Aroon v. Shenoy (Auth.) - Rheology of Filled Polymer Systems-Springer Netherlands (1999)

Rheology of Filled
Polymer Systems
Rheology of Filled
Polymer Systems
Aroon V. Shenoy
Advisory Consultant
Pune,India
....
"
Springer-Science+Business Media, B.V.
Library of Congress Cataloging-in-Publication data
ISBN 978-90-481-4029-9 ISBN 978-94-015-9213-0 (eBook)

DOI 10.1007/978-94-015-9213-0
Printed on acid-jree paper
All Rights Reserved

1999 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1999.
Softcover reprint ofthe hardcover 1st edition 1999
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
inciuding photocopying, recording, or by any information storage and
retrieval system, without prior pennission from the copyright owner.
Contents
Preface ix
1 Introduction 1
1.1 Polymers 1
1.1.1 Thermoplastics, thermosets and elastomers 1
1.1.2 Linear, branched or network polymers 2
1.1.3 Crystalline, semi-crystalline or amorphous
polymers 5
1.1.4 Homopolymers 6
1.1.5 Copolymers and terpolymers 7
1.1.6 Liquid crystalline polymers 9
1.2 Fillcrs 9
1.2.1 Rigid or flexible fillers 10
1.2.2 Spherical, ellipsoidal, platelike or fibrous fillers 10
1.2.3 Organic or inorganic fillers 11
1.3 Filled polymers 11
1.4 Filler-polymer interactions 16
1.4.1 Filler geometry 18
1.4.2 Volume fraction 19
1.4.3 Filler surface 19
1.4.4 Wettability 19
1.4.5 Filler surface treatment 21
1.5 Rheology 39
References 43
2 Basic rheological concepts 54

2.1 Flow classification 55
2.1.1 Steady simple shear flow 55
2.1.2 Unsteady simple shear flow 59
2.1.3 Extensional flow 62
vi Contents
2.2 Non-Newtonian flow behavior 66

2.2.1 Newtonian fluids 66
2.2.2 Non-Newtonian fluids 67
2.2.3 Viscoelastic effects 71
2.3 Rheological models 79
2.3.1 Models for the steady shear viscosity function 79
2.3.2 Model for the normal stress difference function 84
2.3.3 Model for the complex viscosity function 86
2.3.4 Model for the dynamic modulus functions 90
2.3.5 Models for the extensional viscosity function 93
2.4 Other relationships for shear viscosity functions 99
2.4.1 Viscosity-temperature relationships 99
2.4.2 Viscosity-pressure relationship 103
2.4.3 Viscosity-molecular weight relationship 104
References 104
3 Rheometry 112
3.1 Rotational viscometers 113
3.1.1 Cone and plate viscometer 115
3.1.2 Parallel-disc viscometer 117
3.2 Capillary rheometers 118
3.2.1 Constant plunger speed circular orifice capillary
rheometer 119
3.2.2 Constant plunger speed slit orifice capillary
rheometer 124
3.2.3 Constant speed screw extrusion type capillary
rheometers 124
3.2.4 Constant pressure circular orifice capillary
rheometer (melt flow indexer) 126
3.3 Extensional viscometers 128
3.3.1 Filament stretching method 128
3.3.2 Extrusion method 130
References 131
4 Constitutive theories and equations for suspensions 136

4.1 Importance of suspension rheology 136
4.2 Shear viscous flow 137
4.2.1 Effect of shape, concentration and dimensions
on the particles 137
4.2.2 Effect of size distribution of the particles 147
4.2.3 Effect of the nature of the particle surface 150
4.2.4 Effect of the velocity gradient 150
4.2.5 Effect of flocculation 151
4.2.6 Effect of the suspending medium 153
Contents vi i
4.2.7 Effect of adsorbed polymers 154

4.2.8 Effect of chemical additives 160
4.2.9 Effect of physical and chemical processes 160
4.2.10Effect of an electrostatic field 162
4.3 Extensional flow 164
References 167
5 Preparation of filled polymer systems 175

5.1 Goodness of mixing 175
5.2 Mixing mechanisms 183
5.3 Compounding techniques 186
5.3.1 Selection criteria 186
5.3.2 Batch mixers 189
5.3.3 Continuous compounders 192
5.3.4 Dump criteria 218
5.4 Compounding/mixing variables 221
5.4.1 Mixer type 223
5.4.2 Rotor geometry 224
5.4.3 Mixing time 225
5.4.4 Rotor speed 229
5.4.5 Ram pressure 229
5.4.6 Chamber loadings 231
5.4.7 Mixing temperature 232
5.4.8 Order of ingredient addition 236
References 237
6 Steady shear viscous properties 243

6.1 Effect of filler type 244
6.2 Effect of finer size 246
6.3 Effect of filler concentration 248
6.4 Effect of finer size distribution 262
6.5 Effect of finer agglomerates 272
6.6 Effect of filler surface treatment 273
6.7 Effect of polymer matrix 279
6.8 Unification of steady shear viscosity data 287
References 303
7 Steady shear elastic properties 312

7.1 Effect of finer type 313
7.2 Effect of finer size 315
7.3 Effect of finer concentration 317
7.4 Effect of finer size distribution 321
7.5 Effect of finer agglomerates 321
7.6 Effect of finer surface treatment 323
viii Contents

References 332
8 Unsteady shear viscoelastic properties 338

8.1 Effect of fiBer type 344
8.2 Effect of fiBer size 344
8.3 Effect of filler concentration 345
8.4 Effect of fiBer size distribution 350
8.5 Effect of filler agglomerates 356
8.6 Effect of fiBer surface treatment 360
8.8 Effect of matrix additives 387
References 390
9 Extensional flow properties 395

9.1 Effect of fiBer type 396
9.2 Effect of fiBer size 400
9.3 Effect of fiBer concentration 402
9.4 Effect of fiBer surface treatment 405
References 409
10 Concluding remarks 416
Appendix A Glossary 425

Appendix B ASTM conditions and specifications for MFI 430
Appendix C Data details and sources for master rheograms 433
Appendix D Abbreviations 439
Appendix E Nomenclature 441
Appendix F Greek symbols 449
Author index 455

Subject index 469
Preface
Polymerie materials have been replacing other conventional materials

like metals, glass and wood in a number of applications. The use of
various types of fillers incorporated into the polymer has become quite
common as a means of reducing cost and to impart certain desirable
mechanieal, thermal, electrieal and magnetic properties to the polymers.
Oue to the energy crisis and high priees of petrochemieals, there
has been a greater demand to use more and more fillers to cheapen
the polymerie materials while maintaining and/or improving their
properties.
The advantages that filled polymer systems have to offer are
normally offset to some extent by the increased complexity in the
rheological behavior that is introduced by the inclusion of the fillers.
Usually when the use of fillers is considered, a compromise has to be
made between the improved mechanieal properties in the solid state,
the increased difficulty in melt processing, the problem of achieving
uniform dispersion of the filler in the polymer matrix and the
economics of the process due to the added step of compounding. It has
been recognized that addition of filler to the polymer brings a change in
processing behavior. The presence of the filler increases the melt
viscosity leading to increases in the pressure drop across the die but
gives rise to less die swell due to decreased melt elasticity. The decrease
in melt elasticity can raise the critieal shear rate at which melt fracture
during extrusion starts to occur and hence one could often consider
increasing throughput rate in the case of filled polymer melt
processing.
The purpose of the present book is to treat the rheology of filled
polymer systems in as much detail as possible. With the idea of
addressing readers of this book who may come from different
x Preface
backgrounds, a concerted effort has been made to provide the initial

three chapters with material needed for familiarizing with the basies
about polymers, fillers, physieo-chemieal interactions between the two,
rheology and rheometry.
The first chapter introduces the subject and gives an overview. It
briefly discusses the various types of polymers and fillers that can
go into the formation of filled polymer systems. It also gives an
outline about the physieo-chemieal interactions between polymers
and fillers.
The second chapter deals with the fundamentals of rheology and
provides definitions of all the basie rheologieal parameters. It dwells on
the non-Newtonian character of filled polymerie systems and explains
the various anomalies that are encountered during the flow of
viscoelastie materials. Various viscoelastie phenomena are depieted and
these give an idea about the complexities involved in the flow of
polymerie materials, which gets further complicated in the presence of
fillers.
The third chapter presents some of the different methods of
rheological measurements. The entire range of rheometers has not been
explained here as the focus in this chapter has been to include only
those that find relevance to filled polymer characterization.
The fourth chapter presents some constitutive theories and equations
for suspensions. Suspension rheology normally deals with the flow
behavior of two-phase systems in whieh one phase is solid partieies like
fillers but the other phase is water, organie liquids or polymer solutions.
Literature on suspension rheology does not include flow characteristies
of filled polymer systems. Nevertheless, this chapter needs to be
included as the foundations for understanding the basies of filled
polymer rheology stern from the flow behavior of suspensions. In fact,
most of the constitutive theories and equations that are used for filled
polymer systems are borrowed from those that were initially developed
for suspension rheology.
Chapter 5 goes into the details of how to prepare filled polymer
systems. It discusses the criteria for good mixing and the various
mixing mechanisms by which fillers get compounded with polymers.
The compounding techniques are discussed and compounding/mixing
variables are highlighted so that the sensitivity of these variables is
understood in order to obtain well-dispersed filled polymer systems
under optimum conditions.
Chapters 6 to 9 discuss the steady shear viscous properties, steady
shear elastic properties, unsteady shear viscoelastic properties and
extensional flow properties, respectively. The effect of filler type, size,
size distribution, concentration, agglomerates, surface treatment as well
as the effect of polymer type are elucidated. The tenth chapter has been
Preface xi
included to recapitulate the irnportant aspects discussed in the

presented work.
It is hoped that this book will provide all the necessary. background
needed to understand the various aspects relating to the rheology of
filled polymer systems so that even new entrants to this exciting field
may benefit from the information. For those who have already whetted
their appetite with a taste for this research area, it is hoped that this
book will provide complete details under one cover and entice them to
probe into vacant areas of research that may become obvious to them
on reading this book.
Aroon V. Shenoy
Introduction 1
1.1 POLYMERS
Polymers are high molecular weight organic substances that have
usually been synthesized from low molecular weight compounds
through the process of polymerization, using addition reaction or
condensation reaction.
In addition polymerization, the reaction is initiated by a free radical
which is usually formed due to the decomposition of a relatively
unstable component in the reacting species. In this reaction, repeating
units add one at a time to the radical chain, and reasonably high
molecular weight polymers can be formed in a short time by this
polymerization.
In condensation polymerization, the reaction takes place between
two polyfunctional molecules to produce one larger polyfunctional
molecule with the possible elimination of a sm all molecule such as
water. Long reaction times are essential for forming high molecular
weight polymers by this step reaction.
An elementary introduction to polymers is given here and those
wishing to gain more knowledge about the physics, chemistry and
engineering aspects of polymers should consult some of the standard
references [1-13] on the subject.
Polymers formed through the polymerization processes discussed
above can be classified in a number of different ways based on
certain chosen characteristics for comparison.
1.1.1 THERMOPLASTICS, THERMOSETS AND ELASTOMERS
Thermoplastics are those polymers that can be made to soften and take
on new shapes by application of heat and pressure. The changes that
occur during this process are physical rather than chemical and hence
products formed from such polymers can be remelted and reprocessed.
A. V. Shenoy, Rheology of Filled Polymer Systems

Springer Science+Business Media Dordrecht 1999
2 Introduction
Table 1.1 Some candidate polymers used in the formation of filled

polymer systems
Thermosets Elastomers Thermoplastics
Epoxies Neoprenes Nylons

Phenolics Nitriles Polypropylene
Unsaturated polyesters Styrene butadienes Polystyrene
Thermosets are materials that have undergone a chemical reaction,

known as curing in A, Band C stages depending on the degree of
eure by the application of heat and catalyst. The A stage is the early
stage, B stage is the intermediate stage and C stage is the final stage
of the curing reaction. The crosslinked structure that forms in the
polymer during the reaction is stable to heat. Hence products formed
through these polymers cannot be made to flow nor can they be
melted and thus are not reprocessible. Not all thermosets go through
A, Band C stages, and in fact, processors are often interested in the
flow behavior of those that have not undergone eure.
Elastomers are rubbery polymers that deform upon the application
of stress and revert back to the original shape upon release of the
applied stress. They are lightly crosslinked molecular networks above
their glass transition temperatures. They are often capable of rapid
elastic recovery. They are available as natural rubbers or synthetic
rubbers. Natural rubbers are elastic substances that are obtained by
coagulating the milky extracts from certain tropical plants; while
synthetic rubbers are those that are artificially prepared by combining
two or more monomers through a chemical reaction.
Some of the candidate polymers from the above three categories
which are used in the formation of filled polymer systems are given
in Table 1.1.
1.1.2 LINEAR, BRANCHED OR NETWORK POLYMERS

A polymer can be classified as linear or branched depending upon its
structure. The thermoplastic polyethylene serves as a good example
because it exists with linear as weIl as branched structure as can be
seen from Figure 1.1. Based on the pressure (low or high), the
reaction temperature and the choice of the catalyst during the
polymerization process, polyethylenes with different densities and
structures are formed. High-density polyethylene (HOPE) has a linear
molecular structure and a density ~ 0.94 g/ cm3 , low-density poly-
Polymers 3
LOW PRESSURE H DPE
HIGH PRESSURE LDPE
LOW PRESSURE LLDPE
Figure 1.1 Comparison 01 structures 01 HDPE, LDPE, and LLDPE.
ethylene (LOPE) has a branched structure and a density :::::;0.92g/cm3 ,

whereas linear low-density polyethylene (LLOPE) with a density of
0.92-0.93 g/ cm3 , although branched is significantly different from
LOPE due to the absence of secondary branching and presence of
short branches.
Polycondensation of compounds with a functionality of three or
more with the addition of special hardening agents to form chemical
crosslinks results in polymers with three-dimensional network
structure.
A classical example of the formation of a network polymer is the
polycondensation of phenols with aldehydes. The reaction between
phenol and formaldehyde in the absence of a catalyst is very slow
and hence in a11 commercial synthesis, catalysts are always added to
4 Introduction
accelerate the reaction. The nature of the end product and the
reaction rate depend greatly upon the type of catalyst and the mole
ratio of the two reactants.
When one mole of phenol is reacted with 0.8--0.9 mole of
formaldehyde in an acidic medium, the reaction product is a soluble,
fusible resin which can be converted into an insoluble, infusible
product only upon the addition of excess formaldehyde. These resins
are therefore termed two-stage resins known as novolacs. On the
other hand, when one mole of phenol is reacted with one or more
moles of formaldehyde at a pH of 8 or above (Le. alkali-catalyzed
medium), then insoluble, infusible products are directly formed.
These resins are termed one-stage resins and known as resols, which
are linear or branched low molecular products.
OH OH OH OR
---@-~~-@-~-@---
Resols on further heating change into resitols, a three-dimensional
network polymer of low cross link density as
tc~-@ra,ta~~2---
CR 2 CR 2
Oll
~44~
Oll OH
CH---
2
The last stage of the heating process results in the formation of

resites, which is a network polymer of high crosslink density as
Polymers 5
It should be noted that the structure of phenolics is much more

random than that shown above. The pictorial representation is
basically a simplified version only for the sake of exemplifying the
formation of a three-dimensional network.
Other thermosets besides phenol-aldehyde which are formed into
network polymers by similar reactions are urea-aldehyde and
melamine-aldehyde polymers.
1.1.3 CRYSTALLINE, SEMI-CRYSTALLINE OR AMORPHOUS POLYMERS

Polymers can also be classified as crystalline, semi-crystalline or
amorphous polymers depending on their degree of crystallinity. A
crystal is basically an orderly arrangement of atoms in space.
Polymers that are able to crystallize under suitable temperature
conditions are called crystalline polymers. The primary transition
temperature, when a crystalline polymer transforms from asolid to a
liquid, is the melting temperature designated Tm.
On the other hand, an amorphous polymer does not crystallize
under any conditions. The phase transition for this type of polymer
occurs from the glassy state to rubbery state at a temperature termed
the glass transition temperature and often designated T g
Most thermoplastics have both Tg and Tm. This is because it is
relatively difficult to get to the extreme case of a completely
crystalline polymer with an ideal formation of single crystals having
the relative arrangement of atoms strictly the same throughout the
volume. In fact, deviations from the completely ordered arrangement
as weH as completely disordered arrangement always exist. Thus, it
is the degree of crystallinity that truly determines whether a polymer
could be classified as a crystalline, amorphous or semi-crystalline
polymer.
6 Introduction
1.1.4 HOMOPOL YMERS

When a single repeating unit such as A or B exists in a polymer, it is
termed a homopolymer. Thus, homopolymer is AAAAAAAA or
BBBBBBB. For example,
A. i-t-H
when R == H, then the result is the homopolymer polyethylene (PE);
when R == CH3 , it is polypropylene (PP); when R == C6H s , it is
polystyrene (PS) and when R == Cl, it is polyvinyl chloride (PVC).
The materials mentioned above namely, PE, PP, PS and PVC are
among the largest volume thermoplastics utilized. They are used in a
maximum number of applications, mostly in those which do not
require high performance or special properties. In terms of cost they
are among the cheapest of the thermoplastics. Hence they are often
referred to as commodity plastics.
Another important dass of polymers which are formed by addition
polymerization like the above are based on one of the following three
repeating units
B ~ -{- f --- ~
H X
= ~ --- t-}
H
or -{- t---!6- ---}
H x
or {- ~~ ---!6H ---}
1,4 addition 3,4 addition 1,2 addition
When X == H, the resulting polymer is polybutadiene; when X == CH3 ,

it is polyisoprene and when X == Cl, it is polychloroprene. The double
bond may be 'cis' or 'trans' and would thus give the cis or trans
forms of these polymers. It is the 1,4 addition form that
predominantly goes into the formation of commercial dienes which
are all elastomers.
Typical examples of homopolymers that are formed by
condensation polymerization are the polyamides and polyesters
rHO 0- 0
A~ -L- NH --- R~! -t or ~- NH --- R'_ NH _! - R"-!_t

r 0 0
B ,. -L- 0 - x - 0 - ~ - X'_ ~ -}
Polymers 7
When R == (CH 2 h, the resulting polymer is polyamide: nylon-6; when

R' == (CH2)6 and R" = (CH2)4, it is nylon-66; when X == (CH2h and
X' ==C 6 H s , it is polyester: polyethylene terephthalate (PET).
These thermoplastics have properties which are superior to those of
commodity plastics (namely, olefinics and styrenics). They go into a
number of engineering applications and are termed engineering
thermoplastics. Besides polyamides (nylons) and polyesters, some of
the other hornopolymers which fall into this category of engineering
thermoplastics are the acrylics, acetals and polycarbonates.
High performance engineering thermoplastics have recently assumed
increasing importance due to their exceptional properties at elevated
temperatures. A number of such specialty polymers have been intro-
duced into the market for high temperature applications and examples
of some of the outstanding ones are polyphenylene oxide (PPO),
polyphenylene sulfide (PPS), polyether sulfone (PES), polyaryl sulfone
(PAS), polyether ketone (PEEK), polyether imide (PE I) and polyarylate
(PAr).
Each of the above mentioned specialty polymers exhibits enhanced
rigidity at high temperatures. This is a consequence of their high
glass-transition temperatures, presence of aromatic ring structures in
the backbone chain and relatively strong hydrogen bonds.
1.1.5 COPOLYMERS AND TERPOLYMERS

When two different monomers are used in the polymerization
process, the result is a copolymer. The repeating units A and B both
exist in the polyrnerized product and their varying configurations
give different types of copolymers
(i) Random copolymer: AA B AAA BB A BBB
(ii) Uniform copolymer: AB AB AB AB AB
(iii) Block copolymer: AAA BBB AAA BBB AAA
B
B
(iv) Graft copolymer: AAAAAAAAAAAAA.
B B
B B
B B
B
Block copolymers may be arranged in various star arrangements,
wherein polymer A radiates from a central point with a specified
number of arms and polymer B is attached to the end of each
arm.
8 Introduction
Copolymerization is often used to alter the properties of homo-

polymers and to achieve specific performance. For example, the flow
behavior of PVC is considerably improved by incorporating vinyl
acetate as comonomer. Similarly, the thermal stability of polyoxy-
methylene is improved considerably by incorporation of -CH2-CH2-O
units in the chain yielding an oxymethyline or acetal copolymer.
If either of the comonomers on its own could yield a crystalline
homopolymer, then copolymerization can have a very marked effect
on properties by inhibiting crystallization. For example, PE crystal-
linity is decreased by increasing the amount of vinyl acetate content in
the copolymer leading to a softer, tougher product, namely, ethylene-
vinyl acetate (EV A).
The properties of block copolymers are dependent on the length of
the sequences of repeating units or domains. The domains in typieal
commercial block copolymers of styrene and butadiene are suffi-
ciently long to produce flexible plastics called thermoplastic elastomers.
In fact, the copolymer butadiene-styrene is a good example of how the
thermoplastie characteristies can be changed by altering the portion of
two components of the copolymer. Polybutadiene is a synthetic rubber
with a high level of elasticity, while polystyrene is a dear brittle plastie
whieh is often used for making disposable containers. A copolymer
made with 75% butadiene and 25% polystyrene is styrene butadiene
rubber (SBR) with direct applications to carpeting, padding and seat
cushions. On the other hand, a copolymer of 25% butadiene and 75%
styrene gives an impact styrene which is often used for the manufacture
of equipment cabinets and appliances. Most commercial varieties of
high-impact polystyrene (HIPS) are graft copolymers in which the main
chain is that of butadiene while styrene forms the branches.
Copolymers of styrene, with acrylonitrile (SAN) and maleic anhydride
(SMA) are typical examples of uniform altemating copolymers.
Copolymers represent an industTially important dass of polymerie
materials, due to their unique combination of properties such as
impact resistance, elasticity and processibility. Block copolymers, in
particular, have great technological importance because of the ability
of these materials to form thermoplastic elastomers which can be
processed by conventional thermoplastic processing techniques. Readers
wishing to know more about copolymers may refer to the excellent
monographs [14-20] that are available.
Polymerization of acrylonitrile and styrene in the presence of buta-
diene rubber results in a terpolymer called acrylonitrile-butadiene-
styrene (ABS). Besides grafting styrene and acrylonitrile into
polybutadiene in latex form, ABS may also be produced by blending
emulsion latexes of styrene-acrylonitrile (SAN) and nitrile rubber
(NBR). Since ABS is a three component system, many variations are
Fillers 9
possible. Acrylonitrile imparts chemical resistance while butadiene

provides increased toughness and impact resistance. A variety of
grades are available - some for general purposes, some for various
levels of impact resistances and others for ease of plating. The major
applications include plumbing systems, telephone housings and auto-
mobile grills (either painted or electroplated).
1.1.6 LIQUID CRYSTALLINE POLYMERS

Polymers in which rigid, anisotropie moieties are present in the
backbone of the polymer chain are known to give rise to liquid
crystalline behavior and are therefore known as liquid crystalline
polymers (LCP) [21]. Such types of polymer have attained immense
importance due to the possibility of producing ultrahigh modulus
fibers and plastics. The main interest in the subject of LCP was
kindled by the commercialization of the aromatic polyamide fiber,
namely, Kevlar which was as stiff and strong as steel but at one-fifth
the density of steel, and with excellent chemieal and heat resistance.
Kevlar is a lyotropie liquid crystal, that is, it attains liquid crystalline
order only when dissolved in an appropriate solvent. Since the
removal of the solvent is a necessary step during fabrieation of the
product, such lyotropie LCPs are restrieted to the formation of thin
fibers and films. For thieker products, however, polymers are needed
whieh become liquid crystalline upon heating Le. 'thermotropie'
LCPs. There has been increasing interest in using LCPs as rein-
forcing additives in polymers to form blends and composites [22,23].
But moldable LCPs, regrettably, do not have immense commercial
importance.
The exceptional physieal properties of these uniquely structured
systems are a direct consequence of the morphology and orientation
induced into the polymers due to the flow history during processing.
Thus understanding the rheologieal behavior associated with liquid
crystallinity is undoubtedly essential for processing the LCPs into the
appropriate structure to exhibit their desirable properties [24].
1.2 FILLERS
The term 'filler' in the present context is used for describing those
inert, solid materials whieh are physieally dispersed in the polymer
matrix, without significantly affecting the molecular structure of the
polymer. Further, the term is restrieted to those materials which are
in the form of discrete particles or of fibers not exceeding a few
inches in length. Continuous filaments or fabrics either woven or
nonwoven are not included in this category of fillers discussed
10 Introduction
Table 1.2 Examples of rigid and flexible fillers
Filler type
Rigid Flexible
Aluminum oxide ASbestos fiber

Barium carbonate Cotton flock
Calcium carbonate Cotton linters
Calcium hydroxide Jute fiber
Calcium silicate Kevlar fiber
Clay Nylon fiber
Glass fiber Po Iyeste r fi ber
Magnesium hydroxide Sisal
Metal fiber
Mica
Talc
Wollastonite
herein. Readers wishing to know more about fillers may refer to the
excellent handbook on the subject [25].
Filler categorization can be done in a number of different ways as
shown in Tables 1.2-1.4. In the following, abrief discussion is given
under a variety of headings based on certain chosen characteristics
for comparison.
1.2.1 RIGID OR FLEXIBLE FILLERS

Rigid fillers are those fillers that do not change their shape or spatial
configuration within the polymer matrix. An example of such type of
filler is glass fiber. On the other hand, flexible fillers are those fillers
whose spatial configuration within the polymer matrix is not rigidly
defined. For example, asbestos fibers, nylon fibers, polyester fibers,
etc. would lie in folded, coiled or twisted positions within the
polymer matrix. This type of filler classification is shown in Table 1.2.
1.2.2 SPHERICAL, ELLIPSOIDAL, PLATELIKE OR FIBROUS FILLERS

Fillers can be classified based on their physieal form and shape as
shown in Table 1.3. Among the classifications shown, only spherical
fillers are symmetrie in physieal form and hence provide symmetric
changes in properties in all three spatial directions. It is normally rare
to find exactly spherieally well-formed fillers. There is always a slight
defect in shape, especially for finer size particles. For instance, even
when controlled conditions are used in the preparation of mono-
disperse siliea spheres in the mieron size range [26,27], all partieles
Filled polymers 11
Table 1.3 Filler classification by physical form
Filler form
I
3-dimensional 2-dimensional i-dimensional
I I
I
Spherical
I
Ellipsoidal
~
Flakes Platelets
I
Fibers
I
Whiskers
I
Glass beads
I
Wood flour
I
Mica
I
Clay
I
Glass fibers
I
Wollastonite
produced are not exactly spherical when viewed under the scanning
electron microscope. Thus, the terms spherical or ellipsoidal can be
viewed as those referring to nearly spherical or nearly ellipsoidal
fillers.
When the physical form of the filler is two-dimensional, the fillers
may be available as flakes (larger size plates) or platelets (smaller size
plates). Thus, mica particles exist as flakes whereas day particles exist
as platelets.
In the one-dimensional form, filler may be available in the thicker
variety as a fiber or thinner (acicular-needle-shaped) variety as a
whisker. Fillers available as fibers are glass, nylon, polyester, carbon
and so on. Wollastonite stands out as a good example of an acicular
filler.
1.2.3 ORGANIC OR INORGANIC FILLERS

Classification of fillers can also be based on their chemical form
[28,29] as shown in Table 1.4. Organic fillers fall within the sub-
category of cellulosics, lignins, proteins and synthetics. On the other
hand, inorganic fillers indude carbonates, oxides, silicates, sulfates,
carbon, metal powders and so on.
1.3 FILLED POLYMERS

The use of fillers in polymers has been going on for years. In the
early history of filled polymers, fillers were added to the polymers
rather empirically. Woodflour was one of the first fillers used in thermo-
setting phenol-formaldehyde resins because the combination was found
to be valuable in enhancing certain properties whereas the addition of
some other finely divided material to such resins conferred no benefit at
all and hence was never done. The presence of the woodflour increased
Table 1.4 Different types of fillers
Organic Inorganic
Cellulosics Lignins Proteins Synthetics Carbonates Hydroxides
Alpha cellulose Processed Soybean meal Acrylics Calcium Calcium
Cotton flock lignin Keratin Nylons carbonate hydroxide
Sisal Ground bark Polyesters Barium Magnesium
Jute carbonate hydroxide
Wood flour Magnesium
Shell flour carbonate
Cotton-seed hulls
Cotton linters
Cork dust
Inorganic
Oxides Silicates Sulfates Carbon Metals Miscellaneous
powders/fi bers
Aluminum oxide Calcium silicate Calcium sulfate Carbon black Aluminum Barium
Antimony trioxide Magnesium silicate Barium sulfate Graphite Copper ferrite
Zinc oxide Clay Bronze Magnetite
Magnesium oxide Talc Lead Molybdenum
Quartz Mica Steel disulphide
Diatomaceous earth Asbestos Zinc
Tripoli Feldspar
Hydrogel Wollastonite
Aerogel Pumice
Vermiculite
Slate flour
F uller's earth
Source: Reis 28 and 29 (Reprinted with kind permission Irom Society 01 Plastics Engineers, Inc., Connecticut, USA and Gull Publishing Co., Houston, Texas,
USA).
Filled polymers 13
Table 1.5 Some typical examples of lilled polymer systems
Polymer Filler
Thermoset: Phenol-formaldehyde resin Wood flour/cotton flock

Elastomer: Styrene butadiene rubber Carbon black
Thermoplastic: Polypropylene Calcium carbonateltalc
strength and prevented cracking of the resin by reducing the exotherm in

the cu ring reaction.
Similarly, the use of carbon black as a reinforcing agent in rubber
has been going on since early in the century as it was a major factor
in the development of durable automobile tyres. Glass fiber in nylon
and asbestos in polypropylene confer useful properties but, if the
filler and polymer are switched, i.e. asbestos is put into nylon and
glass into polypropylene the results are not nearly so good unless the
fillers are treated with appropriate coupling agents. Polypropylene is
also often filled with calcium carbonate and talc with constructive
results. Little thought was given in the early days towards the
reasons for the observed behavior. Nowadays, however, the marriage
of filler to polymer is done on a scientific basis and the reason for
the addition of the specific filler can be elucidated on the desired
property it imparts.
Some of the typical examples of filled polymer systems using a
thermoset, elastomer and thermoplastic are given in Table 1.5.
The escalating cost of engineering thermoplastics over the last
couple of decades and the awareness of dwindling supply of petro-
chemicals has created renewed incentives to restrict the quantities of
resins used through the addition of fillers to the polymer matrix.
Besides savings in cost, certain fillers provide the added advantage of
modifying specific mechanical, thermal and electrical properties of
thermoplastic products as can be seen from Table 1.6.
When stiffness, strength and dimensional stability are desirable, the
polymers are extended with rigid fillers; for increased toughness as
Table 1.6 Reasons lor the use 01 lillers in thermoplastics
1. To increase stiffness, strength and dimensional stability

2. To increase toughness or impact strength
3. To increase heat deflection temperature
4. To increase mechanical damping
5. To reduce permeability to gases and liquids
6. To mOdily electrical properties
7. To reduce the cost 01 the product
14 Introduction
in the case of high-impact polystyrene or polypropylene, deformable

rubber particles are added; asymmetric fillers such as fibers and
flakes increase the modulus and heat distortion temperature; and
electrical and thermal properties are modified by the use of
metallized fibrous fillers. With fibrous fillers, the improvements can
be further magnified due to the influence of the fiber aspect ratio and
anisotropy as weIl as fiber orientation. The most effective reinforcing
fillers are fibers of high modulus and strength. Glass fibers, which are
non-crystalline in nature, or asbestos - a crystalline fiber - provide the
reinforcement in most commercial fiber-reinforced thermoplastics.
Carbon fibers or whiskers, single crystal fibers, are the other crystalline
fibers used as reinforcement.
The improvements in mechanical properties through the use of
fillers acting as reinforcing agents have been discussed in detail by
Nielsen and Landel [30]. Such filled systems wherein the fillers
provide reinforcements are often referred to as reinforced polymer
systems or reinforced plastics. However, in the present book, the
term 'filled polymer systems' is used in the most general sense and
includes all systems wherein fillers are present as cost reducing
agents as weIl as reinforcing or property modifying agents.
One or more of the physical, mechanical and thermal properties of
polymers can be effectively modified by the use of different types of
fillers. For example, in the tyre industry, the presence of the filler
carbon black in vulcanized rubber enhances properties like elastic
modulus, tear strength and abrasion resistance [31-33] and also
influences extrusion characteristics like extrudate distortion, extensional
viscosity and die swell behavior [34-40]. Thus, carbon black functions
as a reinforcing agent and a processing aid in the rubber industry.
Different types of fillers serve different types of purposes. For example,
titanium dioxide acts as a delustering agent in the fiber industry and
aluminum trihydroxide as an economic flame retardant and smoke
suppressing agent. In most applications, the proper balance of properties
is no less important than an improvement of an individual property. It
must be accepted that an improvement in one property can in all
likelihood lead to deterioration of others and consequently, it is the overall
performance of the filler in a given formulation that determines its choice.
The predominant function of some typical fillers is given in Table 1.7.
Selection of a filler is not just an art but a science and various
factors would have to be considered in the choice such as,
1. Cost and availability

2. Wettability or compatibility with the polymer
3. Effect on polymer flow characteristics
4. Physical properties
Filled polymers 15
Table 1.7 Predominant function of some typical fillers
Function Typical fillers
Cost savings Wood flour, saw dust, cotton flock

Reinforcement Glass fibers, cellulosic fibers, synthetic fibers, asbestos fibers
Hardness Metallic powders, mineral powders, silica, graphite
Thermal insulation ASbestos, ceramic oxides, silica
Chemical resistance Glass fibers, synthetic fibers, metallic oxides, graphites
5. Thermal stability
6. Chemical resistivity
7. Abrasiveness or wear
8. Toxicity
9. Recyclability
Undoubtedly the idea of adding the fillers is to achieve reduction
in cost. However, there are some special type of fillers which are
used purelyon a functional basis with an accepted trade-off in the
cost reduction, for example, some fiber glass reinforcements for
polyesters, barium ferrite as a magnetizable filler, metallic powders
for electrical and thermal conductivity improvement. In fact all these
specialty fillers are more expensive than general purpose fillers and
in some cases even more expensive than the polymer which they fill.
In any case, the cost-effectiveness of the filler ought to be determined.
The objective should be to compare the full cost of the completed
product with and without the filler.
The first step involves obtaining the raw material costs which must
be converted from cost per pound to cost per volume. This is because
cost per pound of the filler is meaningless unless adjusted for specific
gravity differences. The volume of the polymer that is displaced by
the filler becomes the main consideration. A three-step calculation
method [41] can be used to get the polymer saved and thus to
determine the cost-effectiveness of filled systems. If the filled polymer
system is compounded in-house, then that cost has to be included.
Similarly, added labour cost or savings due to the use of filled polymer
systems must be considered. Often it is found that a minimum of 30
volume percent of low-cost filler is required to get a cost benefit
when switching from unfilled polymer to filled polymer system.
When selecting a filler, it is important to bear in mind that for
adequate stress transfer, wettability and good adhesion between the
filler and the polymer is essential. Physical properties like, for example,
the density should be low so that the filler stays in suspension or at
16 Introduction
worst is able to be resuspended with mlllimum mixmg. Thermal

stability and chemical resistivity are also very important so that the
filler does not change characteristics during the preparation of the filled
polymer system. Fibrous materials and non-symmetrical fillers are more
abrasive than others and could cause increased wear to the processing
equipment. Hence care has to be taken when selecting such fillers as
they may not turn out to be cost-effective due to excessive damage to
the equipment. Also the effect of fillers on polymer flow characteristics,
namely, the rheology must be carefully assessed as that determines its
processibility and hence is a very important parameter.
1.4 FILLER-POL YMER INTERACTIONS

When a filler is added to a polymer with the specific idea of
reinforcement, it is. expected that the reinforcing filler component
which is strong and stiff should bear most of the load or stress
applied to the system while the polymer which is of low strength,
fairly tough and extensible should effectively transmit the load to the
filler. Maximum reinforcement benefits would be achieved from fillers
when conditions occur in accordance with this concept [42]. In order
that the load transfer takes place effectively, the matrix must have
sufficiently high cohesive and interfacial shear strength. Thus, apart
from the filler and the polymer, it is the inevitable region between
them, namely, the interphase which plays a vital role in the
fabrication and subsequent behavior of the filled polymer systems in
service. The interphase is that region separating the filler from the
polymer and comprises the area in the vicinity of the interface. It
would be synonymous with the words 'interfacial region' but different
from the term 'interface' which would be the contacting surface
where two materials under consideration meet. Thus, for some filled
polymer systems, there could exist more than one interface as in the
case of coated fiber-filled polymer. In such cases, the fiber-coating
interface and the coating-polymer interface would have characteristics
of their own. However, normally a less atomistic view is taken and
the characteristics of the 'interfacial region' as a whole are generally
investigated.
Good mechanical strength can be achieved only by uniform and
efficient stress transfer through a strong interfacial bond between the
filler and the polymer. It is important that the bond is uniform on a
fine scale rather than unevenly strong in local regions as areas of the
filler-polymer interface which are not in contact begin to act as
cracks under an applied stress. In the absence of a good interfacial
bond, fibrous fillers will pull out of the polymer and result in an
annulment of the reinforcing effect [43]. Controlled debonding at the
Filler-polymer interactions 17
weak fi11er-polymer interface, on the other hand, results in increased

toughness of the system, but at the cost of a concurrent decrease in
the transverse strength on fatigue resistance [44]. The toughness of a
fi11ed polymer material can be adjudged by the behavior of the fi11er-
polymer interface during fracture. Toughness is said to be enhanced
when the state of stress ahead of a crack tip is blunted during
interfacial failure due to weak interfacial bonding.
Such a phenomenon of filler-polymer delamination has been
observed [45] at stresses less than half of the ultimate tensile strength
in the case of glass fiber reinforced resin. Thus one can see why it is
difficult to achieve a simultaneous increase in mechanical strength
and toughness. Attempts have been made to solve the tensile
strength/toughness dilemma [46,47] through the use of duplex fibers
or coupled rubber fillers or duplex systems of metal coated carbon
fibers but with only limited success. In any case, it is the behavior of
the interphase during service that fina11y decides the performance of
the filled polymer product. It is, therefore, prudent to understand the
interphase through a careful study of the polymer.
Three possible types of filler-polymer interactions can be visualized.
Case 1
The filler is only physica11y present in a nonpolar polymer with no
interaction at a11. The fi11er then merely acts as a diluent and is
expected to weaken the material by its presence.
Case 2
The fi11er is physically present in the polymer and its surface is
wetted by the polymer either because of the inherent polymer affinity
for the fi11er or because the fi11er is appropriately surface treated to
provide this affinity. A physical bond is developed causing an
increase in the frictional resistance to the movement of the filler and
thereby resulting in an increase in the tensile strength and a decrease
in the elongation at break. The extent of the increase in the
mechanical properties is dependent on the strength of the mechanical
bonding between the filler and the polymer.
Case 3
The fi11er establishes a true chemical bond with the polymer. This
results in an exceptional strengthening effect. This case of interaction
may be present in carbon-black reinforced rubber and glass-fiber
reinforced plastics, though in both cases it might be debatable
18 Introduction
whether an actual chemical bond or a strong physical adhesion as in

Case 2 is present. For carbon-black filled rubbers, the nature of the
interaction has been studied [48,49] and though it is generally agreed
that van der Waals forces are sufficient to give reinforcing effects,
there is evidence [50] of chemical grafting between carbon black and
rubber. The process by which polymer molecules are grafted to
carbon-black surfaces is by a free radical mechanism, as carbon black
is an efficient free radical acceptor. The high degree of adhesion
produced by such chemical grafting probably contributes to the extra-
ordinary reinforcing properties of these materials. However, excessive
grafting can lead to difficulties in dispersing the filler, formation of an
undesirable large gel fraction be fore vulcanization and other deleterious
effects which might affect product properties.
There are a number of factors which affect filler-polymer
interaction.
1.4.1 FILLER GEOMETRY

The filler-polymer interaction can be adjudged from the effect of filler
addition on the stiffening and strengthening characteristics of the
polymers. At a given volume concentration of the filler, the degree of
stiffening is directly proportional to the filler surface area. It has been
shown [51] that high mechanical strength is achieved through strong
interfacial bonds when interfacial areas are extremely high, e.g.
through the use of 1 mm 3 of a 50% by volume fiber composite with a
fiber diameter of 7.5 J..Lm giving an approximate interfacial area of
6500 mm 2 However, large interfacial area would lead to physico-
chemical instability resulting in spheroidization and agglomeration of
the filler due to high interfacial energy. The presence of undispersed
or agglomerated zones of fillers is gene rally detrimental to the
properties of the filled polymer systems. Surface area depends upon
the particle size, particle shape and porosity of the filler. It has been
shown [52] that there is a linear relations hip between the increase in
stiffness and particle size for fillers below 0.2 mm in average particle
diameter. The same cannot be said about larger particle sizes. For
carbon-black filled elastomers, it has been shown [48] that for
significant reinforcement, the mean particle diameter between 0.02 J..Lm
and 0.05 J..Lm is most effective. Small particle size is, therefore, a
prerequisite for reinforcement. Particle consideration, such as inability
to attain satisfactory dispersion and interference with vulcanization
reactions due to high adsorptive capacity, place a lower limit on the
particle size, which in the case of carbon blacks is around 150 A.
Porosity too, has a direct influence on filler-polymer interaction as in
the ca se of non-crystalline fibers which have room inside their
amorphous structures for other materials like water causing a

detrimental effect on adhesion and reinforcing properties.
1.4.2 VOLUME FRACTION

Concentrations of fillers are preferably measured by volume than by
weight due to the wide variations in the densities of available fillers.
A number of the filled polymer system properties like tensile
strength, abrasion resistance, viscosity of the melts, etc. have been
found to show change at some critical volume fraction. Areduction
in tensile strength, for example, is observed when the pigment
content in paints is above 'the critical pigment volume concentration'
(cpvc). Anomalies in the behavior at high levels of extender pigment
in the coating area have led to the development of the concept of
cpvc, which is the pigment volume content at which enough binder
is present to fill all the voids between the pigment particles. The cpvc
is directly related to the surface area of the pigment particles and
hence affects the filler-polymer interaction. It can be calculated by the
method described in Bierwagen [53].
1.4.3 FILLER SURFACE

Apart from surface area and volume fraction of the filler, it is the
micro-configuration and frictional properties of the filler surface that
plays an important role in the filler-polymer interaction [54]. Friction
implies the presence of a compressive force normal to the interface;
however, studies show that friction itself is a mere local welding
between the filler and the polymer and is dependent to a great extent
on the filler surface. Smooth filler surfaces offer no opportunity for
keying adhesion of the polymer but they are more easily wetted than
those with less regular surfaces. Of course, smooth fillers would have
on their surfaces uneven and undeclared adsorbed layers of water
and contaminants which can seriously affect adhesion. In any case,
perfect wetting i.e. complete exclusion of voids on the filler surface is
generally an ideal situation which is never achievable.
1.4.4 WETIABILITY
It has been shown [55,56] that aprerequisite for a good bond is an
intimate contact between the filler and the polymer brought together
by good wetting. The wetting of asolid by a liquid is dependent
upon the relative interfacial energies among the solid, liquid and
vapour phase above them as shown in Figure 1.2. The contact angle
()' of the liquid drop on the flat solid is given as
20 Introduction
rc'SV
Figure 1.2 Schematic diagram showing the contact angle when a liquid drop comes
into contact with a flat solid surface.
cos (J' = y~v - y~ (1.1)

y~v
where y' is the interfacial energy and subscripts S, L, V refer to solid,
liquid and vapour phases, respectively. When the liquid drop on the
solid surface exhibits a finite contact angle with the solid, the surface
is not completely wetted and only particle bonding is possible. H,
however, the liquid drop collapses on the solid surface spontaneously
by spreading and wets the surface uniformly, the contact angle is
zero. It thus seems logical to aim for situations where the critical
surface tension, y~ va lues on the filler surface are considerably less
than those of the polymer. The foregoing condition for good wetting
is based on the presence of the solid, liquid and vapour phases to be
in chemical equilibrium, though in reality, this is not truly the case.
There are normally adsorbed gases on the solid surface leading to an
increase in the contact angle. Also the solid surface is not smooth
leading to a decrease in the contact angle. The liquid itself contains
contaminants which prevent chemical equilibrium. All these factors
greatly affect the wetting behavior. In filled polymer systems, if a
polymer does not wet the filler then there is entrapment of air
bubbles, which act as stress risers and represent areas of zero load
transfer, thereby weakening the filled polymer product. The strength
realized in many reinforced systems is limited by the presence of
voids or air inclusion in the system [57]. There are other aspects of
wetting that significantly affect the filled polymer properties. For
example, the rate at which a polymer wets a particular filler and the
final degree of wetting determines the strength of the system.
Wettability also affects the ease of dispersion of the filler in the

polymer which in turn is a factor in the property effectiveness. It has
been shown that in the case of carbon black reinforced rubber,
wettability of the pigments not only ensures easy dispersion of the
filler in the rubber but also implies a favorable relation between
carbon black-elastomer adhesion and elastomer cohesion which
ensures that the effectiveness of the filler would hold even up to high
ultimate elongations of several 100% and survive strains that would
befall during normal service conditions.
1.4.5 FILLER SURFACE TREATMENT

Fillers which are generally used as reinforcement are fibers with
diameters of the order of 10 Ilm corresponding to a surface area of
the order of 103 _105 cm 2 /g. The surface chemistry and physics of the
filler-polymer interface show considerable variations affecting the
wetting and bonding characteristics which are determining factors in
the ultimate bond strength of the polymer to the filler. The best way
of determining whether a satisfactory strong bond has been
established is by correlating the final physical properties of the filled
system based upon maximum fiber density. In practice, as pointed
out earlier, it is difficult to form a strong bond between the filler and
the matrix due to poor wettability of the filler especially in nonpolar,
high melt viscosity polymerie systems, and due to the presence of
contaminants or multimolecular layers of water on the mostly
hydrophilie surfaces of fillers, which prevents physical or chemi-
adsorption of the polymer molecules. The interfacial bond can be
enhanced and the mechanical performance of the composites improved
by suitable surface treatment. These days, most of the fillers are
pretreated before they are used as secondary phases in composite
materials. A surface treatment helps in a number of ways:
(a) helps to protect surface cracks, surface steps, notches and other
imperfections from damage during processing and thereby
preserve the strength of the materials;
(b) helps to eliminate the influence of surface flaws and abrasion
during processing of the filled systems;
(c) helps to keep out excessive damp and protects the filler from
water attack which weakens the composite;
(d) helps to develop a stronger interfacial bond and hence improves
the strength of the composite.
The most common pretreatments involve surface cleaning and the
use of surface modifiers in the form of sizes, finishes and coupling
agents. The type of pretreatment to be given depends on the type of
22 Introduction
the filler. For example, in the case of carbonaceous or graphite fibers

which are useful for ablative and structural purposes, it has been
found [58] that the fibers are difficult to wet with conventional
thermosetting resins, are contaminated with pyrolysis products and
alkali salts, and contain moisture - all of which are detrimental for
interfacial bonding. The surface of graphite fibers is essentially
chemically neutral and possesses low and variable surface area.
Hence, a surface cleaning is first done by way of controlled oxidation
through a 24-hour boiling process in 60% nitric acid which increases
the chemical functionality and surface area of the fiber. The surface
cleaned fibers are then protected by means of a polymeric coating of
polyvinyl akohol, polyvinyl acetate, polyacrylonitrile or polyurethane.
Surface cleaning of graphite fibers and protecting the altered surface
by polymeric coating is very important [59]. Oxidized graphite fibers
are known to give three times as high composite shear strength as
non-oxidized fibers and the reason for this is attributed more to
higher chemical activity than increased surface area. This is under-
standable because the pores induced during oxidation would be too
small to be occupied by the large polymer molecules of the matrix.
Other means of physically interlocking graphite fibers with the
polymer matrix have been recently contemplated through the growth
of whiskers like those of silicon carbide, for example, with successful
results in achieving higher interlaminar strengths.
In the ca se of glass fibers which are by far the most widely used
inorganic fillers as reinforcing agents in unsaturated polyesters and
epoxide resins, the surface treatment is done through the use of
surface modifiers which may be in the form of finishes, sizes or
coupling agents. Coatings improve the strength of the fiber. Further-
more, the fracture of a composite containing coated fibers is known
to occur without fiber pull out, unlike the case of uncoated fibers.
The coatings, which are generally applied to 'as drawn' glass fibers,
improve wetting and adhesion and help to provide sufficient
protection to withstand the rigors of mechanical abrasions and
chemical attacks, and also exclude moisture from the interface in
filled polymer systems. A good example of this is the proprietary
HTS epoxy finish which is applied to some glass fibers as they are
drawn. In the case of fused silica fibers, another way of achieving the
same benefits as those through finishes and sizes is by the deposition
of carbon on freshly drawn fibers.
Finishes, which are commonly used for coating fibers, include
vinyltrichlorosilane, styrene, ethylene oxide, epichlorohydrin,
phenylsilane and vinyldimethylethoxysilane. These, when applied to
the fibers, help to eliminate or reduce polymer crazing or strains
adjacent to the fiber apart from improving the interfacial bonding.
Amine and silane finishes provide strong interfacial bonding with

oxide-type fibers but they are worthless for accomplishing the same
function with carbonaceous or graphite fibers for which surface
cleaning, as discussed earlier, is necessary for providing interfacial
bonding.
Commercially used sizes contain about 94% of water along with
other components like
(a) a film-forming polymer such as polyvinyl acetate, polyester or
starch which gives protection to the glass fibers and cohesion
required during the formation of multiple filaments in which
groups of fibers are collected into a bundle or a strand by a
gathering device.
(b) a plasticizer which helps to make the fiber softer and more
extensible and helps to lower the tack temperature of the polymer
matrix to which the fiber is added, thereby increasing the
tendency for adhesion.
(c) a lubricant such as a silicone to facilitate drawing and reduction
in friction against guide parts during the process of winding the
strands into a forming package called a cake.
(d) an antistatic agent to prevent retention of electrical charges which
may attract dust, cause plastics to stick to metal surfaces or even
cause fires.
(e) a coupling agent which improves the adhesion of the fiber to the
polymer matrix.
From the above list, it is the coupling agent which is sometimes
applied to the fiber in aseparate surface treatment step and at times
even added directly to the polymer allowing it to migrate to the
filler-polymer interface during processing. This is understandable
because the most effective glass lubricants, which are necessarily
required to prevent glass abrasion during fiber formation unfortun-
ately act as deterrents to the glass-polymer bond. Similarly, when the
polymer matrix is that of a silicone resin, the presence of starch in
the size is detrimental to the fiber-resin bond.
In such cases, a two-step process becomes essential, one in which
the fiber is coated with the optimum size containing the lubricant or
film-forming polymer but no coupling agent, which is then bumed
off generally by heat cleaning, followed by the application of the
coupling agent as a second step.
Glass fiber surfaces do not adhere well to most polymers, especially
to polyester resins, where strength properties are severely reducedby
the accumulation of water at the interface. Hence the most common
pretreatment involves the putting of a coupling agent on to the filler
surface to form a water resistant interface and to act, eventually, as a
24 Introduction
bridge between the filler and the polymer resulting in an improve-

ment in the interfadal bond and mechanical properties of the
composites.
In order to achieve optimum properties from a polymer matrix
through the addition of fillers and surface modifiers, it is essential to
enhance the statistical probability of uniform coupling and chemical
wetting through proper compounding technique. There are essentially
three methods of incorporating surface modifiers in filled systems:
1. pretreating fillers before compounding
2. dispersing surface modifiers in processing oils, waxes or on
spedfic carriers
3. integral blending of undiluted surface modifier, filler and polymer.
Pretreatment is done in one of the following three ways - through
an aqueous medium, through a solvent (alcohol, benzene, chlorinated
hydrocarbon, etc.), or through spraying. In an aqueous medium or a
solvent containing traces of water for hydrolysis, a small proportion
of the surface modifier is stirred in and the filler to be treated is
immersed in this solution, filtered off or expressed, and dried at
120-130C. Pretreatment by spraying involves the atomizing of the
surface modifier in the diluted form on to a fluidized or agitated
filler bed and thoroughly mixing the system. The fineness of spray
and length of time of spray are more important for uniform coupling
than the amount of time spent during mixing. A convenient device
for mixing could be high shear mixers (such as, Henschel, Wellex
and Pappenmeir or blenders of the Patterson-Kelly Twin Shell and
Littleford Lodige types) or low shear mixers (such as ribbon
blenders). In high shear or impingement type equipment, the mixing
time has to be carefully controlled to avoid mechanical reduction in
filler particle size. Hence in such equipment mixing is done for only
about 3 minutes in contrast to the mixing times of 6 minutes and 20
minutes in the twin shell blender and low shear ribbon blender,
respectively. Pretreated fillers offer the advantage of easy handling
and assurance that the surface modifier is uniformly distributed on
the filler surface. Since the hydrolyzable portion of the coupling agent
is chemically bonded to the filler surface, the organofunctional
portion is available for reaction with the organic matrix. Hence, when
compounding a pretreated filler with a polymer matrix, the
compounding technique used for unmodified fillers is quite adequate
for obtaining the maximum surface modifier effidency in the
pretreated filler case. The only disadvantage of using pretreated fillers
is that the amount and type of surface modifier in the system cannot
be adjusted. This is circumvented by the use of the other methods of
compounding enlisted above.
The surface modifier is often dispersed in a proper medium so that

uniform wetting and coupling can be achieved. Some examples of
these are given below.
Filled liquid resin: The surface modifier is first dispersed into the
liquid resin before mixing with the filler.
Filled flexible PVC: The surface modifier is first dispersed in the
dioctyl phthalate (OOP) or other ester plastieizer before adding
filler, stabilizer and PVC in that order.
Filled polyolefins: The surface modifier is dispersed in the mineral
oil on a 1: 1 basis and applied to the filler as a coat before
extrusion.
Filled elastomers: The surface modifier is first added to the process
oil and dispersed into the elastomers during the early stages of
extrusion.
In contrast to pretreated fillers, the above method of incorporating

surface modifiers in filled systems provides the flexibility for making
the proper choiee of the type and loading of both the surface
modifier and the finer.
In order to convert fillers from mere extenders to reinforcing agents
and property enhancers, surface modifiers are used so that greater
compatibility and binding between the filler and polymer matrix can
be achieved. Various types of surface modifiers are commercially
available and they can be broadly dassified as chrome complexes,
silanes, azidosilanes, titanates, zircoaluminates, organopolysiloxanes,
polymerie esters and chlorinated paraffins. Some important surface
modifiers are given in Table 1.8.
Chrome complexes are among the first surface modifiers to be
used. The one whieh provided the coupling between a glass fiber
and aresin, was methacrylato chromie chloride marketed by Dupont
as Volan. The chromie chloride portion of this bifunctional molecule
forms a good bond with the glass fiber and the vinylidene group
reacts with the styrene and fumarate unsaturations of polyesters to
produce a chemieal bridge between finer and resin. These systems
give:
Improved bonding
Improved impact and flexural strength
Silanes are represented by the general formula R'Si(ORh wherein

OR is the hydrolyzable alkoxy group whieh forms silanolsthat react
with the OH group on the finer surface and R' is an organofunctional
group that attaches itself to the resin. These systems give:
Table 1.8 Some typical surface modifiers
Surface modifier type Typical examples Trade names Manufacturersa
Silanes Vinyltrimethoxy silane A-150/CV4917IVTMO M1/M2/M3

Vinyltriethoxy silane A-151/CV4910IVTEO M1/M2/M3
Vinyltri(2-methoxyethoxy)silane VTMOEO/Z -6082 M3/M4
Vinyltriacetoxy silane CV4800/Z-6075 M2/M4
Vinyltrichlorosilane CV4900IVTC M2/M3
Chloropropyltrimethoxy silane CC3300/CPTMO/Z -6076 M2/M3/M4
y-Glycidoxypropyltrimethoxy silane A-187/CG6720/GLYMO/Z6040 M1/M2/M3/M4
y-Methacryloxypropyltrimethoxy silane A-174/CM8550/MEMO/Z6030 M1/M2/M3/M4
y-Aminopropyltriethoxysilane A-11 00/CA0750/AMEO M1/M2/M3
N--Aminoethyl-y-aminopropyl-trimethoxy silane A-1120/CA0700/DAMO-P/Z-6020 M1/M2/M3/M4
Sulfonylazide functional silane Al-CUP M5
Titanates Isopropyltriisostearoyl titanate KR TTS M6
Iso pro pyltri (d ioctylpyro phosphato )titanate KR38S M6
Titanium di(cumylphenylate)oxyacetate KR 134S M6
Titanium di(dioctylpyrophosphate)oxyacetate KR 138S M6
Tetraoctyloxytitanium di(ditri-decylphosphite) KR 468 M6
Neoalkoxy,tri(dioctylphosphate)titanate L1CA 12 M6
Neoal koxy, tri (N-ethylamino-ethylam in0 )tita n ate L1CA 44 M6
Dicyclo(dioctyl)pyrophosphate Iitanate KR OPP2 M6
Zirconates Neoalkyl,trisneodecanoyl zirconate LZ 01 M6
Neoalkoxy,trisdodecylbenzene sulfonyl zirconate LZ 09 M6
Neoalkoxy-tris(dioctyl)pyrophosphate zirconate LZ 38 M6
Neoalkoxy-tris(ethylene diaminol)ethyl zirconate LZ 44 M6
Zireoaluminates Amino funetional zireoaluminate CAVCO MOD A or APG M7
Carboxy funetional zireoaluminate CAVCO MOD C or CPG or CPM M7
Oleophilie funetional zireoaluminate CAVCO MOD F or FPM M7
Methaeryloxy funetional zireoaluminate CAVCO MOD M or MPG or MPM M7
Mereapto funetional zireoaluminate CAVCO MOD S or SPM M7
Hydrophobie Polymerie esters W-900, W-905 M8
wetting agents Salt of unsaturated fatty aeid W-910 M8
Fluorinated alkyl esters FC-430, FC-431, FC-740 M9
Perfluoroalkyl sulfonates FC-93, FC-95, FC-99, FC-120 M9
a M1 OS: Speeialties Ine., 39 Old Ridgebury Road, Danbury, CT 06810-5124.

M2 Petrareh Systems Ine., Bartram Road, Bristol, PA 19007.
M3 Kay-Fries, Ine., Chemieal Div. of Dynamit Nobel of Ameriea Ine., 10 Link Drive, Roekleigh, NJ 07647.
M4 Dow Corning Corporation, Midland, MI 48640.
M5 Hereules Ineorporated, Hereules Plaza, Wilmington, DE 19894.
M6 Kenrieh Petroehemieals Ine., 140 East 22nd SI., PO Box 32, Bayonne, NJ 07002-0032.
M7 Cavedon Chemieal Co. Ine., Woonsoeket, RI 02895.
M8 BYK-Mallenekrodt, USA Ine., 19W075 Barbizon, Oak Brook, IL 60521.
M9 Commereial Chemieals Division/3M, 223-65E, 3M Center, St Paul, MN 55144.
Souree: Ref. 29 (Reprinted with kind permission from Gulf Publishing Co., Houston, Texas, USA).
28 Introduction
Improved filler loading capacity

Improved adhesion
Enhanced filler dispersion, improved processibility and property
uniformity
Enhanced mechanical and electrical properties with their retention
after environmental aging
Azidosilanes which can effectively bond mineral fillers to
hydrocarbon polymer have a general formula (CH3 0hSi-R-S02 N 3
wherein the hydrolyzable silane forms siloxane bonds on the filler
surface and the sulfonyl azide decomposes at the high temperatures
during surface treatment to form nitrene which chemieally bonds the
polymer to the filler. These systems give:
Improved tensile strength, flexural strength and flexural modulus
Improved heat distortion temperature
Titanates react with free protons (H*) and water available as
chemieally bound, physieally bound, absorbed or free on the
inorganic filler surface to produce a monomolecular organie layer
whieh bridges and binds the filler and the matrix. These systems
give:
Improved impact strength
Reduced viscosity
Improved filler loading capacity without increase in viscosity
Improved heat stability
Improved chemie al resistance
Organopolysiloxanes are thermoset materials called 'glass resin'
(Owens-Illinois Corporation) containing methyl and phenol
functionality and serve as good coupling agents. These systems give:
High temperature electrieal properties
Dimensional stability
Chemie al resistance to organie solvents as well as inorganie acids
Polymerie esters provide hydrophobie encapsulation of discrete filler
particles and give
Uniform wetting and ease of dispersion
Improved impact strength
Improved physieal properties
Chlorinated paraffins are solid resins containing around 70% by
weight chlorine whieh can be used alone or in combination with
vinyl silanes for coupling. These systems give:
Improved dispersion
Improved processing
Improved tensile strength, flexural strength and flexural modulus
Improved heat distortion temperature
An effective coupling agent must have the following characteristics
[60]
(a) a high modulus
(b) be non-melting
(c) chemically adhere to the glass fiber surface
(d) not be removed during molding
(e) be chemically compatible with the polymer matrix
If such are the properties of coupling agents then their presence
would result in increased flexural and tensile strengths and longer
retention of the strength under wet conditions.
The performance of some typical filled systems is tabulated in
Table 1.9. Dry and wet flexural strength of nylon 6, for example,
filled with wollastonite treated with A-1100, shows an increase of
over 50%. Significant increases in the impact strengths are also seen.
Surface modifying agents do have an effect on the heat distortion
temperature too as can be seen from Table 1.10.
The presence of surface modifiers helps to stabilize the wet-
electrical properties of filled systems. In the absence of surface
modifiers, water absorption and accumulation at the filler-polymer
interface would lead to unsatisfactory dielectric constants and
dissipation factors. The electrical property protection afforded by
surface modifiers is exemplified in Table 1.11. It should be noted that
several hours of boiling increases the dielectric constant to 22.16 and
14.66 when wollastonite and quartz, respectively, are present in the
epoxy composites in the untreated form. However, treatment with
surface modifiers in as small an amount as 0.5 phf stabilizes the
dielectric constants even after hours of boiling to a value equivalent
to that before boi!.
If proper choice of the surface modifier is made so that its
functionality matches the polymer functionality, then maximum
increases in the final product properties can be achieved. A guideline
for the use of the more effective surface modifiers in specific systems
is given in Table 1.12.
The first commercially successful coupling agent used in glass-
reinforced thermo setting material was a chrome complex, namely,
methacrylato chromic chloride sold under the trade name of Volan
by Dupont. However, for reinforced thermoplastics, silane coupling
agents are the most commonly used type. Silanes include relatively
simple compounds such as vinyltrichlorosilane and combinations of a
Table 1.9 Effect of the surface modifiers on the mechanical strength of some typical filled systems
Polymer Filler, Surface Tensile, Tensile Flexural Flexural Impact Ref.

filler loading modifier strength modulus strength modulus strength
(phr) amount (MPa) (MPa) (MPa) (MPa) (J/m)
(phf)
Dry Wet Dry Wet Dry Wet Dry Wet
Nylon 6 Wollastonite, 100 61 38 77 41 106 61 57 41 25 [61)

Nylon 6 Wollastonite, 100 A-1100,0.5 72 52 71 42 128 83 53 42 53 [61)
Nylon 6 Wollastonite, 230 52 28 99 55 84 42 66 25 20 [61)
Nylon 6 Wollastonite, 230 A-1100,0.5 82 65 104 66 145 112 68 44 49 [61)
Nylon 6 Glass bead, 70 46 32 85 40 27 10 27 [62)
Nylon 6 Glass bead, 70 A-1100, 1.0 66 50 23 54 27 14 67 [62)
Nylon 6,6 Wollastonite, 100 54 43 95 66 94 66 74 44 [62)
Nylon 6,6 Wollastonite, 100 A-1100, 1.0 55 52 92 68 118 85 75 48 [62)
Nylon 6,6 Glass bead, 70 49 38 98 60 34 19 [62)
Nylon 6,6 Glass bead, 70 A-1100, 1.0 76 65 131 83 37 21 [62)
Nylon 6,6 Processed mineral 74 59 151 100 [62)
fiber, 70
Nylon 6,6 Processed mineral A-1100, 1.0 107 85 188 130 [62)
fiber, 70
PBT Wollastonite, 100 43 36 78 69 155 [61)
PBT Wollastonite, 100 A-1100,0.5 50 46 99 96 267 [61)
PBT Wollastonite, 100 A-187,0.5 165 [61)
PBT Wollastonite, 230 32 31 111 84 51 50 72 61 [62)
PBT Wollastonite, 230 A-187, 1.0 52 51 128 119 80 75 74 66 [62)
PC Wollastonite, 100 44 48 79 72 82 68 65 60 [61)
PC Wollastonite, 100 A-1100,0.5 56 55 82 85 99 85 63 63 [61)
PVC Wollastonite, 100 63 [62)
PVC Wollastonite, 100 A-1100, 0.5 94 [62]
PVC Quartz, 100 91 [62]
PVC Quartz, 100 A-1100, 0.5 110 [62]
Polyester Siliea, 120 71 59 [62]
POlyester Siliea, 120 A-174,0.5 122 100 [62]
Polyester Miea high aspeet 19 18 [62]
ratio, 40
Polyester Miea high aspeet A-174,0.5 45 24 [62]
ratio, 40
Polyester Tale, 100 61 30 [62]
POlyester Tale, 100 A-174,0.5 71 50 [62]
Polyester Wollastonite 72 53 [62]
Polyester Wollastonite A-174,0.5 108 86 [62]
POlyester Alumina trihydrate 50 32 [62]
Polyester Alumina trihydrate A-174,0.5 83 57 [62]
Phenolie Aluminum oxide 35 15 [62]
Phenolie Aluminum oxide A-1100 41 32 [62]
HDPE Wollastonite, 50 16 50 30 [61]
HDPE Wollastonite, 50 KR-TTS,3 15 60 41 [61]
Wet conditioning has been done by immersing 16 hr in water at 50C and then testing.
32 Introduction
fable 1.10 Effect of surface modifiers on the heat distortion temperature of some
typical filled systems
Polymer Filler, loading (phr) Surface Heat Ref.

modifiers, distortion
amount (phf) tempo (0C)
Nylon 6 56 [61)
Nylon 6 Wollastonite, 100 150 [61)
Nylon 6 Wollastonite, 100 A-1100, 0.5 133 [61)
Nylon 6 Glass bead, 66 90 [62)
Nylon 6 Glass bead, 66 A-1100, 0.5 98 [62)
Nylon 6 Clay, 100 153 [62)
Nylon 6 Clay, 100 A-1100, 0.5 151 [62)
Nylon 6,6 75 [62)
Nylon 6,6 Wollastonite, 100 202 [62)
Nylon 6,6 Wollastonite, 100 A-1100, 0.5 215 [62)
Nylon 6,6 Glass bead, 66 127 [62)
Nylon 6,6 Glass bead, 100 A-1100, 0.5 126 [62)
Nylon 6,6 Processed mineral, 66 230 [62)
Nylon 6,6 Processed mineral, 66 A-1100, 0.5 231 [62)
PBr 63 [62)
PBr Wollastonite, 100 143 [62)
PBr Wollastonite, 100 A-187,0.5 150 [61)
PBr Wollastonite, 100 A-1100, 0.5 144 [61)
PBr Wollastonite, 230 186 [61)
PBr Wollastonite, 230 A-187,1.0 186 [61)
PC 131 [61)
PC Woliastonite, 100 130 [62)
PC Wollastonite, 100 A-1100, 1.0 133 [62)
Cycloaliphatic Alumina trihydrate 121 [62)
epoxide
Cycloaliphatic Alumina trihydrate A-186, 1.0 130 [62)
epoxide
[62)
Cycloaliphatic Alumina trihydrate A-187, 1.0 132 [62)
epoxide
silane with a resin such as the epoxy type. They invariably contain
an organic functional group such as vinyl and allylic groups for
coreacting with polyester matrix and amino groups for epoxides
together with inorganic or organo inorganic groupings which can
exert strong physico-chemical interaction with the hydroxyl groups of
the glass fiber surface. In addition to chemically bridging the polymer
to the glass surface, the coupling agent reduces the rate at which
water can accumulate at the interface. The water has to first hydrolyze
the -O-Si-O- bonds at the interface before displacing the polymer
and the coupling agent. Porous carbon fibers, for example, are noted
for their capacity to absorb appreciable amounts of water from the
Table 1.11 Effect of surface modifiers on the electrical properties of some typical filled systems
Polymer Filler, filler loading Surface modifier, Dielectric constant Dissipation lactor Rel.
(phr) amount (phI) (1000 Hz-ASTMD-150) (1000 Hz-ASTMD-150)
Initial Wet Initial Wet
Epoxy Wollastonite, 180 3.48 22.16 a 0.009 0.238a [61]

Epoxy Wollastonite, 180 A-186,0.5 3.42 3.57 a 0.014 0.023 a [61]
Epoxy Wollastonite, 180 A-187,0.5 3.30 3.42 a 0.014 0.016 a [61]
Epoxy Wollastonite, 180 A-1100, 0.5 3.48 3.55 a 0.017 0.028a [61]
Epoxy Quartz, 180 3.39 14.66b 0.017 0.305b [62]
Epoxy Quartz, 180 A-187,0.5 3.40 3.44 b 0.016 0.024 b [62]
Epoxy Quartz, 180 A-1100, 0.5 3.46 3.47 b 0.013 0.023 b [62]
Crosslinked Titanium dioxide 90.00a 0.110a [62]
polyethylene
Crosslinked Titanium dioxide A-172, 1.0 8.50 a 0.013a [62]
polyethylene
Crosslinked Titanium dioxide A-174,1.0 9.00 a 0.037a [62]
polyethylene
Polyethylene Wollastonite, 100 2.8 4.20 c 0.009 0.147c [61]
Polyethylene Wollastonite, 100 A-174,1.0 2.8 2.9 c 0.007 0.014c [61]
Polyethylene Wollastonite, 100 A-186,1.0 2.8 2.9 c 0.007 0.013c [61]
Polyethylene Quartz, 100 2.7 5.2 c 0.029 0.228c [62]
Polyethylene Quartz, 100 A-174,1.0 2.7 2.5 c 0.010 0.012c [62]
Polyethylene Clay, 100 2.7 3.0c 0.003 0.082 c [62]
Polyethylene Clay, 100 A-174,1.0 2.7 2.7c 0.002 0.003c [62]
Polyethylene Clay, 100 A-186,1.0 2.7 2f 0.002 0.005c [62]
Urethane Wollastonite, 33 5.32 9.61 a 0.024 0.047a [62]
Urethane Wollastonite, 33 A-174,1.0 4.84 5.62 a 0.021 0.027 a [62]
Urethane Clay,33 5.36 8.25 a 0.025 0.093a [62]
A-174, 1.0 4.70 5.43 a 0.023 0.022 a [62]
a 72-hour boi I. b 8-hour boil. c 16-hour immersion in 50'C water.

34 Introduction
Table 1.12 Suggested surface modifiers for different polymers
Polymers Surface modifiers commonly used
THERMOSETS
Diallyl phthalate (DAP) A-150, A-151, A-174, CV4917, CV4910, CM8550, VTMO,
VTEO, VTMOEO, Z6082
Epoxide, cycloaliphatic A-187, CG6720, GLYMO, Z-6040
Epoxy A-187, A-11 00, A-1120, CG6720, CA0750, CA0700,
GLYMO, AMEO, DAMO-P, Z-6040, Z-6020, KR-TTS,
KR-38S, KR-46B, KR-138S, LlCA 44.
Furan A-1100, CA0750, AMEO, KR-46B, KR-138S
Melamine A-1100, A-1120, CA0750, CA0700, AMEO, DAMO-P,
Z-6020, KR-38S, KR-138S
Phenolic A-187, A-11 00, A-1120, CG6720, CA0750, CA0700,
GLYMO, AMEO, DAMO-P, Z-6040, Z-6020, KR-134S,
KR-138S
Polybenzimidazole A-1100, A-1120, CA0750, CA0700, AMEO, DAMO-P,
Z-6020
Polybutadiene A-150, A-151, CV4917, CV4910, CM8550, VTMO, VTEO,
MEMO, VTMOEO, Z-6082
Polyester A-151, A-174, CV4910, CM8550, VTEO, MEMO, Z-6030,
KR-TTS, KR-46B, KR-138S
Polyethylene, crosslinked A-150, A-151, A-174, CV4917, CV4910, CM8550, VTMO,
VTEO, MEMO, VTMOEO, Z-6030, Zc 6082
THERMOPLASTICS
Acetal A-1100, CA0750, AMEO

Acrylonitrile butadiene A-174, A-187, CM8550, CG6720, MEMO, GLYMO,
styrene Z-6030, Z-6040
Nylon A-187, A-11 00, A-1120, CG6720, CA0750, CA0700,
GLYMO, AMEO, DAMO-P, Z-6020, KR-38S, LlCA 44
Polybutylene terphthalate A-187, A-1100, CG6720, CA0750, GLYMO, AMEO,
Z-6040
Polycarbonate A-1100, A-1120, CA0750, CA0700, AMEO, DAMO-P,
Z-6020
Polyethylene A-17 4, CM8550, MEMO, Z6030, KR-46B, KR-138S
Polymethacrylate A-174, A-1100, CA0750, CM8550, AMEO, MEMO, Z6030
Polypropylene A-174, CM8550, MEMO, Z6030, KR-TTS, KR-38S,
KR-138S
Polystyrene A-174, A-187, CM8550, CG6720, CC3300, CPTMO,
MEMO, GLYMO, Z-6030, Z-6040, Z-6076, KR-38S,
KR-138S
Polysulphone A-1100, CA0750, AMEO
Polyvinyl chloride A-1100, CA0750, AMEO, KR-TTS, KR-38S, KR-134S,
KR-138S,LlCA 44
Styrene acrylon itrile A-174, A-187, MEMO, GLYMO, Z-6030, Z-6040
atmosphere. However, once adhesion of carbon fibers to dry resin

has been achieved through coupling agents, wet conditions (even
with boiling water treatment) do not significantly affect the bonds.
Theoretically, coupling agents are most effective when applied to
the fiber surface in a monomolecular layer as otherwise it tends to
form a resinous layer of low cohesive strength. Infrared and radio-
tracer tests have shown that these agents do accumulate and remain
at the fiber-polymer interface and, though maintained as a mono-
layer, their beneficial effects are not always restricted to this monolayer.
The property improvements with silane coupling agents in glass-fiber
reinforced thermosetting and thermoplastic polymers have been de-
scribed by a number of workers [63-65]. The use of silane coupling
agents to achieve property improvements in non-glass, particulate,
mineral systems was investigated [66-68] with successful results. In
fact, it has been shown [69,70] that silane coupling agents are very
effective in improving the physical, mechanical and processing
characteristics of particulate mineral-filled engineering plastics in
general, and of nylon 6 and nylon 6,6 composites in particular. In
polyamides, organofunctional silane coupling agents have helped to
increase the capacity for higher filler loading which is essential to
achieve attractive cost/performance ratios.
The mechanism by which silane coupling agents act, and in
particular bond to glass fibers, has been the subject of considerable
interest and study. As mentioned in the review by Erickson and
Plueddemann [71], systematic studies of composite interfaces really
started in eamest in the USA only in 1963 and it was only later in
the seventies that the complex coupling mechanism of organic-
mineral interfaces was fairly wen understood as noted in the work of
Plueddemann [72]. Investigators believe that the coupling mechanism
involves a two-fold reaction of ambifunctional silanes through actual
covalent bonding with both the organic polymer and the reinforcing
filler surface. The monomeric silanes, which act as coupling agents,
have a general structure R' -Si(ORh in which two distinct centers of
reactivity exist and these are able to build a 'molecular bridge' to link
the oxide or hydroxide surface groups on the filler with the organic
groups of the polymer. The first site R' is an organofunctional group
bonded to the silicon atom by a short alkyl chain and consists of
either an amino, vinyl, epoxy, methacryloxy or mercapto group which
reacts with the organic polymer matrix. The second site is centered
around the silicon atom and consists of alkoxy groups Si(ORh which
hydrolyze to form silanols (Si-OH) which can react or otherwise
condense in the presence of active silica, day, wollastonite or metal
oxide surfaces. The surfaces of most fibers like glass, asbestos, silicon
carbide, boron, etc. either possess or may easily be prepared with
36 Introduction
surface oxides which are readily hydrolyzed. However, for any

coupling agent to be effective in a given composite system, it must
possess some degree of reactivity with both the organic and the
inorganic components. Possible reaction mechanisms have been
suggested and discussed [73,74] in detail. Available results suggest
that the mechanisms are complex and that they are different for
different systems. For example, grafting and crosslinking have been
suggested [75] as possible mechanisms for coupling of polypropylene
and polystyrene to glass via organofunctional silanes. When bonds
between the fibers and the matrix have been developed by cross-
linking, then due to their low sensitivity to temperature changes and
time factors, the composites are found to be superior in properties at
high temperatures and have better creep performance. Some re-
searchers [76,77] have specifically used crosslinked coatings whose
network density gradually decreases towards the bulk of the matrix
so that a modulus gradient between the fibers and matrix could be
obtained for better performance. Systems which crosslink the matrix
at the interface could include, for example, peroxide in chlorinated
alicyclic compounds as in the ca se of polyolefin composites.
Another example of the varied complex reaction mechanism of
coupling agents [78] is the one wherein the high reactivity with
polyester, epoxies and other thermosetting resins of the coupling
agent XZ-8-5069 from Dow Corning, which is a silane derivative
containing a vinyl benzylamine hydrochloride group, is attributed to
the effects of several structural features of the molecules combining
and mutually reinforcing. The idea of using such unsaturated
cationic-functional silane coupling agents was first introduced in
glass-reinforced thermosetting resin composites [77] and later
exploited for use in thermoplastics [72]. The idea of a two component
coupling system has also been introduced [60] to achieve significant
improvements in the strength of glass fiber/polystyrene and glass
fiber/styrene-acrylonitrile composites. The two components consist of
a silane coupling agent applied to the glass-fiber surface and overcoated
with a tough thermosetting resin leading to an extra protection of the
silane layer through the polymer coating which reduces disruption of
the coupling during the processing of the composite.
It is acceptable that the physico-chemical interactions at the filler-
polymer interface involve complex phenomena. However, it is
instructive to briefly review the various theories that have been
formulated to date to explain filler-polymer interface behavior. The
basis of all theories sterns from the accepted fact that, to achieve
enhanced mechanical properties, effective stress transfer from filler to
filler across the filler-polymer interface is essential. Five general
theories have been evoked, namely,
1. Chemieal bonding theory

2. Surface wettability theory
3. Deformable layer theory
4. Restrained layer theory
5. Reversible hydrolyzable bond theory
Chemie al bonding theory encapsulates the idea of chemieal

functional groups present in the coupling agent whieh react
both with the filler at one end and the polymer at the other forming
a chemie al bond by way of a molecular bridge. The origin of this
theory can be traced back to the late forties and is probably even
today one of the most reported concepts for filler-polymer
interactions.
Surface wettability theory sterns from the fact that intima te contact
between the filler and the polymer, which is essential for effident
stress transfer, is only possible through good surface wetting of the
filler by the polymer. Thus, the 'surface wettability theory' necessi-
tates maximum contact area at the interface [79,80]. The degree of
property enhancement achieved through the use of coupling agent
depends to a great extent on the relative natural affinity of the
polymer towards the filler. Thus hydrophilie polymers (e.g. nylons,
polysulfones, phenoxy resins) give better reinforcement than hydro-
phobie polymers (e.g. polyolefins, polystyrenes). In practice, however,
moisture and other contaminants on the filler surface prevent
physieal adsorption of the polymer whieh alone could produce
greater adhesive force between the filler and the polymer compared
to the cohesive strength of the polymer itself. Thus, surface wetta-
bility cannot be considered as a truly determining factor for bonding
the filler and the polymer.
Deformable layer theory, in its original proposed form [81],
included the concept that a silane finish modified the polymer next
to the interface to make it flow plastically and act as a deformable
buffer zone for mechanical relaxation and prevention of crack propa-
gation. It seemed to also provide an adequate explanation for
increases in flexural strength of composites that results on the
application of coupling agents. It was, however, soon realized that
this was untenable as the layer of the silane in a typieal glass finish
would be too thin for the mechanism of stress relaxation to operate
through mechanical flexibility. A modification of this theory was
suggested [82-84], which included the concept of preferential
adsorption based on the fact that different combinations and types of
finishes have different degrees of activities for adsorbing out certain
components of the uncured resin leading to a final polymer in the
interphase region different from that in the bulk. In other words,
38 Introduction
there would be incomplete cu ring, resulting in the formation of a

potentially flexible, ducti1e interphase region greater than 100 A
thick whieh is capable of relieving and transferring stresses between
the fillers in load bearing situations. Infrared spectra of an epoxy
resin were obtained [84] before and after filtration of glass fibers
and actually indieated the preferential adsorption of amine catalyst.
The modified deformable layer theory might be rightly applicable to
the bonding of rigid polymers to hydrophobie fillers such as
graphite fibers but its validity is questionable in the case of rubbery
polymers whose known moisture sensitivity is bound to result in
debonding.
Restrained layer theory originated from the suggestion made [85]
that stress transfer between a high modulus filler and a low modulus
resin can most uniformly occur if the interface between them has a
modulus which is intermediate between that of the filler and the
resin. Supporting this suggestion is also the demonstrated fact [86]
that the packing of polymer molecules around the filler is more elose
than in the bulk and their influence can extend up to a distance as
great as 1500 A, thereby giving a systematic gradation of the
mechanieal properties as desired by this theory. Based on the above
two suggestions, it was coneluded [60] that coupling agents 'tighten
up' the polymer structure at the interface while simultaneously
providing chemieal bonding on the filler surface and produce a layer
having an intermediate modulus between that of the glass and the
polymer. This, however, is not acceptable because then the restrained
layer concept elashes with that of the need for stress relaxation at the
interface to compensate for differential thermal shrinkage between the
filler and the polymer. On the other hand, there is evidence of rigid
adhesion due to local reduced mobility of polymer chains in the
vieinity of the filler in the case of bound rubber which is crack-
sensitive and resistant to temperature cyeling [87-89] for which the
restrained layer theory might be suitable.
Reversible hydrolyzable bond theory was born out of the very
interesting attempt made [72] to combine the salient feature of the
chemie al bonding theory, the restrained layer theory and the deform-
able layer theory. The concept ineludes adynamie equilibrium
adhesion mechanism wherein a reversible breaking and remaking of
stressed bonds at the interface between a hydrophilic mineral filler
and a polymer matrix in the presence of water allows relaxation of
stresses with loss of adhesion. Since stress relaxation by such reverse
hydrolysis is limited to molecular dimensions, the concept of this
theory would be most applicable to fine fibers and particulate fillers
in whieh the strains in the polymer between partieles are limited to
small distances of molecular dimensions.
Rheology 39
1.5 RHEOLOGY
Rheology is concerned with the description of the deformation of the

material under the influence of stresses. Deformation and flow
naturally exist when polymers are softened or melted and then
reformed into solid products of various shapes. All softened or
molten polymers are viscoelastic materials, that is, their response to
external load lies in varying extent between that of a viscous liquid
and an elastic solid. In an ideal viscous liquid, the energy of
deformation is dissipated in the form of heat and cannot be
recovered just by releasing the external forces; whereas, in an ideal
elastic solid, the deformation is fully recovered when the stresses are
released.
A softened or molten polymer represents a cluster of entangled,
flexible strings of varying lengths. Molecular weight or the degree of
polymerization signifies the length of the string, whereas the
molecular weight distribution signifies the extent of length variation
in the cluster. If the ethylene molecule were magnified 100 million
times, then its length would be about 1 cm. On the same scale, the
polymer molecule of LDPE would be 15 m long whereas that of
ultrahigh-molecular-weight polyethylene (UHMWPE) would be about
3-8 km in length. It is obvious that these chains cannot be found in
extended form, but they rather exist in an entangled and twisted
state. It is these entanglements that provide the resistance to
deformation and therefore, with increasing molecular weight, the
viscosity goes up, processibility worsens though, of course, mech-
anical properties improve. The sensitivity of rheological tests is mainly
due to chain entanglements resulting in large differences in flow behavior
even for small differences in chain length or branching. Change in
deformation rate shows changes in flow behavior. Rheological measure-
ments are used as an effective tool for
(a) quality control of raw materials, manufacturing process/final
product
(b) predicting material performance
Sensitivity of rheological properties to structural differences in
materials forms a handy aid to quality control engineers when
deciding whether to accept or reject an incoming material.
A typical viscosity vs. shear rate curve for softened or molten
unfilled polymer would be like the one shown in Figure 1.3. There is
a Newtonian region in the low shear and very high shear where the
viscosity does not change with shear rate. However, the Newtonian
plateau at the very high shear rates is rarely observed as it is often
beyond the measuring range. The curve in Figure 1.3 should thus be
40 Introduction
IUNPILLID POLNI!lI 1 1JP1IIB.

