduced flammability.
The main attraction is that, because of the high surface area and aspect ratio, these
benefits are potentially obtainable at much lower volume fractions than with most other
established fillers. This has several potential advantages, notably: lower cost, lower density,
less opacity, and potentially less reduction in other properties such as impact strength.
Because of viscosity effects associated with the plate shape and potential particle damage,
and difficulties in obtaining and maintaining exfoliation, the practical loading level is,
however, limited to about 10% which severely restricts the absolute property values
achievable. These various aspects are discussed further next, with the emphasis on
thermoplastic applications, which are currently of most interest.
10.4.3.4. Modulus, heat distortion temperature and strength
Low levels of nano-plates have a big effect on these properties in thermoplastic composites,
and this was the first area to arouse interest [16]. Typical results are presented in Table 10.1
and show how much benefit can be achieved at very low loadings, and when conditions
favour exfoliation, dispersion and strong interaction with the polymer.
Table 10.1 The effect of an amino acid based nano-clay in a Nylon 6 polymer
Flexural Modulus Tensile Modulus Heat Distortion
Wt% of nano-clay
MPa MPa Temperature C
0 2,800 2,900 55
2 4,320 4,400 125
However, the real test is how the nano-plates compare with other reinforcing fillers like
talc, mica and glass fibre. Currently there is much controversy over the ability of nano-
plates to provide real benefits in properties such as stiffness, compared to conventional
reinforcing fillers, especially glass fibres. Present results are very mixed and complicated
502
by factors such as the amount of dispersion and orientation achieved and by nucleation
effects. As an example, Motha and co-workers have found low levels of talc to be able to
give similar modulus increases in polypropylene to similar levels of a nano-clay [28].
Most interest is in thermoplastic applications, but these are probably the most complex
systems to model. The effect of a filler can arise from a number of means:
1. The simple volume fraction of strong, non-extensible, material present.
2. The shape of the particles.
3. Changes in any polymer crystallinity arising from the presence of the particles.
4. Changes in the polymer morphology near to the filler surface, creating a third phase
(interphase).
5. The strength of interaction between the particles and the polymer.
6. Secondary effects due to adsorption of stabilisers, promotion of degradation, etc.
The relative importance of these factors will vary markedly from system to system and
even from one property to another. As an example, not all thermoplastics contain
crystallinity, and filler polymer interaction will be more important in high strain
situations. They also make the interpretation of much of the present experimental data
relating to nano-clay filled composites difficult. It is thus appropriate to look at
theoretical predictions first.
Starting with the simplest case, where there are no changes in crystallinity or polymer
morphology and no secondary effects to consider, the effect of anisotropic fillers on the
modulus and strength of a polymer composite (but not impact strength) can be described
by a number of equations, the most successful approach being that of Halpin [29] and
Tsai. The reader is referred to works, such as those by Chow [30] for a detailed discussion
of what is a very complex topic. The authors much simplified view is presented next.
The main features for the limiting case where the plates are fully dispersed plates are:
The stiffness and strength should be predictable by the rule of mixtures, i.e. the
volume fraction of filler will be the ultimate determining factor. In practice this ideal
state is very difficult to obtain, due to various processing problems, especially affecting
dispersion and particle alignment. (Note, the linear rule of mixtures also only strictly
applies for two components that have the same Poissons ratios and have interfacial
coherence [31]).
503
With plates or fibres, the main effects will be in the plane of the particles. (Flexural
testing is a special case, where the best effects can be obtained with the particles
oriented normal to the applied force).
Modulus will increase with aspect ratio, up to a certain limiting value. This aspect
ratio limit will depend on the modulus difference between the plate and the
polymer, but is about 100:1 for the types of material with which we are concerned.
The actual amount of modulus increase will depend on the plate modulus. Data
for the relevant moduli of filler particles are scarce, and somewhat inconsistent,
but all mineral fillers are much stiffer than common thermoplastics.
Yield strength will also increase with aspect ratio. Again, it is expected that a
limiting value will be reached at similar aspect ratios (about 100:1) as for the
modulus.
Modulus is little affected by filler/polymer interaction, while it does play a major

role in composite strength. Strong interaction is needed to maximise strength,
and would normally be achieved by the use of a suitable coupling agent. As
discussed in Section 10.4.3.1, the surface of nano-clays is complex, due to the
presence of intercalation agents, and in many cases may not give optimum results.
In real systems, the other factors described previously may come into play. Thus:
Polymer close to a filler surface can become modified by that surface. In elastomers
and thermoplastics, this usually means an increase in rigidity. With conventional
fillers, the amount of modified polymer is usually small enough to be ignored,
but calculations show that up to about 20% of the polymer could be affected by
the surface of nano-particles. One could thus expect an additional increase in
modulus and yield strength from this source.
It is well known that fillers can affect the level and type of crystallinity in polymers
such as polypropylene and polyamides. Nano-clays are known to promote
significant changes in crystallinity in polyamides [32]. Mixed results have been
reported for polypropylene, with most studies reporting no changes in the level
of crystallinity, but some orientation of the polymer crystallites. Where these
effects are present, they could contribute to the modulus and yield strength.
One of the biggest problems with plates and fibres is in achieving good dispersion
and alignment while avoiding degradation in aspect ratio during processing.
Alignment efficiency varies very significantly with the type of processing, being
especially high in extrusion processing. In injection moulding and some other
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processing methods, the orientation varies throughout the thickness of the sample,
being good near the surface and poor in the centre. In this case, there can be
marked effects of sample thickness.
The flexural modulus is of most interest in many applications. This is much more
complex than tensile, compressive or shear moduli. It not only has elements of
both tensile and compression, but is very much influenced by particle orientation
and by the surface layers. These are often polymer rich, an effect that becomes
greater as the filler size increases.
To summarise:
1. From the rule of mixtures predictions, nano-plates should not give higher modulus
and tensile strength than is obtainable from the same volume fraction of thicker
plates and fibres of the same modulus, strength and aspect ratio.
2. In practice, results should be better than for equivalent amounts of mica and talc,
because of higher effective aspect ratios, nearer to the optimum level. The higher
aspect ratio should also lead to better orientation. Aspect ratio retention could
also be better than for larger platy or fibrous particles.
3. For the same reasons, results are unlikely to be superior to good, long glass fibre
composites. In reality, this is bourne out in practice.
4. Polymer modification through interface and crystallisation effects will be

superimposed on the classical effects discussed. These may be most marked for
nano-particles, due the much greater surface area, and this could give significant
deviations from theoretical predictions.
Despite the apparent limitations of nano-clays compared to more conventional

anisotropic fillers, the nano-clays appear to combine their effects with other benefits
such as: good surface finish and better scratch and mar resistance than can be achieved
with talc, mica or glass fibres and thus, if the costs are not too high, they appear to
have a good future in applications where these are important considerations.
10.4.3.5. Toughness and impact strength
These are important properties, and usually decrease as the stiffness is increased. One of
the great expectations for nano-plates in thermoplastics was that they would give products
with better toughness for a given stiffness.
505
As a general rule, large particles give rise to a loss of impact strength. So for example
classical mica composites show a marked decrease in impact strength because the particles
act as stress concentrators. In contrast, nano-particles are able to provide the benefits of
high anisotropy (increased modulus and yield strength) while keeping a low particle size
so that impact strength is retained.
Unfortunately, this is not an area that is readily treated by theoretical analysis, and present
experimental results are mixed. Many factors contribute to toughness, including: particle
size and shape, polymer degradation and crystallinity and interface properties. Some of
the current problems with nano-plates in this area probably stem from formulation issues
and from the present sub-optimum nature of surface treatments and a clearer picture
should emerge as these are eliminated.
10.4.3.6 Gas and Fluid Barrier Properties
This is an area where the nanoclays appear to offer very distinct advantages and is
already undergoing commercialisation. Thus, as little as 2 wt% of a nano-clay is
sufficient to decrease the oxygen transmission rate of a polyamide film by over 40%.
Their performance is believed to be due to the creation of a tortuous diffusion path, as
shown in Figure 10.8. (Note alignment is necessary for this. Truly random dispersion
would not give the same effect).
According to Lopez, the theoretical permeability coefficient of a composite containing