INIlWTONIAN
I'
I VBlY BICIl
1 SIII!A1
lAl1
lANOB
"I I~
11.
Figure 1.3 A typical viscosity vs. shear rate curve for a softened or molten unfilled
polymer, showing the effect of physical structural changes during flow (coiled and
wavy lines denote polymer chains).
considered as the 'ideal' flow curve. In the low to medium shear rate
range, at some critical shear rate there is a continuous drop-off of
viscosity with shear rate. The drop-off of viscosity with shear rate
would occur sooner if the molecular weight distribution is widened.
This is because the shorter molecular chains are of lower viscosity
and cause the viscosity to decrease sooner from the Newtonian
region. However, at higher shear rates, the viscosity of the polymer
having wide molecular weight distribution would be higher. The
molecular chains that are very long tend to act tenaciously and
elastically at higher shear rates, giving higher viscosity. Therefore, the
slope of the viscosity vs. shear rate curve can be used as a tool to
describe the molecular weight distribution. The height of the low
shear (Newtonian) viscosity can relate to the average molecular
weight. However, these relationships are considerably affected by
influences such as branching, crosslinking and molecular
entanglement.
The following is somewhat of a behavioral presentation of how
branching, crosslinking or entanglement will affect the polymer
viscosity vs. shear rate function assuming the molecular weight and
molecular weight distribution remain constant. Higher levels of
branching, crosslinking or entanglements can give the appearance of
having a higher average molecular weight at low shear rate testing in
comparison to a reference polymer having low entanglement and a
small amount of branching and/or crosslinking. As the shear rate is
increased, the viscosity drops off sooner. At higher shear rates, the
Rheology 41
viscosity will be much higher than that of the reference material

having little branching, entanglement or crosslinking.
Due to the dependence of rheology on the structure and the basic
inherent chemistry of the polymers, rheological data can be effectively
used to control material parameters like molecular weight, molecular
weight distribution, branching, crosslinking etc. so that the right
choice of the polymer to be processed can be made under a given set
of processing conditions.
The subject of polymer rheology has received the unabated
attention of a number of research workers and various books [90-102]
have been written each giving a different perspective of this rather
complex subject. In filled polymers, presence of the fillers affects the
rheological characteristics of the polymer system. There is extensive
literature on the rheology of filled polymer systems [28,35,40,103-175]
including comprehensive chapters in a number of books [29,94,96,
176-180]. The bulk of the literature deals with the rheology of
systems in the range of 20 to 40% filler loading by volume. Aspects
relating to this loading level have been effectively reviewed by
Utracki and Fisa [141]. Rheology of highly filled polymer melt
systems in the range of 40 to 60% filler loading by volume has also
attracted sufficient attention [143-145,154,160-163,166-170,174] due to
the extended use of polymers as binders during ceramic and metal
processing [166-170,174,181-191] as well as for the preparation of
functional filler composites [160-163,192-194]. Aspects relating to the
rheology of highly filled polymer melt systems have been reviewed
by Shenoy [29].
Typical viscosity vs. shear rate curves for a softened or molten
filled polymer would appear as one of those shown in Figure 1.4.
The low shear rate range viscosity could be constant Newtonian,
slightly variable or unbounded depending upon the characteristics of
the filled polymer system. Besides the effect of filler agglomerates as
shown in Figure 1.4, there are a number of other factors that could
be responsible for changing the curve from Figure 1.3 for the unfilled
polymer to one of the curves in Figure 1.4 when it is filled. Similar
changes would be observed in all other flow parameters which
respond to deformation.
The rheological properties of filled polymers are determined, not
only by the type of the filler, but also by its size, shape, size
distribution and amount. A key factor in the use of fillers without
adversely affecting the material properties is the stress transfer at the
filler-polymer interface as discussed in section 1.4. The interfacial
adhesion can be substantially enhanced via a coupling agent that
adheres well to both the polymer and the filler particles. The type
and amount of the surface treatment on the filler are thus additional
42 Introduction
LOW
SHE.AR
RATE
IFIU.ED POLYMER I
MEDIUM Ta HIGH
SHEAR.
log YI
log 'Y
Flgure 1.4 Typical viscosity VS. shear rate curves for a softened or molten filled
polymer, showing the effect of physical structural changes during flow (crosses
denote filler agglomerates, straight lines denote unagglomerated filler, coiled and
wavy lines denote polymer chains).
parameters affecting the rheological properties of filled polymerie

systems. There are other additives such as those listed in Table 1.13
whieh are added to alter the flow properties of the polymer matrix.
The presence of fi11ers with or without coupling agents and with or
without matrix additives affects the flow behavior of the softened or
molten polymer and hence a thorough knowledge of the inflicted
changes is essential for proper equipment design, process
optimization and troubleshooting.
The present book deals with a11 aspects relating to the rheology of
fi11ed polymer systems. Chapters 2 and 3 which discuss the basie
References 43
fable 1.13 Some commonly used matrix additives
Matrix additive type Typical examples
Plasticizers Acid-modified pOlyesters

Alcohol-modified polyesters
Unmodified polyesters
Chlorinated paraffins
Dialphenol phthalate
Di-2-ethylhexyl phthalate
Di-isooctyl phthalate
Dioctyl sebacate
Tritolyl phosphate
Trixylyl phosphate
LUbricants Barium stearate
Calcium stearate
Lead stearate
Ethyl diamino-stearate
Glyceryl monostearate
Stearic acid
Paraffin waxes
Source: Ref. 29 (Reprinted with kind permission from Gulf Publishing

Co., Houston, Texas, USA).
rheological concepts and rheometry, respectively, undoubtedly in-

clude a great deal of information that is available in other books as
weIl [90-102,195-210]. This is because they deal with the funda-
mentals which are applicable to filled as well as unfilled systems.
Chapter 4 discusses the constitutive theories and equations applicable
to flow of suspensions in a limited manner just enough to lay the
foundation for understanding the basics of filled polymer rheology.
The rest of the book is focused on filled polymer systems, and treats
the preparation and rheological characterization of such systems in a
detailed manner.
REFERENCES
1. Flory, P.]. (1953) Principles of Polymer Chemistry, Comell University Press,
Ithaca.
2. Tanford, C. (1960) Physical Chemistry of Macromolecules, Wiley, New York.
3. Billmeyer, F.W. ]r. (1962) Textbook of Polymer Science, Wiley, New York.
4. Meares, P. (1965) Polymers: Structure and Bulk Properties, Van Nostrand,
London.
5. Tager, A. (1978) Physical Chemistry of Polymers, Mir Publishers, Moscow.
6. Schultz, ].M. (1974) Polymer Materials Science, Prentice Hall, Englewood
Cliffs.
44 Introd uction
7. Morawetz, H. (1975) Macromolecules in Solution, 2nd edn, Wiley, New York.

8. Collins, E.A, Bares, J. and Billmeyer, F.W. Jr. (1973) Experiments in
Polymer Seience, Wiley, New York.
9. Allen, P.W. (1959) Techniques of Polymer Characterization, Butterworths,
London.
10. Roff, W.J. and Scott, J.R. (eds) (1971) Handbook of Common Polymers, CRC
Press, Boca Raton, Florida, and Butterworth, London.
11. Frados, J. (ed.) (1976) Plastics Engineering Handbook, SPE 4th edn, Van
Nostrand Reinhold, New York.
12. Saechtling, H. (1987) International Plastics Handbook, 2nd edn, Hanser,
Munich.
13. Brandrup, J. and Immergut, E.H. (eds) (1989) Polymer Handbook, 3rd edn,
Wiley, New York.
14. Aggarwal, S.L. (ed.) (1970) Block Polymers, Plenum Press, New York.
15. Ester, G.M., Cooper, S.L. and Tobolsky, AV. (1970) Block Copolymers
and related heterophase elastomers, J. Macromol. Rev. Macromol. Chem. 4,
313-66.
16. Molau, G.E. (ed.) (1971) Colloid and Morphological Behaviour of Block and
Graft Copolymers, Plenum Press, New York.
17. Allport, D.C and James, W.H. (eds) (1973) Block Copolymers, Wiley, New
York.
18. Burke, J.J. and Weiss, Y. (eds) (1973) Block and Graft Copolymers, Syracuse
University, Syracuse.
19. Platzer, N.A.J. (ed.) (1975) Copolymers, Polyblends and Composites,
Advances in Chemistry Series 142, American Chemical Society, Washington,
D.C
20. Noshay, A and McGrath, I.E. (eds) (1977) Block Copolymers: Overview and
Critical Survey, Academic Press, New York.
21. Collyer, AA. (ed.) (1992) Liquid Crystal Polymers: From Structures to
Applications, Chapman & Hall, London.
22. Folkes, M.J. and Hope, P.5. (1993) Polymer Blends and Alloys, Blackie,
Glasgow.
23. Baird, D.G. (1997) Composites based on thermoplastics reinforced with
liquid crystalline polymers, Paper 5-E presented at the 13th international
meeting of the Polymer Processing Society, June 10-13, 1997.
24. Acierno, D. and Collyer, AA (ed.) (1996) Rheology and Processing of Liquid
Crystal Polymers, Chapman & Hall, London.
25. Katz, H.5. and Milewski, I.V. (eds) (1978) Handbook of Fi/lers and
Reinforcements, Van Nostrand Reinhold, New York.
26. Stober, W., Fink, A. and Bohn, E. (1968) Controlled growth of mono-
disperse siliea spheres in the mieron size range, J. Colloid Interf Sei.,
26,62-9.
27. Tan, CG., Bowen, B.D. and Epstein, N. (1987) Production of mono-
disperse colloid siliea spheres: Effeet of temperature, J. Colloid Interf Sei.,
118,290-3.
28. Shenoy, AV., Saini, D.R. and Nadkarni, V.M. (1983) Rheograms of filled
polymer melts from melt flow index, Polym. Composites, 4, 53-63.
29. Shenoy, AV. (1988) Rheology of highly filled polymer melt systems, in
Encyclopedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf Publishing
Co., Houston, Texas, 7, 667-701.
References 45
30. Nielsen, L.E. and Landel, RF. (1994) Mec1umical Properties of Polymers and
Composites, Marcel Dekker, New York.
31. Mullins, L. (1963) The Chemistry and Physics of Rubberlike Substances (ed. L.
Bateman), MacLaren, London.
32. Snyder, J.W. and Leonard, M.H. (1965) Introduction to Rubber Technology
(ed. M. Morton), Van Nostrand Reinhold, Princeton, New Jersey.
33. Studebarker, M.L. (1965) Reinforcement of Elastomer (ed. G. Kraus), Wiley
(Interscience), New York.
34. McCabe, CC and Mueller, N. (1961) Trans. Soc. Rheol., 5, 329-40.
35. Zakharenko, N.V., Tolstukhina, F.S. and Bartenev, G.M. (1962) Flow of
rubber-like polymer with and without carbon black, Rubber Chem. Technol.,
35,326-34.
36. Hopper, J.R (1967) Rubber Chern. Tech., 40, 463-75.
37. Cotton, G.R (1968) Rubber Age, 100, 51.
38. Medalia, A.L (1970) J. Colloid Inter! Sci., 32, 115-31.
39. Vinogradov, G.V., Malkin, A.Ya., Plotnikova E.P., Sabsai, O.Yu. and
Nikolayeva, N.E. (1972) Int. J. Polym. Mater., 2, 1-27.
40. White, J.L. and Crowder, J.W. (1974) The influence of carbon black on the
extrusion characteristics and rheological properties of elastomers:
polybutadiene and butadiene-styrene copolymer, J. Appl. Polym. Sei., 18,
1013-38.
41. Forger, G. (1980) New cost/property profiles for mineral-filled thermo-
plastics, Plastic World, pp. 61-3 (August).
42. Maine, F.W., Riseborough, B.E. and Theberge, J.E. (1976) Polymer
structures and properties, SPE RETEC, Toronto.
43. Cessna, L.C, Thomson, J.B. and Hanna, RD. (1969) SPE J., 25, 35-9 (Oct.).
44. Cook, J. and Gordon, J. (1964) A mechanism for the control of crack
propagation in all brittle systems, Proc. Roy. Soc., 4282, 508.
45. Broutman, L.J. (1966) Glass-resin joint strength and their effect on failure
mechanisms in reinforced plastics, Polym. Eng. Sei., 6, 263-72.
46. Morley, J.G. (1974) Call for reinforcements, Chem. Brit, 10, 478-82.
47. Morley, J.G. and Millman, RS. (1974) J. Mat. Sei, 9, 1171.
48. Kraus, G. (1965) Interaction between elastomers and reinforcing fillers, in
Reinforcement of Elastomers (ed. G. Kraus), Interscience, New York, pp.
125-50.
49. Bachmann, J.H., Sellers, J.W., Wagnes, M.P. and Wolf, RF. (1959) Rubber
Chem. Tech., 32, 1286.
50. Waston, W.F. (1965) Chemical interactions of fillers and rubbers during
cold milling, in Reinforcement of Elastomers (ed. G. Kraus), Interscience,
New York, pp. 247--60.
51. Channis, CC (1974) in Composite Materials, 6, Interfaces in Polymer Matrix
Composites (ed. E.P. Plueddemann), Academic Press, pp. 32-72.
52. Alter, H. (1965) Filler particle size and mechanical properties of polymer,
J. Appl. Polym. Sei., 9, 1525-31.
53. Bierwagen, G.P. (1972) CPVC calculations, J. Paint Tech., 44, 46-55.
54. Davis, I.H. (1971) Plastics and Polymer, 39, 137-40.
55. Zisman, W.A. (1963) Ind. Eng. Chem., 35, 18-38 (Oct.).
56. Zisman, W.A. (1969) Ind. Eng. Chem. Prod. Res. Dev., 8, 98.
57. Schwartz, RT. and Schwartz, H.5. (1968) Fundamental Aspects of Fiber-
reinforced Materials, Wiley, New York.
46 Introduction
58. Laskaris, A., Herrick, J., Lurie, R, McAllister, L. and Roy, P. (1967)
Carbon fibers in reinforced plastics, in Advances in Structural Composites,
12, Western Periodicals, North Hollywood, California.
59. Herrick, J. and Travers, A. (1968) Paper presented at Annual Reinforced
Plast. Tech. Manag. Conf., Washington D.C (Feb. 8).
60. Hartlein, RC (1971) Ind. Eng. Chern. Prod. Res. Develop., 10, 92.
61. Copeland, J.R and Rush, O.w. (1978) Wollastonite short-fiber filler /
reinforcement, Plastics Compounding, 1, 26-36 (Nov.jDec.).
62. Union Carbide Corporation (1979) Bulletin: Silane coupling agents in
mineral filled composites.
63. Sterman, S. and Bradley, H.B. (1961) A new interpretation of glass
coupling agent surface through use of electron microscopy, SPE Trans.
(Oct.).
64. Plueddemann, E.P. (1962) Evaluation of new silane coupling agents for
glass fiber reinforced plastics, 17th Ann. SPI preprints (Feb.).
65. Sterman, S. and Marsden, J.G. (1963) Silane coupling agents as integral
blends in resin filler systems, 18th Ann. SPI preprints (Feb.).
66. Ziemanski, L.P. (1966) A survey of the effect of silane coupling agents in
various non-glass filled thermosetting resin systems, 22nd Ann. SPI
preprints (March).
67. Sterman, S. and Marsden, J.G. (1966) The effect of silane coupling agents
in improving the properties of filled or reinforced thermoplastics, Part I,
21st Ann. SPI preprint (March 1965); Part 11, 22nd Ann. SPI preprints
(March).
68. Sterman, S. and Marsden, J.G. (1966) Ind. Eng. Chem., 58, 33.
69. Ramney, M.W., Berger, S.E. and Marsden, J.G. (1972) Silane coupling
agents in particulate mineral-filled composites, 27th Ann. SPI preprints
(Feb.).
70. Berger, S.E., Orenski, P.1. and Ramney, M.W. (1974) Silane coupling
agents in particulate mineral-filled nylon, in Fillers and ReinJorcement Jor
Plastics (eds RD. Deanin and N.R Schott), Adv. Chem. Series, B4, 73-85.
71. Erickson, P.W. and Plueddemann, E.P. (1974) in Composite Materials, Vol.
6, Interfaces in Polymer Matrix Composites (ed. E.P. Plueddemann),
Academic Press, pp. 1-31.
72. Plueddemann, E. (1973) Polym. Plast. Tech., 2, 89-106.
73. Crabtree, J.D. and Pickthall, D. (1969) Paper presented at the IR! Corno on
Polymer Blends and Reinforcements, Loughborough, England (Sept.).
74. Cameron, G.M. and Marsden, J.G. (1972) Chemistry in Britain, 8, 381-5.
75. Plueddemann, E. (1972) 27th Conf Reinf Plastics/Composites Division, SPI
paper l1-B.
76. Nicolais, L., Driol, E. and Laude, RF. (1973) Polymer, 14, 21-5.
77. Hartlein, RC (1970) 25th SPI Technical ConJerence, ReinJorced Plastics/
Composite Division, Sect. 16-B, pp. 1-9.
78. Plueddemann, E. (1965) Polym. 20th Conf SPI, Paper 19-A.
79. MacGarry, F.}. (1959) Proc. 6th Saga more Ordnance Mat. Res. Conf (Aug.
18-21).
80. Schrader, M.E. and Lerner, I. (1965) Proc. 20th Ann. Tech. Conf ReinJorced
Plast. Div. SPI, Sec 3-C
81. Hooper, RC (1956) 11th Ann. Tech. Corno Reinforced Plast Div. SPI, Sec
8-B.
References 47
82. Erickson, p.w. and Volpe, AA (1963) NOL Tech. Rep., 63-10.
83. Erickson, P.W., Volpe AA and Cooper, E.R (1964) Proc. SPI Conf Reinf
Plast. Div., 19th Sec. 21-A
84. Erickson, P.W. (1970) Proc. 25th Ann. Tech. Conf Reinforced Plastics Div.,
SPI, Sec. 13-A
85. Kumins, CA and Roteman, J. (1963) J. Polym. Sei., lA, 527-40.
86. Kwei, T.K. (1965) J. Polym. Sei., 3A, 3229.
87. Mullins, L. (1959) Proc. Int. Rubber Conf Washington, USA.
88. Harwood, J.A.C (1967) J. Appl. Chem., 17, 333-8.
89. Payne, AR and Whittaker, RE. (1970) Proc. IRI Conf, Loughborough
University (Sept. 1969); Comp., 1, 203-14.
90. Severs, E.T. (1962) Rheology of Polymers, Reinhold, New York.
91. Middlemen, S. (1968) The Flow of High Polymers, Interscience, New York.
92. Ferry, J.D. (1969) Viscoelastic Properties of Polymers, 2nd edn, Wiley, New
York.
93. Han, CD. (1976) Rheology in Polymer Processing, Academic Press, New
York.
94. Nielsen, L.E. (1977) Polymer Rheology, Marcel Dekker, New York.
95. Lenk, RS. (1978) Polymer Rheology, Appl. Sei. Pub., London.
96. Vinogradov, G.V. and Malkin, A.Y. (1980) Rheology of Polymers, Mir
Publishers, Moscow.
97. Brydson, J.A (1981) Flow Properties of Polymer Melts, Godwin, London.
98. Cogswell, FN. (1981) Polymer Melt Rheology, Wiley, New York.
99. Janeschitzkriegl, H. (1983) Polymer Melt Rheology and Flow BireJringence,
Springer-Verlag, Berlin.
100. Barnes, H.A., Hutton, J.F. and Walters, K. (1989) An Introduction to
Rheology, Elsevier, Amsterdam.
101. Dealy, J.M. and Wissbrun, K.F. (1990) Melt Rheology and Its Role in
Plastics Processing, Van Nostrand Reinhold, New York.
102. Shenoy, AV. and Saini, D.R (1996) Thermoplastic Melt Rheology and
Processing, Marcel Dekker, New York.
103. Chapman, F.M. and Lee, T.5. (1970) Effect of tale filler on the melt
rheology of polypropylene, SPE Journal, 26, 37-40.
104. Mills, N.J. (1971) The rheology of filled polymers, J. Appl. Polym. Sei., 15,
2791-805.
105. Nazem, F. and Hill, CT. (1974) Elongational and shear viscosities of
bead-filled thermoplastic, Trans. Soc. Rheol., 18, 87-101.
106. Han, CD. (1974) Rheological properties of calcium carbonate-filled
polypropylene melts, J. Appl. Polym. Sei., 18, 821-9.
107. Minagawa, N. and White, J.L. (1976) The influence of titanium dioxide
on the rheological extrusion properties of polymer melts, J. Appl. Polym.
Sci., 20, 501-23.
108. Faulkner, D.L. and Schmidt, L.R (1977) Glass bead-filled polypropylene.
Part I: Rheological and mechanical properties, Polym. Engg Sei., 17,
657-64.
109. Boira, M.5. and Chaffey, CE. (1977) Effects of coupling agents on the
mechanical and rheological properties of mica-reinforced polypropylene,
Polym. Engg Sci., 17, 715-18.
110. Bigg, D.M. (1977) Rheology and wire coating of high atomic number
metal low density polyethylene composites, Polym. Engg Sei., 17, 745-50.
48 Introduction
111. Kataoka, T., Kitano, T., Sasahara, M. and Nishijima, K. (1978) Viscosity
of partic1e filled polymer melts, Rheol. Acta, 17, 149-55.
112. Kataoka, T., Kitano, T. and Nishimura, T. (1978) Utility of parallel-plate
plastometer for rheological study of filled polymer melts, Rheol. Acta, 17,
626-31.
113. Chan, Y., White, J.L. and Oyanagi, Y. (1978) Influence of glass fibers on
the extrusion and injection molding characteristics of polyethylene and
polystyrene melts, Polym. Engg Sei., 18, 268-72.
114. Chan, Y., White, J.L. and Oyanagi, Y. (1978) A fundamental study of the
rheological properties of glass fiber-reinforced polyethylene and
polystyrene melts, J. Rheol., 22, 507-24.
115. Han, CD., Sandford, C and Yoo, H.J. (1978) Effects of titanate coupling
agents on the rheological and mechanical properties of filled polyolefins,
Polym. Engg Sei., 18, 849-54.
116. Menges, G., Geisbusch, P. and Zingel, U. (1979) Kunststoffe, 7, 485.
117. Arina, M., Honkanen, A. and Tammela, V. (1979) Mineral fillers in low
density polyethylene films, Polym. Engg Sei., 19, 30-9.
118. Monte, S.J. and Sugerman, G. (1979) A new generation of age and
water-resistant reinforced plastics, Polym. Plastics Tech. Engg, 12, 115-35.
119. Lobe, V.M. and White, J.L. (1979) An experimental study of the influence
of carbon black on the rheological properties of a polystyrene melt,
120. Wu, S. (1979) Order-disorder transitions in the extrusion of fiber-filled
poly(ethylene terephthalate) and blends, Polym. Engg Sei., 19, 638-50.
121. Kataoka, T., Kitano, T., Oyanagi, Y. and Sasahara, M. (1979) Viscous
properties of calcium carbonate filled polymer melts, Rheol. Acta, 18,
635-9.
122. Kitano, T., Kataoka, T., Nishimura, T. and Sakai, T. (1980) Relative
viscosities of polymer melts filled with inorganic fillers, Rheol. Acta, 19,
764-9.
123. Kitano, T., Nishimura, T., Kataoka, T. and Sakai, T. (1980) Correlation of
dynamic and steady flow viscosities of filled polymer systems, Rheol.
Acta, 19, 671-3.
124. Crowson, R.J., Folkes, M.J. and Bright, P.F. (1980) Rheology of short
glass fiber-reinforced thermoplastics and its applications to injection
molding 1. Fiber motion and viscosity measurement, Polym. Engg Sei., 20,
925-33.
125. Crowson, R.J. and Folkes, M.J. (1980) Rheology of short glass fiber-
reinforced thermoplastics and its application to injection molding II. The
effect of material parameters, Polym. Engg Sei., 20, 934-40.
126. Goel, D.C (1980) Effect of polymerie additives on the rheological
properties of talc-filled polypropylene, Polym. Engg Sei., 20, 198-201.
127. Tanaka, H. and White, J.L. (1980) Experimental investigations of shear
and elongational flow properties of polystyrene melts reinforced with
calcium carbonate, titanium dioxide and carbon black, Polym. Engg Sei.,
20,949-56.
128. Czamecki, 1. and White, J.L. (1980) Shear flow rheological properties,
fiber damage and mastication characteristics of aramid, glass and
cellulose-fiber reinforced polystyrene melts, J. Appl. Polym. Sei., 25,
1217-44.
References 49
129. White, J.1., Czamecki, I. and Tanaka, H. (1980) Experimental studies of

the influence of particle and fiber reinforcement on the rheological
properties of polymer melts, Rubber Chern. Tech., 53, 823-35.
130. Hancock, M., Tremayne, P. and Rosevear, J. (1980) Pillers in poly-
propylene 11. J. Polym. Sei. Polym. Chern. Ed., 18,3211-17.
131. Knutsson, B.A., White, J.1. and Abbas, K.A. (1981) Rheologieal and
extrusion characteristics of glass-fiber reinforced polycarbonate, J. Appl.
Polym. Sei., 26, 2347-62.
132. Cope, D.E. and Linnert, E. (1980) The lowdown on loading down resins
using hydrophobie encapsulation, Plastic Engg, 20, 37-9 Oune).
133. Kitano, T., Kataoka, T. and Shirata, T. (1980) An empirical equation of
the relative viscosity of polymer melts filled with various inorganic
fillers, Rheol. Acta, 20, 207-9.
134. Han, CD., Van der Weghe, T., Shete, P. and Haw, J.R (1981) Effect of
coupling agents on the rheological properties, processing and mechanical
properties of filled polypropylene, Polym. Engg Sei., 21, 196-204.
135. Stamhuis, J.F. and Loppe, J.P.A. (1982) Rheological determination of
polymer-filler affinity, Rheol. Acta, 21, 103-5.
136. Sharma, Y.N., Patel, RD., Dhimmar, I.H. and Bhardwaj, LS. (1982)
Studies of the effect of titanate coupling agent on the performance of
polypropylene-calcium carbonate composite, J. Appl. Polym. Sei., 27,
97-104.
137. Nakatsuka, T., Kawasaki, H., Itadani, K. and Yamashita, S. (1982)
Phosphate coupling agents for calcium carbonate filler, J. Appl. Polym.
Sei., 27, 259-69.
138. Lee, W.M., Abe, D.A., Chipalkatti, M.H. and Liaw, T.F. (1982)
Rheologieal properties of partieulate-filled linear low density poly-
ethylenes, Proc. Ann. Conf Reinf Plast. Compos. Inst. Soc., Plast. Ind.,
vol. 37, paper 12D, p. 7.
139. Juskey, V.P. and Chaffey, CE. (1982) Rheology and tensile properties of
polypropylene reinforced with glycerol-treated miea, Can. J. Chem. Engg,
60, 334--41.
140. Hinkelmann, B. (1982) Zur analytischen beschreibung des fullstoffein-
flusses auf das fliessverhalten von kunststoff-schmelzen, Rheol. Acta, 21,
491-3.
141. Utracki, 1.A. and Pisa, B. (1982) Rheology of fiber or flake-filled plastics,
Polym. Composites, 3, 193-211.
142. White, J.1. (1982) Rheological behavior of highly filled/reinforced
polymer melts, Plastics Compounding, 47-64 Oan./Feb.).
143. Bigg, D.M. (1982) Rheologieal analysis of highly loaded polymerie
composites filled with non-agglomerating spherieal filler particles, Polym.
Engg Sei., 22, 512-18.
144. Bigg, D.M. (1983) Rheological behavior of highly filled polymer melts,
Polym. Engg Sei., 23, 206-10. .
145. Althouse, 1.M., Bigg, D.M. and Wong, W.M. (1983) Evaluating the
effectiveness of filler surface treatments, Plastics Compounding (March/
April).
146. Lern, K.W. and Han, CD. (1983) Rheological behavior of concentrated
suspensions of particulates in unsaturated polyester resin, J. Rheol., 27,
263-88.
50 Introduction
147. Daley, L.R and Rodriguez, F. (1983) Flow properties of ethylene-

propylene terpolymer filled with siliea modified by silane coupling
agents, Ind. Eng. Chem. Prod. Res. Dev., 22, 695-8.
148. Mutsuddy, B.C. (1983) Influence of powder characteristics on the
rheology of ceramie injection molding mixtures, Proe. Brit. Ceram. Soe.,
33, 117-37.
149. Chaffey, C.E. (1983) Reinforced thermoplastics: Through flow to use,
Ann. Rev. Mater. Sei., 13, 43-65.
150. Johnson, RO. and Teutsch, E.O. (1983) Thermoplastic aromatic polyimide
composites, Polym. Composites, 4, 162-6.
151. Shenoy, AV. and Saini, D.R (1983) Interpretation of flow data for
multieomponent polymerie systems, Colloid Polym. Sei., 261, 846-54.
152. Suetsugu, Y. and White, J.L. (1983) The influence of partic1e size and
surface coating of calcium carbonate on the rheologieal properties of its
suspension in molten polystyrene, J. Appl. Polym. Sei., 28, 1481-501.
153. Luo, H.L., Han, C.D. and Mijovie, J. (1983) Effects of coupling agents in
the rheological behavior and physieal mechanieal properties of filled
nylon 6, J. Appl. Polym. Sei., 28, 3387-98.
154. Bigg, D.M. (1984) Complex rheology of highly filled thermoplastie melts,
Proc. 9th Int. Congress on Rheology in Mexico, Adv. in Rheology, 3,
429-37.
155. Kitano, T., Kataoka, T. and Nagatsuka, Y. (1984) Shear flow rheological
properties of vinylon and glass-fiber reinforced polyethylene melts, Rheol.
Acta, 23, 20-30.
156. Kitano, T., Kataoka, T. and Nagatsuka, Y. (1984) Dynamie flow
properties of vinylon fiber and glass fiber reinforced polyethylene melts,
Rheol. Acta, 23,408-16.
157. Suetsugu, Y. and White, J.L. (1984) A theory of thixotropie plastic
viscoelastic fluids with a time-dependent yield surface and its com-
parison to transient and steady state experiments on small partic1e filled
polymer melts, J. Non-Newtonian Fluid Meeh., 14, 121-40.
158. Hinkelmann, B. and Mennig, G. (1985) On the rheologieal behavior of
filled polymer melts, Chem. Engg Comm., 36, 211-21.
159. Bretas, RES. and Powell, RL. (1985) Dynamie and transient rheologieal
properties of glass-filled polymer melts, Rheol. Acta, 24, 69-74.
160. Saini, D.R, Shenoy, A.V. and Nadkarni, V.M. (1985) Effect of surface
treatment on the rheologieal and mechanical properties of ferrite-filled
polymerie systems, Polym. Engg Sei., 25, 807-11.
161. Saini, D.R and Shenoy, AV. (1986) Viscoelastic properties of highly
loaded ferrite-filled polymerie systems, Polym. Engg Sei., 26, 441-5.
162. Shenoy, AV. and Saini, D.R (1986) Quantitative estimation of matrix
filler interactions in ferrite-filled styrene-isoprene-styrene block wpolymer
systems, Polym. Composites, 7, 96-100.
163. Saini, D.R, Shenoy, AV., Nadkarni, V.M. (1986) Melt rheology of highly
loaded ferrite-filled polymer composites, Polym. Composites, 7, 193-200.
164. Shenoy, A.V. and Saini, D.R (1986) Wollastonite reinforced poly-
propylene composites: Dynamie and steady state melt flow behavior,
J. Reinf Plastics Comp., 5, 62-73.
165. Mute!, AT. and Kamal, M.R. (1986) Characterization of the rheological
behavior of fiber-filled polypropylene melts under steady and oscil-
References 51
latory shear using cone-and-plate and rotational parallel plate geometry,

166. Edirisinghe, M.J. and Evans, J.RG. (1987) Rheology of ceramic injection
molding formulations, Br. Ceram. Trans. J., 86, 18-22; \1987} Properties of
ceramie injection moulding formulations, Part 1, Melt rheology, f. Mat. Sei.,
22,269-77.
167. Sacks, M.D., Khadilkar, CS., Scheiffele, G.w., Shenoy, AV., Dow, J.H.
and Sheu, RS. (1987) Dispersion and rheology in ceramie processing,
Advances in Ceramics, 24, 495-515.
168. Dow, J.H., Sacks, M.D. and Shenoy, AV. (1988) Dispersion of ceramie
partic1es in polymer melts, Ceram. Trans. (Ceram. Powder Sei. II, A), 1, 380-8.
169. Hunt, K.N., Evans, J.RG. and Woodthorpe, J. (1988) The influence of
mixing route on the properties of ceramie injection moulding blends, Br.
Ceram. Trans. J., 17-21.
170. Takahashi, M., Suzuki, S., Nitanda, H. and Arai, E. (1988) Mixing and
flow characteristic in the alumina/thermoplastic resin system, J. Am.
Ceram. Soc., 17, 1093-9.
171. Poslinski, AJ., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Frechette, F.J.
(1988) Rheological behavior of filled polymerie systems I. Yield stress
and shear-thinning effeets, f. Rheol., 32, 703-35.
172. Poslinski, AJ., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Freehette, F.J.
(1988) Rheologieal behavior of filled polymerie systems 11. The effeet of a
bimodel size distribution of particulates, f. Rheol., 32, 751-71.
173. Ishigure, Y., Nagaya, K., Mitsumatsu, F., Otabe, S., Hayashi, K.,
Sobajima, A and Murase, I. (1989) Relationship between the flow
eharacteristics of highly filled alumina or zirconia-organie binder and the
properties of sintered products in injeetion molding processing, Rep. Gifu
Pref Ind. Res. Tech. Center, 21, 51-70.
174. Dow, J.H., Sacks, M.D. and Shenoy, AV. (1990) Dispersion of alumina
partic1es in polyethylene melts, Ceram. Trans. (Ceram. Powder Sei. III), 12,
431-42.
175. Edirisinghe, M.J., Shaw, H.M. and Tomkins, K.L. (1992) Flow behavior of
ceramie injection moulding suspensions, Ceramics Intl., 18, 193-200.
176. Nielsen, L.E. (1974) Mechanical Properties of Polymers and Composites,
Mareel Dekker, New York, Vol. 2, Ch. 7,379-86.
177. Han, CD. (1981) Multiphase Flow in Polymer Processing, Aeademie Press,
New York.
178. Yanovsky, Yu.G. and Zaikov, G.E. (1990) Rheologieal properties of filled
polymers, in Encyclopedia of Fluid Mechanics, (ed. N.P. Cheremisinoff),
Gulf Publishing, Houston, TX, 9, 243-76.
179. Carreau, P.J. (1992) Rheology of filled polymerie systems, in Transport
Processes in Bubbles, Drops and Particles (eds RP. Chhabra and D. Dekee),
Hemisphere Publishing, New York, 165-90.
180. Advani, S.G., ed. (1994) Flow and Rheology in Polymer Composites
Manufacturing, Elsevier Scienee B.V.
181. Whalen, T.J. and Johnson, CF. (1981) Injeetion molding of eeramies, Am.
Ceram. Soc. Bull., 60, 216-20.
182. Mangels, J.A (1983) Fabrieation of eomplex shaped eeramie artieies by
slip easting and injeetion molding, Progress in Nitrogen Ceramics (ed. F.L.
Riley), Martinus Nijhoff, Boston, 231-6.
52 Introduction
183. Mangels, ].A and Williams, RM. (1983) Injection molding ceramics to
high green densities, Am. Ceram. Soe. Bull., 62, 601-6.
184. Mutsuddy, B.C and Ford, RG. (1995) Ceramie Injection Molding,
Chapman & Hall, London.
185. Bandyopadhyay, G. and French, K.W. (1984) Near net shape fabrication
and densification of silicon nitride, Proe. of Workshop in Conservation and
Substitution Teehnology for Critieal Metals in Bearings and Related Components,
Vanderbilt University, Nashville, TN, March 12-14.
186. Mangels, ].A and Trela, W. (1984) Ceramic components by injection
mol ding, Adv. in Ceramies, 9, 234-8.
187. Mutsuddy, B.C (1986) Overview on organic binder for whiteware
ceramics, 39th Pacific Coast Regional Meeting, Washington, Oct.
22-24.
188. Sehurtz, J.F. (1986) Methylcellulose polymers as binders for extrusion
of ceramics, 39th Pacific Coast Regional Meeting, Washington, Oct.
22-24.
189. Edirisinghe, M.J. and Evans, J.RG. (1986) Review: Fabrication of engin-
eering ceramics by injection moulding, I. Materials selection, Int. J. High
Teeh. Cera mies, 2, 1-31; II. Techniques, Int. J. High Teeh. Ceramies, 2,
249-78.
190. Bhattacharya, S.K. (ed.) (1986) Metal-Filled Polymers: Properties and Appliea-
tions, Marcel Dekker, New York and Basel.
191. German, RM. (1990) Powder Injection Molding, Metal Powder Industries
Federation, Princeton, NJ.
192. Runt, J. and Galgoci, E.C (1984) Polymer /piezoelectric ceramic com-
posites: Polystyrene and poly(methyl methacrylate) with PZT, J. Appl.
Polym. Sei., 29, 611-17.
193. Runt, J. and Galgoci, E.C (1984) Piezoelectric composites of PZT and
some semi-crystalline polymers, Mat. Res. Bull., 19, 253-60.
194. Newnham, RE. and Runt, J.P. (1984) Polymer-piezoelectric ceramic
composites, Polymer News, 10, 132-8.
195. Lodge, AS. (1964) Elastie Liquids, Academic Press, New York.
196. Coleman, B.D., Markovitz, H. and Noll, W. (1966) Viseometrie Flow of
Non-Newtonian Fluids, Springer-Verlag, New York.
197. Seott Blair, G.W. (1969) Elementary Rheology, Academic Press, New York.
198. Hutton, J.F., Pearson, J.RA and Walters, K. (1975) Theoretieal Rheology,
Appl. Sei. Pub., London.
199. Darby, R (1976) Viseoelastie Fluids, Marcel Dekker, New York.
200. Harris, J. (1977) Rheology and Non-Newtonian Flow, Longman, London.
201. Schowalter, W.R (1978) Meehanies of Non-Newtonian Fluids, Pergamon
Press, Oxford.
202. Petrie, CJS. (1979) Elongational Flows, Pitman, London.
203. Zahorski, S. (1981) Meehanies of Viscoelastic Fluids, Martinus Nijhoff Pub.,
Boston.
204. Tanner, RI. (1985) Engineering Rheology, Clarendon Press, Cambridge,
UK.
205. Collyer, AA and Clegg, D.w. (1988) Rheological Measurements, Chapman
& Hall, London.
206. Collyer, AA. and Utracki, L.A (eds) (1990) Polymer Rheometry and
Processing, Elsevier Appl. Sei., New York.
References 53
207. Van Wazer, J.R, Lyons, J.W., Kim, K.Y. and Colwell, RE. (1963) Viscosity
and Flow Measurement (A Laboratory Handbook of Rheology, Interscience
Pub.).
208. Walters, K. (1975) Rheometry, Chapman & Hall, London.
209. Whorlow, RW. (1979) Rheological Techniques, Ellis Horwood, Wiley, New
York.
210. Dealy, J.M. (1982) Rheometers for Molten Plastics: A Practical Guide to
Testing and Property Measurement, Van Nostrand Reinhold, New York.
Basic rheological
concepts 2
Filled polymer rheology is basically concerned with the description of

the deformation of filled polymer systems under the influence of
applied stresses. Softened or molten filled polymers are viscoelastic
materials in the sense that their response to deformation lies in varying
extent between that of viscous liquids and elastic solids. In purely
viscous liquids, the mechanical energy is dissipated into the systems in
the form of heat and cannot be recovered by releasing the stresses. Ideal
solids, on the other hand, deform elastically such that the deformation
is reversible and the energy of deformation is fully recoverable when
the stresses are released.
Softened or molten filled polymer may behave as a viscous liquid or
elastic solid during processing operations depending upon the relation-
ship between the time scale of deformation to which it is subjected and
the time required for the time-dependent mechanism to respond. The
ratio of characteristic time to the scale of deformation is defined as the
Oeborah number by Reiner [1,2] as
Oe = Ac/As
where Ac is the characteristic time, As is the time scale of deformation.
The characteristic time, Ac, for any material can always be defined as
the time required for the material to reach 63.2% or [1 - (1/e)] of its
ultimate retarded elastic response to a step change. If Oe > 1.0, elastic
effects are dominant while if Oe< 0.5, viscous effects prevail. For any
values of Oeborah numbers other than these two extremes given above,
the materials depict viscoelastic behavior.
Filled polymer systems display the ability to recoil by virtue of their
viscoelastic nature. However, they do not return completely to their
original state when stretched because of their fading memory.
Viscoelasticity allows the material to remember where it came from, but
the memory of its recent configurations is always much better than that

Flow classification 55
of its bygone past, thus lending it the characteristics of a fading memory.

Meissner [3] found that a filament of low density polyethylene (LOPE) at
423 K, which is stretched rapidly from 1 to 30 cm length, and then
suddenly set free, recovers to a length of 3 cm, thereby giving a recovery
factor of 10. If the filament were made of filled LOPE, the recovery
factor would be much smaller because the presence of the filler greatly
reduces the stretchability as well as the recoil of the material.
2.1 FLOW CLASSIFICATION

Flow is broadly classified as shear flow and extensional flow. A catalog
of various types of shear flow has been given by Bird et al. [4]. In the
present book, the discussion is restricted to only simple shear flow that
occurs when a fluid is held between two parallel plates. Simple shear
flow could be of the steady or unsteady type. Similarly extensional flow
could be steady or unsteady. In the case of extensional flow, it is often
difficult to keep the measuring apparatus running for a long enough
time to achieve steady state conditions and therefore unsteady con-
ditions are quite often encountered.
Thus, flow is classified here under three headings:
1. Steady simple shear flow
2. Unsteady simple shear flow
3. Extensional flow.
Extensional flow (steady and unsteady) is treated under one heading
for convenience. The definitions of important rheological parameters
under each of the three headings are given below.
2.1.1 STEADY SIMPLE SHEAR FLOW

Fluid deformation under steady simple shear flow can be aptly
described by considering the situation in Figure 2.1 wherein the fluid is
held between two large parallel plates separated by a small gap dX 2 and
sheared as shown.
The lower plate is moving at a constant velocity VI while the upper
plate is moving at a constant velocity of VI + dV I under the action of a
force f applied to it. A thin layer of fluid adjacent to each plate moves
at the same velocity as the plate, assuming the no-slip condition at the
solid boundary. Molecules in the fluid layers between these two plates
move at velocities which are intermediate between VI and VI + dv l
Under steady-state conditions, the force f required to produce the
motion becomes constant and is related to the velocity. The velocity
profile of the fluid within the gap is given by dV I = YdX2 where Y is a
constant.
56 Basic rheological concepts
Xl
Figure 2.1 Simple shear flow of a fluid trapped between two parallel plates.
A. Shear rate
The velocity gradient [dv 1 jdx 2 ], which is termed the shear rate y can
also be written as
(2.1)
The term [dxddx 2 ] represents the deformation of the material and is

defined as the shear strain y. Thus, the shear rate is the rate of
deformation or the rate of shear strain and is expressed as reciprocal
seconds (sec-I).
B. Shear-stress and extra stress tensor

The force per unit area [f jA] required to shear the material between
two parallel plates is defined as the shear stress '<21' and it is basically a
function (Jen) of the velocity gradient. Thus,
(2.2)
The units of shear stress are dynes/cm2 or Newtons1m 2 (Le. Pascals).

It must be noted that '21 is just one component of the stress and, in
principle, there are a number of components of stress that must be
specified to completely define the state of stress. For example, a general
constitutive equation which describes the mechanies of materials in
classieal fluid dynamies can be written as:
(2.3")
where Tex, t) denotes the symmetrie Cauchy ~ress tensor at positron x

and time t, p(x, t) is the pressure in the fluid [I being the unit tensor), r
is the extra stress tensor, '1v is the volume viscosity and D is the
symmetrie part of the gradient tensor of the velocity field v(x, t):
= _
D(x t) =-1 [aV
-+-avi]
i
(2.4a)
'J' 2 ax. ax.
J '
Note that Cartesian coordinates are used and vectors are denoted by
single bar [ - ] above the letter while tensors are denoted by double bars
[=] above the letter.
If the fluid does not undergo a volume change, i.e. it is density
preserving or incompressible, then the mass balance equation, better
known as the continuity equation, reduces to
=
trD=-'=O av (2.4b)
aXi
In such cases, the last term on the right-hand side of equation (2.3)
drops out and the volume viscosity has no role to play. It should also be
noted that, for flow of an incompressible fluid, the absolute value of the
pressure p has no significance because it is only the press ure differences
that are truly relevant. Thus, in essence, the constitutive equation (2.3)
f9r aD incompressible fluid connects only the 'extra stress tensor' r or
T + pI uniquely with the local motion of the fluid but always leaves
the pressure p indeterminate.
A general form of the constitutive equation can be written as
(2.5a)
The apparent viscosity '1 in the above equation is a function of the first,
second and third invariants of the rate of deformation tensor. For
incompressible fluids, the first invariant i becomes identicaIly equal to
zero. The third invariant iII vanishes for simple shear flows and is
normally neglected in non-viscometrie flows as weIl. The apparent
viscosity then is a function of the second invariant TI alone. Hence
equation (2.5a) is written in the simplified form as
(2.5b)
In steady shearing flow, only a limited number of stress components

of the extra stress tensor are necessary to completely define the fluid
motion and these are written as follows:
'11 '12 0
'f = '21 '22 0 (2.6)
o 0 '33
The subscript 1 denotes the direction of flow, the subscript 2 denotes

the direction perpendicular to the flow (i.e. the direction along the
velocity gradient) and the subscript 3 denotes the neutral direction. The
various stress components are shown on a representative cubic volume
of the fluid in Figure 2.2. All the components are not shown in the
figure in order to maintain clarity. Note that in steady shearing flow,
the stress components '13' '23' '31' '32' are identically equal to zero.
'12 = '21 is called the shear stress and 'n, '22' '33' are called normal
stresses.
<::22
X3
Figure 2.2 Various stress components on a representative cubic volume of fluid

(stress components 't"12' 't"13' 't"31. 't"32' have not been shown in order to maintain clarity
of the figure).
C. N onnal stress difference

The absolute value of any particular component of normal stress is of
no rheological relevance, whereas the values of the normal stress
differences '11 - '22 and '22 - '33 do have considerable rheological signifi-
cance. The first is termed the primary normal stress difference while the
latter is termed the secondary normal stress difference. Thus,
N1 = '11 - '22 (2.7)
N2 = '22 - '33 (2.8)
For most fluids, N 1 N2 and hence the latter is often excluded in

rheological discussions. Attempts to determine the value of secondary
normal stress difference experimentally have been made by several
rheologists but without success. It is still achallenge to quantitatively
determine this material function. Nevertheless, it is not very important
in most hydrodynamic calculations barring, of course, wire coating [5]
wherein the secondary normal stress difference helps in providing the
necessary restoring force for stabilizing the wire position whenever it
becomes off-centered.
D. Viscometric functions
The viscosity function I] (referred to as the steady shear viscosity), the
primary and secondary normal stress coefficients 1/11' and 1/12' respec-
tively, are the three viscometric functions which completely determine
the state of stress in any rheologically steady shear flow. They are
defined as folIows:
'12 = '21 = I](Y))' (2.9)
'11 - '22 = 1/11(Y)l (2.10)
'22 - '33 = l/1z{yW (2.11)
Viscosity is the resistance of the material to any irreversible positional

change of its volume elements while the normal stress coefficients
exemplify the response of the material due to its elasticity or its ability
to recover from the deformation.
2.1.2 UNSTEADY SIMPLE SHEAR FLOW

Unsteady simple shear flow would occur when the stresses involved
are time-dependent. Small-amplitude oscillatory flow, stress growth,
stress relaxation, creep and constrained recoil are some examples of
such types of flows [4]. In the following, small-amplitude oscillatory
flow is treated in sufficient detail while others are briefly described
and readers are encouraged to refer to Bird et al. [4] for more
information.
A. Small-amplitude oscillatory flow

Small-amplitude oscillatory flow is often referred to as dynamic shear
flow. Fluid deformation under dynamic simple shear flow can be
described by considering the fluid within a small gap dX 2 between
two large parallel plates of which the upper one undergoes small
amplitude oscillations in its own plane with a frequency w. The
velocity field within the gap can be given by dVI = l' dX 2 but l' is not a
constant as in steady simple shear. Instead it varies sinusoidally and is
given by
1'(t) = Yo cos wt (2.12)
The shear stress in simple dynamic shear flow is expressed in terms
of the amplitude and phase shift functions of the frequency as,
'21(t) = 1'o[G'(w)sinwt + G"(w) cos wt] (2.13)
(2.14)
where b is the phase angle, 1'0 and '~I are the amplitudes of the 'strain
and stress, respectively, and G', G" are linear viscoelastic material
functions, respectively, referred to as the dynamic storage modulus and
dynamic loss modulus.
,0
Dynamic storage modulus: G'(w) = ~ cos b (2.15)
1'0
,0
Dynamic loss modulus: G"(w) = ~ sinb (2.16)
1'0
Another term of importance is the ratio of loss to storage modulus,
defined as
G"(w)
Loss tangent: G'(w) = tanb (2.17)
It is also possible to define a dynamic complex viscosity in terms of G'

and G" as follows:
Dynamic viscosity: 1]'(w) = G"(w) (2.18)

w
Imaginary part of the complex viscosity: 1]"(w) = G'(w) (2.19)

w
Complex viscosity function: 1]*(iw) = 1]'(w) - i1]"(w) (2.20)
In the same manner as above, a complex modulus can be defined as

below:
Complex modulus: G*(iw) = G'(w) + iGI/(w) (2.21)
The storage modulus G'(w) and the imaginary part of the complex
viscosity, i.e. rl'(w), are to be considered as the elastic contributions to
the complex functions. They are both measures of energy storage.
Similarly, the loss modulus GI/(w) and the dynamic viscosity '1'(w) are
the viscous contributions or measures of energy dissipation.
B. Stress growth
The aim of a stress growth experiment is to observe how the stresses
change with time as they approach their steady shear flow values. This
is done by assuming that the fluid sampie trapped in a small gap
between two parallel plates is at rest for all times previous to t = 0
implying that there are no stresses in the fluid when steady shear flow
is initiated at t = O. For t > 0 when a constant velocity gradient is
imposed, the stress is monitored with respect to time till it reaches
steady state value.
C. Stress relaxation
The aim of a stress relaxation experiment is to observe how the stresses
decay with time (i) after cessation of steady shear flow or (ii) after a
sud den shearing displacement. In case (i) the fluid sampie trapped in a
small gap between two parallel plates is allowed to maintain constant
shear rate that was started long before t = 0 so that all the transients
during the stress growth period have evened out. Then at t = 0, the
flow is stopped suddenly and the decay of the stress is monitored with
respect to time till it becomes insignificant or dies out. The stress would
relax monotonically to zero and more rapidly as the shear rate in the
preceding steady shear flow is increased.
In case (ii), a constant shear rate lasting only for a brief time interval
is imposed. The decay of the stress that is genera ted by this sudden
small displacement is monitored. The stress would decrease
monotonically with time. For small shear displacements the relaxation
modulus is known to be independent of shear rate.
D. Creep
The aim of a creep experiment is to observe the changes in shear
displacement as a function of time expressed in terms of creep
compliance, after a constant shear stress has been applied and

maintained at that value ort a sampie trapped in a small gap between
two parallel plates. The steady-state compliance Je is defined as -y /7: 21 ,
If the driving shear stress 7:21 is small enough then the value of the
compliance is independent of the driving shear stress.
E. Constrained recoil
The aim of a constrained recoil experiment is to observe the shear
displacement in a fluid sampie trapped in a small gap between two
parallel plates when driving shear stress is suddenly removed after
steady-state and then held at zero. The shear rate would then only be a
function of time in the recoiling fluid. The ultima te recoil of the fluid at
infinite time can be determined in this manner.
2.1.3 EXTENSIONAL FLOW

Problems associated with fiber spinning, film blowing and foaming
process have indicated that the shear flow material functions discussed
earlier are not truly the crucial parameters. This realization led to the
study of another type of flow, namely, the extensional flow. Extensional
flow differs from both steady and unsteady simple shear flows in that it
is a shear-free flow. In such a flow, the volume of a fluid element must
remain constant. Extensional flow can be visualized as that occurring
when a material is longitudinally stretched as, for example, in fiber
spinning. In this case, the extension occurs in a single direction and
hence the related flow is termed uniaxial extensional flow. Extension or
stretching of polymer takes place in other processing operations as weIl,
such as film blowing and flat-film extrusion. In such cases, the
extension occurs in two directions simultaneously, and hence the flow
is referred to as biaxial extensional flow in one ca se and planar
extensional flow in the other. Extensional flows can orient polymer
chains as weIl as fillers which are of the 1-dimensional or 2-dimensional
type and hence determine the performan~e and appearance of a
product.
A. Uniaxial extension
Uniaxial extensional flow may be best visualized as adeformation
caused by forces acting in a direction perpendicular to the opposite
faces of a cylindrical body as shown in Figure 2.3. The velocity field in
simple uniaxial extensional flow is given by
~x
V1 = " 1' v-
2 - - 2 "l~X'
"2' (2.22)
I- 10 - - - - + 1
(a,) llEFORE ElCl'iNSIONAL DEFORllATION
(b) AFTI!It EXl'ENSIONAL DEPOawJION
Figure 2.3 Schematic diagram 01 a Iluid element in uniaxial extensional flow.
where f. is the uniaxial extensional rate. For such a flow field, the rate of
deformation tensor is given as
o o
D= 0 -f./2 0 (2.23)
o 0 -f./2
in which
. dV I
B=-- (2.24)
dX I
The uniaxial extensional rate may be constant or vary in the Xl
direction of flow. When f. is constant, i.e. when the axial velocity is
proportional to Xl' the resulting flow is steady uniaxial extensional flow.
In such a flow situation, a cylindrical rod of length 1 is stretched along
its axis according to the following equation:
d1 = f.l (2.25)
dt
Integrating this equation for a constant strain rate gives,
1 = 10 exp(U) (2.26)
From equation (2.26), it is evident that extensional flow involves severe

deformation since fluid parts are separated exponentially. The dimen-
sions of the fluid elements change drastically in contrast with shear
flows where particles in neighboring shearing surfaces separate linearly
in time.
B. Biaxial extension
In biaxial extensional flow, too, the dimensions of the fluid elements
change drastically but they change in two directions as against the one-
direction in uniaxial extensional flow. Thus, biaxial extensional flow can
be visualized as adeformation caused by forces acting in two directions
perpendicular to the opposite faces of a plate as shown in Figure 2.4.
The velocity field in simple biaxial extensional flow is given by,
(2.27)
where eB is the biaxial extensional rate. For such a flow field, the rate of
deformation tensor is given as,
(a) BEFORE EXI'ENSIONAL DEFORMATION
(b) AFTER EXI'ENSIONAL DEFORMATION
X3
Figure 2.4 Schematic diagram of a fluid element in biaxial extensional flow.

es 0 0
D= 0 es 0 (2.28)
0 0 -2es
C. Planar extension
Planar extensional flow is the kind of flow where there is no deforma-
tion in one direction and the velocity field is represented as follows:
(2.29)
where ep is the planar extensional rate. In this case, the rate of

deformation tensor is given as,
ep 0 0
D = 0 -ep 0 (2.30)
o 0 0
Extensive reviews [6-10] and a monograph [11] summarize the litera-
ture covering significant aspects of extensional flows in various
commercial processes, theoretical treatment for the hydrodynamics of
such flows and different methods of determining material functions such
as uniaxial, biaxial and planar extensional viscosities.
D. Material functions in extensional flow

The material function of prime importance in extensional flow is the
extensional viscosity which is basically a measure of the resistance of
the material to flow when stress is applied to extend it.
In extensional flow, the diagonal components of 7: ij are non-zero (i.e.
7:ij = 0 for i =1= j). In the case of uniaxial extension, 7: 11 is the primary
stress that can be measured, while 7: 22 and 7:33 are gene rally equal to the
pressure of the environment. Thus, the uniaxial extensional viscosity 'lE
is defined by,
(2.31)
By the same token, the biaxial extensional viscosity 'lES can be defined
as,
(2.32)
and further, the planar extensional viscosity 'lEP can be written as,
(2.33)
2.2 NON-NEWTONIAN FLOW BEHAVIOR

The viscoelastic nature of polymers (filled or unfilled) and their
peculiarities in the viscous as weIl as elastic response to deformation
under applied stresses bring them under the category of non-
Newtonian fluids. There is distinctive difference in flow behavior
between Newtonian and non-Newtonian fluids to an extent that, at
times, certain aspects of non-Newtonian flow behavior may seem
abnormal or even paradoxical [12-16]. An interesting movie about
polymer fluid mechanics has been prepared [17] which dearly depicts
certain peculiarities of such fluids. The dramatic differences between
the qualitative responses of Newtonian and non-Newtonian fluids
grossly affect their industrial and practical applications.
2.2.1 NEWTONIAN FLUIDS

Isaac Newton was the first to propose the basic law of viscosity
describing the flow behavior of an ideal liquid as,
(2.34)
where the constant 110 is termed the Newtonian viscosity.
Fluids, whose flow behavior follows the above constitutive equation,
are known as Newtonian fluids. Some of the common Newtonian
fluids with which most people are familiar are water (110 ~ 1 mPa.sec),
coffee cream (110 ~ 10 mPa.sec), olive oil ('10 ~ 102 mPa.sec) and honey
(110 ~ 104 mPa.sec).
For a Newtonian fluid, equation (2.34) yields the following stress
components in simple shear flow:
'tn = 't = 't = -p
22 33 (2.35)
't = 't12 = 't21 = 110 Y (2.36)
All other stress components vanish. According to equation (2.35), it can

be seen that the three normal stress components are equal. The non-
vanishing shear stress 't varies linearly with shear rate and has a pro-
portionality constant 110 which is the shear viscosity of the Newtonian fluid.
In general, incompressible Newtonian fluids at constant temperature
can be characterized by just two material constants: the shear viscosity
110 and the density p. Once these quantities are measured, the velocity
distribution and the stresses in the fluid can, in principle, be found for
any flow situation. In other words, different isothermal experiments on
a Newtonian fluid would yield a single constant material property,
namely, its viscosity. On the other hand, a variety of flow experiments
performed on a softened or molten filled polymer system, which is a
Non-Newtonian flow behavior 67
non-Newtonian fluid, would yield a host of material functions that

depend on shear rate, frequency and time.
When the viscosity is a function of shear rate, then the relationship
between shear stress and shear rate is given by equation (2.9). Since its
form is similar to equation (2.36) except for the shear rate dependent
viscosity, the equation is said to represent a Generalized Newtonian
fluid. In such a fluid, the presence of normal stresses defined by
equations (2.10) and (2.11) is considered to be negligible for a specific
flow situation. In effect, equation (2.5b) represents the constitutive
equation for a Generalized Newtonian fluid. The hypothesis of a
Generalized Newtonian fluid differs from the simple Newtonian case
by the assumption that the functional relationship between the stress
tensor and the kinematic variable need not be only linear. It holds,
however, the suggestion that only the kinematic variable of the first
order can influence the state of stress in the fluid and no attempt is to
be made to describe the normal stresses in it.
2.2.2 NON-NEWTONIAN FLUIDS

Non-Newtonian fluids are rheologicaHy complex fluids that exhibit one
of the foHowing features:
(a) Shear rate dependent viscosities in certain shear rate ranges with
or without the presence of an accompanying elastie solid-like
behavior.
(b) Yield stress with or without the presence of shear rate dependent
viscosities.
(c) Time-dependent viscosities at fixed shear rates.
The definitions of various types of non-Newtonian fluids along with
examples of common real systems falling into each category are given
in Table 2.1. Detailed discussions relating to non-Newtonian fluids are
available in a number of books [18-27] as weIl as other review articles
[28-33]. From Table 2.1, it can be seen that filled polymer systems fall
within the non-Newtonian category of pseudoplastic fluids, pseudo-
plastie fluids with a yield stress, thixotropie fluids and viscoelastic
fluids.
For pseudoplastic fluids, the shear rate at any given point is solely
dependent upon the instantaneous shear stress, and the duration of
shear does not play any role so far as the viscosity is concerned. The
shear stress vs. shear rate pattern for a pseudoplastie fluid with and
without yield stress is shown in Figure 2.5.
In the case of thixotropie fluids, the shear rate is a function of the
magnitude and duration of shear as weH as a function possibly of the
time lapse between consecutive applications of shear stress. The shear
Table 2.1 Various types of non-Newtonian fluids
Fluid type Definition Typical Examples
Pseudoplastic These fluids depict a Filled polymer systems

decrease in viscosity with Polymer melts
increasing shear rate and Polymer solutions
hence are olten referred to Printing inks
as shear-thinning fluids. Pharmaceutical
Preparations
Blood
Dilatant These fluids depict an Wet sand
increase in viscosity with Starch suspensions
increasing shear rate and Gum solutions
hence are olten referred to Aqueous suspension of
as shear-thickening fluids. titanium dioxide
Bingham Plastics These fluids do not flow Thickened hydrocarbon
unless the stress applied greases
exceeds a certain Certain asphalts and
minimum value referred to bitumen
as the yield stress and Water suspensions of clay/
then show a linear shear fly ash/metallic oxides
stress vs. shear rate Sewage sludges
relationship. Jellies
Tomato ketchup
Toothpaste
Pseudoplastic with a yield These fluids have a non- Filled polymer systems
stress linear shear stress vs. Heavy crude oils with high
shear rate relationship in wax content
addition to the presence of
a yield stress.
Thixotropie These fluids exhibit a Filled polymer systems
reversible decrease in Water suspensions of
shear stress with time at a bentonite clays
constant rate of shear and Drilling muds
fixed temperature. The Crude oils
shear stress, of course, Coal-water slurries
approaches some limiting Yoghurt
value. Salad dressing
Mayonnaise
Rheopectic These fluids exhibit a So me clay suspensions
reversible increase in
shear stress with time at a
constant rate of shear and
fixed temperature. At any
given shear rate, the shear
stress increases to
approach an asymptotic
maximum value.
Viscoelastic These fluids possess the Filled polymer systems
added feature of elasticity Polymer melts
apart from viscosity. These Polymer solutions
fluids exhibit process
properties which lie in-
between those of visco us
liquids and elastic solids.
PSEUDOPLASTIC
FL1JIDWIIH
YlELD STBESS
/
l'SEODOPI.ASTlC
FL1JID
NEWTONIAN
PLUID
Figure 2.5 Variation of shear stress vs. shear rate for pseudoplastic fluids with and
without yield stress.
stress pattern with time for such fluids is shown in Figure 2.6. If the
shear stress is measured against shear rate which is steadily increasing
from zero to a maximum value and then immediately decreasing
steadily to zero, a hysteresis loop is obtained as shown in Figure 2.7.
Viscoelastic fluids have a certain amount of energy stored in the
fluids as strain energy thereby showing a partial elastic recovery
upon the removal of a deforming stress. At every instant during the
deformation process, a viscoelastic fluid tries unsuccessfully to
recover completely from the deformed state but lags behind. This lag
is a measure of the elasticity or so-called memory of the fluid. Due to
the presence of elasticity, viscoelastic fluids show some markedly
peculiar steady state and transient flow behavior patterns. Viscoelastic
effects become important when there are sud den changes in the flow
rate (e.g. during start-up and stopping operations of the polymer
processing), in high shear rate flows (e.g. in processes like extrusion
and injection molding) and in flows where changes in cross-section
are encountered (e.g. entry into the mold cavity during injection
molding). Some of the common encountered effects due to visco-
elasticity are discussed below.
t
Figure 2.6 Variation of shear stress with time for a thixotropie fluid.
THIXonOPIC FLUID
HYS'IERESlS LOOP
Figure 2.7 Variation of shear stress with shear rate (whieh is steadily inereased from
zero to maximum and brought down) for a thixotropie fluid.
Figure 2.8 Weissenberg effect showing how the viscoelastic fluid climbs up the
stirrer-rod when stirred at moderate speeds. (Reprinted from Ref. 34 with kind
permission from Chapman & Hall, Andover, UK.)
2.2.3 VISCOELASTIC EFFECTS
A. Weissenberg effect
When a viscoelastic fluid is stirred with a rod at moderate speeds, the
fluid begins to climb up the rod instead of forming a vortex as shown
pictorially in Figure 2.8. The first normal stress difference is much
larger than the shear stress and hence gives rise to this startling effect.
This type of phenomenon is commonly termed the Weissenberg effect,
as Weissenberg was the first to explain such an effect in terms of the
stresses in fluids undergoing a steady shear flow [34-36]. In actuality,
this effect was observed earlier by Gamer and Nissan [37].
B. Extrudate swell
When a viscoelastic fluid flows through an orifice or a capillary, the
diameter of the fluid at the die exit is considerably higher than the
diameter of the orifice. This happens because, at the die exit, the
viscoelastic fluid partially recovers the deformation it underwent when
it was squeezed through the capillary. This type of phenomenon is
known variously as extrudate swell, die swell, jet swell, Barus effect or
Merrington effect. Metzner [38] discusses the history of extrudate swell
Figure 2.9 Extrudate swell effect showing how the viscoelastic fluid swells in diameter
when it exits from a die or oritice. (Reprinted trom Re!. 34 with kind permission from
Chapman & Hall, Andover, UK.)
and argues against using the last two names. A review on extrudate
swell has been given by Bagley and Schrieber [39]. Extrudate diameter
(OE) of up to three or four times the orifice diameter (0 is possible 0 )
with some polymers. The swell ratio Sw (i.e. 0dOo) decreases with the
increase of tube length because of the fading memory of the viscoelastic
fluid to deformation. This implies that if longer and longer tubes are
used, Sw should ultimately approach unity. But it is known [40] that the
limiting value of the swell ratio is greater than unity even as the length
to diameter ratio of the orifice approaches infinity. The phenomenon of
die swell is shown pictorially in Figure 2.9.
Theoretical analyses of this phenomenon, for flow in round capil-
la ries, are available [41-45] in which the most basic [44] of them is built
upon the free recovery calculations set down by Lodge [13] using the
theory of Berstein, Kearsley and Zapas [46]. The developed expression
for die swell Sw in which the elastic strain recovery SR is balanced by
the shear stresses arising in the die, is given by,
Sw = (1 + ~S~)1/6 + 0.1 (2.37)
where,
(2.38)
The above analysis does not include the rearrangement of the stress
and velocity fields at the die exit, and consequently, it was found
necessary [44] to empirically modify the die swell expression by
including a factor of 0.1 in the above expression. The 0.1 term has been
added to improve the fit with data for small values of ('11 - '22)w/'21.w
and the ratio ('11 - '22)/'~1 has been taken to be constant. Later work
[47] has shown that die swell depends not only on the recoverable
shear strain, but also on the ratio of the second to first normal stress
difference coefficients 1/12NI as weIl.
The influence of this phenomenon in the filled polymer industry can
hardly be overlooked. The industrial problems involving extrudate
swell are particularly complex and challenging because the diameter
increase depends not only on the particular type of polymer but also on
the type and amount of filler as weIl as on the operating conditions
such as temperature and flow rate.
C. Draw resonance
Draw resonance or surging is defined as the non-uniformity in the
diameter of the extrudate when a polymer is stretched at different
take-up speeds as it comes out of an orifice. This phenomenon is shown
schematically in Figure 2.10. When take-up speed is small or when
there is no stretching, only die swell is observed as can be seen from
Figure 2.10(a). When take-up speed is higher and the stretched
extrudate is solidified by quenching, then the contour appears as shown
in Figure 2.1O(b). Now draw ratio is defined as the ratio of the linear
velocity v of the extrudate settled in the quenching bath to the smallest
linear velocity V o at the die swell region. When the draw ratio DR goes
beyond a critical value DR c , then the resulting phenomenon is draw
resonance as shown in Figure 2.10(c). The theory of draw resonance has
been developed and a method for calculating the critical draw ratio is
also available [48]. Once draw resonance occurs its severity enhances
with increasing take-up speed.
D. Melt fracture
When softened or molten polymer flows out of a capillary, a striking
phenomenon of the distortion of the emerging stream is observed at
shear stresses beyond a critical higher value and this is termed melt
fracture [49,50]. The extrudate distortion is a result of polymer
molecules reaching their elastic limit of storing energy, thus causing
1
[al (cl
Figure 2.10 Draw resonance effect occurring when polymer melt is extruded from
an orifice at various take-up speeds. (a) Extrudate without stretching, (b) extrudate
with stretching DR < DRc and no draw resonances, (c) extrudate with stretching
DR> DRc showing draw resonance.
melt fracture as a means of stress relief either at the capillary wall or at

the capillary entrance. Another view [51] is that the extrudate distortion
is due to differential flow-induced molecular orientation between the
extrudate skin holding highly oriented molecules and the core wherein
there is no significant molecular orientation. It is, of course, possible
[52] that the melt fracture occurs due to a combination of the stress
relief theory and the differential flow-induced molecular orientation.
A number of other mechanisms [53-65] have been suggested for melt
fracture. Based on a stick-slip mechanism, it is purported [53] that,
above a critical shear stress, the polymer experiences intermittent
slipping due to a lack of adhesion between itself and die wall, in order
to relieve the excessive deformation energy adsorbed during the flow.
The stick-slip mechanism has attracted a lot of attention [53-63], both
theoretically and experimentally. The other school of thought [64,65] is
based on thermodynamic argument, according to which, melt fracture
can initiate anywhere in the flow field when reduction in the fluid
entropy due to molecular orientation reaches a critical value beyond
which the second law of thermodynamics is viola ted and flow instability
is induced [64].
It is important to distinguish between melt fracture, which is a gross
distortion or waviness, and a fine scale high frequency surface
1
2
3
4
S
6
..... 7
~
Figure 2.11 Difference between the phenomenon of matte and melt fracture (on
distorted extrudates of different polymers): (1) rigid polyvinyl chloride, (2) polyethylene,
(3) polypropylene, (4 & 5) polypropylene viewed from two angles, (6) polymethy-
methacrylate, (7) pOlytetrafluoroethylene. (Reprinted from Ref. 66 with kind permission
from Society of Plastics Engineers, Inc., Connecticut, USA.)
roughness [40]. The latter may commence at output rates below those at
which melt fracture is observed and is termed matte or mattness. The
extreme case of mattness is referred to as shark skin. The distinction
between shark skin and melt fracture has been convincingly demon-
strated [66] as shown pictorially in Figure 2.11.
E. Capillary entry flow patterns

A characteristic flow pattern at the capillary entrance develops when a
polymer flows at high shear rates from a cylindrical reservoir through a
capillary or die as shown in Figure 2.12. The qualitative difference
between the capillary entry flows of linear and branched polyethylenes
has been convincingly presented by Tordella [50] and discussed by
others [67-70]. For linear polymers, the converging flow at the die entry
fills the available space, while for branched polymers there is a large
Figure 2.12 Capillary entry flow pattern for a branched polymer showing the flow
cone and the recirculating vortex.
dead space filled by recirculating vortices. Vortices are induced by the

viscoelastic characteristics of the converging fluid [71,72]. Polymers
exhibiting larger extensional viscosities have been observed [71] to
exhibit larger vortices and vice versa.
The vortex or the circulating stagnant region encompasses a flow
cone which becomes unstable with increasing flow rate and even-
tually fractures periodically as the flow rate is increased further.
When the flow cone fractures, the result is melt fracture and the flow is
sustained by the intermittent drawing of the fluid from the recirculating
vortices.
F. Abnormal fringe patterns in calendering

During the process of calendering, very stable abnormal fringe patterns
may appear on the roll surface at regular intervals. Though the exact
mechanism for abnormal fringe patterns in calendering is as yet
unclear, it is certainly related to the viscoelasticity of the material.
Depending on the frequency of roll rotation and clearance of roll nip,
its intensity would increase or decrease on account of the effect of such
changes on the viscoelastic response of the calendered material.
------ r---~
---------+
.. +~22
----, :--...... - - -"' .......... __ JI"

,~---+
--~
PRfSlURETRAN8DUCER
NEWTONIAN FlUID IVISCOEI.ASTIC FLUID
Figure 2.13 Pressure hole error oeeurs in a viseoelastie fluid while it is absent in a
Newtonian fluid. (Reprinted from Ref. 23 with kind permission from John Wiley & Sons,
Ine., New York, USA)
G. Pressure hole error

For Newtonian fluids, the pressure measured at the bottom of the
pressure hole PM is the same as the true pressure P at the wall. For a
viscoelastic fluid, on the other hand, the pressure (p + '22)M measured
at the bottom of the pressure hole is always lower than the true
press ure (p + '21) at the wall, no matter how small the hole iso This
press ure difference arises because the elastic forces tend to pull the
fluid away from the hole and results in the pressure hole error
PH = (p + 'n)M - (p + '21)' This effect is illustrated in Figure 2.13. The
possible sources of error in the measurement have been considered by
Higashitani and Lodge [73] along with a review of published data. The
effect of PH has been well substantiated for polymer solutions but the
same is not the case for polymer melts with or without fillers.
H. Parallel plate separation

When a viscoelastic fluid is trapped between two parallel plates with
one of the plates rotating, then there is a non-zero pressure P due to
NXWTONIAN VlSCOl!LAS'llC
FLUID
l
FLUID
Figure 2.14 Parallel plate separation oeeurs in a viseoelastie fluid while it is absent
in a Newtonian fluid. (Reprinted from Ref. 33 with kind permission from Gulf
Publishing Co., Houston, Texas, USA)
elasticity which tends to separate the two plates. This effect is

illustrated in Figure 2.14.
I. Tubeless siphon
Ouring the siphoning process, when the siphon tube is lifted out of the
fluid, a Newtonian fluid will stop flowing whereas a viscoelastic fluid
will continue unabated. At times, even 75% of the viscoelastic fluid in
the container may get siphoned out in this manner. This effect is
illustrated in Figure 2.15.
,
r -..... _ - , .. \~
f(- - -
""
11
"", "\
"I .:'
r
~ "
"
"
"
"
""
'I
NEWTONIAN FLUID VISCOnASllC FLUID
Flgure 2.15 Tubeless siphoning ean be done for a viseoelastie fluid but not for a
Newtonian fluid. (Reprinted trom Ret. 23 with kind permission trom John Wiley & Sons,
Ine., New York, USA.)
Rheological models 79
This viscoelastic effect indieates the stability of a stretching filament

of fluid with respect to small perturbations in its cross-sectional area. It
has definite implications in the fiber spinnability of polymers.
J. Uebler effect
It has been observed [74,75] that when a polymerie fluid flows in a tube
with a sud den contraction, large bubbles of the order of 1/6 to 1/8 of
the small tube diameter, come to a sudden stop right at the entrance of
the contraction along the centerline before finally passing through after
a hold-time of ab out one minute. This particular behavior has been
termed the Uebler effect [74,75].
This phenomenon has implieations in the production of foamed
plastics wherein agas, normally nitrogen, is added to polymers such as
PE, PP and PS during two-phase processing.
2.3 RHEOLOGICAL MODELS

There have been a number of rheologieal models proposed for
representing the flow behavior of softened or molten polymer and these
are readily available in a number of books [18-27] and review articles
[10,28,29,31,32,76]. The constitutive equations, which relate shear stress
or apparent viscosity with shear rate, involve the use of two to five
parameters. Many of these constitutive equations are quite cumbersome
to use in engineering analyses and hence only a few models are often
popular. Only such models are described and discussed in this section.
2.3.1 MODELS FOR THE STEADY SHEAR VISCOSITY FUNCTION

From the typieal viscosity vs. shear rate curve for unfilled polymer
shown in Figure 1.2, it can be seen that in the low shear rate range, the
material is essentially Newtonian in flow behavior with a constant
apparent viscosity, which at zero shear rate, is termed the zero-shear
viscosity 110. In the medium shear rate range, the apparent viscosity 11
be gins to decrease, depieting the shear-thinning characteristic until it
stabilizes to a constant value 11 00 at a considerably high shear rate in the
upper Newtonian region. It is quite obvious from this figure, that a
constitutive equation with about three to four parameters would be
necessary to describe the rheologieal behavior of an unfilled polymer
over the entire shear rate range. However, when dealing with
processing problems, only certain shear rate ranges attain significance
and hence only portions of the flow curve need to be described by the
constitutive equations thereby requiring less parameters. As a matter of
fact, the very high shear rate range is invariably never reached and
hence 1'/00 is often ignored. On neglecting the very high shear rate range,
the curve in Figure 1.3 for unfilled polymer can be seen to be identical
in shape to the Curve 1 in Figure 1.4 for filled polymer. Thus, any
rheological model applicable to Figure 1.3 would also hold good for
Curve 1 in Figure 1.4. Some of the simple flow models with a minimum
of parameters which would be applicable to the curves in Figure 1.4 for
filled polymers in different ranges of shear rates are discussed below.
A. Ostwald-de Waele power-Iaw model

This is the most popular and simple two-parameter model originaHy
proposed by Ostwald [77,78] and de Waele [79] and has since then been
fuHy described by Reiner [1]. The equation for this model is given as
follows:
(2.39)
or
(2.40)
where K reflects the consistency index of the polymer, with higher
values representative of more viscous materials, and n is the power-Iaw
index giving a measure of the pseudoplasticity, with greater departures
from unity showing more pronounced shear-thinning characteristics.
The power-Iaw index n basically represents the slope of the , vs. y
curve and n - 1 is the negative slope of the 1'/ vs. Ycurve in the medium
to high shear rate range. It should be noted that all three curves for
filled polymers in Figure 1.4 can be fitted by this model in the medium
to high shear rate range.
B. EIlis model
In this model proposed by Ellis and discussed by Reiner [1], the
apparent viscosity vs. shear rate relationship is given in the following
form:
1'/0
1'/= , (2.41)
1 + ('/'1/2)"-1
where '1/2 is the shear stress at the viscosity of 1'/0/2.
The Ellis model is a three parameter model and has the advantage of
exhibiting a limiting viscosity 1'/0 in the limit of zero shear rate and
shear-thinning viscosity at higher shear rates. rx' - 1 is related to the
slope of the viscosity vs. shear rate curve and describes the shear-
thinning behavior. The model is able to fit data in the low to medium
shear rate ranges. The model has an added advantage because the ratio
YJO/'C 1/2 constitutes a characteristic time of the fluid and is often

considered to be related to the fluid elasticity, an idea which was
intuitively asserted by Bird [80]. There are certain controversies as
regards the ability of relaxation time constant of EHis fluid in truly
describing elastic behavior [81] but the simplicity of its constitutive
equation more than overrides any deficiencies that this model may have
in representing a viscoelastic fluid. In fact, in the years following the
controversy there have been studies [82-84] in support of using the EHis
model to determine the viscoelastic behavioral patterns in different flow
situations. It should be noted that this model would be appropriate in
the low to medium shear rate ranges for Curve 1 in Figure 1.4.
C. Carreau model
The Carreau model [85] has basically four parameters, namely, YJo, YJoo' A
and N. The relaxation time A is considered to be the characteristic time
available as the inverse of the shear rate at which the shear-thinning
behavior begins. N is a measure of the shear-thinning characteristics.
Both A and N are considered to be adjustable parameters and the model
is written as follows:
(2.42)
In the above form, the Carreau model can be fitted to the entire
viscosity vs. shear rate curve. However, such a complete set of data up
to YJoo is rarely determinable. Hence, the popular form of the Carreau
model that is used as the truncated three-parameter model after
neglecting YJoo is given below:
YJ = YJo(1 + A2 y2)-N (2.43)
It should be noted that, similar to the EHis model, this model too would
be appropriate in the low to medium shear rate ranges for Curve 1 in
Figure 1.4 for filled systems. Though the applicability ranges of shear
rates for the two models is the same, the Carreau model is more
popular than the EHis model and is more frequently used.
D. General rheological model

This model is formulated by Shenoy et al. [86] along the lines originally
proposed by Churchill and Churchill [87] but with the following
differences:
(i) The model [86] relates viscosity YJ with shear rate y while Churchill
and Churchill [87] prefer to work with a model relating viscosity YJ
and shear stress 'C.
() The power-Iaw model is used as the limiting behavior for high

shear [86] whereas 11 00 is assumed to be a limiting value as r ~ 00
(or Y ~ (0) in the latter [87].
(iii) The model [86] requires four constants while the latter [87] involves
five constants in its most general form.
(iv) The Churchill and Churchill [87] model essentially requires
postulating the asymptotic behavior at either large or low shear
stress (or rate) since the two limiting values are insufficient
information to apply the Churchill and Usagi approach [88].
The general rheological model [86] was developed for master curves
[142] of viscosity vs. shear rate for polymer melts using the melt flow
index (MFI) as a normalizing parameter.
K Y (n-l)p ~P
[
P
]
11 x MFI = 110 x MFI 1 + (110 x MFI) x (MFI)
It can be written in a general form applicable to any viscosity vs. shear

rate curve of a softened or molten polymer simply by putting MFI as
unity replacing K by K to give.
(2.44a)
The four constants in the general rheological model [86] are evaluated
as follows:
(i) A plot of 11 vs. Y on a log-log scale for low /medium shear rate
yields the limiting zero-shear viscosity 110 by mere read-out as
shown in Figure 2.16.
(ii) The functional behavior at large shear rates on the same log-log
plot in Figure 2.16, being linear defines K and n directly. The slope
of the straight line defines [n - 1] while K is the value of 11 when
y = 1 (provided the point satisfies the power-Iaw equation). The
best values of K and [n -1] can be easily computed by regressional
analysis of the data at high shear rates.
(iii) The exponent P is readily evaluated by determining the point of
intersection of the two limiting solutions that corresponds to the
point (YA' 110)' Thus,
(2.44b)
It should be noted that this model can cover the shear rate range from
low to medium to high and is applicable to the entire Curve 1 in Figure
1.4 for filled systems.
LOO - LOG PLOT
110 1"--=::::::::=:-----,..,
K
~
.
'Y
Figure 2.16 Typical viscosity vs. shear rate curve depicting the method for
determining the parameters of the general rheological model. (Reprinted from Ref. 86.)
E. Herschel-Bulkley model
This model was developed by Hersehel and Bulkley [89] specifieally for
deseribing pseudoplastie fluids with yield stress and is useful for filled
polymer systems, especially for Curve 3 in Figure 1.4. The model form
r = ry +Ky" for Irl > Iryl
(2.45a)
y=O for Irl < Iryl
It ean be seen that when the yield stress is absent, this model is akin to
the Ostwald-de Waele power-Iaw model.
The Hersehel-Bulkley model predicts power-Iaw flow behavior at all
shear rates and henee will not be able to fit data whieh are in the form
of Curve 2 in Figure 1.4 Where a Newtonian plateau is seen at low
shear rates.
F. Modified Herschel-Bulkley model

Using the Bird-Carreau expression [90] in plaee of the power-Iaw
portion in equation (2.45a), Poslinski et al. [91] wrote the following
expression which could serve well in describing the flow behavior of

filled systems that have plots similar to Curve 2 in Figure 1.4.
(2.45b)
Here 1'/N is taken as the viscosity of the filled polymer system in the
Newtonian plateau region at low shear rates. It would not be the zero
shear viscosity because of the presence of the yield stress. This equation
is based on the assumption that the power-law index does not change
with the addition of fillers to the polymer matrix, and that the onset of
shear-thinning occurs at lower shear rates in the filled system than in
the unfilled matrix. If the yield stress is dominant at low shear rates
then equation (2.45b) would reduce to the Herschel-Bulkley equation
given by equation (2.45a); on the other hand, if the yield stress is
negligible, it reduces to the Carreau type expression given by equation
(2.43).
There has been a debate over the reality of a true yield stress [92-94]
which warrants the use of very different constitutive equations on
appropriate sides of the yielding surface when dealing with
inhomogeneous flows typical to those involving filled polymer systems.
Nevertheless, it is certain that in a number of pragmatic situations, the
time scale of operation is small and then the presence of the yield
stresses is close to reality in filled polymer systems.
2.3.2 MODEL FOR THE NORMAL STRESS DIFFERENCE FUNCTION

The elasticity of softened or molten polymer is manifested through two
material functions, namely, the primary normal stress coefficient "'1'
and the secondary normal stress coefficient "'2.The secondary normal
stress coefficient is not as well characterized as the primary normal
stress coefficient due to its small magnitude. The primary normal stress
measurements are themselves difficult and require highly sophisticated
equipment to produce reasonably accurate data, and that too in a
limited low shear rate region.
The relative ease in the experimental measurements of viscosity
functions renders them amenable to extensive study in comparison to
the normal stress functions. Hence there have been attempts [90,95,96]
to find methods for the prediction of the normal stress difference from
the viscosity function.
Abdel-Khalik et al. [90] and Bird et al. [95] presented a relation
between the steady state values of the primary normal stress coefficient
"'1 and the viscosity function 1'/ as
./,'1'1 (.)_!["(y)-,,W)
')' - 12.2
d'
')' (2.46)
TC 0 ')' - ')'
Wagner [96], too, provided a method for the prediction of normal stress
difference from shear viscosity data using a strain dependent single
integral constitutive equation of Berstein, Kearsley and Zapas [BKZ]
[46] type as follows:
1/1 (y) = _2. d,,~y) (2.47)

1 m d')'
where m is an adjustable parameter, whose value lies between 0.13 and
0.2, thereby defining the upper and lower limits of the predicted normal
stress difference curve.
The same set of experimental data taken from the literature [97-100]
has been used by Abdel-Khalik et al. [90] and Wagner [96] and these
have been shown to agree reasonably weIl with the theoretical
predictions.
It is implicitly presumed in equation (2.47) that if the viscosity
increases, then the normal stress difference coefficient also increases
and the adjustable parameter with value 0.13 ::: m ::: 0.2 will help to fit
the data. This fact holds good for unfilled polymers and works weIl for
them [90,96]. However, in the case of filled systems, some fillers
increase normal stress difference while others decrease it. Hence,
equation (2.47) is unlikely to be valid at all times. Only in certain
specific cases, the equation may be applicable while in other cases of
filled polymers, prediction of steady shear elastic properties from the
viscous counterpart may lead to erroneous results. Hence, caution
should be exercised when using equation (2.47) for filled polymer
systems.
In the following, equation (2.47) is used for obtaining the relationship
between primary normal stress coefficient and the shear rate. One of
the models described earlier, namely, the Carreau model, is used for
the viscosity function. Thus, from equations (2.43) and (2.47), the
primary normal stress coefficient 1/11 can be readily obtained as
(2.48)
The above expression would be valid within the low to medium shear
rate range, Le. 0 ::: Y ::: 10 sec-I. Other expressions for 1/11 could have been
obtained by considering the other viscosity functions described in the
earlier seetion. However, this has not been done because the effective
upper limit of shear rate of not greater than 10 sec- 1 for actual primary
normal stress experimental measurements lies in a range consistent
with only the Carreau model. In ca se measurements of primary normal
stress at higher shear rates ever become possible in future due to

improved sophistication in experimental techniques, then it is recom-
mended that equation (2.44) from the general rheological model [86] be
used along with equation (2.47) to obtain a new expression for t/Jl' Such
an expression would then be valid over a larger shear rate region
ranging from low to high.
It has been established [101] that the primary normal stress difference
exhibits a strong dependence on molecular weight distribution as
predicted from the theory of second-order fluids. Thus the fo11owing
expression is known [101] to hold
(2.49)
where the form for the steady state compliance Je is given [101-103]
as
Je = Kle (M
- -
z / M w)
3.5
(2.50)
2.3.3 MODEL FOR THE COMPLEX VISCOSITY FUNCTION

Earlier investigations of the rheological properties of polymer melts
have shown that the data under dynamic conditions can be related to
that obtained under steady shear within certain ranges of shear rates
and frequencies. Though there is a considerable amount of literature
advocating an analogy between the steady and dynamic measurements,
there is no genera11y accepted method. The problem which arises in
comparing dynamic and steady-state data is in the choice of the
appropriate rheological model for calculating the material parameters
from the measured values. Of a11 the diverse methods of correlating
dynamic and steady-state data based on theoretical models available in
the literature, the empirical method suggested by Cox and Mertz [104]
for relating steady-shear viscosity with the absolute value of complex
viscosityr,. is even to this date the most attractive of a11. According to
the Cox-Mertz method
aty =w (2.51)
The relationship simply indicates that for prediction purposes, the

magnitude of complex viscosity is comparable with that of shear
viscosity at equal values of frequency and shear rate. The relationship
has been found to hold good largely for flexible chain thermoplastic
melts, particularly in the lower and intermediate ranges of wand y.
Combining equations (2.43) and (2.51), the fo11owing expression for the
complex viscosity 1'/* based on a modification of the Carreau model is
written as
(2.52a)
where 110 is the zero-frequency viscosity function. A similar expression

can be derived based on a modification of the general rheological model
[86] by combining equations (2.44) and (2.51).
Equation (2.52a) has been used to fit dynamic viscosity vs. frequency
data for wollastonite-filled polypropylene [105] as shown in Figure
2.17(a). It can be seen that the fit between theory and experimental data
is excellent. However, when the Cox-Mertz rule is tested for this filled
system, it fails in the presence of fillers. Figure 2.17(b) shows the plots
of 11 vs. Y superimposed with those of 11* vs. w for all levels of loading of
wollastonite in polypropylene. The difference between the steady-state
and dynamic data increases with increasing loading, with the steady-
state data being consistently higher than the dynamic data. This is so
because particle-particle interaction would be predominantly greater
under steady-state conditions than in the dynamic state, in which a
104
WOllASTONm FILI.ED POLYFROPYLENE
I I III
UNITS
17* - PA SEC
UI - RADISEC
w
~
&
~ -v- h ,.... ~~~
I'-
~
"'I!. ""
Q-.. ::-s.
O'~ t-.....
~~
c-- FILLERehr I's
<;7
60
r-- [J
40
0 0
I
Figure 2.17(a) Variation of complex viscosity with frequency at 220C for wollastonite-
filled polypropylene (solid lines indicate the theoretical model (equation 2.52a) fit
through experimental data points). (Reprinted from Ref. 105 with kind permission from
Technomic Publishing Co., Inc., Lancaster, Pennsylvania, USA.)
t:f WOllAS!ONm FlI.IJID POLYFROPYLENE I ~

~
UNITS
...
11,11 -PASEC
-1
r - SEC
.
W -RAD/SEC
~ ,.. r--
~ 220 DC
/-
~
~ '" '" ~
o C ~ '" '" ~
. n []
I-" ~ r "'"
...
STEADY DYNAMIC FILLERphr
'" 60
r--- 0 40
0 0
Figure 2.17(b) Comparison between steady shear and complex viscosity data for
wollastonite-filled polyprapylene. (Reprinted fram Ref. 105 with kind permission fram
Technomie Publishing Co., Ine., Laneaster, Pennsylvania, USA.)
continuous forming and breaking of the network-type configuration of

the particles would prevent viscosity build-up. For higher levels of
loading, this effect would be consistently greater, and hence the differ-
ence between the steady-state and dynamic data increases with
increasing loading. However, it may be noted that the shape of the
curves through both types of data is essentially the same.
A rigorous correlation analogous in form to the Cox-Mertz rule, has
been shown [106] to exist between the steady shear viscosity and the
complex viscosity in terms of a newly defined 'effective shear rate',
given as y = Ymw, where Ym is the amplitude of oscillation. For filled
polymer systems with a yield stress value and a recoverable strain, it
has been purported [106] that the complex viscosity vs. maximum (or
effective) shear rate (Ymw) curve is identical to the steady state viscosity
vs. shear rate. Figure 2.18(a) shows the experimental complex viscosity
data for 70 volume percent silicon in polyethylene at 140C. The three
curves are for three different strains. lnstead of the frequency w, when
the abscissa is chosen as Ymw, then it is seen from Figure 2.18(b) that a
ISILICON FIllED POLYETHYLENE I UNII'S

TI -PASEC
f-

W-RADISEC
I

r- 1140 0 C
r

STRAIN
r- 3"10

20%
50%

I I I
Figure 2.18(a) Variation of experimental complex viscosity with frequency under

various strains at 140C for 70vol.% silicon filled polyethylene. (Reprinted from Ref.
106 with kind permission from Society of Rheology, USA.)
107
x zz
zx~
ISIUCON FII.l.ED POLYE'l'HYI..ENE I UNITS
...'.....
10 6 x~ 71*. 11- FASEC
~, W-RADISEC
r-SEC,l
10 5
T1~T1
1140 0 C I
10 4 '.'iI'.,
............
STll.AIN
3% ....
10 3 20%
50%
z STEADY
102 I I I ~
10,4 10,2
10'3 10,1 100 101 102
rm W. r
Figure 2.18(b) Comparision of the steady shear and complex viscosity data under
various strains using the effective shear rate concept for superposition. (Reprinted
from Ref. 106 with kind permission from Society of Rheology, USA.)
superposition of the three curves occurs. The spread in the data at high
effective shear rates (or, in other words, at high strains and high
frequencies) was explained [106] to be probably due to the fracture of
the sampie as was observed visually. In Figure 2.18(b) the steady shear
viscosity data are also plotted against shear rate. It is seen that there is
a elose agreement between the steady shear data and the dynamic data
when plotted in this manner using the concept of the effective shear
rate. The experimental verification of the equivalence between the
steady shear viscosity and complex viscosity has thus resulted in the
extended version of the Cox-Mertz rule.
Getting back to the discussion of the models, it can be seen that
equation (2.52a) is ideal for use when the complex viscosity curves
show a plateau region in the low frequency range along with a
decreasing trend in the higher frequency range, like for example, Curve
1 in Figure 1.4. Since equation (2.52a) presumes no yield stress, it is not
applicable to curves like Curve 2 and 3 in Figure 1.4. For highly filled
systems which may have curves resembling Curve 3 in Figure 1.4, Saini
and Shenoy [107] proposed a modified form of equation (2.52a) which
K n'-1
* W (2.52b)
1'/ = (1 w2in' -n")/2
where K is the complex viscosity at frequency of 1 radi sec and
n' = n"; n' is the slope of the 1'/* vs. w curve in the region 0.1 :::: w :::: 1;
n" is the slope of the 1'/* vs. w curve in the region 1 :::: w :::: 102 .
Equation (2.52b) was found to fit experimental data rather well [107],
because of the existence of two distinct straight lines above and below
the frequency of 1 rad/sec. Only in such cases, equation (2.52b) would
be applicable. However, when the curve shape is like the one shown in
Curve 2 of Figure 1.4, neither (2.52a) nor (2.52b) would fit experimental
data. In such cases, it might be necessary to split the entire curve into
two or three convenient regions and then fit appropriate equations to
each region. Alternatively, an equation which is similar in form to
(2.45b) may be tried by replacing 1'/*, I'/~ and w for 1'/, I'/N and y,
respectively.
2.3.4 MODEL FOR THE DYNAMIC MODULUS FUNCTIONS

Relating the steady-state normal stress difference '11 - '22 and the
dynamic storage modulus G', both characterizing the elasticity of the
material or the ability to store the energy of external forces, has
invariably been a more difficult task and has been the subject of
controversy. Though the shapes of the '11 - '22 vs. Y and the G' vs. w
curves are generally similar, a relationship between the two has to be

based on a suitable rheological model derived through an appropriate
constitutive equation such as was done by Pao [108], Spriggs [109],
Bogue [110] or Meister [111]. The results obtained by Pao [108] for
correlating the dynamic functions and stresses in the steady-state are
limited to only low-shear or low-frequency data. The adjustable
parameters among the material constants of the Spriggs [109], Bogue
[110] and Meister [111] models make them more adaptable for wide
ranges of shear rate or frequency data. The Bogue [110] and Meister
[111] models represent integral-type models, each having a different
physical origin in its derivation. The Spriggs [109] model is of the
differential type and involves material constants which are simple to
determine and also have relevance to molecular parameters. In the
present case, the Spriggs model has been chosen for correlating the
dynamic and steady-state elastic characteristics. The choice is somewhat
arbitrary as each of the models is known to have almost the same
capability for prediction [112] and by no means indicates the superiority
of this modelover that of Bogue [110] and Meister [111].
The dynamic functions that conform to the Spriggs model are
expressed as folIows:
(2.53)
(2.54)
while the steady state functions are given as
(2.55)
2'10 ~ (ey;l
"11 - "22 = e2 AZ(a) f;t ptii + (eYA)2 (2.56)
where '10' A, a and Z(a) are model parameters and e is an arbitrary

adjustable constant expressed in terms of an independent parameter
e as
(2.57)
A comparison of the above equations (2.53-2.56) yields the following:
"= e-1C" at w = ey (2.58)

"11 -"22 = 2e-2 C'
or
G"
1'/ = -
W
't11 - 't22 2G' at w = cy (2.59)
'l = c-w2
Thus, it is obvious that the dynarnie and steady-state characteristics of a
polymerie system would be equivalent when appropriately shifted by
an arnount c relative to each other. In order to determine the shift factor
c, the procedure suggested by Spriggs [109] needs to be followed,
namely, of superimposing the plot of 1'/fl)/1'/o vs. cy on the plot of
1'/'(w)/1'/o vs. w. For example, a value of c = (2/3) has been found [113] to
correlate the dynamie and steady-state viscoelastic data of a particular
grade of LLDPE over a wide range of shear rate and frequency.
It is to be noted that only in the case of e = -1 and hence c = 1, the
Spriggs model prediets a correlation at y = w. This correlation is
equivalent to that given by the phenomenological theory of Coleman
and Markovitz [114] at low-shear rates and frequencies. Since the
deformation at very low frequencies can be considered as nearly a
steady-state flow, it is natural to expect that at c = 1, a plot of ('t n - 't 22 )
vs. y2 superimposed on a plot of 2G' vs. w 2 (with y = w) would give a fit
in the low-shear and low-frequency region. In this region, combining
(2.47), (2.51) and (2.59), the following can be written,
G' 1 d'1*(w)
w2 = - 2m'----cIW (2.60)
The derivation of the above equation is based on the assumption that

c = 1. However, even if this assumption is relaxed and c i= I, the
present (2.60) should hold as m' is merely an adjustable parameter.
Thus the equation may be rewritten in more general terms through a
new adjustable parameter m" incorporating the multiplying factor 2 in
(2.60) as well as any anomalies that are introduced for c i= 1, as
G' 1 d1'/*(w)
w 2 = - m"~ (2.61)
Now, combining (2.52) and (2.61) gives
~: = (1'/~)(~~~~)(Jc2W)(1 + Jc2w2r(N+l) (2.62a)
for low filler loadings whose viscosity curves resemble Curve 1 in

Figure 1.4. For high filler loadings with viscosity curve shapes
resembling Curve 3 in Figure 1.4, the relevant equation is obtained by
combining (2.52b) and (2.61) to give the following:
G' = K (1 _ n')wn' -2(1 + w2in" -n')/2 [1 _ (n' - n")w2 ] (2.62b)

w 2 m" (1 - n')(l + w 2 )
Normally the adjustable parameter m" taken as a constant should
suffice for theoretical fit of the storage modulus vs. frequency curves
using equation (2.62). However, in filled polymer systems, it sometimes
becomes necessary [105] to assurne m" as an adjustable variable
dependent exclusively on the frequency in order to get a good
theoretical fit of the experimental data. Shenoy and Saini [105] have
chosen the following form based on the shape of the plot of m" vs.
11was,
m" =---=--~
Cl
(2.63)
(1 + c2 /w 2Y3
Substituting (2.63) into (2.62a) would then give the appropriate depen-
dence of G' on the frequency w. It can be seen from Figure 2.19 that the
theoretical fit to the experimental data is good.
Since by definition,
(2.64)
the relationship between the dynamic loss modulus G" and frequency w
can be easily established. The predicted values can be seen to fit
experimental data rather wen in Figure 2.20. The values used in Figures
2.17, 2.19 and 2.20 for the parameters are given in Table 2.2. It is seen
from Table 2.2 that only N is a constant while all the other parameters
vary with filler loading as shown in Figures 2.21 and 2.22. It is
interesting to note that a linear relation is obtained for Cl' C3 and A. on an
ordinary scale while C2 and IJ~ show linearity on a semi-logarithmic
scale. Using such plots, the parametric values at any filler loading can
be determined and equations (2.52a) and (2.62a) then become defined at
the desired filler loading.
2.3.5 MODELS FOR THE EXTENSIONAL VISCOSITY FUNCTION

The type of extensional flow which is of importance in polymer
processing and is studied in greater detail, is the uniaxial extensional
flow, which is known to occur when a material is uniaxially extended
as in fiber spinning operations or when the flow lines converge as in
the entrance of a die in an extruder.
When a material is undergoing uniaxial stretching, the flow can be
characterized by a single material function, namely, the extensional
viscosity (1JE) defined in equation (2.31).
Extensional viscosity for a Newtonian fluid was first determined by
Trouton [115], who studied the flow of pitch, tar, shoemaker's wax both
R WOu.ASTONIrE FILLED POLYPROPYLENE

1 1 1 11
t-- UNII'S
t-- G' - PASCALS
l1) - RADJSEC "" ""P'
~ ~
~ .,. ~ /" i"""p'"
//
'/...n rr
/ ./
py t' c/o
V lt
G'
~O/ f1 / P
JI ~
/ /~
10 3
/V /
//
AI Of
I /
/ /
/
/0
~V 0/
/
FIllERphr
r uV 'V60
0 V o 40
/ 0 0
Flgure 2.19 Variation ot dynamie storage modulus with trequeney at 220C tor
wollastonite-tilled polypropylene (solid lines indieate theoretieal model (equation
2.62a) tit through experimental data points). (Reprinted trom Ret. 105 with kind
permission trom Teehnomie Publishing Co., Ine., Laneaster, Pennsylvania, USA.)
under constant tensile load and uniaxial compression and examined the
flow of a freely descending stream of these materials issuing from a
circular die. Trouton found that the extensional viscosity was
independent of the strain and equal to three times the shear viscosity
(110). Thus
10 5
t - - - WOllASTONITE FIU.ED POLYFROPYLENE
I-- UNITS
I-- G'- PASCALS

U)- RAD/SEC
vV
L..L / I:> v~
220C ~ J;V ~
~
~
yV
/ ~V
/Gf
IV
0' I<
.; /
lA i~/
/ ~ /'
t~
~
V
/
1/
I /
I tvl
b FlI.LE.R Ehr
/~V <;1 60
rI / [l 40
iI o 0
) -
Figure 2.20 Variation of dynamie loss modulus with frequeney at 220C for
wollastonite-filled polypropylene (solid lines indieate theoretieal model (equation 2.64)
fit through experimental data points). (Reprinted from Ref. 105 with kind permission
from Teehnomie Publishing Co., Ine., Laneaster, Pennsylvania, USA.)
''Ir = 3'10 (2.65)
where '1r is termed the Trouton viscosity in uniaxial stretching. Non-

Newtonian polymer systems in steady extensional flows show
considerable departure from Trouton viscosity. In fact, Meissner
Table 2.2 Model parameters for equations (2.52a) and (2.62a)
Filler N t/; A. c1 c2 c3
concentration (Pa. sec)
(phr)
0 0.195 8.2 x 103 0.17 0.63 43.0 0.62

40 0.195 1.25 x 103 0.36 0.82 4.5 0.79
60 0.195 1.8 x 103 0.45 0.91 2.1 0.89
Souree: Re!. 105 (Reprinted with kind permission from Teehnomie Publishing Co. Ine., Laneas-
ter, Pennsylvania, USA).
[116,117] showed that for polyethylene, extensional viscosity increases

drastically with time, and only at very low strain rates ("'0.001 sec-I) is
the steady-state Trouton viscosity reached. Furthermore, the onset of
the rapid increase in viscosity was found to occur at adefinite value of
total strain (e ~ 1.0). Similar results were reported by Vinogradov et al.
1.3
IWOLIASTONlTE FIWJ) POLYPROPYLENE I
1.1
0.9
0.1
Cl 'C3 ' "
0.5
0.3
0.1
0 20 40 60 80
~
,,-0
C3- .
]00 120
phr
Figure 2.21 Variation of the model parameters C1, C3 and A. with filler concentration.
(Reprinted from Ref. 105 with kind permission from Technomic Publishing Co., Inc.,
Lancaster, Pennsylvania, USA.)
WOllASTONlTE FIllED POLYFROPYLENE r--

.Yl UNITS
o
-
-PASEC -
~
~
~
--
r "
" K
"\.
~
""~n\
20 40 60 80 100
phr
Figure 2.22 Variation of the model parameters C2 and 11; with filler concentration.
(Reprinted from Ref. 105 with kind permission from Technomic Publishing Co., Inc.,
Lancaster, Pennsylvania, USA.)
[118] for polyisobutylene. For more details, the review of Pipkin and
Tanner [119] may be referred to.
A number of researchers have tried to develop expressions for
extensional viscosity in the case of non-Newtonian fluids so that the
deviations from Trouton viscosity could be clearly understood. As an
example, for the three-constant Oldroyd model, the following
expression was obtained from Bird and Spriggs [120]
(2.66a)
Using the convected Maxwell model, Denn and Marrucci [121]

predicted the existence of a critical extension rate Be above which the
extensional viscosity increased without bound. The following
expression for extensional viscosity was derived at the onset of a
constant extension rate Bin an initially unstressed fluid
-(1-2cll/ -(1+,.l/
3Yfo 2'1o e---r- Yfoe---r-
YfE(t) = (1 - 2f:A)(1 + f:A) (2.66b)
(1 -2f:A) (1 +i:A)
In the above equation, Yfo and Aare adjustable constants describing the
viscosity coefficient and relaxation time of the Maxwell model. Equation
(2.66b) predicts that a steady state extension is obtained if and only if f: c
takes a value less than O.5A. Agarwal et al. [122] successfully applied
equation (2.66b) to extensional viscosity data obtained with polystyrene
and showed a good correlation between va lues of YfE and A calculated
using the Dean-Marrucci equation and those obtained from steady
shear and dynamic experiments.
Using a converging flow analysis, Cogswell [71] has shown that a
relationship between the extensional viscosity and shear viscosity can be
easily derived. In his view, as fluid flows from a reservoir into a die, the
streamlines converge and the simple shear flow field gets superimposed
by an extensional deformation. He suggested that each component can
be studied separately and subsequently added to describe the total
effect. The relationships between the various parameters of extensional
flow and those of shear flow are given by Cogswell [71,123]
O'E 1
= (2.67a)
t tane
f: tane
- = (2.67b)
y 2
and
YfE 2
(2.67c)
'1
=
tan2 e
where O'E is the average extensional stress, i; the average extensional
rate, t the shear stress at the die wall, y the shear rate at the die wall, YfE
the extensional viscosity, Yf the shear viscosity, and the half-angle of e
convergence of the streamlines at the entrance of the die.
Cogswell [71,123] has found good agreement between the calculated
values of YfE from a convergent flow analysis and that measured in a
steady-state experiment [123] using a constant stress melt tensile
rheometer for poly(methyl methacrylate). Though predictions of the
convergent flow analysis of Cogswell have been verified by the other
researchers, and the proposed simple method [71,123] for extracting
extensional flow data is correct to an extent, it is to be considered with
caution. Other analyses [124,125] have appeared in more recent times
and could be used as better alternatives when higher accuracy is
desired and especially when dealing with filled polymer systems.
Other relationships for shear viscosity functions 99
2.4 OTHER RELATIONSHIPS FOR SHEAR VISCOSITY

FUNCTIONS
2.4.1 VISCOSITY- TEMPERATURE RELATIONSHIPS
An understanding of the mechanism of polymer flow processes in

relation to the nature and composition of the material can be elucidated
by a study of the temperature dependency of shear viscosity. The
temperature sensitivity of the shear viscosity has a profound effect on
the choice of processing conditions as weH as on the quality of the end
product. An increase in temperature sets up thermal motion of the
molecules, resulting in their displacement based upon the available free
motion and the overcoming of forces of intermolecular interactions.
Presently, there are two commonly used expressions to evaluate the
temperature dependency of the viscosity - one based on free-volume
concepts, namely the equation proposed by Williams, Landel and Ferry
(W-L-F) [126] and the second, of the Arrhenius type, based on the
absolute theory of rate processes as derived by Eyring [127].
W-L-F equation
log!L = Cj(T - Ts ) (2.68)
rJ s C2 + (T - T s )
where rJ and rJ s are the viscosities at temperatures T and Ts' respectively;
C~ and C; are constants; and T s is the standard reference temperature
taken as Tg + 50 K, where Tg is the glass transition temperature.
Modification of equation (2.68) using different constants and different
characteristic ternperatures has been proposed. But since Tg is a
practical and easily available parameter, (2.68) is used preferentiaHy.
Arrhenius-Eyring equation
rJ = AoeXP(:T) (2.69)
where rJ is the viscosity at temperature T, R is the gas constant, A o is the

frequency term depending on the entropy of activation for flow, and E
is taken to be the energy of activation for viscous flow.
The temperature dependence of activation of the flow process as
defined by,
E = R lnrJ = 2.303C~C;RT2 (2.70)
(1fT) (C; + T - TJ
is predicted by the W-L-F equation, and rightly so, because free volume
and its changes with temperature playa dominant role at temperatures

relatively near Tg At temperatures (T > Tg + 100), the temperature
dependence of viscosity is decisively affected by the overcoming of the
forces of intermolecular interactions, and hence the curved plot of In Yf
vs. 1fT approaches linearity in short temperature ranges at around
100C above the highest glass transition temperature of the polymer.
Normal processing ranges for most polymers, excepting polystyrene (PS)
and polycarbonate (PC), fall within temperatures much greater than
Tg + 100. For all such systems, equation (2.69) would then provide a
valid and useful means of predicting the viscosity-temperature
dependence. E and Ao in equation (2.69) vary from polymer to polymer
and must be evaluated empirically for each polymer system investi-
gated. Within the narrow width of the processing range for each
polymer, E can be expected to be fairly constant, to give a single value
for each polymer. However, since polymers are non-Newtonian
materials, their viscosity at fixed temperature is dependent on shearing
stress or shearing rate. Thus, Ao in equation (2.69), which normally
would be a constant for Newtonian materials, would additionally
depend on shear stress or shear rate. Bestul and Belcher [128] have
shown mathematically that in the non-Newtonian (shear-thinning)
region of polymer flow, a clear differentiation between E at a constant
shear stress and E at a constant shear rate must be done. Thus,
(2.71)
(2.72)
where Er > Ei' for shear-thinning non-Newtonian viscosity, as can be

easily shown both graphically or analytically. A number of authors
[129-132] have shown that Er remains constant over a broad range of
temperature and shear-stress, while Ei' does not. Porter and Johnson
[132], on evaluating Ei' and Er for a variety of polymers studied by
different authors [133-139], concluded that Er remained constant from
the low-shear Newtonian range up to shear stresses of '" 105 Pascals
well within the non-Newtonian region (Table 2.3). From a fundamental
viewpoint, constant shear rate 'activation energies' are incorrect because
the Arrhenius equation is a rate equation, and hence holding the rate
process constant would make data treatment meaningless. Thus, strictly
speaking, the validity of equation (2.69) is restricted to only constant
shear stress though it has been extensively used for both Er and Ei"
Saini and Shenoy [140] suggest a simple and standard procedure for
obtaining Evalues as Er through a modified form of equation (2.69). In
contrast to the conventionally followed method of determining the
labte 2.3 Flow activation energies found independent of shear stress in the non-
Newtonian regions for representative undiluted, linear, amorphous polymers a
Polymer E Temp. range Shear stress Ref.

(kJ/mol) (0C) (x10 4 Pa)
Linear polyethylenes 26.4 150-300 0.13-22.0 [133]

29.7 150-300 8.6 [134]
24.3-34.3 150-220 2.2--8.9 [135]
28.5 163-274 3.0-15 [136]
Polypropylene 33.5-41.9 195-260 4.0-12.0 [137]
Polystyrene 96.3 177-232 0.69-13.8 [138]
96.3 204-227 1.2-13 [139]
aReprodueed in part from Ref. 132 with kind permission fram John Wiley & Sons. Ine .. New York.
USA.
activation energy of flow through viscosity measurements, especially

from zero shear viscosity, their work makes use of MFI for estimating E
values. The advantage of the method lies in the fact that MFI is a much
more easily determinable parameter in comparison to the zero shear
viscosity. Further, due to the MFI measurement being at a constant
shear stress, it naturally results in a standard and meaningful value of
E from the Arrhenius-type relation (2.69) which has been shown earlier
to be truly valid only at constant shear stress.
Porter and Johnson [132] have concluded that from somewhat above
104 to somewhat around 106 dynesl cm2 of shear stress, the Evalues
obtained at fixed shearing stress are justified to represent true viscous
behavior. The loading conditions in MFI determinations are such as to
develop shear stress in the range of 3 x 104 to 2 X 106 dynes/cm2 , as can
be seen from Appendix B, thus falling naturally within the justifiable
range of reliable results The modified form of Arrhenius-type equation
(2.69) is written [140] as
MFI = 110 exp ( - :~) (2.73)
Er can be calculated from the slope of the lnMFI vs. y-l plot and would
give a more meaningful and invariant result representing the activation
energy of flow at a constant shear stress than those predicted through
earlier analyses in the literature. Er developed from MFI values has the
advantage of simplicity and easy availability as against the zero shear
viscosity, which is difficult to obtain and amenable to questionable
techniques for its determination.
The concept of obtaining activation energy from MFI can be extended
to copolymers as weH. Shenoy and Saini [141] have shown that, in the
case of copolymers, there exists an anomalous temperature dependence
of viscosity leading to the existence of two distinct values of activation

energies for each copolymer.
Copolymers have polymer chains comprised of more than one type
of monomeric building block. The nature of comonomers and their
placement in the chain have a major influence on the rheology. Except
for random copolymers, all other types of block copolymers show
microphase separation. Their viscosities are a manifestation of the
existing two-phase structured system, probably a weaker version of the
three-dimensional network which exists at lower temperatures. As the
temperature is raised, only one of the domains of the two-phase system
melts, but the system is able to flow as a whole due to the fluidity
created by one of the domains despite the fact that the two domains are
not compatible. However, such a flow involves disruption of the melted
domain and transfer of the segments through a thermodynamically
incompatible unmelted second domain. This requires additional energy,
giving rise to a high value of activation energy. As the temperature
rises, a stage is reached when both domains become fluid and the
additional resistance to flow due to the presence of the unmelted
domain is removed. The temperature at which this occurs would then
become the crossover point to the lower activation energy level.
The va lues of the two activation energies on either side of the crossover
point would be such that one would be tending to the activation energy
of one phase while the other would tend to the activation energy of the
second phase. For example, in the case of SBS, between 1l0-150C,
the activation energy EI has a value of 28.7 kcal/mole which is not
too different from the activation energy for homopolystyrene (E =
25.5kcal/mole); whereas in the temperature range between 150 to
210C, the activation energy tends to that of polybutadiene (E = 4.5
to 7.9kcal/mole) and takes a lower value of E2 = 10.0kcal/mole.
It is essential to exercise caution when determining the activation
energy for viscous flow in the case of copolymers. If the attempt at such
determinations is done through few data points, there is a likelihood of
error as the crossover point would not come out distinctly and the plot
of viscosity or MFI vs. y-I may be mistaken for a curve that cannot be
approximated by a straight line. Values of Er calculated from the slope of
In MFI vs. y-I plots for a number of common polymers and copolymers
are available in the book on Thermoplastic Melt Rheology and Processing
[142].
Feldman and Boiesan [143] have given experimental evidence to
show that viscosity of filled systems at different temperatures could be
estimated by the well-known Arrenhius equation whose form is given
by equation (2.69).
When the filled system is non-Newtonian in character, the activation
energy of the filled system takes different values depending on whether
the filled system is under constant shear stress or constant shear rate,
and naturally so, as has been explained earlier.
The effect of temperature on the solid phase of the filled system is
shown by the variations in the void fraction and consequently in 4>m.
With an increase in temperature, Jinescu [144] has shown that the value
of 4>m is increased due to variation in the density of the system with
temperature.
The viscosity of a polymerie system decreases with increasing
temperature due to the greater free volume available for molecular
motion at the higher temperature. In the ca se of filled polymer systems,
the free volume change is limited only to the polymer fraction of the
composite. It is therefore expected that the filled polymer viscosity
would be less temperature sensitive than the unfilled viscosity. This
point will be discussed in detail in section 6.3.
An interesting effect of temperature on the viscosity of plastisol (Le.
fine partieles of poly(vinyl chloride) dispersed in a plasticizer) has been
shown by Collins et al. [145]. With an increase in the temperature, the
viscosity of plastisol was seen to first decrease up to about 45C due to
a decrease in the viscosity of the suspending medium. At higher
temperatures, the resin begins to dissolve in the suspending medium
thereby showing a sud den viscosity increase.
2.4.2 VISCOSITY-PRESSURE RELATIONSHIP

Several theories [146-150] support the idea that viscosity is largely
dependent on the free volume of the system. Since the most direct
influence on free volume is that of pressure, viscosity also depends on
press ure [151-156]. Viscosity generally increases with increasing
pressure, and can be correlated generally by an equation of the type,
YJ = A~ exp(B~p) (2.74)
where A~ and B~ are constants and p is the pressure. The pressure

reduces free volume and as a result, it reduces molecular mobility;
however, this effect becomes noticeable only at very high pressures.
High pressure raises both Tg and Tm which also reflects in an increase
in viscosity. In general, during most practieal situations, polymer
systems are assumed incompressible for ease and simplification. Carley
[151] coneluded that pressure effects are of minor significance in most
processing situations, provided the temperature is not too elose to
transition. However, it has been noticed in polymer processing
operations that the combination of high pressure and low temperature
tends to promote crystallization [157,158], orientation [159] and struc-
tural changes [160].
2.4.3 VISCOSITY-MOLECULAR WEIGHf RELATIONSHIP

Experiments [161-164] have shown that the following relationship
between zero-shear viscosity and molecular weight holds good.
rJo = koMw for Mw < Mwc (2.75a)
rJo = ko x;t5 for Mw > M wc (2.75b)

where Mwc is the critical weight average molecular weight, thought to
be the point at which molecular entanglement begins to dominate the
rate of slippage of molecules.
REFERENCES
1. Reiner, M. (1949) Deformation and Flow, Lewis, London; (1960) Deformation,
Strain and Flow, Wiley - Interscience, New York.
2. Reiner, M. (1964) The Deborah Number, Physies Today, 17, 62.
3. Meissner, J. (1971) Dehnungsverhalten von Polyathylen-Schmelzen, Rheol.
Acta, 10, 230-42.
4. Bird, RB., Armstrong, RC and Hassager, O. (1977) Dynamics of Polymerie
Liquids, Vol. 1, Fluid Meehanies, Wiley, New York, p. 131.
5. Tadmor, Z. and Bird, RB. (1974) Rheological analysis of stabilizing forces in
wire-coating dies, Polym. Engg Sei., 14, 124-36.
6. CogsweH, F.N. (1975) Polymer melt rheology during elongational flow, Appl.
Polym. Symp., 27, 1-18.
7. Dealy, J.M. (1971) Extensional flow of non-Newtonian fluids - a review,
8. Dealy, J.M. (1978) Extensional rheometers for molten polymers: a review, J.
Non-Newtonian Fluid Meeh., 4, 9-21.
9. Hill, J.W. and Cuculo, J.A. (1976) Elongational flow behavior of polymerie
fluid, J. Maeromol. Sei., Rev. Maeromol. Chem., 14, 107-53.
10. Bird, RB. (1982) Polymer kinetic theories and elongational flows, Chern.
Engg Commun., 16, 175-87.
11. Petrie, CJ.S. (1979) Elongational Flows, Pitman Publieations, London.
12. Walker, J. (1978) Serious fun with polyox, silly putty, slime and other non-
Newtonian fluids, Sei. Am., 239, 142-9.
13. Lodge, A.S. (1964) Elastie Liquids, Academic Press, New York.
14. Fredrickson, A.G. (1964) Prineiples and Applieations of Rheology, Prentice-HaH,
Englewood Cliffs.
15. Coleman, B.D., Markovitz, H. and NoH, W. (1966) Viseometrie Flows of Non-
Newtonian Fluids, Springer, New York.
16. TruesdeH, C (1974) The meaning of viscometry in fluid dynamies, Ann. Rev.
Fluid Meeh., 6, 111-46.
17. Markovitz, H. (1965) Rheologieal Behaviour of Fluids, Education Services,
Watertown, Mass.
18. Wilkinson, W.L. (1960) Non-Newtonian Fluids, Macmillan (pergamon), New
York.
19. TruesdeH, C and NoH, W. (1965) The Non-Linear Field Theories of Meehanies,
Springer-Verlag, Berlin.
References 105
20. Skelland, AH.P. (1967) Non-Newtonian Flow and Heat Transfer, Wiley, New
York.
21. Astarita, G. and Marrucci, G. (1974) Prineiples of Non-Newtonian Fluid
Meehanies, McGraw-Hill, London.
22. Darby, R (1976) Viseoelastie Fluids, Marcel Dekker, New York.
23. Bird, RB., Armstrong, RC and Hassager, O. (1977) Dynamies of Polymerie
Liquids, Vols 1 and 2, Wiley, New York.
24. Middleman, S. (1977) Fundamentals of Polymer Proeessing, McGraw-Hill, New
York.
25. Schowalter, W. (1977) Meehanies of Non-Newtonian Fluids, Pergamon, Oxford.
26. Tanner, RI. (1985) Engineering Rheology, Clarendon Press, Oxford.
27. Barnes, H., Hutton, J.F. and Walters, K. (1989) Introduction to Rheology,
Elsevier, Netherlands.
28. Rosen, M.R (1979) Characterization of non-Newtonian flow, Polym.-Plast.
Teehnol. Engg, 12, 1-42.
29. Becker, E. (1980) Simple non-Newtonian fluid flows, Adv. Appl. Meeh., 20,
177-226.
30. Schramm, G. (1981) Introduetion to Practieal Viseometry, Gebruder Haake,
GmbH, Karlsruhe, Germany.
31. Cheremisinoff, N.P. (1986) Properties and concepts of single fluid flows,
in Encyclopedia of Fluid Meehanies, Gulf Publishing, Houston, TX, Vol. I,
Chap. 10, 277-352; (1988) Rheological characterization and processibility
testing, in Encyclopedia of Fluid Meehanies, Vol. 7, Chap. 32, 991-
1059.
32. Rudraiah, N. and Kaloni, P.N. (1990) Flow of non-Newtonian fluids, in
Encyclopedia of Fluid Meehanies, Gulf Publishing, Houston, TX, Vol. 9, Chap.
I, 1--69.
33. Chung, J.T. (1988) Fundamentals of polymer materials, in Encyclopedia of
Fluid Meehanies, Gulf Publishing, TX, Vol. 7, Chap. 33, 1061-80.
34. Walters, K. (1975) Rheometry, Chapman & Hall, London, pp. 25, 26.
35. Weissenberg, K. (1946) Rep. Gen. Conf Brit. Rheol. Club, Nelson, Edinburgh,
p. 36; (1947), A continuum theory of rheological phenomena, Nature, 159,
310-11.
36. Russell, RJ. (1946) PhD Thesis, Imperial College, University of London.
37. Garner, F.H. and Nissan, AH. (1946) Rheological properties of high
viscosity solution of long molecules, Nature, 158, 634-5.
38. Metzner, AB. (1969) Historical comments on stress relaxation following
steady flow through a duct or orifice, Trans. Soe. Rheol., 13, 467-70.
39. Bagley, E.B. and Schreiber, H.P. (1969) Elastic effects in polymer extrusions,
in Rheology (ed. F.R Eirich), Academic Press, New York, Vol. 5, Chap. 3,
93-125.
40. Clegg, P.L. (1958) Elastic effects in the extrusion of polyethylene, in Rheology
of Elastomers (eds P. Mason and N. Wookey), Pergamon Press, Oxford,
174-89.
41. Nakajima, N. and Shida, M. (1966) Trans. Soe. Rheol., 10, 299-316.
42. Bagley, E.B. and Duffey, H.J. (1970) Recoverable shear strain and Barus
effect in polymer extrusion, Trans. Soe. Rheol., 14,545-53.
43. Graessley, W.W., Glasscock, S.D. and Crawley, RL. (1973) Die swell in
molten polymers, Trans. Soe. Rheol., 14, 519--44.
44. Tanner, RI. (1970) A theory of die swell, J. Polym. Sei., A8, 2067-78.
45. Pearson, J.RA and Trottnow, R (1978) On die swell: some theoretical
results, J. Non-Newtonian Fluid Mech., 4, 195-215.
46. Berstein, 8., Kearsley, E. and Zapas, L. (1963) A study ofstress relaxation
with finite strain, Trans. Soc. Rheol., 77, 391-410.
47. Reddy, K.R and Tanner, RL (1978) J. Rheol., 22, 661-5.
48. Petrie, c.rS. and Denn, M.M. (1976) Instabilities in polymer processing,
AIChE J., 22, 209-36.
49. Tordella, J.P. (1969) Unstable flow of molten polymers: A second site of melt
fracture, in Rheology, Vol. 5 (ed. F.R Eirich), Academic Press, New York.
50. Tordella, J.P. (1956) Fracture in the extrusion of amorphous polymers
through capillaries, J. Appl. Phys., 27, 454-8.
51. Spencer, RS. and Dillon, RE. (1949) The viscous flow of molten polystyrene,
J. Colloid Sei., 4, 241-55.
52. Schreiber, H.P., Bagley, E.8. and Birks, AM. (1960) Filament distortion and
die entry angle effects in polyethylene extrusion, J. Appl. Polym. Sei., 4,
362-3.
53. Benbow, J.J., Charley, RV. and Lamb, P. (1961) Unstable flow of molten
polymers, Nature, 223-4.
54. Uhland, E. (1976) Rheol. Acta, 15, 30-9.
56. Janssen, L.P.8.M. (1980) A thermodynamic approach to the understanding
of slip phenomena, Rheol. Acta, 19, 32-7.
57. Okubo, S. and Hori, Y. (1980) J. Rheol., 24, 253-7.
58. Weill, A (1980) About the origin of shark skin, Rheol. Acta, 19, 623-32.
59. Weill, A (1980) Capillary flow of linear polyethylene melt: sudden increase
of flow rate, J. Non-Newtonian Fluid Mech., 7, 303-14.
60. Akay, G. (1982) Rheology of reinforced thermoplastics and its application to
injection molding IV. Transient injection capillary flow and injection
molding, Polym. Engg Sei., 22, 1027.
61. Akay, G. (1983) Unstable capillary flow of reinforced polymer melts, J. Non-
Newtonian Fluid Mech., 13, 309-23.
62. Bersted, B.H. (1983) Investigation of the oscillatory flow phenomena in high
density polyethylene, J. Appl. Polym. Sei., 28, 2777-91.
63. Ruckenstein, E. and Rajora, P. (1983) On the no slip boundary condition of
hydrodynamics, J. Colloid. Interf Sei., 96, 488-91.
64. Balmer, J. (1974) Entropy and melt fracture, J. Appl. Polym. Sei., 18, 3127-36.
65. Hlavacek, B., Carreau, P. and Schreiber, H.P. (1979) In Seience and Technology
of Polymer Processing, (eds N.P. Suh and N.H. Sung), MIT Press, Cambridge,
Mass.
66. Benbow, J.J. and Lamb, P. (1963) New aspects of melt fracture, SPE Trans.,
3,7.
67. Oyanagi, Y. (1973) A study of irregular flow behavior of high density
polyethylene, Appl. Polym. Symp., 20, 123-36.
68. Southem, J.H. and Paul, D.R (1974) Elastic fracture of polystyrene solutions,
J. Polym. Engg Sei., 14, 560.
69. White, J.L. (1975) Critique on flow patterns in polymer fluids at the entrance
of a die and instabilities leading to extrudate distortion, Appl. Polym. Sei., 20,
155-74.
70. Boudreaux, E. Jr and Cuculo, J.A (1977) Polymer flow instability - a review
and analysis, J. Macromol. Sei., Rev. Macromol. Chern., C16, 39-77.
References 107
71. Cogswell, F.N. (1972) Converging flow of polymer melts in extrusion dies,
Polyrn. Engg Sei., 12, 64-73.
72. White, J.L. and Kondu, AJ. (1977) Ends pressure losses in extrusion of
polymer melts through die, J. Appl. Polyrn. Sei., 21, 2284-92.
73. Higashitani, K. and Lodge, AS. (1975) Hole pressure error measurements in
pressure-generated shear flow, Trans. Soc. Rheol., 19, 307-35.
74. Metzner, AB. (1967) Behaviour of suspended matter in rapidly aeeelerating
viseoelastie fluids: the Uebler effect, AIChE J., 13, 316-18.
75. Metzner, AB., Uebler, E.A. and Chan, C.F. (1969) Converging flow of
viseoelastie materials, AIChE J., 15, 750-58.
76. Bird, RB. (1976) Useful non-Newtonian models, Ann. Rev. Fluid Mech., 8,
13-34.
77. Ostwald, W. (1925) Ueber die Gesehwindigkeitsfunktion der Viskositat
Disperser Systeme, 1., Kolloid-Z., 36, 99-117.
78. Ostwald, W. (1926) Ueber die Viskositat Kolloider hosungen in Struktur-
Laminar und Turbulezgebiet, Kolloid-Z., 38, 261-280.
79. De Waele, A (1923) Viseometry and plastometry, J. Gil Color Chern. Assoc., 6,
33-69.
80. Bird, RB. (1965) Experimental tests of generalized Newtonian models
eontaining a zero-shear viseosity and a eharaeteristie time, Can. J. Chern.
Engg, 43, 161-8.
81. Astarita, G. (1966) Letter to the Editor eommenting on the paper by Bird
(1965), Can. J. Chern. Engg, 44, 59-60.
82. Carreau, P., De Kee, D. and Daroux, M. (1979) An analysis of the viseous
behavior of polymer solutions, Can. J. Chern. Engg, 57, 135-40.
83. Cross, M.M. (1979) Relation between viseoelasticity and shear-thinning
behavior in liquids, Rheol. Acta, 18, 609-14.
84. Chhabra, RP., Tiu, C. and Uhlherr, P.H.T. (1981) Creeping motion of
spheres through Ellis model fluids, Rheol. Acta, 20, 346-51.
85. Carreau, P.J. (1972) Rheological equations from moleeular network theories,
Trans. Soc. Rheol. 16,99-127.
86. Shenoy, U.V., Bamane, S.V. and Shenoy, AV. (1990) A general rheologieal
model for polymer melts, 40th Canadian Chern. Engg Conference, Halifax,
Canada Guly).
87. Churehill, S.W. and Churehill, RW. (1975) A general model for the
effeetive viseosity of pseudoplastie and dilatant fluids, Rheol. Acta, 14,
404-9.
88. Churehill, S.W. and Usagi, R (1972) A general expression for the correlation
of rates of transfer and other phenomena, AIChE. J., 18, 1121-28.
89. Hersehel, W.H. and Bulkley, R (1926) Konsistenzmessungen von Gummi-
Benzollosungen, Kolloid-Z., 39, 291-300.
90. Abdel-Khalik, 5.1., Hassager, O. and Bird, RB. (1974) Predietion of melt-
elasticity from viscosity data, Polyrn. Engg Sei., 14, 859-62.
91. Poslinski, AI., Ryan, M.E., Gupta, R.K., Seshadri, S.G. and Freehette, F.J.
(1988) Rheologieal behavior of filled polymerie systems. I. Yield stress and
shear-thinning effeets, J. Rheol., 32, 703-35.
92. Barnes, H.A. and Walters, K. (1985) The yield stress myth?, Rheol. Acta, 24,
323-6.
93. Hartnett, J.P. and Hu, R (1989) Teehnieal note: The yield stress - an
engineering reality, J. Rheol., 33, 671-9.
94. Astarita, G. (1989) Letter to the Editor: The engineering reality of the yield
stress, J. Rheol., 34, 275-7.
95. Bird, RB., Hassager, O. and Abdel-Khalik, S.1. (1974) Co-rotational
rheologieal models and the Goddard expansion, AIChE J., 20, 1041--66.
96. Wagner, M.H. (1977) Prediction of primary stress differenee from shear
viseosity data using a single integral eonstitutive equation, Rheol. Acta, 16,
43-50.
97. Huppier, J.D., Ashare, E. and Holmes, L.A. (1967) Rheologieal properties
of three solutions, Part I. Non-Newtonian viseosity, normal stresses, and
eomplex viseosity, Trans. Soc. Rheol., 11, 159-79; also, Ashare, E. (1968)
Rheologieal properties of monodisperse polystyrene solutions, PhD thesis,
University of Wiseonsin, USA.
98. Carreau, P.J., Maedonald, LF. and Bird, RB. (1968) A non-linear
viscoelastie model for polymer solutions and melts - 11. Chem. Eng. Sei., 23,
901-11.
99. Ballenger, T.F., Chen, LJ., Crowder, J.W., Hagler, G.E., Bogue, D.C and
White, J.L. (1971) Polymer melt flow instabilities in extrusion: investigation
of the mechanism and material and geometrie variables, Trans. Soc. Rheol.,
15,195-215.
100. Chen, LJ. and Bogue, D.C (1972) Time-dependent stress in polymer melts
and review of viseoelastie theory, Trans. Soc. Rheol., 16, 59-78.
101. Oda, K., White, J.L. and Clark, ES. (1978) Correlation of normal stresses in
polystyrene melt and its implications, Polym. Engg Sei., 18, 25-8.
102. Masuda, T., Takahashi, M. and Onogi, S. (1973) Steady state eomplianee of
polymer blends, Appl. Polym. Symp., 20, 49--60.
103. Minoshima, W., White, J.L. and Spruiell, J.E. (1980) Experimental investi-
gation of influenee of moleeular weight distribution on the rheologieal
properties of polypropylene melts, Polym. Engg Sei., 20, 1166-76.
104. Cox, W.P. and Mertz, EH. (1958) Correlation of dynamie and steady flow
viseosities, J. Polymer Sci., 28, 619-21.
105. Shenoy, A.v. and Saini, D.R (1986) Wollastonite reinforeed polypropylene
eomposites: dynamic and steady state melt flow behavior, J. Reinforced
Plastics & Comp., 5, 62-73.
106. Doraiswamy, D., Mujumdar, AN., Tsao, 1., Beris, A.N., Danforth, S.C and
Metzner, A.B. (1991) The Cox-Mertz rule extended: A rheologieal model
for coneentrated suspensions and other materials with a yield stress, J.
Rheol., 35, 647-85.
107. Saini, D.R and Shenoy, A.v. (1986) Viscoelastic properties of highly loaded
ferrite-filled polymerie systems, Polym. Engg Sei., 26, 441-5.
108. Pao, Y.-H. (1957) Hydrodynarnie theory for the flow of a viscoelastie fluid,
J. Appl. Phys., 28, 591-8; (1962) Theories for the flow of dilute solutions of
polymer and of non-diluted liquid polymers, J. Polym. Sei., 61, 413-48.
109. Spriggs, T.W. (1965) A four eonstant model for viscoelastie fluids, Chem.
Engg Sei., 20, 931-46.
110. Bogue, D.C (1966) An explicit constitutive equation based on integrated
strain history, Ind. Engg Chem. Fundam., 5, 253-9.
111. Meister, B.J. (1971) An integral eonstitutive equation based on moleeular
network theory, Trans. Soc. Rheol., 15, 63-89.
112. Han, C.D. (1976) Rheology in Polymer Processing, p. 54, Aeademie Press,
New York.
References 109
113. Saini, D.R and Shenoy, AV. (1984) Dynamic and steady-state rheological
properties of linear-Iow-density polyethylene melt, Polym. Engg Sei., 24,
1215-18.
114. Coleman, B.D. and Markovitz, H. (1964) Normal stress effects in second
order fluids, J. Appl. Phys., 35, 1-9.
115. Trouton, F.T. (1906) Proe. Roy. Soe. Lond., 77, 426-40.
116. Meissner, J. (1969) Rheol. Acta., 8, 78.
117. Meissner, J. (1972) Trans. Soe. Rheol., 16, 405-20.
118. Vinogradov, G.V., Radushkevich, B.V. and Fiekhman, V.D. (1970) Exten-
sion of elastic liquids: Polyisobutylene J. Polym. Sei., A-2(8), 1-17.
119. Pipkin, AC. and Tanner, RI. (1977) Steady non-viscometric flows of
viscoelastic liquids, Ann. Rev. Fluid Meeh., 9,13-32.
120. Bird, RB. and Spriggs, T.w. (1965) Elongational viscosity of viscoelastic
fluids, Phys. Fluids, 8, 1390-2.
121. Denn, M.M. and Marrucci, G. (1971) Stretching of viscoelastic liquids,
AIChE J., 17, 101-3.
122. Agarwal, P.K., Lee, W.K., Lornston, J.M., Richardson, c.J., Wissbrun, K.F.
and Metzner, AB. (1977) Rheological behavior of molten polymers in
shearing and in extensional flows, Trans. Soe. Rheol., 21, 355-79.
123. Cogswell, F.N. (1972) Measuring the extensional viscosities of polymer
melts, Trans. Soe. Rheol., 16, 383-403.
124. Binding, D.M. (1991) Capillary and contraction flow of long glass fiber
reinforced polypropylene, Composites, 2, 243-52; (1988) An approximate
analysis for contraction and converging flows, J. Non-Newtonian Fluid
Meeh., 27, 173-89.
125. Gibson, AG. (1989) Die entry flow of reinforced polymers, Composites, 20,
57-64.
126. Williams, M.L., Landel, RF. and Ferry, J.D. (1955) The temperature depen-
dence of relaxation mechanism in amorphous polymer and other glass
forming liquids, J. Am. Chern. Soe., 77, 3701-7.
127. Eyring, H. (1936) Viscosity, plasticity and diffusion as examples of absolute
reaction rates, J. ehern. Phys., 4, 283-91.
128. Bestul, AB. and Belcher, H.V. (1953) Temperature coefficients of non-
Newtonian viscosity at fixed shearing stress and at fixed rate of shear, J.
Appl. Phys., 24, 696-702.
129. Philippoff, W. and Gaskins, F.H. (1956) Viscosity measurements on molten
polyethylene, J. Polym. Sei., 21, 205-22.
130. Mendelson, RA (1965) SPE Trans., 5, 34.
131. Meissner, J. (1965) The effect of temperature on the flow properties of low
density polyethylene melt, in Proe. Inst. Congr. Rheol. (ed. E.H. Lee),
Interscience, New York, pt. 3, p. 437.
132. Porter, RS. and Johnson, J.F. (1966) Temperature dependence of polymer
viscosity: The influence of shear rate and stress; The influence of polymer
composition, J. Polym. Sei., CIS, 365-71, 373-80.
133. Mendelson, RA (1965) Polyethylene melt viscosity: shear rate temperature
superposition. A continuum theory of rheological phenomena, Trans. Soe.
Rheol., 9, 53-63.
134. Ferguson, J., Wright, B. and Haward, RN. (1964) The flow properties
of polyethylene whole polymer and fractions, J. Appl. Chem., 14,
53-63.
135. Sabia, R (1964) On the characterization of non-Newtonian flow, J. Appl.

Polym. Sei., 8, 1651-7.
136. Schott, H. and Kaghan, W.s. (1961) Viscous flow of molten polyethylene
resins, J. Appl. Polym. Sei., 5, 175-83.
137. Schott, H. and Kaghan, W.s. (1963) SPE Trans., 3, 145.
138. allman, RL. and Simon, RH.M. (1964) The influence of molecular weight
distribution on some properties of polystyrene melt, J. Polym. Sei., A2,
3557-75.
139. Rudd, }.F. (1960) The effect of molecular weight distribution on the
rheological properties of polystyrene, J. Polym. Sei., 44, 459-74.
140. Saini, D.R. and Shenoy, A.V. (1983) A new method for the determination
of flow activation energy of polymer melts, J. Macromol. Sei.-Phys., B22,
437-49).
141. Shenoy, A.V. and Saini, D.R (1988) Effects of temperature on the flow of
copolymer melts, Materials Chem. Phys., 19, 123-30.
142. Shenoy, A.V. and Saini, D.R. (1996) Thermoplastic Melt Rheology and
143. Feldman, D. and oiesan, V. (1971) Mat. Plastics, 8, 536.
144. }inescu, V.V. (1974) The rheology of suspensions, Int. Chem. Engg, 14,
397-420.
145. Collins, E.A., Hoffman, D.}. and Sani, P.L. (1979) Rheology of plastisols of
poly(vinyl chloride), Rubber Chem. Tech., 52, 676-9.
146. Litovitz, T.A. and Macedo, P.. (1965) Physics of Non-Crystalline Solids (ed.
}. Prins), Interscience, New York, p. 220.
147. Macedo, P.. and Litovitz, T.A. (1965) J. Chem. Phys., 42, 245-56.
148. Hildebrand, }.H. and Lamoreaux, RH. (1972) Proc. Nat. Acad. Sei., 69, 3428.
149. Sanchez, I.C (1974) J. Appl. Phys., 45, 4204-15.
150. Cohen, M. and Turnbull, D. (1959) J. ehem. Phys., 31, 1164-9.
151. CarIey, J.L. (1961) Effect of static pressure on polymer melt viscosities,
Mod. Plastics, 39,123-30.
152. Penwell, R.C, Porter, R.S. and Middleman, S. (1970) Determination of t:he
pressure coefficient and pressure effects in capillary flow, J. Polym. Sci.,
A2(9),731-45.
153. Cogswell, F.N. (1973) The influence of pressure on the viscosity of polymer
melts, Plastics & Polymer, 41, 39-43.
154. Maxwell, . and Jung, A. (1957) Hydrostatic pressure effect on polymer
melt viscosity, Mod. Plastics, 35, 174-82.
155. Ito, K., Tsutsui, M., Kasajima, M. and Ojama, T. (1973) Capillary flow of
polymer melts under hydrostatic pressure, Appl. Polym. Symp., 20, 109-22.
156. Utracki, L.A. (1983) Pressure dependence of Newtqnian viscosity, Polym.
Engg Sei., 23, 446-51.
157. Sauthem, J.H. and Porter, R.S. (1970) The properties of polyethylene
crystallized under orientation and pressure effects of apressure capillary
viscometer, J. Appl. Polym. Sei., 14,2305-17.
158. ludell, D.J., Cogswell, F.N., Holdsworth, P.}. and Willmouth, F.M. (1977)
Melting behavior of stress crystallized high density polyethylene, Polymer,
18,204-06.
159. Wasiak, A. and Ziabicki, A. (1975) Effect of spinning conditions and
orientation on the degree of crystallization of nylon and polyester, Appl.
Polym. Symp., 27, 111-20.
References 111
160. Spruiell, J.E. and White, J.L. (1975) Structure development during the melt
spinning of fibers, Appl. Polym. Symp, 27, 121-58.
161. Baumann, G.F. and Steingiser, S. (1963) Rheological measurements on
polycarbonate, J. Polym. Sei., Al, 3395-406.
162. Fox, T.G., Grateh, S. and Loshach, S. (1956) Viscosity Relationships for
Polymers in Bulk and in Concentrated Solution, in Rheology, Vol. 1 (ed.
F.R Eirich), Academic Press, New York.
163. Kraus, G. and Gruver, J.L. (1965) Rheological properties of cis-
polybutadiene, J. Appl. Polym. Sei., 9, 739-55.
164. Proter, RS. and Johnson, I.F. (1963) The effect of molecular weight and
distribution on polymer rheology near the entanglement region, Trans. Soc.
Rheol., 7, 241-52.
Rheometry 3
Rheometry is the measuring arm of rheology and its basic function is to

quantify the rheological material parameters of practical importance.
A rheometer is an instrument for measuring the rheological
properties and can do one of the following two things:
1. It can apply a deformation mode to the material and measure the
subsequent force genera ted, or
2. It can apply a force mode to a material and measure the subsequent
deformation.
The best designs of rheometers use geometries so that the forcesl
deformation can be reduced by subsequent calculation to stresses and
strains, and so produce material parameters. It is very important that
the principle of material independence is observed when parameters
are measured on the rheometers. The flow within the rheometers
should be such that the kinematic variables and the constitutive
equations describing the flow must be unaffected by any rigid rotation
of both body and coordinate system - in other words, the response of
the material must not be dependent upon the position of the observer.
When designing rheometers, care is taken to see that the rate of
deformation satisfies this principle for simple shear flow or viscometric
flow. The flow analyzed can be considered as viscometric (simple
shear) flow if sets of plane surfaces (known as shear planes) are seen
to exist and each is moving past the other as a solid plane, Le. the
distance between every two material points in the plane remains
constant.
The importance of viscometric flows becomes apparent when one
appreciates that the equation of motion for most viscometric flows can
be solved analytically. This is the reason why viscometric flows have
been used for evaluating the viscosity function from viscometric data
and this fact has brought about the alternative name for simple shear

Rotational viscometers 113
flows. All flows that do not conform to the viscometric behavior as

described above are termed non-viscometric flows. All rheometers
have viscometric flows or at least 'near-viscometric' flows in them and
hence are amenable to produce reliable material functions.
Rheometers used for determining the material functions of filled
polymer systems can be divided into two broad categories - (a) rotational
type and (b) capillary type. Further subdivisions are possible and
these are shown in Table 3.1. In what follows only those
rheometers which are popularly used for rheological characterization
of filled polymer systems are described and discussed in detail. For
example, though the bob and cup rotational viscometer has been used
[1] in the fifties for polyethylene melts, it has not been inc1uded in
further detail. This is because this geometry is not at all popular even
for unfilled thermoplastic melt studies, though Cogswell [2] did
suggest it in the seventies for measuring shear viscosities under
conditions of controlled pressure. Similarly, other rheometers which
were developed for rheological measurements of filled systems,
particularly suspensions such as cement [3], red mud [4] or other
slurries [5,6], sealants [7], paints, foodstuffs or greases [8], dental
composites [9-11], propellants [12], etc. are also not described here, as
they are considered to be beyond the scope of this book. For a general
discussion on rheometry, as applicable to various types of fluids, it is
advisable to refer to some of the excellent monographs on this subject
[13-18].
3.1 ROTATIONAL VISCOMETERS

For filled polymer studies, rotational viscometers with either the cone-
plate or parallel-disc configuration are used.
The major advantages of cone and plate viscometers are:
(i) a constant shear rate is maintained throughout the melt sampie,
(ii) a small quantity of sampie is required for measurement.
On the other hand, the chief advantage of the parallel disc
configuration is that it can be used for filled polymer systems of
extremely high viscosity and elasticity.
The basic limitation in rotational viscometers is that they are
restricted in their use only to low shear rates for unidirectional shear
and low frequency oscillations during oscillatory shear.
At higher shear rates as well as at higher frequencies, a flow
instability normally sets in the polymer sample which then begins to
emerge out of the gap between the cone and plate or parallel-disc
[19,20], thereby giving erroneous results. As a consequence of the
above, the measured material functions do not actually conform to the
Table 3.1 Rheometers for filled polymer systems
Rotational Capillary
I I
I -1
Unidireetional Oseillatory Constant Constant
shear shear speed pressure
I I I -I I
Plunger Serew Plunger
type extrusion type
-I type I
Cone-n-plate Parallel Cireular
dise I orifiee
Cireular Slit
orifiee orifiee
Cireular Slit
orifiee orifiee
(a) Rheometries meehanieal (a) Monsanto Han's (a) Haake rheoeord* Melt flow
speetrometer* automatie slit (b) Brabender plastieorder* indexer
(b) Sangamo Weissenberg rheometer* rheometer (a) Kayeness*
rheogoniometer* (b) Instron (b) Ceast*
eapillary (e) Davenport*
rheometer*
* Commercial instrument.
higher deformation rates which are normally prevalent in processing

operations.
Commercially available rotational instruments, such as the
Mechanical Spectrometer (Rheometrics Inc., Piscataway, N], USA) and
Weissenberg Rheogoniometer (Carri-Med Ud, Dorking, England)
can be used for unidirectional rotational shear as weIl as oscillatory
shear and come with interchangeable cone and plate/paraIlel-disc
configurations.
3.1.1 CONE AND PLATE VISCOMETER

The cone and plate viscometer is a widely used instrument for shear
flow rheological properties of polymer systems [21-32]. The principal
features of this viscometer are shown schematically in Figure 3.1. The
sampie whose rheological properties are to be measured is trapped
between the circular conical disc at the boUom and the circular
horizontal plate at the top. The cone is connected to the drive motor
which rotates the disc at various constant speeds while the plate is
AXIALmausr
MEASURlNG DEVlCE
TORQUE
I
MEASURlNG t - - c:==::::j
DEVICE srATIONAB.Y
FLAT DISK POLYl4n
MELT
Figure 3.1 Schematic diagram showing the principal features of a cone and plate
rotation al viscometer.
116 Rheometry
connected to the torque-measuring device in order to evaluate the

resistance of the sampie to the motion. The cone is truncated at the top.
The gap between the cone and plate is adjusted in such a way as to
represent the distance that would have been available if the
untruncated cone had just touched the plate. The angle of the cone
surface is normally very small (80 :::: 4 or 0.0696 radius) so as to
maintain [14] cosec2 80 = 1. The cone angles are chosen such that for
any point on the cone surface, the ratio of angular speed and distance
to the plate is constant. This ensures that the shear rate is constant from
the cone tip to the outer radius of the conical disco Similarly, the shear
rate can be assumed to be constant for any point within the gap because
of the predesigned method of gap adjustrnent as described earlier.
The flow curve for a sampie held between the cone and plate is
generated from measurements of the torque experienced by the plate
when the cone is rotated unidirectionally at different speeds. The
various parameters of relevance are determined as follows.
A. Shear rate
For a constant speed of rotation of N rpm, the linear velocity (v = wr) is
2nrNj60m/sec where w is the angular velocity (rad/sec) and r is the
radial position in meters. The gap height at r is r tan 80 where 80 is the
cone angle. Hence shear rate in reciprocal seconds at r can be written
as,
. 2nrN nN nN
y= = ~-- (3.1)
60r tan 80 30 tan 80 3080
Since the cone angle is always maintained to be very small, the
approximation of tan 80 = 80 does hold good.
B. Shear stress
The following expression defines the relationship between the
measured torque and the shear stress:
T = 2n'21 l R
y2 dr = ~ nR '21
3 (3.2)
Thus,
3T
'21 =---=3 (3.3)
2nR
The shear stress is then obtained in pascals when T is expressed in
newtons.m and R in meters. The ratio of equation (3.3) to equation
(3.1) results in the apparent viscosity expressed in Pa.sec.
C. Normal stress difference

The cone and plate configuration can be used for estirnating the
primary normal stress difference of the sampie. If p is the pressure at a
point on the plate in excess of that due to the atmospheric pressure,
then it can be shown [14] that the total normal force NF on the plate is
given by,
(3.4)
which on integration gives
(3.5)
Thus
2NF
NI = -2 (3.6)
nR
Using equations (3.1) and (3.6), a plot of primary normal stress vs. shear
rate can be genera ted.
The shear stress and primary normal stress measurements can be
done simultaneously on the sampie when it is subjected to
unidirectional rotational shear in the gap of a cone and plate
viscometer.
D. Oscillatory shear
The cone and plate viscometer can be used for oscillatory shear
measurements as weIl. In this case, the sampie is deformed by an
oscillatory driver which may be mechanical or electromagnetic. The
amplitude of the sinusoidal deformation is measured by a strain
transducer. The force deforming the sampie is measured by the small
deformation of a relatively rigid spring or tension bar to which is
attached a stress transducer. On account of the energy dissipated by the
viscoelastic polymer system, a phase difference develops between the
stress and the strain. The complex viscosity behavior is determined
from the amplitudes of stress and strain and the phase angle between
them. The results are usually interpreted in terms of the material
functions, r!" G', G" and others [33-40].
3.1.2 PARALLEL-DISC VISCOMETER

The parallel-disc viscometer used for measuring the shear stress and
normal stress difference of filled polymer systems is similar in principle
118 Rheometry
to the cone and plate viscometer except that the lower cone is replaced
by a smooth circular disco This type of viscometer was initially
developed for measuring the rheological properties of rubber [41-45]
and hence made use of serrated discs placed in a pressurized cavity to
prevent rubber slippage. When it was adapted for other polymerie
systems [27,46,47], measurements were performed using smooth discs
and without pressure.
The rheological properties in the parallel-disc viscometer are based
on the shear rate at the outer radius of the disco Thus,
Ya = wR/H (3.7)
where w is the angular velocity (rad/sec), R is the radius of the disc (m)
and H is the gap between the two parallel discs (m).
Shear stress and normal stress differences are given by the following
relationships:
3T ( 1 dlnT) (3.8)
r R =2nR3 1+3dlnYa
(r11 - r22) - (r22 - r 33) =

2T(1 + 1dlnN
-2. 2~
F)
(3.9)
nR Ya
Oscillatory shear measurements can be done with the parallel-disc
arrangement in a similar manner as in the case of the cone and plate
viscometer and similarly the material functions, rl', G', GO and others
can be generated. However, a slightly different technique [48] is at
times used wherein the polymer sample is deformed between two
oscillating parallel eccentric discs as shown in Figure 3.2. In this case,
too, it has been shown that the fluid elements undergo a periodie
sinusoidal deformation and the forces exerted on the disc are thus
interpreted in terms of G' and GO [14].
3.2 CAPILLARY RHEOMETERS

Capillary rheometers of various types are used for determining the
rheological properties of polymer melts as can be seen from Table 3.l.
The principal feature is that these rheometers are capable of extruding
polymer samples at different speeds through the capillary of
appropriate size. They are broadly categorized as
(i) those operating at constant speed and
(ii) those operating at constant pressure.
A further categorization is possible based on the melt transport
mechanism being of the plunger or the screw type and on the orifice
Capillary rheometers 119
AXIALmRUS!
M&AStm.ING DEVICE
i
TORQUli
MEASURING ~ '------i
DEVICE STATIONAli. Y
FLATDJSK
Figure 3.2 Schematic diagram showing the principal features of a parallel eccentric
discs rotational viscometer.
shape, through which the melt is extruded, being of the circular or slit
type. Each type of capillary rheometer is discussed in detail in the
following subsections.
3.2.1 CONSTANT PLUNGER SPEED CIRCULAR ORIFICE CAPILLARY

RHEOMETER
Commercially available instruments such as the Monsanto Automatic
Rheometer and the Instron Capillary Rheometer are examples of
equipment which extrude the polymer through a capillary with a
circular orifice using a plunger at constant speeds. The principal
features of this rheometer are shown schematically in Figure 3.3.
The major advantage of this type of capillary rheometer is that
higher shear rate levels than those attainable in rotational viscometers
can be achieved. In fact, the achievable shear rates are within the
realistic ranges that are actually observed in processing operations,
thus making the rheological data more meaningful for simulating
processing behavior. Of course, the highest attainable shear rate data
120 Rheometry
l t - - - USlR.VOm.
Figure 3.3 Schematic diagram of a constant plunger speed circular orifice capillary
rheometer.
are limited due to the occurrence of flow instabilities resulting in

extrudate distortion or melt fracture at die wall shear stress levels
greater than 105 Pa [49-53]. The die wall shear stress 'w can be easily
calculated by taking a force balance across the capillary die as,
(3.10)
or
RN~Pdie
'w = 2ZN (3.11)
where RN and ZN are the radius and length of the capillary die, while
dPdie is the pressure drop required to extrude the polymer melt. Since
the polymer flows from a wide reservoir into a capillary die in a
converging stream and then exits into open air or another wide
reservoir in a divergent stream, it is necessary to correct the shear stress
value for these entrance and end effects. The use of long capillaries in
the vain hope that the end effects might be negligible is not
recommended and in fact, should be discouraged. In capillaries longer
than Do, pressure dependence effects become significant. Hence, end

effects can never be assumed to be negligible. The customary method of
incorporating end effects correction is through the use of an effective
capillary length (ZN + (RN) as suggested by Bagley [54]. It must be
emphasized here that basically there is no alternative but to carry out
the Bagley procedure to make end corrections. The wall shear stress for
fully developed flow over the length (ZN + ,RN) is then written as,
RNdPdie
r - ---0--'-'-----'-':'-- (3.12)
W - 2(ZN + ,RN)
The shear rate at the die wall is expressed by the Rabinowitsch-

Weissenberg [55] equation for steady laminar flow of a time-
independent fluid as,
. _ 4Q [~ ~ d In (4Q/1tR~)] (3.13)
1tR~ 4 + 4 dlnrw
"lw -
The term dln(4Q/1tR~)/dln r w is basically equal to 1/n where n is

the power-Iaw index depicting the non-Newtonian character of the
polymer system. Thus, from equations (3.12) and (3.13), the following
relationship is written
(3.14a)
or,
(3.14b)
The above equation is a straight line when a plot of IN/RN vs. dPdie
is constructed at different constant values of (4Q/1tR~) as shown in
Figure 3.4(a). This is done using dies of various IN/RN ratios and the
intercept on the IN/RN ordinate at dPdie = 0 determines the value of
-,. There are possibilities of observing slight non-linearity in the plots
as can be seen for data at 3.6 and 10.8 S-1 in Figure 3.4(a). These are
probably due to the breakdown of the assumptions made du ring the
derivation of equation (3.14) of time-independence and no wall slip.
True mechanical wall slip can occur during polymer flow when the
shear stresses are large enough to overcome the static friction between
the wall and the flowing material [56-62]. Mechanical slip can occur as
either a steady-state phenomenon or as an unsteady phenomenon
known as 'stick-slip' [62-64]. This wall slip may induce the slight non-
linearity in the plots shown in Figure 3.4(a). It must be shown that the
Bagley plot is linear before any capillary viscometry data are regarded
122 Rheometry
20
PWSU]EDROP
(10 6 PASCALS)
10
10 16
Figure 3.4(a) Plot for determination of the Bagley correction term during polymer
melt flow through a capillary rheometer.
as meaningful. Hence, only those plots which are basically linear in

Figure 3.4(a) are to be used. Once the plots have been shown to be
linear for a particular capillary length and dass of material, it is only
then the capillary can be selected for viscometric measurements. From
a linear regression. of these plots, the correction term is determined.
Using equation (3.12), the corrected shear stress value at the wall is
estimated. It should be noted that, since polymers are viscoelastic, the
entrance effect needs an elastic-energy correction too. This is because
when the melt converges into the capillary, elastic stresses develop
and begin to relax inside the capillary. This effect is taken into account
[65] by modifying equation (3.12) to indude the recoverable shear term
as follows:
APdie
'r = -::-::----::::---==--=--= (3.15)
w 2(lN/RN + , + SR/2)
Thus, the elastic energy stored at the capillary entrance is related to the
correction term by the following expression [65].
SR
ec = , +"2 (3.16a)
Assuming Hooke's law in shear, 'rw = G X SR where G is the apparent

melt shear modulus, the correction term is rewritten as
8 I I I
7
IGLASS BEAD FIllED I
POLYPROPYLENE
6
.,-
,/
/' .,-
5
"
.".
,/
;' , ;'
;'
ec 4
,/
,/
;'
;'
I~w-U::ALS I
o tI - 0
'" , .. 0.06
2 v , - 0.10
, !240 CC! , .. 0.16

~ , .. 0.21
Cl , - 0.26
0 I ' - 1_ _' - 1
0 1.4 2.8 4.2 5.6 7.0 8.4 9.8 112 12.6
~w x 10- 4
Figure 3.4(b) Variation of capillary correction term with true wall shear stress for
glass bead filled polypropylene. (Reprinted from Ref. 66 with kind permission from
Society of Plastics Engineers Inc., Connecticut. USA)
(3.16b)
This suggests that when ec is plotted against 'w' a straight line

should emerge with a slope of ~G. When such a plot is prepared in the
ca se of filled polymer systems, an interesting behavior is observed [66]
as can be seen from Figure 3.4(b). The corrections for various
concentrations of glass beads in polypropylene have been plotted. It
can be seen that the correction term decreases with increasing filler
volume concentration at constant shear, with the exception of the filled
polypropylene system containing 26 vol. % of glass beads. The
decreasing trend of the correction term with increasing glass beads is
consistent with studies such as the one using glass bead filled styrene
acrylonitrile (SAN) systems [67]. The decreasing trend indicates that
the amount of stored energy must be decreasing and hence the
recovered energy or die swell would also decrease with increasing
glass bead volume fraction. This was indeed found to be the case [66]
when a few measurements of die swell were qualitatively compared.
The slope ec vs. t w lines are seen to be constant, except for <p = 0.21
and hence can be assumed to be independent of glass bead
124 Rheometry
concentration [66]. In the case of glass bead filled SAN systems,

however, the ec vs .w lines are highly non-linear [67].
The capillary rheometer can be used for estimating the normal stress
difference using the total ends pressure loss [65,68] and the exit
pressure loss [69-71], wherein the latter has a more rigorous
theoretical basis. However, the assumption of fully developed flow
existing up to the tube exit may not hold true, especially in slow flows
[72] and the errors introduced by the velocity field distortions at the
exit may prove significant.
3.2.2 CONSTANT PLUNGER SPEED SLIT ORIFICE CAPILLARY

RHEOMETER
This rheometer is similar in all respects to that discussed in section 3.2.1
except for the fact that it has a slit orifice cross-section rather than a
circular one. The major credit for the development of the concept and
use of this rheometer goes to Han [69,71,72] though others [73] have
also used it for polymer melt studies. The instrument makes use of a
series of flush mounted transducers located along the flow channel wall
which measure the pressure gradients along the flow direction. These
are then converted into wall shear stress values [69] as follows:
dP
w = bo dX (3.17)
where bo = half thickness of the channel.
The wall shear rate is determined from the following expression
given in Refs 14 and 69:
y = 3Q2 [~+~In(3Q/4aob~)J (3.18)

w 4aobo 3 3 In .w
where ao is the half width of the channel.
In general, this instrument is capable of providing data in the higher
shear rate ranges comparable to those obtainable from the circular
orifice capillary rheometer described in section 3.2.1. Using exit
press ure losses, this instrument can also be used for determination of
normal stresses. However, the probable velocity-profile distortions at
the exit may introduce errors that may not be negligible though
experimental evidence based on llmited data [26,71] suggests otherwise.
3.2.3 CONSTANT SPEED SCREW EXTRUSION TYPE CAPILLARY

RHEOMETERS
These capillary rheometers are principally the same as those described
in sections 3.2.1 and 3.2.2 except for the melt transport system which is
lll!l.T Tl!la1!lA'I"IlU
HOl'PEl. POLn.II!R POWDl!R POLn.II!R Ml!LT TBl!Blo!OCOllPLE
OI.PELUTS
ElCIJ.USlON SCREW CAPILI.AI.Y

])JE
POLnlEl MELT - - - - /
Figure 3.5 Schematic diagram showing the principal features of a constant speed
screw extrusion type capillary rheometer.
of the screw extrusion type rather than the plunger type discussed
earlier. A schematic diagram of an extrusion capillary rheometer is
shown in Figure 3.5. Commercially available extrusion capillary
rheometers are the Haake Rheocord (Haake Buchler Instruments Inc.,
Saddle Brook, NJ, USA) and the Brabendar Plasticorder (Brabendar,
Duisburg, Germany). The rheologie al property measurements can be
done using a circular or slit orifice as these are separate attachments for
the miniaturized single screw extruder.
These types of capillary rheometer are capable of generating
rheological data from medium-to-high shear rates. The applicable
equations for shear stress and shear rate are the same as those
discussed in seetions 3.2.1 and 3.2.2. The data generated are auto-
matically corrected for the Bagley correction and the Rabinowitsch-
Weissenberg correction through a computer software program
[74].
The screw extrusion type capillary rheometers have been used for
rheological studies of polymers [75,76] but have not become as
popular as the plunger type capillary rheometers because they need a
much larger quantity of feed. Care has to be taken that the material
completely fills the extruder screw during transportation in order to
avoid cavitation and erroneous results. Nevertheless, the utility of
these types of instrument cannot be undermined. The single screw
extrusion capillary rheometer is only one of the functions performed
by the commercially available Haake Rheocord and Brabendar
Plasticorder. They come with a number of other accessories such as
the miniaturized internal mixer and miniaturized twin screw extruder
as weIl. In fact, the miniaturized internal mixer too has at times been
used for assessing the rheological properties of polymer systems. The
126 Rheometry
torque vs. rpm data genera ted by internal mixer can be easily
converted [77-79] to shear stress vs. shear rate data. A more detailed
understanding of torque rheometry and instrumentation can be
obtained from the excellent article by Chung [74].
3.2.4 CONSTANT PRESSURE CIRCULAR ORIFICE CAPILLARY

RHEOMETER (MELT FLOW INDEXER)
This rheometer is also similar to the one described in section 3.2.1
except for two differences. Firstly, the capillary used is of very short
length and secondly, the polymer is extruded by the use of dead
weights (i.e. constant pressure) rather than constant plunger speed. This
instrument, popularly known as the Melt Flow Indexer, is very popular
in the thermoplastics industry due to its ease of operation and low cost,
which more than compensates for its lack of sophistication. The
parameter measured through the melt flow indexer contains mixed
information of the elastic and viscous effects of the polymer. Further,
no end loss corrections have been developed for this capillary
equipment nor can the melt flow index be easily related to the
Weissenberg-Rabinowitsch shear rate expression.
In most monographs and texts on polymer rheology, the Melt Flow
Indexer has been treated in a very brief manner because it has
generally been considered as an instrument meant only for quality
control. It was specified as a standard rheological quality control test
in the ASTM, BS, DIN, ISO and JIS (see Appendix D, Abbreviations
list for complete forms of these standards). However, it has been
shown in the recent past [80] that the Melt Flow Indexer provides
more than just a quality control rheological parameter. In fact the book
on Thermoplastic Melt Rheology and Processing [81] shows the multiple
uses of the data from the Melt Flow Indexer, and treats this particular
instrument in the utmost detail. Hence, in the present book the Melt
Flow Indexer and the Melt Flow Index are discussed rather briefly;
and readers are encouraged to refer to the other book [81] for more
comprehensive discussion on the subject.
The basic principle employed in the MFI test by any of the
standards is that of determining the rate of flow of molten polymer
through a closely defined extrusion plastometer whose important parts
are shown in Figure 3.6. The cylinder is of hardened steel and is fitted
with heaters, lagged, and controlled for operation at the required
temperature with an accuracy of O.soc. The piston is made of steel
and the diameter of its head is 0.075 0.015 mm less than that of the
interna1 diameter of the cylinder, which is 9.5mm. The die (or 'jet')
has an internal diameter of 2.095 0.005 mm or 1.180 0.005 mm
(depending on the procedure used) and is made of hardened steel. All
LOAD
PISTON
\l(XXlC--- HEATER. & IN'SUlATION
REMOVAlSLE DIE
POLYMER
Figure 3.6 Schematic diagram of the melt flow index apparatus showing a cross-
sectional view of the important parts.
surfaces of the apparatus which come into contact with the molten
polymer are highly polished.
MFI is basically defined as the weight of the polymer (g) extruded
in 10 min through a capillary of specific diameter and length by
pressure applied through dead weight under prescribed temperature
conditions. ASTM D1238 specifies the details of the test conditions as
summarized in Appendix B for commonly used polymers. The test
conditions include temperatures between 125 and 300C and different
applied dead loads from 0.325 to 21.6 kg giving pressures from 0.46 to
30.4 kgf/ cm2 The specifications have been selected in such a way as to
128 Rheometry
give MFI values between 0.15 and 25 for reliable results. ASTM 01238
gives the accuracy of the MFI value obtainable from a single measure-
ment as carried out by different operators at different locations to be
in the range of 9 to 15% depending upon the magnitude of the
MFI.
3.3 EXTENSIONAL VISCOMETERS

The rotational viscometers and the capillary rheometers described in
sections 3.1 and 3.2 are those applicable for shear flows. However, there
are processing operations that involve extensional flows. These flows
have to be treated differently for making measurements of extensional
viscosity. The extensional viscosity of a material is a meaSUre of its
resistance to flow when stress is applied to extend it. In general,
measurement of steady-state extensional viscosity has proven to be
extremely difficult. Steady extensional rate would be achieved by
pulling the ends of the sample apart such that 1 = 10 exp(i;t) Or in other
words, at a rate that increases exponentially with time. Steady-state is
reached when the force is constant. However, often the sample breaks
before steady-state is achieved or the limits of the equipment are
exceeded or at the other extreme, the forces become too small for the
transducer to differentiate between noise and response signal.
Nevertheless, there have been various methods attempted for the
measurement of extensional viscosity.
3.3.1 FILAMENT STRETCHING METHOD

The most common method for measurement of extensional viscosity is
to stretch the filament of material shown in Figure 3.7 vertically as done
by Ballman [82] Or horizontally as done by Meissner [83]. The polymer
must have a high enough melt viscosity of 104 Pa.sec Or greater in order
to be amenable for such extensional experiments.
Hence such data are restricted to high viscosity polyolefins such as
polyethylene and polypropylene rather than low viscosity nylon and
polyester. Further, the deformation rates are to be maintained at low
values to prevent breakage of filament and hence the deformation
rates are limited to 5 sec- 1 or less.
In the method of Ballman [82], which has been used by others
[84,85], a vertical thermostated filament is clamped at both ends and
stretched at the rate dl/dt such as to maintain a constant deformation
rate. Thus,
. 1 dI
B=-- (3.19)
I dt
Extensional viscometers 129
(a) VEltnCAL FII.AMEm" S'l"RETCBINO
(8) HORlZONTAL PlLAlofENT mEI'CHlNG
Figure 3.7 Schematic diagram showing the principal features of the filament
stretching method for extensional viscosity measurements: (a) vertical filament
stretching; (b) horizontal filament stretching.
130 Rheometry
In the method of Meissner [83], a horizontal filament immersed in

thermostated immiscible oil is held at both ends between pairs of
toothed wheels rotating with a linear velocity of V /2. Thus,
deformation rate is written as,
. V/2 V
B= 1/2 = T (3.20)
There are other variations of the filament stretching technique. For

example, filaments are clamped at one end and taken up on a rotating
roll [86,87]. This reduces the amount of filament stretching to a more
uniform level and produces a more constant extensional rate. In fact,
when the following filament is taken up on a cold roll [87] a better
constancy in the extensional rate is obtained.
Extensional viscosity based on constant stress measurements [88]
has also been reported [89,90]. In one ca se [89], the filament is
extended vertically on top of a bath whereas in the other case [90], the
vertical sample is immersed in the bath. The cornrnercial equipment
available for the measurement of extensional viscosity from
rheometrics is based on the latter [90].
A new universal extensional rheometer for polymer melts has been
described by Mnstedt [91]. It was specifically designed with the idea
of making measurements on small samples possible in research
laboratories under a variety of physical conditions, e.g. at constant
stress or constant stretching rate, as well as relaxation and recoil
experiments.
The rotary clamp consisting of a pair of gears is a basic construction
element for the design of various types of extensional rheometer
described earlier. The fact that the design is amenable for use in
uniaxial and biaxial extensional rheometry has been shown by
Meissner et al. [92]. Other biaxial extensiometers have also been
described [93,94] by other researchers.
A method for measurement of viscoelastic properties of polymers in
the prestationary extensional flow has been investigated by Leitlands
[95]. A special experimental device using a vibrorheometer with
automatie control has been suggested. Some other methods of experi-
mental studies with regard to the extension of polymer melts have
been discussed by Prokunin [96]. In terms of uniform extensional flow
of polymers, a rather comprehensive review is that of Petrie and Dealy
[97] which may be referred to for further information on the subject.
3.3.2 EXTRUSION METHOD