aligned and overlapping plates can be calculated using Equation 10.1 [33]:
Pp
Pc = (10.1)

where Pc and Pp are the permeability coefficients for the composite and polymer,
respectively, and is the tortuosity. This equation only accounts for the tortuosity and
not for the dilution of polymer. See also Equation 8.3 which allows for both effects to
give more accurate predictions.
Vf .AR
is defined as = 1 + ; where Vf is the volume fraction of filler and AR is the
2
aspect ratio. (Note: this assumes good wetting between the filler and polymer).
Because of their high aspect ratios, nano-plates have the potential to give very good
results at low volume fractions, accompanied by good clarity and low density. However,
as with other properties, their absolute performance is restricted by the volume fractions
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Figure 10.8 Tortuous diffusion path created by aligned plate particles in a polymer film
that are obtainable and with the difficulties of dispersion, alignment and plate damage.
The film formation processes usually used, do appear to favour optimum alignment
however. The main attraction of the nano-plate approach is the ability to use thinner
films (down-gauging) to achieve the same barrier properties as for a thicker unfilled film.
There is also growing pressure on some of the conventional barrier film materials
containing chlorine and nano-plate prospects in this area look bright.
10.4.3.7 Fire Retardancy
Platy nano-particles, such as nano-clays and micas, have some potentially useful flame
retardant effects, and are currently receiving a lot of attention for this application. This
topic has recently been reviewed [34, 35]. The other forms of nano-particle do not seem
to have the same effectiveness. This subject, which was briefly treated in Chapter 6, is
discussed in more detail here, but the earlier chapter should be referred to for details of
fire retardant tests, especially the cone calorimeter which is widely used in studies involving
nano-plate fillers.
The flame retardant potential of nano-clays was recognised as early as 1976 [36], but
serious work has only begun recently. A comprehensive study of the subject is under
way, led by workers at the National Institute of Standards and Technology (NIST) in the
United States, and commercial products and applications are starting to appear, notably
in cable applications. Scientific understanding is still rudimentary, but is evolving fast.
Only a limited number of nano-clays and polymers have so far been studied, so
generalisations are risky.
It has already been shown that delaminated clays have excellent gas barrier properties.
Both delaminated and intercalated clays have also been found to improve the thermal
507
stability of some polymers, especially under oxidative conditions. There is thus reason to
expect that nano-clays might posses some fire retardant properties.
There is a paucity of data for the standard small scale oxygen index and UL 94 tests [37],
but what little there is strongly suggests that nano-clays are not very good in these tests
at the normal loadings (up to 10%) that they are used at. Thus, 7% of a nano-clay was
found to have little effect on the oxygen index of an ethylene methylacrylate copolymer
[38]. This may be the reason why interest in this area was slow to develop. Nearly all of
the available data is with the more recently developed cone calorimeter test, where excellent
results are achievable.
Nano-clays have been tested in a number of polymers, including; PP, PS, epoxy,
polyamide 6 and ethylene vinyl acetate (EVA). Similar results have been reported in all
cases and are:
Effects on time to ignition vary considerably, with a decrease in this parameter

sometimes being reported.
A marked decrease in the very important, peak rate of heat release, accompanied by
a similar decrease in the rate of mass loss.
Some increase in the time to peak heat release and a lengthening of the time taken for
complete combustion.
No significant decrease in total heat of combustion, smoke generation or carbon

monoxide formation. Indeed, increases in smoke and carbon dioxide levels have
sometimes been reported [28].
Typical results for a cone calorimeter experiment are shown in Figure 10.9.
These effects were obtainable with only 3-5% by weight of additive, but did not change
much when higher loadings were used. While not firmly established, present results indicate
that both intercalated and delaminated forms of the same nano-clay have similar effects.
This is perhaps surprising, given that the delaminated form is by far the best gas barrier.
The lack of effect on total heat release, smoke and carbon monoxide, is different from
halogenated flame retardants, and is taken to show that the effects are all in the
condensed phase. Using gasification equipment, which duplicates the pyrolysis
conditions in the cone calorimeter, without flaming taking place, Gilman and co-workers
found that the melt that formed on the surface of unfilled polymer was quickly converted
to a solid, black char when nano-clays were present [39]. It is postulated that this char
is reinforced with nano-particles and slows down the combustion processes. It is,
508
Figure 10.9 Schematic of the sort of cone calorimeter results obtainable from low
levels of nano-clays. Note the much lower peak heat and slower combustion. The
decrease in ignition time and double peak are often observed, but are not always seen.
however, eventually consumed under the radiant heat flux of the cone test and so the
final char content is not greatly increased.
Recent work has indicated that the acidic sites on the clay surface become exposed by
decomposition of the organic treatment and play a significant role in promoting char
formation [40].
The workers at NIST have published quite widely [41-44]. They have reported that there
seems to be little difference between intercalated and delaminated forms of nano-clay,
despite evidence that polymer thermal stability can be more improved by the intercalated
structure. They have also reported that the reduction in ignition time may be due to instability
of the quaternary ammonium salt and could be overcome by use of an alternative intercalant.
The primary effect of the nano-clays seems to be related to char formation. The workers
at NIST have found that a reduction in mass loss and heat release rate only starts once
the surface of the polymer is at least partly covered by char. Le Bras has also reported
that, while no char was produced by burning unfilled EVA, the nano-clay filled composite
formed a strong char early in the process [45]. Once the amount of clay is taken into
account, final char levels are often similar to unfilled polymer, indicating that, while a
stronger, more insulating, char may form and retard combustion, it is eventually consumed.
Given this char effect, the lack of performance in the oxygen index test is surprising. It
may be because the sample is vertical and the melt flows away, preventing a char layer
from forming, while the sample is horizontal in the cone experiment.
509
The workers at NIST found that the processing conditions had to be carefully controlled
if good results were to be obtained. In particular, when working with PS, they found that
all fire retardant effects could be lost if the processing temperature was too high, or if air
was not rigorously excluded. They put this down to degradation of the quaternary
ammonium species on the clay. It has also been claimed that this degradation is the cause
of the reduction in ignition time sometimes seen. As discussed earlier, more stable
treatments are now being developed.
While the reduction in peak rate of heat release, the increase in time to peak, and the
general slowing down of combustion are all very valuable effects, they are probably not
enough, on their own, to meet final application tests. Considerable effort is thus being
spent on examining nano-clays in conjunction with other flame retardants.
Beyer has reported how replacement of a small amount of aluminium trihydrate (ATH)
in an EVA compound can significantly improve performance in the cone calorimeter
test. Alternatively, a larger amount of ATH can be removed allowing the same performance
at a lower overall filler level and with improved physical properties [46].
Burbigot and co-workers have shown improved performance when replacing part of the
ammonium polyphosphate in an intumescent formulation for PP [47].
Inoue and Hosakawa have shown good effects in a number of polymers using melamine
intercalated into nano-clay structures [48].
Finally, nano-clay combinations with halogen/antimony oxide systems are showing some
promise [49].
10.5 Summary and Future Perspectives
The topic of nano-fillers and nano-composites is in vogue at present. This is predominately

due to the surprisingly good properties that are attainable at low loading levels of nano-
plates, and the ability to produce such plates from certain clays.
As we have seen in this chapter, absolute property levels in many polymer types, are
currently much restricted by the combined problems of dispersion, alignment, polymer
and intercalant degradation, plate damage and obtainable volume fraction. These
problems limit nano-plate filler levels in composites to 10% or less. Glass fibre filled
composites, on the other hand, are commonly made with 40% or more of fibre,
where the properties far exceed those attainable from present technology nano-clay
filled composites. Doubtless progress will be made with the absolute performance
levels of nano-plates and they do have some advantages over glass fibres in terms of
510
surface finish and scratch resistance which are important in some major applications.
However, if they are to achieve widespread commercial importance they must become
more cost-competitive with conventionally filled polymers.
Much progress still needs to be made on the theoretical understanding of these materials.
This is particularly important with the plate like particles derived from natural sources,
which are currently of most commercial interest. These are complicated by the competing
contributions from the shape, surface area, delamination and alignment, polymer
degradation and surface chemistry issues.
This area is still largely at the research stage and even so the materials produced are
rather close to being commercially attractive on a wide-scale. With some further work
it is certain that improvements in performance will be seen and that the cost will decline
once large volumes are sold. At some point it is expected that the performance:cost
ratio will become attractive compared to the traditionally filled composites and a break-
through will occur, leading to wide-scale commercialisation of nano-filler composites.
Acknowledgements
The authors would like to thank Dr Chris Liauw of Manchester Metropolitan