A typical example of extensional flow is the flow at the entrance of a
capillary die. Besides the converging flow analysis of Cogswell [98,99],
References 131
there have been other analyses [100,101] in more recent times which are
improved versions of the same ideas, and these can be used as better
alternatives especially when dealing with filled polymer systems.
Cogswell [102] has shown that the pressure losses through such dies
can be used as a measure for the extensional viscosity. This method has
not gained popularity because of the skepticism in accepting the
complex converging flow patterns at the die entrance as representative
of true extensional flow with constant extensional rate. Cogswell [103]
did suggest later that the die ought to be lubricated to reduce the shear
flow and the profile of the die wall should vary at all cross-sections in
such a way as to ensure constant extensional rate along the die axis.
Such a rheometer has been known to be developed and used for
extensional viscosity data of polystyrene melt [104].
The extrusion method using a lubricated die [104,105] allows the
measurements of systems with viscosity levels as low as 102 Pa.sec.
Thus, it can be used for extensional viscosity determinations in the
case of nylon and polyester which are often spun to make synthetic
fibers. Higher extensional rates, even 200 sec- 1 are also achievable in
this apparatus [104,105], thus making the information relevant for the
polymer processing industries involved in fiber spinning.
REFERENCES
1. Philippoff, W. and Gaskins, F.H. (1956) Viscosity measurements on molten
polyethylene, J. Polyrn. Sei., 21, 205--22.
2. Cogswell, F.N. (1973) The influence of pressure on the viscosity of polymer
melts, Plastics & Polymer, 41, 39-43.
3. Kalousek, G.L. (1973) A new instrument for measuring thixotropy, Cernent
and Concrete Res., 3, 315--23.
4. Sarmiento, G., Crabbe, P.G., Boger, D.V. and Uhlherr, P.H.T. (1979)
Measurement of the rheologieal characteristics of slowly settling flocculated
suspensions, Ind. Eng. Chern. Process Des. Dev., 18, 746-51.
5. Horie, M. and Pinder, K.L. (1979) Time-dependent shear flow of artificial
slurries in coaxial cylinder viscometer with a wide gap, Can. J. Chern. Engg,
57,125-34.
6. Tuft, P. (1977) A tube viscometer for slurry investigations, 6th Australasian
Hydraulics and Fluid Mech. ConJ, Adelaide, Australia (5-9 Dec.).
7. Lippe, RJ. (1980) Rheological parameters: a versatile tool for the sealant
formulator, Plastics and rubber: Processing, 51-54 Gune).
8. Hodgetts, G.. and Freestone, A.R!. (1977) Extrusion rheometer for
characterising thixotropie materials, Rev. Sei. Instrum., 48, 411-13.
9. Jacobsen, P.H., Whiting, R and Richardson, P.c.A. (1977) Viscosity of
setting anterior restorative materials, Brit. Dent. J., 143, 393--6.
10. Whiting, Rand Jacobsen, P.H. (1979) The evaluation of non-Newtonian
viscosity using a modified parallel-plate plastometer, J. Mat. Sei., 14,
307-11.
132 Rheometry
11. Verrnilyea, S.G., Huget, E.F. and De Simon, L.B. (1979) Extrusion rheometry
of fluid materials, J. Dental Research, 58, 1691-5.
12. Baker, F.5., Carter, RE. and Warren, RC. (1980) The rheological assessment of
propellants, Paper presented at the 8th Int. Congr. Rheol., Naples (1-5 Sept.).
13. Van Wazer, J.R, Lyons, J.W., Kim, K.Y. and Colwell, R.E. (1963) Viscosity
and Flow Measurement: A Laboratory Handbook of Rheology, Interscience, New
York.
14. Walters, K. (1975) Rheometry, Chapman & Hall, London; (1980) Rheometry:
Industrial Applications, Research Studies Press, Chichester, England.
15. Whorlow, RW. (1980) Rheological Techniques, Ellis Horwood, Chichester,
England.
16. Schramm, G. (1981) Introduction to Practical Viscometry, Gebruder HAAKE
GmbH, Karlsruhe, Gerrnany.
17. Dealy, J.M. (1982) Rheometers for Molten Plastics, Society of Plastics Engineers
and Van-Nostrand Reinhold, New York.
18. Meissner, J. (1985) Rheometry of polymer melts, Ann. Rev. Fluid Mech., 17,
45-64.
19. Connelly, RW. and Greener, J. (1985) High shear viscometry with a
rotational parallel-disk device, J. Rheol., 29, 209-26.
20. Kosinski, L.E. and Carruthers, J.M. (1986) The effect of particle concentration
on the rheology of polydimethylsiloxane filled with fumed silica, Polym.
Engg Sei., 32, 3323.
21. Weissenberg, K. (1948) Proc. Inst. Int. Rheol. Cong.
22. Pollett, W.F.O. and Cross, AH. (1950) J. Sei. Inst., 27, 209.
23. King, RG. (1966) Rheological measurement of three polyethylene melts,
Rheol. Acta, 5, 35.
24. Chapman, F.M. and Lee, TS. (1970) Effect of tale filler on the melt rheology
of polypropylene, SPE J., 26, 37-40 Gan.).
25. Meissner, J. (1972) Modification of the Weissenberg rheogoniometer for
measurement of transient rheological properties of molten polyethylene
under shear, J. Appl. Polym. Sei., 16, 2877-99.
26. Han, C.D., Kim, K.u., Siskovic, N. and Huang, CR. (1973) A comparison of
measurements of the viscoelastic properties of polymer melts by means of
the Han slit/capillary rheometer and the Weissenberg rheogoniometer, J.
Appl. Polym. Sei., 17, 95-104.
27. Lee, B.L. and White, J.L. (1974) Trans. Soc. Rheol., 18,467; (1975) Trans. Soc.
Rheol., 19, 481.
28. Minagawa, N. and White, J.L. (1976) The influence of titanium dioxide on
the rheological and extrusion properties of polymer melts, J. Appl. Polym.
Sei., 20, 501-23.
29. Kataoka, T., Kitano, T., Sasahara, M. and Nishijima, K. (1978) Viscosity of
particle filled polymer melts, Rheol. Acta, 17, 149-55.
30. Lobe, V.M. and White, J.L. (1979) An experimental study of the influence of
carbon black on the rheological properties of a polystyrene melt, Polym.
Engg Sei., 19, 617-29.
31. Saini, D.R and Shenoy, AV. (1983) Viscoelastic properties of linear low
density polyethylene melts, Eur. Polym. J., 19, 811-16.
32. Saini, D.R. and Shenoy, AV. (1984) Dynamic and steady-state rheological
properties of linear-Iow-density polyethylene melt, Polym. Engg Sei., 24,
1215-18.
References 133
33. Andrews, RD., Hofrnan-Bang, N. and Tobolsky, A.V. (1948) Elastoviscous

properties of poly (isobutylene) relaxation of stress in whole polymer of
different molecular weights at elevated temperature, J. Polym. Sei., 3, 669-92.
34. Adams, J.W.c., Janeschitz-Kriegl, H., Den Otter, J.L. and Wales, J.L.S. (1968)
J. Polym. Sei., A2, 6, 871-83.
35. Mills, N.J. and Nevin, A. (1971) Oscillatory shear measurements, J. Polym.
Sei., A2, 9, 267-8l.
36. Chen, LJ. and Bogue, D.C. (1972) Time-dependent stress in polymer melts
and review of visco-elastic theory, Trans. Soe. Rheol., 16, 59-78.
37. Vinogradov, G.V., Malkin, A.Ya., Plotnikova, E.P., Sabsai, O.Yu. and
Nikolayeva, N.E. (1972) Int. J. Polymerie Mat., 2, 1-27.
38. Baily, E.D. (1974) Trans. Soc. Rheol., 18, 635-40.
39. Mnstedt, H. (1976) Proe. 7th Int. Rheol. Congr., 496.
40. Aoki, Y. (1979) J. Soe. Rheol., Japan, 7, 20.
41. Mooney, M. (1934) A shearing disk plastometer for unvulcanized rubber,
Ind. Engg Chern. (Anal. Ed.), 6,147-51.
42. Taylor, R, Fielding, J.H. and Mooney, M. (1947) Symposium on Rubber
Testing, ASTM, p. 36.
43. Mooney, M. (1947) The rheology of processing quality of raw rubber, J.
Colloid. Sei., 2, 69-80.
44. Mooney, M. (1959) Proe. Int. Rubber Conf (Washington), p. 368.
45. Mooney, M. (1962) Some neglated problems in the rheology of high
polymers, Rubber Chem. Technoi., 35, 27-3l.
46. Sakamoto, K., Ishida, N. and Fukusawa, Y. (1968) Normal stress effect of
molten polyethylenes, J. Polym. Sei., A2, 6, 1999-2007.
47. Blyler, L.L. (1969) Normal stress behavior of linear polyethylene melts in a
rotational parallel plate rheometer, Trans. Soe. Rheol., 13, 39-58.
48. Maxwell, B. and Chartoff, RP. (1965) Studies of polymer melts in an
orthogonal rheometer, Trans. Soc. Rheol., 9, 41-52.
49. Spencer, RS. and Dillon, RE. (1949) The viscous flow of molten polystyrene
11, J. Colloid Sei., 4, 241-55.
50. Tordella, J.P. (1956) Fracture in the extrusion of amorphous polymers
through capillaries, J. Appl. Phys., 27, 454-8.
51. White, J.L. (1973) Critique on flow patterns in polymer fluids at the entrance
of a die and instabilities leading to extrudate distortion, Appl. Poly. Symp.,
20,155-74.
52. Schott, H. (1964) Elastic effects and extrudate distortions in capillary flow of
molten polyethylene resins, J. Polym. Sei., 2, 3791-80l.
53. McIntire, L.V. (1972) On the initiation of melt fracture, J. Appl. Polym. Sei.,
16,2901-8.
54. Bagley, E.B. (1957) End corrections in the capillary flow of polyethylene, J.
Appl. Phys., 28, 624-7.
55. Eisenschitz, R, Rabinowitsch, B. and Weissenberg, K. (1929) Mitt. Dtseh.
Mat. Pruf Anst. Sonderheft, 9, 91.
56. Wales, J.L.S. (1975) A collaborative study of capillary flow of a highly
lubricated unplasticized poly(vinyl chloride), J. Polym. Sei., Symp. No. 50,
469-85.
57. Angerer, G. and Wolff, D. (1976) Rheol. Acta, 15, 57-63.
58. Menning, G. (1976) Rheol. Acta, 15,199-205.
134 Rheometry
60. Lin, Y.H. (1985) Explanation for slip melt fracture in terms of molecular
dynamics in polymer melts, J. Rheol., 29, 605-37.
61. Knappe, W. and Krumbock, E. (1986) Slip flow of non-plasticized PVC
compounds, Rheol. Acta, 25, 296-307.
62. Ramamurthy, A.V. (1986) Wall slip in viscous fluids and influence of
materials of construction, J. Rheol., 30, 337-57.
63. Lau, H.C and Schowalter, W.R (1986) A model for adhesive failure of
viscoelastic fluids during flow, J. Rheol., 30, 193-206.
64. Leonov, A.1. (1984) A linear model of the stick-slip phenomena in polymer
flow in rheometer, Rheol. Acta, 23, 591-600.
65. Philippoff, W. and Gaskin, F.H. (1958) The capillary experiment, Trans. Soc.
Rheol., 2, 263-84.
66. Faulkner, D.L. and Schmidt, L.R (1977) Glass bead-filled polypropylene,
Part I: Rheological and mechanical properties, Polym. Engg Sci., 17,
657-64.
67. Newman, S. and Trementozzi, Q.A. (1965) J. Appl. Polym. Sci., 9, 3071-89.
68. White, J.L. and Kondo, A. (1977) End pressure losses in extrusion of
polymer melts through dies, J. Appl. Polym. Sei., 21, 2289-92.
69. Han, CD. (1976) Rheology in Polymer Processing, Academic Press, New York.
70. Han, CD., Charles, M. and Philippoff, W. (1969) Measurement of the axial
pressure distribution of molten polymers in flow through a circular tube,
Trans. Soc. Rheol., 13, 455-66.
71. Han, CD. (1974) Trans. Soc. Rheol., 18, 163-90.
72. Han, CD. (1971) Measurement of the rheological properties of polymer
melts with slit rheometer. I. Homopolymer systems; 11. Blend systems;
III. Two phase systems - high impact polystyrene and ABS res ins, J. Appl.
Polym. Sei., 15, 2567-77, 2579-89, 2591-6.
73. Wales, J.L.S., den Otter, J.L. and Janeschitz-Kriegl, H. (1965) Comparison
between slit viscometry and cylindrical capillary viscometry, Rheol. Acta, 4,
146.
74. Chung, J.T. (1988) Torque rheometer technology and instrumentation,
Encyclopedia Fluid Mechanics, (ed. N. Cheremisinoff), Gulf Publishing,
Houston, TX, Vol. 7, pp. 1081-139.
75. Blake, W.T. (1958) Determining molecular weights of thermoplastics
materials, Plastics Technol., 4, 909-12, 930.
76. Schmitz, A.O. (1966) How to use the torque rheometer to solve the pressing
problems, Plastics Techno!., 12, 49-52.
77. Goodrich, J.E. and Porter, RS. (1967) A rheological interpretation of torque
rheometer data, Polym. Engg Sei., 7, 45.
78. Blyler, L.L. and Daane, J.H. (1967) An analysis of torque rheometer data,
79. Rogers, M.G. (1970) Rheological interpretation of Brabender plasti-corder
(extruder head) data, [nd. Eng. ehern. Process Des. Develop., 9, 49-52.
80. Shenoy, A.V. and Saini, D.R (1986) Melt flow index: more than just a
quality control rheological parameter, Advances Polymer Technol., 6, (Part I}
1-58, (Part TI) 125-45.
81. Shenoy, A.V. and Saini, D. R (1996) Thermoplastic Melt Rheology and
82. Ballman, RL. (1965) Extensional flow of polystyrene melt, Rheol. Acta, 4,
137-40.
References 135
83. Meissner, J. (1969) A rheometer for investigation of deformation-

mechanical properties of plastic melts under defined extensional straining,
Rheol. Acta, 8, 78-88.
84. Vinogradov, G.V., Radushkevich, B.V. and Fikham, V.D. (1970) Extension
of elastic liquids; polyisobutylene, J. Polym. Sei., A2 (8), 1-17.
85. Stevenson, J.F. (1972) Elongational flow of polymer melts, AIChE J., 18,
540-7.
86. Macosko, CW. and Lomtsen, J.M. (1973) The rheology of two blow
moulding polyethylenes, SPE Antee Teeh. Papers, 461-7.
87. Ide, Y. and White, J.L. (1978) Experimental study of elongational flow and
failure of polymer melts, J. Appl. Polym. Sei., 22, 1061-79.
88. Dealy, I.M. (1978) Extensional rheometers for molten polymers: a review, J.
Non-Newtonian Fluid Meeh., 4, 9-21.
89. Cogswell, F.N. (1968) The rheology of polymer melts under tension,
Plastics & Polymers, 36, 109-11.
90. Mnstedt, H. (1975) Viscoelasticity of polystyrene melts in tensile creep
experiments, Rheol. Acta, 14, 1077-88.
91. Mnstedt, H. (1979) New universal extensional rheometer for polymer
melts measurements on a polystyrene sampie, J. Rheol., 23,421-36.
92. Meissner, J., Raible, T. and Stephenson, S.E. (1981) Rotary clamp in uniaxial
and biaxial extensional rheometry of polymer melts, J. Rheol., 25,1-28.
93. Denson, CD. and Hylton, D.C (1980) A rheometer for measuring the
viscoelastic response of polymer melts in arbitrary planar and biaxial
extensional flow fields, Polym. Engg Sei., 20, 535-9.
94. Rhi-Sausi, J. and Dealy, J.M. (1981) Abiaxial extensiometer for molten
plastics, Polym. Engg Sei., 21, 227-32.
95. Leitlands, V.V. (1980) Investigations of unsteady elongational flow of
polymer melts, Int. J. Polymerie Mater., 8, 233-42.
96. Prokunin, AN. (1980) Some methods of experimental studies into the
extension of polymerie liquids, Int. Polymerie Mater., 8, 303-21.
97. Petrie, CJS. and Dealy, J.M. (1980) Uniform elongational flow of molten
polymers, in Rheology (ed. G. Astarita, G. Marrucci and L. Nicolais), 1,
177-94.
98. Cogswell, FN. (1972) Converging flow of polymer melts in extrusion dies,
99. Cogswell, FN. (1972) Measuring extensional viscosities of polymer melts,
Trans. Soe. Rheol., 16, 383-403.
100. Binding, D.M. (1991) Capillary and contraction flow of long glass fiber
reinforced polypropylene, Composites, 2, 243-52; (1988) An approximate
analysis for contraction and converging flows, J. Non-Newtonian Fluid
Meeh., 27, 177-89.
101. Gibson, A.G. (1989) Die entry flow of reinforced polymers, Composites, 20,
57-64.
102. Cogswell, FN. (1969) Tensile deformations in molten polymers, Rheol. Acta,
8,187-94.
103. Cogswell, F.N. (1978) Converging flow and stretching floW: a compilation,
J. Non-Newtonian Fluid Meeh., 4, 23-38.
104. Everage, A.E. and Ballman, RL. (1978) The extensional flow capillary as a
new method for extensional viscosity measurement, Nature, 273, 217-15.
105. Winter, H.H., Macosko, CW. and Bennett, K.E., (1979) Rheol. Acta, 18, 323.
Constitutive theories
and equations for
.
suspensions 4
4.1 IMPORTANCE OF SUSPENSION RHEOLOGY
A suspension is a system in which denser particles, that are at least
microscopically visible, are distributed throughout a less dense fluid
and settling is hindered either by the viscosity of the fluid or the
impacts of its molecules on the particles. In the present terminology of
filled polymer systems, the fillers form a disperse phase and the
softened or molten polymers form the continuous phase and together
they could represent a suspension. However, suspension rheology does
not normally refer to filled polymer rheology. In fact, it commonly
discusses the rheological behavior of two-phase systems in which one
phase is solid particles like fillers but the other phase is water, organic
liquids (e.g. benzene, fuel oil) or polymer solutions. These systems are
much easier to study than filled polymer systems as the preparation
and rheological characterization of the systems can be done at room
temperature. Further such systems are encountered in a number of
areas other than polymer technology, namely, biotechnology [1-17],
cement and concrete technology [18], ceramic processing [19], coal
transportation [20-28], coating and pigment technology [29-32], dental
research [33-38], propellants and explosive science [39], poultry waste
handling [40,41], mineral processing [42-46], soil science [47] and
various slurry flow technology [48]. Hence, the rheology of suspensions
has received a lot of attention.
There are a number of reviews [49-61] which discuss various aspects
of the rheology of suspensions and may be referred to for detailed
study. In the present chapter, the topic is touched upon rather briefly
and only certain aspects are discussed in a limited manner just enough
to lay the foundations for understanding the basics of filled polymer
rheology.
Suspensions basically show strong departures from simple
Newtonian laws of fluid flow and hence form complex rheological

Shear viscous flow 137
systems. When the dispersing medium is a Newtonian fluid or behaves

like one under a given range of shear rates, then the suspension exhibits
Newtonian behavior at low concentration of solids and non-Newtonian
behavior with increasing concentration. When the suspending medium
is a polymer solution which itself is non-Newtonian in character, the
presence of solid particles magnifies the complexities of its rheological
behavior.
The important rheological properties which need to be studied and
measured in order to be able to characterize suspensions are the same as
those which have already been indicated in Chapter 2. However, only
the viscous flow behavior in shear and extensional flow will be discussed
in this chapter. In particular, shear viscosity will be dealt with in
sufficient detail because of the wealth of information that exists on it.
4.2 SHEAR VISCOUS FLOW

Several theoretical and empirical relationships have been proposed to
describe the viscosity of suspensions in Newtonian or non-Newtonian
viscous liquids. These relationships have also been used, with ranging
degrees of success, to correlate viscosity data when the suspending
medium is viscoelastic [62]. In the following various relationships
are reviewed. The viscosity of Newtonian as weIl as non-Newtonian
suspensions is affected by the characteristics of the solid phase such
as shape, concentration and dimensions of the particles, its size
distribution, the nature of the surface, etc. The influence of each of these
factors is examined below.
4.2.1 EFFECT OF SHAPE, CONCENTRATION AND DIMENSIONS OF THE

PARTICLES
Spherical filler particles have received more attention than non-
spherical and asymmetrie particles. In the following, the effect of
concentration and dimensions of the particles are presented under the
sub-sections of different shapes of particles.
A. Spherical particles
(a) Dilute suspensions

Einstein [63-65] was the pioneer in the study of the viscosity of dilute
suspensions of neutrally buoyant rigid spheres without Brownian
motion in a Newtonian liquid. He proposed the following relations hip
between the relative viscosity of the suspension Ylr and the volume
fraction of the suspended particles cp
138 Constitutive theories and equations for suspensions
'1, = 1 + r:t.E4> (4.1)
where '1r is the ratio of the viscosity of the suspension '1. to the viscosity
of the suspending medium '10 and r:t.E is Einstein's constant. r:t. E equals 2.5
when the suspended particles are neutrally buoyant, hard and spherical
in shape, the mean interparticle distance is large compared to the mean
particle size, the particle movement is so slow that its kinetic energy
can be neglected and there is no slip relative to the particle surface.
Experimental determinations of Reiner [66] and Kurgaev [67]
revealed that for filler concentrations of 4> = 0.003-0.05, r:t.E was indeed
equal to 2.5. Rutgers [68] concluded through experimental evidence that
equation (4.1) with r:t.E = 2.5 was valid for values up to 4> < 0.1.
However, a slight disagreement in the value of r:t. E = 2.5 was established
from the works of Hatschek [69], who theoretically found that r:t. E = 4.5
for 4> = 0-0.4 and Andres [70] who found that for dilute magnetic
suspensions (J(E = 4.5 for 4> = 0-0.09. In fact Kurgaev [67] showed that
when 4> = 0.15-0.18, r:t. E = 4.5-4.75 depending upon the nature of the
solid particles. The disagreement was accentuated when Happel [71]
suggested a value of r:t.E = 5.5 and Pokrovskii [72] a value of 1.5. It was
revealed by Kambe [73] that the lack of agreement among the
experimental results was due, among other things, to differences
between the dimensions of the particles under study and the velocity
gradients used for the experiments. It appears that for solid spheres
with diameters large enough compared to the molecular dimensions
hut small enough compared to the characteristic length of the
measuring instrument and for no slip at the sphere surface, the value of
r:t. E = 2.5 is generally accepted though values ranging from 1.5 to 5.5
have been suggested.
Based on the theoretical analysis of Simha [74] for concentrated
suspensions. Thomas [75] proposed the following expression for dilute
suspensions (4) < 0.1)
254
'1, = 1 +2.54> ( 1 +-3 (4.2)
4a 1
where a1 is an empirical coefficient whose value lies between 1 and 2.
Thomas [75] suggested that a1 = 1.111 for 4> < 0.15. Simha and
Somcynsky [76] suggested that the expression (4.2) proposed by
Thomas [75] could be written as follows:
'1, = 1 + 2.54>I( 4 (4.3)
where
-A(4)) = (254))
1 +-3 '
4a 1
when higher terms in <P in the expression suggested [76] are dropped.
When <P = 0.10, however, higher terms in <P are not negligible and to
compensate for this, Thomas [75] had to use the value of a j = 1.111
when actually aj = 1.85 in the unapproximated expression of I(<p) gave
excellent results.
Ford [77] modified Einstein's equation (4.1) using a binomial
expression and wrote
1
- = 1 - rxE<p (4.4)
I1r
where 1/l1r is defined as the fluidity and is equal to zero when
<P = l/rxE' Equation (4.4) has been shown to be valid for <P < 0.15 by the
experimental data of Cengel et al. [78].
Though there is varied opinion about the relationship between the
relative viscosity of a suspension and the volume concentration of the
spheres for dilute suspension, one could get a reasonable estimate on
using the simplest equation (4.1) of Einstein for <p < 0.1. When
0.1 < <p < 0.15, Thomas's [75] equation (4.2) or Ford's [77] equation (4.4)
could be used for a reliable estimate. Of course for <p < 0.1 too, these
equations could be used and the result averaged out with the prediction
from equation (4.1) to obtain a good conservative estimation.
(b) Concentrated suspension

Generally, when 0.1 < <p < <Pm the suspensions are considered to be
concentrated and the above discussed equations do not apply. Here <Pm
is defined as the maximum attainable concentration and has the
following form: CPm = 1 - e, where e is the void fraction or porosity, and
is defined as the ratio of the void volume to that total volume.
Theoretically, the value of <Pm is 0.74 for equal spheres in compact
hexagonal packing, but in practice it is more like 0.637 for random
hexagonal packing or 0.524 for cubic packing ([79]).
When the filler concentration is increased, various phenomena take
place, for example (i) the number of particles per unit volume which
come in contact during the flow increases, (ii) the interparticle attraction
and repulsion effects become stronger due to electrostatic charges,
which depend upon the polarity of the medium, (iii) the rotation of the
particles during flow, as weIl as the formation of doublets and their
rotation during flow, produces additional dissipative effects which lead
to an increase in the viscosity.
Unlike the dilute suspensions, the size of the filler drastically changes
the viscosity behavior of concentrated suspensions. De Brujin [80]
showed that when the filler diameter is less than 10 I!m, a concentrated
suspension exhibits non-Newtonian behavior and the viscosity
increases with a decrease in the filler diameter. Clarke [81] found that
for a filler diameter greater than 10 11m, the viscosity increases linearly
with the diameter. For spheres, with increasing diameter the lateral
displacement of the particles towards the centre of the tube (central
tube effect) increases, thereby increasing the energy dissipated resulting
in a tendency for the viscosity of the suspension to increase with
increasing diameter.
As there are many-fold effects of increasing the concentration of the
fillers, a variety of physical models have been proposed but most of
them (theoretical or experimental) can be expressed by the nonlinear
relationship between '1r and cp in the following power series form as
given in Thomas [75]
(4.5)
where (Xl is generally assumed to have a value of 2.5 as given by
Einstein [63], while the coefficients (X2' (X3' have been assigned
different values by different authors. For example, the value of (X2 was
14.1 as determined by Guth and Simha [82], 7.349 by Vand [83], 12.6 by
Saito [84]. 10.05 by Manley and Mason [85] and 6.25 by Harbard [86].
These varied values of (X2 are the result of taking into account one or
several effects appearing due to the increase in solid concentrations.
Similarly, (X3 values of 16.2 and 15.7 have been proposed by Vand [83]
and Harbard [86], respectively. Alfrey [87] has also developed
relationships of the power series form (4.5) and enlisted values of (Xj
based on the works of Arrhenius [88], Fikentsher and Mark [89],
Bungenberg de Jong et al. [90], Papkov [91], Hauwink [92] as weIl as
Brede and Oe Boojs [93].
As an example of the use of equation (4.5) to determine the viscosity
of suspensions, one can refer to tht! works of Mullins [94] and Feldman
and Boiesan [95] on rubbers containing fillers which are chemically
inactive like wood flour or chemically active like carbon black. When
the filler introduced is chemically inactive (with any cp) or chemically
active (with cp < 0.10), the quadratic form of equation (4.5) with (Xl = 2.5
and (X2 = 14.1 could be used to give a good estimate of the viscosity of
the suspension. For higher concentrations of the chemically active filler
(carbon black), partic1e interaction begins and the viscosity of the
suspension increases markedly and equation (4.5) as such cannot then
be used for an estimate. However, if partic1e interaction leads to
agglomeration, then Mullins [94] and Feldman and Boiesan [95]
recommend the use of (Xl = 0.67a j and (X2 = 1.62a; in equation (4.5),
where aj is the index of asymmetry of the elastomer macromolecules.
The main drawback of equation (4.5) is that the termination of the
series after cp2 term means an error of 10% or more in the relative
viscosity for cp > 0.15-0.20. The validity of the series increases to
4> : : : : 0.40 on the indusion of 4>3 term. However, the values of the
coefficients of higher order terms are less accurate since they must indude
more complicated interactions than it is theoretically possible to treat.
Based on the work of Eyring et al. [96] who suggested that the term
rx34>3 in equation (4.5) should be of the exponential form, Thomas [75]
arrived at the following expression
'1 r = 1 + 2.54> + 10.054>2 + 0.00273 exp(16.64 (4.6)
Thus a dosed form expression is obtained which fits experimental data
as well as the power series form with three or four adjustable
coefficients. The validity of expression (4.6) is for a filler concentration
varying between 0.15 and 0.60.
Another power series type of expression is given by Ford [77], who
added higher order terms to his expression (4.4) for dilute suspensions,
making use of the data of Vand [83], to give
.!. = 1 - 2.54> + 114>5 - 11.54>7 (4.7)

'1r
He suggested that the indusion of the term 4>5 takes into account the
onset of the inhibition of partide rotation, and the term 4>7 takes into
account the onset of partide interlocking.
Mooney [97] proposed that at very high concentrations an Arrhenius
type equation (with the addition of crowding factor (1 - rxc 4) of the
following form could be used:
'1r = exp [ (1 2.54>

_ rxc 4
]
(4.8)
where etc has a value between 1.35 and 1.91. Mooney's relationship
has been known to be in good agreement with experimental data
([66], [98]).
The empirical expression (4.3) as suggested by Simha [74] can also be
used for concentrated suspensions if the relationship for I.(4)) given by
him is not approximated and all the higher order terms in 4> are
retained. Simha's analysis was based on the idea that the neighbors of
each sphere in the suspension can be replaced by a rigid spherical
endosure, and that the finite size of the partides effectively shields the
central partide from interaction with any other partide than the nearest
neighbors as the concentration is increased.
For concentrations up to 4>m' experimental data are seen to validate
the following empirical expression obtained by Eilers [99]
[ 1.25]2 (4.9)
'1r = 1 + (1 - 4>l4>m)
Note that for 4> --+ 4>m' '1 r --+ 00 and rightly so.
142 Constitutive theories and equations tor suspensions
Frankel and Acrivos [100] did away with all empiricisms and
artificial boundaries and provided an expression for highly
concentrated suspensions of uniform solid spheres intending to
complement the classical Einstein's equation (4.1) valid only for very
dilute suspensions.
Their final result is written as follows:
9 (cP/cPm)1 /3
(4.10)
I1 =
r 8 1 _ (cP / cPm)1 /3
With so many theoretical expressions (4.5) to (4.10), it is increasingly
difficult to make a choice between them and decide which one would
give the most reliable estimate. for the relative viscosity of a
concentrated suspension. For concentrated suspensions, it is necessary
to account for the hydrodynamic interaction of particles, particle
rotation, particle collisions, doublet and higher order agglomerate
formation and mechanical interference between particles as packed bed
concentrations are approached. Different authors have taken into
account one or several aspects mentioned above during the derivation
of their theoretical expressions. For concentrated suspensions of
uniform solid spheres, the use of expression (4.6) of Thomas [75] is
recommended for 0.15< cP < 0.60 and the expression (4.10) of Frankel
and Acrivos [100] for cP --+ cPm to obtain reliable estimates.
Though equation (4.10) predicts the correct experimental trends at
large values of 4> --+ 4>m' it does not reduce to equation (4.1) when
cP --+ O. Further, the averaging process used for deriving equation (4.10)
has been shown to be incorrect [101] and it has been argued that the
dissipation in pair interactions is too small to explain the observed
trends. But since equation (4.10) does fit experimental data rather well
for high solids concentrations, it can be simply considered as yet
another empirical equation.
Attempts [102-104] to fit the entire range of volume fraction from
cP --+ 0 to cP --+ cPm have resulted in equations which give a unique curve
through the use of a plot of relative viscosity versus the ratio of cP/cPm'
The work of Chong et al. [102] has shown a good fit between
experimental results and an equation of the following type:
I1r = [ 1 + 0.75 ( 1 -cPjcjJm

cP/cPm
)]2 (4.11)
cPm is normally determined from the experimental data. It is to be noted

that equation (4.11) reduces to equation (4.1) at low values of cP when
<Pm takes a value of 0.6.
One of the best available empirical expressions which fits the entire
range of volume fraction, is the Maron-Pierce type equation that was
carefully evaluated by Kitano, Kataoka and co-workers [103,104], and

extensively tested by Poslinski et al. [105,106].
(4.12a)
For suspensions of smooth spheres, a value of ,pm = 0.68 has been
suggested [107] and a value of ,pm = 0.60-0.62 has been determined
through liquid displacement experiments [105,106]. In reality, of course,
using ,pm as 0.6 or 0.62 or 0.68 does not improve the data fit appreciably.
But at times it may be best to view ,pm as an adjustable parameter and
then equation (4.12a) is rewritten as follows:
(4. 12b)
The adjustable parameter A p is now considered to give some measure
of the thickness of the immobilized polymer adsorbed on the filler
surface and thereby indicates the affinity of the polymer for the filler
[108].
B. Ellipsoidal particles
The theory of the viscosity of dilute ellipsoidal suspensions without
Brownian motion was developed by ]effrey [109]. He observed that
Einstein's equation (4.1) could be used to estimate the viscosity by
appropriately defining the Einstein constant OC E ]effrey [109] has
tabulated the values of OCE for prolate and oblate spheroids. He found
that OCE depended on the ratio of the semi-axes of the ellipsoid of
rotation.
For a prolate spheroid, Guth [110,111] developed the following
relationship based on ]effrey's theory [109] when the axis ratio re 1.
Thus,
(4.13)
where
re
OC r1 = (2ln2re _ 3) + 2 (4.14a)
0.04r!
(4.14b)
OC r2 = (2 ln 2re - 3)
Pokrovskii [112] demonstrated theoretically that concentrated

suspensions of solid ellipsoidal bodies in a Newtonian fluid give rise to
a viscoelastic behavior. He showed that for such suspensions it is
possible to use the concept of trans verse viscosity which expresses the
effect of normal stresses and found that the transverse viscosity
increases with velocity gradient.
C. Rod-shaped particles
Suspensions of rod-shaped particles have received greater attention
than ellipsoidal particles due to the obvious increasing demand for
fiber-reinforced plastics. Exact theories exist for the viscosity of very
dilute suspensions of rod-shaped particles. However, this is not the case
for higher concentrations. The reason is evident from the fact that
differences in viscosities of suspensions of different shaped particles are
small at low concentrations. With an increase in the concentration,
particle rotation causes the frequency of contacts between adjacent
particles to increase, resulting in an increase in the viscosity (Figure
4.1). For rod-shaped particles, the above effect is accentuated with an
increase in the aspect ratio as can be seen from the work of
60~------------------------------------------
GL.ASS RODS
o GL.ASS PL.ATES
QUARTZ GRAl HS
~O
D GL.ASS SPHERES
V EINSTEl H'S EOUATIOH
40
~ 30
20
10
-----v---~--+---9----~---9-------
0~------0~'1-------0~'~2~----~0~~3------~0~.~4------~0'5
Flgure 4.1 Effect of concentration on the relative viscosity of different shaped

particles in water at a shear rate of 327.7 sec- 1 . (Reprinted from Ref. 81 with kind
permission from The Institution of Chemical Engineers, Rugby, UK.)
Maschmeyer and Hill [113] who showed that the presence of only a few
percent of relative long fibers in the particle distribution doubled or
tripled the suspension viscosity. From the work of Clarke [81] shown in
Figure. 4.1, it can be conclusively seen that the viscosity of a suspension
is higher for the same concentration of the particles for larger
departures in shapes from spheres.
In the case of dilute suspensions of rod-shaped particles, too,
Einstein's equation (4.1) can be used with the appropriately defined
constant C(E' Burgers [114] has established the following relationship for
straight rigid rod-shaped suspensions under shear
C(E = [6(ln 2r.r. _ 1.8)].sm

4(} .
sm
22.1,
'I'
(4 15)
.
where r. is the aspect ratio (lp/D) and () and '" are the spherical
coordinates giving the orientation of the rod (see Figure 4.2). Burgers
[114] found that rod-shaped particles (and also elongated ellipsoidal
particles) cause an increase in the Einstein' s coefficient with increasing
aspect ratio (r.) as shown in Figure 4.3, for randomly oriented particles
such as would occur at very low rates of shear. At high shear rates, of
course, orientation of the rods would result in a decrease in the effective
value of the Einstein coefficient.
Figure 4.2 Coordinate system for a rigid rod in a field of simple shear.
100r---------------------------------------------~
90
80
70
60
4'0
30
2~~~----~~--~~----~----~----~----~----~
1 16
Figure 4.3 Einstein's coefficient as a lunction 01 the aspect ratio 01 randomly

oriented rod-shaped particles.
For dilute suspensions in rotational motion, Mason [115] gave the

following expression for critical concentration 4>er below which the
interaction between the rods can be neglected. Thus,
4>
er r.
= 1.5 (4.16)
Blankeney [116] observed that below this critical concentration the

relative viscosity of a rod-shaped particle suspension increases slowly
and linearly with 4>. A slight non-linear region then follows after which
the relative viscosity increases rapidly. Experimentally, it was found
that the value of 4>er depended .upon the nature of the solid phase. For
example, Clarke [81] found that for glass rods 4>cr = 0.15 and for PMMA
spheres 4>er = 0.40.
For concentrated suspensions of rod-like particles (Le. for 4> > 4>er)'
the following relations hip was suggested by Simha [117] and later
verified by Blankeney [116]
(4.17)
For randomly oriented rods with purely hydrodynamic interactions
between them, Simha [117] determined the value of ~ to be equal to
0.73.
For concentrated fiber suspensions in tube flow, Brodnyan [118]
suggested the following equation:
_ [2.5<P + 0.399(ra -l l48 <p] (4.18)

YJr - exp 1 - (t.c<P
but the experimental data of Brodnyan [118] themselves were not found
to fit for high concentration of suspension.
Taking into account the particle interaction and the degree of
flocculation, Ziegel [119] proposed the following equation:
) r;./3 <p
YJr = (-y-
3~20o
+1- 2 0 9.668 + 1 (4.19)
where ~ is an interaction parameter, o is a rate constant for the

equilibrium between free particles and floccules and 2 0 is the degree of
flocculation.
Hashin [120] used the flow-elasticity analogy to give the following
equation which was valid only for parallel, randomly placed infinitely
long fibers
2<p
YJr = 1 + 1 - 4> (4.20)
Nielsen [121] used the same analogy, but his equation has not been
tested for concentrated fiber suspensions.
The shape of the rod (whether straight or curved) does affect the
relative viscosity of the suspension. The viscosity for curved fiber
suspension is known to be higher than that for a straight fiber
suspension and the difference increases with increasing concentration
(Figure 4.4).
4.2.2 EFFECT OF SIZE DISTRIBUTION OF THE PARTICLES

Clarke [81] observed that mixed suspensions of mainly coarse particles
and relatively few fine particles showed a marked decrease in the
viscosity compared to an all coarse suspension. Contrarily, suspensions
with mainly fine particles and few coarse particles showed very little
change from an all fine suspension. It could thus be concluded that
104r----------------------_---.
---- STRAIGHT FIBERS
- - CURVED FIBERS
o dp' 16-9 )Jm I 'a' 0-1 ancl 111.' 176"
A dp=43-1)Jm J'a' 232 and .,176"
(a)A
--- --- ----

L:~
0-001 0002 0003 0004 0005
Figure 4.4 Variation of the relative viscosity of suspensions with concentration for
(a) curved fibers and (b) straight fibers.
smaller particles are interposed between larger particles, causing a

reduction in the interparticle impact resulting in a decrease in viscosity.
Ward and Whitmore [122], Ting and Luebbers [123] and Moreland
[124] also noticed similar results using different techniques of
measurement.
Shaheen [125] suggested that the addition of a Httle amount of small
particles acts as a lubricant to facilitate the rotation of larger particles,
leading to areduction in the relative viscosity. Experimentally, it was
shown that the viscosity of a mixture of two different-sized particles
goes through a minimum at about a volume fraction of small particles
equal to 0.25. Shaheen [125] wrote the modified form of Mooney's
equation (i.e. equation (4.8 for a mixture of spherical particles of two
different sizes as follows:
(4.21)
where
r
"~ ~ 06(V:~:P'r~ (r;;; (4.22)
.: ~ O.6(V:~:pf~ e:;,'f (4.23)
Parkinson et al. [126] arrived at a Mooney type equation for the

relative viscosity of a dispersion of polydisperse spheres containing i
size fractions as
where <P1' <P2 ... <Pi are the volume concentrations of each size fraction,
and the values of k1 , k2 ki are derived from an empirical equation of
the following general form
ki = 1.079 + exp(0.01008/Dpi ) + exp(0.0029/D~i) (4.25)
The above equation (4.24) is not suitable for a continuous distribution

of particle diameters and the equation given by Mooney [97] has to be
then resorted to: .
PdO" )
11 r = exp ( 2.5<p [ 2
;U2 J (4.26)
GI 1 - <P J GI (Xji~ dO"j
where <P is the total volume concentration of spheres, IY. ji the crowding
factor, Pi the particle size frequency function and 0"1' 0"2 the upper and
lower limits of the dimensionless radius, respectively.
The two main difficulties in the use of equation (4.26) are that the
nature of (Xji is known only in special cases and hence the distribution
function to accurately describe the particle size distributions of different
grades of the same filler is almost impossible to find.
Hsieh [127] suggested a quadratic model of the following canonical
form for an M-component system of particle size distribution.
(4.27)
where Xi is the weight proportion of the ith component in the blend of

the total number of M components. The coefficients Bi and B ij were
determined experimentally and for a tetramodal size distribution, Hsieh
[127] has given the derived expression from equation (4.27) which was
seen to agree wen with the experiments for four basic aluminum
trihydroxides with distinctively different particle sizes in an
unsaturated polyester resin.
150 Constitutive theories and eq uations for suspensions
4.2.3 EFFECT OF THE NATURE OF THE PARTICLE SURFACE

Moreland [124] obtained viscosity data of suspensions of coal in mineral
oil during which he concluded that slurry viscosities for irregular
particles were greater than for spherical particles. A similar result was
obtained by Clarke [81], who showed that suspensions of sharp-edged
particles have a much larger viscosity than those of round-edged ones.
Roughened particles are likely to increase the viscosity of suspensions
in two ways: (a) primarily by harsh frictional contact and (b) secon-
darily, by trapping layers of inert liquid on its surface thereby causing
an effective increase in the concentration as suggested by Ward and
Whitmore [128].
4.2.4 EFFECT OF THE VELOCITY GRADIENT

In the flow of suspensions, velocity gradient is known to cause two
major effects, (a) migration of the particles towards the centre of the
axis in a tube flow situation and (b) rotation of the particles.
A. Wall effect and the central tube effect

In pipe flow of a suspension, the presence of a wall and a velocity
gradient causes the particles to migrate towards the tube axis and
correspondingly decrease the concentration of the solid phase near the
wall. This effect known as the wall effect has been observed by
Goldsmith and Mason [129] for suspensions of different shaped
particles in Poiseuille flow.
A consequence of the wall effect is the central tube effect wherein the
migration of the particles towards the tube axis causes an increase in
the solid phase concentration within a narrow region of about 0.6Ri
(where Ri is the internal radius of the tube). The wall effect and the
central tube effect appear simultaneously and after a certain time from
the start of the flow due to the velocity gradient being set up. Segre and
Silberberg [130,131] have shown that these effects manifest themselves
only at small concentrations of the solid phase. These effects have been
taken into account during the estimation of the suspension viscosity of
PMMA spheres in a ternary mixture of water, glycerol and 1.3-
butanediol by Segre and Silberberg [132]. A detrimental effect in the
measurement of properties of a suspension, other than the viscosity,
could result due to the presence of the wall and the central tube effect.
Care should be taken during property measurements with probes
through tube walls as the measured quantities could easily be the
properties of the suspending medium rather than of the suspension.
The migration of the particles towards the tube axis due to the
velocity gradient also leads to a characteristic slippage at the wall

surface (Morrison and Harper [133]). A direct consequence of the slip is
the increased flow rate through the tube compared to that which would
occur if slip were absent. The value of shear rate caleulated from the
famous Mooney-Rabinowitsch equation will, therefore, be erroneous
and a correction ought to be made as given by Jastrzebski [134].
B. Particle rotation
At high concentrations of the solid phase, the existence of a velocity
gradient results in rotation of the partides, followed by an increase in
the viscosity of the suspension. Concentrated suspensions are known to
exhibit non-Newtonian behavior and hence viscosity would change as
the shear rate (velocity gradient) changes.
It is generally assumed that the viscosity dependence on shear rate is
due to some structural changes in the suspensions such as the breaking
up of agglomerates during shear. For example, Chapman and Lee [135]
as weIl as Goel [136] found that, at low shear rates (Y < 1 sec- 1 ) tale-
fil1ed polypropylene was more viscous than the base propropylene, but
such was not the ca se at higher shear rates (y > 1 sec- 1 ) wherein break
up of the network-like structure took place, resulting in the viscosity of
the tale-filled systems equivalent to that of propropylene alone. Similar
behavior was observed by Ferraro [137] for other systems.
Concentrated suspensions often exhibit a yield stress below which no
shear deformation takes place and after which the suspension could
behave as a Newtonian, pseudoplastic or dilatant fluid. Shear
dependent theories for such flows have been considered by Krieger and
Dougherty [138] as weH as Gillespie [139].
4.2.5 EFFECT OF FLOCCULATION

The degree of flocculation of dispersed partides strongly influences the
rheology of suspensions ([140]). The viscosity of the suspension is
known to increase sharply with flocculation, probably due to the
relative irnmobilization of a fraction of the suspended particles trapped
in the agglomerates. In shearing flow, both shear-thinning and shear-
thickening behavior have been observed. Govier and Winning [141]
found concentrated day suspensions to be shear-thinning. Heywood
and Richardson [45] found that flocculated kaolin suspensions were
shear-thinning and could be characterized by the power-Iaw model at
shear rates below 2000 sec- 1 With increasing solid concentration, the
flow behavior index n was seen to fall progressively while the
consistency index K was seen to increase exponentially. At shear rates
above 2000 sec- l , the behavior would be characterized by the Bingham

plastic model with the yield stress and the plastic viscosity increasing
monotonously with increasing solid concentration.
Dilatant behavior is observed in certain flocculated systems with
extremely high concentration of suspensions. Umeya and Kanno [142]
found that concentrated suspensions of titanium dioxide in water
stabilized with sodium pyrophosphate showed dilatancy. The effect of
shear history on the dilatant behavior is shown in Figure 4.5, and is
seen to be pronounced at high shear rates. A suspension deflocculated
by shear does not recover its structure immediately after the removal of
shear since the thermal energy of the particles isinsufficient to
overcome the energy barrier for the flocculation. As the degree of
flocculation is decreased by applying high shear rates, the onset of
dilatant flow occurs, the dependence of apparent viscosity on shear rate
and the increase in the apparent viscosity decreases. Umeya and Kanno
[142] also found that dilatant behavior of flocculated systems did
UNl1'S TlIIl - W'ater 11.1 'fIlI ".

(.AaItu., d-0.4 1')
,,--PA'SEC N'4 P2 Oy . H20 :> mWl 1'ID2
. .,.,,.-1
y.---.,
o - 0
I -1.2 z 10 3
- 12 I: 10 3
Figure 4.5 The effect of shear histories on the flow properties of titanium dioxide
(Ti0 2) water 27.7% suspensions stabilized with 5 mg/g Ti0 2 of Na4P207.10H20.
(Reprinted from Ref. 142 with kind permission from Society of Rheology, USA)
depend upon the size of the particles as the degree of dispersion of

larger particles was better than that of smaller ones.
Hudson et al. [31] studied the time dependent effect of suspensions of
pigment particles. Experimental work was undertaken to relate steady,
transient and time dependent oscillatory flow in a unified manner.
Hudson et al. [31] also developed a theory to explain the suspension
behavior in terms of the structure formed as a result of flocculation. The
viscosity fit of a homogeneous suspension of floccules containing N;
floccules was given by
In fit = f(<pt) + vIn(N;) (4.28)
flo
where flo was the viscosity of the suspending medium, f was a function
of the volume fraction (<Pt) of the floccules in the suspension and v as a
constant. A comparison of the experimental data with the theory
enabled values of the model constants to be calculated.
4.2.6 EFFECT OF THE SUSPENDING MEDIUM

The nature of the suspending medium, whether Newtonian, viscous
non-Newtonian, viscoelastic or viscoplastic affects the viscosity of the
suspension. This has been the subject of research of a number of
workers.
Nieodemo et al. [143] studied the shear rate dependence of the
viscosity of suspensions in non-Newtonian liquids and compared it
with that of suspensions in Newtonian liquids. The relative viscosity,
when the suspending medium was Newtonian, decreased with
increasing shear rate toward an asymptotic value which was a function
of the filler content. The concentration dependence could be correlated
by equations given in section 4.2.1.
When the suspending medium was non-Newtonian, Nicodemo et al.
[143] found that the dependence of relative viscosity on shear rate was
similar and could be correlated by a modified form of the equation of
Krieger and Dougherty [138]. However, as the relative viscosity at high
shear rates did not fit the existing equation, Nieodemo and Nieolais
[144] searched for a mechanistic explanation. It was found that two
different mechanisms in the range of low and high shear rates,
respectively, existed for suspensions in polymerie solutions.
When the suspending medium could be described by the power-law
model, Kremesec and Slattery [145] derived the following expression
for the viscosity of a dilute suspension of spheres
fl s = (1 + ao<p )Ky n-l (4.29)
The coefficient ao was defined by the rate of energy dissipation within
the neighborhood of a typical sphere in the suspension. For n = I,

(Xo= 2.5 could be easily derived as in Einstein's equation (4.1).
However, for n =1= I, the equations of motion, being nonlinear, are
difficult to solve and hence only the upper and lower bounds for (xo as a
function of n were obtained and compared with the available
experimental data of Highgate and Warlow [146] to find reasonable
agreement.
4.2.7 EFFECT OF ADSORBED POLYMERS

Polymers are often added as processing additives to suspensions used
in ceramic forming operations [19]. Under certain conditions, the
polymers adsorb on ceramic particles and alter the interparticle forces
which control the state of dispersion and rheological properties of the
suspension. An important criterion for achieving good particulate
dispersion through steric stabilization is to ensure good coverage of the
particle surfaces with the adsorbed polymer [147,148]. With low
adsorption densities, the steric repulsive forces are likely to be too weak
to prevent close approach of particles, thereby leading to flocculation
due to van der Waals attractive forces as weIl as bridging flocculation
due to polymer segments from one particle surface attaching
themselves to the available surface site of another particle. Sacks et al.
[19] studied the amount of polymer adsorbed and the state of
particulate dispersion in aqueous silica suspensions containing different
concentrations of poly(vinyl alcohol) (PVA).
An adsorption isotherm for suspensions of 20 vol% silica at pH = 3.7,
wherein the zeta potential for the chosen silica is zero, is shown in
Figure 4.6. It can be seen that initial additions of PVAare almost
completely adsorbed on the silica particles and very Httle polymer
remains in solution. When overall PVA concentration is increased, the
particle surface tends to become saturated with adsorbed polymer and
then higher amounts of residual polymer are left in solution. The initial
plateau region of the adsorption isotherm is associated with
approximately monolayer coverage of the particle surface. The second
plateau is probably an indication of either the development of denser
packing of polymer molecules in the adsorbed monolayer or the
development of multilayer adsorption.
Figure 4.7(a) shows the relative viscosity versus shear rate behavior
for suspensions at pH = 3.7 with varying polymer adsorption in the
range of 0 to 1.1 mg adsorbed PV AI g silica. For the sake of comparison,
the relative viscosity versus shear rate plot is also shown in the same
figure for an electrostatically stabilized suspension prepared at
pH = 7.0 with no PVA. At pH = 7.0, wherein the zeta potential is
approximately -55mV, the silica suspension is extremely weIl
.." 5
20 vol% SIIICI
ii
GO
~
> 4
0.
GO
~
...Z 3
;:,
0
2
oe
Q 2
'"
eil
Ir
0
In
Q
oe
RESIDUAL POLYMER CONCENTRATION 'Oil/l."
Figure 4.6 Adsorption isotherm obtained from suspensions prepared with 20 vol%
silica and varying concentrations of poly(vinyl alcohol). (Reprinted from Ref. 19 with
kind permission from The American Ceramic Society Inc., Westerville, Ohio, USA)
dispersed judging from its low relative viscosity and Newtonian

behavior over the entire shear rate range. In contrast, at pH = 3.7 when
the zeta potential is approximately OmV, the silica suspension with no
PVA is flocculated, adjudging from the high viscosity and highly shear-
thinning behavior.
In Figure 4.7(a), it can be seen that initial additions of PVA result in
higher viscosity and greater shear-thinning characteristics, thus
indicating the occurrence of bridging flocculation at the low PVA
adsorption densities. With additional PVA adsorption, the trend
observed in Figure 4.7(a) is reversed as can be seen from Figure 4.7(b).
Beyond the adsorbed amount of 1.1 mg adsorbed PV AI g silica, the
bridging flocculation gives way to steric stabilization. Low suspension
viscosity, approximately Newtonian behavior over the entire range of
shear rate and absence of any yield stress are observed when the
adsorption of PVA is such as to ensure monolayer coverage of particles.
It is known that maximum flocculation occurs at approximately half
coverage of the particles [44,149]. In the adsorbed PV AI silica
suspension case, too, the maximum flocculation did occur at
approximately half coverage of the particles as evidenced from the
maximum value of the yield stress at that adsorption level as shown in
, .... __-----------.......--------_
.~ (a) v., . . 20 SI~
.
~
ii
'.00
..
o
u
..,.
'.0
5
....:
~
10
'"IAR R ..TI I.',
2. v.1 "" SIO.
=
a
1000
..
o
u
..; .. .... nl A....._ (""lU)

, 10.
5..
~
I.' 2
0'
E 1/;.4
================/2.
,./
___ I.t
=
---------------1pM . 7.0'
n. ,"y ..
.., '0
'"E .. II II ..TI 10-"
100 100
Flgure 4,7 Variation ot relative viseosity with shear rate tor 20 vol% siliea suspensions
prepared at pH = 3.7 with varying eoneentrations ot poly(vinyl aleohol). The relative
viseosity vs. shear rate plot tor an eleetrostatieally stabilized suspension (pH = 7.0) with
no poly(vinyl aleohol) is also shown. (Reprinted trom Ret. 19 with kind permission trom
The Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA)
Figure 4.8. It should be noted that the amount of adsorbed polymer

depends not only on the overall suspension polymer-particle, polymer-
liquid and particle-liquid interactions. The adsorption densities are
known to depend on the amount of isolated or free surface hydroxyl
groups on the particles [150,151].
The effect of the adsorbed polymer in achieving different levels of
dispersion also depends on the 'goodness' of the solvent for that
polymer. For example, when the solvent is good, it is known [147,148]
that steric stabilization is promoted because the loops and tails of the
4.0
3.5
..
3.0
~ 2.5
I/)
I/)
1&1
a: 2.0
~
I/)
0
~ 1.5
1&1
>
t.O
0.5
0.0
3 4 6
ABSORBEb AMOUNT (mg PVAlg Sille.'

Figure 4.8 Variation of yield stress with adsorption density of poly(vinyl aleohol) on
siliea for suspensions prepared at pH = 3.7 with 20 vol% siliea and varying
eoneentration of poly(vinyl aleohol). Yield stress values were determined from shear
stress vs. shear rate eurves. (Reprinted from Ref. 19 with kind permission from The
Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA)
polymer which extend out from the particle surface are weIl solvated.
When the solvent is not good for the polymer, then bridging
flocculation is likely to occur.
The effect of solvent quality on particulate dispersion was
investigated [19] using alumina (Alz03 )/poly(vinyl butyral) (PVB)
suspensions prepared in methanol (MEOH), which is a poor solvent,
and in a 3: 1 volume ratio mixture of methyl isobutyl ketone (MIBK)
with MEOH, which is a better solvent.
Figure 4.9(a) and (b) shows the relative viscosity versus shear rate
behavior in these two solvents for varying PVB concentration from 0 to
2.0 vol%. In either of the solvents, highly shear-thinning behavior is
observed when no PVB is added. These suspensions show poor stability
against flocculation due to relatively low zeta potentials 25 m V) and
therefore, low electrostatic repulsive forces [152].
The effect of PVB additions on the dispersion behavior can be seen
from Figure 4.9 to be dependent on the suspension liquid composition.
In MEOH suspension, though addition of PVB reduces the viscosity of
the suspension, the system is shear-thinning indicating that the
suspensions remain flocculated in poorer solvents for the added
'~r-------------------------------------~
CI"AIIIC.: ao ..., "&,p.
(a) "VI'."'"
0- LIOUIO :.011
0 . - -
1.0....
.1.0--
~
~
..>
fjj
o
u
..,. '00
.....
;:
e
c
.0
.~ __~uu~~~~~~__~~~~~__~. .~
o. '.0 '0.0 '00.0 , 000.0
SHE"" "ATE e.-II
.~or--------------------------------------'
.,
(b) pva....... I ..... "
C
CI"""'tC:~O ...,
LIQUID: 2:'.
"2)
_.,.IOM
.-
.
~
;;;
o
...>
u
..
~
.00
...e
I '0
1.0
1.0
{ --=========~~+!!Pi--
0.5
Figure 4.9 Variation of relative viscosity with shear rate for 30 vol% alumina
suspensions prepared with (a) methanol and (b) 3: 1 methyl iso butyl ketone/methanol
with indicated poly(vinyl butyral) concentrations. (Reprinted from Ref. 19 with kind
permission from The American Ceramic Soeiety Ine., Westerville, Ohio, USA.)
polymer. In 3:1 MIBK/MEOH suspensions, PVB additions (0.5 to

2.0 vol%) give much lower relative viscosity and almost Newtonian
behavior. A slight dilatancy has been observed which is not unusual
in highly loaded suspensions in which repulsive forces are large
[153,154].
The level of loading makes a lot of difference in the adsorption of the
polymer. It can be seen from Figure 4.10(a) that for 30vol% Ah03, there
is only a small difference in the shear stress versus shear rate flow
curve for the two polymer concentrations of 0.25 vol% and 0.5 vol%
CERAYC : ;'0 """ Al 1 0 3

LIOUCI; 3;1. Mac "OH
4
(a)
O~~-L----'~~---'~~--~2~~~~2~~~~'~~~3~
SIiEAII RA~ 11-'1
350
CfRAMIC : 41 ....... Al 2 0 3
3~
UOUID: 3:1 ....K/MEOH
...~ 2~ 0.25 """ PVI
...
oll 2~
"",,-
a:
ti ,~
~
..
!
1~
~
(b)
0
0 10 1~ 110 ~ 210 300 3~
Figure 4.10 Variation of shear stress VS. shear rate for 3:1 methyl isobutyl ketone/
methanol suspensions prepared using (a) 30 vol% alumina and (b) 45 vol% alumina
with indieated poly(vinyl butyral) eoneentrations. (Reprinted from Ref. 19 with kind
permission from The Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA.)
PVB. In both cases, approximately Newtonian behavior is observed and

the viscosities are relatively low, indicating that the suspensions are
weIl dispersed. However, when the fiIler loading is 45 vol% Ah03, the
0.25 vol% PVB suspension shows a yield stress and an initial region of
highly shear-thinning behavior, indicating that the suspension is highly
flocculated at low shear rates (Figure 4.10(a. This happens because
complete monolayer coverage of the Alz0 3 particle does not occur at
this concentration of polymer. In contrast, the system is far better
dispersed when the 0.5 vol% PVB suspension is used, due to the higher
adsorption density.
4.2.8 EFFECT OF CHEMICAL ADDITIVES

Small additions of various common 'processing aids' such as
surfactants, dispersants, coupling agents and lubrieants do affect the
rheological properties of suspensions. The effect of various surface
modifiers on the viscous behavior and dispersion of alumina in water
has been studied by Dow [155]. The suspensions were prepared by first
adding 1.25 g of surface modifier to 125 cc distilled (01) water and then
adding alumina powder after 1 hr. There were visually observed
differences between the four surface modifiers studied. The zircoalumi-
nate CAVCO MOD APG and the silane Z-6020 were completely
dissolved to form dear solutions. On the other hand, the silane Z-6076
and titanate LICA 12 were found to form emulsions whieh showed
small droplets suspended in the water. This was explained as due to
the difference in the solubility of the different surface modifiers. On
account of this, the alumina powders were not coated homogeneously
by the later surface modifiers with poorer solubility [155].
Figure 4.11 shows the plots of shear stress versus shear rate for the
suspensions prepared with alumina powder and different surface
modifying agents. The suspension with zircoaluminate is well dispersed
as indicated by the Newtonian flow behavior and low suspension
viscosity which was determined to be about 2.8 centipoise. The good
dispersion is also indieated from a comparison with the electrostatically
stabilized alumina suspension prepared at pH = 4.0 with no chemie al
additives as shown in Figure 4.12.
Suspensions containing silane Z-6076 and titanate LICA 12, on the
other hand, showed large yield stresses, higher viscosities and highly
thixotropie flow behavior, indieating that the suspension is highly
flocculated. The suspension prepared with silane Z-6020 is also not as
well dispersed as the suspension with the zircoaluminate but the
relatively low yield stress, lower viscosity and absence of thixotropy
indieates a much improved dispersion as compared with the silane Z-
6076 and titanate LICA 12.
4.2.9 EFFECT OF PHYSICAL AND CHEMICAL PROCESSES

Physieal processes (e.g. crystallization) and chemieal processes (e.g.
polymerization) are known to modify the viscosity of a suspension with
time.
For a crystallization process, for example, Mistry and Warburton
[156] have shown that if the solid phase concentration is small such that
160 32
20 vol'; Alz0:! in Water
a-
e
120 24 UI
~
(/)
(/)
tal UI
~ 80 18 ~
CI)
CI!
r.o
~
3: -:u
8 .....,
11
(/)
40
0 0
0 50 100 150 200 250 300
160 4
20 vol" Ala0:! in Water
a- 120 3 CI!
:J:
~ t'!I
(/)
(/)
r
tal CI!
a:
r< 80 2;J
(/) t'!I
CI!
CI!
~
!I: -:u
(/)
40 1~
Zlrcoaluminate CAVCO ),lOD G
'\
r
0 0
0 50 100 150 200 250 300
SHEAR RATE (1/3)
Figure 4.11 Variation of shear stress vs. shear rate for suspension prepared with
20 vol% alumina in distilled water along with (1 wt% of filler) various surface modifiers
as indicated. (Reprinted fram Ref. 155.)
Einstein's equation (4.1) holds and the crystals in the disperse phase
increase with time, the relative viscosity can be estimated from the
following expression.
(4.30)
where <Po is the initial volume of the crystals, Ko the rate constant for
volume increase of the crystals and t the time. Similarly, for
concentrated suspensions, expressions like (4.6), (4.7) or (4.8) could be
162 Constitutive theories and equations tor suspensions
1.0 ~--------------~
20 1'01" AIz03 in lt'ater
-;;
~ ZircoalumlDate
r/I CAVCO WaD !PG"
cn
Cd
0:
(-0
0.5
./'
CI]
~
Iol
:x::
CI]
" ..":;: pH.. " DI Weter
0.0 ~~-'----,,_.L--<---l._,--~~----I_..L-...J
o 50 100 150 200 250 300

SHEAR RATE (l/s)
Flgure 4.12 Variation of shear stress VS. shear rate for suspensions prepared with
20 vol% alumina in pH = 4 distilled water and with (1 wt% of filler) zircoaluminate.
(Reprinted from Ref. 155.)
used as first approximation with 4> appropriately being replaced by

4>0 + Kot.
4.2.10 EFFECT OF AN ELECTROSTATIC FJELD

When suspension particles are charged, the electroviscous effects that
arise strongly influence the viscosity of the suspension as was shown
by the experiments of Fryling [157] as weH as Krieger and Eguiluz
[158]. Pseudoplastic as weH as dilatant behavior was observed in the
data of Fryling [157] and when the electroviscous effects were at their
maximum, the suspensions of Krieger and Eguiluz [158] were seen to
have a yield stress. Electroviscous effects are essentiaHy of three types -
first, second and third, and are discussed in detail by Conway and
Dobry-Duclaux [159].
The combined effect of the three electroviscous effects on the
viscosity of a suspension can be written as foHows:
(4.31)
where ev1 , ev2 and ev3 correspond to each of the three electroviscous
effects. Separation of the constituent effects is difficult but was attempted
by Dobry [160]. The three effects are discussed below separately in
order to appreciate the influence of each one of them on viscosity.
A. First electroviscous effect

The first electroviscous effect is due to the electrostatie contribution of
charged colloidal particles and its effect on the viscosity of a dilute
suspension can be expressed in an extension of Einstein's equation (4.1)
as follows:
(4.32)
Smoluchowsky [161] and Booth [162] both accounted for the increase in
viscosity as due to the electrieal double layer round a charged particle
in an electrolyte and gave expressions for ev whieh included the specific
conductivity of the electrolyte, the dielectrie constant of the suspending
medium, the electrokinetie potential of the particles with respect to the
electrolyte and the radius of the particle (which was to be large in
comparison with the thiekness of the double layer for the validity of the
expression). Experimental verification by Chan and Goring [163] of the
expressions for ev provided by Smoluchowsky [161] and Booth [162]
gives confidence for their use.
B. Second electroviscous effect

The second electroviscous effect is due to the electrostatic repulsion
between partieies approaching each other and is directly proportional
to the square of the particle concentration. The essential feature about
this effect is that it occurs at high concentrations of the suspensions
(unlike the first electrostatic effects) and when there is an overlap of the
double layer. The additional dissipative effects that appear as a result
of the repulsion bring about an increase in the viscosity. Chan et al.
[164] showed that an expression of the form (4.17) can be used to
account for the second electroviscous effect but the coefficient ff would
then strongly depend on the distance between the centers of the
particles and consequently, on the particle concentration. The second
electroviscous effect is, at times, known to give rise to non-Newtonian
behavior of a suspension as observed by Harmsen et al. [165].
C. Third electroviscous effect

The third electroviscous effect is due to the change of shape of
suspending particles when their electrical free energy is modified by
ionization and the presence of neutral salts. If a polymer molecule can
undergo ionization. e.g. by reaction with a base or by reaction with
some other ion-producing substance, electrostatic repulsion between the
like charges introduced on the polymer chain modifies the partial
molecular free energy of the polymer in the solution. With polymerie
electrolytes, non-Newtonian viscosity behavior is not uncommon,

particularly at low salt concentrations or high polyion concentrations
and the effect is known to increase with degree of ionization.
4.3 EXTENSIONAL FLOW

Addition of fillers during the spinning of synthetic textile fibers and the
phenomenon of drag reduction with fibers inculcated an interest in the
study of the rheological properties of suspensions in extensional flows.
The first of such studies was that of Bachelor [166,167], who provided
expressions for extensional viscosity of suspensions with long slender
partic1es subjected to extension. The analysis of Batchelor [166] resulted
in the following expression for suspensions which are so dilute that the
velocity field surrounding one partic1e remains unaffected by
neighboring partic1es. Thus,
2 cf>r. [0.64 + In2r. 1.659

11.=3110 {1+ 9ln2r 1.5+ln2r. + (ln2r.)2+0 (ln2r.)3
(I)]} (4.33)
110 denotes the viscosity of the suspending medium, cf> the volume
fraction of the partic1es having an aspect ratio r . It is obvious from
equation (4.33) that partic1es with large aspect ratios would give large
values of the extensional viscosity even at small concentrations of the
partic1es.
Batchelor [167] considered the effect of hydrodynamic interaction of
parallel elongated partic1es in pure extension on the bulk stress. The
governing equations were solved under the assumption that the effect
on one partic1e by all the others could be replaced by a cylindrical
boundary condition (cell model) and the geometry and concentration of
the partic1es satisfied the following inequality.
r. > d> 1 (4.34)
where d = HdD f (Hf being the average distance between the fibers and
Df the diameter of the fiber). The resulting expression for extensional
viscosity was as follows:
4 cf>r. ] (4.35)
11. = 3110 [ 1 + 9ln (n/cf
Equation (4.35) predicts the extensional viscosity only for high

concentrations and does not give results akin to equation (4.33) at lower
concentrations. However, at an intermediate concentration of the
suspended partic1es, both theories are known to predict nearly identical
results and hence in this region the extensional viscosity can be
estimated by interpolation.
Extensional flow 165
An expression similar to the above was obtained by Insarova [168]

for the extensional viscosity of uniformly distributed rigid rods
subjected to axially symmetrie extension as folIows:
l1 e =
3 [ 4 </>r.
110 1+ 9(</>_ln</>_1)
] (4.36)
Insarova [168] showed by calculation that for a particle with an

aspect ratio r. = 50, the viscosity is increased by a factor of 4 for
</> = 0.01 and by 80 for </> = 0.1. Equation (4.36) has not been tested with
experimental data but the equations of Batchelor [166,167] have been
the subject of experimental verification.
With the then available data of Weinberger [169], Batchelor [166,167]
compared the bulk stress in a suspension of glass-fiber rods (with
</> = 0.013) in each of the liquids, 'Indopol' and 'Silicone' but found that
the extensional viscosity was much higher than that predieted by the
close-partiele theory. Later, Weinberger and Goddard [170] noted that
suspensions used in Weinberger's work neither satisfied the dilute-
suspension nor the close-partiele description, but fell somewhere
between the two. Proper interpolation was shown to prediet that the
tensile stress was 8.4 times that of the suspending medium from
Batchelor's theory and was found to be in good agreement with the
values of 9 to 10 found by Weinberger and Goddard [170] through
experiment.
Mewis and Metzner [171] studied the extensional flow of fiber
suspensions (with 0.001 < </> < 0.01) and large aspect ratios
(280 < r. < 1260). Experimental data showed that the extensional
viscosities were independent of strain rate and up to 260 times larger
than that of the suspending medium. The effect of partiele con-
centration was as predieted by equation (4.35) proposed by Batchelor
[167]. On the other hand, the effect of partiele geometry was in elose
agreement with the theory only for lower values of ra like 282 and 586,
but for ra = 1259 the experimental data were found to be about 30%
lower than that predieted by Batchelor [167].
Kizior and Seyer [172] experimentally determined stress levels in
extensional flow of suspensions with fibers having an aspect ratio of
340 and volume fraction of 0.001. It was found that the experimental
value of the stress was higher than that predieted by Batchelor's theory.
However, the dependence of stress on concentration and aspect ratio
was weIl predicted by the theoretieal expressions of Batchelor [167].
From the above experimental efforts, it can be concluded that
sufficient evidence has been genera ted to verify the propriety of
equations (4.33) and (4.35) given by Batchelor [166,167]. Equation (4.33)
for dilute suspensions, equation (4.35) for elose-partiele distribution and
an interpolation between the two could predict the extensional flow

behavior of suspensions of slender particles over a large range of
particle concentration. However, the results of Batchelor [166,167] are
valid only when the suspending medium is Newtonian. The entire
body of literature which analyses the extensional flow of slender
particles in non-Newtonian fluids goes to the credit of Goddard
[173-175].
Goddard [173] derived a formula to describe the stress Held for dilute
suspensions of oriented slender fibers in a non-Newtonian fluid. The
treatment was quite rudimentary but brought out an important result
that particle-stress effect was considerably smaller in a shear-thinning
non-Newtonian fluid compared to the Newtonian case, possibly due to
tensile stiffening in the fluid itself. Qualitative agreement with the
experimental data of Charrier and Rieger [176] was observed. A more
sophisticated analysis of the same problem was presented by Goddard
[174] using a general quasi-steady state rheological model for the
suspending medium, with the assumption that in the near-field of the
suspended particles the flow is shear-dominated and extends
asymptotically to the extension-dominated flow in the far field. The
conclusions of this analysis were the same as those arrived at earlier
in Goddard [173]. The complex theoretical treatment of Goddard
[173,174] are not included here. Results are available for the simplified
case of the suspending medium being a power-law fluid in Goddard
[175].
Goddard [175] carried out a qualitative comparison with the
rheological data of Chan et al. [164] for simple shear and simple
extension of polymer melts containing chopped glass fibers. It was seen
that the agreement with the power-law theory was not satisfactory and
even worse for the Newtonian case. Goddard concluded that the
dis agreement was not due to failure of the theory, but possibly because
of lack of fiber alignment during experiments.
Nicodemo et al. [177] were the first to show, experimentally, the
spectacular reductions (at times by an order of magnitude) in the
extensional viscosities of polymer solutions containing spherical
particles (namely, glass microbeads) in contrast to solutions containing
rod-shaped particles (namely, fibers), which are known to increase the
extensional viscosities.
The extensional viscosity of fiber suspension depends to a large
extent on the orientation of the fiber and this has been the subject of
study of a number of investigators (e.g. Taksermann-Krozer and
Ziabicki [178], Bell [179], Goettler [180,181], Nicodemo et al. [182],
Takano [183], Lee and George [184]). In polymer processing, as most of
the flow takes place through converging dies, the study of the
rheological properties in extensional flow and the orientation of the
References 167
polymer molecules and fiber are extremely important in order to

control the quality of the end products.
Despite the importance of extensional viscosity studiesin filled-
polymer processing it is unfortunate that the effects of various factors
like size distribution of the filiers, nature of the surface, flocculation,
etc. as in the case of shear viscosity (section 4.2), has not been studied
at all. Only the effect of the shape of the filler on the extensional
viscosity has been brought out by Nicodemo et al. [177]. A lot more
research in this area is thus warranted. The main reason for the dearth
of information in this area is probably due to the absence of a cheap
and simple apparatus for the measurement of extensional viscosity.
Most of the workers have had to design their own apparatus for
determining extensional viscosities depending on the system to be
measured and the facilities available.
REFERENCES
1. Carr, Rand Cokelet, G.R (1981) Rheology of suspensions of normal and
hardened erythrocytes and their mixtures, J. Rheol., 25, 67-82.
2. Cokelet, G.R (1972) The rheology of human blood, in Biomechanics: Its
Foundations and Objectives (eds Y.c. Fung, N. Perrone and M. Anliker),
Prentice-Hall, Englewood Cliffs, pp. 63-104.
3. Cokelet, G.R and Smith, J.H. (1973) The effect of concentric-cylinder
viscometer gap size on the experimental rheological properties of human
blood, Biorheology, 10, 51-56.
4. Dintenfass, L. (1973) On the possible liquid crystalline structures in artificial
thrombi formed at arterial shear rates: effects of disease, proteins
concentrations, and ABO blood groups, Mol. Cryst. Liq. Cryst., 20, 239--66;
(1982) On changes in aggregation of red cells, blood viscosity and plasma
viscosity during normal gestation, Clinical Hemorheol., 2, 175-88; (1982)
Haemorheology of cancer metastases: An example of malignant melanoma,
survival times and abnormality of blood viscosity factors, Clinical
Hemorheol., 2, 259-71.
5. Dintenfass, L., Jerdrzejczvk, H. and Willard, H. (1982) Photographic,
stereological and statistical methods in evaluation of aggregation of red cells
in disease: Part I: Kinetics of aggregation, Biorheology, 19, 567-77.
6. Dintenfass, L. and Fu-Iung, L. (1982) Plasma and blood viscosities, and
aggregation of red cells in racehorses, Clin. Phys. Physiol. Meas., 3, 293-301.
7. Evans, RL., Kirkwood, RB. and Opsahl, D.G. (1971) The dynamic viscosity
of some human blood, Biorheology, 8, 125-28.
8. Fu-Iung, L. and Dintenfass, L. (1983) Effect of microrheology of blood on
the apparent flow instability in a rotational viscometer, Biorheology, 20,
327-42.
9. Thurston, G.B. (1979) Erthrocyte rigidity as a factor in blood rheology:
viscoelastic dilatancy, J. Rheol., 23, 703-19; (1979) Blood viscoelasticity
and relaxation processes: influence of aggregation tendency, Symposium
European, Hemorheologie et Pathologie, Nancy, France, 17-19 Oct.; (1979)
Rheological parameters for the viscosity, viscoelasticity and thixotropy of

blood, Biorheology, 16, 149-62.
10. Lightfoot, E.N. (1974) Transport Phenomena in Living Systems - Biomedical
Applications of Momentum and Mass Transfer, Wiley, New York.
11. De Kee, D. and Turcotte, G. (1990) Viscosity of biomaterials, Chern. Enng
Commun., 6, 273-82.
12. De Kee, D., Code, RK. and Turcotte, G. (1983) Flow properties of time-
dependent foodstuffs, J. Rheol., 27, 581-604.
13. Lefebvre, J. and Sherman, P. (1977) Rheological properties of aqueous
sunflower protein dispersions, J. Texture Stud., 8,449-62.
14. Szczesniak, AS., Loh, J. and Mannell, W.R (1983) Effect of moisture transfer
on dynamic viscoelastic parameters of wheat flour /water systems, J. Rheol.,
27,537-56.
15. Blanch, H.W. and Bhavaraju, S.M. (1976) Non-Newtonian fermentation
broths: Rheology and mass transfer, Biotech. Bioeng., 18, 745-90.
16. Charles, M. (1978) Technical aspects of the rheological properties of
microbial cultures, Adv. Biochem. Eng., 8, 1-62.
17. Metz, B., Kossen, N.w.F. and Van Suijdam, J.c. (1979) The rheology of
mould suspensions, Adv. Biochem. Eng., 11, 103-56.
18. Kalousek G.L. (1973) A new instrument for measuring thixotropy, Cement
Concrete Res., 3, 315-23.
19. Sacks, M.D., Khadilkar, C.S., Scheiffele, G.W., Shenoy, AV., Dow, J.H. and
Sheu, RS. (1987) Dispersion and rheology in ceramic processing. Adv.
Ceram., 21, 495-515.
20. Borghesani, AF. (1988) Non-Newtonian flow behavior of coal-fuel oil
suspensions, in Encyclopedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, TX, Vol. 7, pp. 89-134.
21. Adams-Viola, M., Botsaris, G.D., Filymer, W.G., Jr., Glazman, Yu.M. and
King, K.D. (1982) The effect of coal particle aggregation on the
sedimentation and rheology of coal-oil mixtures, Colloids Surfaces, 4, 255-69.
22. Anderson, P.c., Veal, c.J. and Withers, V.R (1982) Rheology of coal-oil
dispersions, Powder Tech., 32, 45-54.
23. Castillo, C. and Williams, M.C. (1979) Rheology of very concentrated coal
suspensions, Chem. Eng. Commun., 3, 529-47.
24. Darby, R and Rogers, B.A (1980) Non-Newtonian viscous properties of
methacoal suspensions, AIChE J., 26, 310-12.
25. Davis, P.K., Muchmore, C.B., Missavage, RJ. and Coleman, G.N. (1981)
Rheological and pumping characteristics of ethacoal, J. Pipelines, 1,
139-44.
26. Munro, J.M., Lewellyn, M.M., Crackei, P.R and Bauer, L.G. (1979) A
characterization of the rheological properties of coal-fuel oil slurries, AIChE
J., 25, 355-8.
27. Thurgood, J.R, Hanks, RW., Oswald, G.E. and Youngblood, E.L. (1982) The
rheological characterization of coal liquefaction preheater slurries, AIChE J.,
28,111-16.
28. Veal, C.L and Wall, D.R (1981) Coal-oil dispersions - an overview, Fuel,
60,873-6.
29. Erenrich, E.H. and Van Doren, RE. (1977) Instrumental techniques for the
rheological control of coatings, Paper presented at Pacific Paint OCCAA
Convention, Canberra.
References 169
30. Heertjes, P.M., Smits, CI. and Vervoorn, P.M.M. (1979) Some aspects of
adsorption processes occurring on titanium dioxide particles, Prog. Organic
Coatings, 7, 141-66.
31. Hudson, N.E., Bayliss, M.D. and Ferguson, J. (1978) The rheology of
pigment dispersions, Rheol. Acta, 17, 274-87.
32. Saarnak, A (1979) Characterisation of the interaction between pigments and
binder solution using rheological measurements, J. Oi! Col. Chern. Assoc., 62,
455-60.
33. Dulik, D., Bernier, R and Brauer, G.M. (1981) Effect of diluent monomer on
the physical properties of bis-GMA-based composites, J. Dent. Res., 60,
983-9.
34. Vermilyea, S., Powers, J.M. and Craig, RG. (1977) Rotational viscometry of
a zinc phosphate and zinc polyacrylate cement, J. Dent. Res., 56, 762-7.
35. Vermilyea, S.G., Powers, J.M. and Koran, A (1978) Ihe rheological
properties of fluid denture-base resins, J. Dent. Res., 57, 227-31.
36. Vermilyea, S.G., De Simon, L.B. and Huget, E.F. (1978) The rheological
properties of endodontic sealers, Oral Surg., 46,711-16.
37. Jacobsen, P.H., Whiting, R and Richardson, P.CA (1977) Viscosity of
setting anterior restorative materials, Brit. Dent. J., 143, 393-6.
38. Whiting, R and Jacobsen, P.H. (1979) The evaluation of non-Newtonian
viscosity using a modified parallel-plate plastometer, J. Mat. Sei., 14, 307-11.
39. Baker, F.S., Carter, RE. and Warren, RC (1980) The rheological assessment
of propellants, Paper presented at the 8th International Congress on
Rheology, Naples, 1-5 Sept.
40. Chen, Y.R and Hashimoto, AG. (1976) Rheological properties of aerated
poultry waste slurries, Trans. ASAE, 19, 128-33; (1976) Pipeline transport of
livestock waste slurries, Trans. ASAE, 19, 898-902, 906.
41. Hashimoto, AG. and Chen, Y.R (1976) Rheology of livestock waste slurries,
Trans. ASAE, 19, 93{}-4.
42. BrownelI, W.E., Caso, G.B. and Braun, D.B. (1978) An additive to increase
plastic strength, Amer. Cer. Soc. Bull., 57, 513-16.
43. Farooqui, S.1. and Richardson, J.F. (1980) Rheological behaviour of kaolin
suspensions in water and water-glycerol mixtures, Trans. Inst. Chern. Engrs,
58,116-124.
44. Heath, D. and Iadros, Th.F. (1983) Influence of pH, electrolyte, and
poly(vinyl alcohol) addition on the rheological characteristics of aqueous
dispersions of sodium montmorillonite, J. Colloid Inter! Sei., 93, 307-19;
(1983) Influence of pH, electrolyte, and poly(vinyl alcohol) addition on the
rheological behaviour of aqueous silica (aerosol) dispersions, J. Colloid Interj.
Sei., 93, 320-28.
45. Heywood, N.1. and Richardson, J.F. (1978) Rheological behavior of
flocculated and dispersed aqueous kaolin suspensions in pipe flow, J. Rheol.,
22, 599-613.
46. James, AE. and Williams, D.J.A. (1982) Flocculation and rheology of
kaolinite/ quartz suspensions, Rheol. Acta, 21, 176-83.
47. Verreet, G. and Berlamont, J. (1988) Rheology and non-Newtonian behavior
of sea and estuarine mud, in Encyclopedia of Fluid Mechanics (ed. N.P.
Cheremisinoff), Gulf Publishing, Houston, IX, Vol. 7, pp. 135-49.
48. Cheremisinoff, N.P. (ed.) (1986) Encyclopedia of Fluid Mechanics, Vol. 5: Slurry
Flow Technology, Gulf Publishing, Houston, IX.
49. Brenner, H. (1972) Suspension rheology, in Prog. Heat Mass Transfer (ed.
W.R. Schowalter), Pergamon Press, Oxford. Vol. 5.
50. Batchelor, G.K. (1974) Transport properties of two-phase materials with
random structure, Ann. Rev. Fluid Meeh., 6, 227-55.
51. Jinescu, V.V. (1974) The rheology of suspensions, Int. Chern. Engg, 14, 397-420.
52. Jeffrey, D.J. and Acrivos, A (1976) The rheological properties of suspensions
of rigid particles, AIChE J., 22, 417-32.
53. Cheng, D.C-H. (1980) Viscosity-concentration equations and flow curves for
suspensions, Chem. Indus.; 403-6.
54. Mewis, J. (1980) Rheology of suspensions, in Rheology (eds G. Astarita,
G. Marrucci and L. Nicolais), Plenum Publishing, New York, Vol. 1,
pp. 149-68.
55. Russel, W.B. (1980) Review of the role of colloidal forces in the rheology of
suspensions, J. Rheol., 24, 287-317.
56. Metzner, AB. (1985) Rheology of suspensions in polymerie liquids, J. Rheol.,
29,739-75.
57. Darby, R. (1986) Hydrodynamics of slurries and suspensions, in Encyclopedia
of Fluid Meehanies (ed. N.R. Cheremisinoff), Gulf Publishing, Houston, TX,
Vol. 5, pp. 49-91.
58. Utracki, L.A. (1988) The rheology of two-phase flows, in Rheologieal
Measurements (eds AA Collyer and D.W. Clegg), Elsevier Applied Science
Publishers, London, 479-594.
59. Barnes, H.A (1989) Shear-thickening ('Dilatancy') in suspensions of non-
aggregating solid partic1es dispersed in Newtonian liquids, J. Rheol., 33,
329-66.
60. Adler, P.M., Nadim, A and Brenner, H. (1990) Rheological models of
suspensions, Adv. Chem. Eng., 15, 1-72.
61. Nguyen, Q.D. and Boger, D.V. (1992) Measuring the flow properties of yield
stress fluids, Ann. Rev. Fluid Meeh., 24, 47-88.
62. Nielsen, L. (1977) Polymer Rheology, Marcel Dekker, New York.
63. Einstein, A. (1906) Eine neue bestimmung der molekl dimension, Ann.
Physik., 19, 289-306.
64. Einstein, A (1911) Ann. Physik., 34, 591-2.
65. Einstein, A (1956) Investigations on the Theory of the Brownian Movement,
Dover, New York.
66. Reiner, M. (1965) Rheologiya, Izd. Nauka, Moscow, p. 164.
67. Kurgaev, E.F. (1960) Dokl. Akad. Nauk SSSR, 132, 392.
68. Rutgers, I.R. (1962) Relative viscosity of suspensions of rigid spheres in
Newtonian liquids, Rheol. Acta, 2, 202-10; (1962) Relative viscosity and
concentration, Rheol. Acta, 2, 305-48.
69. Hatshek, E. (1910) Kolloid Zh., 79, 301.
70. Andres, U.T. (1959) Gormi Zh., 1, 65.
71. Happel, J. (1957) Viscosity of suspensions of uniform spheres, J. Appl. Phys.,
28,1288.
72. Pokrovskii, V.N. (1968) Kolloid Zh., 30, 881.
73. Kambe, H. (1969) Int. Chern. Eng., 9, 164-71.
74. Simha, R. (1952) J. Appl. Phys., 23, 1020-4.
75. Thomas, D.G. (1965) Transport characteristics of suspension: VIll. A note on
the viscosity of Newtonian suspension of uniform spherical partic1es. J.
Colloid Sei., 20, 267-77.
References 171
76. Simha, R and Someynsky, T. (1965) J. Colloid Sei., 20, 278-81.

77. Ford, T.F. (1960) J. Phys. Chern., 64, 1168-74.
78. Cengel, J.A, Faruqui, AA, Finnigan, J.W., Wright, CH. and Knudsen, J.G.
(1962) AIChE J., 8, 335-9.
79. MeGeary, RK. (1961) J. Arner. Cerarn. Soc., 44, 513-22.
80. Oe Brujin, H. (1951) Disc. Faraday Soc., 11, 86.
81. Clarke, B. (1967) Trans. Instn Chern. Engrs, 45, 251-6.
82. Guth, E. and Simha, R (1936) Kolloid Z., 74,266.
83. Vand, V. (1948) Viseosity of solutions and suspensions. 1, J. Phys. Chern.
Colloid Chern., 52, 277-99; (1948) II, J. Phys. Chern. Colloid Chern., 52,
300-14.
84. Saito, N. (1950) J. Phys. Soc. Japan, 5,4.
85. Manley, R St. J. and Mason, S. G. (1955) Can. J. Chern., 33, 163.
86. Harbard, E.H. (1956) Chern. Ind., 22, 491.
87. Alfrey, T., Jr. (1952) Mekhanicheskie Svoistva ViskopoIirnerov, Izd. Innostranoi
Literaturi, Moseow, p. 479.
88. Arrhenius, S. (1887) Z. Phys. Chern., 1, 285.
89. Fikentseher, H. and Mark, H. (1930) Kolloid-Z. 49, 135.
90. Bungenberg de Jong, H.G., Kruyt, H.R and Lens, W. (1932) Kolloid-Beihefte,
36,429.
91. Papkov, S. (1935) Kunststoffe, 25, 253.
92. Hauwink, R (1937) Kolloid-Z., 79, 138.
93. Brede, H.L. and Oe Boojs, J. (1937) Kolloid-Z., 79, 31.
94. Mullins, L. (1968) Knuchuk i Rezina, 7, 10.
95. Feldman, D. and Boiesan, V. (1971) Mat. Plastics, 8, 536.
96. Eyring, H., Henderson, 0., Stover. B.J. and Eyring. E.M. (1964) Statistical
Mechanics and Dynarnics, Wiley, New York, p. 460.
97. Mooney, M. (1951) The viseosity of a eoneentrated suspension of spherical
particles, J. Colloid Sei., 6, 162-70.
98. Severs, E.T. (1963) Rheology 0/ Polyrners, Reinhold, New York, p. 65.
99. Eilers, H. (1941) Die viskositat von emulsionen hochviskoser stoffe als
funktion der konzentration, Kolloid Zh., 97, 313.
100. Frankei, N.A and Aerivos, A (1967) On the viscosity of a eoneentrated
suspension of solid spheres, Chern. Engg Sei., 22, 847-53.
101. Marrueci, G. and Denn, M.M. (1985) On the viscosity of a eoneentrated
suspension of solid spheres, Rheol. Acta, 24, 317-20.
102. Chong, J.S., Christiansen, E.B. and Baer, AD. (1971) Rheology of
coneentrated suspensions, J. Appl. Polyrn. Sei., 15, 2007-21.
103. Kataoka, T., Kitano, T., Sasahara, H. and Nishijima, K. (1978) Viseosity of
104. Kitano, T., Kataoka, T. and Shirata, T. (1981) An empirical equation of the
relative viseosity of polymer melts filled with various inorganic fillers,
Rheol. Acta, 20, 207-9.
105. Poslinski, A.J., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Freehette, F.J.
(1988) Rheologieal behavior of filled polymerie systems. I. Yield stress and
shear-thinning effeets, J. Rheol., 32, 703-35.
106. Poslinski, A.J., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Freehette,
F.J. (1988) Rheologieal behavior of filled polymerie systems. 11. The
effeet of abimodal size distribution of partieulates, J. Rheol., 32,
751-71.
107. Wildemuth, CR and Williams, M.C (1984) Viscosity of suspensions

modeled with a shear-dependent maximum packing fraction, Rheol. Acta,
23,627-35.
108. Stamhuis, J.E. and Loppe, J.P.A (1982) Rheological determination of
109. Jeffrey, J.B. (1922) The motion of ellipsoidal particles immersed in a viscous
fluid, Proc. Roy. Soc., AI02, 161-79.
110. Guth, E. (1936) Kolloid-Z., 74, 147.
111. Guth, E. (1938) Phys. Rev., 53, 926A
112. Pokrovskii, V.N. (1967) Kolloid Zh., 29, 576.
113. Maschmeyer, RO. and Hill, CT. (1975) Trans. Soc. Rheol., 21, 183-94.
114. Burgers, J.M. (1938) Second Report on Viscosity and Plastieity, Nordemann,
New York, p. 113.
115. Mason, S.G. (1950) Pulp Paper Mag. Can., 51, 83.
116. Blankeney, w.R. (1966) J. Colloid Sei., 22, 324-30.
117. Simha, R. (1949) J. Res. Nat. Bur. Stand., 42, 409.
118. Brodnyan, J. (1959) Trans. Soc. Rheol., 3, 61-8.
119. ZiegeL K. (1970) J. Colloid Interf Sei., 34, 185-96.
120. Hashin, Z. (1969) in Contributions to Mechanics (ed. D. Abir), Pergamon
Press,Oxford.
121. Nielsen, L. (1970) J. Appl. Phys., 41, 4626-7.
122. Ward, S.G. and Whitmore, RL. (1950) Studies of the viscosity and
sedimentation of suspensions. Part I: The viscosity of suspensions of
spherical partic1es, Br. J. Appl. Phys., 1, 286.
123. Ting, AP. and Luebbers, RH. (1957) AIChE J., 3,111-16.
124. Moreland, C (1963) Viscosity of suspensions of coal in mineral oil, Can. J.
Chern. Engg, 41, 24.
125. Shaheen, E.I. (1971) Rheological study of viscosities and pipeline flow of
concentrated slurries, Powder Tech., 5, 245.
126. Parkinson, C, Matsumoto, S. and Sherman, P. (1970) J. Colloid Interf Sei.,
33,150-60.
127. Hsieh, H.P. (1978) Polyrn. Engg Sei., 18, 928-31.
128. Ward, S.G. and Whitmore, RL. (1950) Br. J. Appl. Phys., 1,325-8.
129. Goldsmith, H.L. and Mason, S.G. (1965) Proc. 4th Int. Congr. Rheol.,
Interscience, New York, p. 65.
130. Segre, G. and Silberberg, A (1961) Radial partic1e displacements in
Poiseuille flow of suspensions, Nature, 189, 209-10.
131. Segre, G. and Silberberg, A (1962) Behaviour of macroscopic rigid spheres
in Poiseuille flow, Parts 1 & 2, J. Fluid Mech., 14, 115-35, 136-57.
132. Segre, G. and Silberberg, A. (1962) Non-Newtonian behavior of dilute
suspensions of macroscopic spheres in a capillary viscometer, J. Colloid
Sci., 18, 312.
133. Morrison, S.R. and Harper, J.C (1965) Ind. Eng. Chern. Fundarnentals, 4, 176.
134. Jastrzebski, Z. (1967) Entrance effects and wall effects in an extrusion
rheometer during the flow of concentrated suspensions, Ind. Eng. Chern.
Fundarnentals, 6, 445-54.
135. Chapman, F.M. and Lee, T.5. (1970) Effect of tale filler on the melt rheology
of polypropylene, SPE J., 26, 37-40.
136. Goel, D.C (1980) Effect of polymer addition on the rheological properties
of tale-filled polypropylene, Polyrn. Engg Sei., 20, 198-201.
References 173
137. Ferraro, CF. (1968) SPE J., 24, 74-8 (April).

138. Krieger, I.M. and Dougherty, T.J. (1959) A mechanism to non-Newtonian
flow in suspensions of rigid spheres, Trans. Soc. Rheol., 3,137-52.
139. Gillespie, T. (1966) J. Colloid Sei., 22, 554-62.
140. Fischer, E.K. (1970) Colloidal Dispersion, Wiley, New York, p. 154.
141. Govier, G.W. and Winning, M.D. (1948) AIChE Meeting, Montreal,
Quebec.
142. Umeya, K. and Kanno, T. (1979) Effect of flocculation on the dilatant flow
for aqueous suspensions of titanium dioxides, J. Rheol., 23, 123-40.
143. Nicodemo, L., Nicolais, L. and Landei, RF. (1974) Shear rate dependent
viscosity of suspensions in Newtonian and non-Newtonian liquids, Polym.
Engg Sei., 29, 729.
144. Nicodemo, L. and Nicolais, L. (1974) J. Appl. Polym. Sei., 18, 2809-18.
145. Kremesec, V.J. and Slattery, J.C (1977) Trans. Soc. Rheol., 21, 469-91.
146. Highgate, D.J. and Whorlow, RW. (1970) Rheol. Acta, 9, 569-76.
147. Napper, D.H. (1977) Steric stabilization, J. Colloid Interf. Sei., 58, 390-407.
148. Tadros, Th.F. (1982) Polymer adsorption and dispersion stability, in The
Effect of Polymers on Dispersion Properties (ed. Th.F. Tadros), Academic
Press, New York, pp. 1-37.
149. Eisenlauer, J., Killman, E. and Kom, M. (1980) Stability of colloidal silica
(aerosil) hydrosols. 11. Influence of the pH value and the adsorption of
polyethylene glycols, J. Colloid Inter! Sei., 74, 120-35.
150. Tadros, Th.F. (1978) Adsorption of polyvinyl alcohol on silica at various
pH values and its effect on the flocculation of the dispersion, J. Colloid
InterJ. Sei., 64, 36-47.
151. Rubio, J. and Kitchner, J.A. (1976) The mechanism of adsorption of
poly(ethylene oxide) flocculant on silica, J. Colloid InterJ. Sei., 57, 132-42.
152. Sacks, M.D. and Khadilkar, CS. (1983) Milling and suspension behavior of
Al20 3 in methanol and methyl isobutyl ketone, J. Am. Ceram. Soc., 66,
488-94.
153. Sacks, M.D. (1984) Properties of silicon suspensions and cast bodies, Am.
Ceram. Soc. Bull., 63, 1510-15.
154. Morgan, RJ. (1968) A study of the phenomena of rheological dilatancy in
an aqueous pigment suspension, Trans. Soc. Rheol., 12, 511-33.
155. Dow, J.H. (1992) PhD Thesis, University of Florida, Gainesville.
156. Mistry, D.B. and Warburton, B. (1971) Rheol. Acta, 10, 106-12.
157. Fryling, CP. (1963) J. Colloid Sei. 18, 713-32.
158. Krieger, I.M. and Eguiluz, M. (1976) The second electroviscous effect in
polymer lattices, Trans. Soc. Rheol., 20, 29.
159. Conway, B.E. and Dobry-Duc1aux, A. (1960) in Rheology (ed. P.R Eirich),
Academic Press, New York, Vol. 3, pp. 83-120.
160. Dobry, A. (1950) J. Chim. Phys., 50, 507.
161. Smoluchowsky, M. (1916) Kolloid-Z., 18, 190.
162. Booth, F. (1950) The electroviscous effect for suspensions of solid spherical
partic1es. Proc. Roy. Soc., A203, 533-51.
163. Chan, F.S. and Goring, D.A. (1966) J. Colloid Sei., 22, 371-7.
164. Chan, Y., White, J.L. and Oyanagi, Y. (1977) Polym. Sei. Eng. Report No. 96,
University of Tennessee, Knoxville. May.
165. Harmsen, G.J., Schooten, J.V. and Overbeek, J.Th.G. (1953) J. Colloid. Sei., 8,
64-71.
174 Constitutive theories and eq uations for suspensions
166. Batchelor, G.K. (1970) Slender-body theory of particles of arbitrary cross-

seetion in Stokes flow, J. Fluid Mech., 44, 419.
167. Batchelor, G.K. (1971) The stress generated in a non-dilute suspension of
elongated particles by pure straining motion, J. Fluid Mech., 46, 813-29.
168. Insarova, N.I. (1970) Inzh.-Fiz. Zh., 18, 347.
169. Weinberger, CB. (1970) Extensional flow behavior of non-Newtonian
fluids, PhD dissertation, University of Michigan.
170. Weinberger, CB. and Goddard, J.D. (1974) Extensional flow behaviour of
polymer solutions and particle suspensions in a spinning motion, Int. J.
Mu/tiphase Flow, 1, 465-86.
171. Mewis, J. and Metzner, AB. (1974) The rheological properties of
suspensions of fibres in Newtonian fluids subjected to extensional
deformations, J. Fluid Mech., 62, 593-600.
172. Kizior, T.E. and Seyer, F.A (1974) Axial stress in elongational flow of fiber
suspension, Trans. Soc. Rheol., 18, 271-85.
173. Goddard, J.D. (1976) Tensile stress contribution of flow-oriented slender
particles in non-Newtonian fluids, J. Non-Newtonian Fluid Mech., 1, 1-17.
174. Goddard, J.D. (1976) The stress field of slender particles oriented by a non-
Newtonian extensional flow, J. Fluid Mech., 78, 177-206.
175. Goddard, J.D. (1978) Tensile behavior of power-Iaw fluids containing
oriented slender fibers, J. Rheol., 22, 615-22.
176. Charrier, J.M. and Rieger, J.M. (1974) Fibre Sei. Tech., 7, 161.
177. Nieoderna, L., De Cindio, B. and Nieolais, L. (1975) Elongational viscosity
of microbead suspensions, Polym. Eng. Sci., 15, 679-83.
178. Takserman-Krozer, R. and Ziabieki, A (1963) Behaviour of polymer
solutions in a velocity field with parallel gradient. I. Orientation of rigid
ellipsoids in a dilute solution. J. Polym. Sei., Al, 491-506.
179. Bell, J.P. (1969) Flow orientation of short fibre composites, J. Comp. Mat., 3,
244-53.
180. Goettler, L.A (1970) Flow orientation of short fibers in transfer molding,
25th Annual Tech. Conf, SPI, Paper 14-A
181. Goettler, L.A (1974) Molding of oriented short-fiber composites, Report No.
HPC-70-130, Monsanto/Washington University Association.
182. Nicoderno, L., Nicolais, L. and Aciemo, D. (1973) Orientation of short
fibers in polymerie materials resulting from converging flow, Ing. Ch. Ital.,
9,113-16.
183. Takano, M. (1973) Flow orientation of short fibers in rectangular channels,
ARPA Report, HPC 73-165.
184. Lee, W.K. and George, H.H. (1978) Flow visualization of fiber suspensions,
Preparation of filled
polymer systems 5
In context with the preparation of filled polymer systems, there are

three terms, namely, compounding, blending and mixing, which are
often synonymously or interchangeably used and though various
researchers have defined these terms, one is at times faced with the
dilemma of terminology [1]. In the present case, definitions of the terms
are given as applicable to the subject matter and hence exclude any
other connotations of the terms.
Compounding is the term used for those cases wherein polymers are
softened, melted and intermingled with solid fillers and other liquid
additives to form filled polymer systems.
Blending is defined as a process in which two or more components
or ingredients are physically intermingled without engendering any
significant change in the physical state of the components. The com-
ponents are, normally, polymers to form polymer blends, and hence in
the present context, will not be used to describe the intermingling of
fillers with polymers.
The word mixing is applied to both the processes of compounding
and blending, and describes the process of intimate intermingling of
polymers with fillers/additives or two polymers without any specific
restrictions. It covers a broad spectrum of dispersion of various
ingredients to form a homogeneous mixture on some definable small
scale.
5.1 GOODNESS OF MIXING

The important aspect in mixing is to evaluate the quality of mixtures [2]
or the goodness of mixing [3]. The most straightforward method of
characterizing the quality of the mixtures is to measure to what extent
the desired properties have been attained. Industrial quality control
follows that route whenever feasible. However, this requires a detailed

176 Preparation of filled polymer systems
description of the structure of the mixture and to theoretically establish

this, the spatial position of each ultima te minor particle in the matrix
must be determined. It is often not possible to predict the exact path of
individual ultimate particles during the mixing process because most
compounding equipments achieve the mixed state randomly, though,
of course, there are some in which mlxing progresses at least in a partly
ordered fashion.
In the random mixed state there are more possible arrangements of
the minor component than in the completely unmixed state. In the
latter state the probability is unity and in the former case it is very large
equal to
(N; + N;)!
~ixed = N'IN'I (5.1)
1 2
N; and N; are the number of ultimate particles of the major and minor
component respectively. A very great number of possible random
distributions have to be considered [4] to be the most uniform
distribution which can be achieved with cornmon random type
compounding equipments as shown in Figure 5.1. From the inspection
of Figures 5.1(d) and 5.1(e), it can be seen that in the case of filled
polymer systems, this type of regular random state would undoubtedly
be preferable to any other random state. In the ca se of sma11 ultimate
particles which cluster together to form large agglomerates (hlobs), the
clusters have to be broken up into ultima te particles (aggregates) and
uniformly distributed by the dispersive mixing action. The random
distribution of a component 'A' in a component 'B' is achieved if the
probability of finding an ultima te particle of 'A' is the same at a11 points
in the mixture and is equal to the volume fraction a of the component
'A' in the mixture. In the completely unmixed state as shown in Figure
5.1(a), a sampie of volume Vs will have a concentration of component A
of either 1 or O.
The probability to find X A = 1 is 'a' and to find X A = 0 is b, as shown
in Figure 5.2 on the left-hand side. The mean is given by
(5.2a)
and the variance as
(5.2b)
The probability distribution for finding a particular level of

concentration in a sampie after drawing a great number of sampies can
be caIculated [4] from the fo11owing expression
(a) THE COMPlETEl Y (b) THE PERFECTLY
UNMIXED STATE. MIXED STATE
0=1 (N, + N~!
DUIlCED
l'
= ... IN 2'I
T I~ ~ I. 1-'.
~~-.j---'1 I_I~ !;r :...

~
lii7<~
~I.
l~
.,..
~
1
..... _
...!=~
L.. ,~ ~ La ~, ~. t.
L" .... ~
..-- I.. ~ ~
1-1:
-.
I.o.~ ~.
1"' ..
;,:
I
-r-.,.. ~ ,. .,. l__ ~ aCf!. .~ ~ I ~
'~ ~ !" I! ii
=<i ~
~. "" i- - La........, I- . .
-. -: ~ .;. !I' ..
~ .~ -'- .. .. -..
~
~.~ ':. ~ri
~l:! /!l. ~
..
_.~
."
.-,."'1 - D ,~
t
~
-, t-
,
. ~ I-
L.I -c" ,.. -je .. ~ 1.....
~. .. t-""' ~ ~
'" ,- - -.
,,"' w' -'"
je ~. ~
~ ~ I~ ,~
,. .
I- It.. I:, .~
," ."
~~ ~ .. ...j..!:J ~-
-, ....
1". It. I ..". I: ;- I, I~
~ L..a~ H=1 ~,-' ",. .1
... ~ i.
~I .!II'~~ ~ ;I]ii ' 11 J ~. r.. r-
I. 111' ...
I.
,. -. ,. .. ... ...
I l~
i"''I '- liJ -
'. .1 : -1 tltl Ir- ~ r.. I- [ii
H Itj
" ,. - -. -- - .
.,
!".I r1I'~ ~ J" .!
:~ ~~rr-t-1 ~ I; t- I.
.. ~
.-.. 11 I.'... ~ ~~
., II - ~ 1.1 _
~~
t.. .~
I ~ ~ .;:
Fi!J
,.. ,,..,. ,- "'~-: .. 1 ..
fj ...... ~ _ ~ r.. .4
.'"
-',.
",'" I. ...
~. tw 7 I'" ~
~- ,- i. ~ .. "I '1 .j::I
(a) {bI (c) Cd) (e)
COMPONENT: A,B
VOLUME FRACTION: atb
ULTI MATE PARTICLE SIZE: a,/J
Flgure 5.1 Number of possible random distributions of fitiers in a pOlymer matrix whieh ean be aehieved with eommon random type
eompounding equipments. (Reprinted from Re!. 4 with kind permission from John Wiley & Sons, Ine., New York, USA)
STATISTICAL DEFINITION OF
THE STATE OF MIXTURE.
THE COMPLETELY SAMPLE SIZE V6 THE COMPLETELY

1.0 UNMIXED STATE. oe 1.0 MIXED STATE.
)( p(X,,)
oe I P(X~
)( &I.
l&.
o
0 Z
z I ,. o
0
i= I Q)
::l b
Q) --tf., t., r--
Ci: ~
: I I
&I.
:ni5
I I I o
~
::; ~.
iii
I I I -'
.c: ii
Q) I I
0 ~
a::
Q.
I I I
I I I iQ.
OL I I"
o VOLUME OF CONCENTRATION
1.0 x" VOLUME OF CONCENTRATION 1.0 X"
OF COMPONENT A MEAN:,. a = OF COMPONENT A
MEAN:" = a
VARIANCE: ",= a.b VARIANCE: r = a.b Vs
Figure 5.2 Variation ot the probability ot tiller distribution with its eoneentration in the polymer matrix. (Reprinted trom Ret. 4 with kind
permission trom John Wiley & Sons, Ine., New York, USA)
Goodness of mixing 179
P(XA ) = ..j(2na2) (5.3a)
where the mean is given by

(5.3b)
and the variance as
r:t.
~=ab (5.3c)
Vs
Again it can be seen that for a sampie of the size of an ultimate
partic1e, the variance and the probability are the same as for the
completely unmixed state. On the other end of the spectrum is a sampie
of very large size, possibly a whole batch, in which case the measured
concentration will always indicate that the sampie is weH mixed.
Obviously, in order to make a statement about the quality of mix, series
of varying sampie sizes have to be analyzed. Ouring each series N"
sampies of the same size are collected. Using equation (5.3c), the
variance for the completely mixed state for each series can be calculated
introducing the sampie size for that serve. The actual mean concen-
tration XA and the actual variance 52 can be calculated [4] from the
measured values XAi as follows (Iable 5.1)
(5.4)
(5.5)
If the mixture has been properly sampled then )CA should not be
significantly different from a. The normal proportion test can be used to
determine if any observed difference is significant. The test is applied
by calculating the quantity
Z = ()CA - a)..jN"
(5.6)
5
Numerous indices to quantify the extent of mlxmg have been
proposed and these are reviewed by Fan and co-workers [5,6]. In
general these are based on standard deviation 5 or the variance 52 of
the composition of spot sampies taken from the mixture. The simplest
such index [7] is given by
5 _ a
mI =- or mI =- (5.7)
a 5
where a is the standard deviation of composition for a random
Table 5.1
Mean: XA
_ = W'1" NU
~ XA,;
1=1
.
Vanance. S
. 2 1" NU
-
= W' = 1 ~(XA, = XA) 2
1=1
NU. . . number of sampies

Significance of XA Significance of ~
Z = (XA - a)JN" chi-square test
S
Mixing index
Mixing index Perfectly mixed Completely unmixed
~ Vs
(/ (1.
u~-~
o
u~ - u2
Inu~ -In~
o
Inu~ -lnu2
~ _u2
o
a
u~ = a. b = a(1 - a) the variance of the completely unmixed state
Souree: Ref.4 (reprinted with kind permission from John Wiley & Sons, Ine., New York, USA).
homogeneous mixture defined as a mixture in which the probability of

finding a particle of a given component is the same at a11 the locations
in the mixture and (1 is equal to J[a(l - a)/N'] for a binary number of
mixture where a is the proportion of one component and N' is the
number of particles in the sampIe [7]. The number of particles in the
sampIe are often difficult to estimate and in that case, the value of N'
may be taken as Vsi IX. The sampling of mixtures and treatment of results
has been extensively reviewed by Weidenbaum [8] as weH as by Hold
[4] and may be referred to for better understanding. Different ways of
characterizing the degree of mix by a mixing index based upon rl and
52 have also been proposed [9]. They are summarized in Table 5.1. The
chi-square test is the statistical test of significance used in comparing 52

with (12. The chi-square test can be used to determine whether the
difference between 52 and (12 is significant indicating a deviation from a
random mix or adeviation by chance [10]. If the mixing index is plotted
vs. the size of the sample, the size of the domains with nonuniform
Goodness of mixing 181
composition and the degree of nonuniformity can be established from

the graph. Two properties which are useful in adjudging the goodness
of mixing are the scale and intensity of segregation.
Scale of segregation is a measure of the average separation between
regimes comprising the same component and may be correlated to the
average striation thickness, which is the average distance between like
interfaces in a mixture [11]. On other hand, intensity of segregation is a
measure of concentration [11].
Danckwerts [3] defines the scale of segregation SL as the integral of
the coefficient of correlation between concentrations at two points
separated by a distance
SL = l R(f.l)dr (5.8)
The definition of the coefficient of correlation is given by the following

equation
Nil
~)X~i - XA)(X~i - X A)
R(I) = ..:...i=...:...1_ _---::--,-;;--_ __
(5.9)
NI/s2
where X~i' X~i are the concentrations at two points at a distance r. The
variance S2 is calculated from the concentrations at all points using
equation (5.5). The coefficient of correlation R(r) ranges from 1 to -1. A
value of 1 indicates that both points in each couple have the same
concentration. The value -1 indicates that the concentration in one
point is pure minor and in the other is pure major.
The intensity of segregation is defined as follows:
S2
1=2 (5.10)
0'0
It expresses the ratio of the measured variance to the variance of a

completely segregated system. The intensity of segregation as defined
in equation (5.10) reflects to some extent 'gross uniformity' on ascale of
examination reduced to the scale at which texture or local structure is
being examined.
Danckwerts [3] thus introduced a different method of characterizing
texture and local structure. In Figure 5.3, the sampie on the left-hand
side has a large scale of segregation and unless the intensity of
segregation, Le. the difference in concentration between these areas is
very low, the sampie is poorly mixed. The specimen on the right-hand
side shows a small scale of segregation: in this case a higher intensity of
segregation can still be tolerated without classifying the state of mix as
poor. This provides a good insight into the importance of the scale of
SCALE OF SEGREGATION:
r
SL = rr)dr
N
t
1.1
- -
(XAI- X,A) (X-AI - X,A)
R(r) = NS'
INTENSITY OF SEGREGATION:
SI
1=-
,,2
o
GROSS
UNIFORMITY
SCALE OF EXAMINATION
TEXTURE
LOCAL
STRUCTURE
Flgure 5.3 Definition of the scale and intensity of segregation along with the scale
of examination. (Reprinted from Ref. 4 with kind permission from John Wiley & Sons,
examination in relation to the interpretation of the results of the

examination. Large scale examination renders information about the
gross uniformity of a mixture. With decreasing scale, information is
gained about the texture and finally the local structure of a
mixture.
Gross uniformity is important in most mixtures. However, the degree
of fineness in the texture that is needed is, of course, dependent upon
the individual application requirements of the mixed material. In order
to evaluate the texture, the size of the analyzed sampies has to be
reduced to the level which permits eharaeterization of the texture
signifieant to a spedfie applieation. On the other hand, the loeal
strueture has to be examined at the seale of the ultimate particles.
Naturally, the loeal strueture would depend upon the effideney of the
mixing aetion and also upon the eompatibility of the materials.
In summary, the proeess of mixing involves the breaking down of the
individual eomponents into smaller elements and then dispersion of the
Mixing mechanisms 183
elements of one component in the space occupied by the other [12],

thereby reducing compositional non-uniformity. In the ca se of the filled
systems, the process includes the breaking down of agglomerates, their
separation and segregation, until a final random distribution is achieved
of each component in the system. The purpose of mixing is to attain an
acceptable degree of homogeneity or uniformity of composition,
assessed through the appropriate scale of scrutiny, which is defined
[11,13,14] as the minimum size of the segregation region that would
cause the mixture to be imperfect for the intended purpose. It is thus
reasonable to define the perfect admixture as the state in which no
variations in composition or morphology are observed at the relevant
closeness of examination.
5.2 MIXING MECHANISMS

Having discussed the various methods of characterizing the quality
(uniformity) of a mixture, the next step is to find functional
relationships between these quantitative measures of the quality of the
mixture and the mixing process, the mixer geometry, operating
conditions, properties and initial conditions of the components.
Theoretically each ultimate minor particle has to be followed
throughout the mixing process to establish the final spatial distribution
and evaluate it by applying these measures of quality. During the
movement of the particles in the mixing action, three basic types of
motion can be encountered as shown in Figure 5.4: molecular diffusion;
eddy diffusion (turbulent flow); convection.
In a viscous polymer system, the influence of molecular and eddy
diffusion is generally negligible, leaving forced convective flow as the
main mixing process [9]. If convection causes (a) the movement of the
melt elements and the solid fillers from one spatial loeation to another
such that the interfacial area between them increases or (b) that solid
filler particles are distributed throughout the polymer matrix without
necessarily increasing interfacial area, then distributive mixing is said
to have occurred.
Distributive or simple mixing is induced by plug or bulk conveetion.
Bulk convection can be random or ordered. Ordered bulk convection
rearranges constant volumina in a well defined way, and the progress
of mixing action can be predicted mathematically. In random bulk
convection, chunks of material are randomly redistributed, and model-
ing the mixing action is for most cases not possible.
Distributive mixing is basically defined as an operation which is
employed to increase the randomness of the spatial distribution of the
minor constituent within the major base with no further change in size
of that minor constituent. Distributive mixing is influenced by the strain
EDDY MOLECULAR
DIFFUSION CONVECTION
DIFFUSION
NON EXISTENT i I ,
PLUG (BULK) LAMINAR
CONVECTION CONVECTION
w CJ
> ~
:i )(
ci
CD 4(
iC w Z CI
I- ...I Z
(I) Cl.
~ )(
~
j :i CI
z
l f!:~
(I)
)(
ORDEREb RANJOM :i
BULK BULK w u.i w
CO/llVECTION CONVECTION ~ re.
(l)CJ
> >
ii5 1ii
a:
Zz
w_ z
w Cl.
w
I- (I)
~~
IMPROVES: w~ ~
GROSS
UNIFORMITY U 4 U
TEXTURE
LOCAL

STRUCTURE
4' U .~
Figure 5.4 Various types of mixing meehanisms. (Reprinted from Ref. 4 with kind
permission from John Wiley & Sons, Ine., New York, USA.)
imposed on the mixture. However, in the case of a viscoelastic

polymer system containing agglomerated fine filler particles which
show yield stress characteristics, the application of strain is necessary,
but insufficient, to achieve mixing. The strain rate and hence shear
stress imposed on the material determine the extent of mixing and
this is known as dispersive mixing [9]. This type of mixing is
accomplished by laminar convection through various types of flow:
shear, extensional and squeezing. However, shear plays the major
role during the mixing process and the main action occurs along
streamlines.
Dispersive mixing is basically defined as an operation which reduces
the agglomerate size of the minor constituent to its ultimate particle
size. During compounding of polymer melts with filler, it is the effect
of the mixing action on the solid filler particle that achieves importance.
Available research results for predicting the effect of a specific flow
field on agglomerates indicates that there are a number of possible
motions corresponding to the initial conditions of the velocity field and
the shape of the particles. The motions are periodic and the resultant of
Mixing mechanisms 185
a11 the forces acting on the surface and their moments equal to zero.
The periodic motion of the particles is necessary to maintain the forces
and their moments in equilibrium. The forces create a stress distribution
throughout the agglomerate which will result in the rupture of the
agglomerate along a surface or surfaces where the stress exceeds the
local cohesive forces between the ultimate particles. The breakdown of
agglomerates in shear flow is described quantitatively by Tadmor and
Gogos [9]. It has been shown that the maximum forces tending to
divide a dumbbe11 shaped agglomerate in a fluid of viscosity '1 is given
by
(5.11)
where '1 and'2 are the radii of the two particles and y is the rate of
change of shear experienced by the fluid, and occurs when the
dumbbe11 axis is at an angle of 45 to the direction of shear. Thus
improved mixing is achieved at higher shear stresses and, clearly, small
filler particles are more difficult to separate than large filler particles,
because the magnitude of the attracting forces increases with decreasing
particle diameter. High shear stresses may be applied to non-
reinforcing filler particles to achieve better dispersion. However, mixing
of a polymer with a reinforcing fiber presents a different problem. In
this case it is of importance not to break the fiber because only if the
bond strength of the fiber with the matrix on both sides of a point of
high stress is equal or greater than the strength of the fiber, is it possible
to utilize the fiber optimally. Hence, stress levels will have to be
maintained reasonably low to prevent drastic fiber br-eakage. Another
point of importance that must be borne in mind is that dispersive
mixing is laminar or streamline mixing. The streamlines never cross
during the laminar flow of the mixing action. Hence initial
nonuniformities of the distribution of the minor component across the
streamlines of the mixing flow can only be eliminated if laminar mixing
is combined with plug convection.
Viewing mixing as distributive or dispersive is clearly an oversimpli-
fication when applied to practical mixing problems since both actions
will occur simultaneously. Homogeneity will have been achieved when
both the dispersive elements and the distributive elements of the
mixing have achieved a fluctuation in average composition below a
certain fixed and acceptable level.
However, before either distributive mixing or dispersive mixing can
effectively take place, there is an initial step in which the originally
separate ingredients form a coherent mass. This process is known as
incorporation or wetting.
Filler particles, especially those of submicron size, are available in an
aggregated form. At times, this is done on purpose by the suppliers
because agglomerates are easier to handle, are dustless, and are therefore
less hazardous to health. However, due to a variety of forces such as
van der Waals, electrostatic, liquid bridges, etc. [15] it is often the strong
filler bonds that tend to hold finely divided particles together. In the
preparation of filled polymer system, difficulties arise in dispersing the
fillers in the polymer matrix due to the basic incompatibility between
filler and polymer. Polymers, being organic in nature, have surface
tensions that are quite different from those of most inorganic fillers.
They have, thus, a natural tendency to resist wetting of the filler during
compounding. Hence, during preparation of filled systems, there is
certainly a possibility for increased agglomeration in this non-wetting
environment, as well as an enhanced probability of forming microvoids
around particle clusters.
In summary, compounding of fillers with polymers basically involves
four steps - the initial incorporation, then wetting, followed by de-
agglomeration and finally distribution of the fillers within the polymer
matrix. This is achieved through the use of a variety of compounding
techniques that are discussed below.
5.3 COMPOUNDING TECHNIQUES

There are a number of types of compounding equipment that can
potentially carry out the compounding of fillers with polymers.
Compounding has traditionally been carried out on two-roll mills,
internal mixers and nowadays single and twin screw extruders. The
extruders are being increasingly adopted as a means of giving a
consistent product in a readily usable form, Le. pellet or sheet.
The several techniques available to produce filled polymer materials
vary greatly in their methods and results. Extensive experience with
pre-compounded glass-reinforced polymers reveals that the physical
properties of the product vary significantly (Table 5.2) with various
compounding techniques [16--19]. What one should look for in a
compounding machine and what one should consider when setting up
a compounding operation are very important to understand.
5.3.1 SELECTION CRITERIA

When selecting a compounding equipment, careful consideration should
be given to the size of the unit required. The full cost at the maximum
daily or hourly production rate must be established. It should be borne
in mind that use of several small equipment units rather than one large
unit will usually increase labor costs and initial investment.
Bearing in mind process economics, equipment availability and
preference, the decision as to what compounding technique and what
Compounding techniques 187
Table 5.2 Effect of compounding on mechanical properties of fiber glass-filled

polypropylene
Compounding technique
Single- Continuous Twin-screw Twin-screw Twin-screw Twin-screw

screw mixer compounder compounder compounder compounder
extruder 1 2 3 4
wt% glass fiber 25 25 25 23 25 25
Type of fibers 1/8 in 1/4 in Roving Roving Roving 1/8 in

chopped chopped chopped
glass glass glass
Tensile strength 6100 4700 4900 5800 8000 8000

(psi)
Flex. modulus 580 460 600 550 550 550

(mpsi)
Izod impact 1.45 0.7 0.9 1.1 1.2 1.3

ft Ib/in notched
Heat defl. tempo 264 153 203 184 268 266

C 264 psi (OF)
% of fibers 29
smaller than
0.5mm
Remarks Glass was Screw with Moderate Mild screw

fed into very strong screwafter after
the feed sections addition of addition of
section after glass glass
addition of (No. 14)
glass
Source: Ref. 16 (reprinted with kind permission from American Chemical Society, Washington
OC, USA).
compounding equipment to utilize often centers around the question of

how much shear is required. Compounding of non-reinforcing fillers
usually requires the highest degree of dispersion. Therefore, equipment
should be able to generate high shear stresses to separate the
agglomerates, particularly since these fillers usually have very small
partide sizes. In compounding reinforcing fillers, the opposite approach
is taken as low shear compounding must be used to prevent damage to
the fillers. The main consideration is to wet the filler uniformly,
devolatilize and discharge.
Each material formulation presents a distinct problem. It is important
to know how sensitive the compound and/or compounding ingredients
are to temperature. The need to control or change the temperature and
press ure during compounding should be considered. Purchase of light-
duty equipment should not be overlooked if the material will be

dispersed at a high temperature.
Also, thought should be given to the materials which will come in
contact with the final product. When dealing with glass fibers, abrasion
or corrosion of the compounding equipment plays a substantial role in
economics. Although a product may not be contaminated by plain steel,
a polished stainless steel unit is easier to clean. Labour that is saved
may more than justify the additional cost of a stainless steel unit. Other
constructions such as the use of high manganese steel may also be
considered. The flexibility of the unit is also worth a good look. Can the
compounding equipment be readily cleaned to change from one
product to another and adapt to future production demands? Thus, the
simplidty, accuracy and adaptability of the compounding process are
important.
The equipment for compounding fillers and polymers must fulfil the
following requirements: (a) provide steady-state running conditions, (b)
give reprodudbility of processing conditions, (c) have ease of cleaning
and (d) show versatility to adapt to new formulations. The equipment
has to be chosen with care to ensure that correct product properties are
achieved while no undesirable effects are introduced. Proper selection
of compounding equipment and optimizing equipment parameters can
substantially increase the mechanical properties of the final product.
To achieve optimum material quality, the equipment for compounding
fillers into a polymer must be capable of performing some of the
following process tasks:
1. Incorporation and homogenization of fillers without exceeding
degradation temperatures;
2. Generation of suffidently high internal shear stresses to facilitate
good dispersion of non-reinforcing fillers;
3. Provision of uniform shear stress to each filler particle at any heat
history;
4. Provision of short and uniform residence time distribution to
minimize heat history;
5. Provision of predse temperature control over the process to ensure
narrow temperature distribution throughout the process and at
discharge, again to regulate and minimize heat history.
Using the above discussed factors as the criteria for analysis, the
processor can select either aseparate or in-line system, whichever is
most effident for his needs. Each has its merits and each. its limitations.
A batch system may be considered more flexible since it need not be
tied in with other in-line equipment, but, on the other hand, batch to
batch variations, for whatever reason, may not be acceptable in the final
product. A continuous system should give a consistent product, but to
be fully effective it must have the back-up of reliable feeding and take-
off equipment.
Some of the factors which need to be considered in the choice of
machinery have been dealt withi the various categories of machine
available and the important features of each category [20-32] are
discussed next.
5.3.2 BATCH MIXERS
A. Open mills
The mixing mill predates all the other mixing devices [21]. Originally
many mixing operations were carried out on two- or three-roll open
mills [20]. As shown in Figure 5.5, it consists of two counter-rotating
differential speed rolls with an adjustable nip and imposes intense
shear stresses on the material as it passes the nip.
The major component, Le. the polymer, is first melted by the
introduction of heat to the rolls and from the shearing action between
the rolls. Once the polymer is melted, fillers and other additives are
introduced.
Extensive mixing takes place at the entrance of the nip due to
extensional flow. Intensive (dispersive) mixing is accomplished in the
nip. To achieve homogenization some means of lateral mixing of the
banding action must be included. There is little transverse mixing and
thus constant operator attention is needed to displace the strip trans-
versely. Folding of the sheet by the operator prior to reintroduction to
the milling action takes care of a random plug flow distributive mixing.
This method allows very good temperature control of the product
since the rolls can be cooled or heated and they present a very large
surface area to the polymer system. The region of high shear is very
Figure 5.5 Schematic diagrams of a two-roll open mill showing the banding action
and nip. (Reprinted trom Ret. 20.)
small avoiding large temperature build-up. The degree of dispersion

obtained with such a system can be very high.
The two-roll mill is a mixer ideally suited to the processing of high
viscosity materials and was used by Birchall et al. [33] to produce very
high solids content moldable cement pastes. Although still available for
use, this type of system would not be considered for anything but very
specialist operations.
Obvious disadvantages arise from the open nature of the operation,
difficulty in obtaining an initial melt and initial incorporation of
pigments and fillers, giving long cydes. The system is inevitably dirty
and it is difficult to achieve a uniform product.
B. Internal mixers
The internal mixer too is among the oldest members of the mixer family.
The cross section of such a mixer is shown in Figure 5.6. It has adopted
the open mill mixing principle but has a completely endosed mixing
chamber in which two rotors are mounted. The rotors are sealed at each
end to avoid leakage of material from the chamber. The internal mixer
is generally a very high powered machine with drives up to 3000 kW
for a machine with 600 litre mixing chamber [20]. Maximum capacity is
about 1000Ib/batch, and depending upon the material to be mixed,
production rates can be as high as 40 batches/hr.
Three different mixing actions take place in the internal mixer [21]:
intensive or dispersive mixing around the tips of the rotor blade;
extensive mixing due to simple shear flow and extensional flow
between the chamber walls and the cylindrical portions of the rotors
and in the entrance region to the narrow gaps between rotor tip; and
distributive mixing due to random plug convection, as a result of the
interaction between the two rotor tips.
The rotors can be fully intermeshing in which case they must
obviously rotate at identical speeds, or non-intermeshing when, as on a
two-roll mill, friction ratios (generally 1.3 to 1) can be applied. The
speed of the rotors can be changed and even varied during the mixing
cyde. It can be lowered for a certain period of time to cool the material
down and then increased again to restart the mixing. The residence
time of the material in the mixer, for instance, can be changed by
changing the cyde time. eyde times as low as 2-3 minutes are daimed
and with use of refrigerated cooling still shorter times may be made
possible. The amount of material put into the chamber can be varied to
change the intensity of mixing and the cyde can be interrupted to add
material at times which are most favorable to obtain optimum results.
An internal mixer is never operated completely full of material, though
pressure is maintained in the mixing chamber by me ans of a piston or
Figure 5.6 Cross-seetional view of an internal mixer. (Reprinted from Ref. 21 with kind
permission from John Wiley & Sons, Ine., New York, USA)
ram. It is found that by inereasing ram press ures eertain polymers ean
be eompletely massed even without heating to rotors or ehamber.
One of the earlier shorteomings of the internal mixer system when
used for polymers was that of the single mass form of diseharge, whieh
was diffieult to handle. Nowadays effeetive dump extruders are
employed which can accommodate up to three batches from the mixer
to give a continuous product through some form of pelletizing system.
These dump extruders can be fitted with screens for elimination of
agglomerates or foreign matter, and venting ports for removal of
volatiles.
One of the problems inherent in an internal mixer is that of batch to
batch variation in the product. However, accurate automatie weighing
Table 5.3 Advantages and disadvantages of the internal mixer
Advantages
Versatility of operations
Generally good temperature control
Robust machines
Relatively simple to operate
Short mixing times
Disadvantages
High capital cost
High and uneven power load
Batch to batch variations dependent on accurate feeding and process control
Rapid temperature rise needs good control
Source: Ref. 20.
and dosing devices minimize changes in formulation, while automatie

cyde control operating on parameters such as temperature, time or
power input can reduce mixing variations. In fact, the internal mixer
can be incorporated into a continuous flow of production by complete
automation and buffering of its pulsating output.
The advantages and disadvantages of the internal mixer are
summarized in Table 5.3. The three most common internal mixers
available are those of Farrel Bridge (Banbury), Frances Shaw (Interrnix),
and Guix. The internal mixer is certainly a versatile equipment and its
operation can easily be adapted to a wide variety of mixing problems.
Prime applications are for rubber and PVC compounding. These equip-
ments are also being used for processing polyolefins, ABS, and
polystyrene, along with thermosets such as melamines and urea.
In the tire industry which faces the most difficult mixing problems,
this type of mixer is still practically the only accepted mixing device.
The tire industry has accepted the fact that the batch type mixer will
not be replaced by a continuous mixing device in the near future,
especially since the radial ply tire came into being, because this tire
requires very tough types of rubber. The same is not the case as far as
the plastics industry is concerned. In fact, predictions made several
years ago that the batch type mixer will disappear and be replaced by
continuous mixing equipment has come true in the filled polymers
industry. Some of the continuous mixing devices are discussed below.
5.3.3 CONTINUOUS COMPOUNDERS

To meet the present demands for higher product quality and
uniformity, combined with higher volume requirements, continuous
compounding equipments are required [17]. In continuous com-

pounding systems, variation between batches is eliminated and the
possibilities of human error are minimized. Because of economics and
the large volume requirements of filled polymers, continuous systems
are usually preferred. Any effident processing system will allow the
compounder to operate economically at high volume, and continuous
compounding systems, being more effident than batch systems, have
capadties of 3000 kg/hr and higher [16]. The two essential elements in a
successful. continuous system are absolute control over residence time
and residence time distribution.
Continuous compounding and mixing [23,24] is accomplished by a
variety of machines ranging from single-screw to twin screw extruders
with variations in design and additional equipment units to achieve a
range of end products. The type of compounder or mixer chosen
depends upon the spedfications and properties required of the end
product, volume requirements, overall economics, and whether the
compounding is done in-house or by a custom compounder.
The basic functions of any compounding extruder are to melt the
polymer and to introduce a closely controlled amount of shear energy
into the melt to properly disperse and distribute additives or fillers.
A. Conventional single screw extruders

The simplest form of continuous compounding equipment is the single
screw extruder [20,25]. The single screw extruder has been used for
many years in polymer forming operations. The advantages and
disadvantages of the single screw extruder are given in Table 5.4. There
is much to be said for the mechanical simplicity of such machines,
where motor drive can be transmitted through a straightforward gear
box designed to accept the high thrust forces generated.
labte 5.4 Advantages and disadvantages of the single screw extruder
Advantages
Mechanicaily fairly simple
Relatively easy to operate
Capable of high pressure generation
DIsadvantages
Lack of positive conveying characteristics
Limited compounding and homogenizing capabilities
Large machines with long LID
Source: Ret. 20.

In the single screw extruder, aseries of unit operations combine to

transform the solid polymer in pellet or granular form at room
temperature to a molten mass at elevated temperatures and further
drive the mass at sufficiently high pressures into downstream shaping
devices. The sequence of events is accomplished by different sections
of the screw, namely, the feed, melting and metering zones. The
polymer pellets or granules (virgin or sometimes in combination with
regrind of scrap) are normally fed to the extruder throat through a
conical hopper. The hopper geometry, the height of the fill and the
physical properties of the particulate solids dictate the rate of delivery
of solids to the feed zones of the extruders as weIl as the press ure under
the hopper. The feeding through the hopper relies on the influence of
gravity as weIl as the interparticle and particle/wall friction forces for
the rate at which the material is picked up at the extruder feed throat.
At times there are aberrations such as arching, piping and funneling
flow in the hopper because of which the feed is improper and
uncontrolled. Feeding by hopper is at times referred to as 'flood
feeding' as against 'starve feeding' which occurs when material is
metered into the extruder feed throat by special feeding devices at
controlled rates.
Single screw extruders [9,10,34] are pumps that convey the material
by a combination of pressure and drag flows. The operation of a single
screw extruder relies on the frictional forces between the polymer and
the barrel to push the polymer forward. When the ratio of polymer /
barrel friction vs. polymer/screw friction is low, then the polymer will
adhere to the screw and simply rotate with it, resulting in no forward
motion. If the ratio is high enough, then forward motion will occur. The
lack of positive displacement characteristics means that the machines
are far from self wiping.
The section which is downstream of the feed zone is the melting
zone. When frictional forces are present, their energy becomes apparent
as heat, resulting in increased product temperatures. This effect assists
the melting process, which is enhanced by press ure generation in the
screw. At times, very large temperature differentials are generated
between melt and unmelt. In an extreme, the region of unmelt may be
surrounded by low viscosity melt and effectively insulated from the
thermal or shear energy of the screw.
The actual melting process in a single screw extruder is fairly weIl
understood [34-47], and a good understanding of the extruder action
too has been developed due to theoretical and computer modeling
[48-51]. It is now widely accepted that, in a cold feed extruder, melting
occurs at the barrel and screw surfaces and a melt pool accumulates on
the leading edge of the extruder screw fight (see Figure 5.7). Melting of
the solid bed takes place slowly over a length equivalent to several
SOLID
FIIJ4 OF
B.ARiEL MOLTEN MELT
SUiFACE POLYMER INT.ERPACE SOLID
I
FUGBT-~v
cm.CUI.Aroi,Y
FLOWOF ~~"#I
PREVlOUSLY
YEL.11ID
POLYMEll
Figure 5.7 Melting process in the conventional single screw extruder. (Reprinted Irom
Rel. 29 with kind permission Irom Society 01 Plastics Engineers Inc., Connecticut,
USA)
screw diameters and the rate of melting is dependent on heat transfer

across the relatively small interfacial area with the melt. Eventually the
solid bed breaks up and complete melting is finally achieved. This
gradual process often results in very long screws and length to
diameter ratios as high as 30: 1 are not uncommon. Single screw sizes
may range from 0.06 m to 0.2 m in diameter with lengths of 20 to 42
times length to diameter ratio. The fact that the process is gradual does
mean that different regions of polymer within a flight experience
different thermal histories. Difference in heat history often can lead to
non-uniformity of the product.
The conventional single screw extruder is designed mainly to melt
material and to pump it against press ure [21]. The flow rate Q with
which the material is transported is expressed by the following
equation
- -(P)
Q=aN- ;j (5.12)
The extruder is also capable of mixing because of the shear action

which moves the material along a spiral path through the screw
channel. This happens in the metering zone which is downstream of
the melting zone. However, the degree of mixing in the conventional
single screw extruder is somewhat limited owing to the fact that the
movement of the material through the extruder and the mixing action
are derived from the same shearing action.
In the conventional single screw extruder, fluid flows through a
channel of approximately rectangular cross section with either variable
or constant depth. The two sides of the rectangle are the leading and
trailing surfaces of the flight, the botlom corresponds to the screw root,
and the top is the inside surface of the barrel. Fluid mechanical analyses
are based on a frame of reference fixed to the channel. For shallow
channels, curvature effects can be neglected and the channel visualized
as being uncoiled and laid flat with barrel as an infinite flat plate
moving diagonally across the channel at an angle defined by the angle
of the helix. Unlike the more complex extruders,the helical flow
behavior in single screw machines is weH characterized [52] and well
documented in books [34,53].
Fluid is conveyed forward along the channel as a result of the drag
flow induced by the axial component of the relative motion between
the barrel and the screw, while apressure flow builds up in the reverse
direction due to the resistance offered by the die at the outlet. The axial
flow largely determines the extruder throughput, but it is the trans verse
flow, generated by the transverse component of barrel rotation, that is
primarily responsible for mixing. An element of fluid traces a helical
path as it undergoes deformation in its passage through the channel;
the helix angle at any point being determined by the local velocity field.
Simplified velocity profiles based on the work of Carley et al. [54],
which neglects end effects at the flights, provide the basis for most
theoretical analyses of mixing in extruders. Although most materials to
be mixed in extruders exhibit non-Newtonian behavior, Newtonian
behavior is frequently assumed for simplicity. Extensions to account for
purely viscous non-Newtonian effects are straightforward [34,55] and
few significant qualitative differences in mixing behavior are observed.
Mohr et al. [2] were the first to theoreticaHy investigate the mech-
anism of mixing in extruders; they assumed an inverse linear relation
between the striation thickness and strain by analogy to large uni-
directional shear. McKelvey [10] used an average strain as a measure of
mixing. Pinto and Tadmor [56] extended this approach to account for
the distribution of strains experienced by different fluid elements. Bigg
and Middleman [55] obtained similar relations for power law fluids,
and Erwin [57] presented modifications to account for the effect of
mixing sections.
In the mixing aspect of the extrusion process, velocity distributions
and, subsequently, stress distributions are the most important
parameters [18]. The stress distribution inside the screw channel
determines the degree of mixing which can be achieved (Figure 5.8).
The mixing action in the extruder channel occurs only on the portion of
c-, (+, T,t
VELOCITY DISTRIBUTION OF STRESS DISTRIBUTION OF

DOWN CHANNEL FLOW DOWN CHANNEL FLOW
VELOCITY DISTRIBUTION OF STRESS DISTRIBUTION OF

CROSS FLOW CROSS FLOW
Figure 5.8 Velocity and stress distributions in single screw extruders. (Reprinted from
Ref. 18 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA.)
the material which passes over the flights as it alone is exposed to the
shear action.
The velocity distribution in the extruder channel in the down channel
and the cross channel direction result in the spiral path of the material.
The material does not back flow even at higher back pressures, but
rather moves back and forth in a spiral fashion over a relatively short
distance. Due to the spiral motion, the residence time in the extruder is
reasonably uniform but the mixing action is very limited.
By observing the velocity and stress profile of down channel and
cross flow, it can be seen that the zero shear point exists inside the
channel. In this area, very little or no mixing will occur. This has been
confirmed by actual experiments.
Further, the lack of effective reorientation of the material elements at
the flights causes the bulk of the interfacial area to be oriented parallel
to the channel bottom in a relatively short downstream distance,
regardless of the initial orientation. Consequently, the mixing achieved

in single screw extruders is generally poor [58]. Efforts to improve the
mixing effidency of the single screw extruder have, therefore, never
ceased.
B. Modified single screw extruders

When mixing is required then variations to the basic machine are
usually considered. This involves installing mixing devices which
would shift the zero shear stress point to various locations in the screw
channel and hopefully achieve an adequate mix, if the equipment has a
suffident processing length. Most of these devices are designed to break
down the smooth flow of material through the extruder, thereby mixing
the melt with unmelt to give a more uniform distribution of polymer.
(Figure 5.9).
The devices being used include spedalized screws for use with
mixing flights or pins along with variations in pitch and screw form
designed to break down the normal melt pattern or smearing seetions
where the polymer stream is forced over narrow gaps in the screw.
There are a number of single-screw systems available with improved
mixing devices such as the EVK, the fluted screw, the Maillefer type
and others, which improve the mixing effidency of the flow by
redistribution of streamlines and reorientation of the intermaterial area
at the expense of only a small increase in power requirements.
In the simplest mixing device consisting of mixing pins, each mixing
pin divides the helical flow into two streams, which are again combined
into one upon passing the pin. This leads to growth of the interfadal
area upon the division and combination of flow and introduces further
velodty gradients, thereby increasing the total strain on the material.
In the patented EVK screw design, material distributing elements are
installed over the whole length of the screw which ensure an
homogeneous temperature distribution. The screw length and shearing
clearance requirement, however, vary depending on the material to be
processed and the type of filler used. Wherever the same material
formulation is run continuously without any major changes, the system
performs quite well.
In the fluted screw design, the barrier-type restrictions basically
introduce narrow, albeit short, gaps through which all the melt
elements are forced to pass at high shear stresses. This brings in some
level of dispersing action besides reorienting the interfadal area,
redistributing the streamlines and increasing the imposed total strain.
These barriers may take different forms. A simple form is the dams or
series of dams of almost the full channel height welded ac ross the
channel at selected locations. The potential problems with the fluted
Parallel interrupte-d mixing tlights
Mixing pins
Ring barr ier type
Union carbide fluted mixing section

barri.r type
Und.reut spiral barrier type
Figure 5.9 Mixing section designs in single screw extruders. (Reprinted trom Ret. 25
with kind permission trom The Institution ot Chemical Engineers, Rugby, UK.)
screw are the hold-up of the material and dead spots [59,60]. These can
be minimized by proper selection of the helix angle, tapering the inlet
channel to zero depth and by reversing the depth profile in the outlet
channel.
In the Maillefer type screw design, there is a spiral barrier or
secondary screw flight extending over the entire length of the modified
section of the screw. The mass and force balances across the Maillefer
type screw are available [61] and can be used to estimate the increase in
power requirements due to this modification. Additional barriers or
flights may be introduced to split the flow into two or more streams,
which in the limit arrives at aseries of longitudinal grooves or flutes
spread around the circumference of a cylinder.
Static mixers, Le. those which are motionless and do not contain any
moving parts, may be incorporated into single screw extruders between
the screw and the die in order to introduce distributive mixing. A
review of the various types of static mixers, their mixing characteristics
and performance is available [62]. They consist of a string of alternating
right and left handed helical elements fixed in a tubular housing which
helps in splitting and recombination of streams, resulting in a predicted
increase in the number of striations. The energy for mixing is derived
from the pressure loss incurred as the melt flows through the static
mixer. On account of the substantial pressure drop introduced by a
battery of these mixing elements, they have restricted use in filled
polymer melt systems especially those with higher loading and high
viscosities.
Many different modifications of the geometry of the single screw
extruder have been contrived (all of which are not described herein)
but even then, the achievable level of dispersion of fillers is limited.
Improvement in filler dispersion can be achieved only by powerful
shear forces. If the speed is increased to intensify mixing, the output
increases at the same time, whereby back pressure control is lost but,
more importantly, the energy input to the polymer due to the viscous
shear forces rises even more rapidly and can lead to excessive melt
temperatures. It is this heat build-up which eventually limits screw
speeds to even as low as 100-150rpm.
In summary, the limited compounding and homogenizing ability of
single screw extruders usually restricts their application to straight-
forward melting and extrusion operations but use of mixing devices
can extend their range. Their favorable economics makes them
attractive for low volume compounding jobs especially for filled
systems of mainly commodity plastics [63]. For tougher applications,
such as compounding fillers with engineering polymers at low as well
as high loadings, single screw kneaders and twin screw extruders are
more ideally suited.
C. Single screw kneaders

This form of continuous compounding equipment may appear as a
variation of a single screw extruder. But truly it is not and hence not
included in the category of modified single screw extruders, because of
the radically different mixing action in it [27,64].
In this single screw compounding equipment, various types of
protrusion, grooves or profiles are built into the barrel with correspond-
ing elements along the flights of the screw in the particular section
known as the 'kneading seetion' as shown in Figure 5.10. This induces
dispersive mixing as the material passes repeatedly through the high
shear stress zones in the narrow gaps formed by the interrupted screw
flights and the kneading teeth on the barrel (Figure 5.11). The mixing
action is unique in that the rotational motion gets superimposed by
reciprocating motion, thereby giving a kneading effect to the melt. This
results in a good dispersion of fi11ers in the polymer system even at
relatively low shear rates, thus a110wing good processing control for
temperature sensitive materials.
The kneading action is illustrated in Figure 5.12. It can be seen that
the kneading teeth wipe off a11 the corresponding flanks of a flight
during one fu11 turn, and the material thus gets subjected to high shear
stresses in the sma11 gap between the flight flank and the barrel teeth,
thereby giving good dispersive mixing. As a consequence of the good
mixing action such extruders are generally only one half or even one-
third of the length of conventional single screw units. Further, since the
unit does not generate high pressures, when pe11etized product is
required, the kneader is generally coupled to a single screw extruder to
pump the polymer up to die pressures.
COOIJID SOLmS CONVEYlNG SECT.lON
++--- mD SCUW
r-~~..J
KNEADINQ SCREW
roms
Figure 5.10 Schematic diagram of a single screw kneader. (Reprinted from Ref. 23
with kind permission from Gulf Publishing Co., Houston, Texas, USA.)
1 spur BAlUW.
2 BEATING JACKET
3XNEADINGTOOTH
4 SCREW FUOlIT
SNAllOW GAP
6 CLAMPING B.AR
Figure 5.11 Cross-sectional view 01 a single screw kneader. (Reprinted lrom

Rel.20.)
Typical examples of the single screw kneader are the Buss Ko-
kneader and the Baker-Perkins Ko-kneader.
D. Twin screw extruders

Twin screw extruders evolved as a result of the desire to overcome
some of the limitations of single screw extruders [65]. They are the most
expensive mixers per kilogram of output. The advantages of twin screw
extruders are listed in Table 5.5. The term 'twin screw extruder' is
basica11y a generic term but to treat a11 twin serew maehines in one
general eategory is truly not eorreet. Various types of twin serew
extruders are eommercia11y available and these differ widely in their
operating principles and funetion [18] as ean be seen from Figure 5.13.
They differ in their abilities for distributive and dispersive mixing and
henee in their applieation areas. A possible classifieation of twin serew
extruders [30] is shown in Table 5.6 along with eommercial examples
for eaeh eategory. However, it should be borne in mind that this listing
is by no means exhaustive. The main distinetion is made between
intermeshing and nonintermeshing twin serew extruders (Figure
STAlTIN'O POsmON FUU.. TOl\N

COUPI..E'IliD
Figure 5.12 Kneading action in a single screw kneader. (Reprinted from Ref. 23 with
kind permission from Gulf Publishing Co., Houston, Texas, USA.)
Table 5.5 Advantages and disadvantages of the twin screw extruder
Advantages
Positive displacement characteristic gives throughputs independent of the nature of
the product being processed
Earlier and more complete melting allows machines to be shorter and gives better
mixing
Self-wiping characteristic avoids any product hang-up in the machines
Disadvantages
High capita/ cost
Mechanically more comp/ex with difficu/ties of fitting adequate thrust bearings to
two closely positioned shafts
Source: Ref. 20.

SCREW SYSTEM COUNTtRROTATING COROTATING

ENGAGEMENT
~. .
LENGTHWISE AND THEORETICALLY
NOT POSSIBLE
i CROSSWISE CL.OSED 1 2
~~
... w
~~w
LENGTHWISE OPEN
AND
CROSSWISE CL.OSED 3
THEORETICALLY
NOT POSSIBL.E 1;4 4
I ~
,
I:z: I-
l!': L.ENGTHWISE AND THEORETICALL.Y POSSIBL.E c ..
....'" =1=
I
BUT PRACTICAL.L.V
CROSSWISE OPEN 5 NOT REALIZED ~i!I~ 6
L.ENGTHWISE OPEN
~ 8 NOT POSSIBLE
AND THEORETICAL.L.Y
Cl)
CROSSWISE CLOSEO 7
~~
s13
1-:2
a:a:
iH!
LENGTHWISE AND 9A ~ 10A ~
CROSSWISE OPEN
~ IOB~
l!':
9B
Cl) Cl)
z z
% %
~ ~
1-'" 1-f3 L.ENGTHWISE AND
0 141 o~
z:E
a: za: CROSSWISE OPEN
~
l!': ~ 11 12
Figure 5.13 Types of twin screw extruders. (Reprinted from Ref. 18 with kind
permission from Society of Plastics Engineers Inc., Connecticut, USA)
5.14(a, each of which may be divided on the basis of the direction of

the rotation of the screw into co-rotating or contra-rotating (Figure
5.14(b, also termed counter-rotating.
The benefits and the drawbacks of each system have been discussed
in many publications. However, arguments in favor of one system more
often seem to be based on a personal preference or bias than on an
objective engineering analysis. The plain fact that the systems have
coexisted for a number of years must be sufficient evidence that these
systems fulfil a practical need. In some applications, the co-rotating
extruders may be better suited; in other ca ses, counter-rotating
extruders may be preferred. For many filling operations, however, twin
screw co-rotating systems have the widest application because of their
high degree of flexibility. Instead of arguing against or in favor of a
particular system, it is more useful to determine both the advantages
and the disadvantages of the systems and to identify the applications
for which each system would be best suited.
The first known twin screw device was an intermeshing co-rotating
extruder invented in 1939, and patented in 1949 [66]. Developments in
twin screw extruders have come a long way since then. The mech-
anisms of different types of twin screw extruders shown in Figure 5.13
make a distinction between axially open machines, where there is a
labia 5.6 Classification of twin screw extruders
Low speed extruders
-LMP Colombo
-Windsor
-Bamberger
Corotating extruders
High speed extruders
-Werner and Pfleiderer
-Baker Perkins
-Berstorff
Intermeshing extruders Conical extruders

-Kraus Maffei
-Cincinnati Milacron
-AGM
-Cylindrical extruders
Counterrotating extruders -Leistritz
-Kraus Maffei
-Maillefer
Twin screw extruders -Reifenhauser
-Mapre
-Kesterman
- Troester, etc.
Equal screw length

-Bausano
-Japan Steel Works
Counterrotating extruders 1
. Unequal screw length
Nonintermeshing extruders I -Welding Engineers
Corotating extruders -No commercial examples known
Source: Ref. 30 (reprinted with kind permission from Society of Plastics Engineers Inc., Connecticut, USA).
intermeshing non.jntermeshing
(a)
00
co-rotatlng co-rota ting
contrarotating
00 contrarotating
(b)
00
Figure 5.14 Diagram showing the difference between (a) intermeshing and non-
intermeshing as weil as (b) co-rotating and contra-rotating or counter-rotating types
01 twin screw extruders. (Reprinted Irom Rel. 20.)
continuous passage between the inlet and outlet, and the axially closed
machines, where the passage is interrupted at regular intervals.
Considerable variations of screw design are possible to balance
pumping and mixing characteristics [67]. The right-handed, forward,
regular flighted elements shown in Figure 5.13 are only one of many
types of elements employed in twin screw extruders. The other types
may include left-handed, reverse, regular flighted elements, forward
and reverse kneading discs, shearing discs, etc.
Most twin screw extruders can be assembled using the building block
principle, which involves the use of screw elements of different
lengths/pitches and special kneading elements of various widths
available as blocks that are interchangeable. This makes it possible to
design the processing section exact1y as required for obtaining optimum
processing conditions because the screw elements and kneading
elements blocks can be varied to tailor-make the screw configuration for
the shear intensity required by a specific material. If properly designed,
twin screw extruders provide maximum process control, especially

with respect to shear and stock temperature. Also, twin screw com-
pounders aHow the removal of large quantities of volatiles.
The diversity among twin screw extruders is so large that a compre-
hensive discussion of aH the various types would be an enormous
undertaking. A description of some of the important characteristics of
three basic types of twin screw extruders is given below. Non-
intermeshing co-rotating twin screw extruders are not produced
commerciaHy and hence are not treated in this section.
(i) Intermeshing co-rotating screw extruders

These have the flights of one screw protruding into the channel of the
other screw, thereby providing positive displacement pumping [68]
when both screws rotate in the same direction. The degree of
intermeshing can range from almost fuHy intermeshing to almost non-
intermeshing with a corresponding range in the degree of positive
conveying characteristics. The design of intermeshing screws includes
variations in lengthwise and crosswise open and closed positions,
which directly affect the conveying conditions, the mixing action, and
the pressure buildup capacity of the screw system.
Co-rotating twin screw extruders are commonly produced only as
fuHy intermeshing and operate on the building block principle. De-
pending on the requirements of the compounding task at hand, proper
screw elements are selected and assembled along with the right choice
of kneading elements blocks. Commonly employed elements include
right-handed and left-handed (forward and reverse) regular flighted
elements, forward and reverse kneading discs, as weH as mixing and
shearing pins. For regular flighted elements, fully intermeshing co-
rotating screws are open lengthwise, but are closed crosswise, except
for leakage over the flights.
When the twin screws are intermeshing, the extruder can be
considered to be self-wiping, that is, all the surfaces within the
processing chamber are wiped of polymer. This characteristic is
important when heat sensitive materials are being processed. Self-
wiping is advantageous to the operational economics as the screws
require much less downtime for cleaning. Efficient self-wiping ensures
no material hang-up in the machine and can be demonstrated by a
short residence time distribution for the material being processed
(Figure 5.15).
In intermeshing co-rotating twin screw extruders, self-wiping
characteristics can be improved through the use of kneading elements
within the screw configuration which can allow varying degrees of
mixing energy to be developed in the machine. Such elements are
lNDICAIOR t-- GOOD SELP WlPING

CONCEN-
l'RATION
,------
- -- .... ~ POOR SELF WlPING
Figure 5.15 Residence time distribution for selt-wiping twin screw extruders.
(Reprinted from Ret. 25 with kind permission trom The Institution of Chemical
Engineers, Rugby, UK.)
particularly useful in achieving good dispersion of fillers in the

polymers. The co-rotation of the screw helps in the homogenization and
dispersion because material is transferred back and forth between the
screws.
Co-rotating twin screw extruders allow for the possibility of adjusting
the amount ofaxial mixing. Mathematical modeling can be found in the
works of Erdmenger [69], Armstroff [70], Kim et al. [71] and Booy
[72,73]. Mixing studies were done by Todd [74], Wyman [75], Maheshri
and Wyman [76,77]. Experimental data have been obtained by Wemer
[78], Jewmenow and Kim [79], and Kim et al. [71,80,81].
In co-rotating machines, the flow pattern of polymer system is such
that the material is actually conveyed in a figure 8-shaped pattern.
Observing the velocity profile and the shear stress distribution for co-
rotating machines as shown in Figure 5.16, it is seen that zero shear
stress point can be influenced by operating variables, such as by
changing the throughput and/or screw speed as well as by changing
geometry. It is imperative that uniform stress distribution is
maintained even with increased throughput. This is possible in co-
rotating machines, because the degree of uniform dispersion is direct1y
related to stress/ strain distributions, and the most uneven stress
distribution occurs at c10sed discharge which is meaningless in actual
operation. In co-rotating machines, the proper selection and arrangement
of individual screw sections and kneading elements [82] is customary in
(T) (T) (1. )
--v.-<l4 32 _ Vo 3 2 0- 3 2 2
'7 -.Q... , o Vo
oo l!.l
V -
'7- '7- o
'7-
h 0.1 h 0.1 h 0.1 h
0.2 0.2 0.2
0.3 0.3
0.4
0.5
0.6 0.6
0.7 0.7 0.7
0.8 0.8 0.8
0.9 0.9 0.9
1.0 1.0 1.0 1.0
Y Y Y Y
2 h Y. h h h
Yoz
-:-
Y. Y.
-2!.. = I ~Z -1.5 ....2!. -+00
h 3 h h
A B C 0
Figure 5.16 Shear stress distribution in a co-rotating twin screw extruder. (Reprinted fram Ref. 18 with kind permission fram Society of
Plastics Engineers Inc .. Connecticut. USA.)
(4.) (b)
Figure 5.17 Screw design for (a) co-rotating (b) counter-rotating twin screw
extruders. (Reprinted trom Ref. 18 with kind permission trom Society ot Plastics
Engineers Inc., Connecticut, USA.)
order to further improve the uniformity of stress distribution (Figures

5.17 and 5.18).
Depending upon the design of the screw, number of tips or flights,
the material forms a number of continuous tapes which spiral around
both screws. In a three flighted screw, the material moves in five
parallel channels which are continuous from one end of the extruder to
the other, similar to a multi-flighted single screw. By selecting different
numbers of flights, the intensity of the shearing action can be changed.
Special shearing sections can be arranged between screw sections to
perform intensive dispersive mixing.
Co-rotating screws usually achieve compression by some means of
restriction, either in the barrel or on the screw themselves. Overlapping
disc or reverse flight screw threads can achieve the desired effect.
Transfer of product from one screw to the other ensures rapid
homogenization of melt with unmelt resulting in earlier and more
complete melting in a relatively short distance. As a consequence of this
rapid melting, co-rotating twin screw extruders tend to be much shorter
than comparable single screw units.
The residence time in the co-rotating twin screw extruder is in
general more narrow than in the single screw extruder. Because of that
uniformity, it is possible with a twin screw mixer, provided it is
properly designed, to achieve the desired degree of mix with less
Figure 5.18 Screw design with kneading elements for co-rotating twin screw
extruders. (Reprinted trom Ref. 18 with kind permission from Society of Plastics
mechanical energy input and, therefore, less heat buildup than with
other mixers.
By starve feeding of a twin screw mixer, the amount of mechanical
work input to the material can be varied. The materials to be mixed
have to enter the twin screw mixer continuously in their proper
proportions because the twin screw mixer, owing to the fact that the
material passes through in almost a plug flow fashion, does not
intermix in the axial direction. Since the material in this extruder is
transported by positive displacement and not by frictional and viscous
forces, the melt temperatures do not rise and, in fact, generally heat has
to be applied externally.
The intermeshing co-rotating extruders can be further subdivided
into low and high speed machines as can be seen from Table 5.6. These
low and high speed extruders are very much different in design,
operational characteristics, and applications. The low speed extruders
have a closely fitting flight and channel profile. Therefore, they have a
high degree of positive conveying characteristics. However, because of
the small mechanical clearances, they have to run at low screw speeds
(generaHy 10-20 rpm) to avoid buildup of high local pressures that
cause machine wear. These machines are used primarily in profile
extrusion applications.
In high speed co-rotating extruders, the design is such that there is
considerable opportunity for the material to leak back from one screw
channel into a channel of the other screw. Thus, these machines have a
low degree of positive conveying characteristics. Because of the open-
ness of the channels, material is easily transferred from one screw to
another and pressure generation in the intermeshing region is less
pronounced. This allows extruders to run at high screw speeds, as high
as 500 rpm. These machines are primarily used in compounding
operations, where use is made of the high shear rates and frequent
reorientation of the material in the extruder.
(ii) Intermeshing counter-rotating twin screw extruder

This acts as a positive displacement pump due to the intermeshing
of the screws as discussed earlier. The conveying capa city of the
machine is virtuaHy independent of the nature of the material being
processed, especiaHy when the screws are counter-rotating. However,
it should be noted that fuH intermeshing is necessary but not
sufficient condition for positive conveying. In some geometries, there
is very little sealing of the screw channels, even when the screws are
fuHy intermeshing. Positive conveying requires that the screw
channels are closed off so that the material contained in the various
channel sections is fuHy occIuded. Any amount of back leakage into
upstream channel seetions will adversely affect the positive conveying

behavior. The output in volume per unit time is given by the
difference between the theoretical flow rate and the sum of the
leakage flows described in Figure 5.19
(5.13)
where m is the number of thread starts per screw, Vc is the volume of
the C-shaped channel between the flanks of successive flights and N is
the rotation rate. Qr is the leakage between screw flight and barrel wall,
Qc is the leakage between the screw flight and the other screw, Qt is the
leakage between the flanks of screw flights and Qs is the leakage
between flanks perpendicular to the plane through the screw axis. The
leakage paths have a strong influence on residence time in the extruder.
The intermeshing point for counter-rotating screws acts as a 'calender
nip' forcing material through it. Only a small proportion of the material
passes through the nip between the screws, while the remainder is
carried along axially in closed chambers. Since the relative speeds of
TRANSPOllT DIRBC'IION
Figure 5.19 Leakage flow paths in an intermeshing counter-rotating twin screw

extruder. (Reprinted trom Ret. 65.)
the two screws must be identical, high 'calender nip' shear forces are
not genera ted. Material is forced through the nip but then out against
the sides of the barrel. This effect can aggravate sticking to the barrel
walls. The passage of material between the 'calender nip' generates
normal stresses which tend to force the screws apart leading to
potentially higher barrel wear and limitations on screw speeds for
counter-rotating screw extruders. This is one of the reasons why
counter-rotating extruders generally operate at lower screw speeds than
co-rotating units, typically at less than 200 rpm [83].
Oue to the lower relative velocities of the screws at the meshing
point, the shear stresses in the counter-rotating extruders would be
lower. In an analysis of the velocity and stress distribution in counter-
rotating twin screw machines, it is seen that there is actually no
improvement regarding velocity profile and zero shear stress point
location, in comparison to single screw machines. When superposition
of the shear stress distribution of down channel and cross flow (for a
given coordinate system) is done for counter-rotating machines, a
characteristic minimum inside the screw channel is observed in the area
of y/h = 0.38 (Figures 5.20 and 5.21). Shearing takes place in each
individual spiral chamber between two contacts of the faces of flights
with the surface of the root of the screw. The residence time distribution
is therefore very narrow which is important for processing of heat
- - - . I o t - - - - - - t 1.0
Y
h
COUNTER-ROTATING MACHINES:
SUM OF STRESSES OF DOWN CHANNEL
AND CROSS FLOW COMPONENTS
Figure 5.20 Sum of stresses of down channel and cross flow components for
counter-rotating twin screw extruders. (Reprinted from Ref. 18 with kind permission
from Society of Plastics Engineers Inc., Connecticut, USA)
-+-1
I :' "
~\\
DOWN CHANNEL FLOW CROSS FI,.OW
Figure 5.21 Schematic flow orientation in counter-rotating twin screw extruders.

(Reprinted from Ref. 18 with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA)
sensitive materials. The mlxmg efficiency can be increased by the

introduction of special mixing seetions.
Since closely intermeshing counter-rotating twin screw units convey
material by positive displacement in aseries of closed C-shaped segments,
compression is generally achieved, as in single screw extruders, by
continuously decreasing the pitch or the flight depth. Thus the melting
process can be an extended one and takes place gradually over a length
equivalent to several diameters. Intermeshing counter-rotating twin
extruders are available with conical as well as cylindrical screws.
Conical twin screw extruders provide more space for the installation of
thrust bearings while the cylindrical ones have the advantage of being
amenable to be built by the building block method [30].
The intermeshing counter-rotating twin screw extruders are normally
used when narrow residence times for compounding are required, for
example, PVC profile extrusion and color-concentrate preparations [84].
(iii) Non-intermeshing counter-rotating twin screw extruders

These have the two screws rotating at the same frequency in different
directions with the respective screw flights placed either facing each
other or in a staggered fashion. Since the flights of one screw do not
protrude into the channel of the other screw, the kinematics of the melt
flow are quite similar to those in a single screw extruder except for the
difference caused by the interaction of the flow field between the two
screws. The meeting of the streams at the interface between the two
screws increases the efficiency of extensive mixing and hence non-
intermeshing counter-rotating twin screw extruders perform better than
single screw extruders when called upon to do the same job. In fact it
has been shown experimentally that the leakage flow at the nip can
penetrate and form re-oriented regions across the channel depth [85]. If
the flights of the screw are staggered, this mode gives rise to even
better extensive mixing, but, of course, at the cost of decrease in
pumping efficiency. The disadvantage of the excessive leakage flow is
that the residence time distribution in non-intermeshing counter-
rotating twin screw extruders is broader than that in single screw
extruders [86].
Forward flighted, reverse flighted as weil as cylindrical screw elements
have been used [87] in non-intermeshing counter rotating twin screw
extruders. The reverse flighted elements are often introduced with the
idea of inducing extensive mixing in the longitudinal direction while
the cylindrical elements are for sealing purpose when liquid additions
are to be done in sm all quantities and hence located near to the liquid
addition ports. Non-intermeshing screws are always open both
lengthwise and crosswise.
Non-intermeshing counter-rotating twin screw extruders are generally
used in applications where dispersive mixing is not a necessity. The
applications include polymer blending, preparation of hot melt
adhesives and pigment concentrates. They can be used in the prep-
aration of filled systems such as incorporation of glass fiber reinforce-
ments in engineering polymers because the non-intermeshing screws
will certainly protect the glass fiber from damage.
E. Continuous internal mixers

This form of mixing equipment is basically the conversion of the
popular Banbury mixer of Farrel Corporation from the batch to
continuous mode of operation [88]. In fact, the cross-section of the
continuous internal mixer in the direction perpendicular to the axis of
rotation of the rotors resembles that of the batch type Banbury mixer as
shown in Figure 5.6.
The design of the continuous interna I mixer in the direction of the
axis of rotation of the rotors can be seen from Figure 5.22. The twin
rotors do not intermesh and rotate at slightly different speeds. Their
special design ensures a high degree of longitudinal mixing and the
discharge is adjusted to control the amount of material in the mixing
chamber. The design of the continuous interna I mixers follows, in most
cases, the philosophy of controlling the forward action of the material
through the mixer and the mixing action independently. Thus, the
mixer basically involves aseparate conveying section which propels the
ingredients forward and a further section which tends to move the
ingredients in the opposite direction for intensive mixing. In the
intensive mixing section, the material is dispersed by passage through
small gaps found between the rotors and the chamber walls, coupled
FEEO
MI)"NG CHAMBER
Figure 5.22 Sehematie diagram of the eontinuous internal mixer in the direetion of the axis of rotation of the rotors. (Reprinted from Ref.
21 with kind permission from John Wiley & Sons, Ine., New York, USA.)
with kneading action between the rotors and roll-over of the material
itself.
There exists a very sensitive equilibrium condition under which the
material is being moved forward against low resistance in the discharge
orifice. If the resistance at the outlet is changed, the degree to which the
mixer body is filled changes until the forward blades are able to
overcome that resistance. If there is more material in the mixer, the
actual residence time is longer and, if the throughput is kept constant,
the mechanical work done on the material increases.
Another way of changing the input of mechanical work to the
material is by change of rotor speed without changing the throughput
which is possible because the throughput is determined by the feed rate
into the mixer. The materials have also to be fed continuously in the
proper proportion because the mixing action in the axial direction is not
very effective. The distribution of residence time and shear deformation
in the continuous internal mixer with non-intermeshing mixing blades
is broader than for the twin screw extruders of any type.
Since this type of mixer cannot generate any appreciable discharge
pressure necessary to extrude the material, it is often combined with an
extruder for pelletizing. The continuous internal mixer is employed in
applications involving polyolefin homogenization, PVC compounding
as well as in the preparation of low filler loaded polyolefin composites.
F. Co-rotating disk extruders

The co-rotating disk extruder introduces the concept of two moving
drag inducing surfaces [89,90]. This is in contrast to all the earlier
discussed continuous compounders wherein there was one moving
boundary (the screw) along with one stationary surface in the channel
(the barrel). This particular equipment known as the Disk pack
processor manufactured by Farrel Corporation, consists of a single rotor
with toroidal processing chambers fitted in a circular housing. The
processing chambers may be connected in parallel, in series or in
combination, and are assembled on the building block principle.
In the co-rotating disk extruder, the material is transported by the
action of two moving walls, the sides of the disks, which can form a
parallel-faced or a wedge-shaped chamber as shown in Figure 5.23. An
analysis of the velocity distribution in the parallel-faced chamber with a
restriction to flow at the outlet shows two flow patterns [21]. A circular
flow in planes perpendicular to the axis of rotation and another circular
flow in cylindrical surfaces around the axis of rotation. The super-
position of both flows is conducive to extensive mixing.
To achieve intensive mixing, mixing blocks with narrow clearances
between the surfaces of the blocks and rotating walls are introduced as
CHA"O"'c.L. glOCr.
PAFtAL.LE1.-FACeO INEOOt$ttAPEO
R'-'OIAL.-THICK.NUS RAOIAl I H1CKNESS
PAOf llE .PFI<JFII.E
SHAFl SM"'"
OIS", DISt!;
I'AOCESS C .rI:AMBER
(a) (b) (c)
Figure 5.23 Sectional view of co-rotating disk extruder without mixing blocks.
(Reprinted from Ref. 21 with kind permission from John Wiley & Sons, Inc., New York,
USA.)
shown in Figure 5.24. The extensive mlxmg action described above

takes place in the material accumulated in front of the mixing blocks.
Mixing pins are often necessary to impose high strains and reorient the
melt. This is because, at the same pressurization capability, the shear
rates with two walls moving are considerably smaller than with only
one moving wall.
Co-rotating disk extruders are useful in the preparation of color
concentrates, polymer blending as weIl as in the compounding of fillers
with polymers.
5.3.4 DUMP CRITERIA

From among the compounding techniques discussed earlier, the most
common practice for incorporating fillers in polymers has been to make
use of internal mixers such as the Banbury mixer for batch mixing and
the twin screw mixer / extruder for continuous operation. In laboratory
small-scale processes, the Brabender plasticorder (Brabender, Duisburg,
Germany) or the Haake Rheocord (Haake Buchler Instruments, Inc.,
Saddle Brook, NJ) is often used for conducting the mixing operation.
They have accessories for batch mixing as wen as continuous operation,
but the batch mixer is most popularly used for laboratory research
purposes. It is most important to determine the dump criteria, i.e. the
moment when the mixing is deemed complete.
CHAHHIL 'LOCIC
IHLV
Figure 5.24 Sectional view of co-rotating disk extruder with mixing blocks. (Reprinted
from Ref. 21 with kind permission from John Wiley & Sons, Inc., New York, USA)
In the batch mixers, the completion of the mixing operation is

normally adjudged by the observed constancy of the torque level in the
mixer's motor drive unit after a certain length of time. A constant
torque implies internal homogeneity of the mixture that is achieved
within the system' s capability limits. A typical torque-time curve
generated during a mixing operation [91] of filler and polymer is shown
in Figure 5.25. The major peak represents the moment when the
addition of all the filler and polymer to the mixing bowl is complete
and when the shearing action be gins to disperse the filler into the
polymer matrix. As the filler becomes better dispersed, the viscosity of
the composite be gins to decrease, as exemplified by the recorded
torque, till it reaches its equilibrium value beyond which the mixedness
would not improve or would improve only marginally due to the
system constraints. In fact, it is not advisable to continue mixing once
the equilibrium torque level is reached because it could only lead to
thermomechanical degradation of the polymer, especially in highly
5r--------------------------------,ZSO
4~---....,
- 200
-
ISO c:;-
f..
..,
:::I
111
CI:
:::I
o
CI: 2 JOO~
o CI:
~ 111
CL
2
...
111
80
~----':----~-----_=_--~ .....--~O
8
TIME
Flgure 5.25 A typieal torque-time eurve generated in an internal mixer during

eompounding of fillers into polymers. (Reprinted from Ref. 91 with kind permission
from Mareel Dekker, Ine., New York, USA)
filled systems, where local shear rates between filler particles eould be
extremely high.
Time and temperature have been the most eommonly used eriteria to
determine when to terminate the mixing proeess. The aims are to
guarantee the quality of the end produet, avoid overmixing, and reduee
variation between batehes. There is an inereasing body f evidenee that
a more precise and reproducible eontrol of the mixing eyde ean be
obtained by following the energy inputs at various stages in the eyde.
This is beeause the ehanges in power eonsumption are indicative of the
wetting, deagglomeration and dispersion stages in the process.
Mixing to apreset time does not allow for variations in metal
temperature at the start of the mix, for eooling rate or for ingredient
addition times. Thls ean result in significant bateh to bateh variation.
When mixing to a predetermined temperature the major limitation is
the aeeuraey with whieh the bateh temperature ean be measured. The
large heat-sink provided by the machine often makes temperature
measurement inaeeurate, though there are now available infra red probe
thermoeouples that are more accurate.
Mixing to a predetermined power input into the bateh overeomes
these limitations and gives improved bateh to bateh eonsisteney for
mixes requiring longer mixing times. However, following the work or
Compounding/mixing variables 221
energy input alone is not sufficient. In addition, one has to establish the
effect of process variables on the shape of the power curve. In other
words, a recording chart, which indicates both the instantaneous power
and the integrated power or work done is required. Furthermore, these
data should be additional to the established control criteria of time and
temperature and not a completely separate alternative set of criteria.
5.4 COMPOUNDINGIMIXING VARIABLES

A number of variables affect the final quality of the mix. Some variables
are more sensitive to the changes than others. It is important to identify
these variables and understand their sensitivity so that the mixing can
be carried out under optimum conditions.
Variables affecting the compounding operation could be the machine
variables or operating variables as shown in Table 5.7. It has been
recognized that these variables influence the quality of the compounded
filled systems, but the separate effects of these changes are often
'difficult to determine. This is mainly due to the strong interactions
between most of these variables. Hence, in the discussion of these
variables and their effects, some general statements may have to be
made and elear-cut guidelines may at times be difficult to give. In all
cases, the efficacy of the compounding action is adjudged by the level
of dispersion achieved as exemplified by a study of the rheological
characteristics of the compounded filled polymer system rather than
through the product properties in the solid state.
Capillary rheometry has been the most popular technique for obtain-
ing the steady state rheological response, as it provides information at
deformation rates high enough to be elose to those encountered during
polymer system processing. However, the high shear rates achievable
in the capillary rheometer do not permit the rheological parameters to
labte 5.7 Variables affecting the compounding operation
Compounding variables
I
Machine variables Operating variables
h
Mixer Rotor Mixing Rotor Ram
I
Chamber Mixing Order of
type geometry time speed pressure* loading* temperature ingredient
addition
Applicable particularly to internal mixers.

remain sensitive to the internal material structure, and hence, the

mieroscopie inhomogeneities get masked. Further, within the capillary
tube, there exists a velocity gradient whereby the shear stress at the
wall is higher than that at the center of the tube. In filled polymer
systems, this leads to migration of the filler particles from the wall
towards the center of the tube where the stress is lower, thereby leaving
a thin film at the wall whieh is low in filler concentration or devoid of
it. This effect would be more pronounced with large filler particles,
especially at higher shear rates. The measured value of apparent
viscosity, which is obtained as the ratio of wall shear stress to the shear
rate, would not, therefore, be truly representative of the actual
rheologieal characteristic of the material.
One method of overcoming these steady-state measurement problems
would be to generate data at lower shear rates by changing from a
capillary rheometer to a cone-and-plate or a parallel-plate viscometer.
For filled polymer systems, the parallel-plate is recommended for use
either in steady shear mode or dynamie oscillatory mode. Again, the
steady shear mode does not provide very reliable data, especially at
higher loadings and for highly agglomerated systems. The internal
structure of the material gets broken down du ring the shearing action,
and the centrifugal force developed during the plate rotation throws
the sampIe out of the measuring gap [92,93], thereby leading to
erroneous results. Especially when a thixotropie sweep is used to
evaluate the degree of agglomeration, a spurious response may result
due to the sampIe throw-out at higher end of the shear, thereby giving
a lower viscosity in the return curve during this measurement.
The most reliable rheologieal data on filled sampIes, especially at
high loadings, can be obtained through the use of oscillatory measure-
ments. The dynamie rate sweep and the dynamie strain sweep would
be the most suitable for assessing the internal structure of the system.
Ouring a strain sweep, a plot of storage modulus vs. percentage strain
at low frequency would be the best indieator of the level of the
homogeneity in the system. A decrease in storage modulus with
percentage strain would be an added indieator of the occurrence of the
structural breakdown in the system. Ouring a frequency sweep, it is
best to maintain the strain as low as possible within the system
constraints, in order to be in the linear viscoelastie region of the
material. The response of complex viscosity, storage modulus, loss
modulus, and tangent delta that is then obtained would give a measure
of the degree of dispersion of the filler in the matrix. A highly
agglomerated system would show the existence of a yield at low
frequency, the storage modulus would be high and vary minimally
with frequency giving a more solid-like response, and the tangent delta
would be lower. However, generation of reliable and consistent data in
the case of filled systems depends to a large extent on the preparation

of the sampIe for the rheological test. Premolding sampIes under high
press ure to a shape and size as would be used for the patallel-plate
rheometer test, would ensure that the variation in the observed
rheological response is related to the composite characteristic and is not
an experimental artifact.
5.4.1 MIXER TYPE
It is obvious that the choice of the mlxmg equipment used in the

compounding operation has an effect on the rheology of the prepared
filled systems [94,95]. This is due to the differences in the mixing
mechanisms, the degree of the shear stress and stress patterns
developed, and hence the filler dispersion levels in the different
equipments.
Experiments to study such differences have been carried out [95]
using two identical compositions of ultra fine zirconia powder
(84.6wt%, Le. 45.3vol%) in atactic polypropylene APP (12.3wt%, i.e.
45.1 vol%) with plasticizer dioctyl phthalate DOP (3.1 wt%, i.e. 9.6vol%)
prepared by (1) a Z-type double-blade mixer and (2) a twin screw
extruder.
In the double-blade mixer, filled system 1 was prepared by pre-
heating zirconia to 160C and stirring for half an hour after which APP
was added. Again after a half hour mixing, DOP was added and
mixing was carried on for a further half hour.
In the second ca se, first apre-mix was prepared by mixing all
components for three minutes in a Henschel FM lO/L low shear mixer.
The mixture was then cornpounded by a Gay's TS40-DV-L twin screw
extruder. This consisted of two co-rotating screws in four separately
heated barrel sections. A screw speed of 60 rpm was used with the
barrel temperatures set at 120-130-140-150C feed to exit.
The filled systems were examined by capillary rheometry to assess
differences caused by two methods of mixing. The range of shear rates
was chosen to be 287-1430 sec-I. Figure 5.26 is a log (viscosity)-log
(shear rate) plot for (1) the filled system produced by the Z-type double-
blade mixer and (2) the filled system produced by the twin screw
extruder. A large difference in the viscosities of the two filled systems at
low shear rates was observed. At the shear rate of 287 sec- I the viscosity
of filled system 1 was found to be 130 Pa sec and the viscosity of filled
system 2 was 320 Pa sec. There was also a large difference in the gradients
of the two plots, giving respectively flow behavior indices of 0.91 and
0.38. Gel-permeation chromatography and infrared spectroscopy showed
that these differences could be attributable to considerable oxidative
degradation of the polymer during double-blade mixing, arising from
~.,---------------------------~
TEMPERAlURE =160 C
~~--~--~~~~~--~~~~~~
1)0
Flgure 5.26 Variation of steady shear viscosity with shear rate for filled systems
produced by (1) Z-type double-blade mixer and (2) twin-screw extruder. (Reprinted
from Ref. 95.)
the long residence time. Scanning electron microscopy suggested that the
twin screw extruder produced a weIl dispersed system, without signi-
ficant degradation [95]. Twin screw extruders have been known to yield
mixtures with a greater degree of dispersion than those produced by
blade-type mixers [96] and the experimental work [95] confinns the same.
5.4.2 ROTOR GEOMETRY
A number of types of internal mixers are available as discussed earlier,

and whatever their design, they are built in with two common features.
These are: (a) the ability to exert a high, localized shear stress on the
material (a nip-action) and (b) a lower shear rate stirring or homo-
genizing action. It is the combination of these two effects, high shear
stress plus large shear deformation, that is effective in achieving both
dispersive mixing and distributive mixing.
To some extent mixer rotors can be designed to meet specialized
requirements, but the majority of the available ones are of a
compromise design, based on experience, to best fit a wide range of
compounds.
When considering laboratory scale compounding equipment units, a
number of different types of mixer blades are available for the
Brabender plasticorder and the Haake Rheocord, such as the roller type,
O SIGMA G'
0 - SIGMA "1*
- ROLLERS G'
- ROLLER 5 ?*
IOI~~~~.I~~~~.I~~~lw.lL-~~WW
10'" 10 0 10' 10 2
W (RAD./ue.)
Figure 5.27 Effeet of mixer design on dynamie rheologieal praperties of alu mi na-
filled, low-density polyethylene at 200C. (Reprinted fram Ref. 91 with kind permission
from Mareel Dekker, Ine., New York, USA)
sigma type, eam type or Banbury type, which give different levels of
shear during the mixing proeess. Normally the roller type or the sigma
type is preferred for use in the preparation of filled polymer systems,
espedally at high loadings, beeause of the high level of shear that they
give. Bigg [91] found a elose similarity in the responses of the two
mixers when similar eompositions were prepared in a similar manner
in the roller blade and the sigma blade mixer. Figure 5.27 shows the
identieal rheological response of alumina-filled low density poly-
ethylene at 200C using different mixer designs.
In the ease of eontinuous eompounding equipments, the effect of the
ehanges in serew geometry is obvious by following the stress distri-
bution pattern ehanges. Use of different types of patented serew
designs leads to eonsiderable variations in the mixing effideney and the
rotor geometry beeomes a reasonably sensitive variable in the ease of
eontinuous eompounders.
5.4.3 MIXING TIME