University and Dr Kevin Breese of Electrolux for useful discussions regarding the
contents of this chapter. They would also like to thank Massimo Sanit of Electrolux
for the information regarding the effects of maleinised polypropylene on composite
stability and Monica Celotto, also of Electrolux for the electron micrograph. We
also thank Professor Ulf Gedde of KTH Stockholm for discussions on the permeability
of nano-composites.
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514
Abbreviations and Acronyms
ABS Acrylonitrile-butadiene-styrene
AES Auger electron spectroscopy
AFM Atomic force microscopy
amu Atomic mass units
AN Acceptor number
APP Ammonium polyphosphate
AR Aspect ratio
ASTM American Society for Testing and Materials
ATH Aluminium hydroxide
BE Binding energy(s)
BET Brunauer, Emmett and Teller surface area
BOPP Blown oriented PP
C944 Chimassorb 944
CALDOS Calorimeter Digital Output and Sequencer
CD Compact disk
CPU Central processing unit
CTAB Cetyl trimethyl ammonium bromide
CTE Thermal expansion coefficients
DBP Dibutyl phthalate absorption
DMC Dough-moulding compound
DMTA Dynamic mechanical thermal analysis
DN Donor number
DPA David P Ashton
DRIFTS Diffuse reflectance Fourier transform infrared spectroscopy
DSC Differential scanning calorimetry
515
EDS Easy dispersing silicas

EMI Electromagnetic interference
EPDM Ethylene-propylene-diene elastomer
ESCA Photoelectron spectroscopy
esd Equivalent spherical diameter(s)
ETP Engineering thermoplastics
EVA Ethylene vinyl acetate
FID Flame ionisation detectors
FIGRA Fire growth rate index
FMC Flow microcalorimetry
FTIR Fourier transform infrared spectroscopy
GPPS General purpose polystyrene
HDPE High density polyethylene
HDRS Highly dispersible and reactive silicas
HDS Highly dispersible silicas
HDT Heat distortion temperature
HIPS High impact polystyrene
HMDS Hexamethyldisilazane
HPLC High pressure liquid chromatography
HSAB Hard and soft acids and bases
I1010 Irganox 1010
IGC Inverse gas chromatography
IR Infra-red
IRHD International rubber hardness degrees
ISO International Standards Organisation
KI Kovats indices
KM Kubelka-Munk
l/d Length to diameter
LDPE Low density polyethylene
LLDPE Linear low density polyethylene
516
m/m Mol/mol
MA Maleic anhydride
MCS Magnesium carbonate subhydrate
MDPE Medium density polyethylene
MFI Melt flow index
MFR Melt flow rate
MMA Methyl methacrylate
MMT Montmorillonite
Mn Number average molecular weight
MPBD Maleanised polybutadiene
MPS 3-(Trimethoxysilyl)propyl methacrylate
MVI Melt viscosity index
Mw Weight average molecular weight
NBS National Bureau of Standards
NIST National Institute of Science and Technology
NMR Nuclear magnetic resonance spectroscopy
NR Natural rubber
OEL Occupational exposure limits
OIT Oxidation induction time
PA Polyamide
PBT Polybutylene terephthalate
PC Personal computer
PCC Precipitated calcium carbonate
PE Polyethylene
PET Polyethylene terephthalate
phr Parts per hundred resin
PMMA Poly(methyl methacrylate)
POSS Polyhedral oligomeric silsesquioxanes
PP Polypropylene
ppb Parts per billion
517
ppm Parts per million

PPO Polypropylene oxide
PPS Polyphenylene sulfide
PS Polystyrene
PTFE Polytetrafluoroethylene
PVC Polyvinyl chloride
PVDF Polyvinylidene fluoride
QMS Quadrupole mass spectrometer
R&D Research and Development
RFS Resorcinol-formaldehyde-silica
RI Refractive index
RIM Reaction injection moulding
rpm Revolutions per minute
RR Roger N. Rothon
RRIM Reinforced reaction injection moulding
RTM Resin transfer moulding
SBR Styrene-butadiene rubber
scCO2 Supercritical CO2
SEM Scanning electron microscopy
SG Specific gravity
SI Systme Internationale
SIMS Secondary ion mass spectroscopy
SL Linear scale of segregation
SMOGRA Smoke growth rate index
TCD Thermal conductivity detectors
TEM Transmission electron microscopy
TEPO Triethylphosphine oxide
Tg Glass transition temperature
TGA Thermal gravimetric analysis
Tm Melting temperature
518
ToF Time-of-flight
ToF-SIMS Time-of-flight secondary ion mass spectroscopy
UHV Ultra-high vacuum
UL Underwriters Laboratory
uPVC Unplasticised PVC
UV Ultraviolet
WATS Weighted average total strain
WAXS Wide angle x-ray diffraction
WLF Williams Landel Ferry
XPS X-Ray photoelectron spectroscopy
-MPS [-(Methacryloxy)-propyl] trimethoxy silane
519
520
Author Index
A Breese, K.D. 388, 394

Briggs, D. 101
Adamson, A.W. 384 Broutman, L.J. 455, 457
Ahsan, T. 169 Brown, S.K. 454
Aivazyan, G.B. 28 Burbigot, S. 510
Alexandre, M. 296 Burditt, N. 360
Allen, N.S. 118
Antunes, F.V. 472
Armistead, C.G. 180
C
Ashley, R.J. 266, 273, 274, 276, 281, Callopy, D.G. 118
286 Cans, C.H.F. 195
Ashton, D.P. 101, 110, 114, 115, 177 Case, J.R. 274, 277, 278, 279, 280
Cave, N.G. 164
B Celotto, M. 498
Chacko, V.P. 45
Babrauskas, V. 267
Chibowski, S. 40
Bagheri, R. 459, 460, 462
Chow, T.S. 372, 373, 503
Baillet, C. 290, 294, 295
Chung, S.I. 482
Barnett, C.E. 37
Cohen, L.B. 199
Bascom, W.D. 182
Cohen, L.J. 458
Bastioli, C. 129
Connolly, W.J. 269
Beekman, G. 292
Cook, P.M. 298
Berg, J.C. 383, 385, 387
Cotten, G.R. 185
Bergstrm, L. 388
Cusack, P. 298
Berlin, A.A. 277
Beyer, G. 297, 510
Birchall, J.D. 176 D
Birchenough, C.L. 164 Dannenberg, E.K. 185
Bohlin, L. 171 Darlington, M.W. 44, 172
Bohren, C.F. 11 DeArmitt, C. 357, 388, 394, 489
Bolodyan, L.A. 277 Delfosse, L. 290, 293, 294, 295
Boonstra, B.B. 40, 81 Donnet, J-B. 79
Brault, A. 294 Doyle, M. 94
Brault, D. 294 Drago, R.S. 105, 106
521
E Guild, F.J. 448