In bateh mixers, the mixing time is often the most eommon eriterion to
determine when to terminate the mixing process. Mixing to apreset
time does not allow for variations in metal temperature at the start of
the mix, for cooling rate, or for ingredient addition times.
The best way to decide the mixing time is to observe the torque-time
curve as shown in Figure 5.25. Once the equilibrium torque level is
reached, it is prudent to stop the mixing. The equilibrium torque
implies that internal homogeneity of the mixture has been achieved
within the constraints of the mixer's capabilities. Further mixing will
not improve the mixedness and even if it does, it will be only marginal.
Extended mixing time invokes the danger of thermomechanical
degradation of the polymer in the rather abrasive environment created
by most fillers. In any case, mixing time is not a very sensitive variable
and only large differences (minutes vs. hours) would show substantial
change in the rheology of the prepared systems.
Boonstra [97,98] reported the mixing profile of rubber with carbon
black, and noted that carbon blacks which are compatible in size and
total surface area, but vary in structure and hence void volume, require
different mixing times to achieve the same level of dispersion.
Cotten [99,100] suggests that the time required for full carbon
incorporation can be determined by measuring the time required to
reach the second power peak during a mixing cyde. Cotten [100] per-
formed mixing studies in a Banbury mixer and studied the progression
of carbon black dispersion at different times by microscopic ex-
amination of the rubber / carbon black compounds. The rates of carbon
black dispersion were computed from maximum torque data. The
rubber was first masticated for about two minutes and then the rotors
were stopped. Carbon black was charged in the chute and the mixer
ram was then inserted and the rotors were started again. Mixing times
were measured from the instant when the rotors were restarted. Cotten
[100] found that the fraction of undispersed carbon black decreases
linearly with the time of mixing at the point where the second power
peak occurs. At shorter mixing times, the compound appeared
inhomogeneous and crumbly. The mixing times were observed to be
inversely proportional to the rotor speed.
Turetsky et al. [101] have shown a good correlation between the
measured carbon black incorporation time and weight average
molecular weight of the polymer. They found that incorporation times
increase sharply with increasing polymer molecular weight.
In continuous mixers, the mixing time is the lapse of time for which
the material resides in the equipment units. To minimize heat history,
the residence time must be short and uniform during the entire process.
Residence time is primarily a function of machine design, screw rpm
and throughput. All continuous machines do not have an exactly
defined residence time but rather a residence time spectrum. Uniformity
of a continuous operation is illustrated by the type of spectrum. With
screw machines in general, four principal types of residence time

spectra can be found [16,17] as shown in Figure 5.28. The two
identifying characteristics of a residence time distribution are the
distance IQ between the points of inflection and the overall width 12. of
the distribution curve. A small distance between the points of inflection
indicates little back and forth mixing; a great distance indicates a
TI"'E~
Figure 5.28 Four typical residence time curves for extruder processes. (Reprinted
from Ref. 16 with kind permission from American Chemical Society, Washington, DC,
USA.)
greater longitudinal mixing. The overall width l2. of the distribution

curve is influenced by so-called distribution tails whieh indieate the
cleaning efficiency of the machine. Long distribution tails indieate poor
self-cleaning efficiency.
The best characterization of self-cleaning is the self-cleaning time, ~
defined as: ~ = l2. - IQ. As ~ increases, the cleaning efficiency decreases.
Using average residence time, a dimensionless value for self-cleaning
characterization with various processes and average residence times is
obtained as:
(5.14)
As the value of ~ increases, the self-cleaning characteristics

deteriorate. Average residence time is defined as the time in which half
of the particles in residence time spectrum pass through the machine.
When average residence time cannot be determined from a residence
time spectrum, it can be calculated by:
t= Vfef (5.15)
Qv
where V f is the free volume, ef the degree of fill and, Q the volumetrie
flow per unit time.
Curve a in Figure 5.28 is typieal for a machine with little longitudinal
mixing and poor self-cleaning characteristics. Curve b is typieal for a
machine with greater longitudinal mixing but still poor self-cleaning
characteristics. These two curves are typieal for single screw extruders
and for twin screw extruders without a sealing profile.
Curves c and d show only short residence time tails which indieate
good self-cleaning characteristics. The latter curves vary only in the
amount of back and forth mixing and are typieal of twin screw
extruders with a sealing profile. In machines with good self-cleaning,
no particles remain excessively long in the unit where they might be
subjected to severe heat. There are no dead corners where material
could accumulate. A good example of an extruder with a sealing profile
is the intermeshing co-rotating twin screw extruder.
Techniques for measuring residence time distributions and methods
for characterizing axial flow behavior have been developed [74].
Residence time distribution data are most useful in diagnosing axial
mixing phenomena and making appropriate design changes in the
equipment. For example, twin screw equipment units can be designed
for very little axial mixing either by using very low helix angle screws
or by using straight segments whieh impose no axial forwarding. In this
way, the sensitivity of the mixing time to the rheology of the
compounded filled polymer system can be altered.
5.4.4 ROTOR SPEED

Rotor speed directly affects total shear strain or deformation and thus
the speed of mixing. A higher mixing speed would result in higher shear
and hence, can be expected to be more beneficial in breaking
agglomerates during the compounding of filled polymer systems. The
importance of developing high shear forces to break down agglomerates
has been illustrated by Dow et al. [102] by varying the rpm of the roller
blades in the bowl mixer of Rheomix 540/Rheocord system 40 from
Haake Inc. Figure 5.29 compares the torque curves obtained during
mixing of 50vol% AI20 3 /50vol% polyethylene at lOrpm and 200rpm.
The low torque genera ted at 10 rpm indicates that the shear forces are
insufficient to break down powder agglomerates. This is confirmed
by rheological measurements in Figure 5.30 which shows that the
sampie mixed at 10 rpm has much higher viscosities and undergoes
a large decrease in viscosity with increasing frequency. However, at
the same time, higher speeds are known to induce microbubble
formation in the composite melts, which would be extremely difficult to
remove and hence, create inhomogeneity in the composite. Lower speed
would certainly help in preventing air entrapment, but would then
produce a lower level of shear and would not break agglomerates.
Again, a balance has to be achieved and a medium speed might be
most appropriate depending, of course, upon the filler-polymer
combination.
The speed of mixing is usually limited by the maximum allowable
temperature; that is by the balance between heat generation and heat
removal. Dispersive mixing, although dependent on shear stress, does
not seem to be directly affected by the rotor speed; this is probably
due to the effect of extensional flow, which also creates higher shear
stress. However, the reduction in viscosity which results from tempera-
ture rise, results in decreased shear stress and, therefore, decreased
dispersive action. Thus, there is a trade-off between increased speed of
mixing and a less well dispersed or homogenized product. Therefore in
most commercial mixers there is a limit to practicable rotor speeds.
5.4.5 RAM PRESSURE

This variable is particularly applicable to interna I mixers. The main
function of the ram is to keep the ingredients trapped within the mixing
area. However, in addition, high ram pressure has definite advantages,
especially for high viscosity mixes. High ram pressures decrease voids
within the mixture and increase shear stress by increasing the contact
forces between the ingredients and the rotor surface. This helps greatly
in the breaking down of agglomerates thus allowing higher loadings to
~r----------------
50 vol% AI 2 0 3
Mixlng Condilions: 150C, 10 rpm
i'
,g 300
1&1
:l
oIr

~ 200
100
5 10 15 20 2S 30
TIME (mln)
500,---------------------------------------------~
50 vol% AI 2 0 3
Mlxlng Condilions: 1S0C. 200 rpm
400
"
.2
1&1
:l
0
Ir
300
15 20 2S 30
TIME (mln)
Figure 5.29 Plots of torque vs. mixing time tor 50 vol% AI 2 0 3 /50 vol% poly-
ethylene sam pies mixed at 10 rpm (top) and 200 rpm (bottom). (Reprinted trom
Ret. 102 with kind permission trom Ameriean Ceramie Soeiety Ine., Westerville,
Ohio, USA)
50 vol% A12~
Mixing Temperatur. = 1S0C
1000
>-
!::
Cf)
o
(.)
Cf)
>
~ 200 rpm
~ 100
ce
Z
>-
Q
10 100
FREOUENCY (radIs)
Figure 5.30 Plots of dynamie viseosity vs. frequeney for SO vol% AI 2 0 3 /S0 vol%
polyethylene sampies mixed at 1S0C and the rpm indieated. Viseosity measurements
were made at 12SoC. (Reprinted from Ref. 102 with kind permission from Ameriean
Ceramie Soeiety Ine., Westerville, Ohio, USA.)
be achieved if desired. With increasing ram pressure, the mixing time is

often shortened considerably.
5.4.6 CHAMBER LOADINGS

This variable is also appIicable particularly to internal mixers.
Sufficient material in the chamber is required to produce the ram
pressure effects described above. However, if the mixer chamber is
excessively overloaded, much longer times are required for good
dispersion and there is a danger of some undispersed filler being
still left. With severe underloadings, poor mixing mayaiso result,
because of the insufficient level of developed stresses. Thus, it is
important to optimize chamber loading. The optimum batch weight
for a particular mix depends on the type and level of fillers in the
polymer system. Arbitrary use of rules of thumb is not recommended.
Instead, it is best to use a few tracer experiments to determine the
favored level of chamber loading for a particular filler-polymer
combination.
5.4.7 MlXING TEMPERATURE

The mixing temperature is a rather sensitive variable as has been shown
by systematic control1ed experiments [102-104] involving highly filled
systems prepared in the bowl mixer of Rheomix 540/Rheocord system
40 from Haake Inc.
A plot of dynamic viscosity vs. oscillation frequency for 50 vol%
alumina in 50 vol% low molecular weight polyethylene at different
mixing temperatures of 125, ISO, 175, and 220C is shown in Figure
5.31. The dispersion in the sampie prepared at 150C is seen to be better
than at other temperatures, as adjudged by lower viscosity values and
smaller changes in viscosity with increasing frequency. A plot of
storage modulus vs. frequency, as shown in Figure 5.32, also confirms
the conclusions. The highest storage moduli values are observed in the
sampie mixed at 220C, indicating the presence of extensive particle-
particle interactions and poorest dispersion; so also the storage
modulus is independent of frequency, implying the existence of more
solid-like behavior due to predominantly strong network formation.
The radial effects on dispersion observed due to changes in mixing
temperature alone could be attributed to differences in wetting behavior
l
ii
,;,
Cl.
>
....
in
o
(.J
cn
:;
u
i
c
z 100
>
Q
10~--~-L~~~~ __J--L~~~U-__-L~~-LLnDa__~
0.1 10 100
FREQUENCY erad/,1
Figure 5.31 Variation of dynamie viseosity with frequeney measured at 125C for
50 vol% alumina in polyethylene prepared using different mixing temperatures as
indieated. (Reprinted from Ref. 104 with kind permission from Ameriean Ceramie
Soeiety Ine., Westerville, Ohio, USA.)
W"'~-------------------------------------------.
~ tOOO
:1
8
:.
tII
"~
":.
'00
50 wol'llo AIz03/50 wol'llo Polyethy'''.
10L-__L-J-~~~L-__L-~~~~____L-~~~~~~
0.1 '0 100
FUQUENCY Cr.d/.,
Figure 5.32 Variation of storage modules with frequeney measured at 125C for
50vol% alumina in polyethylene prepared using different mixing temperatures, as
indieated. (Reprinted from Ref. 104 with kind permission from Ameriean Ceramie
Soeiety Ine., Westerville, Ohio, USA)
of the polymer and its viscosities at different temperatures. Figure 5.33

shows plots of the contact angle, e', of polyethylene melts on sintered
Al2 0 3 substrates as a function of time for different temperatures in the
range 125-220C. It is evident that the wetting kinetics is highly
dependent on temperature. Spreading ((J' < 5) occurs in less than
10 min at 220C. In contrast, the high viscosity polyethylene melts at
125C maintain a contact angle above 40 after 55 min. Thus, at low
temperatures, difficulties may arise in achieving optimum particulate
dispersion due to less favorable wetting characteristics. Figure 5.34
shows that the viscosity of the polyethylene melts decreases
significantly as the temperature is increased in the range 125-250C.
Hence, part of the reason for the poor dispersion achieved in the 220C
sampie is that the shear forces available for breaking down agglom-
erates were decreased. This was also indicated by experiments in which
the torque generated during mixing at various temperatures was
monitored. Figure 5.35 shows plots of the measured torque vs. mixing
time for mixing temperatures in the range 125-220C. It is evident that
the maximum torque generated increases dramatically as mixing tem-
perature decreases. Lower mixing temperatures would preferentially
help to increase the level of shear during the mixing. However, at
temperatures very dose to the melting point of the polymer, wettability
60~------------------------------------------~
POlyethylene/AI 2 0 3
50
125C
TIME (mln)
Figure 5.33 Plots ot the eontaet angle tor polyethylene melts on sintered AI 2 0 3
substrates VS. time at the temperatures indieated. (Reprinted trom Ret. 102 with kind
permission trom Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA.)
1.0
0.1 POLYETHYLENE
ii 0.6
:.
~
)0-
I- 0."
in
0
(J
111
>
(J
i
~
z)0- 0 .2
e
Figure 5.34 Plot ot the dynamic viseosity 01 polyethylene vs. temperature. (Reprinted
trom Ret. 102 with kind permission trom American Ceramie Soeiety Ine., Westerville,
Ohio, USA.)
800
50 vol'% AI 2 0 3
700
Mhdng Conditlons: 12SC. 200 rpm
600
~ 500
S
w
:;:, 400
0
a:
.-
0
300
200
100
400
50 vol'% AI 2 0 3
E .
.!!!
300 Mixing Conditions: lS0C. 200 rpm
w
:;:, 200
)\
0
a:
....0 100
l(.
0 I I I I I I
E 200
.! 50 vol'% AI20J
w
~
:;:, 100 Mixlng Condilions: 17S"C. 200 rpm
0
a:
.-0 0 I I I
- I I
E 200
i! 50 vol'% AI 2 0 3
w
:;:, 100
Mixing Conditions: 220C. 200 rpm
0
a: f
...
....0 0 I
10
I
15
I
20 25 30
I
0 5
TIME (mln)
Figure 5.35 Plots ot torque vs. mlxlng time tor SOvol% A12 0 3 /S0vol% poly-
ethylene sampies mixed at the temperature indieated. (Reprinted trom Ret. 102
with kind permission trom Ameriean Ceramie Soeiety Ine., Westerville, Ohio,
USA)
of the polymer would be poorest. A moderate balance between these two

extremes would thus result in optimum mixing conditions for better
dispersion, as indicated by a temperature of 150C in the case of an
alumina-polyethylene AC-PE9 system [102-104]. The other study avail-
able in this area is that of Lee [105] who used a cyc1ic mixing procedure
with temperature as a processing variable to reduce the concentration of
voids and carbon black agglomerates in the elastomer mix.
5.4.8 ORDER OF INGREDIENT ADDITION

The order of addition of the finer and polymer during the mlxmg
operation could make a difference to the quality of mix because of the
differences in the nature of polymer-finer contact. This would be
especiany true when handling highly loaded systems. This aspect has
not been addressed in the literature yet. In fact, most of the investigators
chose their own fixed method of the order of finer and polymer addition
during their experiments. For example, Bigg [106-108] consistently
preheated about one-third of the finer to the mixing temperature of
200C, then added an the required polymer amount and anowed it to
melt while continuing mixing at a moderate rotation speed of 50rpm. To
this premixed polymer-finer system, the remainder of the finer was
added and the mixing continued at the same speed until equilibrium
torque was reached. Saini et al. [109-112] preheated the entire required
finer quantity to the mixing temperature while under rotation at a
mixing speed of SO rpm. The polymer was then added an at once and the
rotation increased to 125 rpm. The mixing was then continued till
equilibrium torque was reached. Sacks et al. [104] did not preheat the
finer, but rather started by first adding an the required polymer quantity
to the mixing bowl and letting it melt while in rotation at a high speed of
200rpm. The finer was then added graduany and the mixing continued
for a fixed length of time of 30 minutes.
Preheating the finer certainly has the advantages of much better
temperature control throughout the mixing operation. However, when
the polymer is added an at once to the preheated finer [109-112], the
matrix is suddenly faced with the high loading of the finer that it needs
to wet. On the other hand, starting with the polymer system addition
first [104] could make it easier to disperse the finer because the loading
occurs in graduany increasing steps as more and more fiIler gets added.
It is probably for this reason that Bigg [106-108] preheated only one-
third of the finer. Hence, this method appears to be a sort of compromise
between the two extremes chosen by Saini et al. [109-112] and Sacks et
al. [104]. The information in this area is as yet far too limited to make
anusions regarding the superiority of one method over another and
hence, no distinct recommendations can be made for the order of finer
References 237
and polymer addition during the mlxmg operation. Comparison

between the mixing methods is difficult also because different mixing
speeds and times were used during the mixing by the different
investigators [104,106-112].
Order of ingredient addition is one area in which the compounder's
expertise is the most needed. The number of alternatives is large and
the optimum order of ingredient addition depends on the size, type
and degree of wear of the machine, the available speeds and ram
pressures, and the types and levels of polymer, filler, plasticizers and
other minor ingredients.
Although each mix has to be considered separately, some general
rules may be followed. For example, it is generally preferable to add
fillers early in the mixing cyde so that good dispersion is achieved
because of the higher viscosity, and thus higher shear stress, at the
lower temperature then prevailing. For the same reason, plasticizers
and lubricants which reduce viscosity, if present in large quantities,
should be added later as they slow down dispersion. However, if
plasticizers are added after the fillers are incorporated, they can coat
the metal surface and lower the shear stresses, thereby slowing down
both distributive and dispersive mixing. In such cases, at times, the
plasticizers and fillers are added together so that the plasticizers are
absorbed on the filler rather than the metal surface of the mixer.
REFERENCES
1. Matthews, G. (1982) Polymer Mixing Technology, Applied Science, New
York.
2. Mohr, W.D., Saxton, R.L. and Jepson, CH. (1957) Mixing in laminar flow
systems, Ind. Engg Chem., 49, 1855-6.
3. Danckwerts, P.V. (1952) The definition and measurement of some charac-
teristics of mixtures, Appl. Sei. Res., A3, 279.
4. Hold, P. (1982) Mixing of polymers - an overview, Part I, Advances in
Polymer Technol., 2, 141-51.
5. Fan, L.T., ehen, S.J. and Watson, CA. (1970) Solids mixing, Ind. Engg Chem.,
62,53-69.
6. Fan, L.T. and Wang, R.H. (1975) On mixing indices, Powder Technoi., 11,
27-32.
7. Lacey, P.M.C (1954) Developments in the theory of particle mixing, J. Appl.
Chern., 4, 257-68.
8. Weidenbaum, 5.5. (1958) Mixing of solids, in Advances in Chemical
Engineering 11 (eds T.B. Drew and J.W. Hooper), Academic Press, New York,
211-321.
9. Tadmor, Z. and Gogos, CG. (1979) Prineiples 01 Polymer Processing, Wiley,
New York.
10. McKelvey, J.M. (1962) Polymer Processing, Wiley, New York.
11. Mohr, W.D. (1959) in Processing of Thermoplastic Materials (ed. E.C

Bernhardt), Van Nostrand Reinhold, New York, Ch. 3.
12. Palmgren, H. (1974) Part 1, Part 2, A review of the processing conditions
in the batch operated internal mixer, Eur. Rubber J., 156, 30-44, 70-83
(May /June).
13. Danckwerts, P.V. (1953) Continuous flow system, Chern. Engg Sei., 2, 1-13.
14. Danckwerts, P.V. (1953) Theory of mixtures and mixing, Research, London, 6,
355-61.
15. Deryagin, B.V., Krotova, N.A. and Smilga, V.P. (1978) Adhesion of Solids,
Consultants Bureau, New York, p. 282.
16. Jakopin, S. (1974) Compounding of fillers, Advances in Chern., Series No. 134,
pp. 114-27.
17. Jakopin, S. (1977) Compounding filled materials for automotive appli-
cations, SPE Mid-Michigan Retec, Midland, Michigan, June 14-15.
18. Jakopin, S. (1979) Compounding of additives, Antec, New Orleans, Louisiana,
May 7-10.
19. Eise, K. (1981) Compounding of additives and fillers, presented by D.
Mie1carek at AIChE Summer National Meeting, Detroit, Michigan.
20. Swanborough, A (1979) Machinery for the production of coloured
thermoplastic compounds, Conference on Colour Compounding in Western
Europe, Europa Hotel, London, Nov. 28-29.
21. Hold, P. (1982) Mixing of polymers - an overview, Part II, Advances in
Polymer TechnoI., 2, 197-228.
22. Edirisinghe, M.J. and Evans, J.R.G. (1986) Review: Fabrication of engin-
eering ceramics by injection moulding II Techniques, Int. J. High Technol.
Ceramies, 2, 249-78.
23. Kalyon, D.M. (1988) Mixing in continuous processors, in Encyclopedia of
Fluid Mechanics (eds. N.P. Cheremisinoff), Gulf Publishing, Houston, TX,
Vol. 7, pp. 887-926.
24. Mack, W.A (1979-80) Continuous compounding, Modem Plastics Encyclo-
pedia, 347-52.
25. Swanborough, A (1980) Plastics compounding extruders, The Chem. Eng.,
July.
26. Wood, R. (1979) Continuous compounding equipment, Plastics Rubber Int.,
Part I, Sept.-Oct.; (1980) Part 2, Jan.-Feb.
27. Stade, K. (1977) Techniques for compounding glass fiber-reinforced
thermoplastics, Polym. Engg Sei., 17, 50-7 (Jan.).
28. Todd, D.B. and Baumann, D.K. (1977) Compounding glass into plastics,
Chem. Engg Prog., 65-8 (Jan).
29. Todd, D.B. and Baumann, D.K. (1978) Twin screw reinforced plastics
compounding, Polym. Engg Sei., 18,321-5.
30. Rauwendaal, CJ. (1981) Analysis and experimental evaluation of twin screw
extruders, Polym. Engg Sei., 21, 1092-1100.
31. Rauwendaal, C (1991) Mixing in Polymer Processing, Marcel Dekker, New
York.
32. Cheremisinoff, N.P. (1987) Polymer Mixing and Extrusion Technology, Marcel
Dekker, New York.
33. Birchall, J.D., Howards, AJ. and Kendall, K. (1981) Imperial Chemical
Industries Ltd, UK, Cementitious product, Eur. Patent 0021682, 7 Jan. Date
of filing: 6 June 1980.
References 239
34. Tadmor, Z. and Klein, I. (1970) Engineering Prineiples of Plasticating Extrusion,

Van Nostrand Rheinhold, New York.
35. Maddock, B.H. (1959) A visual and analysis of mixing in extruder screw,
SPE J., 15, 383-9.
36. Tadmor, Z. (1966) Fundamentals of plasticating extrusion - I. A theoretical
model for melting, Polym. Engg Sei., 6, 185-90.
37. Donovan, RC (1971) A theoretical melting model for plasticating extruders,
38. Vermeulen, J.R, Gerson, Ph.M. and Beek, W.I. (1971) The melting of a
bed of polymer granules on a hot moving surface, Chem. Engg Sei., 26,
1445-55.
39. Sundstrom, D.M. and Young, CC (1972) Melting rates ofcrystalline
polymers under shear conditions, Polym. Engg Sei., 12,59--63.
40. Tusim, M.H. and Chung, CI. (1975) Frictional behavior of glassy polymers
on metal surfaces, SPE 33rd ANTEC Trans., 21, 418-22.
41. Mizoguchi, M. (1973) Application example of a computer to screw design
extruder, Plastic Age, 24, 60-8 (July).
42. Fukase, H., Kunio, T., Shinya, S. and Nomura, A. (1976) Study on plastics
extruding mechanism - 1st report: Experiment and consideration on molten
film, The Japan Soc. Mech. Engrs, 51st Kansai District General Meeting
Transactions No. 764-5, March, pp. 30-2.
43. Fukase, H., Kunio, T., Shinya, S. and Nomura, A. (1977) Study on plastics
extruding mechanism - 2nd report: Influence of the screw channel depth
variation on solid bed, The Japan Soc. Mech. Engrs, 54th General
Transactions No. 770-4, April, pp. 130-5.
44. Shinya, S., Fukase, H. and Nomura, A. (1978) Studies on the melting process
of plastics extruders, IHI Engg Rev., 11, 16-29.
45. Fukase, H., Kunio, T., Shinya, S. and Nomura, A. (1982) A plasticating
model for single-screw extruders, Polym. Engg Sei., 22, 578-86.
46. Mount, E.M. m, Watson, J.G. m and Chung, c.I. (1982) Analytical melting
model for extrusion: melting rate of fully compacted solid polymers, Polym.
Engg Sei., 22, 729-37.
47. Chung, K.H. and Chung, CI. (1983) Analytical melting model for extrusion:
Stress of fully compacted solid polymers, Polym. Engg Sei., 23, 191-6.
48. Cheremisinoff, N.P. (1988) Principles of polymer mixing and extrusion, in
Encyclopedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf Publishing,
Houston, TX, Vol. 7, pp. 761-865.
49. Agur, E.E. and Vlachopoulos, J. (1982) Numerical simulation of a single-
screw plasticating extruder, Polym. Engg Sei., 22, 1084-94.
50. Sebastian, D.H. (1988) Computer modeling and analysis of extrusion
operations, in Encyclopedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, TX, Vol. 7, pp. 927-52.
51. Harris, S.L. (1988) Control of single screw extrusion, in Encyclopedia of Fluid
Mechanics (ed. N.P. Cheremisinoff), Gulf Publishing, Houston, TX, Vol. 7,
pp. 953-60.
52. Fenner, RT. (1979) Principles of Polymer Processing, Macmillan, London,
Ch.6.
53. Fisher, E.G. (1979) Extrusion of Plastics, Butterworths, London.
54. Carley, J.F., Mallouk, RS. and McKelvey, J.M. (1953) Simplified flow theory
for screw extruders, Ind. Eng. Chem., 45, 974.
55. Bigg, D. and Middleman, S. (1974) Laminar mixing of a pour of fluids in a

reetangular eavity, Ind. Eng. ehern. Fundam., 13, 184.
56. Pinto, G. and Tadmor, Z. (1970) Polym. Engg Sei., 10, 279-88.
57. Erwin, L. (1978) Theory of laminar mixing, Polym. Engg Sei., 18, 572.
58. Irving H.F. and Saxton, RL. (1967) Mixing of high viseosity material, in
Mixing Theory and Practice 11 (eds V.W. Uhl and J.B. Gray), Aeademic Press,
New York, Ch. 8.
59. Rauwendaal, C. (1984) SPE ANTEC Tech. papers, 30, 62.
60. Espesito, R (1986) Plastics Engng, Oet., 39-4l.
61. Pearson, J.RA. (1985) Mechanics of Polymer Processing, Elsevier Applied
Scienee, London.
62. Godfrey, J. (1985) Statie mixers, in Mixing in the Process Industries (eds N.
Hamby, M. Edwards and A. Nienow), Butterworths, London.
63. Wigotsky, V. (1986) Plastics Engng, Feb. 19-23.
64. Kalyon, D. and Hallouche, M. (1986) Adv. Polym. Tech., 6, 237-49.
65. Janssen, L.P.B.M. (1978) Twin Screw Extrusion, Elsevier, Amsterdam.
66. Martelli, F. (1983) Twin Screw Extruders, Van Nostrand, New York.
67. SpA Plastie Materials Laboratory (1949) Improvements in or relating to
moulding thermoplasties synthetie resins by extrusion, UK Patent 629 109,
13 Sept. Date of filing: 2 May 1946.
68. Schenkel, G. (1966) Plastics Extrusion Technology and Theory, lliffe Books,
London.
69. Erdmenger, R (1964) Chernie Ing. Tech., 36, 175.
70. Armstroff, O. (1973) Kunststofftechnik, 12,240.
71. Kim, WS., Skatschkow, W.w. and Jewmenow, S.D. (1973) Plaste Kautschuk,
20,696.
72. Booy, M.L. (1978) Polym. Engg Sei., 18, 973-84.
73. Booy, M.L. (1980) Polym. Engg Sei., 20, 1220-8.
74. Todd, D.B. (1975) Residenee time distribution in twin serew extruders,
Polym. Engg Sei., 15, 437.
75. Wyman, C.E. (1975) Polym. Engg Sei., 15, 606-11.
76. Maheshri, J.c. and Wyman, C.E. (1979) Ind. Engg Chem. Fundam., 18, 226.
77. Maheshri, J.c. and Wyman, C.E. (1980) Polym. Engg Sei., 20, 601.
78. Wemer, H. (1976) Doetoral thesis, Technishe Universitt Mnchen.
79. Jewmenow, S.D. and Kim, W.S. (1973) Plaste Kautschuk, 20, 356.
80. Kim, WS., Skatsehkow, W.W. and Jewmenow, S.D. (1975) Plaste Kautschuk,
22,730.
81. Kim, WS., Skatsehkow, W.W. and Jewmenow, S.D. (1978) Plaste Kautschuk,
25,348.
82. Anon (1982) UK laboratory eompounding extruder sets high standards,
European Plastics News, June, 9.
83. Niehols, R (1986) Modern Plastics, 90-94 (Sept.).
84. Janssen, L. and Schaart, B. (1981) 2nd World Congress of Chemical
Engineering, 6, 543, Montreal.
85. Howland, C. and Erwin, L. (1983) SPE ANTEC Technical Papers, 29, 113-16.
86. Walk, C. (1982) SPE ANTEC Technical Papers, 28, 423.
87. Nichols, R and Yao, J. (1982) SPE ANTEC Technical Papers, 28, 416.
88. Hold, P. (1969) US Patent 3,154,808.
89. Tadmor, Z., Hold, P. and Virbsom, L. (1979) A radical design that promises
an extruder revolution, Plastics Engg (Nov.).
References 241
90. Tadmor, Z., Hold, P. and Virbsom, L. (1979) New approval promises to
revolutionize extrusion, Plastics Engg (Dec.).
91. Bigg, D.B. (1984) Interrelation among feedstock form; product
requirements, equipments type, and operating parameters in polymer
mixing processes, Polym. Plast. Technol. Eng., 23, 133-68.
92. Connelly, RW. and Greener, J. (1985) High shear viscometry with a
rotational parallel-disk deviee, J. Rheol., 29, 209-26.
93. Kosinski, L.E. and Caruthers, J.M. (1986) The effect of particle
concentration on the rheology of polydimethylsiloxane filled with fumed
silica, J. Appl. Polym. Sei., 32, 3393-406.
94. Kitano, T. and Kataoka, T. (1980) The effect of the mixing methods on the
viscous properties of polyethylene melts filled with fibers, Rheol. Acta, 19,
753-63.
95. Hunt, K.N., Evans, J.RG. and Woodthorpe, J. (1988) The influence of
mixing route on the properties of ceramie injection moulding blends, Br.
Ceram. Trans. J., 87, 17-21.
96. Hornsby, P.R (1983) Design and application of a laboratory twin-screw
compounding extruder, Plastic Compounding, 6, 65-70.
97. Boonstra, B.B. and Medalia, A.1. (1963) Rubber Chem. Tech., 36, 115.
98. Boonstra, B.B. (1977) Rubber Chem. Tech., 50, 194.
99. Cotten, G.R (1972) Rubber Chern. Tech., 45, 129.
100. Cotten, G.R (1984) Rubber Chern. Tech., 57, 118.
101. Turetsky, S.B., Van Buskirk, P.R and Gunberg, P.F. (1976) Rubber Chem.
Tech., 49, 1.
102. Dow, J.H., Sacks, M.D. and Shenoy, AV. (1988) Dispersion of ceramie
particles in polymer melts, Ceramic Trans. (Ceramic Powder Sei. HA), 1,
380-8.
particles in polyethylene melts, Ceramic Trans. (Ceramic Powder Sei. HA),
12,431.
104. Sacks, M.D., Khadilkar, CS., Scheiffele, G.W., Shenoy, AV., Dow J.H. and
Sheu, RS. (1987) Dispersion and rheology in ceramic processing, Adv. in
Ceramies, 21, 495-515.
105. Lee, M.CH. (1984) The effects of degree of mixing on the properties of
filled elastomer, J. Appl. Polym. Sei., 29, 499-508.
106. Bigg, D.M. (1982) Rheological analysis of highly loaded polymerie
composites filled with non-agglomerating spherieal filler particles, Polym.
Engg Sei., 22, 512-18.
108. Bigg, D.M. (1984) Complex rheology of highly filled thermoplastic melts,
Proc. 9th Int. Congress on Rheology in Mexieo, Adv. in Rheology, 3, 429-37.
109. Saini, D.R, Shenoy, AV. and Nadkami, V.M. (1985) Effect of surface
treatment on the rheological and mechanical properties of ferrite filled
polymeric systems, Polym. Engg Sei., 25, 807-11.
110. Saini, D.R, Shenoy, AV. and Nadkarni, V.M. (1986) Melt rheology of
highly loaded ferrite-filled polymer composites, Polym. Composites, 7,
193-200.
111. Saini, D.R and Shenoy, AV. (1986) Viscoelastic properties of highly loaded
ferrite-filled polymeric systems, Polym. Engg Sei., 26, 441-45.
112. Shenoy A.V. and Saini D.R. (1986) Quantitative estimation of matrix finer
interactions in ferrite-filled styrene-isoprene-styrene block copolyrner
Steady shear viscous
properties 6
There is extensive literature on the rheology of filled polymer systems

[1-75] induding reviews [41,42,49] and chapters in a number of books
[76-85]. The bulk of the literature deals with rheology of systems in the
filler loading range of 20-40% by volume. In the present context, this
range will be considered as the low filler loading range and will be
referred to thus whenever necessary. Aspects relating to this loading
level have been effectively reviewed by Utracki and Fisa [41]. The filler
loading range between 40 to about 60% by volume will be referred to
here as the high filler loading range. A review of the rheology of highly
filled polymer melt systems is also available [82]. The enhanced interest
in the rheology of highly filled polymer systems is the intended use of
the polymers as binders during ceramic processing [48,66-70,73-75] and
for the preparation of functional composites [60-63].
Table 6.1 Various types 01 lillers used in Rel. 29
Fillers Source Specific Size,l1m Aspect ratio

gravity (particle or
liber
diameter)
Carbon black Continental Carbon 1.8 0.045

Titanium dioxide du Pont 4.1 0.18
Calcium carbonate Pfizer 2.7 0.5
Mica Hayden Mica Company 2.9 "'5 Flake, 25'" 50
Glass beads Potters Industries, Inc. 2.48 10
Franklin fibers Certain Teed Corp. 2.96 0.5-2 "'100
Aramid fibers du Pont 1.44 12.2 "'60
Cellulose fibers Westvaco 1.5 12 "'100
Glass fibers Fiberfil 2.5 12.7 "'10
Source: Ref. 29 (reprinted with kind permission from American Chemical Society, Washington
OC, USA).

244 Steady shear viscous properties
The rheology of filled polymer systems will be discussed in this and

subsequent chapters under various headings, namely steady shear
viscous properties, steady shear elastic properties, unsteady shear
viscoelastic properties and extensional flow properties. The effects of
filler type, size, size distribution, concentration, agglomerates, surface
treatment as weH as the effect of the polymer type will be elucidated
wherever information is available.
The material parameters that are involved in steady shear measure-
ments are the steady shear viscosity and the normal stress difference.
These will be treated in separate chapters as the information available
on these two parameters is not balanced equaHy.
The information on steady shear viscosity of filled polymer systems
far outweighs that which is available on other parameters. Hence, the
effect of a number of variables on the steady shear viscosity is discussed
in utmost detail.
6.1 EFFECT OF FILLER TYPE

The effect of filler type on the steady shear viscosity of a filled polymer
system has been brought out in the work of White et al. [29]. The
polymer used was polystyrene of one specific grade, namely, Dow
Styron 678U. The filler loading was fixed at 20 vol%. Nine different
types of filler were used as summarized in Table 6.1. The filler types
included rigid fillers (such as glass fibers, mica, glass beads, calcium
carbonate, carbon black, titanium dioxide and Franklin fibers) and
flexible fillers (such as aramid fibers and cellulose fibers). They covered
different types of shapes such as spherical (glass beads), particulate
(calcium carbonate, carbon black, titanium dioxide) and fibrous (glass
fibers, aramid fibers, cellulose fibers, Franklin fibers).
Steady shear measurements were carried out using the Rheometrics
Mechanical Spectrometer at a fixed temperature of 180C using a cone-
plate mode.
Plots of steady shear viscosity '1 as a function of shear rate y for
various filled systems at a fixed loading of 20 vol% are shown in
Figures 6.1 and 6.2. The curves exhibit qualitative as well as quanti-
tative differences. The filled systems containing glass fibers, aramid
fibers, cellulose fibers, mica and glass beads exhibit qualitatively similar
behavior with low shear rate Newtonian viscosities and a decreasing
viscosity function at higher shear rates. On the other hand, the filled
systems containing calcium carbonate, carbon black, titanium dioxide
and Franklin fibers exhibit unbounded viscosity buildup at low shear
rates. Generally, the viscosity levels in these systems are higher than
those found in the former group of fillers.
The extent of the steady shear viscosity increase is the lowest for 3-
Effect of filler type 245
10 6
10 5
~II
17
104
.. CaC0 3
-CB
::~ UNII'S
c n0 2
17 -PA'SEC
FR.ANXLIN FIBERS -1
o PS r -SEC
103
10"3 10- 2 10- 1
r
Figure 6.1 Variation of steady shear viscosity with shear rate for filled-polystyrene
melts at 20vol% of various types of fillers as indicated. (Reprinted from Ref. 29 with
kind permission from American Chemical Society, Washington OC, USA.)
107 r;:::::======::;-----------,
FII.LlID POL YS'mENE
~
C GLASS BEADS 11800CI
- ARAMID FlBERS TI -PASEC
CELLULOSE FIBEiS -1
o MICA
o GLASS FlBERS
r- SEC
'Y
Figure 6.2 Variation of steady shear viscosity with shear rate for filled-polystyrene
melts at 20 vol% of various types of fillers as indicated. (Reprinted from Ref. 29 with
kind permission from American Chemical Society, Washington OC, USA.)
dimensional spherical fillers such as glass beads, higher for 2-

dimensional platelet fillers such as mica and highest for I-dimensional
fibrous fillers such as glass fibers. When considering rigid and flexible
fillers, the increase in the level of steady shear viscosity would be more
for rigid fillers than for flexible fillers because they resist deformation to
a greater extent. This is evident when the effect of glass fibers is
compared with aramid and cellulose fibers filled PS systems in Figure
6.2. All three fibers have nearly the same fiber diameter (Table 6.1), yet
the filled system with glass fiber shows the highest viscosity even when
the aspect ratio of the glass fiber is the lowest.
The existence of unbounded viscosity buildup at low shear rates as
shown in Figure 6.1 is not an effect of the filler rigidity or shape, but of
the filler size and will be discussed in the next sub-section.
6.2 EFFECT OF FILLER SIZE

Systems in Figure 6.1 exhibit the yield stress which is a manifestation of
strong particle-particle interaction and has direct relation to the particle
size. From Table 6.1, it can be seen that carbon black, titanium dioxide
and calcium carbonate have a much smaller particle size than mica and
glass beads. Similarly, from among the fibers, it is the Franklin fiber
that has a much smaller diameter than the other three fiber types. It is
only the smaller size fillers, specifically those having diameters below
O.5l!m, that have shown the yield stress. The smaller the particles, the
higher is the yield value [27]. In fact, with decreasing particle size, the
entire steady shear viscosity curve is pushed to a significantly higher
level [19,27]. The existence of yield stress in the steady shear viscosity
curve for filled polymer systems containing small size fillers has been
noted by other researchers [2,3,7,11,12,52] as well. Yield stress is
observed when the filler particles are extremely small as with carbon
black [19] or finely divided mineral particles [2,3,11,12,52]. Apparently,
the particles link temporarily into a network of finite strength. It must
be borne in mind that there may be a difference between yield stress
values obtained by extrapolating a flow curve to zero shear rate [7,11]
and those obtained by stressing a sample at rest until it yields [12].
For filled systems with larger particles, the response to deformation is
determined by hydrodynamic interaction and not by particle-particle
interaction. These non-interacting particle systems would not show the
yield stress as can be seen from Figure 6.2 wherein the smallest particle
dimension exceeds 10 l!m (Table 6.1).
Tanaka and White [86] have developed a cell theory of the steady
shear viscosity of a suspension of interacting spheres to account for the
viscous behavior of filled polymer systems. Essentially, they compute
the enhanced energy dissipation through the existence of interaction
Effect of filler size 247
energy between the particles, Ein!' and hydrodynamic viscous dissi-

pation Evis . Specifically the ratio of the viscosity 1] of the suspension to
that of the matrix 1]0 is
(6.1)
This energy-based method of calculation of viscosity 1] is due to
Einstein [87], who considered hydrodynamic dissipation in a very
dilute suspension of non-interacting spheres. Tanaka and White [86]
base their calculations on the Frankel and Acrivos [88] cell model of a
concentrated suspension, but use a non-Newtonian (power law) matrix.
The interaction energy is considered to consist of both van der Waals-
London attractive forces and Coulombic interaction, i.e.
Eint = Ev + Ec (6.2)
which are computed from the calculations of Hamaker [89] and
Derjaguin [90] for interacting spheres. It is shown that
Eint/EeiS = B1 (4), n)!y, EviS/Eeis = B2 (4), n) (6.3)
so that
(6.4)
where
CA H[ 1 ]2 CBoket/l~
Ir
(6.5a)
!y = 03 (4)m/4>)1/3 -1 + 0
1]*(4), y) = ~ K[(4)m/ 4>~1/3 _ yn-l (6.5b)
In equations (6.5a) and (6.5b), !y is the yield stress, n is the power

law index, K is the consistency index, C is a positive constant
representing the total number of nearest neighbours of each sphere, AH
is Hamaker's constant, 4>m the maximum volume fraction, Bo the
dielectric constant of the matrix, ke the thickness of the electrostatic
interaction layer, t/lo the surface potential of the particulates, 0 the
particle diameter and y the shear rate. Basically, equation (6.4) along
with (6.5b) is identical to the empirical Herschel-Bulkley [91] model
given by equation (2.45), and has been suggested also by Jarebski [92].
There are other theories which relate yield stress to volume fraction and
particle size, and these are available in Rajaiah [93].
From equation (6.5a), it can be seen that the yield stress increases
when volume fraction or surface potential or Hamaker's constant
increases and when particle size decreases. The usefulness of equation
(6.5a) is limited by the fact that most filler particles are neither
monodisperse particles nor are values of Hamaker's constant, the
surface potential and thickness of the interaction layer readily available.

If the electrostatic interaction is assumed to be negligible compared to
van der Waals interaction, then!y may be expressed as follows
!y= D3
CA H [ 1
(4)m/cl>)1 13-1
]2 (6.6)
If a value of 4> of 0.2 is taken, this predicts !y to be 101 '" 102 pascal for a
diameter of 111m, 103 '" 104 pascal for 0.1 11m and 104 '" 105 pascal for
0.01 11m if Hamaker's constant is 10-12 '" 10-13 erg.
Tanaka and White [86] were able to show semi-quantitative agree-
ment between calculated and experimental values of yield stress for
typical fillers such as carbon black, titanium dioxide and calcium
carbonate.
Yield stresses are generally observed in dispersions with fine particle
size having a high specific surface area and when the filler loading is
high. Increasing filler concentration has a pronounced eHect on the
rheology of the filled systems.
6.3 EFFECT OF FILLER CONCENTRATION

With increasing concentration of the filler, the interparticle interactions
increase weakly at first and then rather strongly as the concentration
becomes higher and higher. The concentration at which particle-particle
interactions begin depends on the geometry and surface activity of the
filler particles. For example, high aspect ratio fillers would begin to
interact at much lower concentrations, while non-agglomerated large
size spherical particles would not interact until about 20 vol% [94]. The
final concentration-dependent regime is that when a complete network
formation occurs due to particle-to-particle contact, which would occur
at concentrations of less than 1% for fibers and 40 vol% for non-
agglomerated, randomly dispersed spherical particles. This is exempli-
fied by the sharp rise in the relative viscosity '1r at the concentration
beyond which particle-to-particle contact occurs as can be seen from
Figure 6.3(a).
Various fillers were dispersed in different polymer matrices [21,22]
and their relative viscosity vs. volume fraction was plotted as shown in
Figure 6.3(a). It is seen that the relative viscosity of the filled polymer
system adjudged at the same volume fraction varies with the properties
of the filler such as shape, size, size-distribution, surface appearance,
etc. It is quite obvious what the effect of the physical nature of the filler
surface would be on the steady shear viscous properties of the filled
polymer systems. The higher the surface roughness the greater the
resistance to flow deformation and hence the viscosity of filled system
Effect of filler concentration 249
I I I
IFIllED POLYETHYLENE AND POLYPROFYI.ENE I

CF
10 I - 27
, ,,-
o NC/PE
ID NC/PP
c. Tl{ (PP
o GF(6)/PE
o GF(8) IPE
+ CF(18)/PE
.,. GF(23)/PP
,., CO(27)/PE
I
o 0.1 0.2 0.3 0.4
Figure 6.3(a) Variation of relative viscosity at constant shear stress with filler volume
fraction 4> for various filled polymer systems. The capital letters indicate the filler and
the numbers designate the average aspect ratio of the fiber. The dashed lines
represent the curve through the experimental points. (Reprinted from Ref. 22 with kind
permission from Steinkopff Verlag Darmstadt, Germany.)
would be higher. This can be deduced intuitively. Experiments to

verify this are not easy because it is very difficult to find two fillers
with the same size and size distribution but different surface
roughness. Some indication of the effect of roughness can be got from
the data available in the works of Kataoka et al. [21] and Kitano et al.
[22]. This is shown in Figure 6.3(b) which gives the relative viscosity
of systems filled with precipitated calcium carbonate (CC) and natural
calcium carbonate (NC). The surface of the precipitated calcium
carbonate is much rougher than that of the natural calcium carbonate,
and as a consequence, the viscosity of systems filled with CC is seen to
be higher than those filled with Ne. Of course, this is not the isolated
effect of roughness alone. The CC particles had a much smaller size
and a much narrower size distribution than the NC particles and hence
these factors would also contribute to the viscosity increase.
In Figure 6.3(a), the va lues of IJr of materials filled with natural
calcium carbonate powder NC are the lowest because they are basically
ICAI.,CIUU CARBONAIR FlLLED l'oLYE'Ilm.ENE1
10
I. I
ONC
cc
o 0.1 0.2 0.3 0.4
Figure 6.3(b) Variation of relative viscosity as a function of the volume fraction for
polyethylene melts filled with precipitated calcium carbonate (CC) and natural
calcium carbonate (NC). (Reprinted using data from Refs 21 and 22 with kind
permission from Steinkopff Verlag Darmstadt. Germany.)
particulate systems with an average of about 10 ~m particle size. The

result of NC in polyethylene (PE) and in polypropylene (PP) can be
approximated by a single curve, indicating that the matrix does not
influence I'/r as long as the filler surface is not treated with any specific
treating agents.
The talc particles (TK) being disk-shaped show a relative viscosity
higher than those of natural calcium carbonate (NC) filled polymer
systems. Further, it can be seen that the value of I'/r for systems filled
with glass fibers (GF) and carbon fibers (CF) increases rather sharply
with increasing average aspect ratio.
It should be noted that the relative viscosity shown in Figures 6.3(a)
and (b) is the one determined at constant shear stress, rather than at
constant shear rate, because it is independent of shear stress. This fact
was reaffirmed by Polinski et al. [71] as shown in Figure 6.4. Where the
data are plotted using relative viscosity at a constant shear rate then
a set of curves with varying shear rate would be obtained as shown
in Figure 6.5. The solid lines are the predictions of equation (6.7)
given by Jarzebski [92] as
I GLASS SPHERE FII.I.ED THE.RMOPLASTIC POLYMER I

UNITS
"'C 12 - PASCALS
OCOOo
+
.13%
tHt *...,~O'O 26%
... 35%
............... os:zOSVVuvv .46%
60%
rfbo 0 c - - -

q D [J
-1
10 .... ..... .. t*** ***~ .... Je AM..:.
CONE-AND-PLAIE
[JCAPII.I.ARY
- EXPERlMENTAI.
CURVES
Figure 6.4 Variation ot relative viscosity at constant shear stress as a tunetion ot

the shear stress tor a suspension ot 151lm diameter glass spheres in a thermoplastic
polymer. (Reprinted trom Ret. 95 with kind permission trom Elsevier Science-NL, Sara
Burgerharlstraat 25, 1055 KV Amsterdam, The Netherlands.)
('1r)y = 89 [ (4)m/<p)113-1
1 ]" (6.7)
Agreement between data and theory can be seen to be excellent. 4>m is

taken as 0.62 and the va lues of power law index n are chosen to be
different during the calculation depending on the chosen shear rate. At
shear rates below 1 S-l the polymer matrix and the filled system at most
concentrations is near Newtonian while the value of n reduces to 0.75 at
10 S-l and finally to 0.5 at shear rates in excess of 10 S-l. Of course, the
point of onset of shear thinning moves to lower shear rates with
increasing filler concentrations.
It is also seen in Figure 6.5 that the data at three different
temperatures superimpose on a single curve for each shear rate
considered. This is in contrast to the findings of Saini et al. [63] who
also prepared plots of relative viscosity with filler volume fraction for
four different polymer matrices at three levels of loading as shown in
I GI.ASS SPBERlt FILLED "IlmRMOPLAS1IC POLn& I

130Dc l~oC 1-
-- 110C A.
...
0 0 .t::::. 10. 1 1.0
10' 075
() 11 ~ 10 3 0.50
- JARZDSKI' S RQUAnON
AS AFUNcnON OF a
l::.
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Figure 6.5 Variation of relative viscosity at constant shear rate with filler volume
fraction. (Reprinted from Ret. 95 with kind permission from Elsevier Science-NL, Sara
Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)
Figures 6.6-6.9. The curves are distinctly different at the various

temperatures in all cases and the change in viscosity with filler
concentration is exponential, in particular, with a major rise occurring
beyond a filler volume concentration of 0.25 to 0.30. Note that the plot
in Figure 6.5 is on a semi-logarithmic scale while Figures 6.6-6.9 are
not. Hence, it is possible that the differences in values are masked in
Figure 6.5, thereby leading to a conelusion that the plot is unique and
independent of temperature. A eloser look at the plot does indicate this.
The temperature sensitivity of the relative viscosity can be easily
estimated [63] as follows.
The viscosity of a polymer melt decreases with increasing
temperature due to the greater free volume available for molecular
motion at the higher temperature. In the case of filled systems, the free
volume change is limited only to the polymer fraction of the composite.
10.0
ILO:=~~1
o - 220'b
6 - 20:S'b
Ylf ,T o- 190'b
5.0
l'Jo,r
1.0
o 0.2 0.4 0.6
Figure 6.6 Variation of the relative viscosity with volume fraction of ferrites for low
density polyethylene at three different temperatures. (Reprinted from Ref. 63 with kind
6.0 ..--------,..-------,--------,
'IPOL=-~~I
4.0 0 - 1?cf'c
A - 160De
3.0 0 - 1500e
2.0
].0
I) 0.2 0.4 0.6
Figure 6.7 Variation of the relative viscosity with volume fraction of ferrites for
polyurethane thermoplastic elastomer at three different temperatures. (Reprinted from
Ref. 63 with kind permission fram Society of Plastics Engineers Inc., Connecticut,
USA)
3
lWUUU FlilWI'B FILl.'ED
STYRENE - ISOPRENE - STYREliIE
BLOCK COPOLYhIiR
2 o - 220C
~ -190'b
o -160'b
o
o 0.2 0.4 0.6
styrene-isoprene-styrene block copolymer at three different temperatures. (Reprinted
from Ref. 63 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA)
13.0
110 IBABlUl4 FEnm ~ I

. POlYES"lER. ELASrOlomR. .
D - 2400C
9.0 ~ -:no't;
o - 220't;
fI',T 1.0
11 0 , T
5.0
3.0
10
0 0.2 04 0.6
~
polyester elastomer at three different temperatures. (Reprinted from Ref. 63 with kind
It is therefore expected that the filled polymer melt viscosity would be

less temperature sensitive than the unfilled melt viscosity. Referring to
Figures 6.6 through 6.9 at a given filler loading, the relative viscosity
increases with increasing temperature. This is because the drop in the
unfilled melt viscosity with increasing temperature is more than the
drop in the filled melt viscosity.
The Arrhenius type equation, (2.6a), proposed by Eyring [96], is most
commonly used to analyze the temperature dependence of melt viscosity.
For unfilled polymer systems, the viscosity IJO,T at a temperature T can
be related to the viscosity 'lO,TR at a reference temperature by the
following expression:
IJO,T = 'lO,TR exp(~~) (6.8)
where Eo is the activation energy of the flow process for the unfilled
system and R is the universal gas constant.
For a filled system, with volume fraction <p of the filler equation (6.8)
can be written as
'ltjJ,T = 'ltjJ,TR exp(~~) (6.9)
where 'ltjJ,T and 'ltjJ,TR are the viscosities for a filler concentration of <p.
Thus combining equations (6.8) and (6.9) gives
In 'ltjJ,T = In 'ltjJ,TR + (EtjJ - Eo) (6.10)
'lO,T lJo,TR RT
It is obvious that a plot of 'ltjJ,Y/IJO,T vs. l/T on a semi-Iogarithmic scale
would result in a straight line from whose slope D.E which is the
difference in the activation energy of viscous flow due to presence of
the filler can be calculated.
The va lues of Eo (i.e. the activation energy for viscous flow of unfilled
systems) and values of EtjJ (i.e. activation energy for viscous flow for
filled systems) are shown in Table 6.2. It is seen that the EtjJ values are
lower than Eo values in all cases, indicating that 'ltjJ,T is less temperature
sensitive as compared to 'lO,T which is obviously true because the fillers
provide very Httle free volume change with temperature in relation to
the matrix.
In Figures 6.3, 6.5--6.9, the x-axis is not normalized though this is a
common practice to be followed if a theoretical equation fit of the
Maron-Pierce [97] type is sought as shown in Figure 6.10. The simplest
one parameter equation which has been evaluated [21,22], and tested
extensively [71,72] is given as
(6.11)
Table 6.2 Values of activation energies calculated fram equation (6.10)
Filler amount 0% 40% v/v 47% v/v 57% v/v

E (kJ/mole) @ y= 100sec- 1 Eo E40 E47 ES7
SIS block co polymer 23.5 18.3 15.8 12.0

POlyurethane thermoplastic elastomer 71.9 50.2 42.9 39.7
Polyester elastomer 53.8 36.9 34.7 28.7
Low density polyethylene 15.9 5.7 5.1 4.9
Source: Rel.63 (reprinted with kind permission Irom Society 01 Plastics Engineers Inc., Connecticut,
USA).
IGLASS SPRm: FILLED POLY.ME.RS I

CHEVRON GRADE - 18
...CHEVRON GRADE - 24
CHEVRON GRADE -32
...CHEVRON GRADE -122
o 11IERMOPLASTIC @ 130 0 C
D 11IERMOPLASTIC @ 1S0 o C
~ 11IERMOPLASTIC @ 170C
- EQUATION (6.11)
o 0.2 0.4 0.6 0.8 1.0
Figure 6.10 Variation of average relative shear viscosity as a function of the reduced
volume fraction of filler. (Reprinted from Ref. 71 with kind permission fram Society of
Rheology, USA)
In Figure 6.10, the maximum packing parameter <Pm was determined

[71] experimentally by liquid displacement technique as 0.62. Several
different values have been reported in the literature. From geometrical
considerations, <Pm ranges from 0.52 for simple cubic packing to 0.74 for
rhombohedral packing. However, Kitano et al. [22] have suggested an
average value of 0.68 for spherical particulates whose aspect ratio is
dose to one. Nielsen [78], on the other hand, noted that maximum
packing usually ranges from 0.601 to 0.637 for random packing of
spheres, and it is generally smaller for agglomerated and non-spherical
fillers. Chong et al. [98] used a value of 0.605 for uniformly sized glass
beads which is in agreement with the observation of Nielsen [78].
Another method of interpreting flow data of filled polymer systems
is by following the route suggested by Shenoy and Saini [51]. Since the
relative viscosity 11r at constant shear stress gives a uniqueness to the
plot (Figure 6.3 vs. Figure 6.5), it is logical to choose a rheological
parameter which is determined under constant shear stress conditions,
and also one which is far from the zero shear rate region wherein filled
systems generally show the yield stress. The melt flow index (MFI)
becomes an ideal choice because it is determined at constant shear
stress in the medium shear rate range.
Using the inverse relationship between steady shear viscosity and
MFI [99], Shenoy and Saini [51] write the modified form of Doolittle's
equation [100] in the following form:
lnMFI(T, <p) = lnA" - f(/ <p) (6.12)
where MFI(T, <p) is the melt flow index of the filled polymer system at
temperature T and containing <P volume fraction of filler, A" is a
constant. It is now assumed that the addition of filler alters the free
volume state of the unfilled polymer. The free volume of the polymer is
specified by f(T, 0). Its melt flow index is written as MFI(T,O) and the
following relationship derived from equation (6.12) would then hold:
lnMFI(T,O) = lnA" - f(; 0) (6.13)
The altered free volume state of the filled polymer system is given, of
course, by equation (6.12).
As a first approximation, the free volume in the altered free volume
state resulting from the addition of a filler can be considered to reduce
the free volume of the reference medium and to be a linear function of
the volume fraction <p of the added entity similar to that given by Fujita
and Kishimoto [101]:
f(T, <p) = f(T, 0) - (T)<p (6.14)
where (T) represents the difference between the free volumes of the
polymer and the filled system.
Combining equation (6.12) to (6.14) and rearranging the terms gives
1 = -2.303f(T, 0) + 2.303P(T, 0) 1 (6.15)

log aMFI (T) </>
where
a MFI = MFI(T, O)/MFI(T, </
Based on the assumptions made during the derivation of equation
(6.15), it is imperative to choose MFI(T,O) > MFI(T, </. In the case of
filled systems, this condition is naturally satisfied when the polymerie
matrix is taken as the reference medium. Equation (6.15) prediets that a
plot of I/log aMFI vs. IN should be linear, and the propriety of this
model has been examined quantitatively in the light of the reported
experimental data. Existing viscosity data in the literature available for
all filled systems are in the form of viscosity vs. shear rate or shear stress
vs. shear rate curve. In each case the data are transformed into specific
MFI values using the method discussed in Shenoy and Saini [99].
Figures 6.11--6.16 show plots of 1/logaMF1 vs. I/</> for different filled
4
IQl1ARTZ F1llED r.oW DENSlTY POLYEmYLENE I
Inollc I
3
o
2 3 4
1
~
Figure 6.11 Melt Flow Index variation with filler composition for low density
polyethylene/quartz powder composite at 220C and 2.16 kg test load condition for
MFI using data from Ref. 16. (Reprinted from Ref. 51 with kind permission from
Steinkopff Verlag Darmstadt Germany.)
I
CALCIUM CABBONAIE FlU.lID l'OLYPROl'YLENE I
6 I220C I
4
Ioga JIIIII
o
o 2 3 4 6 1 8 9 10 11 12
Figure 6.12 Melt Flow Index variation with tiller composition tor polypropylene/
calcium carbonate composite at 200C and 2.16 kg test load condition tor MFI using
data trom Ret. 5. (Reprinted trom Re!. 51 with kind permission trom Steinkopff Verlag
Darmstadt, Germany.)
polymer systems. The systems are so chosen as to include different

generic types of polymers as the matrix, and to include fi11ers with
different shapes and types. In a11 cases, despite the apparent diversity,
there is a uniqueness in the altered free volume state model, adjudging
from the straight line fits obtained in a11 plots.
Though it is recommended that the relative viscosity 17r or the
relative MFI value aMFI be used for estimating the rheological changes
due to filler concentration, at times a simple plot of MFI vs. the weight
fraction of the filler can certainly provide the same information as
done by Arina et al. [17]. The effect of fillers on the melt flow
properties of polyethylene were investigated [17] by determining the
melt flow indices of the compounded filled systems. It was found that
finely divided fillers reduced the melt flow index of polyethylene more
than coarsely divided fillers, a result similar to that discussed in
section 6.2. As regards the effect of concentration, the melt flow index
was not affected much at small concentrations but there was a sharp
6
ICAUON lILACK FILI.ED POLYSl"YiENE1
11SOoC I
o 2 4 5 1 8 9 10 11 12
1
T
Flgure 6.13 Melt Flow Index variation with filler composition for polystyrene/carbon
black composite at 180C and 5.0 kg test load condition for MFI using data from
Ref. 27. (Reprinted from Ref. 51 with kind permission from Steinkopff Verlag Darmstadt,
Germany.)
IMANIOld DIOXIDE FIWll POLYSTYlmNE I

11gooe I
o
o 2 3 4 5 6 1 8 9 10 11 12
I
T
Flgure 6.14 Melt Flow Index variation with filler composition for polystyrene/titanium
dioxide composite at 180C and 5.0 kg test load condition for MFI using data from
Germany.)
IaLA5S FIm. FIllED rotYCAllBONATE I

1290DC I
o
o 5 7 9 10 11 12
Figure 6.15 Melt Flow Index variation with filler composition for polycarbonate/glass
fibers composite at 290C and 1.2 kg test load condition for MFI using data from
Germany.)
IOLASS Fml!B. FlI.lED POLYEl"BYUNI! TEREPBTHALA1'! I

1215"<:1
4 7 10 11 12
Figure 6.16 Melt Flow Index variation with filler composition for poly(ethylene
terephthalate)/glass fibers composite at 275C and 2.16 kg test load condition for MFI
using data from Ref. 20. (Reprinted from Ref. 51 with kind permission from Steinkopff
Verlag Darmstadt, Germany.)
drop with increasing concentration as can be seen in Figures 6.17(a)

and (b).
6.4 EFFECT OF FILLER SIZE DISTRIBUTION

In order to study the effect of filler size distribution, it is necessary to
work with uniform monodisperse particles. These would have to be
available in different sizes so that controlled mixtures of two or three
different sizes can be studied. There are various methods of getting
uniform-sized particles and these have been discussed in a number of
articles [102-106].
The simplest technique of getting uniform mono-sized particles is by
precipitation from solution due to the controlled generation of solutes
by a single burst of nuclei [102]. This method is commonly used to form
hydra ted metal oxides by hydrolyzing the appropriate metal salto Thus,
spherical aluminum hydroxide can be obtained [102] from alum and
spherical colloidal rutile can be prepared from TiCl4 Similarly, mono-
-=="..---+--+-1
--------
8 TALe I DOLOMIrE FILLED
LOW DENSrrr POLYETHYlENE
5
4
3(V--;~~~~~-r~~~~
I ~~~
2
0.5
0.2
:88015 + TALCA
~ () 11 3(124 + TALe 11
e 11 3024 + DOLOMITE
\ \
o 11 3(124 + TALC A
9
o 0.1 0.2 0.3 0.4 0.5 0.6
~J
Figure 6.17(a) The influence of some fillers on the melt flow indices of B3024 and
B8015 polyethylene grades. (Reprinted from Ref. 17 with kind permission from Society
of Plastics Engineers Inc., Connecticut, USA.)
Effect of filler size distribution 263
---""~
MICA FII.UID LOW DENSlTY POLYETHYlENE
50
........
30
20
,... - ~
~~
"W
10
-S
~- \~
(~
r-- ~
~
\
\.:I
3 ~ I~
'\.. \ \
\\
2 ~
0.5
UNIIS
MFI -
I-- .300De
pt 0 l1l/I
I \\ \
0.3 \
~
(t 2SOoC
0.2 r - ~ mOc ~
e 220C
o 190Dc \
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7
.'
Figure 6.17(b) The influence of mica A on the melt flow index of B 8015 polyethylene
at various temperatures. (Reprinted from Ref. 17 with kind permission from Society of
Plastics Engineers Inc., Connecticut, USA)
sized silica particles can be prepared by precipitation of solutes

[103,104].
The other method of developing fine, spherical particles is through
the use of plasma techniques which may involve a physical
phenomenon or a chemical reaction [lOS]. In the former case, a simple
spherodizing process takes place when irregular shaped powder is
introduced into the plasma which melts it and then vaporizes it to form
uniform spheres. When a chemical reaction is involved, the reactants in
the solid or gaseous form in contact with the plasma are allowed to
react in the vapor phase and the products are allowed to condense as
deposits of fine powder on the cooler regions of the chamber after
leaving the plasma. Colloidal spheres of aluminum, copper, aluminum
nitride and silicon carbide are made in this way.
Uniform-submicron size polymer spheres can be made through

emulsion polymerization [106]. When a sparingly water-soluble vinyl
monomer like styrene that polymerizes by a free radical mechanism is
dispersed in water in the presence of a surfactant and a water-soluble
initiator, uniform-sized polystyrene beads can be obtained by
controlling the number of micelles and ensuring that each micelle traps
an initiator at ab out the same time.
The various methods employed to get uniform-sized partic1es have a
set goal to get model filler partic1es so that filled system experiments
can be controlled effectively to isolate the effects of various parameters.
This is especially important when studying filler size distribution effect
on the rheology. Despite all efforts to get uniform-sized partic1es, there
is often a distribution involved, however narrow it may be. Hence, to
study the effect of a bimodal size distribution on the rheological
behavior of filled polymer systems, glass spheres obtained from Potters
Industries Incorporated were fractionated by Poslinski et al. [72] into
narrow size ranges. Two size ranges of spheres were picked in the
preparation of the bimodal mixtures, and Table 6.3 lists their partic1e
size distribution, with the number of fractions of the ith component fi
vs. the diameter of the ith component D i being tabulated.
Polydispersity tends to reduce the viscosity of filled systems at a
fixed loading level [107-112]. For dilute suspensions having a volume
fraction of solids less than 0.2, the effect of variation of partic1e size on
filled system viscosity is minimal [108,111]. However, at high loading
levels the viscosity can be reduced dramatically when the partic1e size
Table 6.3 Average particle size and particle

size distribution using digital image analyzer
Small spheres Large spheres
0, (11m)
0.04 2 0.01 45
0.11 5 0.04 50
0.15 9 0.04 56
0.24 12 0.15 62
0.10 16 0.10 70
0.13 19 0.20 78
0.08 21 0.21 83
0.06 25 0.15 90
0.04 29 0.06 99
0.03 32 0.03 105
0.02 35 0.01 110
Source: Rel. 72 (reprinted with kind permission Irom

Society 01 Rheology, USA).
modality is increased [98,113-115]. Henderson et al. [114] reported a

reduction in filled system viscosity as high as 96% when the modality
was changed from a unimodal to a bimodal size distribution of spheres
at a fixed volume fraction of 0.66.
Theories on the viscosity of polydisperse systems have been developed
[109,113] and a method to predict the viscosity of multimodal filled
systems from the data for monomodal filled systems is also available
[113].
Farris [113] has shown that the relative viscosity of the filled polymer
system can be described by
(6.16)
where k is a constant which varies according to the particle size
distribution and depends on the number of components making up the
distributions. In practice, k varies from 21 for monomodal to 3 for
infinite-modal distributions. Figure 6.18(a) graphically shows the
relationships. For uniform spherical particles viscosity increases steeply
after 4J = 0.5, approaching infinity at 4J = 0.74.
However, if the total volume of particulate filler is split into 25% fines
and 75% coarse, very high loading can be obtained without increase in
viscosity; this is shown in Figure 6.18(b).
103
.. WONOUODAL t-21 /
IJ BIllODAL t-S.8
o TRD40DAL t- 3.6
I
INPINIl'E WODAL t-
3
I"r-<t-;)"tl
102
'J r
10
0.2 0.4 0.6 0.8 1.0
Flgure 6.18(8) Comparison of calculated relative viscosily for the best multimodal
system. (Reprinted from Ref. 113 with kind permission from Society of Rheology, USA)
10 4 C------------------r------,
1O~ __ ~ ___ ~ ___ ~ _____ ~ _____ ~
0.60 065 070 0.75
Figure 6.18(b) Variation of relative viscosity as a function of vol% solid spheres in

monomodal and bimodal suspensions, with volume fraction 01 small spheres being
25%. (Reprinted Irom Ref. 113 with kind permission lrom Society 01 Rheology, USA.)
If the ratio of the coarse to fine particle diameters is 7:1 the volume of
filler can be increased to 4> = 0.73 from the monomodal loading of
4> = 0.59 without increase in viscosity. Figure 6.18(c) shows the pro-
portion of coarse and fine particles to give minimum viscosity for a
range of total filler loading, indicating minima in the region of 30% fines.
Further reductions may be possible with increasing modality; but for
modalities greater than trimodal, the cffects are not dramatic.
A natural consequence of the above findings is that for a given level
of filled system viscosity, it is always possible to increase the loading
level of the fillers through a careful choice of particle size distribution.
This particular point has a direct significance when dealing with
ceramic and metal processing [48,66-69,73-75,116-127] as well as during
the preparation of functional filler composites [60-63] where the prime
intention is to have as high a filler loading as possible and yet maintain
good processibility.
Mangels [116,117] has made use of the reduced viscosity of wide size
distribution powders to produce injection molding blends of high
powder loading (73.5vol%). Working with silicon powder, particle size
distributions were obtained [116] by dry ball milling and air classifying,
and it was subsequently shown that a 140 h dry ball-milled powder
with the broadest particle size distribution yielded the best viscosity in
0.40
0.30
020
" 0.10
0.20 0.40 0.60 0.80 1.0
Figure 6.18(c) Comparison of calculated relative viscosity for bimodal suspension

of various blend ratios and concentrations. (Reprinted from Ref. 113 with kind
permission from Society of Rheology, USA)
a spiral flow mold test [117]. In general, by altering the partiele size
distribution from a sharp, monomodal type [118] distribution to a very
broad distribution, the solids content can be increased without
increasing the viscosity of the system [119]. Similar requirements have
been noted by Adams [120] for slip cast ceramics and there is a
similarity with the requirements for achieving high compaction density
in a pressed powder [121-123].
Chong et al. [98] were able to achieve volume concentrations elose to
Eiler's value of 0.74 for rhombohedral packing by using abimodal
mixture of spheres. They identified the diameter ratio of sm all to large
spheres, b, and volume percent of smaller particulates in the total solids
mixtures, 4>., as two important parameters characterizing a bimodal
solids mixture. By fixing 4>. at 25%, Chong et al. [98] showed that the
filled system viscosity was reduced as b decreased from 1.0 to 0.138;
however, they surmised that no significant reductions would occur
below a limiting partiele size ratio of approximately 0.1 as the sm all
spheres could easily migrate through the interstices of the large spheres.
Calculations with varying 4>. [98] suggested that there also exists an
optimum volume percent of smaller spheres where the filled system
viscosity is minimized.
Higher packing densities can be achieved if the particle sizes are not
uniform. This enables the finer particles to fill the holes between the
larger particles. The particles size range can be broadened in two ways.
Mixtures of two particles sizes can be blended, for example, coarse and
fine particles, or a continuous wide distribution of particle sizes can be
selected.
Increasing the number of particles sizes in the mixture can increase
the calculated packing density [123]. Table 6.4 shows the maximum
packing density attainable for random packing mixed spheres (with
from one to four sizes) [124]. An extension of the idea of bimodal
packing of spheres, is the packing of combined fibers and spheres.
These have been well described and discussed in detail by Milewski
[128]. It is pointed out that packing parameters change with respect to
fiber length to diameter ratio and choosing proper size combinations of
the mixed fillers optimizes the benefits from packing.
Gupta and Seshadri [129] used Ouchiyama and Tanaka's results [130]
to calculate the maximum packing parameter of polydisperse systems
of spheres given the value for the monodisperse sampies and taking
into account particle size, size distribution and modality as follows
4> = 'L,Dfh (6.17)

1
m 3

'L,(D; '" Da) 'j; + [(D; + Da)
3 3
- (D; '" Da) ]h
where
'L,(D; 8~D a ] h
+ D a )2 [ 1 -
= 1 +.i. (84)0 _ l)D + Da)
(D; (6.18)
13 m a 'L,[Df - (D; '" Da?Jh
and
Da = I:DJ (6.19)
Table 6.4 Efleet of partiele size distribution on maximum paeking density

of randomly dispersed spheres
Ratio of Ratio of fraetions Maximum paeking

partiele diameter(s) of (wt%) density
the size fraetions (vol%)
d1 100 64
d 1 , 1/7d1 84/15 86
d 1 , 1/7d1 , 1/49d1 75/14/11 95
d1 , 1/7 d1 , 1149d1 , 1/343d1 72114110/3 98
Souree: Ref. 124 (reprinted with kind permission from Ameriean Chemieal Soeiety
Ine., Westerville, Ohio, USA).
Here <P~ denotes the maximum packing of spheres of uniform size

which may be taken to be the average value of 0.619 as suggested by
Nielsen [78]. Da is the average diameter of the different sizes of the
particulates, Di is the diameter of the ith component, and the abbrevi-
ation (Di ....., Da) is defined as:
for Di ~ Da (6.20a)
and
(Di ....., Da) = Di - Da for Di > Da (6.20b)
In addition, J; is the number fraction of the ith component defined by:
V'/~V'
J;=D~ ~D~ (6.21)
, I
where Vi is the volume fraction of the ith component in the mixture.

The number fraction may also be directly obtained if a size distribution
of the solids, J; vs. Di , is available as in Table 6.3. The maximum
packing parameter can be calculated with equations (6.17)-(6.21) for
any solids mixtures of spherical particulates, and equation (6.11) may
then be used to estimate the value of the filled system viscosity at a
fixed shear stress level.
Poslinski et al. [72] undertook the study of the influence of a bimodal
size distribution of glass spheres on the rheology of filled polymer
systems. They used small and large glass spheres of sizes as given in
Table 6.3. The average diameter of the two size ranges calculated by
equation (6.19) was 15 and 78 11m, respectively, and therefore the
particle size ratio was 0.192 based on these average values. Bimodal
size distributions were prepared by mixing together various volume
percents of the smaller 15 11m spheres with the larger 78 11m spheres;
specifically, <Ps = 0, 10,30,50,75 and 100%. Figure 6.19 shows the maxi-
mum packing data obtained for a bimodal solids mixture of 15 and

781lm glass spheres with <Ps' the volume percent of smaller spheres,
ranging from to 100% of the total solids mixture. The experimental
values of the maximum packing fraction were obtained by the
sedimentation technique, and these indicated that <Pm increased for a
bimodal system depending on the amount of the smaller spheres. Also
shown in Figure 6.19 is the value of the maximum packing calculated
from the data of Chong et al. [98] for a bimodal distribution of spheres
at <P = 0.60 and >s = 0.138 as well as Sweeny's da ta [115] at <P = 0.55
and 15 s = 0.048. The highest value of the maximum packing parameter,
0.752, was obtained by mixing approximately 15% of the 15 11m and
85% of the 781lm glass spheres in the total solids volume. The error
bars shown in Figure 6.19 represent the random error in the experi-
mental measurements of the maximum packing.
DATA OF POSLINSXl ET AI.. [72 J

0.8 0 DATAOFCHONGETAL[98J
[115J
0.6
0.5 L...---'--..l.._'----'---'-_'--...l...----'-_L.-...l
o 0.2 0.4 0.6 0.8 1.0
Figure 6.19 Variation 01 maximum packing as a function 01 the bimodal size

distribution of the 15 and 781lm glass spheres. (Reprinted lrom Rel. 72 with kind
permission from Society of Rheology, USA.)
Various bimodal mixtures were compounded into a polybutene grade

24 polymer obtained from the Petrochemical Division of the Chevron
Company, at total solids concentrations up to 60% by volume. The
polybutene polymer was a Newtonian liquid at room temperature
whose viscosity and density at 22C were 25 Pa sec and 898kg/m3 ,
respectively. Due to the relatively high viscosity of the polybutene, it
was found that the glass spheres suspended in the polymer remained
dispersed for at least 24 h before complete settling occurred.
Upon addition of glass spheres to the polybutene grade 24 matrix,
the magnitude of the shear viscosity at 22C was observed to increase
and it remained approximately constant for shear rates ranging from
0.1 to 100 sec-I. As a result, the relative viscosity data determined at the
same shear stress were obtained by averaging data over the entire shear
rate range of measurement.
To see the effect of particle size and size distribution, the average
relative viscosities of the various glass sphere suspensions are plotted
against c/>s' the volume percent of the 151!ffi spheres, ranging from 0 to
100% of the total solids mixtures as shown in Figure 6.20. When the
103 !=""",;:~:;::;;:;;:;::;;;:::;::;;;;;;::;;::::;::;;;:::;:;-'-~-=l
IGUlSS SPml! FIWll POLYBll'mIE I
~ TOTAl. SPHE\Il!S
0.10 ... 040
. . 0.20 0.50
.030 0.60
- EQUATION(611l
o DKrA OF CBONO ET KL. (98)
o DATA OF SWEENY [mi
1.0
Figure 6.20 Variation of average relative shear viseosity as a funetion of rPs' the
vol% of the 1511m glass spheres in the total solids mixture suspended in a polybutene
grade 24 matrix at 22C. (Reprinted from Ref. 72 with kind permission from Soeiety
of Rheology, USA)
two sizes were mixed together, the relative viscosities were actually
reduced, especially for volume fractions of total solids greater than 0.3.
The lowest values of 17r were obtained for <Ps = 10 to 30% of the smaller
spheres, the same range in which the maximum packing parameter was
observed to be highest. The 60% by volume loading level could not be
achieved for a unimodal size distribution due to difficulty in obtaining
a fully homogeneous compound; however, it was possible to reach this
high concentration for <Ps = 10, 30 and 50%.
The solid lines in Figure 6.20 represent the predictions of equation
(6.11) with the maximum packing fraction determined by equation
(6.17) using the particle size distribution values of the bimodal
components listed in Table 6.3. The agreement between theory and
experiment is excellent. The optimum reduction in the relative
viscosity is correct1y predicted by equations (6.11) and (6.17) to be
<Ps = 15%, which corresponds to the highest value of the maximum
packing.
6.5 EFFECT OF FILLER AGGLOMERATES

The presence of agglomerates has a considerable effect on the maximum
possible loading of the filler, as can be seen from Table 6.5. If the
agglomerates are all broken down into individual particles, then
63.7vol% of the filler can be incorporated into the polymer. However, if
a dozen particles are clustered together in each agglomerate, then the
maximum loading possible would be only 43 vol%. At maximum filler
loading, the viscosity of the filled system is close to a hundred to a
thousand times greater than that of the polymer itself, as can be seen
from Figure 6.10. Agglomerates occlude liquid in their interparticle
voids, thereby increasing the relative viscosity value at any given solids
loadings. Thus, the viscosity would be the same for 43 vol% of
agglomerated filler with a dozen particles in each agglomerate as it is
for 63.7vol% of non-agglomerated particles.
For highly filled polymer systems, it is therefore important to reduce
the degree of agglomeration to a minimum level, in order to decrease
the system viscosity for easier processing and to increase the extent of
filler loading.
The adhesion forces between particles have been discussed by Rumpf
and Schubert [131]. In addition to electrostatic and van der Waals
forces, the presence of liquid and solid bridges contributes to high
agglomerate strength. The dispersion of powders in liquids is
influenced in part by the wetting characteristics of the liquid on the
solid surface, and is related to the hydrogen-bonding capability of the
liquid which can be expressed as its cohesive energy density [132]. The
initial drying of powders and the heating associated with processing of
a high molecular weight organic vehicle help to reduce the effect of
labia 6.5 Effect 01 aggregration on maximum liller concentration 4>m
Number 01 particles in Maximum Iiller concentration

aggregated spheres 4>m' (vol%)
1 63.7
3 60
5 53
8 47
12 43
18 39
32 37
57 35
122 34
250 32
Souree: Ref. 76 (reprinted with kind permission from Mareel Dekker Ine., New
York, USA).
Effect of filler surface treatment 273
liquid bridges. The presence of solid bridges when a sm all amount of

additive has been incorporated in the powder via a salt by spray
drying, such as magnesia in alumina or yttria in zirconia, gives rise to
more serious problems. Such agglomerates can only be broken down by
milling of the powder or by using mixing devices which impose high
shear stresses.
High shear mixing generates velocity gradients which are normally
strong enough to break agglomerates in fillers of micron size or larger.
In the case of submicron fillers, the forces holding the particles together
are stronger than the shear force created by the velocity gradient. In such
circumstances, even high shear mixing does not break the agglomerates
or eliminate the microvoids within the filled system, and one has to
take recourse to filler surface treatment [9,15,34,36,37,43-45,52,54,60]
which is capable of altering the interparticle forces, resulting in
deagglomeration, better dispersion, and hence lower viscosity with
maximum possible loading.
6.6 EFFECT OF FILLER SURFACE TREATMENT

An approach to improving filler-polymer compatibility is the use of
surface-modifiers on the filler through apretreatment process. Surface
treatment is meant to help the polymer wet the filler and disperse it.
However, the extent of wetting and degree of adhesion are different
for each polymer, filler, and surface modifier combination. Some
modifiers that will effectively coat the filler surface may not interact
with the polymer, whereas others that are compatible with the
polymer may not adhere to the filler, and hence, will not effectively
modify its surface. It is thus very difficult to predict the performance
of the surface modifier apriori for any filler-polymer combination. It
is, therefore, a common practice to select the appropriate surface
modifier for a filler-polymer combination rather empirically. One
could, of course, refer to the extensive information available in the
form of books, reports and papers [133-135] on various types of
surface modifiers listed in Table 1.5.
Surface modifiers are generally bifunctional molecules with one end
capable of adhering to the filler and the other end compatible with the
polymer, and at times even capable of reacting with it. There have been
extensive studies on the effect of surface treatment on the steady shear
viscous properties of filled polymer systems [9,13,15,18,32,34,36,38,
39,52,53,60].
There is enough evidence that the increased melt viscosity introduced
by filler addition can be significantly reduced by the application of
surface modifiers to the fillers. Some typical examples of viscosity
reductions achieved through the addition of surface modifiers to
selected filled polymer systems are given in Table 6.6. The maximum
reduction in viscosity is seen to be 73% in the 40phr high aspect ratio
mica in unsaturated polyester.
Reductions in viscosity can also be achieved through the use of
wetting agents such as W-900 manufactured by Bye-Mallinckrodt as
shown by Cope and Linnert [32]. With low-profile fillers like day, silica
and mica, viscosity reductions of 70, 80 and 90% respectively have been
observed. Presence of low-profile filler in a 50% blend of wollastonite
and polyester have been seen to give 35 to 41% lower viscosity. Cope
and Linnert [32] observed an interesting synergistic effect when wetting
agents and silanes were used in combination. A 60% quartz/epoxy
Table &.& Effect of surface modifiers on so me selected filled polymer systems
Polymer Filler, loading (phr) Surface Viscosity Melt flow Source

modifier, (Pa sec) index Ref.
amount (g/10 min)
(phf)
Unsaturated polyester WOllastonite, 150 90 [13]

Unsaturated polyester WOllastonite, 150 A-174,0.5 54 [13]
Unsaturated polyester Calcined kaolin clay, 100 56 [13]
Unsaturated pOlyester Calcined kaolin clay, 100 A-174,0.5 37 [13]
Unsatu rated polyester Hydrous kaolin clay, 88 95 [13]
Unsaturated pOlyester Hydrous kaolin clay, 88 A-174,0.5 36 [13]
Unsaturated pOlyester Tale, 100 58 [13]
Unsaturated polyester Tale, 100 A-174,0.5 30 [13]
Unsaturated polyester Mica (high aspect ratio), 104 [13]
40
Unsaturated polyester Mica (high aspect ratio), A-174,0.5 28 [13]
40
Unsaturated pOlyester Silica 10/1, 120 52 [13]
Unsatu rated pOlyeste r Silica 10/1, 120 A-174,0.5 14 [13]
Unsaturated polyester Alumina trihydrate 65 [13]
Unsaturated pOlyester Alu mi na trihydrate A-174,0.5 48 [13]
HOPE Wollastonite,43 16.5 [13]
HOPE Wollastonite,43 TTS,3 16.5 [13]
HOPE Calcium carbonate, 150 16.3 [13]
HOPE Calcium carbonate, 150 TTS, 3 17.8 [13]
HOPE Barium sulfate, 150 16.3 [13]
HOPE Barium sulfate, 150 TTS,3 22.0 [13]
pp Calcium carbonate, 50 4.4 [30]
pp Calcium carbonate, 50 Stearic 5.2 [30]
acid,1.0
pp Calcium carbonate, 100 3.6 [30]
acid,0.2
acid,1.0
acid,1.5
system produced a 60% viscosity reduction with a hydrophobie wetting

agent and an 80% reduction with a silane/BYK additive combination.
The general conclusions of Cope and Linnert [32] are that greater effects
occur with increasing filler concentration and with those fillers that are
most difficult to wet and disperse. Similarly, thermoplastic filled systems
produce greater effects than those seen in thermosets because these
resins do not wet fillers well. Cope and Linnert [32] have shown how
wetting agents can be effectively used in low density sheet molding
compound (SMC) for lowering viscosities.
Observing the published data, it is seen that, in some ca ses, the effect
on the steady shear viscosity is only marginal. There are a few select
cases [9,18] wherein the viscosity is seen to reduce even below that of
the virgin polymer (Figures 6.21(a) and (b. Figure 6.21(b) taken from
Monte and Sugerman [18] shows how the concentration of the titanate
changes the flow behavior of 70% calcium carbonate filled
polypropylene. The work of Han et al. [15] also indicates that the melt
viscosity decreases with the addition of TTS to CaC03-PP and fiber
glass-PP system. The extent of decrease depends on the type of the
surface modifier and the type of the filler-polymer combination. It was
found that the effect of TTS in decreasing the viscosity was more than
in the ca se of ETDS-201; so also there was a profound effect on the
viscosity of CaC03-PP system than fiberglass-PP system. A possible
I-=~~~~II-
TI -PASE9

r- SEC-I
I
Inoc I
TI I~
t
Figure 6.21(a) Variation 01 steady shear viscosity with shear rate. (Reprinted Irom
Rel. 9 with kind permission Irom Society 01 Plastics Engineers Inc., Connecticut, USA)
WII'H 0.5 ... %:n m

c 70% Fll.lEll TBEA1'ED
WII'Hl.o ... %om
102 L..:::====:::r=====---L___
o UNFILI.I!D
L -_ _-.J
Figure 6.21(b) Variation ot steady shear viseosity with shear rate. (Reprinted trom
Ret. 18 with kind permission trom Mareel Dekker Ine., New York, USA.)
explanation for this viscosity decrease has been suggested by Han et al.
[15,34] to be due to the plasticizing effect of the organie groups in
titanate coupling agents. It is more likely that the titanium oxide
monomolecular layer formed by monoalkyl titanates and the silanol
monomolecular layers formed by silanes on the filler surface, modify
the surface energy so that the viscosity of the filled polymer system is
reduced. The effect of viscosity reductions in these systems [15,34] was
not as drastic as observed [9,18] in Figures 6.21(a) and (b).
The normal expected behavior from the use of surface modifiers is
one in which the viscosity reduction occurs to a different extent
depending on the type of surface modifier, its amount and method of
treatment. The maximum achievable reduction would most likely be
very dose to the flow behavior of the unfilled polymer at least at higher
shear rates. This is well illustrated in the work of Saini et al. [60] for
highly filled polymer systems.
Saini et al. [60] used pretreated fillers in their study of the effect of
surface modifier on the melt rheology of styrene-isoprene-styrene block
copolymer. The platelet-shaped barium ferrite that was used as filler
was not monosized, and had an average partide size of about 311m.
Two silanes: Z6075 and Z6076; and three titanates: KR38S, KR 138S,
and KR TIS (Table 1.5 for chemical description) were used as surface
modifiers. The treatment method consisted of using a solution of 95
parts methanol and 5 parts of water by volume for the silanes and 100
parts of xylene for the titanates. Surface modifiers of an amount equal
to 1% by weight of barium ferrite were dispersed in the solvent. The

slurry was formed by wetting the required quantity of barium ferrite
with the prepared solution and stirring for about 30 minutes. It was
then allowed to stand overnight and the solvent was removed in the
oven at 105C for silanes and 130C for titanates.
The viscosity vs. shear rate data obtained by Saini et al. [60] for
57 vol% of barium ferrite pretreated with different surface modifiers is
shown in Figure 6.22(a). It can be seen that all titanates aid in reducing
the viscosity of the filled polymer system while the silanes show a very
marginal effect. Though there have been a number of articles in the
literature [7,9,15,34,36,44,133-135] on the mechanism by which surface
modifiers act, not all seem to show coherent agreement. Some have
105 r------;:::::;:;;;;:::;::======;:::::;:::;::::=;::;:;~~
IBARIOM FERRIT!! FILLJ!D STYRENE-ISOPRENE-STYRl!NE I
UNITS
TI -PASEC
r - SEC-I
1 OD eI
FERRIT!! UNnEATIID (57 v% FII.I.ER)

A FERRIT!! TRl!Al1!D WITH SILANE - U076
B FERRIT!! TRl!Al1!D wrm SILANE U075
e FERRIT!! TRl!Al1!D wrm mANATE - D38S
D FERRIT!! TRl!Al1!D wrm mANATE - lO!.I38S
E FERRIT!! TRl!Al1!D wrm mANATE - lO!. TIS
o UNFlI.LED
Flgure 6.22(a) Variation of apparent viscosity with shear rate at 220C for unfilled,
57 vol% untreated ferrite filled, and 57vol% treated ferrite-filled SIS block copolymer
systems. (Reprinted from Ref. 60 with kind permission from Society of Plastics
Engineers Inc., Connecticut. USA.)
postulated [15,43] that there is a tendency to produce a plasticizing

effect, due to the modification of the interfacial characteristics of the
filled system. The titanates in the case of Saini et al. [60] could have
acted as good dispersing agents, but not as coupling agents, and
provided no chemical bridge between the polymer and the filler
particles. The scanning electron micrographs shown by Saini et al. [60]
give evidence of the fact that the dispersion level is better with the
titanates than with the silanes. However, since no low steady shear data
were presented, this conclusion cannot be ascertained with confidence.
It is quite plausible that the titanates act as good dispersing agents and
provide a plasticizing effect as well, thereby resulting in drastic reduc-
tions in viscosity of the filled polymer systems [60].
The effect of surface modifier concentration was also studied by Saini
et al. [60] as shown in Figure 6.22(b). It is seen that the optimum
concentration is in the range of 0.6-0.8% by weight of filler. Their
results confirm the range suggested by Monte and Sugerman [18] and
Sharma et al. [36]. The exact optimum concentration would, of course,
vary for each filler, polymer, and surface modifier combination, and
may need to be determined each time.
It must be emphasized here that the method of pretreatrnent also
plays an important role in the final performance of the filled polymer
system. This point has not been addressed by earlier investigators. The
silanes, for example, are known to undergo hydrolysis/condensation
1.0
VISCOSllY
RAlIO
0.5
0.4
o O.S 1.0 1.5 2.0
%TrS
Figure 6.22(b) Variation of viscosity ratio at a shear rate = 100 sec- 1 of treated to
untreated 57 vol% ferrite-filled SIS with different percentages of KR TTS for
determining the optimum treatment level. (Reprinted from Ref. 60 with kind permission
from Society of Plastics Engineers Inc., Connecticut, USA.)
Effect of polymer matrix 279
reactions, and the extent of these reactions is a function of the nature of

the solvent phase, silane concentration in solution, pH of the solution,
and filler treatment time [133]. Prehydrolysis of the silane is known to
be beneficial because the silanols formed in the reaction can then react
with the filler surface. However, two silanols can undergo a parallel
self-condensation reaction reducing the systems activity towards the
filler. By adjusting the pretreatment variables in a favorable manner, it
would thus be possible to make either of the possible reactions dominate.
This would naturally result in differences in the efficacy of the filler
surface modification. Further, it is known that the preferred orientation
of a silane molecule at the inorganic filler surface is with silanol function
attached to it and the organofunctional group extending away from it.
Deposition of the silane from water or alcohol would naturally assist
this favorable orientation, provided the pH is equal to or less than the
isoelectric point of the inorganic surface. By altering the pH, it might be
possible to deposit the silane in an inverted fashion as suggested by
Plueddeman [133]. This would alter the rheological characteristics of
the filled polymer system. It is not known to what extent the rheology
of the filled system could be altered by manipulations in the treating
method, and this may need systematic investigation.
6.7 EFFECT OF POLYMER MATRIX

The effect of the polymer matrix on the steady shear viscosity of filled
systems would depend on the chemical nature of the polymer as
well as its unfilled viscous characteristics. The polymer melt itself
could be Newtonian, moderately shear-thinning or predominantly
shear-thinning.
In the case of polymers like nylon, polyethylene terephthalate (PET)
and polycarbonate (PC), the steady shear viscosity is near Newtonian
up to even a shear rate of a little over 100 S-1 as can be seen from
Figures 6.23-6.25. As an example of a moderately shear-thinning
polymer, polyetherimide (PEI) could be considered [136] as shown in
Figure 6.26; while, for a predominantly shear-thinning polymer, poly-
propylene (PP) is a reasonable example as shown in Figure 6.27. Note
that in Figures 6.24 and 6.27, the plots are shown as shear stress vs.
shear rate which is, of course, another method of representation of the
same information.
In a11 cases, it can be seen that the addition of fillers whether they are
particulates like calcium carbonate (CaC03 ) or glass fibers (CF), sys-
tematically moves the entire curves to a higher level. The viscosity
increase is greater at lower shear rates whereas lower at higher shear
rates. The extent of the effect would, of course, depend on the nature of
the polymer and the filler type, size, size distribution, etc.
103 , . . . - - - - - - - - y - - - - - - r - - - - - - , - - - - - ,
IGLASS FIBER FIllED NYlON 66 I

UNITS
TI - PASEC
'Y - SEC,l
102
MARANYL Al00
Figura 6.23 Variation of steady shear viscosity with shear rate at 280C for nylon 6,6
unfilled grade (Maranyl A 100) and filled grade with 3~% glass fibers (Maranyl A 190).
Connecticut, USA)
IGLASS FIBER F1WJ) POLYF:IHYLENE 'I'E.RE.1'KI'H.1

UNITS
PETIFIBER.
C -PASCALS
y_SEC'1
CAPILI.ARlES :
o O.000381M RADIUS, O.0254M LENGTH
O.000656M RADIUS. O.0254M LENGI'H
.... O.000903M llADIUS, 0.0254 M LENGI'H
Figure 6.24 Variation of shear stress with shear rate at 275C for polyethylene
terephthalate unfilled and filled with glass fibers. (Reprinted from Ref. 20 with kind
TI CONE-PLATE C.APJI.LARY MAKROLON

DKrA DATA G1tADE % FlI.1.ER
'"'" "7
'0"
8324
8344
20
40
0
8035
9410
30
10
...
0 2805 0
I:>. 6S55 0
1
100 10 102 103 104
r
Figure 6_25 Variation of steady shear viscosity with shear rate at 290C for glass
fiber filled polycarbonate of different grades of Makroion. (Reprinted from Ref. 31 with
kind permission from John Wiley & Sons, Inc., New York, USA)
104 ,..---.,------.-----.-----,r-----,----,
GLASS FIBER FILLED POLYETBERIMIDE
UNlTS
TI -PASEC
r _SEC- 1
TI 103
GF
Cl 30%
X 20%
o 10%
I:>. CO!.
10 2
2 4
10 1 10 103 10
r
Figure 6.26 Variation of steady shear viscosity with shear rate for polyetherimide
unfilled and filled. (Reprinted from Ref. 136 with kind permission from Society of
Plastics Engineers Inc., Connecticut, USA)
3zIIY r;:::::::::::::;:~~~~~~~~::;::;--I
ICALCIUM CARlIONAIE FlLLlID POLYFROPYLENE I
UNITS I200C I
"t: -PASCALS
r-SEC I
.ff.
0 70'10
... 40'10
t:l 20'10
... 10'10
0 0'10
40 60 100
Figure 6.27 Variation of shear stress with shear rate at 200C for polyprapylene
unfilled and filled as shown. (Reprinted from Ref. 5 with kind permission fram John
Wiley & Sons, Ine., New York, USA)
As against the normal expected behavior as shown in Figures

6.23-6.27, there is at times an abnormal behavior observed [137] as
depicted through Figures 6.28 and 6.29. These two figures show two
sets of steady shear viscosity data reported [137] for polystyrene melt
filled with carbon black. The difference is only in temperature of
measurement. Figure 6.28 shows an expected increase in viscosity and a
yield stress behavior at low shear rate with increasing filler
concentration. The behavior at 230C as shown in Figure 6.29 is
considerably different from that at 180C in Figure 6.28, especially for
low levels of filler loading wherein viscosities fall below even the
unfilled matrix. The main difference arises because the polymer matrix
at 230C is near-Newtonian while at 180C it is considerably shear-
thinning. When it is near-Newtonian, the polymer chains are not
entangled and hence the small amount of carbon particles act as ball-
bearings thereby reducing the friction between the chains during flow
measurement. With increasing filler concentration, this effect is
overpowered by the resistance offered by the undeformable filler
particles to flow. On the other hand, when the polymer is shear-
thinning, the polymer chains are entangled to start with and the
addition of filler particles does not in any way facilitate the disentangle-
ment. In fact, the particles are assisted by the entangled polymer chains
10 5
IC~~:~FIIllD I
UNITS
1'/- PASEC
-Y-SEC- I
11 104
I180C I
10 3 ' - - - - - ' - - - - - ' - - - - ' - - - - - ' - - - - - '

-2 -I
10 10
Figure 6.28 Variation of steady shear viscosity with shear rate at 180C for high
molecular weight polystyrene filled with carbon black (24 m2 /g) as shown. (Reprinted
from Ref. 137 with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA.)
10 5 ,---.,...----,------r----,.----,
BLACK FlIl.ED I
I. CARBON
POLYSTYRENE .
UNITS
11 -PASEC
i' - SEC-I
I:230 oc I
10 2 '--_ _-'-_ _-''--_ _-'-_ _-''--_ _-1
-2 -1
10 10
Figure 6.29 Variation of steady shear viscosity with shear rate at 230C for high
molecular weight polystyrene filled with carbon black (24 m2 /g) as shown. (Reprinted
from Ref. 137 with kind permission fram Society of Plastics Engineers Inc.,
Connecticut, USA.)
in forming their own network structure. Such abnormal behavior as

shown in Figure 6.29 has been observed [84] for other polymers such as
high density polyethylene (HOPE) as well.
The most appropriate method of studying the effect of the polymer
matrix is by understanding the steady shear viscosity changes using
different polymer systems but with the same filler and at a fixed level
of loading. This has been done by Saini et al. [63].
The filled systems studied by them consisted of the same filler type,
namely, barium ferrite of about 3 ~ average particle size, mixed under
the same mixing conditions in four different matrices: 5-1-5 block
copolymer, Hytrel polyester elastomer, thermoplastic polyurethane, and
low density polyethylene. The dispersion achieved was determined
through steady-state high shear rheology [63] measured in a capillary
rheometer.
Figure 6.30(a) shows the rheological response of three of the matrices
at the same temperature of measurement. It can be seen that 5-1-5 block
copolymer has the highest viscosity while Hytrel polyester elastomer
has the lowest. Though low density polyethylene lies in between it is
highly shear-thinning in behavior, unlike the other two.
When each of these matrices is filled with 57 vol% of ferrites, the
resulting relative viscosity behavior of the filled system is different, as
can be seen from Figure 6.30(b). One of the reasons for these differences
is that the level of shear during the mixing operation is different in each
case due to the differences in the viscosities of the base matrix. On this
basis alone, one can expect the relative viscosity in the case of Hytrel
polyester elastomer to be the highest. However, there are other reasons
such as the matrix-filler affinity that would also contribute to the
differences in the filled system viscosity. For example, polyethylene is
nonpolar and has no affinity for the filler; while 5-1-5 due to the
presence of polystyrene and polyisoprene blocks is polar, and hence,
has better affinity to the filler. The result of this affinity is the presence
of a greater force to break filler-filler bonds as the polymer pulls the
particles away from each other during high shear mixing. This could
lead to a better dispersion and lower viscosity. However, when the
matrix-filler affinity is high, the system behaves like a bead-spring
structure wherein the particles are like beads and the polymer acts as
springs. This exemplifies itself as a higher viscosity of the filled system.
The final rheological response is the sum total of the response due to a
better dispersion and the restrained deformation behavior due to the
bead-spring structure.
Chemical bonding of the polymer with the filler results in an increase
in the effective particle size and decreased molecular mobility. For
example, the active filler carbon black in rubber was shown to greatly
increase the viscosity over that of equal-sized inert filler particles by
IUNFILLED POLYMERSI
UNITS
1'/ -PASEC
1
r- SEC
I220C I
103
1'/
o Sl-S BLOCK COPOLYMER
10 1 L----'--'-L.....L...I-LJ...J....L_-'--'-...l-JL.l..-L....W...l...-_-'--.1-.I.--I.....L..L..W-l
10
Figure 6.30(a) Variation of the apparent steady-shear viseosity with shear rate for
unfilled polymers. (Reprinted trom Ret. 63 with kind permission trom Society ot Plastics
Engineers Ine., Conneeticut, USA.)
Bartenev and Zakharenko [138]. To account for this chemical bonding

in a filled polymer system, Droste and Dibenedetto [139] proposed that
the relative viscosity of the system should be thought of as the product
of two effects, namely, the mechanical reinforcement and modification
of the polymer matrix due to the filler. The relative viscosity could then
be written as
I1c I1c I1mc
11 = - = - -
r I1mo I1 mc I1 mo
where I1 c is the viscosity of the filled composite material, I1 mo the

viscosity of the unaffected polymer and I1mc the viscosity of the polymer
matrix.
10
r
Figure 6.30(b) Variation of the relative steady-shear viscosity with shear rate for
57 vol% barium ferrite filled polymers. (Reprinted fram Ref. 63 with kind permission
fram Society of Plastics Engineers Inc., Connecticut, USA.)
Under certain restrictive assumptions, Droste and Dibenedetto [139]

simplified equation (6.22) to give the following explicit expression
for '1r'
(6.23)
where Gc , GmO are the storage moduli for the filled composite and
unfilled polymer, respectively, and Tgc Tgo are the characteristic glass
transition temperatures of filled composite and unfilled polymer, respec-
tively. Hard fillers, such as silica, are known to raise the glass transition
temperature of the host polymer. A detailed study of this effect can be
found in Peyser [140] as weIl as Lipatov and Sergeeva [141]. The effect
of temperature on the ratio Gc/Gmo has been studied by Kolarik et al.
[142]. They found the ratio to decrease with decreasing temperature
due to an increase in the magnitude of the induced stress near the filler
particle.
The above equation (6.23) can be used in all cases, except for
extremely low filler concentration, to estimate the relative viscosity of a
composite system when there is interaction between the filler and the
polymer matrix. The strong dependence of viscosity on the surface
properties is brought out also in the work of Dufresne [143] as stated by
Unification of steady shear viscosity data 287
2.8
ICARBON BLACK FlLLIiD mOH DENsnY POLnnM.ENE I
2.6 o C'P.l
<> C'P. 2
2.4 ... C'P. 3
o
/
CB 4
2.2 v CI! $
l.O
1.8
IJ r
1.6
1.4
1.2
10
0.9
01 0.2 0.3 0.4
"
Figure 6.31 Relative steady shear viscosity at shear rate of 10sec- 1 of weight fraction
of high density polyethylene filled with various types of carbon black used in Ref.
143. (Reprinted from Ref. 84 with kind permission from Hemisphere Publishing, New
York, USA)
Carreau [84]. Different carbon blacks with different characteristics [143]

were obtained from two suppliers and used for the preparation of filled
systems of high density polyethylene (HOPE). The viscosity data were
compared at a shear rate of 10 sec- 1 against concentration on a weight
basis. The relative viscosity of HOPE filled with five different carbon
blacks is shown in Figure 6.31 and can be seen to be radically different
from each other.
6.8 UNIFICAnON OF STEADY SHEAR VISCOSITY DATA

It has been shown [50] that the steady shear viscosity vs. shear rate flow
curves of filled polymer melts at various temperatures and filler loadings
can be unified when plotted on a log-log scale in terms ofa reduced
viscosity parameter of (1'/ x MFI) vs. a reduced shear rate parameter of
(y jMFI). As already indicated in Chapter 3, melt flow index (MFI) is
defined as the weight of polymer in grams extruded in 10 min through
a capillary of specific dimensions by pressure applied through dead
weight via a piston. The geometrie parameters of the melt flow indexer
and description of the test conditions are summarized in Appendix A,
as per ASTM 01238 for commonly used polymers and as per

ASTM 03364 for polyvinyl chloride (PVC). Since the melt flow indexer
is basieally an extrusion rheometer, it is possible to calculate a value of
shear stress and apparent shear rate corresponding to an MFI value
using the conventional expressions given below:
r = - RNF
-2- (6.24)
2nRp ZN
. 4Q
')'=--3 (6.25)
nRN
where piston radius Rp = 0.4737 cm, nozzle radius RN = 0.105 cm,
nozzle length ZN = 0.8 cm as per ASTM 01238 and ZN = 2.326 cm as per
ASTM 03364, force F = test load L(kg) x 9.807 x 105 dynes, volume rate
Q through the nozzle = (MFI/600p cc/s). (Conventional units used [99]
instead of SI units.)
Using the above geometrical parameters, the expressions for 11 and y
in an MFI apparatus can be simplified to give
r = 1 9.13 x 104 L (for all commonly used polymers except PVC) (6.26a)
3.1 x 104 L (for PVC) (6.26b)
y = 1.83 MFI (6.27)

p
As each MFI is taken under fixed load conditions, it is evident from
equation (6.26) that the MFI test is truly a constant shear-stress measure-
ment. Moreover, from equation (6.27) it is clear that for each value of
MFI of a given system at a specific temperature, a value of shear rate
can be obtained at the specific shear stress. This would then be a
single point on the shear stress vs. rate curve at that specific
temperature. With rearrangement of equations (6.26) and (6.27), it can
be seen that
11 x MFI
= 14.98 x 104 pL (for all commonly used polymers except PVC) (6.28a)
1.7 x 104 pL (for PVC) (6.28b)
So, also from equation (6.27), it can be seen that
y 1.83
(6.29)
MFI P
For a given polymerie system, as the density and testing load
conditions are fixed, the right-hand sides of equations (6.28) and (6.29)
become constant. It is easy to see that the proportionality between MFI
and (1/1]) would hold over the entire flow curve merely by changing
the dead weight conditions and hence the proportionality constant in
equation (6.28). Therefore, it would be rational to expect the viscosity
vs. shear rate curve to coalesce irrespective of the type of formulation
when 1] x MFI is plotted against y/MFI (for convenience on a log-log
scale). The coalescence would be governed by the shape of the original
rheogram which, in turn, is linked to the molecular weight distribution
and degree of branching. Similar shaped curves would, undoubtedly,
coalesce better. In arriving at the coalesced curves, the viscosity and
shear rate are normalized via the MFI. Since MFI is itself insensitive to
subtle changes in molecular parameters, this limitation would be
expected to be present even in the coalesced curves. The limitation of
molecular weight distribution would be more critical in the very low
and very high shear rate regions. However, the working ranges of shear
rate for most polymer processing operations fall in the intermediate
region, thus rendering coalesced curves effective for use as a handy tool
for the processors.
Within the melt flow indexer die, capillary entrance effects are
important as IN/RN is equal to 7.6 for ASTM D1238 and 22.2 for
ASTM D3364. These have not been accounted for during the derivation
of equations (6.28) and (6.29). From the above discussion it is evident
that MFI would be used merely as a normalizing factor to obtain
reduced viscosity vs. shear rate curves. The MFI values used in
generating the plots as weIl as those which would be used for obtaining
the rheograms from the master plots would have the capillary entrance
effects implicit in them and hence would annul each other.
Menges et al. [44] proposed a method for converting the viscosity
curves for filled systems into those for the unfilled base polymer by a
shift factor under a constant shear stress. Though their viscosity
function is temperature and concentration invariant, their approach
requires a knowledge of the shift factor in the case of each system,
while the method discussed above uses MFI as a normalizing
parameter.
The arguments in the foregone analysis have been developed by
Shenoy et al. [144] and shown to hold good for a number of homo-
polymers [144-150], copolymers [151], liquid crystalline polymer [152],
recycled polymer [153], blends [154], PVC formulations [155] and filled
systems [50].
MFI obtained from the tests specified in ASTM D1238 would give
values which may not be at the temperature of interest. In the case of
homopolymers or filled systems, the modified W-L-F equation
suggested by Shenoy et al. [144] could be used to estimate the MFI at
the temperature of interest through a knowledge of the glass transition
temperature T g of the material.
fable 6.7 Glass-transition temperatures for certain selected polymers
Polymer type Glass-transition temperature (K)
Polyethylene 153
Polypropylene 263
Polystyrene 373
Polymethyl methacrylate 378
Nylons 323
Polyethylene terephthalate 343
Polycarbonate 414
Polyvinylidene fluoride 238
Polyphenylene oxide 481
Polyphenylene sulfide 358-423
Polyether sulfone 493
Polyaryl sulfone 556
Polyether ether ketone 417
Polyetherimide 490
Polyarylate 423-460
The pertinent equation is given below:

MFIT2
Iog--= 8.86(T2 - Ts ) 8.86(TI - Ts)
(6.30)
MFI T1 101.6 + (T2 - T s ) 101.6 + (Tl - T s )
where Tl is the ASTM recommended test temperature in K, T 2 is the
temperature at which MFI is required in K, Ts is the standard reference
temperature in K (= Tg + 50), T g is the glass transition temperature of
the system in K.
The glass transition temperatures of certain selected polymers are sum-
marized in Table 6.7. It is important to note here that the glass-transition
temperature of the polymers is affected by the addition of fillers, as
discussed in detail by Peyser [140]; hence, special care should be taken to
determine the T g of the filled systems when using equation (6.30).
As can be seen from ASTM 01238, there is more than one set of test
load conditions under which MFI measurement can be taken. In order
to obtain estimates of MFI at different load condition, the following
technique can be used [144]. The single point measurement of MFI,
which gives a point in the non-Newtonian or shear-thinning portion of
the shear stress vs. shear rate curve, is merely shifted on the curve by a
change of load condition. It is known that in the non-Newtonian
regime, the relationship between shear stress and shear rate can be weIl
approximated by the following power-Iaw model.
r = K:yn (6.31)
where n is defined as the pseudoplasticity index and K is the
consistency index.
Using equations (6.26) and (6.27), the following relationship can be

derived for different conditions L1 and L2
MFI 2 __ (L2)1/n (6.32)
MFI1 L1
where L1 = test load in kg and L2 = load in kg at which MFI is required.
The value of n can be obtained for a specific system from the slope of
the r vs. y curve on a log-log scale, or calculated from the slope (n - 1)
of the viscosity vs. shear rate curve on a log-log scale. The estimated
values of n to be used in equation (6.32) for certain selected filled
polymer systems, irrespective of the filler type, are given in Table 6.8.
Table 6.8 Rheological parameters of the modified Ostwald-de Waele power-Iaw

model (equation 6.35) for certain selected polymers
Polymer K n Modified Test loadt

(g/cm sec 2- n) shear rate' (kg)
x(g/10min)n (sec-')
x(g/10minr'
Low density polyethylene (LOPE) 1.7 x 105 0.37 1-1000 2.16 a

High density polyethylene (HOPE) 1.24 x 105 0.471 2-1000 2.16 a
Ultrahigh molecular weight polyethylene 1.66 x 106 0.156 10-10000 10.00a
(UHMWPE)
Linear low density polyethylene (LLOPE) 1.0 x 105 0.66 4-100 2.16a
Polypropylene (PP) 1.75 x 105 0.34 4-1000 2.16 a
POlystyrene (PS) 3.32 x 105 0.368 0.4-200 5.00 a
Cellulose ester (C-Ester) 3.2 x 105 0.38 20-1000 2.16 a
Cellulose ether (C-Ether) 1.5 x 105 0.47 2-100 2.16 a
Acrylic 3.2 x 105 0.44 20-1000 3.80a
Nylon 3.4 x 105 0.44 50-1000 2.16 a
Polyethylene terephthalate (PET) 5.0 x 105 0.43 50-1000 2.16 a
Polycarbonate (PC) 2.5 x 105 0.52 80-1000 1.20a
Polyvinylidene fluoride (PVOF) 7.5 x 105 0.40 2-200 12.50
Polyphenylene oxide (PPO) 1.0 x 106 0.25 40-1000 5.00
Polyphenylene sulfide (PPS) 6.0 x 105 0.44 10-100 5.00
Polyaryl sulfone (PAS)/polyether sulfone 3.0 x 105 0.60 10-1000 5.00
(PES)
POlyether ether ketone (PEEK) 6.0 x 105 0.32 20-1000 5.00
Polyetherimide (PEI) 1.4 x 106 0.34 200-1000 5.00
Polyarylate (PAr) 2.4 x 105 0.85 10-100 5.00
Styrene acrylonitrile (SAN) 3.0 x 105 0.33 3-1000 3.80
Styrene-butadiene-styrene (SBS) 1.0 x 106 0.25 20-2000 5.00
Acrylonitrite-butadiene-styrene (ABS) 3.5 x 105 0.38 1-100 5.00a
Vinyl chloride-vinyl acetate co polymer 4.0 x 105 0.33 0.3-7000 20.00
(VCVA)
Ethylene-vinyl acetate (EVA) 1.0x105 0.55 1-1000 2.16
Polyester elastomer 1.4 x 105 0.65 7-300 2.16
Thermoplastic elastomer (TPE) 1.5 x 105 0.40 1-1000 2.16
Polyvinyl chloride formulations (PVC 4.6 x 105 0.36 5-2000 20.00a
formulations)
, Applicability range for Y/MFI.
t Condition for MFI used in the master rheogram.
a ASTM specified.
As noted earlier, MFI represents a point on the shear stress vs. shear
rate curve in the medium shear rate region for most polymers. This fact
is useful for caleulating the value of MFI from a known shear stress vs.
shear rate curve when MFI is not reported. For example, for a load
condition of 2.16 kg, the constant shear stress in the melt flow apparatus
from equation (6.26a) is equal to 1.97 x 105 dynes/cm2 . Thus reading
out the value of shear rate y for this constant shear stress at a specific
temperature, a value of MFI could be caleulated using equation (6.27).
The propriety of this method for obtaining MFI from a shear stress vs.
shear rate curve has been tested [99] for different polymers with
reported MFI. The caleulated values and the reported values are always
found to be in good agreement. This method has also been employed
by Rideal and Padget [156]. They actually measured viscosity on a
Weissenberg rheogoniometer at shear stress equivalent to that in the
MFI apparatus and used it to estimate the MFI of polymers, whose MFI
values were too low to be measured accurately on the melt flow
indexer.
The MFI values needed for the unification process can be got in one
of the three following ways [99]:
1. Method A: MFI can be actually measured using a melt flow indexer
2. Method B: MFI can be estimated from the available shear stress vs.
shear rate curve in the manner discussed above
3. Method C: MFI values along with the detailed measurement con-
ditions can be obtained from the polymer manufacturers
directly or thraugh their specified brochures.
Figures 6.32 to 6.39 show plots of '1 x MFI vs. Y/MFI on log-log scale
for a number of filled polymer systems. Master curves that are charac-
teristic of a generic polymer type have been presented for low-density
polyethylene (LDPE), polypropylene (PP), polystyrene (PS), nylons,
polyethylene terephthalate (PET), polycarbonate (PC), polyetherimide
(PEI) and polyether ether ketone (PEEK) using data fram Refs 5, 9,
14-16, 18, 20, 25, 27, 31, 136, 157-159. The various filled polymer
systems analyzed [50] are summarized in Table Bi of Appendix B.
The viscosity data include the effect of seven filler types, namely,
carbon black, titanium dioxide, quartz powder, calcium carbonate, tale,
mica and glass fibers. These fillers represent a range of particle sizes.
Carbon-black particles are generally very fine, with the median particle
size in the range of 0.02 to 0.08 ~m, depending on the method of
preparation, whereas mica and quartz particles are relatively large, with
the median size ranging fram 10 to 80 ~m. A number of filler particle
shapes are also represented, including particulate, plate-like and fibraus.
The various filler parameters influencing viscosity and their ranges,
covered in the data [50] analyzed, are summarized in Table B2 of
106
1 I I 1111111 I I 1111111 I I 1111111 I I 1111111 I I 1111111
FILLED LOW DENSITY POLYETHYLENE UNITS
A A 'l - POISE
E De IB t - SEC'
MFI-vm/fOmin
I&.
~
~I 111111111 '1'1,1.1111 ,[11111111 111111111
I 11111111
~ I I I I IIIII I I I I I IIII D
-+B
e~I~JI~ljljl~II~III--r1 11111111
11~lfIRII~II~I==t=jjiffi
4 I~
10 A~K
HF
r---t GRADE 24FADDZ z4FS04OlzeMA200IP' IP' I PI PI 1 PI PI PI PI PI I PI
Ru:::re - - I - 1011301110001 ZOOOlJtlOI nOI eCOol"~ u..I ..~~tt~

- B LL ~~III I I I I 11111
A e E
D - I I I I I 1111 I I I I I 111
H K L 11 N o
l'/MFI
Figure 6.32 Master curve for filled LOPE at 2.16 kg test load condition for MFI using data from Refs 16, 138. (Reprinted from Ref. 50 with
kind permission from Society of Plastics Engineers Inc., Connecticut, USA) (Note that SI units have not been used for viscosity in order to be
consistent with the conventional units of MFI as explained in Ref. 99.) (10 Poise = 1 Pa.sec.)
Q
t06 t-O
R
p FILLED POLYPROPYLENE
N ~
UNITS
o-R
Q - POISE
'1 l-
p -1
N t - SEC
aI MF 1- 9m!10 min
105
Cro H-l~
F-9 E .1
F AD1:.t
LI...
~C
::E
,:-'
.,.,
N ffYAD'E':
GRADE tO"OtI to .1.1 & UI I". I MI IMI IH' I ttllttl PRO'''. ".1 '110' "Ot '~
"AK E
LOADING . . . . . ., 0
,,,, 0 0 UCD 1100 alocc ... ce "~D
104 r- "" .... .... ... _.E
TREATED tTTI OoSTTI TTI 0"'-
~ phi - -
-
- 10. . K AD
r- ZOO'C - - G H 1 J K L M - - - - - K
r- Z10'C A D - - - - - - - - - - - -
220'C - - - - - - - - - - - 0 R
I- -
230'C B E - - - - - - - - - - - -
r- 240'C - - - P - -
2S0'C C F - -
-
-- -- -- -- -- -- -tl -0 -
-
103 I 11 I I I I 11
I 2 10 1 100 101 10 2 103
t/MFI
Figure 6.33 Master curve for filled pp at 2.16kg test load condition for MFI using data fram Refs 5, 9,18,157. (Reprinted from Ref. 50 with
kind permission fram Society of Plastics Engineers Inc., Connecticut, USA.) (Note that SI units have not been used for viscosity in order to
be consistent with the conventional units of MFI as explained in Ref. 99.) (10 Poise = 1 Pa.sec.)
107
- -- . -- -.- --.--------.-
I I I
FILLED POLYSTYRENE J
I' UNITS
l N 't - POISE
0 F,
C t - SECI
0
~ I N MFI- 9m/iOmin
106 P F:
G
K-tf ;H-IC
H "-0-0 P
\L. H Fk~
::!: iA LN
ME I
~
H
"\p , H i...
p"
H M
F
ADI M'. 'lU .'IU "IU ,.,IU ., u .'nu .'IU .TI U .,. U
'7' U
LOAD .........1 0 0 TIO
~ ~~ ~ ~
fO!l 0 HctI "TI", H TiO ..... "1' n ...... 10 ......
_u. .... .",U1.
T.IATID - - - - ...
-- "E
taoc G H I K L M N 0 P 0
- zooc
- - D - - - - - - - N
ZIOC A - - - - - - - -
-- --" -- --
- A 6 I'
2Z0-C - E - - - - - - -
- nooc 8 - - -
-- -- -- -- - - - - - 0
240C - - - - E
- - F - - - - - - -
2!10C C - - - - - - - - - - - -
104 I 1 I- 11 11 H-
I 3 f 2 f ' 10 0 10' 102
't/MFI
Figure 6.34 Master curve for filled PS at 5.0 kg test load condition for MFI using data from Refs 14, 18, 27, 157, 160. (Reprinted from Ref.
50 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA) (Note that SI units have not been used for viscosity in
order to be consistent with the conventional units of MFI as explained in Ref. 99.) (10 Poise = 1 Pa.sec.)
105~ - ; . E..:fiC+ . 11
.CHI ~D~
[ ~-
- A
Jtl.H
I I 11111111 FILL!. LioU 1111 i:ff1"rHH .l 11111111 ., ~:"}M

~
J
....
::E
'0'1 111111111 111111111 111111111 ~I 111,tl /I"!'--th 11111I
~
NYLON I NYLON" NYLON" NYLON I I NYLON" NYLON . .

10' &RADI: ~LA&ICON 1101 ZYTEL ZYT1EL ZYTEL MA1tANYL Atoo "AlIAllYL A1'O NYLON 110
L- u:::r - 0 151F IIOG' 0 501' -
- Z51C A - - -
r-- ZIOC I
f---- ZlOC I J K
r--- Z. .C C D G
"tC E F H
102 1 I 11111111 I I 1111111 I I 1111111 I I 1111111 I I 1111111

1 1 IOD 101 10Z 10' 10
i'/MFI
Figure 6.35 Master curve for filled nylon at 2.16 kg test load condition for MFI using data from Refs 25, 158, 161, 162. (Reprinted from
Ref. 50 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA) (Note that SI units have not been used for viscosity
in order to be consistent with the conventional units of MFI as explained in Re!. 99.) (10 Poise = 1 Pa.sec.)
106
11111 J I I 1\1\\ \ I LU I I I I
FILLED POLY (ETHYlENE TEREPHTHALATE)
~
'1 - POISE
t - SEC'
MF I - vm/l0 min
10 K
f-L1r.: 8 A~li::f~ Fo'U :-t=A -na joI-
D=~ ~~u
I _8 P'E
H
IL. Ib~
~
~
~tli
"I k
Kl ! J
GRADE .. ,.ER IRAH r!T I PET I

6"E_
104 L- I.V.-OIl' .O,~J.~~.=:DE r !TI
I LOAD'''I 0 551 .. 55 ...
1"."
f-- Z700C A E I J I(
f-- ZISoC ,. I
- - -
f-- Z9SC C G - - - I,
,oaoc 0 H - - -
10' 1~HI o' 1I -
I 1~ 11
l 2 10' 100 10' 102 10~
t/MFI
Figure 6.36 Master curve for filled PET at 2.16 kg test load condition for MFI using data from Refs 20, 163. (Reprinted from Ref. 50 with kind
permission from Society of Plastics Engineers Inc., Connecticut, USA) (Note that SI units have not been used for viscosity in order to be
consistent with the conventional units of MFI as explained in Ref. 99.) (10 Poise = 1 Pa.sec.)
106
~
-r-tit :::r
IIUIU ~ I I I
FILLED POLYCARBONATE UNITS
'l - POISE
t - SEC'
MFI- gm/tOmin
105
D
,. I"
.... ,.I~ ~Ie
E I I
::t
Hr--DA I--E
~ A
,. H
D
e
E
104 LEXAll MAKIIDLON
It - - MADE 141 ZI05 '4'0 ISZ4 10U 1144 ,.
f-- LOAD'''' - 0 10.,. ZO.,. 50., 40'"
r--- '....' H
f-- ZIO A - - - -
f-- 270 I - -~ >-
-- -
110
-,.
D E N
e
-I
103 -- 111 ~]
l' 10' tOZ 10'
WllJ~tc:P ter
t/MFI
Figure 6.37 Master curve for filled PC at 2.16 kg test load condition for MFI using data fram Refs 31, 164. (Reprinted from Ref. 50 with kind
permission fram Society of Plastics Engineers Inc., Connecticut, USA) (Note that SI units have not been used for viscosity in order to be
consistent with the conventional units of MFI as explained in Re!. 99.) (10 Poise = 1 Pa.sec.)
POLY ETHERIMIOE
R
~
I' 11
UNITS I
"\ - POISE
E
t - SEC f
! "8 11
10 D" MFI- am/fOmin
#l
..-a. 1ft
f I
I> T
4 D
i I
oiO
GRADE 355C 375C 395C 360 C
ULTEM o ".G F iO%GF 20%GF 30%GF
1000 E F G A B C D
3
10 0
10 10 2
r/ MFI
Figure 6.38 Master eurve for filled PEI at 5.0 kg test load eondition for MFI using data
fram Refs 136, 165. (Reprinted from Ref. 149 with kind permission from Teehnomie
Publishing Co. Ine., Laneaster, Pennsylvania, USA) (Note that SI units have not been
used for viseosity in order to be eonsistent with the eonventional units of MFI as
explained in Ref. 99.) (10 Poise = 1 Pa.see.)
Appendix B. It may be noted that all the individual curves in Figures

6.23-6.26 coalesce to form the master curves in Figures 6.35-6.38,
respectively.
Each master curve also contains analyzed data for unfilled systems
from Refs 144, 157, 160-165 as summarized in Table B3 of Appendix B,
thus indicating that the changes in the rheological characteristics due to
the addition of the filler are implicit in the MFI value and, hence, a
unique curve is obtained. In the very low-shear rate region, however,
the curve is not unique due to the yield stress behavior, which is known
to occur for filled systems alone. This aspect is depicted in Figure 6.39
for PEEK, where a clear fork can be seen at low shear rates in the
region of 10-2 to 10-1 S-I. Though, in the other curves, this fork is not
shown, it does not mean that it is absent. Sufficient data in the low
shear region would illustrate such a behavior. Therefore a limitation on
the master curve is its inability to predict the correct rheogram at very
low shear rates for filled systems, where yield stress behavior is seen.
However, the master curve in the higher-shear rate region beyond
10-1 S-1 would be the same irrespective of the filler type and amount, as
weIl as the surface modifier type and amount. Thus, the master
7
10
'POLY ETHER ETHER KETONE
.Y!!!ll.
e II -POISE
10
l' -SEC-I
MFl-gIII/IO lIIin
?-
0
1 F
16
360 :380C I"~'"

~
4
UMFI - - Fre.
10
PE~~:~CF~8~1~~U - B
951 GI/ UNFllLED C
103
PEEK 4530 6l FlllED
GlASS FIBER E - F
10- 1 10 0 10 1 10
1'/ MFI
Flgure 6.39 Master curve for filled PEEK at 5.0 kg test load condition for MFI using
data from Ref. 159. (Reprinted from Ref. 149 with kind permission fram Technomic
Publishing Co. Inc., Lancaster, Pennsylvania, USA.) (Note that SI units have not been
used for viscosity in order to be consistent with the conventional units of MFI as
explained in Ref. 99.) (10 Poise = 1 Pa.sec.)
rheograms given in Shenoy and Saini [99] for a11 unfi11ed polymerie
systems would natura11y hold good even in the presence of fi11ers. This
would be true more so in the higher shear rate region whieh is truly the
region of relevance because the shear rates encountered in most
processing operations, such as compounding, extrusion and injection
molding, are of the order of 10 sec- J or more.
The proposed approach is therefore valid for estimating the rheo-
grams of fi11ed polymers at industria11y relevant temperature and shear
rate conditions from a knowledge of the melt flow index and glass
transition temperature of the system. The rheograms so generated
would give an order of magnitude information on viscosity, adequate
for most exercises in process design, optimization, and trouble
shooting.
Figures 6.32-6.39 can thus be used to estimate the flow curves in the
higher shear rate region at the temperature of interest, merely from the
knowledge of MFI and the glass transition temperature of the specific
system.
The steps involved in generating the flow curves from the master
curves are given next.
MFI value under standard specified temperature and loading con-

ditions should be obtained from the manufacturer or measured in a
standard melt flow indexer.
The loading condition of the obtained MFI value should be checked
with that specified in the master curve. If different, a new value of
MFI ought to be calculated using equation (6.32).
The temperature of measurement of MFI should be checked with the
temperature at which the rheogram is desired. If different, equation
(6.30) ought to be used to get the correct value of MFI at the required
temperature, using the correct value of the glass-transition tempera-
ture of the specific system.
The rheogram can now be obtained by merely substituting the correct
value of MFI in the master curve.
In order to simplify the final step in generating the required steady
shear viscosity vs. shear rate curves from MFI by the above procedure,
appropriate rheological models have been suggested [166,167] for fitting
the unified curves, such as those given below.
Modified Carreau model:

17MFI = 17oMFI[l + (,1,MFIf(y /MFIfr N (6.33)
Modified Ellis model:

(6.34)
Modified Ostwald-de Waele power-Iaw model:

17MFI = K(Y /MFI)"-l (6.35)
General rheological model:

17MFI = 17oMFI[l + (K/17oMFI)p(Y/MFIin-1)p]1IP (6.36)
where 170MFI is the modified zero-shear viscosity function, 17MFI the
modified non-Newtonian viscosity function, y/MFI the modified shear
rate function, and ,1,MFI the modified time constant, K is the consistency
index, N, IX', P and n are dimensionless parameters associated with
power-Iaw behavior, , is the shear stress given by the product of 17MFI
and y/MFI, and '1/2 is that special value of the shear stress for which
17MFI = (17oMFI)/2.
The modified Carreau model and the modified Ellis model are limited
to relatively low values of shear rates and shear stresses, respectively,
whereas the modified Ostwald-de Waele power-law model is applicable
to the higher shear rate region where the data points fall in a straight line
on the log-log plot of l1MFI vs. YjMFI.
The General Rheologieal [167] model is applicable to the entire shear
rate range covering the region of validity of the modified Carreau
model as weIl as the region of validity of the modified Ostwald-de
Waele power-Iaw model. Hence, the General Rheological [167] model is
recommended for use when the entire master rheogram is to be fitted
by a single best-fitting curve.
The model constant and the range of applicability of each model are
available in Shenoy and Saini [99]. For unfilled polymer systems, any of
the above four models may be used depending on the shear rate range
of interest. However, in the case of filled polymer systems, it is the
modified Ostwald-de Waele power-Iaw model that is basieally of
relevance because it fits that region of the curve where the curve is
unique. Table 6.8 lists the model constants and the range of applica-
bility based on this model for master rheograms of certain selected
polymers and may be used for filled systems formed using these
polymers. There are some ca ses, such as those in Figures 6.35-6.38
where the master rheograms do not show a yield stress. In such cases,
the General Rheological Model given by equation (6.36) can be used in
order to cover the entire range of shear rate from low tohigh. Table 6.9
lists the model constants and range of applicability based on the
General Rheologieal model for master rheograms of certain selected
polymers and may be used for filled systems formed using these
polymers when the entire range of shear rate is of interest.
Care should be taken when ta king MFI data of filled polymerie
systems. It might be advisable to modify the melt flow indexer and
even change the ASTM temperature and load conditions in order to
generate sensible data. In filled systems, there would be a tendency of
yield stress behavior, and hence the proper choiee of load condition
would be essential for reliable results. Filled systems would also create
some difficulty due to migration of the fillers towards the capillary
center, thereby giving erroneous results. There is a limitation on partic1e
size and shape of the filler due to the standard diameter of the capillary
and this must be borne in mind when generating filled polymer system
data. In such cases, a modified MFI apparatus may be used by changing
the capillary diameter to suit the needs. If the capillary diameter or load
condition has been changed, then it must be borne in mind that the
shear stress value given by equations (6.26) and the shear rate value
given by equation (6.27) also has to be altered accordingly.
Whatever changes are done in order to obtain MFI data of filled
systems, the values thus obtained must be converted to those at
standard temperature and load conditions using the equations given in
this section before using them in the master rheograms.
References 303
Table 6.9 Rheological parameters of the general rheological model (equation 6.36)
for certain selected polymers
Polymer '10 x MFI K n P Modified Testt

(poise) (g/cm sec 2- n ) shear rate' load
x(g/10min) x(gm/10min)n (sec-') (kg)
x(g/10minr'
LDPE 3.0 x 105 1.70 X 105 0.370 -1.220 0.01-1000 2.16a

HDPE 2.1 x 105 1.24 X 105 0.471 -0.934 0.1-1000 2.16a
UHMWPE 1.66 x 106 0.156 10-10000 1O.00a
LLDPE 9.6 x 104 1.0 X 105 0.66 -2.808 0.01-100 2.16a
pp 1.2 x 105 1.75 X 105 0.34 -1.076 0.1-1000 2.16a
PS 4.0 x 106 3.32 X 105 0.368 -1.253 0.001-200 5.00a
C-Ester 8.5 x 104 3.20 X 105 0.38 -2.58 1-1000 2.16a
C-Ether 8.5 x 104 1.5 X 105 0.47 -2.58 1-100 2.16
Acrylic 2.1 x 105 3.2 X 105 0.44 -1.336 0.1-1000 3.80a
Nylon 9.5 x 104 3.4 X 105 0.44 -1.624 0.1-1000 2.16a
PET 8.3 x 104 5.0 X 105 0.43 -2.031 0.01-1000 2.16a
PC 4.2 x 104 2.5 X 105 0.52 -2.282 1-1000 1.20a
PVDF 6.0 x 10 5 7.5 X 105 0.4 -3.106 0.1-200 12.50
PPO 2.2 x 105 1.0x106 0.25 -1.318 1-1000 5.00
PPS 3.4 X 105 6.0 X 105 0.44 -1.306 0.001-100 5.00
PAS/PES 1.9 x 105 3.0 X 105 0.60 -4.033 1-1000 5.00
PEEK 4.5 x 105 6.0 X 105 0.32 -1.264 0.01-1000 5.00
PEI 1.4 x 10 5 1.4 X 106 0.34 -2.060 1-1000 5.00
PAr 1.8 x 10 5 2.4 X 105 0.85 -12.127 0.001-100 5.00
SAN 3.3 x 105 3.0 X 105 0.33 -1.384 1-1000 3.80
SBS 2.2 x 10 5 1.0 X 106 0.25 -1.318 0.1-1000 5.00
ABS 1.7 x 106 3.5 X 105 0.38 -1.090 0.01-100 5.00a
VCVA 4.0 x 105 0.33 0.3-7000 20.00
EVA 2.5 x 105 1.0 X 105 0.55 -2.110 0.001-1000 2.16
Polyester 9.0 x 104 1.4x105 0.65 -3.802 0.1-300 2.16
elastomer
TPE 1.5 x 105 0.40 1-1000 2.16
PVC 1.2 x 106 4.6 X 105 0.36 -1.286 0.01-2000 20.00a
(formulations)
, Applicability range for Y/MFI.

t Condition for MFI used in the master rheogram.
a ASTM specified.
REFERENCES
1. Park, es., Lee, K.J., Kim, D.H. and Park, H.J. (1977) Rheological charac-
terization of glass fiber filled poly(butylene terephthalate) resin, Paper 10-B
presented at the thirteenth international meeting of the Polymer Processing
Society Gune 10-13).
2. Chapman, F.M. and Lee, TS. (1970) Effect of tale filler on the melt rheology
of polypropylene, 5PE Journal, 26, 37-40.
3. Mills, N.J. (1971) The rheology of filled polymers, J. Appl. Polym. Sei., 15, 2791-805.
4. Nazem, F. and Hill, CT. (1974) Elongational and shear viscosities of bead-
filled thermoplastic, Trans. Soc. Rheol., 18, 87-1Ol.
polypropylene melts., J. Appl. Polym. Sei., 18, 821-9.
extrusion characteristics and rheological properties of elastomers: poly-
butadiene and butadiene-styrene copolymer, J. Appl. Polym. Sei., 18,
1013-38.
the rheological extrusion properties of polymer melts, J. Appl. Polym. Sei.,
20,501-23.
8. Faulkner, D.L. and Schmidt, L.R. (1977) Glass bead-filled polypropylene
Part I: Rheological and mechanical properties, Polym. Engg Sei., 17,657-64.
9. Boira, M.S. and Chaffey, CE. (1977) Effects of coupling agents on the
10. Bigg, D.M. (1977) Rheology and wire coating of high atomic number metal
low density polyethylene composites, Polym. Engg Sei., 17, 745-50.
partic1e filled polymer melts, Rheol. Acta, 17, 149-55.
626-31.
13. Copeland, J.R. and Rush, O.W. (1978) Wollastonite: short fiber fillerl
reinforcement, Plastic Compounding, 1, 26-36 (Nov./Dec.).
14. Chan, Y., White, J.L. and Oyanagi, Y. (1978) Influence of glass fibers on the
extrusion and injection mol ding characteristics of polyethylene and poly-
styrene melts, Polym. Engg Sei., 18, 268-72; (1978) A fundamental study of
the rheological properties of glass fiber-reinforced polyethylene and poly-
styrene melts, J. Rheol., 22, 507-24.
18. Monte, S.J. and Sugerman, G. (1979) A new generation of age and water-
resistant reinforced plastics, Polym. Plastics Tech. Engg, 12, 115-35.
Engg Sei., 19, 617-24.
properties of calcium carbonate filled polymer melts, Rheol. Acta, 18, 635-9.
22. Kitano, T., Kataoka, T., Nishimura, T. and Sakai, T. (1980) Relative viscosities
of polymer melts filled with inorganic fillers, Rheol. Acta, 19, 764-9.
dynamic and steady flow viscosities of filled polymer systems, Rheol. Acta,
19,671-3.
References 305
24. Crowson, RJ., Folkes, M.J. and Bright, P.F. (1980) Rheology of short
glass fiber-reinforced thermoplastics and its applications to injection
molding I. Fiber motion and viscosity measurement, Polym. Engg Sci., 20,
925-33.
25. Crowson, RJ. and Folkes, M.J. (1980) Rheology of short glass fiber-reinforced
thermoplastics and its application to injection molding II. The effect of
material parameters, Polym. Engg Sei., 20, 934-40.
26. Goel, D.C (1980) Effect of polymeric additives on the rheologieal properties
of talc-filled polypropylene, Polym. Engg Sei., 20, 198-201.
27. Tanaka, H. and White, J.L. (1980) Experimental investigations of shear and
elongational flow properties of polystyrene melts reinforced with calcium
carbonate, titanium dioxide and carbon black, Polym. Engg Sei., 20, 949-56.
28. Czamecki, I. and White, J.L. (1980) Shear flow rheological properties, fiber
damage and mastication characteristics of aramid, glass and cellulose-fiber
reinforced polystyrene melts, J. Appl. Polym. Sei., 25, 1217-44.
29. White, J.L., Czamecki, I. and Tanaka, H. (1980) Experimental studies of the
influence of particle and fiber reinforcement on the rheological properties of
polymer melts, Rubber Chem. Tech., 53, 823-35.
30. Hancock, M., Tremayne, P. and Rosevear, J. (1980) Fillers in polypropylene
II. J. Polym. Sei. Polym. Chem. Ed., 18,3211-17.
31. Knutsson, B.A., White, J.L. and Abbas, K.A. (1981) Rheological and extrusion
characteristics of glass-fiber reinforced polycarbonate, J. Appl. Polym. Sci., 26,
2347-62.
using hydrophobie encapsulation, Plastic Engg, 37-9 (June).
33. Kitano, T., Kataoka, T. and Shirata, T. (1981) An empirieal equation of the
relative viscosity of polymer melts filled with various inorganie fillers, Rheol.
Acta, 20, 207-9.
properties of filled polypropylene, Polym. Engg Sei., 21,196-204.
36. Sharma, Y.N., Patel, RD., Dhimmar, LH. and Bhardwaj, I.S. (1982) Studies
of the effect of titanate coupling agent on the performance of polypropylene-
calcium carbonate composite, J. Appl. Polym. Sei., 27, 97-104.
37. Nakatsuka, T., Kawasaki, H., Itadani, K. and Yamashita, S. (1982) Phosphate
coupling agents for calcium carbonate filler, J. Appl. Polym. Sei., 27, 259-69.
38. Lee, W.M., Abe, D.A., Chipalkatti, M.H. and Liaw, T.F. (1982) Rheological
properties of particulate-filled linear low density polyethylenes, Proc. Ann.
Con! Rein! Plast. Compos. Inst. Soc., Plast. Ind., 37(12D), 7.
polypropylene reinforced with glycerol-treated mica, Can. J. Chern. Engg, 60,
334-41.
40. Hinkelmann, B. (1982) Zur analytischen beschreibung des fullstoffein-flusses
auf das fliessverhalten von kunststoffschmelzen, Rheol. Acta, 21, 491-3.
41. Utracki, L.A. and Fisa, B. (1982) Rheology of fiber or flake-filled plastics,
42. White, J.L. (1982) Rheological behavior of highly filled/reinforced polymer
melts, Plastics Compounding, 47-64 (Jan./Feb.).
43. Bigg, D.M. (1982) Rheological analysis of highly loaded polymerie com-
posites filled with non-agglomerating spherical filler particles, Polym. Engg
Sei., 22, 512-18.
45. Althouse, L.M., Bigg, D.M. and Wong, W.M. (1983) Evaluating the effective-
ness of filler surface treatments, Plastics Compounding (March/April).
46. Lern, K.W. and Han, CD. (1983) Rheological behavior of concentrated sus-
pensions of particulates in unsaturated polyester resin, J. Rheol., 27, 263-88.
47. Daley, L.R and Rodriguez, F. (1983) Flow properties of ethylene-propylene
terpolymer filled with siliea modified by silane coupling agents, Ind. Eng.
Chern. Prod. Res. Dev., 22, 695-8.
48. Mutsuddy, B.C. (1983) Influence of powder characteristics on the rheology
of ceramie injection molding mixtures, Proc. Brit. Ceram. Soc., 33, 117-37.
49. Chaffey, C.E. (1983) Reinforced thermoplasties: through flow to use, Ann.
Rev. Mater. Sei., 13, 43-65.
50. Shenoy, A.V., Saini, D.R and Nadkarni, V.M. (1983) Rheograms of filled
polymer melts from melt-flow index, Polym. Composites, 4,53-63.
51. Shenoy, A.V. and Saini, D.R (1983) Interpretation of flow data for multi-
component polymerie systems, Colloid Polym. Sci., 261, 846-54.
52. Suetsugu, Y. and White, J.L. (1983) The influence of particle size and surface
coating of calcium carbonate on the rheological properties of its suspension
in molten polystyrene, J. Appl. Polym. Sei., 28,1481-1501.
53. Luo, H.L., Han, C.D. and Mijovie, J. (1983) Effects of coupling agents in the
rheological behavior and physieal mechanical properties of filled nylon 6, J.
Appl. Polym. Sei., 28, 3387-98.
Proc. IX Intl. Congress on Rheology in Mexieo, Adv. in Rheology, 3, 429-37.
Acta, 23, 20--30.
56. Kitano, T., Kataoka, T. and Nagatsuka, Y. (1984) Dynamie flow properties of
vinylon fiber and glass fiber reinforced polyethylene melts, Rheol. Acta, 23,
408-16.
57. Suetsugu, Y. and White, J.L. (1984) A theory of thixotropie plastic visen-
elastic fluids with a time-dependent yield surface and its comparison to
transient and steady state experiments on small particle filled polymer
melts, J. Non-Newtonian Fluid Mech., 14, 121-40.
58. Hinkelmann, B. and Mennig, G. (1985) On the rheological behavior of filled
polymer melts, Chern. Engg Comm., 36, 211-21.
59. Bretas, RE.s. and Powell, RL. (1985) Dynamie and transient rheological
treatment on the rheological and mechanical properties of ferrite-filled
61. Saini, D.R and Shenoy, A.V. (1986) Viscoelastic properties of highly loaded
62. Shenoy, A.V. and Saini, D.R (1986) Quantitative estimation of matrix fiBer
interactions in ferrite-filled styrene-isoprene-styrene block copolymer
References 307
63. Saini, D.R, Shenoy, AV. and Nadkami, V.M. (1986) Melt rheology of highly
64. Shenoy, AV. and Saini, D.R (1986) Wollastonite reinforced polypropylene
composites: Dynamic and steady state melt flow behavior, J. Rein! Plastics
Comp., 5, 62-73.
65. MuteI, AT. and Kamal, M.R (1986) Characterization of the rheological
behavior of fiber-filled polypropylene melts under steady and oscillatory
shear using cone-and-plate and rotational parallel plate geometry, Polym.
Composites, 7, 283-94.
66. Edirisinghe, M.J. and Evans, J.RG. (1987) Rheology of ceramie injection
molding formulations, Br. Ceram. Trans. J., 86, 18-22.
67. Sacks, M.D., Khadilkar, CS., Scheiffele, G.W., Shenoy, AV., Dow, J.H. and
Sheu, RS. (1987) Dispersion and rheology in ceramie processing, Advances
in Ceramics, 24, 495-515.
68. Dow, J.H., Sacks, M.D. and Shenoy, AV. (1988) Dispersion of ceramic
particles in polymer melts, Ceram. Trans. (Ceram. Powder Sei. IIA), 1, 380-8.
69. Hunt, KN., Evans, J.RG. and Woodthorpe, J. (1988) The influence of mixing
route on the properties of ceramie injection moulding blends, Br. Ceram.
Trans. /., 17-21.
70. Takahashi, M., Suzuki, S., Nitanda, H. and Arai, E. (1988) Mixing and flow
characteristic in the alumina/thermoplastic resin system, J. Am. Ceram. Soc.,
17,1093-9.
71. Poslinski, AJ., Ryan, M.E., Gupta, RK, Seshadri, S.G. and Frechette, F.J.
(1988) Rheological behavior of filled polymer systems 1. Yield stress and
shear-thinning effects, J. Rheol., 32, 703-35.
(1988) Rheological behavior of filled polymerie systems TI. The effect of a
bimodel size distribution of particulates, J. Rheol., 32, 751-71.
73. Ishigure, Y., Nagaya, K, Mitsumatsu, F., Otabe, S., Hayashi, K, Sobajima,
A and Murase, 1. (1989) Relationship between the flow characteristics of
highly filled alumina or zirconia-organie binder and the properties of
sintered products in injection molding processing, Rep. Gifu Pref Ind. Res.
Tech. Center, 21, 51-70.
74. Dow, J.H., Sacks, M.D. and Shenoy, A.V. (1990) Dispersion of alumina
particles in polyethylene melts, Ceram. Trans. (Ceram. Powder Sei. III), 12,
431-42.
75. Edirisinghe, M.J., Shaw, H.M. and Tomkins, KL. (1992) Flow behavior of
ceramie injection moulding suspensions, Ceramics Int., 18, 193-200.
76. Nielsen, L.E. (1974) Mechanical Properties 0/ Polymers and Composites, Marcel
Dekker, New York, Vol. 2, Ch. 7, 379-86.
77. Han, CD. (1976) Rheology in Polymer Processing, Academie Press, New York,
7,182-8.
78. Nielsen, L.E. (1977) Polymer Rheology, Marcel Dekker, New York, Ch. 9,
133-57.
79. Paul, D.R and Newman, S. (1978) Polymer Blends, Academic Press, New
York, 1, eh. 7, 295-352.
80. Vinogradov, G.V. and Malkin, AY. (1980) Rheology 0/ Polymers, Mir
Publishers, Moscow 380-402.
81. Han, CD. (1981) Multiphase Flow in Polymer Processing, Academie Press,
New York.
Encyc/opedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf Publishing,
Houston, TX, 7, 667-701.
83. Yanovsky, Yu.G. and Zaikov, G.E. (1990) Rheological properties of filled
polymers, in Encyc/opedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, IX, 9, 243-76.
Processes in Bubbles, Drops and Partieies (eds RP. Chhabra and D. Dekee),
85. Advani, S.G. (ed.) (1994) Flow and Rheology in Polymer Composites
Manufacturing, Elsevier Science B.V.
86. Tanaka, H. and White, J.L. (1980) A cell model theory of the shear viscosity
of a concentrated suspension of interacting spheres in a non-Newtonian
fluid, J. Non-Newtonian Fluid Mech., 7, 333-43.
87. Einstein, A (1906) Eine neue bestimmung der moleculdimension, Ann.
Physik, 19, 289.
88. Frankei, N.A and Acrivos, A (1967) On the viscosity of a concentrated
suspension of solid spheres, Chern. Engg Sei., 22, 847-53.
89. Hamaker, C. (1937) London-van der Waals attraction between spherical
partic1es, Physics, 4, 1058-72.
90. Derjaguin, B. (1940) On the repulsive forces between charged colloid
partic1es and on the theory of slow coagulation and stability of lyophobe
sols, Trans. Faraday Soc., 36, 203-15.
91. Hersehei, W.H. and Bulkley, R (1926) Konsistenzmessungen von gummi-
benzollosungen, Kolloid-Z., 39, 291-300.
92. Jarzebski, G.J. (1981) On the effective viscosity of pseudoplastic
suspensions, Rheol. Acta, 20, 280-7.
93. Rajaiah, J. (1990) Rheology and thermal conductivity of concentrated
suspensions, PhD. dissertation, Chemical Engg (SUNY, Buffalo).
94. Gurland, J. (1966) An estimate of contact and continuity of dispersion in
opaque sampies, Trans. Met. Soc., AlME, 236, 642--6.
95. Gupta, RK. (1994) Particulate suspensions, in Flow and Rheology in Polymer
Composites Manufacturing (ed. S.G. Advani), Elsevier, Amsterdam.
96. Eyring, H. (1936) Viscosity, plasticity and diffusion as examples of absolute
reaction rates, J. Chern. Phys., 4, 283-91.
97. Maron, S.H. and Pierce, P.E. (1956) Application of Ree-Eyring
generalized flow theory to suspensions of spherical partic1es, J. Colloid
Sei., 11, 80.
98. Chong, J.S., Christiansen, E.B. and Baer, AD. (1971) Rheology of
concentrated suspensions, J. Appl. Polym. Sei., 15, 2007-21.
99. Shenoy, AV. and Saini, D.R (1996) Thermoplastic Melt Rheology and
100. Doolittle, A.K. (1951) Studies in Newtonian flow. 11. The dependence of
viscosity of liquid on free space, J. Appl. Phys., 22, 1471-5; (1952), m. The
dependence of the viscosity of liquids on molecular weight and free space
(in homogeneous series), J. Appl. Phys., 23, 236-9.
101. Fujita, H. and Kishimoto, J. (1961) Interpretation of viscosity data for
concentrated polymer solutions, J. Chem. Phys., 34, 393-8.
102. Matijevic, E. (1985) Production of monodispersed colloidal partic1e, Annu.
Rev. Mater. Sei., 15, 483-516.
References 309
103. Stober, W., Fink, A. and Bohn, E. (1968) Controlled growth of monodisperse
silica spheres in the micron size range, J. Colloid Interf Sei., 26, 62-9.
104. Tan, CG., Bowen, B.D. and Epstein, N. (1987) Production of monodisperse
silica spheres: Effect of temperature, J. Colloid Interf Sei., 118, 290-3.
105. Ahu, CW., Zhao, G.Y., Revankar, V.V.S. and Hlavacek, V. (1992) Design
and development of the d.c. plasma reactor for the synthesis of ultrafine
powders, J. Mat. Sei., 27, 2211-17.
106. Krieger, I.M. (1972) Rheology of monodisperse lattices, Adv. Coll. Interface
Sei., 3, 111-36.
107. Ward, S.G. and Whitmore, RL. (1950) Studies of the viscosity and
sedimentation of suspensions. Part I: The viscosity of suspensions of
spherical particles, Br. J. Appl. Phys., 1, 286.
108. Eveson, G.F. (1959) Rheology of Dispersed Systems (ed. CC Mill), Pergamon
Press, New York.
109. Lee, D.1. (1969) The viscosity of concentrated suspensions, Trans. Soc.
Rheol., 13, 273-88.
110. Groto, H. and Kuno, H. (1982) Flow of suspensions containing particles of
two different sizes through a capillary tube, J. Rheol., 26, 387-98; (1984)
Flow of suspensions containing particles of two different sizes through a
capillary tube. II. Effect of the particle size ratio, 28, 197-205.
111. Mokube, V. (1981) An experimental study of the rheology of non-settling
suspensions, MS thesis, Department of Chemical Engineering, State
University of New York at Buffalo, Amherst, New York, 1981.
112. Gillespie, T. (1983) The effect of aggregation and particle size distri-
bution on the viscosity of Newtonian suspensions, ,. Coll. Inter. Sei., 94,
166-73.
113. Farris, RJ. (1968) Prediction of the viscosity of multimodal suspensions
from unimodal viscosity data, Trans. Soc. Rheol., 12, 281-301.
114. Henderson, CB., Scheffe, RS. and McHale, E.T. (1982) Manuscript prepared
for Cleveland AIChE meeting (August).
115. Sweeny, K.H. (1959) Manuscript presented at the Symposium on High
Energy Fuel, 135th National Meeting, American Chemical Society, Boston,
Ma.
116. Mangels, J.A. (1978) Development of injection moulded reaction bonded
silicon nitride, in Ceramics for High Performance Application - II (eds J.J.
Burke, KN. Lenoe and RN. Katz), Brook Hill Publishing, Chestnut Hill,
Massachusetts, USA, 113-30.
117. Mangels, J.A. and Williams, RM. (1983) Injection molding ceramics to high
green densities, Am. Cer. Soc. Bull., 62, 601-6.
118. Barringer, KA. and Bowen, H.K. (1982) Formation packing and sintering of
monodisperse Ti02 powders, J. Am. Ceram. Soc., 65, C199-C201.
119. Mangels, J.A. and Trela, W. (1984) Ceramic components by injection
molding, Adv. in Ceramics, 9, 234-8.
120. Adams, E.F. (1971) Slip cast ceramics, in High Temperature Oxides, Part IV
(ed. M. Allen), Academic Press, New York, 45.
121. Westman, A.E.R and Hugill, H.R (1930) Packing of particles, J. Am. Ceram.
Soc., 13, 767-9.
122. Lewis, H.D. and Goldman, A. (1966) Theorems for calculation of weight
ratios to produce maximum packing density of powder mixtures, J. Am.
Ceram. Soc., 323-7.
123. Ayer, J.E. and Soppet, F.E. (1965) Vibratory compaction: I, Compaction of
spherical particles, J. Am. Ceram. Soc., 180-83; (1966) II, Compaction of
angular shapes, J. Am. Ceram Soe., 49, 207-10.
124. Willermet, P.A, Pett, RA and Whalen, T.J. (1978) Development and
processing of injection-moldable reaction - Sintered Sie compositions, Am.
Ceram. Soc. Bull., 57,744-7.
125. Edirisinghe, M.J. and Evans, JRG. (1986) Review: Fabrication of engineering
ceramies by injection moulding, I. Materials selection, Int. J. High Tech.
Cera mies, 2, 1-31; (1986) ll. Techniques, Int. J. High Tech. Ceramics, 2, 249-78.
126. Bhattacharya, S.K. (ed.) (1986) Metal-filled Polymers: Properties and
Applications, Marcel Dekker, New York and Basel.
127. German, RM. (1990) Powder Injection Molding, Metal Powder Industries
Federation, NJ.
128. Milewski, J.V. (1978) The combined packing of rods and spheres in
reinforcing plastics, Ind. Eng. Chem. Prod. Res. Dev., 17, 363-6.
129. Gupta, RK. and Seshadri, S.G. (1986) Maximum loading levels in filled
liquid systems, J. Rheol., 30, 503-8.
130. Ouchiyama, N. and Tanaka, T. (1980) Ind. Eng. Chem. Fund., 19, 338; (1981)
20, 66; (1984) 23, 490.
131. Rumpf, H. and Schubert, H. (1978) Adhesion forces in agglomeration
processes, in Ceramie Processing before Firing (eds G.Y. Onoda and L.L.
Hench), Wiley, New York, 357-76.
132. Parish, M.V., Garcia, RR and Bowen, H.K. (1985) Dispersion of oxide
powders in organic liquids, J. Mater. Sei., 20, 996-1008.
133. Plueddemann, E.P. (1982) Silane Coupling Agents, Plenum Press, New York
and London.
134. Monte, S.J. and Sugerman, G. (1985) Ken-React Referenee Manual Titanate
and Zireonate Coupling Agents, Kenrich Petrochemieals, Bayonne, NI 07002-
0032.
135. Cohen, L.B. (1986) The chemistry and reactivity of zircoaluminate coupling
agents for filled and reinforced plastics, SPI RP jC, Atlanta, Ga, January
27-31.
136. Johnson, RO. and Teutsch, E.O. (1983) Thermoplastic aromatic polyimide
composites, Polym. Composites, 4, 162-6.
137. Lakdawala, K. and Salovey, R (1987) Rheology of polymers containing
carbon black, Polym. Engg Sei., 27, 1035.
138. Bartenev, G.M. and Zakharenko, N.V. (1962) Kolloid Z., 24,101.
139. Droste, D.H. and Dibenedetto, AT. (1969) The glass transition temperature
of filled polymers and its effect on their physieal properties, J. Appl. Polym.
Sei., 13,2149-68.
140. Peyser, P. (1978) The effect of fillers on polymer properties, Polym.-Plast.
Technol. Eng., 10, 117-29.
141. Lipatov, Yu.S. and Sergeeva, L.M. (1974) Adsorption of Polymers, Wiley,
New York, Ch. 7.
142. Kolarik, J. Janacek, J. and Nieolais, L. (1976) Dynamic mechanieal behavior
of poly (2-hydroxyethyl methacrylate) - glass beads composites, J. Appl.
Polym. Sei., 20, 841-51.
143. Dufresne, A (1989) Properties mecaniques, electriques et rheologiques de
materiaux thermoplastiques renforces de noir de carbone, MASc thesis,
Ecole Polytechnique of Montreal.
References 311
144. Shenoy, AV., Chattopadhyay, S. and Nadkami, V.M. (1983) From melt
flow-index to rheogram, Rheol. Acta, 22, 90-101.
145. Shenoy, AV., Saini, D.R and Nadkarni, V.M. (1983) Rheograms for
engineering thermoplastics from melt flow index, Rheol. Acta, 22, 209-22.
146. Shenoy, AV., Saini, D.R and Nadkarni, V.M. (1983) Rheology of nylon 6
containing metal halides, J. Mat. Sei., 18, 2149-55.
147. Shenoy, AV., Saini, D.R and Nadkami, V.M. (1982) Rheograms for
cellulosic polymers from the melt flow index, J. Appl. Polym. Sei., 27,
4399-408.
148. Saini, D.R and Shenoy, AV. (1983) Viscoelastic properties of linear low
density polyethylene melts, Eur. Polym. J., 19, 811-16.
149. Saini, D.R and Shenoy, AV. (1985) Melt rheology of some speciality
polymers, J. Elastomers Plastics, 17, 189-217.
150. Saini, D.R. and Shenoy, A.V. (1986) Deformation behavior of poly(vinylidene
fluoride), Ind. Engg Chem. Prod. Res. Dev., 25, 277-82.
151. Shenoy, A.V. and Saini, D.R (1985) Copolymer melt rheograms from melt
flow index, British Polym. J., 17, 314-20.
152. Shenoy, AV. and Saini, D.R (1986) Melt flow behavior of liquid crystalline
polymer, Mol. Cryst. Liq. Cryst., 135, 343-54.
153. Shenoy, AV., Saini, D.R and Nadkami, V.M. (1983) Estimation of the melt
rheology of polymer waste from melt flow index, Polymer, 24, 722-8.
154. Shenoy, AV., Saini, D.R and Nadkami, V.M. (1984) Melt rheology of
polymer blends from melt flow index, Int. J. Polymerie Material, 10, 213-35.
155. Shenoy, AV., Saini, D.R and Nadkami, V.M. (1983) Rheology of poly(vinyl
chloride) formulations from melt flow index measurements, J. Vinyl Tech.,
5,192-7.
156. Rideal, G.R and Padget, J.c. (1976) The thermal mechanical degradation of
high density polyethylene, J. Polym. Sei. (Polym. Symp. Edn), 57, 1-15.
157. Whelan, J.P. (1981) Senior divisional engineer, Amoco chemicals
corporation, lllinois, Private communication.
158. Kohan, M.1. (1973) Nylon Plastics, New York, Ch. 4.
159. Taylor, N.H. (1984) Analytical & Polym. Sei. Group, Res. & Tech. Dept, ICI
Wilton, Middlesbrough, Private communication.
160. Dow Chemicals (1981) Michigan, USA, Private communication.
161. Westover, RF. (1959) in Processing of Thermoplastic Materials (ed. E.C.
Bernhardt), Van Nostrand, New York, 547-679.
162. Pritchard, J.H. and Wissbrun, K.F. (1969) Reversible melt flow rate increase
of branched acetal polymers, J. Appl. Polym. Sei., 13, 233-9.
163. E.1. du Pont de Nemours and Co. (1977) Private communication.
164. Yamada, M. and Porter, RS. (1974) Compressional effects in the capillary
flow of polycarbonate, J. Appl. Poly. Sei., 18, 1711-24.
165. Boume, R (1984) Technical marketing manager, General Electric Plastics,
4600 AC Bergen Op. Zoom, Netherland, Private communication.
166. Shenoy, AV. and Saini, D.R (1984) Rheological models for unified curves
for simplified design calculations in polymer processing, Rheol. Acta, 23,
368-77.
167. Shenoy, U.V., Bamane, S. and Shenoy, AV. (1990) A general rheological
model for polymer melts, Paper 771-MT-EI7 presented at 40th Canadian
Chemical Engg Conference, Halifax (July).
Steady shear elastic
properties 7
Despite the fact that the literature on the rheology of filled systems is
extensive [1-85], the work related to the steady shear elastic properties of
such systems is quite limited [5,19,27,29,31,34]. This is, of course, due to
the experimental difficulties in these measurements. The usual signs of
elastic behavior in filled systems are recognized by the presence of larger
normal stress differences during relatively low shear measurements on a
cone and plate rheogoniometer and by higher exit pressure as weIl as
larger die swell values during high shear capillary or slit rheometry. As
normal stress difference is mathematically connected with exit pressure
and recoverable shear strain and, conceptually, with die swell ratio,
knowledge of these would also provide the same information. The exit
pressure is the small finite value Pexit which is obtained when the
pressure in the capillary or slit is plotted against downstream distance
and the extrapolated pressure at the exit is non-zero. With appropriate
assumptions, it has been shown that Pexit can be related to primary
normal-stress difference [77]. However, since the theory has been
questioned [86] and a controversy arisen [87], it has not gained
popularity as a useful measure of elasticity. The use of the recoverable
shear strain to determine the effect of fillers on the elastic properties of
polymer melts has been uncommon, whereas study of die swell ratio has
been extensive, especially in the determination of the effect of carbon
black on the extrudate swell of elastomers.
Some special problems exist in normal stress measurement of filled
polymer systems. Abnormal effects at low rates are observed due to the
interactions between the measuring equipment and the yield stress
property associated with the filled systems. As a result, a proper zero
point for measurement cannot be obtained. Furthermore, the
uncertainty is proportional to the level of the yield stress [19]. It is thus
difficult to measure normal stresses accurately especially at low shear
rates [27].

In low shear measurements, the difficulty lies in the gap setting of

the cone and plate, firstly, due to the high residual stresses which do
not relax easily and secondly, due to the filler particles which interfere
on account of their individual particle size or the agglomerate size. In
high shear measurements, the particle or agglomerate size again may
interfere with the extrusion process on account of the obstruction that
they may create at the die exit. Nevertheless, with a great deal of
careful experimentation, useful elastic property data on filled polymer
systems can be genera ted as has been shown by some researchers
[5,19,27,29,31,34].
The generated data may appear confusing at the outset if looked at
cursorily. The presence of fillers in the polymers seems to show
decreases as well as increases in elasticity and the reports may appear
contradictory at times. However, a careful look at the elastic properties
data of filled polymer systems shows that it is the method of
representation and certain categories of fillers which show unexpected
trends. The effects of various parameters on the steady shear elastic
properties are discussed in various subsections as was done for the
steady shear viscous properties in the preceding chapter. However, all
subcategories may not be covered and the extent of discussion is at
times concise due to limited information.

The experimental studies of the influence of fillers on the rheological
properties of polymer melts by White et al. [29] best illustrate the effect
of filler type. The steady shear elastic data were generated in terms of
the first normal stress difference using the cone and plate arrangement
of the Rheometrics Mechanical Spectrometer at a fixed temperature of
180C.
The filled systems were prepared with a fixed grade of polystyrene
Dow Styron 678U and involved the use of nine different types of filler
as summarized in Table 6.1. Various filler types were thus covered from
rigid to flexible, as well as spherical, particulate to fibrous. The filler
loading was fixed at 20 vol% and hence the genera ted data bring out
the exclusive effect of the filler type on the elastic properties.
Figures 7.1 and 7.2 show the variation of primary normal stress
difference with shear stress for the various filled systems studied [29]. It
is seen that glass beads hardly affect the values of N j while the presence
of Franklin fibers, titanium dioxide (Ti02 ), calcium carbonate (CaC03 ),
carbon black (CB) and mica, respectively, show greater and greater
reductions in N j However, on the other hand, the addition of certain
fibers like cellulose fiber, glass fiber and aramid fiber, respectively,
increases N j values to a larger and larger extent.
314 Steady shear elastic properties
105 r;:;:::::::::::::;:~~:;::::;--------;;---I
IFILLED POLYS'I'YRBNli I
UNITS
N l' "(:12 - PASCALS
I18o"C I
104 f-r=O==P::'S- - - - - ,
o GLASS BEADS
.... FlANKUN FlBER
[J Ti02
.0. CaC03
CB
o MICA
t: 12
Figure 7.1 Variation of primary normal stress difference with shear stress for filled
pOlystyrene melts containing 20 volume fraction of various types of fillers as indicated.
(Reprinted from Ref. 29 with kind permission from American Chemical Society,
Washington DC, USA)
l:12
Flgure 7.2 Variation of primary normal stress difference with shear stress for filled
polystyrene melts containing 20 volume fraction of various types of fillers as indicated.
(Reprinted from Ref. 29 with kind permission from American Chemical Society,
Washington DC, USA)
From Table 6.1 it can be concluded that fibrous fillers (aramid, glass
and cellulose fiber) tend to increase the normal stress difference value
at a fixed shear stress, particulate fillers (titanium dioxide, calcium
carbonate and carbon black) tend to depress it while spherical fillers
(glass beads) leave it nearly unchanged. The large increase in normal
stresses in fiber-filled polymer systems is probably due to a hydro-
dynamic particle effect, associated with orientation in the direction of
flow [29]. There is an indication that the increase in NI is a function of
the fiber modulus and aspect ratio. The higher the modulus and the
longer the fibers, the larger the value of NI as depicted in Figure 7.2. It
has been noted elsewhere by Czarnecki and White [28] that mastication
of fiber-filled systems breaks up the fibers into smaller lengths and also
reduces the value of NI' Among the fibers studied in Table 6.1, the lone
fiber which depresses the value of NI is the Franklin fiber. Though the
aspect ratio of the fiber is comparable to the other fibers, its diameter is
much smaller. Thus, the observed lowering of the normal stress in this
ca se is more of an effect due to size than its shape and hence is
discussed in the next subsection.

Normal stress measurements for polymer melts filled with large
particles [14,28,29,31] and those filled with small particles [7,15,27,29]
are available. When plotted in terms of NI vs. r12, the primary normal
stress differences are consistently found to be reduced by the presence
of smaller particles (for example, Figure 7.1). From Table 6.1, it can be
seen that titanium dioxide, calcium carbonate and carbon black are
small in size compared with the other fillers and show lower normal
stress differences. From among the fibers, it is the Franklin fiber which
has the smallest dimension, almost in the range of the three particulate
fillers, and thus behaves in the manner similar to that of TiOz, CaC03
and CB. However, the extent of normal stress difference reduction is
less due to the effect of the high aspect ratio which tends to raise the
value as explained in section 7.1.
It should be noted that Figures 7.1 and 7.2 are plotted as NI vs. r12
rather than NI vs. y. Where the latter representation was used then the
data would appear as shown in Figure 7.3(a). Only curves for
particulate fillers - titanium dioxide and carbon black - are shown for
illustration purposes. It can be seen that both these fillers appear to
increase normal stress differences of the polymer melt at the same shear
rate. Thus from Figure 7.3(a) it can be concluded that small particulate
fillers like carbon black and titanium dioxide increase the elasticity of
polymer melts. This is contrary to the trend in Figure 7.1 for the same
filled systems using the same data but different representation wherein
10 5
IFILLED POLYSTYRENE I
UNn'S
N l- PASCALS
1
104 'Y - SEC
Nl
I180C I
103
o Ti0 2
eCB
o PS
10 2 ~----------------~------------------~
10.2
Figure 7.3(8) Variation of primary normal stress difference with shear rate for filled
polystyrene melts containing 20 volume fraction of carbon black and titanium dioxide
fillers. (Reprinted from Ref. 27 with kind permission from Society of Plastics Engineers
Inc., Connecticut, USA.)
it was concluded that small particulate fillers decrease the elasticity of

polymer melts. It is important to establish, therefore, which of the
representations is truly correct.
In order to do this, it is best to deal with another useful parameter of
elasticity, namely, the steady-state shear compliance Je which gives a
measure of the stored energy or the elastic recovery of the system.
When represented mathematically as Je = ("11 - "22)/2"~2' the plot of
Je vs. Ywould give the correct trend based on a molecular interpretation.
The usefulness of plotting normal stress N 1 vs. shear stress "12 for
unfilled polymer melts is known [77,88,89]. Such plots are independent
of temperature and molecular weight (though not its distribution), and
rheological behavior for such viscoelastic fluids is interpretable in terms
of the steady state shear compliance Je' Addition of the carbon black
reduces the N1 values at fixed "12 as already discussed with reference to
Figure 7.1. The same effect would be observed in case Je values are
plotted against shear rate. Another method of representation of
elasticity is through the use of the characteristic time of the system.
Figure 7.3(b) gives the plot of relaxation time vs. shear rate for high
density polyethylene melts containing glass fibers. It is seen that the
presence of glass fibers increases the relaxation time and gives the same
interpretation as Figure 7.2. Thus, it can be concluded that the method
10 1
IClLASS FlBEl!. FILLml l'Ol.mnENE I UNI!S
Xe- SEC
r - SEC.1
Ilsooc I
100
Xc
1
10
o PS 140"1. GLASS Fmn

4 PS 120'1. OLASS Fmtm
o PS
10.2
10.2 1 1
10 10 10 10 2
r
Figure 7.3(b) Variation of relaxation time with shear rate for polystyrene melt filled
with glass fiber. (Reprinted from Ref. 14 with kind permission from John Wiley & Sons,
of representation of NI vs. !12 as given in Figures 7.1 and 7.2 is the

correct one and should be followed. Particularly in the case of filled
systems, the shear rate or velocity gradient may not be continuous at
the interface between the filler and polymer, whereas shear stress is
likely to be continuous at the interface assuming no slippage occurs
between filler and polymer [81]. Hence, interpretation of normal stress
difference through shear stress becomes more meaningful. In systems
showing a yield stress, as the shear stress is decreased towards it, the
normal stress difference approaches zero [27,90] as suggested by the
developed phenomenological constitutive equations [19]. However, this
response is not observable in Figures 7.1 and 7.2 because of lack of
normal stress data at very low shear rates. The view that NI is small
relative to !12 because of the existence of a yield value is, of course, a
reasonable one.