Gutmann, V. 105
Eakins, W.J. 180
Edge, M. 118
Enikolopyan, N.S. 41 H
Ernstsson, M. 388 Hair, K.L. 180
Evans, A.G. 455, 457 Halpin, J.C. 503
Evans, M.B. 37, 38, 40, 176 Han, C.D. 186
Evans, R.M. 392 Hancock, M. 5, 53, 172, 357
Hardwick, S.T. 382
F Haworth, B. 164
Heckman, F.A. 19
Faust, G.T. 92
Heggs, R.P. 191
Fekete, E. 169, 383
Heikens, D. 372
Ferrigno, T.H. 29, 34
Herbert, M.J. 282, 283, 285
Fogel, V. 392
Hertl, W. 180
Folkes, M.J. 386
Hess, G.C. 19
Fourty, G. 20
Hirschler, M.M. 268, 291, 293
Fowkes, F.M. 106, 107, 109, 116
Hobbs, 382
Fowkes, M.J. 382
Hockey, J.A. 180
Franklin, K.R. 118
Hornsby, P.R. 173, 207, 274, 280, 282,
Fulmer, M. 171, 172 292, 363, 366, 387
Furnas, C.C. 34 Hosakawa, T. 510
Furukawa, J. 174 Hsing, H.H. 180
Hsu, E.C. 188
G Huang, Y. 460
Huffman, D.R. 11
Ghde, J. 144
Hughes, P.J. 274, 280, 285
Galeski, A. 41, 45
Huisman, H.F. 30
Garbassi, F. 129, 188
Hussain, M. 455
Gent, A.N. 21, 188
Hutchinson, J. 176
Gerard, I.F. 41
Hutley, T.J. 44, 172
German, R.M. 30
Gilbert, M. 135, 145, 172, 173
Gilman, J. 508 I
Gilman, J.W. 296 Iler, R.K. 81, 180
Gladkikh, Y.P. 164, 167, 169, 171 Ingham, J.D. 292
Godlewski, R.E. 191 Inoue, H. 510
Golander, C.G. 196 Iqbal, Z. 115, 145, 146
Green, D.G. 455 Irwin, G.R. 450
Green, D.J. 456, 457, 458 Ishai, D. 458
522
Author Index
Ishida, H. 110, 115, 143, 144, 158, 183, Le Bras, M. 509

184, 186, 187 Lee, J. 455, 462
Ivanishchenko, G.P. 169 Lees, G.C. 115, 140, 143, 145, 146
Ivanishchenko, O.I. 164, 167, 171 Leidner, J. 464, 468
Iwatsuki, M. 196 Lewis, A.G. 450
Lewis, G.N. 105
J Liauw, C.M. 101, 115, 117, 118, 140,
143, 145, 146, 164, 170, 171, 174
Jackson, G.V. 274, 277, 278, 279, 280, Lipatov, Y.S. 40
285, 425 Lopez, G.A. 506
Jang, J. 187, 188
Jansen, I.J. 43
Jepson, W.B. 64
M
Johansson, L.S. 134 Mallick, P.K. 455, 457
Jones, H.C. 37 Manson, J.A. 371
Jones, P. 279 Markley, K.S. 166
Joslin, S.T. 116 Maurer, F.H.J. 455, 457
McCrum, N.G. 471
K McCullough, R.L. 446, 447, 449
McGee, S. 446, 449
Karlivan, V.P. 37, 38 McGenity, P.M. 44
Kaye, B.H. 19, 23 McMahon, A.W. 123, 130
Keating, L. 292 McReynolds, W.O. 123
Kellar, J.J. 143 Medalia, A.I. 19, 81
Kelly, A. 466 Milewski, J.V. 95
Khalturinskii, N.A. 277 Miller, J.D. 144, 184
Khamis, M.A. 455 Mitsuishi, K. 44
Kim, H.S. 455 Miyata, S. 172, 174, 273, 282
Kinloch, A.J. 164, 460, 471 Mohs, F. 10
Koenig, J.L. 158 Monte, S.J. 191, 193, 197
Kosfeld, R. 40 Mosesman, H. 292
Kowalewski, I. 45 Motha, K. 503
Krupicka, A. 392 Mulliken, R.S. 105, 106, 107
Murthy, N.S. 45
L Musselman, L.L. 298
Lamthe, 394
Landham, R.R. 196, 197 N
Lange, F.F. 454, 455, 456, 457 Nakatsuka, T. 184, 199
Larsson, A. 388 Napper, D.H. 39, 42
Lawson, D.F. 269, 291 Nelson, G.L. 269, 492
523
Nicodemo, L. 468 280, 281, 285, 286, 489

Nicolais, L. 468 Rybnikar, F. 45
Nielsen, L.E. 450 Rychly, J. 285, 287
Nishimoto, K. 273
S
O
St. Germain, F. 373, 387
Occhiello, E. 129 Sahu, S. 455
Orton, M.L. 425 Sanit, M. 501
Ottewill, R.H. 173 Schlumf, H.P. 8
Outwater, J.O. 466 Schmitt, P. 169
Schofield, W.C.E. 140, 143
P Schreiber, H.P. 121, 373, 387
Schultz, J. 121
Panzer, U. 121 Schwaber, D.K. 190
Pape, P.G. 189 Sharma, Y.N. 197
Papirer, E. 167, 169 Shenoy, A.V. 363, 387
Pavlinec, J. 287 Sinicki, R.A. 387
Pearson, R.A. 459, 460, 462 Skelhorn, D. 303
Pearson, R.G. 105 Socha, D.A. 74
Pena, J.M. 130 Spanoudakis, J. 449, 455, 456, 457, 458,
Petrie, S. 292 459, 462
Plueddemann, E.P. 37, 181, 183, 186, Stark, G.L. 37
187, 189 Stewart, C.W. 293
Porter, D. 296 Suess, E. 167, 168, 170
Pugh, R.J. 383 Sugerman, G. 191, 193, 197
Pukansky, B. 41, 172, 175, 373, 383, Sultan, B.A. 196
455, 457 Sutherland, I. 136, 138
Suzuki, N. 143
R
Radford, K.C. 454, 457 T
Ram, A. 371 Tabtaing, A. 164
Raymond, C. 172 Taylor, H. 425
Raymond, C.L. 164 Thevaranjan, T.R. 293
Riddle, F.L. 106 Thoma, S.G. 25
Rodriguez, F. 190 Thomason, J.L. 43
Romano, G. 129 Thornton, A.M. 269
Rothon, R.N. 5, 38, 40, 43, 53, 94, 96, Tiburcio, A.C. 371
110, 115, 140, 143, 145, 146, 153, 158,
Tiffany, J.M. 173
170, 172, 177, 263, 266, 273, 274, 276,
524
Author Index
Timmons, R.B. 182 Y

Touval, I. 96, 298
Tsai, S.W. 503 Yamashita, S. 174
Tsuchiya, E. 196 Yee, A.F. 455
Tudos, F. 41 Yee, R.J. 462
Young, R.J. 448, 449, 455, 456, 457,
458, 459, 462, 471
V
Vaia, R.A. 143, 145 Z
Venables, R. 164
Zettlemoyer, A.C. 180
Vesely, K. 289
W
Watson, C.L. 173, 274, 280, 282, 292
Watson, S.K. 81, 84
Weber, M. 87
Wharton, R.K. 265, 266
Woodhams, R.T. 464, 468
Wu, C.D. 447
Wu, S. 386
525
526
Index
A Aluminates 198
Aluminium hydroxide 85, 113, 138, 162,
Abrasiveness 11 270, 348
Accelerator adsorption 343 cone calorimeter 282
Acetylene black 80, 342 decomposition pathway 86
Acid-base interactions 103 DRIFTS difference spectrum 140
free energy of 120 exothermic decomposition 348
Acid-base theory 104 in PMMA 278
Acoustic properties 362, 363 production 85
Acrylic acid 117, 143 properties 85
Acrylic composites 455, 458, 461, 473, surface modification 87
474 thermal decomposition 86
tensile failure stress 465 uses 87
Acrylic thermoset uses in polymers 464
mica-containing 467 Aluminium trihydrate see aluminium
Acrylonitrile-butadiene-styrene 410 hydroxide
Additive-filler interactions 103, 113, 117 Ammonium polyphosphate 295, 297
Additives Ammonium stearate treated magnesium
distribution 158 hydroxide
reduced adsorption 154 DRIFTS spectra 143
Adsorption isotherms 162 Analytical techniques
Adsorption methods 159 Auger electron spectroscopy 124
Aesthetics 390 FTIR 183
abrasion resistance 391 SIMS 183
colour 390 surface analysis methods 108
gloss 391 XPS 183
pigmentation 390 Antimony oxides 95
scratch 391 Antimony trioxide 95, 295, 297
surface finish 391 Antioxidants 117, 310
Agglomerates 23 Antiozonants 310
rupture 214 Aspect ratio 20
Agglomeration 210, 368 Auger electrons 124, 125
Aggregates 23 Auger parameter 128
527
B occurrence 57
particle size 25
Ballotini 461
precipitated 347
Barites 73, 350
processing 57
occurence 73
properties 57
properties 73
rosin 174
uses 73
stearic acid modification of 101
Barrier properties 370
surface modification 60
Basic carbonates 84
types of 348
Basic magnesium carbonates 91, 272
uses of 61
Bayer process 85
Calcium carbonates 331, 346
Biotite 70
calcite 347
Birefringence 13
limestone 347
Bis-epoxides
marble 347
curing of with anyhrides 440
natural 347
curing of with primary diamines 439
stearic acid coated 169
Bisphenol epoxy resins
Calcium hydroxide 273
preparation of 437
Calcium sulfate 74
Bisphenol A diepoxides 435
dihydrate 272
Bisphenol A-derived resins 435
occurence 74
Bisphenol curing agents 310
properties 74
Blanc fixe 350
Carbon black 78, 340, 369
Boehmite 86, 273
active surfaces 80
Borates 298
channel black process 79
Bravais lattices 54
furnace process 79
Brucite 88
graphitisation 80
Burning behaviour
interaction with stabilisers 130
aluminium hydroxide 337
particle size 341
antimony trioxide 337
production 79
magnesium hydroxide 337
properties 80
precipitated calcium carbonate 337
zinc borate 337 special grades 342
structure 80, 341
surface chemistry 341
C thermal process 80
Calcined clays 66, 67, 331, 369 uses 81
uses 68 XPS analysis of 130
Calcium carbonate 167 Carboxylated polybutadiene 162
chalk 347 Chalk 57
fatty acid coating 174, 177 deposits 58
MPBD coating 177 whiting 58
528
Index
Channel blacks 342 fracture toughness 450, 460

Characterisation properties of 360
electron microscopy 496 Compound characterisation
X-ray diffraction 496 FTIR spectroscopy 240
Chemical analysis 159 image analysis 237, 238
Chemical composition 7, 8 intensity of mixing 238
bulk chemistry 7 light microscopy 236
Chemical impurities 7, 8 methods of analysis 239
Chimassorb 944 118 microstructural analysis 235
China clay. See Kaolin nuclear magnetic resonance 239
Clay 68 on-line flow visualisation 240
calcined clay 345 residence time distribution 229, 230
secondary clay 345 rheological analysis 232
treated clay 346 scale of segregation 238
Clay minerals 344 screen pack analysis 231
china clay 344 specific energy input 231
hard clay 344 specimen preparation 236
kaolin 344 spectral photometry 240
primary clay 344 striation thickness 238
soft clay 344 ultrasonic measurement 233
Clays Compound preparation 207
properties of 332 Compounding 207, 364
silane-treated calcined clay 346 abrasion resistance 322
silane-treated kaolins 346 accelerator adsorption 333
Coating additive feeding 227
lauric acid 169 ancillary equipment 227
Coating level breakdown strength 335
mono-layer 158 burning behaviour 325
Coating structure compression set 323
processing 163 conductive rubbers 334
Coccosphere 59 dispersion 208, 366
Colour 13, 59, 338 dissipation factor 335
Composite dynamic properties
Composite density 362 dynamical mechanical properties 324
Composite modulus 372 fatigue resistance 324
Composite permeability 370 vibration damping 324, 325
Composite properties 154 electrical properties 324, 334
Composites gas permeability 323, 334
flame retardant properties 263 hardness 322
fracture energy 450 high filler levels 208
529
insulating properties 335 Cone calorimeter 508, 509

internal mixers 222 Coupling agents 27, 311, 344, 459, 501
ko-kneader 225 complexes of chromium 27
machine wear 367 organo-borates 27
melt filtration 227 organosilanes 27, 113
mixer designs 220 organo-titanates 27
non-fluxing mixers 221 organo-zirconates 27
pelletising 228 silane 453
permanent set 323, 333 Crack pinning 456
permeability 323 model 455, 458
premixing procedures 220 Crack-tip blunting 458
reactive modification 207 Crosslinking 305
relative permittivity 335 density 426
resistance to liquids 325 Crystalline silicas 76
semi-conductive materials 335 extraction 76
shear sensitive fillers 208 health issues 78
single screw mixer design 224 occurrence 76
single-screw extrusion 224 particle size 76
strength characteristics 322 properties 76
tension set 323 uses 77
ternary-phase 207 Crystallinity 372, 381
thermally sensitive fillers 208 Crystallisation 44
twin-screw extruders 225 Cure exotherms 435
two-roll mills 222 Cure modification 37
volume throughput 365 Curing system 305, 308
Compounding machinery activators 308
functional characteristics 209 bisphenol curing agents 310
high-intensity 221 high-energy radiation 310
internal mixers 222 isocyanates 310
non-fluxing mixers 221 magnesium oxide 309
two-roll mills 222 metal oxides 309
Compounding of particulate fillers organic accelerator 308
effects of dispersion and impact organic accelerators 309
strength 241 peroxides 309
factors affecting dispersion 242 poly-functional amines 310
inclusion of rubber modifiers 243 prevulcanisation inhibitors 308
Compounding plant resin 310
design of 219 retarders 308
Compounds silane crosslinking 310
characterisation 228 Soap/sulfur 310
530
Index
sulfur-based 308 internal standards 138

urethane crosslinking agents 310 Kubelka-Munk equation 137
zinc oxide 309 post FMC analysis 112, 143
Cycloaliphatic epoxides 435 quantitative analysis 137
sample preparation 136
D specular reflection 136
spectra 140
Dawsonite 95, 272 surface specificity 135
Density. See Specific gravity Dry coating 156, 169
Devolatilisation DSC 108, 147
melt 217 data 146
Diene rubbers Dye adsorption 161
sulfur vulcanisation 309 Dynamic fatigue
Differential scanning calorimetry (see also effect of filler-matrix adhesion 472
DSC) 145 effect of filler particle size 471
Diffuse reflectance Fourier Transform effect of water 474
Infrared...(see also DRIFTS) 134 Dynamic properties 336
Diffusion path 507 Dynamic storage modulus 233
Dilatancy 34
Dimethyldihalogenosilane 181
E
Dispersant
fatty acid 113 Effective particle concept 16
Dispersion 366, 371 Einstein equation 125
characterise 496 Elastomers
Dispersion viscosity electrical properties
Einstein equation 364 antistatic 324
conductive 324
Dolomite 61
insulating 324
extraction 61
formulation of 306
occurrence 61
particulate fillers in 303
properties 61
uses of 303
uses 61
Electrical conductivity 369
Drago equation 107
Electrical properties 369
heat of interaction 106, 107, 109
Electromagnetic interference shielding
parameters 109 369
use in FMC 109 Endothermic fillers. See Fire retardant
use in IGC 121 fillers
DRIFTS 108, 147 Epoxide
analysis of cell content 143 protonation 439
comparison with XPS 135 Epoxy novolac resins 435, 436437
DRIFTS cell 136 glycidylation 436
531
Epoxy polymer Filler dispersion 366

dynamic fatigue 476 Filler loading
Epoxy resins calcium carbonate 235
copolymerisation 438 Filler orientation 372
curing of 438 Filler particle
homopolymerisation 438 dispersion 25
Equivalent spherical diameters 22 Filler particle size
ESCA (see also XPS) 124 effect 456
Ester plasticisers 312 Filler particles 457
Etherification 439 Filler production 153
EVA coplymer Filler protection 153
self ignition and incandescence Filler surface functional groups
temperatures 294 hydroxyl groups 104
EVA copolymer Filler surface modifier
cone calorimetry 283 methods of examination 144
heat release rate 283 structural ordering of 143
Extruder Filler surface treatments
clamshell 367 interaction with fillers 109
single-screw 365, 366
Filler surfaces 101
twin-screw 365, 366
characterising 101
Extrusion 364
reaction of monoalkoxytitanates 195
machine wear 367
Filler treatment
volume throughput 365
in situ 155
pre-coating 155
F Filler volume fraction 452
Fatigue Filler-additive interactions 130
effect of fillers 469 Filler-matrix adhesion 101
Fatty acid treatments 171, 173 Filler-surface modifier 101
Fatty acids 145, 165 coupling agent 101
composition 166 dispersant 101
saturated 170 Fillers 313
Filled polymer abrasion resistance 326
processing ageing behaviour 339
supercritical fluid 250 chemical composition 339
Filled thermoplastics colour 339
uses 396 cost reduction 313
Filled thermosets 425 density 340
Filler European consumption 397
particle size 338 general properties 328
specification 338 impurities 339
532
Index
inherent strength 326 endothermic 273

market 360 ignitability 280
modification of physical properties magnesium carbonate sub-hydrate
313 271
modification of processing magnesium hydroxide 271
performance 313 magnesium phosphate octahydrate
moisture content 339 271
natural rubber 326 nesquehonite 271
non-reinforcing 327 oxygen index 277, 279, 280
oil absorption 339 particle size effect 280, 282
organosilane treated 143 smoke formation 291
particle size 339 UL94 vertical burn test 280
performance 326 Flame retardant performance
pH 340 aluminium hydroxide 276
reinforcement 329 MCS 276
reinforcement of rubber 326, 328 Flammability testing 264
particle complexity 327 afterglow and smouldering 265
particle size 327 char integrity 265
polymer-filler bonding 327 cone calorimeter 267
reinforcing 326 corrosive gas tests 268
semi-reinforcing 326 corrosive gases 265
sieve residues 339 dripping 265
specification parameters 340 FIGRA 268
stability 394 heat release 265
stress-induced crystallisation 326 horizontal burn test 267
uses of 396 ignitability test 265, 267
wettability 8 oxygen index test 266
Fire retardancy 507 propagation 265
Fire retardant fillers SMOGRA 268
affect on afterglow 293 smoke 265, 268
historical background 269 toxic gases 265
Flame retardant. See Fire retardancy Underwriters Laboratory vertical burn
Flame retardant fillers (see also flame test 266
retardant fillers) 270, 272 Flexural fatigue
aluminium hydroxide 271 wet and dry 474
ASTM horizontal burn test 280 Flexural modulus 372
basic magnesium carbonate 271 Flow microcalorimetry (FMC) 107, 108,
boehemite 271 109, 110, 115, 147
calcium hydroxide 271 choice of reagents 112
calcium sulfate dihydrate 271 comparison with IGC 119
dawsonite 271 competitive adsorption studies 117
533
data 115, 118 HIPS (see high-impact polystyrene)

HPLC detectors 114, 115 Huntite 92
method of operation 111 applications 95
output from 111 decomposition of 95
Fluid barrier properties 506 general properties 92
Fractal geometry 19 Hydrogen bonding 113
Fracture energy 457 Hydroxides 84
Fracture toughness 457
Fullerenes 492 I
Fumed silicas 83
applications 84 IGC (see inverse gas chromatography)
manufacture of 83 Igneous rocks 55
production 83 Impact strength 380, 505
surface modification 84 effect of fillers 378
Functional fillers 360 Izod and Charpy 377
Furnace blacks 341 toughness 377
Impact testing
notched 378
G
Impurities 55
Gas barrier properties 506 Infra-red methods 159
Gelation 425 Inherent flaw size 462, 464
Gibbs free energy equation 120 Injection moulding machine
Glass ballotini 460 direct compounding 249
Glass spheres 445, 448 Injection moulding technology
Glass transition 41 direct compounding 247
Glass-fibre laminates 478 Intercalants 500
Glycidyl amines 435, 437 organic 499
Griffiths theory 463, 467 Intercalation 496
Gutmann equation 105 Interparticle distance 34
IGC 121 Interparticle spacing 42
Interphase concept 186
H chemisorbed layers 186
effect on processing 186
Hamaker constants 388 physisorbed layers 186
Hardness 10 Inverse gas chromatography (IGC) 108,
HDPE 358 119, 123, 147
Heat deflection temperature 374, 375 comparison with FMC 119
Heat of reaction Kovats indices 123
Gutmann equation 105 method of operation 121
High-energy radiation 310 multiple probe temperature-
High-impact polystyrene 359, 411 programmed 123
534
Index
output 122 M
response curves 123
Magnesium carbonate sub-hydrate 272
thermodynamics 120
Magnesium hydroxide 88, 113, 138,
Irganox 1010 118
146, 162, 273
Isocyanates 310
applications 91
Isostearic acid 113, 116, 117, 143, 145,
brine type 89
146
cone calorimetry 283
DRIFTS spectra 145
K forms available 88
Kaolin 61, 63 isothermal decomposition 91
aspect ratios 65 large-crystal type 89
differential thermal analysis 67 natural form 89
extraction 61 production 88
occurrence 61 properties 88
properties 61 sea-water 89
surface chemistry 65 surface chemistry 91
surface modification 65 surface modification 91
uses 65 thermal decomposition 90
Kaolinite 63 thermal stability 92
crystals 62 Magnesium phosphate octahydrate 272
plates 65 Maleanised polybutadiene (MPBD) 138
Kerner equation 372, 373 DRIFTS infra-red difference spectrum
Kovats indices 123 140
Kubelka-Munk equation 12, 137 infra-red spectrum of 139
surface modifier 177
Marble 57
Maximum packing fraction 29
L
oil absorption procedures 29
Lampblack 342 Mechanical properties 371
Layered silicate modification 477
states of dispersion 497 Melt devolatilisation
Lewis acid-base theory 105 mechanism of 218
Lewis and Bronsted acid sites 64, 65 Melt pressurisation 218
Light stabilisation 117 Melt pumping 218
Limestone 57 Melt viscosity 363
Linear low density polyethylene 117, 357 Metakaolin 66, 369
Low density polyethylene 357 uses 68
Metamorphic rocks 56
Methyltrimethoxy silane 180
Mica 69, 464
535
extraction 69 uses 73
occurrence 69 Montmorillonite clay. See Nano-clay
properties 69 Montmorillonite clay plates
uses 70 dispersion 497
Microcalorimeter Mooney viscometer 320
schematic diagram 110 Morphology
Microcalorimetry effects 274
HPLC detectors 116 Muscovite 69, 70
Mies theory 12
Mineral fillers 53, 56 N
thermal conductivities 367
Mineral oils
aromatic 312 Nano-clays 296
naphthenic 312 co-agents 499
paraffinic 312 composite effects and applications
Minerals 54 502
Mixing 214 dispersion 495
convective 216 exfoliates 495
dispersive 214 freeze drying 499
effect of surface treatment on 216 heat distortion temperature 502
laminar shear 217 intercalates 495
randomisation 220 maleated PP 501
weighted average total strain 217 melt intercalation 497
Mixture characterisation 207 modulus 502
Modulus 322 platy 493
Mohs Hardness Scale 10, 11 polymer composites
Molecular interaction 105 processing strategies 494
Molecular weight polymerisation filling 497
effects of compounding on 243 processing 493
Molecular weight reduction 36 stability of intercalant 500
Molybdates 298 strength 502
Monolayer supercritical fluid 499
concept 156 ultrasonics 499
coverage 142 Nano-fillers 489
determination 160 particle forms 490
theoretical calculation 160 regular shapes 491
level by DRIFTS analysis 143 rods, fibres 492
Montmorillonite 72 Nano-particle
occurence 72 basic types 491
properties 72 Nanocomposites
536
Index
exfoliation 252 O
intercalated 253
Oil-absorption 30
melt compounding 253
Oleic acid 145, 146
microstructure of 252
Optical properties 11, 14
reactive extrusion 253
Organo-silanes 344, 346
silicate layer polymer 251
Organo-silicon compounds. See also
Natural clay-based particles
Silane coupling agents
alternatives 501
applications of non-coupling
Natural fibre filled composites 247
compounds 185
emission standards 248
coating techniques 178
fibre-matrix bonding 247
fillers 178
integrated extrusion compounding
polymer interaction 185
247
reaction with filler surfaces 179
melt processing 247
silane coupling agents 185
moisture removal 247
structure of coatings 183
odour standards 248
Organo-titanates 191
Natural fibre-filled thermoplastics
effects produced 197
woodflour 246
general principles 192
Natural silicas 349
limitations of 198
Nesquehonite 272, 273
monoalkoxy types 194
Nesquehonite in PMMA
types for surface modification 193
oxygen index 278
types of filler 193
Network structures
Organo-zirconates 191
percolation 335
use of 198
Neuburger silica 349
Ozone attack 310
Nielsen equation 372
Novolac resins
preparation of 441 P
Novolacs 443 Packing
Natural rubber 320 multimodal 32
Nuclear magnetic resonance 105 ordered 31
Nucleation of polypropylene random 31, 32
effect of fillers 395 Paris equation 470
Nylon 6 Particle
effect of magnesium hydroxide 286, effects 36
287 dispersion 25
filled matrix adhesion 458
properties 409
packing 33
uses 409
packing fraction 29
shape 16, 17
537
assessment of 19 calcium carbonate fillers 400

measurement of 19 calendered sheet 401
origins of 18 fillers 399
size 16, 20 floor tiles 401
distributions 21 footwear 401
measurement 21
homogeneous flooring 401
spacing 34
hose and profiles 401
structure 19
leather cloth 401
occluded polymer 20
plastisol 402
types 16
sealants 402
volume 39
spread coatings 401
Particulate fillers 53
wall coverings 401
characteristics of 5
Plasticisers 311, 312
chemistry 7
Platy fillers
composition 7
mica 376
cost 6, 477
Platy minerals
dispersion of 217
clays 330
impurities 7
talcs 330
natural origins 53
PMMA 459, 472
types of 53
PMMA
use in thermosets 445
filled with aluminium hydroxide
Particulate materials 5
horizontal burn performance 281
selection and use 5 ignitability 281
Particulate polymer composites ignition times 282
process enhancement 240 oxygen index 275
Percolation 368, 369, 370 Polar species
effect 34 absorption of 37
Permeability 370 Poly-functional amines 310
Permeation Polyamide 6,6
paths 334 aramid fibre-reinforced 245
Phenolic resins 440 glass-fibre-reinforced 246
curing of 442 Polyamide chains
novolacs 441 grafted 499
resols 442 Polyamides
Phlogopite 69 use of fillers 408
Pigment Polybutylene terephthalate 410
twin-screw extruder 231 Polyester
Pipes 359 unsaturated 428, 429
Plastic deformation 375 Polyester resins
Plasticised PVC preparation of unsaturated 426
cable coverings 399 properties 428
538
Index
unsaturated 427 Polymer phase

Polyesters 359 effects of filler 380
Polyethylene 357 interphase 382
filled polyethylene nucleation 380, 381, 382
oxygen index 275 transcrystallinity 382
uses of fillers 406, 407 Polymers
Polyethylene films modulus 322
infra-red spectra 15 stiffness 304
Polyethylene terephthalate 359, 410 strength characteristics 321
Polyformaldehyde 411 stress-induced crystallisation 322
Polyhedral oligomeric silsesquioxanes Polyoxymethylene polymers 411
492 Polyphenylene oxide 411
Polymer Polyphenylene sulfide 411
characteristics 318, 319 Polypropylene 101, 358
direct bonding 28 cone calorimetry 284
fracture toughness 460 effect of magnesium hydroxide 288,
immobilised 38 289
modifications 27 filled
performance characteristics 317 uses 404
performance of 317 heat release rate 284
selection of 306 properties 379
specification 317 smoke level 284
Polymer additives uses of fillers 404
interaction with fillers 109 Polypropylene compositions
Polymer compounding 248 glass-fibre reinforced 245
Polymer compounds Polypropylene homopolymer
characterisation of filled 230 HDT 374
Polymer conformation 42 impact strength 381
Polymer crystallinity 42 tensile modulus 372
Polymer flammability yield strength 377
corrosive gases 290 Polystyrene 410
effects of fillers 263 general purpose 359
smoke 290 Polyvinyl chloride 359
thermal analysis 285 cable sheathing formulation 400
toxic gases 290 fillers 398
Polymer fracture toughness 460 Powder densities 10
Polymer melting Precipitated silica 81
influence of fillers 214 polymer applications 83
mechanism 213 production 81
shear heating 213 properties 82
539
silica structure 82 step addition curing 435

surface modification 83 urethane methacrylate 432
Primary particles 23 vinyl ester 430
Process enhancement 207 vinyl urethane 430
Process oils 311 Resistance to liquids 336
Processing 153, 330 Resols 442
bagging 331 acid cure of 442
cure rate 331 cured crosslinked 442
green strength 330 heat cure of 443
mill sticking 331 Reuss model 446, 447
nerve 330 RFS system 344
viscosity 321, 330 Rolling resistance 344
Properties Rubber
bulk and process 361 elasticity of 303
Pyrolysis 159 formulation 307
specialised additives 307
Q
S
Quadrupole mass spectrometer 133
Quaternary ammonium salts 143 Saturated fatty acids 164
Sedimentary rocks 56
Sedimentation 22
R Settling volume method 160
Reactive diluents 437 Shear heating 213
Reactive techniques 109 Shrinkage 368, 480, 481
Recycleability 396 Silane coupling agents
Refractive index 12 amino functional 188
Refractory material 67 effects in elastomers 190
Reinforcement effects in filled polymers 190
level of 375 effects in thermoplastics 191
Relative density 362 effects in thermosets 190
Resins 310 epoxy functional 188
condensation 440 interpenetration of matrix 187
epoxy 435 methacryl functional 188
free-radical chain-growth curing 427 mixed silane systems 189
low-viscosity 429 oligomeric silanes 189
phenolic 440 polymer interaction 185
preparation of urethane methacrylate sulfur functional 189
432 types 187
preparation of vinyl ester 431 uses 187
preparation of vinyl urethane 431 vinyl functional 188
540
Index
Silane crosslinking 310 odourants 316

Silanes 102 paraffinic wax 314
Silica peptisers 314
fumed 112 pigments 315
natural crystalline 453, 464, 472 polyethylene waxes 314
synthetic 81 polyethylenes 314
Silica filled PMMA polyoctenamer 314
static properties 472 precipitated silica 316
Silica sand process aids 314
natural crystalline 445, 448, 460 resorcinol-formaldehyde-silica 316
Silica-filled smoke suppressants 315
methacrylate composites 475 soaps 314
Silica-filled methacrylate composites 472 tackifiers 315
Silicas and silicates 343 Specific gravity 9. See also Relative
fumed silica 343 density
precipitated silica 343 Specific heat 15
silicates 343 capacity 367
synthetic 343 Specific surface area 22
Spectral absorption 14
Silicate gallery 495
Spectroscopic techniques 124
SIMS 108, 124, 147
DRIFTS 108, 134, 135, 136, 140,
comparison with XPS 133
141, 143, 145, 147
dynamic 130
ESCA 124
instrumental aspects 133
FTIR 104, 183
static 130
SIMS 104, 108, 124, 130, 133, 147,
time-of-flight 133 183
Sinter hydrates 85 ToFSIMS 130, 133
Slip-stick propagation 452 UHV 124
Smoke suppressant 348 WAXS 108, 147
Soap/sulfur systems 310 XPS 104, 124, 133, 135, 183
Specialty additives 314 Spherical fillers 376
antistatic agents 316 Squalane 394
blowing agents 316 stability 394
bonding agents 316 Stabilisation 393
dyes 315 Stabilisation and recycleability 392
emulsified esters 314 Stabilisers 117
fatty acids 314 hindered phenols 393
fire retardants 315 Stability
liquid polymers 314 antioxidant adsorption 394
mill 314 filler chemistry 393
mould-release agents 314 impurities 393
541
Stannates 298 surface coverage 160

Static calorimeter 107 types 163
Static calorimetry 109 Surface modifiers 153
Static fatigue 471 acid functional saturated polymers 175
Static fatigue experiments 470 acid functional unsaturated polymers
Stearate coating. See also Surface treat- 176
ment amino-acids 200
Stearates 26 borates 199
Stearic acid 26, 101, 103, 116, 141, 145, dimaleimides 175
146, 167, 170, 347 dry coating 165
properties 166 fatty acid salts 173
Stearic acid coating functional organic acids 173
effects in composites 171 methods of use 155
Steric barrier 102 organic amines 200
Stokes law 22 phosphates 199
Strain rate 449 polymeric acids 175
Stress whitening 14 reasons for use 153
Stress-induced crystallisation 322 rosin 174
Supercritical fluids wet coating process 165
viscosity reduction effects 249 Surface mono-layers
Surface analysis methods structures for 157
flow microcalorimetry 104 Surface science
Fourier transform infrared adhesion 385
spectroscopy 104 agglomeration 387
inverse gas chromatography 104 dispersion 387
secondary ion mass spectroscopy 104 spreading 384
X-ray photoelectron spectroscopy 104 spreading coefficient 385
Surface chemistry 7 surface energy 383, 384
Surface energies 8 surface tension 383, 384
Surface interactions 7 wetting 384
Surface modification 26, 153 Surface treatments 344
general principles 154 coupling agents 388, 389
Surface modification of particles 453 dispersants 388, 389
Surface modifier Surface treatments. See also Coupling
anhydrides 175 agents
coating level 156 Synthetic particulate fillers 78
coupling 154
effect of surface topography 157
T
effect on polymer crystallinity 172
monomeric organic acids 163 Talc 70, 349
non-coupling 154 occurrence 71
542
Index
processing 71 shrinkage control 480

properties 70 structural adhesives 483
surface modification 72 TiO pigments
2
uses 72 surface analysis of 134
Tensile modulus 372 ToF SIMS
Tensile yield stress spectra 130, 133
effect of fillers 463 Toughness 505
Thermal blacks 342 ductile to brittle transition 462
Thermal conductivity 15, 367 Toughness of composites
Thermal expansion 368 effect of particle size 450
coefficient of 16 effect of strain rate 449
Thermal properties 14 Transcrystallinity 43, 371
Thermoplastic composites 359, 360 Transport of feedstock
Thermoplastics compaction 210
applications 357 flow of particulate solids 211
calcium carbonate 399 frictional effects 212
fillers 360 hopper design 211
particulate fillers 412 particle characteristics 210
use in Western Europe 359 (Trimethoxysilyl)propyl methacrylate
Thermoplastics composites 129. See also Silanes
interfacial shear strength 244 silanes 102, 103
short fibre-reinforced 244 Twin-screw extruders
Thermoset polymers positive-displacement 212
chemistry 427 screw configuration 226
Thermoset recyclate composites
mechanical properties 251 U
Thermoset recyclate fillers 250
Ultra high vacuum spectroscopy 124
Thermosets
Unplasticised PVC
applications 477
conduit 403
cost reduction 477
fillers 402
exotherm control 478
film 403
failure stress 463
fittings 403
fatigue 469
pipes 403
flame retardants 482
profiles 403
fracture energy 450
window 403
fracture toughness 450
Urethane crosslinking agents 310
mechanical properties 444
Urethane methacrylate polymer 449
metal fillers 482
modulus 444
processing aids 481
543
V X
Viscosity measurements 40 X-ray photoelectron spectroscopy (see
Viscosity reduction 160 also XPS)
Vitrification 425 physical basis 124
Voigt model 446, 447 X-ray photoemission 124
XPS 108, 124, 147
Auger electrons 125
W
comparison with DRIFTS 135
Wallace rapid plasticity 320 comparison with SIMS 133
Warpage 368 Einstein equation 125
WAXS 108, 147 information levels 128
Wet flexural fatigue 475 instrumental aspects 128
Wetting 371 penetration depth 125
Wide angle X-ray diffraction 145 TiO pigment 126, 127
2
WLF equation 377
Wollastonite 74
Y
applications 75
occurrence 74 Yield strength 375, 376
processing 74 Youngs modulus 444, 445, 446, 451
properties 74
surface modification 75 Z
Work of adhesion
Lewis acid-base terms 386 Zircoaluminates 198
non-polar case 386
polar case 386
544
ISBN: 1-85957-382-7

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Particulate-Filled

Rapra Technology Limited

Editor: Roger N. Rothon

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Rapra Technology Limited

2003, Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part

Typeset by Rapra Technology Limited

1 General Principles Guiding Selection and Use of Particulate Materials ........... 5

1.4.4 Applications of Packing Principles to Particulate Filled

2 Principal Types of Particulate Fillers ............................................................. 53

2.3 Synthetic Particulate Fillers .................................................................. 78

3 Analytical Techniques for Characterising Filler Surfaces ............................. 101

4 Surface Modification and Surface Modifiers ............................................... 153

4.1 Introduction ....................................................................................... 153

4.2 Reasons for Using Surface Modifiers ................................................. 153

4.3 General Principles of Surface Modification ........................................ 154

4.4 Methods of Using Surface Modifiers .................................................. 155

4.5 Choice of Coating Level ..................................................................... 156

4.6 Techniques for Determining the Amount of Coating Present,

References ................................................................................................... 201

5 Compound Preparation, Mixture Characterisation and Process

5.10 Conclusions ....................................................................................... 254

6 Effects of Particulate Fillers on Flame Retardant Properties of Composites ... 263

7 Particulate Fillers in Elastomers .................................................................. 303

7.4.2 Selection of Polymer .............................................................. 306

References ................................................................................................... 351

8 Filled Thermoplastics .................................................................................. 357

8.6 Aesthetics ........................................................................................... 390

9 Filled Thermosets ........................................................................................ 425

9.3.1 Modulus ................................................................................ 444

10 Composites Using Nano-Fillers ................................................................... 489

Chapter 4, on surface modification, is a good example of the approach taken. Most

David Ashton Christopher Liauw

Chris DeArmitt Roger Rothon

Particulate-filled polymer composites have a long history and consequently newcomers

1.2 Basic Characteristics of Particulate Fillers

In developing a particulate-filled composite, the formulator needs to be able to answer

1. What property benefits are being sought?

4. Are special additives needed?

1.2.2 Chemistry, Composition and Impurities

1.2.2.1 Bulk Chemistry

1.2.2.2 Surface Chemistry

1.2.2.3 Surface Interactions

Wettability of filler by polymer is an indication of compatibility between the two. Wettability

Table 1.1 Surface energies of fillers and plastics

1.2.2.4 Chemical Analysis and Impurities

1.2.3 Density or Specific Gravity

Hardness is the resistance of a mineral to scratching. It is related to the structure of the

Table 1.2 Mohs scale of mineral hardness

1.2.6 Optical Properties

1.2.6.1 Spectral Absorption

1.2.7 Thermal Properties

Figure 1.1 Infra-red spectra of mineral filled polyethylene films

1.2.7.1 Specific Heat

1.2.7.2 Thermal Conductivity

This increased conductivity is of considerable importance in some processing operations,

1.2.7.3 Coefficient of Thermal Expansion

1.2.8 Particle Shape and Size

Figure 1.2 Some particle types likely to be found in common fillers

1.2.9.2 Origins of Particle Shape

1.2.9.3 Assessment and Measurement of Shape

In synthetic fillers it is sometimes difficult to separate fundamental from aggregate shape