In order to obtain data representation in the form of NI (or 1/11 = Nt/:./)
vs. volume fraction lP, attempts [7,71] have been made to obtain
graphical similarity with the viscous counterpart as shown in Figure
6.10. Minagawa and White [7] showed that the ratio of NI or 1/11 of the
filled systems to that of the unfilled polymer matrix atthe same shear
rate was independent of the shear rate and an increasing function of eP.
The function was not found to be unique and depended on the chosen
filler-polymer combination. An empirical Taylor series expansion for
I/Il,r at low volume fraction was shown to successfully describe the
increase with volume fraction in the range of 0 ~ eP ~ 0.25.
Poslinski et al. [71], on the other hand, found that all their glass
sphere data could be correlated by the following form analogous to
equation (6.11) for relative viscosity
1/1
l,r
= N 1(eP, y) = [1-
N 1(0, y)
ePl4>
m
r 2
(7.1)
The I/Il,r experimental values were obtained by averaging the relative

data over the entire range of shear rate measurement from 1 to 100 S-I.
It can be seen from Figure 7.4 that the experimental data are fitted rather
weIl by the above equation (7.1) over the entire volume fraction range
up to as high as 0.6. In Figure 7.4, the value of ePm was taken as 0.62 as
CHEVRON GRADE-18
.... CHEVRON GRADE 24
CHEVRON GRADE .32
... CHEVRON GRADE _122
o TIiElWOFLASTIC @ 130 D C
o 'I'HERl40PLASTIC @ ISOC
C::. 'II!Ell.MOPLASTIC @ 170 C
- EQUAl10N (/.1)
Y'1,r
0.2 0.4 0.6 0.8 1.0
Figure 7.4 Variation of average relative primary normal stress coefficient as a

function of the reduced volume fraction of filler. (Reprinted from Ref. 71 with kind
determined experimentally [71] by the liquid displacement technique.

Despite the fact that theoretical interpretation of experimental data
[7,71] works out weH as represented, intuitively the predicted trend is
reversed. The presence of the particulate fillers has been shown to
decrease the elasticity of the polymer melt as demonstrated in
Figure 7.1. This fact is also supported by exit pressure measurements
[5,34]. With increasing filler concentration, it is thus logical to expect
that normal stress difference would decrease. This has, in fact, been
shown by Han [77,81] as given in Figure 7.5(a). It has also been shown
[7] that extrudate swell decreases with increasing filler concentration as
can be seen from the plot given in Figure 7.5(b) of extrudate swell ratio
vs. filler concentration for high density polyethylene melts filled with
titanium dioxide determined at a constant shear rate (10 sec-I) with a
capillary having an LID ratio of 28. Hopper [91], Cotten [92], Medalia
[93], Vinogradov et al. [94] and White and Crowder [6] all studied the
effect on die swell ratio of carbon black-filled polymer systems. The
unanimous observation was that, as the filler concentration was
increased, the die swell ratio decreased showing a decrease in the
elasticity. The effect of this was an improved extrusion characteristic
and an increased value of the critical shear stress before melt fracture
could occur. Plots of relaxation time vs. filler concentration as given in
Figure 7.5(c) for various polymers filled with TiO z particulate filler,
support the fact that elasticity decreases with increasing concentration.
1~r;;;~~~~~~~~~~~~------------~
ICALCIDM CARBONATE FILI.E.D POLYPROPYl.ENE I
UNITS
N 1 "C 12 - PASCALS
I200C I
oPP
PP I 2.9% CaC0 3
A
PP 16.4% CaC0 3
Cl
o pp 115.4 % CaC03
102~==========~~______~____~____L-__L--L~
102
"C12
Figure 7.5(a) Variation of primary normal stress difference with shear stress for
polypropylene at 200C filled with calcium carbonate. (Reprinted from Refs 77, 81 with
kind permission from Academic Press Inc., New York, USA.)
ImANIUM DIOXIDE FIU.ED ffiGH DENSITY POLYETHYI.ENE I

1.5
1.4 11&OClc i
1.3
Sw 1.2
1.1
1.0
0 0.1 0.2 0.3 0.4
Flgure 7.5(b) Variation of extrudate swell ratio with volume fraetion for high density
polyethylene at 180C filled with titanium dioxide. (Reprinted from Ref. 7 with kind
10
r
l-
Im.Al!OM DIOXIDE FII.LED l'OLYl4Iii.S I
r
l-
r "iii I~~cl
- I 180 C I
Eil
l- sa D
-e-
-
I--
l-
r '<7-
r
I- -.:r-
c- e BDPX
I- o LDl'E
l PS
I I I I
.0.
01 0.2 0.3
Flgure 7.5(c) Variation of relaxation time with volume fraetion for polymer melts filled
with titanium dioxide. Data at shear rate of 0.5 see- 1 . (Reprinted from Ref. 7 with kind
Effect of filler agglomerates 321
It is obvious that the mobility of the polymer chains under the influence
of an applied stress is reduced by the presence of the filler, thereby
decreasing the elastic response of particulate filled polymer systems
with increasing concentration. Note that Figure 7.5(a) is a plot of NI vs.
1'12 rather that y and correct1y so. The trend of increasing elasticity with
increasing filler concentration will be noticed only in fiber-filled systems
as evidenced from Figure 7.3(b).
Thus, it should be borne in mind that equation (7.1) may be used for
data representation but not for data interpretation, as the predicted
trend does not describe the actual situation. In fact, it might be better to
define 1/Il,r as equal to N 1(c/>, 1'12)/N1(0, 1'12) and then seek a relationship
with c/>.
7.4 EFFECT OF FILLER SIZE DISTRIBUTION

Poslinski et al. [72] undertook the study of the influence of a bimodal
size distribution of glass spheres on the rheology of filled polymer
systems as already discussed in section 6.4. The bimodal size
distribution was prepared by mixing together various vol% of the
smaller 15 11m spheres with the larger 78 11m spheres given in Table 6.3.
Various bimodal mixtures were compounded into a polybutene grade
24 polymer obtained from Petrochemical Division of the Chevron
Company, at total solids concentrations up to 60% by volume.
To see the effect of particle size and size distribution on elasticity of
the system, the average relative normal stress difference coefficients are
plotted against c/>s' the volume percent of the 15 11m spheres, ranging
from 0 to 100% of the total solids mixture as shown in Figure 7.6.
Similar to the relative viscosity ca se in Figure 6,20, the relative primary
normal stress coefficient is also reduced when the two sizes of spheres
are mixed together, and again the lowest values are obtained for
C/>S = 10 to 30% of the smaller spheres, which happens to be the same
range when the maximum packing parameter is the highest.
The solid lines in Figure 7.6 represent the predictions of equation
(7.1) with maximum packing fraction determined by equation (6.17)
using the particle size distribution values of the bimodal components
listed in Table 6.3. The agreement between theory and experiment is
quite adequate. However, as discussed in section 7.3, there is a problem
with data interpretation because the curve of 60% by volume of total
spheres shows the highest elasticity which is incorrect.

Agglomerates occlude liquid in their interparticle voids and thereby
leave a less volume fraction of the liquid around it. This would create
IGLASS SPHERE FII.I.ED POLYBtrn:NE I

" TOTAl SPB:E:RES
0.10 ... 0.40
.... 0.20 0.50
.0.30 0.60
- EQUATION (f.l)
o 20 40 60 80 100
Figure 7.6 Variation 01 average relative primary normal stress eoellieient as a

lunetion 01 4>" the volume pereent 01 the 151lm glass spheres in the total mixture
suspended in a polybutene grade 24 matrix at 22C. (Reprinted lram Rel. 72 with kind
permission lram John Wiley & Sons, Ine., New York, USA.)
an apparent situation of higher filler loading than is actually present.

Hence, the effect of filler agglomerates would be similar to that of filler
concentrations; or, in other words, with larger number of filler
agglomerates, the system would behave rheologically in a manner
similar to a system with a higher filler concentration than what actually
exists.
It can be thus expected that with increasing number of filler
agglomerates when dealing with particulate fillers, the normal stress
difference would be lower. The extent of lowering of the normal stress
difference depends on the amount of occluded liquid by the agglomer-
ates, the average number of particles in each agglomerate and hence the
size of the agglomerates. In an unagglomerated filled system, the extent
of normal stress difference lowering would be less if the partic1e size is

larger. When an agglomerate is formed or present, it is as though the
partic1e size of the filler has increased throughout the system. Thus,
with increasing number of partic1es in the agglomerates, the extent of
normal stress difference lowering decreases. On the other hand, because
of the occ1uded liquid in the interpartic1e voids of the agglomerates, the
extent of normal stress difference lowering increases. It is basically the
net effect of these two opposing factors that determines exactly how
much the normal stress difference would be lowered.
In the case of fiber-fi1led systems, too, the effect of agglomerates
would be to lower the normal stress difference. It has already been
shown in section 7.1 that fiber-fi1led systems show increases in
elasticity. The extent of the increase would be thus reduced if
agglomerates are formed because the fibers that gather to make up the
agglomerates are restrained and cannot orient during flow.
There are no experimental data specifically to support the intuitive
thoughts put forth in this section. The reason is that determination of
normal stress difference in the presence of agglomerates is extremely
difficult. The agglomerates interfere with the gap setting during cone
and plate rheological measurements due to their increased size. Despite
lack of actual data, the conc1usions on the effect of agglomerates can be
drawn by carefully understanding the effect in analogous situations as
done here.

One of the effective methods of reducing the number of filler
agglomerates in a filled polymer system is through the use of surface-
modifiers such as those listed in Table 1.5. Surface modifiers are
generally bifunctional molecules with one end capable of adhering to
the filler and the other end compatible with the polymer, and at times
even capable of reacting with it. Surface treatment basically helps the
polymer to wet the filler better and disperse it, thereby reducing and
preventing agglomeration because of promotion of filler-polymer
contact as against filler-filler contact. Research work on the effect of
surface treatment on the steady shear elastic properties of filled
polymer systems is limited [27,34] but good enough to draw adequate
conc1usions.
Figure 7.7 shows the effect of surface treatment on 30% calcium
carbonate filled polystyrene [27]. It can be seen that the data are
presented in both forms of representations. NI vs. y (Figure 7.7(a)) and
NI vs. 1'12 (Figure 7.7(b)). In Figure 7.7(a), it appears that surface
treatment reduces elasticity to a level even below that of the pure
polymer. However, conc1usions drawn from this type of representation
ICALCItJM CAnONATE FILlED POLYSTYlU:NE I

UNII'S IlgoDe I
NI-PASCALS
104 f - SEC-I
30% UNI'REATED
o 0%
30% TREATED
.
'Y
Figure 7.7(a) Variation of primary normal stress difference with shear rate for
calcium carbonate filled polystyrene containing 30% untreated and treated filler.
(Reprinted fram Ref. 27 with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA.)
CALCIUM CARBONATE FILlJID POLYSTYRENE

UNITS
N1.1: 12 -PASCALS
00"/
30"10 TREATED
30"10 UN1"RE.Al'ED
102
102 103
1:: 12
Figure 7.7(b) Variation of primary normal stress difference with shear stress for
calcium carbonate filled pOlystyrene containing 30% untreated and treated filler.
(Reprinted from Ref. 27 with kind permission fram Society of Plastics Engineers Inc.,
Connecticut, USA.)
would not be correct because the untreated 30% CaC03 shows an

increase in elasticity, which is against intuition and logic as discussed
in section 7.2. Thus, the representation given in Figure 7.7(b) is the true
one and shows that surface treatment increases the values of NI as
against that of the untreated system of a fixed filler loading at the same
level of shear stress.
Figure 7.8 gives the plot of first normal stress difference vs. shear
stress for CaC03 filled polypropylene. Similar to the effect observed in
Figure 7.7(b), the use of the surface modifiers, namely, silanes Y9187
and AllOD, shows an increase in the normal stress difference over that
of the untreated system irrespective of the temperature of measurement.
Note that Y9187 is an N-octyltriethoxysilane while AllOD is a y-
aminopropyltriethoxysilane. The same effect is, however, not found to
be the case when considering a different filler such as glass beads in the
polypropylene.
~
NI .1:12 - PASCALS
o PP
"" pp ICaC03
o PP I CaCO 3 I Y9187
'" PP I CaC03 I AllOO
1: 12
Figure 7.8(a) Variation of primary normal stress difference with shear stress at
200C for calcium carbonate filled polypropylene treated with silane surface modifiers.
(Reprinted from Ref. 34 with kind permission from Society of Plastics Engineers Inc ..
Connecticut, USA.)
ICALCIUM CAllllONATE FILLED POLYPROPYlENEI

~
N1 ."C12 - PASCALS
.pp
., pp / C.C03
PP / CaC03/ Y9187
... pp / CaC03 / All 00
1:;12
Figure 7.8(b) Variation of primary normal stress difference with shear stress at
240C for calcium carbonate filled polypropylene treated with silane surface modifiers.
(Reprinted fram Ref. 34 with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA.)
Figure 7.9 shows that neither the silane Y9187 nor AllOO is effective
in influencing the normal stress difference of the untreated glass beads-
pp systems at 200C. However, at 240C, the surface modifier Y9187
decreases the melt elasticity while AllOO increases it. Note that the data
in Figures 7.8 and 7.9 are a11 in the high shear rate range and obtained
using the Han slit/ capillary rheometer.
When the surface modifier is changed from the silane to a titanate in
the ca se of the CaC03-PP system, as in Figure 7.10, the effects are
qualitatively not different from those observed in Figure 7.7(a) or (b). It
is seen that the normal stress difference of the titanate KR-TT5 treated
CaC03-PP system is higher than that of the untreated CaC03-PP
system. In Figure 7.10, the low-shear data were obtained on the
Weissenberg rheogoniometer and the high-shear data were got using
the Han slit/ capillary rheometer.
When the fi11er is changed to glass fiber and the same titanate KR-
TT5 is used as a surface modifier, it is seen that the untreated and
102 103
1:12
Figure 7.9(a) Variation of primary normal stress difference with shear stress at
200C for glass bead filled polypropylene treated with silane surface modifiers.
Connecticut, USA)
"t:12
Figure 7.9(b) Variation of primary normal stress difference with shear stress at
240C for glass bead filled polypropylene treated with silane surface modifiers.
Connecticut, USA)
CARBONATE FILLED I
I.C.ALCIUMPOLYI>:a.OPYUNE .
UNITS
NI '"(:12 - PASCALS
o,e PP
0, PP/CaC0:3 rrrs
I:> , PP/CaC03
Figure 7.10 Variation of primary normal stress difference with shear stress for
calcium carbonate filled polypropylene treated with titanate surface modifier TTS.
Open symbols represent Weissenberg rheogoniometer data and closed symbols
represents Han slitlcapillary rheometer data. (Reprinted fram Ref. 34 with kind
permission fram Society of Plastics Engineers Inc., Connecticut, USA.)
treated filled polypropylene systems do not show any difference in the

normal stress characteristics as shown in Figure 7.11.
The normal stress difference data in Figures 7.7-7.11 all go to show
that the effect of surface modifier is quite system specific. Hence,
l~iJiB:~1
UNITS
Nt ''C t2 - PASCALS
I200C I
0,' PP
o,. PP/GLASS FlBERIITS
t:. , . PP/GLASS FlBER
Flgure 7.11 Variation of primary normal stress difference with shear stress for fiber
filled polypropylene with 50% untreated and treated filler using titanate surface
modifier TTS. Open symbols represent Weissenberg rheogoniometer data and closed
symbols represent Han sliVcapiliary rheometer data. (Reprinted from Ref. 81 with kind
permission from Academic Press Inc., New York, USA)
extrapolation of information with regard to this effect can at times be

dangerous. The efficiency of the surface modifiers will depend on the
type of filler, type of polymer, amount of modifier and method of
treatment as already discussed in section 6.6.

As already mentioned in section 6.7, the effect of polymer matrix on the
rheological properties of filled polymer systems would depend on the
chemical nature of the polymer as weIl as its unfilled rheological
properties. In order to und erstand this effect, it would be essential to
observe normal stress difference response using different polymer
systems but with the same filler of a fixed sizel size distribution and at
a fixed level of loading. This information is not available from one
source as in the steady shear viscous case [63]. Hence, this effect is
exemplified by presenting data from different sources for different
polymer systems but with the same fillers. Of course, the physical
characteristics of the chosen filler are unlikely to be the same and so
also, it is unlikely to find a particular filler loading as a common
denominator in all cases. Nevertheless, the data would give some
general idea of the effect of the polymer matrix.
UNITS
IGUSS ~~/lllED I N1''C 12 - PASCALS
\nsoc, 285C, 295 c I
o NYLON 6,6f33% GUSS FIBER

o NYLON 6,6
102 1_ _ _ _ _ _ _._....JI'--_ _ _ _ _ _ .
103 lot 105
'C 12
Figure 7.12 Variation of primary normal stress difference with shear stress for glass
fiber filled nylon 6,6 with 33 vol% of fiber. (Reprinted from Ref. 95 with kind permission
from Society of Plastics Engineers Inc., Connecticut, USA.)
Figures 7.12-7.14 show the effect of glass fibers at different loading

levels on the normal stress difference behavior of nylon, polycarbonate
(PC), and polystyrene (PS). Since the plots have been made as N 1 vs. '12'
they are independent of temperature. This is specifically clear from
Figure 7.12 which shows a uniqueness of data at the three temperatures
of 275C, 285C and 295C [95].
In Figure 7.13 for polycarbonate [31], it is seen that N 1 does not rise
systematically with filler concentration at a fixed shear stress. The 30%
loaded system coincides with the 10% loaded glass fiber filled
polycarbonate instead of lying between the 20% and the 40%. No
apparent explanation can be presented for such anomalous behavior.
In the case of glass fiber filled polystyrene [28], the loading level is
limited to 10% and 22% and hence whether areversal of the type that
was observed in Figure 7.13 for PC takes place cannot be established.
Figure 7.11, which also gives the normal stress difference information
104 IGLASS FIBER FIllED POLYCARBONATE I

1250't I
MAKROLON % FlLLER
GRADE
8344 40
*
... 8324 20
8035 30
. 9410 10
UNITS 6555 0
2805 0
N1,1::12 - PASCALS
10 1 L:=:::c:::c::t:::cI:rn:C::~.....l-L.L.L.LL..!...L---l--L......L....L...L.J...uJ
10 2 103 104 10 5
1::12
Figure 7.13 Variation of primary normal stress difference with shear stress for glass
fiber filled polycarbonate of different grades of Makroion. (Reprinted from Ref. 31 with
kind permission from John Wiley & Sons, Inc., New York, USA)
105
IGLASS FIBER FIllED POLYSTYRENE I
UNlTS
NI' '(;12 - PASCALS
I180C I
[J PS 122% GLASS FIBER

6. PS {10"10 GLASS FIBER
o PS
'(;12
Figure 7.14 Variation of primary normal stress differenee with shear stress for glass
fiber filled polystyrene with different volume fraetion. (Reprinted fram Ref. 28 with kind
permission fram John Wiley & Sons, Ine., New York, USA.).
on glass fiber filled systems [81] but using a different polymer, namely
polypropylene (PP), presents an unusual behavior. It is seen that this is
the lone case where a fiber filled system shows a decrease in elasticity
of the polymer melt. The behavior is inexplicable considering the fact
that even a Newtonian fluid containing fibers is known to show an
increase in elasticity [96].
REFERENCES
1. Bruch, M., Holderle, M. and Friedrich, C. (1997) Rheological properties of
polystyrene filled with hairy PMMA-partic1es, Paper 8-F presented at the
13th international meeting of the Polymer Processing Society (June 10-13).
2. Chapman, F.M. and Lee, T.5. (1970) Effect of tale filler on the melt rheology
of polypropylene, SPE Journal, 26, 37-40.
3. Mills, N.J. (1971) The rheology of filled polymers, J. Appl. Polym. Sei., 15,
2791-805.
References 333
4. Nazem, F. and Hill, CI. (1974) Elongational and shear viscosities of bead-
filled therrnoplastic, Trans. Soc. Rheol., 18, 87-1Ol.
polypropylene melts., J. Appl. Polym. Sci., 18, 821-9.
butadiene and butadiene-styrene copolymer, J. Appl. Polym. Sei., 18, 1013-38.
20,501-23.
8. Faulkner, D.L. and Schrnidt, L.R. (1977) Glass bead-filled polypropylene
Part I: Rheological and mechanical properties, Polym. Engg Sei., 17, 657~.
9. Boira, M.S. and Chaffey, CE. (1977) Effects of coupling agents on the
12. Kataoka, T., Kitano, T. and Nishirnura, T. (1978) Utility of parallel-plate
62~31.
reinforcement, Plastic Compounding, 1, 2~36 (Nov lDec).
extrusion and injection molding characteristics of polyethylene and
polystyrene melts, Polym. Engg Sei., 18, 268-72; (1978) A fundamental study
of the rheological properties of glass fiber-reinforced polyethylene and
16. Menges, G., Geisbusch, P. and Zingel, U. (1979) Kunststoffe, 7,485.
17. Arina, M., Honkanen, A. and Tarnrnela, V. (1979) Mineral fillers in low
density polyethylene films, Polym. Engg Sei., 19, 30--9.
18. Monte, S.J. and Sugerrnan, G. (1979) A new generation of age and water-
Engg Sei., 19, 617-24.
20. Wu. S. (1979) Order--disorder transitions in the extrusion of fiber-filled
764-9.
23. Kitano, T., Nishirnura, T., Kataoka, T. and Sakai, T. (1980) Correlation of
19,671-3.
24. Crowson, RJ., Folkes, M.J. and Bright, P.F. (1980) Rheology of short glass
fiber-reinforced thermoplastics and its applieations to injection molding I.
Fiber motion and viscosity measurement, Polyrn. Engg Sei., 20, 925-33.
25. Crowson, RJ. and Folkes, M.J. (1980) Rheology of short glass fiber-
reinforced thermoplastics and its application to injection molding II. The
effect of material parameters, Polyrn. Engg Sei., 20, 934-40.
26. Goel, D.C (1980) Effect of polymerie additives on the rheological properties
of talc-filled polypropylene, Polyrn. Engg Sei., 20, 198-201.
27. Tanaka, H. and White, J.L. (1980) Experimental Investigations of shear
calcium carbonate, titanium dioxide and carbon black, Polyrn. Engg Sei.,
20,949-56.
28. Czarnecki, I. and White, J.L. (1980) Shear flow rheological properties, fiber
reinforced polystyrene melts, J. Appl. Polyrn. Sei., 25, 1217-44.
29. White, J.L., Czarnecki, I. and Tanaka, H. (1980) Experimental studies of the
influence of partic1e and fiber reinforcement on the rheological properties of
polymer melts, Rubber Chern. Teeh., 53, 823-35.
11. J. Polyrn. Sei., (Polym. Chem. Edn), 18, 3211-17.
31. Knutsson, B.A., White, J.L. and Abbas, K.A. (1981) Rheologieal and
Polyrn. Sei., 26, 2347-62.
using hydrophobie encapsulation, Plastie Engg, 37-9 Oune).
33. Kitano, T., Kataoka, T. and Shirata, T. (1981) An empirieal equation of the
Acta, 20, 207-9.
coupling agents on the rheological properties, processing and mechanieal
properties of filled polypropylene, Polyrn. Engg Sei., 21,196-204.
35. Stamhuis, J.F. and Loppe, J.P.A. (1982) Rheologieal determination of
36. Sharma, Y.N., Pate!, RD., Dhimmar, I.H. and Bhardwaj, I.S. (1982) Studies
of the effect of titanate coupling agent on the performance of
polypropylene-calcium carbonate composite, J. Appl. Polyrn. Sei., 27, 97-104.
coupling agents for calcium carbonate filler, J. Appl. Polyrn. Sei., 27, 259-69.
38. Lee, W.M., Abe, D.A., Chipalkatti, M.H. and Liaw, T.F. (1982) Rheologieal
Con! Rein! Plast. Cornpos. Inst. Soe., Plast. Ind., 37 (12D), 7.
polypropylene reinforced with glycerol-treated mica, Can. J. Chern. Engg, 60,
334-41.
40. Hinkelmann, B. (1982) Zur analytischen beschreibung des fullstoff-einflusses
Polyrn. Cornposites, 3,193-211.
42. White, J.L. (1982) Rheologieal behavior of highly filled/reinforced polymer
melts, Plastics Cornpounding, 47-64 Oan/Feb).
References 335
43. Bigg, D.M. (1982) Rheologieal analysis of highly loaded polymeric

composites filled with non-agglomerating spherical filler particles, Polym.
Engg Sei., 22, 512-18.
44. Bigg, D.M. (1982) Rheologieal behavior of highly filled polymer melts,
45. Althouse, L.M., Bigg, D.M. and Wong, W.M. (1983) Evaluating the
effectiveness of filler surface treatments, Plastics Compounding, (March/
April).
263-88.
terpolymer filled with silica modified by silane coupling agents, Ind. Eng.
Chem. Prod. Res. Dev., 22, 695-8.
48. Mutsuddy, B.C (1983) Influence of powder characteristics on the
rheology of ceramic injection molding mixtures, Proe. Brit. Ceram. Soe., 33,
117-37.
49. Chaffey, CE. (1983) Reinforced thermoplastics: through flow to use, Ann.
Rev. Mater. Sei., 13, 43-65.
50. Shenoy, A.V., Saini, D.R and Nadkami, V.M. (1983) Rheograms of filled
polymer melts from melt-flow index, Polym. Composites, 4, 53-63.
51. Shenoy, A.V. and Saini, D.R (1983) Interpretation of flow data for
multicomponent polymerie systems, Colloid Polym. Sei., 261, 846-54.
in molten polystyrene, J. Appl. Polym. Sei., 28, 1481-501.
53. Luo, H.L., Han, CD. and Mijovic, J. (1983) Effects of coupling agents in the
rheologieal behavior and physical mechanical properties of filled nylon 6, J.
Appl. Polym. Sei., 28, 3387-98.
Proc. IX Intl. Congress on Rheology in Mexieo, Adv. in Rheology, 3, 429-37.
55. Kitano, T., Kataoka, T. and Nagatsuka, Y. (1984) Shear flow rheologieal
Acta, 23, 20-30.
408-16.
57. Suetsugu, Y. and White, J.L. (1984) A theory of thixotropie plastic
viscoelastic fluids with a time-dependent yield surface and its comparison
to transient and steady state experiments on small particle filled polymer
melts, J. Non-Newtonian Fluid Meeh., 14, 121-40.
polymer melts, Chem. Engg Comm., 36, 211-21.
59. Bretas, R.E.S. and Powell, RL. (1985) Dynamic and transient rheologieal
treatment on the rheologieal and mechanieal properties of ferrite-filled
polymeric systems, Polym. Engg Sei., 25, 807-11.
61. Saini, D.R. and Shenoy, A.V. (1986) Viscoelastic properties of highly loaded
ferrite-filled polymeric systems, Polym. Engg Sei., 26, 441-5.
62. Shenoy, AV. and Saini, D.R (1986) Quantitative estimation of matrix filler
systems, Polym. Composites, 7,9frl00.
63. Saini, D.R, Shenoy, AV. and Nadkami, V.M. (1986) Melt rheology of
highly loaded ferrite-filled polymer composites, Polym. Composites, 7,
193-200.
64. Shenoy, AV. and Saini, D.R (1986) Wollastonite reinforced polypropylene
composites: dynamic and steady state melt flow behavior, J. Reinf Plastics
Comp., 5, 62-73.
65. Mutei, A.T. and Kamal, M.R (1986) Characterization of the rheological
66. Edirisinghe, M.J. and Evans, J.RG. (1987) Rheology of ceramic injection
67. Sacks, M.D., Khadilkar, CS., Scheiffele, G.W., Shenoy, AV., Dow, J.H. and
Ceramics, 24, 495-515.
68. Dow, J. H., Sacks, M.D. and Shenoy, AV. (1988) Dispersion of ceramic
partic1es in polymer melts, Ceram. Trans. (Ceram. Powder Sd. I1A), 1, 380-8.
69. Hunt, KN., Evans, J.RG. and Woodthorpe, J. (1988) The influence of mixing
route on the properties of ceramic injection moulding blends, Br. Ceram.
Trans. J., 17-21.
characteristic in the alumina/thermoplastic resin system, J. Am. Ceram. 50c.,
17,1093-9.
(1988) Rheological behavior of filled polymer systems I. Yield stress and
(1988) Rheological behavior of filled polymerie systems 11. The effect of a
73. Ishigure, Y., Nagaya, K, Mitsumatsu, F., Otabe, S., Hayashi, K, Sobajima,
A and Murase, I. (1989) Relationship between the flow characteristics of
highly filled alumina or zirconia-organic binder and the properties of
sintered products in injection molding processing, Rep. Gifu Pref [nd. Res.
431-42.
ceramic injection moulding suspensions, Ceramics [nt., 18, 193-200.
76. Nielsen, L.E. (1974) Mechanical Properties 01 Polymers and Composites, Marcel
77. Han, CD. (1976) Rheology in Polymer Processing, Academic Press, New York,
7,182-8.
133-57.
York, 1, Ch. 7, 295-352.
References 337
80. Vinogradov, G.V. and Malkin, AY. (1980) Rheology of Polymers, Mir
Publishers, Moscow, 380-402.
81. Han, C.D. (1981) Multiphnse Flow in Polymer Processing, Academie Press,
New York.
Encyclopedia of Fluid Mechnnics, (ed. N.P. Cheremisinoff), Gulf Publishing,
Houston, IX, 7, 667-701.
polymers, in Encyclopedia of Fluid Mechnnics, (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, IX, 9, 243-76.
85. Advani, S.G. (ed.) (1994) Flow and Rheology in Polymer Composites Manu-
facturing, Elsevier Science BV.
86. Boger, D.V. and Denn, M.M. (1981) Capillary and slit methods of normal
stress measurements, J. Non-Newtonian Fluid Mech., 6, 163-85.
87. Han, C.D. (1982) Polymer News, 8, 111-14.
88. Oda, K., White, J.L. and Clark, ES. (1978) Correlation of normal stresses in
polystyrene melts and its implications, Polym. Engg Sei., 18, 15-28.
89. Minoshina, W., White, J.L. and Spruiell, J.E. (1980) Experimental
investigation of the influence of molecular weight distribution on the
rheological properties of polypropylene melts, Polym. Engg Sei., 20, 1166-76.
90. White, J.L. and Tanaka, H. (1981) Comparison of a plastic-viscoelastic
constitutive equation with rheological rneasurernents on a polystyrene rnelt
reinforced with small particles, J. Non-Newtonian Fluid Mech., 8, 1-10.
91. Hopper, J.R. (1967) Effect of oil and black on SBR rheologieal properties,
Rubber Chern. Technoi., 40, 463-75.
92. Cotten, G.R (1968) Rubber Age, 100, 51.
93. Medalia, AT. (1970) Morphology of aggregates VI. Effective volurne of
aggregates of carbon black frorn electron rnieroscopy; application to vehicle
absorption and to die swell of filled rubber, J. Colloid Inter! Sei., 32, 115-31.
94. Vinogradov, G.V., Malkin, AYa., Plotnikova, E.P., Sabsai, O.Yu. and
Nikolayeva, N.E. (1972) Rheologieal properties of carbon black filled
polymers, [nt. J. Polym. Mat., 2, 1.
95. Pisipati, R and Baird, D.G. (1981) Correlation of rheological properties of
filled nylon rnelts with processing performance, SPE ANTEC, 27, 32-4.
96. Mewis, J. and Metzner, AB. (1974) The rheological properties of
suspensions of fibers in Newtonian fluids subjected to extensional
deformations, J. Fluid Mech., 62, 593-600.
Unsteady shear
viscoelastic properties 8
In the preceding two chapters, various effects on steady shear viscous

and elastic properties of filled polymer systems were discussed. The
present chapter focuses on the unsteady shear viscoelastic properties of
these systems. The unsteady shear characteristics are mainly discussed
with respect to small-amplitude oscillations, namely, dynamie
rheological data. In some cases, the thixotropie sweep responses and
the stress relaxation behavior are also included because they bring out
the rheological characteristics in some situations in a much better
manner. The extensive literature [1-85] on the rheology of filled
polymer systems, however, contains quite limited information on the
unsteady shear data [1,8,43-45,54,61,62,64,68,71,72,74,91,92].
The reason for this is because unsteady shear data were normally not
used when dealing with low loading levels of fillers where the bulk of
information is available. For highly filled systems, this is the only mode
of obtaining reliable rheological data, but since the work on highly
filled polymer systems is not extensive, the information on unsteady
shear data is naturally limited.
With higher filler loading, it becomes increasingly difficult to gap set
in a cone and plate arrangement of the rheogoniometer; whereas through
the use of the parallel-plate arrangements, it is possible to obtain
rheologieal data at any level of loading. The use of steady shear in the
case of highly filled systems is not recommended because the material
trapped between the plates of the rheometer during data generation
normally tends to hang outside the plate dimensions, thereby giving
erroneous results. On the other hand, when dealing with unsteady
shear data generation, small-amplitude dynamie oscillation keeps the
material between the plates of the rheometer intact and hence gives
much more reliable and reproducible data. Thus, dynamie data are often
the preferred mode for viscoelastic information of highly filled polymer
systems. Of course, it need not be restrieted only to high filler loadings

Unsteady shear viscoelastic properties 339
as it would ceitainly provide reliable information even in low filler

loadings as well.
As a matter of fact, the most reliable rheological data on filled
polymer systems can be obtained through the use of dynamic
oscillatory measurements. The dynamic rate sweep and the dynamic
strain sweep would be most suitable for assessing the interna1 structure
of the system. Ouring a strain sweep, a plot of storage modulus vs.
percentage strain at low frequency would be the best indicator of the
level of homogeneity in the system. A decrease in storage modulus with
percentage strain would be an indicator of the occurrence of the
structural breakdown in the system. Ouring a frequency sweep, it is
best to maintain the strain as low as possible within the system
constraints, in order to be in the linear viscoelastic region of the
material. The response of complex viscosity, storage modulus, loss
modulus and tangent delta that is then obtained would give a measure
of the dispersion of the filler in the matrix. A highly agglomerated
system would show the existence of a yield at low frequency, the
storage modulus would be high and vary minimally with frequency
giving a more solid like response and the tangent delta would be lower.
However, generation of reliable and consistent data in case of filled
systems depends to a large extent on the preparation of the sampIe for
the rheological test. Premolding sampies under high press ure to a shape
and size as would be used for the parallel-plate rheometer test, would
ensure that the variation in the observed rheological response is related
to the filled system characteristics and is not an experimental artifact.
Ouring generation of dynamic data, it is important to use a fixed low
amplitude when collecting data for comparison on various systems.
The effect of the amount of strain during dynamic data measurement
on filled polymer systems has been brought out by Bigg [44]. Figure 8.1
shows the strong effect of strain on the complex viscosity and storage
modulus for low density polyethylene filled with 50 vol% of spherical
stainless steel partic1es at 160C. It can be seen that the difference
between the complex viscosity at 10- 1 radi s with a 1% strain (1'( =
106 Pa.sec) to that with a 25% strain (1'/' = 2 x 104 Pa.sec) is almost two
orders of magnitude. Much greater differences are observed in the
storage modulus response with increasing strain. When the unfilled low
density polyethylene is tested using different levels of strains, it is seen
from Figure 8.2 that the complex viscosity remains unaffected by strain
and remains so at all temperatures. Thus, for unfilled polymers, it may
be all right to determine dynamic data at any level of strain. However,
for filled systems, because of the sensitivity of the dynamic response to
the level of strain, it is always important to determine the dynamic
viscoelastic properties at a strain that is low enough not to affect the
material response. As the filler loading increases, the level of strain
340 Unsteady shear viscoelastic properties
Figure 8.1(a) Effect of strain on the complex viscosity vs. Irequency curves lor
NA-250 low density polyethylene with 50vol% 01 spherical stainless steel particles at
160C. (Reprinted lram Rel. 44 with kind permission fram Society of Plastics Engineers
Inc., Connecticut. USA.)
below which the response is unaffected is reduced [44]. For loadings

elose to the maximum packing fraction, this strain level may be even
below the minimum obtainable within the experimental constraints. In
such cases, one could use a higher strain level, but keepthis value fixed
in a11 systems studied so that meaningful comparison of information
can be done. This would not induce any errors if the systems studied
have same fi11er loadings, but in systems containing different loadings
levels, this point ought to be borne in mind when drawing conelusions
from the generated data.
In Figure 8.1, it is worth noting that at a11 levels of strains, a yield
stress (indicated by a slope of -Ion the In 1]* -In w plot) is observed at
frequencies below 1 radi sec. This is because the fi11er loading level was
high (50vol%) and the interpartiele network dominated the rheological
behavior of such highly fi11ed polymer systems at a11 levels of strain
[44]. A similar behavior was observed by Saini and Shenoy [61] when
UNll'S
G' -PASCALS
C&l -lI.AD/SEC
STRAIN
00000
0000000000000
I> 000000000000
104 r- 0 0 0 00 00 000 00 0 000 0
POOOO 000 000 000
000000000000000000000000<
3 (~OOOO I I
10
10 2
Figure 8.1(b) Effeet of strain on the storage modulus VS. frequeney eurves for
NA-250 low density polyethylene with 50vol% of spherieal stainless steel partieles at
160C. (Reprinted from Ref. 44 with kind permission from Soeiety of Plastics Engineers
Ine., Conneetieut, USA)
dealing with high filler loading using a different type of filler, namely,
barium ferrite. The theoretical equations for modeling this type of
dynamic response would also be different from the conventional ones.
Theoretical equations for modeling dynamic response of filled
systems have been suggested for low [64] as well as high [61] levels of
loading and have been discussed at length in seetions 2.3.3 and 2.3.4.
However, some important equations are recalled and presented here for
convenience. Shenoy and Saini [64] suggested a form similar to that of
Carreau [86] but modified it appropriately for describing the dynamic
rheological behavior of low filled systems as:
(8.1)
where t/~ = zero-frequency viscosity function, t/* = complex viscosity,

w = frequency, ). = time constant, N = power-law parameter.
1(~-r==~~~============~
I
STEEL SPHERE FIWJ) LOW DENSTY POLYE'I'HYLENE I
UNITS
rt - PA SEC
Ql - RADISEC
STlWN
o lYo
o 5Yo
'" 10Yo
LI 25%
101~ __~__~~~.~~~__~__~~~_~~~
10 0
Figure 8.2 Complex viscosity vs. frequency curves for unfilled NA-250 low density
polyethylene at various temperatures and different levels of strain. (Reprinted fram
Ref. 44 with kind permission from Society of Plastics Engineers Ine., Connectieut,
USA.)
This equation is ideal for use when the complex viscosity curves
show a plateau region in the low frequency range along with a
decreasing trend in the higher frequency range (like Curve 1 in
Figure 1.3). The model given by equation (8.1) thus naturally presumes
no yield stress. On the other hand, when the filler loading increases, the
particle network formed leads to the existence of yield stress in the low
frequency region. In such cases of highly filled systems, Saini and
Shenoy [61] proposed a modified form of the above equation as:
K n'-l
111*1 = (1 + ;)<n'_n )/2
U
(8.2)
where K = complex viscosity at frequency of 1 radis and at n' = n"

n' = slope of the 111*1 vs. w curve in the region of 0.1 ~ w ~ 1
n" = slope of the 111*1 vs. w curve in the region of 1 ~ w ~ 102
Equation (8.2) was suitable for the systems studied by Saini and Shenoy
[61] because the complex viscosity in al1 cases showed the existence of
two distinct straight lines one in the low frequency region below w
equal to 1, and the other in the high frequency region above w equal to
1 (like Curve 3 in Figure 1.4). However, in ca ses where the complex
viscosity vs. frequency curves show an initial yield stress followed by
a plateau and then a frequency-thinning region, (like Curve 2 in
Figure 1.4), neither of the two equations suggested above can be used.
In such circumstances, it might be necessary to break up the curves into
two or three regions and fit separate equations in each region.
A correlation between complex viscosity 1]* and the storage modulus
G' was derived [61,64] by analogously following the method of Wagner
[87,88] for relating the elastic response to the viscous response of the
material (equation (2.61) in section 2.3.4). The expression obtained
[61,64] was as follows:
G' 1 dl1]*I(w)
(8.3)
w2 = m" dw
where m' is an adjustable parameter. Equations (8.1) and (8.3) can be
combined to give:
G: = 2N1]~,~2W (1 + ,fw 2 )-(N+l l (8.4)

w m
for low filler loadings.
Equations (8.2) and (8.3) can be combined to give:
G' = K (1 _ n')wn'-2(1 + w2in"-n'l/2 [1 + ll

(n' - n )w
2
] (8.5)
w2 m" (1 - n')(l + w 2 )
for high filler loadings.
The loss modulus G" vs. frequency can be easily predicted from the
above equations by using the definition:
G" = J[(1]*W)2 - G,2] (8.6)
It was found [61,64] that the theoretical predictions given by
equations (8.1)-(8.6) agreed well with the experimental determinations
for each of the rheological parameters, namely, 1]*, G' and G". All the
model parameters with the exception of N varied with filler loading.
The adjustable parameter m" itself varied with frequency in one case
[61]. Since the model parameter can be correlated with filler
compositions, reasonably good estimations of the various rheological
characteristics can be made for different filler loadings through the use
of equations (8.1)-(8.6).
The effect of various parameters on the unsteady shear viscoelastic
properties are discussed at varying lengths in the following subsections.
The conclusions that can be drawn from unsteady shear data are
most of the times not very different from those that can be got from
steady shear data. However, there are some cases, such as in the effect
of agglomerates or filler surface treatment, where the unsteady shear
data provide a better insight than the steady shear data. In such cases,
the subsections are dealt with in detail. Whereas in other cases, the
discussion is kept to a limited extent as the derived information is
analogous to the steady shear case.

In Chapters 6 and 7, the effect of filler type on the steady shear
rheological properties was elucidated through the response of filled
polymer systems having a fixed polymer but with nine different types
of filler at a single level of loading. This information was available from
one data source [29]. However, the same is not the case with unsteady
shear data. There is no single source wherein different fillers have been
used at a fixed filler loading in a single polymer matrix. The reason is
that where such data were to be genera ted, it would not lead to any
new conclusions other than those which have already been drawn from
the steady shear data.
Complex viscosity vs. frequency data would show that viscosity
increase would be the highest for fibrous fillers and lowest for spherical
fillers whereas particulate and platelet fillers would lie in between.
Further rigid fillers would show higher complex viscosity than flexible
fillers at the same frequency if their dimensions were similar.
When storage modulus data are generated over an entire frequency
range at a fixed strain, the conventional method of representation
would be a plot of G' vs. w. In the case of G' vs. w plots are viewed for
different types of filler, then it would be seen that all fillers increase
storage modulus at any frequency - the extent of the increase being the
highest for fibrous fillers while less for platelike or p(irticulate fillers
and least for spherical fillers. Non-interacting fillers such as spherical
fillers would show variation of G' with frequency whereas interacting
fillers like fibrous fillers would show greater independence with
frequency as they would depict more solid like behavior with higher
storage of elastic energy.

The smaller the size of the filler, the greater the particle-particle
interaction and this reflects greatly on the unsteady shear viscoelastic
properties. In the case of complex viscosity vs. frequency curves, it
would be natural to expect yield stress with decreasing particle size as
was discussed in seetion 6.2. With larger particles, since the response to
deformation is determined by hydrodynamic interaction and not by
particle-particle interaction, such filled systems do not show yield
stress.
In the case of storage modulus, the plot of G' vs. w is comparable
with the plot of N j vs. y shown in the earlier chapter. All conclusions
that could be drawn through the plot of N j vs. y would hold good
when G' vs. ware viewed. But then it must be borne in mind that the
type of data representation (Nj vs. Y or N j vs. T12 ) does make a
difference to the derived conclusions. In the case of storage modulus,
the data representation is always in the form of the G' vs. w curves and
hence the conclusions should be the same as those derived from the N j
vs. y curves. Actual unsteady shear data on filled polymer systems
using a single polymer matrix but different sized fillers at a fixed level
of loading from one source are unfortunately not available for validation.

Dynamic data in the form of complex/ dynamic viscosity and storage/
loss moduli vs. volume fraction </1 are available [8,71]. Faulkner and
Schmidt [8] obtained dynamic modulus data on glass bead filled
polypropylene composites using about 10% strain over the frequency
range of 0.01-10 rad/sec. The data for frequencies between 0.01-
0.1 rad/sec were found to have larger scatter and great deviations from
the higher frequency trends. Hence, the data range was restricted to
0.1-lOrad/sec and the relative storage and loss moduli data were
determined in this range. One representative curve at 11 rad/sec is
shown in Figure 8.3. It is seen that the glass beads enable the polymer
to store more energy elastically and to dissipate more mechanical
energy when compared at equal strains, with trends similar to those
obtained by Mills [3] for glass bead polystyrene systems. Within the
limited range of volume fraction of up to 0.26, it has been shown [8]
that the loss moduli (or, in other words, the dynamic viscosity)
increases at a greater rate than the storage moduli with increasing filler
volume fraction.
Faulkner and Schmidt [8] correlated their data as follows:
G',(</1, w) = 1 + 1.8</1 (8.7a)
G(O, w)
and
G"(</1, w) 2
G"(O, w) = 1 + 2</1 + 3.3</1 (8.7b)
The above equations clearly show how the viscous response dominates
2.0 ....---..,..---.---.,..---.----..,.....--'T""""--r---,
IaLASS iEAD P'JI.tiI) POLm.OPYllNl! I
1.9 4 LOSS UODULUS
o S'I'OlME lo{ODULUS
1.8
I240C I 'Y - 10%
llADt'SEC .
f.I) -
1.1
loS
1.4
1.3
o
1.2
1.1
1.0 ........_-'-_--'-_---'_ _"'---_"'""'-_--'-_---''-----l

o 0.04 0.08 0,12 0.16 0.20 0.24 0.28 0.32
Flgure 8.3 Variation of relative storage and loss moduli with volume fraction of filler
in glass bead filled polypropylene system at frequency w = 1 rad/sec and strain
y = 10%. (Reprinted from Ref. 8 with kind permission fram Society of Plastics
Engineers Inc., Connecticut, USA)
the elastic response with increasing filler concentration in the case of

glass bead filled polypropylene.
Poslinski et al. [71] showed that when average relative dynamic
viscosities in higher frequency ranges are plotted as a function of the
reduced volume fraction, <Pl4>m' the data approximately fall on a single
curve which is independent of the polymer matrix and temperature as
shown in Figure 8.4. The value of <Pm was taken as 0.62 based on an
experimental evaluation. The experimental data in Figure 8.4 are fitted
by two curves using the following theoretical expressions analogous to
those of Kitano et al. [22] and Chong at a1. [89] for the steady shear case
by substituting '1~ for '1r Thus,
(8.8a)
CHEVRON GRADE- 18
... CllFlRON GRADE - 24
CHEVRON GRADE - 32
'Y CHEVRON GRADE - 122
o 'I'BERMOPLASTIC @ 130C
o TEERMOPLASTIC @ lS00C
f::,. 'I'BERMOPLASTIC @ 170C
-- EQUATION (8.8a)
- - EQUATION (8.8\,)
11'r
0.0 0.2 0.4 0.(\ 0.8 1.0
Figure 8.4 Average relative dynamie viseosity at high frequeneies as a funetion of

the redueed volume fraetion of filler. (Reprinted from Ref. 71 with kind permission from
John Wiley & Sons, Ine., New York, USA)
and
(8.8b)
It is seen from Figure 8.4 that equation (8.8a) consistently gives high
values in comparison to (8.8b) but the fit provided by both equations is
reasonably good. It is to be noted that equation (8.8a) is used for
theoretical fit in Figure 8.4 instead of the expression of Kitano et al. [56]
used by Poslinski et al. [71].
Poslinski et al. [71] found that the storage modulus was far too low to
be measurable for polybutene grades 18, 24 and 32 over the entire range
of investigated frequencies. Hence, the relative storage modulus data
were available only for polybutene grade 122 and the therrnoplastic
polymer at three different temperatures. The average relative storage
modulus at high frequencies was plotted vs. the reduced volume
fraction 4J / 4Jm as shown in Figure 8.5. The average values were obtained
for each volume fraction from experimental data between 10 and
100 radi sec. It is seen that experimental data fall on a reasonably
unique curve fitted by the following theoretical expression [71]
analogous to the equations (6.11) and (7.1) by simply substituting G~ for
the material parameter as
(8.9)
The effect of filler concentration on the complex viscosity and storage
.... CHEVRON GB.J.DE -122

o 'IlmRMOPLAS'llC @ 130 C
o 'IlmRMOPLAS'llC @ 150C
L::.. 'IlmRMOPLAS'llC @ 170C
- EQUAllON (8.9)
G'
r
0.0 0.2 0.4 0.6 0.8 1.0
Flgure 8.5 Average relative storage modulus at high frequencies as a function of

the reduced volume fraetion of filler. (Reprinted fram Ref. 71 with kind permission from
John Wiley & Sons, Ine., New York, USA)
modulus vs. frequency has been brought out by the data of Bigg [44] on
alumina filled low density polyethylene systems as shown in Figure 8.6.
For the same system but using a very low viscosity polyethylene, the
effect of fiHer concentration on dynamic viscosity and loss modulus vs.
frequency has been presented by Dow et al. [68] as shown in Figures
8.7(a) and (b). Independent of the base viscosities of the polyethylene
(20 Pa.sec and 0.2 Pa.sec respectively), it is seen that the complex/
dynamic viscosity as weH as storage/loss modulus increase by orders
of magnitudes with increasing fiHer concentration, the effect being more
prominent at lower frequencies. The storage and loss moduli begin to
depict more solid like behavior at higher concentrations, as exemplified
by its independence with respect to increasing frequency.
105 r
~
o
.. 0
o
o
o
o
00
o
'iiii

1~ r-..--==_---,
UNITS
l'/*- PA SEC i
0' - PASCALS
o - 0.32
Cl - 0.48
w- RAD/SEC ~ - 0.57
Figure 8.6 Effect of filler concentration on the complex viscosity and storage
modulus variation with frequency for alumina-filled low density polyethylene.
(Reprinted from Ref. 44 with kind permission fram Society of Plastics Engineers Inc.,
Connecticut, USA)
2
TI' 10
101
0.1 10
Flgure 8.7(a) Plots of dynamie viseosity vs. frequeney for alumina filled low density
polyethylene prepared at the indieated eoneentrations of A1 2 0 3 . Mixing was earried
out at 150C and the rheologieal measurements were made at 125C. (Reprinted from
Ref. 68 with kind permission from The Ameriean Ceramie Soeiety Ine., Westerville,
Ohio, USA)
8.4 EFFECf OF FILLER SIZE DISTRIBUTION

The effect of filler size distribution is normally the most difficult to
isolate due to added complexities in performing reliable controlled
experiments. Hence, it often remains a neglected area. However, in the
case of highly filled systems, Bigg [54] has used a very systematic
procedure to investigate the effect of different particle size distributions
on the packing behavior and the dynamic rheological properties of the
filled systems. Filler particles were chosen very discretely to include
both agglomerating and non-agglomerating types, as well as bimodal,
narrow, and broad particle size distribution. Table 8.1 gives the
characteristics of the particles investigated by Bigg [54] while Table 8.2
104 IALUMINA FlLLED LOW DENSITY POLYETHYLENE I
...J1!lm..
G- PASCALS
W - RAD/SEC
lmac l
10 1
VOL% A1203
A S9
o SO
o 38
0.1
Figure 8.7(b) Plots 01 loss modulus vs. Irequeney lor alumina li lied low density
polyethylene prepared at the indieated eoneentrations 01 A1 2 0 3 . Mixing was earried
out at 150C and the rheologieal measurements were made at 125C. (Reprinted Irom
Rel. 68 with kind permission Irom The Ameriean Ceramie Soeiety Ine., Westerville,
Ohio, USA)
Table 8.1 Charaeteristies 01 liller particies investigated to study the effeet 01 liller
partiele size distribution (PSD)
Type Supplier Grade d,(~m) d2(~m) d 84 -d'6 ds./d'6 PSD
Stainless Amdry 136F 15 30-9.3 3.2 Narrow

steel (SS)
Stainless 6(36%) 54(64%) Bimodal
steel (SS)
Alumina (AI 2 0 3 ) Alcoa A16-SG 0.6 1.2-0.35 3.4 Narrow
Alumina (AI 2 0 3 ) 2(30%) 15(70%) 3.4 Narrow
Zirconia (Zr02 ) Zircoa Type C 3 8.0-1.5 5.3 Broad
Silicon nitride GTE Sylvania SN 5 < 1
(Si 3 N.)
Source: Ref. 54.

Table 8.2 Maximum packaging fraction of various filled systems used in the study
of the effect of filler particle size distribution (PSD)
Type PSD rPm Surface treatment
Stainless steel (SS) Narrow 0.63 None

Stainless steel (SS) Bimodal 0.69 None
Alumina (AI 2 0 3 ) Narrow 0.57 None
Alumina (AI 2 0 3 ) Narrow 0.63 W-91 0, Kemamide E
Alumina (AI 2 0 3 ) Bimodal 0.70 W-91 0, Kemamide E
Zirconia (Zr02 ) Broad 0.60 None
Zirconia (Zr0 2 ) Broad 0.70 W-91 0, Kemamide E
Silicon nitride (Si 3 N4 ) Unspecified 0.62 Kemamide E, W-900, none
Source: Re!. 54.
gives the maximum packing fraction of the filler that could be loaded in
the polyethylene matrix under the same mixing conditions.
As expected, it was found [54] that using a broad distribution or a
bimodal dispersion improved the level of maximum packing fraction
as compared to that using a narrow size distribution. In the case of
random shaped alumina and zirconia, which normally exist in agglo-
merated form, matrix additives were needed to achieve the maximum
packing fraction. In the case of unagglomerated spherical steel particles,
a bimodal distribution alone could produce the desired effect, as the
smaller particles could easily be segregated into the interstices of the
larger particles. Of course, its non-random packing is not completely
achievable in a random mixing process. Broadly distributed powders do
have random packing arrangement at their maximum packing fraction.
Bigg [54] has shown how the difference between the two packing
arrangements can be detected by changes in the storage modulus-
frequency response of the filled polymer melt during dynamic
measurements in the low strain region. Figure 8.8 shows that, though the
complex viscosity for bimodal distribution of stainless steel spheres and
alumina particles is the same, their storage modulus responses are
different. Bigg [54] attributed the initial drop in the modulus value at
low frequency to the movement of the smaller particles during their flow
into the interstitial spaces between the larger particles. The low level of
oscillatory motion provides sufficient energy to initiate the movement
and create a more efficient packing. This occurs favorably for bimodal
distribution but fails for broad distribution of zirconia particles, as
shown in Figure 8.9. Even the use of matrix additive does not show the
effect observed for the bimodal distribution. Bigg [54] concluded that
bimodally distributed powders had the potential of higher loadings than
broadly distributed powder, and one cannot achieve the theoretical
maximum fraction by the usual random mixing procedures.
lOS
1FII.lED LOW DENSlTY POLYETHYlJ!NE1 UNITS
71*- PASEC
G' - PASCALS
W - BADlSEC
107 ~ 1200DC I
~
~~
~a
~
a
~
I. EI
:1
ia
17*, G' EI
8!
a~
EI~
~~
~~
~~
EIEI
'00...0-
1
- 17G'
*'
-STAINLESS STEEL (ifi - 06S) I
EI EI
EIEI
~ P
0 . - ALUMINA (1/1 - 0.60)
10 2
Figure 8.8 Variation of complex viscosity and storage modulus with frequency,
showing the effect of bimodal distribution of stainless steel and alumina in low density
polyethylene at 200C. (Reprinted from Ref. 54.)
The study of the influence of bimodal size distribution of fillers on

the rheology of glass sphere filled polymer systems has also been done
by Poslinski et al. [72]. The bimodal size distributions were prepared by
mixing together various volume percentages of the smaller 15 11m
spheres with the larger 781lm spheres given in Table 6.3. Various
bimodal mixtures were compounded into a polybutene grade 24
polymer obtained from Petrochemical Division of the Chevron
Company, at total solids concentrations of up to 60% by volume.
The effect of the partic1e size and size distribution on dynamic
viscosity is shown in Figure 8.10 through a plot of average relative
dynamic viscosity vs. <Ps' the vol% of the 15 11m spheres, ranging from 0
to 100% of the total solids mixture. It was found that in the limit of low
frequencies, the dynamic viscosities of the filled polymer systems [72]
were equal to the shear viscosities at the same shear rate. However, the
relative dynamic viscosity was found to be a decreasing function of the
frequency approaching a constant value at the higher frequencies.
Consequently, relative values were obtained by averaging the data in
I, LOW DENSlTY
ZIllCONlA. FILLED I UNII'S
POLYETHYLENE . 17*- PASEC
G' _ PASCALS
c.l - RADISEC
0
0 1200C I
0
0 0
o 00
.
00 00
........
o 0
00 0
17*.G' OO~Oi ,
~ ~........
o 00
o 0
0 0 0 0

O~
eO~
i
~. 8@@
10
0 - 17*1
- 0'
g
EI JE!
I.00,. --wtrH
wtrHOUT ADDII1VE (~ - 0.60) I
KWAMIDE ADDII1VE(.p = 0.69).
10 2
Figure 8.9 Variation of complex viscosity and storage modulus with frequency for
zirconia-filled polyethylene at 200C with an additive. (Reprinted from Ref. 54.)
Table 8.3 Summary of important torque values for mixing polyethylene with alumina
powders treated with different surface modifying agents
Sam pie description Peak torque Final torque

(g.m) (g.m)
No additive 370 70
Silane Z-6020 305 60
Silane Z-6076 200 60
Zircoaluminate CAVCO MOD APG 425 15
Titanate LlCA-12 170 50
Source: Ref. 92.
the 10 to 100 rad/sec frequency range. As shown in Figure 8.10, the

experimental data at higher frequencies indicate that the relative
dynamic viscosities are also lowered when the two sizes of spheres are
mixed together, however, the reduction is not as significant as observed
for both I1r and t/ll.r discussed in seetions 6.4 and 7.4, respectively. The
lowest values of relative dynamic viscosity are seen to be obtained for
<Ps = 10 to 50% of the smaller spheres. The solid lines in Figure 8.10
represent the predictions of equation (8.8b) with the maximum packing
fraction determined by equation (6.17) using the particle size distri-
\\'r
o 0.2 0.4 0.6 0.8 ].0
Figure 8.10 Average relative dynamie viseosity as a funetion of rP" the volume
fraction of the 15 Jlm glass spheres in the total solids mixture suspended in a
polybutene grade 24 matrix at 22C. (Reprinted from Ref. 72 with kind permission from
John Wiley & Sons, Ine., New York, USA.)
bution values of the bimodal components listed in Table 6.3. The

agreement between theory and experiment can be seen to be quite
adequate.
In the case of the storage modulus, it was found that G' values of
the polybutene grade 24 matrix measured out as zero. Only at 40, 50
and 60% total glass spheres by volume were the filled polybutene G'
values measurable. Since a relative storage modulus could not be
defined, the investigation [72] of the storage modulus was restricted to
abimodal size distribution at high concentrations. Figure 8.11 shows
the storage modulus for 40, 50 and 60% volume fraction of total
spheres for various volume percentages of the 15 11m spheres at a
frequency of 1.0 rad/sec. It is seen that the storage modulus is also
IGLASS SPHERE FIllED POLYBUTENE I

UNITS
G'-PASCALS
t...I- l!.AD1SEC
!22'lC!
G'
@ t...I .. 1
r/J - TOTAL SPHERES

0.10
A 0.50
0.60
E.XPE.R1MENTAL CURVES
0.0 0.2 0.4 0.6 0.8 1.0
Flgure 8.11 Dynamie storage modulus as a funetion of f/Js' the volume fraetion of
the 15/lm glass spheres in a polybutene grade 24 matrix at 22C and a frequeney of
1 rad/sec. The solid lines represent the best fit of the experimental data. (Reprinted
from Ref. 72 with kind permission from John Wiley & Sons, Ine., New York, USA.)
reduced when two sizes of spheres are mixed together, and the lowest
values are obtained for <Ps = 10 to 30% of the smaller spheres, which
of course happens to be the same range when the maximum packing
parameter is the highest.

As already discussed in sections 6.5 and 7.5, the presence of
agglomerates creates an apparent situation of higher filler loading than
is actually present. This is because the agglomerates trap part of the
surrounding liquid in their interparticle voids thereby decreasing the
volume fraction of the liquid around it.
It is known that high shear mixing helps in reducing the

agglomerates whereas low shear mixing may at times increase the
number of agglomerates. This happens because during mixing the
probability of particle-particle contact as weIl as particle-liquid contact
is increased. If the mixing is done under low shear, then the
agglomerates that are formed during particle-particle contact do not get
an opportunity to break down. On the other hand, the high shear
provides the energy to break the particle-particle bonds and once the
polymer wets the particle, the bonds fail to reform, thereby giving a
better dispersion. The effect of filler agglomerates is thus best illustrated
by observing the unsteady shear response of the filled polymer system
prepared under conditions of low shear and high shear mixing.
Dow et al. [74] prepared alumina filled low density polyethylene
under two different rotor speeds of 10 rpm and 200 rpm. The mixing
temperature was held at 150C which was found by them to be the
optimum for the system under investigation as discussed in section
5.4.7. Figure 8.12 shows the torque curves in the mixing bowl during
the mixing operation. It is seen that the maximum torque genera ted
during mixing at 10 rpm was only 0.33 of the peak value obtained when
mixing at a rotor speed of 200 rpm.
Figure 8.13 shows the plots of dynamic viscosity vs. frequency for
sampies mixed at the two rotor speeds. As expected, the low torque
genera ted during mixing at 10 rpm results in higher viscosities,
indicating poorer dispersion and larger number of agglomerates.
Quantitative microscopy measurements confirmed this [74]. These
measurements were done on plasma etched sampies. Experiments
showed that polymer was preferentially removed from larger inter-
particle regions during etching. Thus, etched sampies tended to have
polymer remaining in the fine pores of agglomerated particles. These
agglomerated regions appear as single particles in micrographs. Thus,
measured particle sizes would be larger in poor-dispersed systems
containing more agglomerates. The particle size measure used was the
projection circumscribing diameter Dpc [90]. The sampie mixed at
10 rpm had an average Dpc value of 0.50 I-lm while the average Dpc was
0.431-lm for the sampie mixed at 200 rpm.
Besides using the smaIl-amplitude oscillation response to understand
the effect of agglomerates on rheology of filled systems, one could also
use the shear stress growth and first normal stress difference growth
function as was done by Kalyon [91]. Figures 8.14 and 8.15 show the
comparison of the rheological behavior of a surface-treated calcium
carbonate filler with an untreated silica-based filler having similar
particle size distribution. The filler loading was 30% in both ca ses and
they were incorporated under identical compounding conditions into
low density polyethylene. The plots show riv and t/ltr which are the
400~---------------------------------------------'
50 vo'% A. 2 0 3 Uncalclned
M'xlllQ Condltlons: 150"C, 200 rpm
300
~
S
w 200
::::I
aa: (A)
0
I-
tOO-
....
o A.
0
J 5 15
I
25 30
TIME (minI
_ 200 50 vo'% A. 20 3
E
Mixing Conditions: 150"C, 10 rpm
S
W
::::I
~100 (B)
o
I-
5 10 15 20 25 30
nliE (mln)
Figure 8.12 Plot of torque vs. mixing time for 50vol% of alumina in low density
polyethylene mixed at rotor speed of 200 rpm (A) and 10 rpm (8), respectively.
(Reprinted from Ref. 74 with kind permission from The American Ceramic Society Inc.,
Westerville, Ohio, USA.)
normalized values obtained by division of the respective parameters

with the values for pure polymer at 0.1 sec-I.
It is seen that the surface treated calcium carbonate filled system
behaves similady to the pure polymer and reaches the steady torque
and normal force values quite instantly. On the other hand, steady-state
shear stress and first normal stress difference values are not reached
with the silica-based filler, particulady the first normal stress difference
which exhibits a spectacular rise with the time of deformation. This
suggests that agglomeration and strong interaction occur between
agglomerates of the silica-based filler. These interactions convert the
structure during simple shear into a network that approaches more
solid-like behavior. The effect of agglomerates is no different from that
10000~----------------------------------------.
50 vol"t. A1 2O:J
IoIlxlng Temperatura = 150C
>-
t:
U)
o
(J
U)
::
(J
:i

~
Q
10 100
FREQUENCY (radis)
Figure 8.13 Plot 01 dynamie viseosity vs. trequeney at 125C tor 50vol% in low
density polyethylene mixed at rotor speeds ot 10 rpm and 200 rpm using a tixed mixing
temperature 01 150C. (Reprinted trom Rel. 74 with kind permission trom The
Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA.)
5
IPllLJiI) LOW DENSlTY POLYnHYL.ENE I A
4 UNITS
+--- 2
"t: 12 - DYNESlCW
t - MIN A 30"!. SlIlCA
+
"t: 12
3
T - 190C
r0.l.- 1
I [J 3O%CaC03
o !'ure LDPl!
A
2
[J [J Cl Cl Cl 0 'b Cl 0 [J
0 0 0 0..:. 0 0 0 0
I:i.
A
10 20
Figure 8.14 Shear stress growth lunetion 01 a low density polyethylene li lied with
two different tillers. (Reprinted Irom Rel. 91 with kind permission trom Gult Publishing
Co., Houston, Texas, USA.)
....
I~L~I ~
UNITS
-+
""1-DYN.ES.SBC 2 JCM2
t -MIN ~
T- t900C
i' - 0.1 ,-1 i:>.
~ 30"1. SILICA.
Vt:
~
10 030% CaC03
P Pure LDPB
00 00
oe 00 e e 0
p i:>.
00 00 00
0 0 0
i:>.
0
:,
o I I
o 8 24 40
t
Figure 8.15 First normal stress difference coefficient growth function of a low density
polyethylene filled with two different fillers. (Reprinted from Ref. 91 with kind
permission from Gulf Publishing Co., Houston, Texas, USA.)
of filler concentration. With larger number of filler agglomerates, the

system would behave rheologically in a manner similar to a system
with a higher filler concentration than actually exists.

Surface modifiers such as those listed in Table 1.5 are often used in
order to achieve better filler dispersion and reduced agglomeration due
to improvement in the wettability of the filler and on account of
promotion of filler-polymer contact rather than filler-filler contact. The
effect of surface treatment on unsteady shear viscoelastic properties has
been studied in highly filled systems [43-45,54,92] and the available
data do provide some basis for understanding the use of surface
modifiers.
The major thrust of the efforts of Bigg [43,44,54] and Althouse et al.
[45] was to investigate the influence of a silane AllOO and a titanate

KR385 (Table 1.5 for chemieal description) and to study the effect of
the method of surface treatment on the rheology. Polyethylene, which
is non-polar, was chosen as the matrix to eliminate the possibility of a
chemical reaction with the filler. 5pherieal steel particles of 15 11m size
were used so that they would remain unagglomerated and be devoid of
any effects due to variation in particle geometry. The surface modifiers,
in one case, were added directly to the polymer melt before adding the
filler to the mixer; while, in the other case, apretreatment step was
carried out wherein 5 g of the modifiers were diluted in 50 ml of
isopropyl alcohol and 500 g of the steel powder were mixed in it. After
drying the powder by evaporating the alcohol und er vacuum at 90C,
the treated powder was mixed with the polymer.
The results obtained by the two methods of treatment for the titanate
KR 385 were different from each other, especially in the low frequency
range, wherein it showed yield stress for the pretreated filler, while
showing a viscosity trend similar to the untreated filler when direct
addition was used. In the ca se of silane AllOO, the viscosity as weIl as
the storage modulus curves for the filled systems prepared by
pretreating the filler were almost identical to the curves for the filled
systems prepared by the addition of the surface modifier directly to the
melt. Figures 8.16-8.19 show the results of the treatment. The titanate
KR 385 and the silane AllOO both increase the viscosity of the filled
systems over the entire frequency range investigated. It is evident,
therefore, that both the surface modifiers couple with the polymer. The
organic functionality of the surface modifier extends into the polymer
phase and creates an apparent increase in the effective radius of the
individual filler particles, thus leading to an effective increase in filler
loading and hence, an increase in the viscosity and storage modulus of
the filled systems due to greater polymer-filler interaction. A similar
effect was observed at lower filler loadings by Luo et al. [53].
Dow [92] conducted a very detailed study of the effect of surface
modifying agents on unsteady shear viscoelastie properties. The
research work included dynamie data through oscillatory measure-
ments, thixotropie sweep data through continuous shear and stress
relaxation data upon cessation of suddenly applied shear stress. The
data were obtained on the Rheometries Mechanieal 5pectrometer at a
fixed measuring temperature of 125C. The filled system was made up
of 50vol% of alumina in low density polyethylene AC-9. Various types
of surface modifier were used - two silanes (Z-6020 and Z-6076), one
titanate (LICA12) and one zircoaluminate (CA VCO MOD APG).
Alumina powder was pretreated using each of the surface modifiers of
an amount equivalent to 1% wt of the filler in deionized water. After
rotating the suspensions for 22 hours in a rotary mixer, they were dried
104 -
::::
=
-
-
1/" r-
Hf ~
I:::
=
-
_
.--D..,-IRE----cr-AD-=Dm=-oN---,
.. - All 00 SJI.ANE
'" - KIl 385 MANATE
- 0 - UNl'REJ\.TED
102 L----'---'--L..LL...l...L..U-_-'---L.....l-L-LU_ll.L1_-1...---,1-1.. 1_,-!
1 ..J.!..J.1...J.1...L
0.1 10 102
Figure 8.16 Variation 01 complex viscosity with Irequency showing the effect 01 direct
addition 01 KR 38S and A1100 in 60vol% alumina-lilled polyethylene. (Reprinted Irom
Re!. 43 with kind permission Irom Society 01 Plastics Engineers Inc., Connecticut,
USA.)
JJlLUMlNA FILLED LOWDENSITY POLYETHYlENE I
G'
DIllC! ADDmON
.. - AllOO SILANE UNITS
'V - KR 38S mANAJE G' -PASCALS
o- UNTREATED W -RAD/SEC
Figure 8.17 Variation 01 storage modulus with Irequency showing the effect 01 direct
addition 01 KR 38S and A1100 in 60vol% alumina-lilled polyethylene. (Reprinted lrom
Rel. 43 with kind permission lrom Society 01 Plastics Engineers Inc., Connecticut,
USA.)
I I
I ,
~ ~v ~ ~
ALUMINA FILLF.D
,LOWDENSITY POLYETHYlENE,
"i7 v~
~O v~ UNITS
00 v6.~
v 6./::, 1']*- PA.SEC
v'V -
- 0000 "i7~ W -RADISEC
000
000 ~+8 ~
2200C
00 Xx
000 HXX"i7
000 ~ 'Z.
- PRETRE.ATMENT ~ -
- A1100 SILANE
0000
~ 00
~
"i7 - KR 38S mANATE
o- TJN'I'RE.ATED
I I
0,1 10
w
Figure 8.18 Variation of complex viscosity with frequency showing the effect of
pretreatment of KR 38S and A1100 on 60vol% alumina-filled polyethylene. (Reprinted
from Ref. 43 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA.)
on a hot plate to get the treated powder. The treated and untreated
alumina were mixed in a Haake torque rheometer with the polymer to
obtain the highly filled polymer systems. The torque vs. time curves
were also recorded and helped to give some insight into the rheological
behavior of the systems.
Figures 8.20(a)-(e) give plots of the torque vs. mixing time for the
50 vol% alumina filled low density polyethylene systems using various
surface modifying agents. The peak torque and the final torque values
for each system are given in Table 8.3. The highest peak torque and the
lowest final torque would signify the best dispersion. This happens in
the ca se of zircoaluminate CA VCO MOD APG treated alumina. The
untreated alumina and that treated with silane Z-6020 should also show
a reasonable level of dispersion but not as good as the zircoaluminate,
especially because their final torque levels are higher. The torque peaks
for the silane Z-6076 and titanate LICA 12 treated alumina are
substantially lower and hence should show the least level of dispersion.
The torque peaks determine the dispersion level more than the final
1cf
:: IALUMINA FIllED LOW DENSITY POLYETIiYLENE I
I200C I '<7
=
- UNITS 9
'<7
G' - PASCALS '<7 9'<7 '<7 "7 <7 '<7 ,:,':'
t.l - RAD/SEC ,:,':' 9X ,:, ,:, ,:,':',:, ,:, ,:,':'
- ,:,':' : 9
,:, ,:, ,:, ,:, '<7 <7
-g ~ 'i 'tI % '<7 ,:,'<7 8 8 ~ <7 '<7 <7 <7
0000
00
104 = 0000
=
- 00000000
000
-
G' - 00000
- 00
0
-A 0
0
103 =
=
-
-
- PR.ETREAIMENT
- ,:, - AllOO SILANE
KR 38S mANATE
- o
<7
-
-
UNI'REATED
10 2 1 L I I I I I II I I I I I I I I I I I I I I I I I
0.1 10 102
t.l
Figure 8.19 Variation 01 storage modulus with frequency showing the effect 01
pretreatment 01 KR 38S and A 1100 on 60 vol% alumina-lilled polyethylene. (Reprinted
Irom Rel. 43 with kind permission fram Society of Plastics Engineers Inc., Connecticut,
USA.)
torque value. The reason is that high initial torques help to break down
the agglomerates. It is an unsteady state instantaneous value and hence
highly sensitive. In the case of the final torque, it is the steady state
value at a very high shear rate and hence would be expected to be less
sensitive. It is known and can also be seen in the subsequent graphs in
this seetion that, at higher shear rates (or higher frequencies) the
rheological behavior of aH alumina treated as weH as untreated systems
behave quite similarly. It is in the low shear or low frequency data that
major differences arise due to the varying efficacy of the surface
modifying agents.
Figures 8.21(a)-(d) show plots of dynamic viscosity, storage modulus,
loss modulus and tangent delta vs. frequency for the various surface
treated alumina fiHed polyethylene systems. Lower dynamic viscosity
and modulus values were observed for the sampies with untreated
~~----------------------------------------,
50 vol'" Al 2 0 3
No Additive
300
~200 (a)
oa:
e
100
,.
o A.
~.------------------------------------------.
300
e-
s
~ 200 (b)
o
a:
e
100
O~~~-.--,---r--.--.-~r--r--.--,---.--.-~
300,------------------------------------------,
~200
.!!!
111
:;) (c)
oa:
e 100
o 5 10 15 20 25 30
TIME (mln)
Figure 8.20(a),(b),(c) Plots of torque vs. mixing time for 50vol% alumina in low
density polyethylene AC-9 with various surface modifying agents as indicated.
alumina and that treated with silane Z-6020 and zircoaluminate CA VCO
MOD APG. This is consistent with lower Dpc values for these systems as
given in Table 8.4 as well as the higher peak torque values given in Table
8.3 which was discussed earlier. On the other hand, higher viscosity and
500.-----------------------------------______~
50 vol% Al 2 0 3
Zlrcoalumlnate CAVCO MOD APG
400
eS 300
w
~
o (d)
a:
g 200
100
O~~F_-r--.--.---r--,_--r__.--._--r__.~;_~
~.-------------------------------------------,
5OVol%Al Z 0 3
1ltanate UCA 12
~200
,g
w (e)
~
oa:
g 100
5 10 15 20 25 30
nME(mln)
Figure 8.20(d),(e) Plots of torque vs. mixing time for 50vol% alumina in low density
polyethylene AC-9 with various surface modifying agents as indicated. (Reprinted
from Ref. 92.)
modulus values (particularly at low measuring frequencies) were

observed for the systems with the silane Z-6076 and titanate LICA 12.
This again was consistent with lower peak torques and higher Dpc va lues
for these systems as given in Tables 8.3 and 8.4, respectively. Though Dpc
values do give some indication of the dispersion level, they are not
sensitive enough to be used as direct measurement. It can be seen from
Figures 8.21(a)-(c) that viscosity and modulus values were consistently
lower for zircoaluminate CA VCO MOD APG than for the untreated
alumina indicating better dispersion but the Dpc va lues in Table 8.4 did
not reflect this. Similarly, the titanate LICA 12 treated alumina system
has significantly higher Dpc va lues compared to the sampie with the
silane Z-6076 treated system in Table 8.4 but the viscosity and modulus
va lues are very similar in Figures 8.21(a)-(c).
10000
~
.
l
50 vol" A1z0~ D Silane Z-8078
o Titanate UCA 12
o No Additive
.!:. 1000 v Silane Z-8020
4 Zlrcoaluminate
~
0
CAVCO WOD APG
u
cn (a)
100
I>
u
~
Q 10
1 10 100
FREQUENCY (rad/s)
1000.r-----------.-:...-----...,
(b)
D Silane Z~8078
o Titanate UCA 12
o No Additive
v Silane Z-8020
4 Zircoaluminate
CAVCO WOD APG
10 100
FREQUENCY (rad/s)
Figure 8.21(a),(b) Plots of dynamic viscosity and storage modulus vs. frequency for
50 vol% alumina in low density polyethylene AC-9 with various surface modifying
agents as indicated. (Reprinted from Ref. 92.)
Thixotropie sweep curves on the various systems were carried out

[92] and the results obtained are shown in Figures 8.22(a),(b) and (c),(d)
in the form of shear stress vs. shear rate curves and shear viscosity vs.
shear rate curves, respectively. Note that this is an unsteady state
measurement as the shear rate is not allowed to reach steady-state at
any value. The shear rate is increased continuously and decreased
continuously in fixed time scale.
It can be seen from Figures 8.22(a),(b) and (c),(d) that the titanate
LICA 12 and silane 2-6076 treated alumina PE systems have obvious
yield stresses and higher viscosities at low shear rates, while those of
10000....-------------------,
50 vo'" AIa03
(c)
[l Silane Z-6076
o Titanate UCA 12
10 o No Additive
v Silane Z-6020
.6 Zircoalummate
CAVCO YOD APG
1 10 100
FREQUENCY (rad/s)
10r--------------------,
[l Silane Z-6076
(d)
o Titanate UCA 12
o No Additive
v Silane Z-6020
.6 Zircoaluminate
CAVCO YOD APG
1 10 100
FREQUENCY (rad/s)
Figure 8.21(c),(d) Plots of loss modulus and tangent delta vs. frequency for
50vol% alumina in low density polyethylene AC-9 with various surface modifying
agents as indicated. (Reprinted from Ref. 92.)
zircoaluminate CA VCO MOD APG and silane Z-6020 have very low
yield stress and much lower viscosities at low shear rates. This again
shows how the former surface modifiers give a poor dispersion while
the latter ones give a better dispersion. The information is, of course,
consistent with the dynamic data measurements discussed earlier
through Figures 8.21(a)-(c) but for a minor difference.
In Figures 8.22(a),(b) and (c),(d) it is seen that the silane Z-6020 and
zircoaluminate CA VCO MOD APG both show lower viscosities than
the untreated alumina throughout the shear rate range from low to
high. On the other hand, silane Z-6020 dynamic data show that at
Table 8.4 Summary of Ope results for 50vol% alumina/50vol% polyethylene sampies
prepared with different surface modifying agents
Surface Ope (~m) Percentage of each category*

modifying
agent Average Standard Small Medium Large
value deviation
No additive 0.43 0.16 40.6 47.7 11.7

Silane Z-6020 0.42 0.16 46.6 40.7 12.7
Silane Z-6076 0.46 0.18 34.7 47.9 17.4
Zircoaluminate 0.42 0.16 44.6 44.8 10.6
CAVCO MOD APG
Titanate LlCA 12 0.51 0.19 22.7 53.1 24.2
* Small if Ope < 0.4 11m; medium if 0.4 11m s: Opc 0.6 11m; and large if Ope > 0.6 11m.
Source: Ref. 92.
higher frequencies the curves of silane Z-6020 treated and the untreated
alumina are identical or the former is slightly higher. Similarly, the
silane Z-6076 and titanate LICA 12 treated systems also show lower
viscosities at higher shear rates compared to the untreated alumina in
Figures 8.22(a),(b) and (c),(d) while this is not consistent with the high
frequency data in Figures 8.21(a)-(c).
The results of the stress relaxation measurements on the various
surface treated systems are shown in Figure 8.23. It can be seen that the
untreated alumina and that treated with zircoaluminate CAVCO MOD
APG have short relaxation times. This would be expected for systems
with good dispersion of the filler. On the other hand, the larger
relaxation times of the silane Z-6076 and titanate LICA 12 treated
alumina systems is understandable from the poorer dispersion of filler
in these systems. However, the extraordinarily high relaxation time
observed for the system containing silane Z-6020 treated alumina is
inexplicable [92].
Despite a reasonably detailed study of the rheological behavior of
filled polymer systems using the unsteady shear measurements, the
various mechanisms to explain the behavior of different surface
modifiers have not been elucidated [92]. The data bring out the
method by which the different rheological behavioral patterns of
various surface treatment can be recognized. Whether the differences in
the rheological behavior are due to the lubrication effect or chemical/
physical bonding of the surface modifiers that may act as a coupling
agent could not be discerned [92]. Another type of filler surface
treatment which has not been mentioned so far can be done. This is the
heat treatment of certain fillers, especially those which have hydroxyl
groups like alumina, which will bring ab out a change in the filler
1000
50 vo'" NZ0 3
800
,...
-
No Adltiw
..: ..
0
D..
CI! 600
'" ...
CI! (a)
w
ct::
t-
CI!
400
~x
CI!
200
0
1000
50 volX Nz0 3
801)
,...
-
Ho Adcfltiw '"
0
D..
CI!
CI!
600
w (b)
~
CI!
400
~x
CI!
200
5 10 15 20 25
SHEAR RATE {l/:I}
Figure 8.22(a),(b) Plots of shear stress vs. shear rate using thixotropie sweep tor
50 vol% alumina in low density polyethylene AC-9 with various surfaee moditying
agents as indieated. (Reprinted from Re!. 92.)
surface. It has been shown [74] that heat treatment of the alumina
powder prior to mixing has a significant effect on the state of dispersion
of the filler. Alumina powder which is calcined at 300C before mixing
when compared with as-received alumina, shows that the calcined
alumina is not as well dispersed adjudging from the dynamic viscosity
vs. frequency response given in Figure 8.24(a). It can be seen that the
peak torque also is lower in Figure 8.24(b) as compared to the peak
torque in Figure 8.12 for uncalcined alumina. Thus, for calcined
alumina the available shear force during the mixing operation is lower
and hence prevents agglomerate breakdown. Ouring the calcination
104~---------------------------------,
50 vol~ AJ20 3
- - Silane Z-6076
. . .. No Additive
- - - Silane Z-6020
,\
.!\ \
(c)
... .....
~~ ~
~:.. -"",
. ':...:...... j ~ .. 7".~
:-:--." lIo!
.c.: . :.: ..........
....
..... ~~_
!o:.:
-~."'.""''''.''.:.;.
101 ~~~~~~~~~--~--~--~~~~
104~-- ______________________________-,
50 vol~ AJ20 3
- - Titanate UCA 12
. . .. No Additive
- - - Z1rcoalumlnate
CAVCO UODAPG
5 10 15 20 25
SHEAR RATE (1/5)
Figure 8.22(c),(d) Plots of shear viseosity vs. shear rate using thixotropie sweep for
50vol% alumina in low density polyethylene AC-9 with various surfaee modifying
agents as indieated. (Reprinted from Ref. 92.)
process, there is a significant loss of molecular water and surface

hydroxyl groups. It is possible that this dehydration/ dehydroxylation
of the alumina surface may lead to inferior wetting of the filler by the
polymer. However, the results of wetting experiments [74] did not
show any differenees between the wetting eharacteristies of poly-
ethylene on the as-received alumina and the calcined alumina. Thus, no
convincing explanation eould be purported [74] for the changes in the
rheological behavior of heat treated alumina in the low density
polyethylene. Further, it was found [74] that the rheologie al eharacteris-
ties of calcined alumina in polyethylene ehanged with time. The aging
10000~-----------------------------------'
1000
-
''
a..
,/ Silane Z-6020
monate UCA 12
100 ,/
Zircoaluminate I'
CAVCO ...00 APG ,/ No Additive
10~--~--~~~~~~--~~~~~~~
0.01 0.1
n"'E (a)
Figure 8.23 Plots of residual stress VS. time for 50 vol% alumina in low density
pOlyethylene AC-9 with various surface modifying agents as indicated. (Reprinted
from Ref. 92.)
effect showed an initial drop in viscosity and then a continual increase

with time when the sampIes were exposed to normal atmospheric
conditions. This further complicated the behavioral pattern and hence
the detailed mechanism responsible for the behavior, when heat treated
alumina was used, did not become obvious.
Once again it must be remembered that the rheological differences
due to the use of the surface modifiers or due to heat treatment of
filler are system-specific. It depends strongly on the chemical type of
filler surface and the matrix polymer as well as the chemical
characteristics of the surface modifier, its amount and method of
surface treatment.

To understand the effect of polymer matrix on the unsteady shear
viscoelastic properties, it is essential to have data on a single type of
filler at a fixed loading level in a variety of polymer matrices. Such data
have been provided by Saini and Shenoy [61]. Barium ferrite of about
3 jlm average particle size was mixed under identical mixing conditions
in different polymer matrices, namely, 5-I-S block copolymer, Hytrel
polyester elastomer, thermoplastic polyurethane and low density poly-
50 vol"" AI 20 3
-.;.. o 300C
e:. o Uncllclned
>
~
in
o
oCI)
:> (a)
o
Si
4(
z
>
Q
FREQUENCY (rld/s)
300 50vol% AI2 03 300C Calcined
Mixlng Condilions: 150C. 200 rpm

E
S 200
w
;:,
0
a:
0
~
100
o 5 10 15 20 25 30
TIME (min)
Figure 8.24 (a) Plots of dynamie viseosity vs. frequeney for 50 vol% alumina in low
density polyethylene using as-reeeived alumina and alumina ealeined at 300C;
(b) Plot of torque vs. mixing time for 50vol% alumina in low density polyethylene
AC-9 using alumina ealeined at 300C (Reprinted from Ref. 74 with kind permission
from The Ameriean Ceramie Soeiety Ine., Westerville, Ohio, USA)
ethylene. The level of dispersion that was achieved was determined

through dynamic low frequency studies [61] measured with parallel
plate geometry using Rheometrics mechanical spectrometer.
Figures 8.25(a)-(c) show the complex viscosity and dynamic storage
modulus data at 220C for each of the three matrices at loadings of 75,
80 and 85 wt% of barium ferrite. The specific form of the complex

viscosity vs. frequency experimental data were found to be fitted weH
by equation (8.2) as shown by the solid lines.
Similarly, the solid lines on the storage modulus vs. frequency curves
in Figures 8.25(a)-(c) are based on equation (8.5) using appropriate
parametrie values as given in Table 8.5. Plots of the tabulated par-
ameters vs. weight fraction of the filler are given in Figures 8.26(a)-(d).
BARIUM FER.RlTE FIllED

STYRENE-ISOPRENE-STYRENE
E UNITS
l')*- PA-SEC
G' - PASCALS
W - RADISEC
~
220C
..,..
"- :-....; --
I":
~ kn t--- ~'" ~
v
~ I..i;~ ic r-....
~
~ l./ L--
j...j...
...
-
~
v
-
4>
... ~ ~ k
Ir-
f' k} ~ j...-: t
4
10 G'
.......
..
..",.
p --.: h<::i ~'" ............
r
~ N: ~ .....
~ I:::e r-...'"
'0--
3
10
FII.LER '10
.:. .... - 85
0 - 80
0.1- 75
Figure 8.25(a) Complex viscosity and dynamic storage modulus vs. frequency at
220C for 75, 80 and 85 wt% ferrite-filled S-I-S block copolymer (solid lines indicate
theoretical model fit through experimental data points). (Reprinted from Ref. 61 with
kind permission from Society of Plastics Engineers Inc., Connecticul, USA.)
BARIUM FERRITE FlllED UNITS

POLYESTER ElASTOMER EG'r/*-- PA SEC
PASCALS
W - RAD/SEC
220C
'" IP v--
L.4'
..
~ ~
.,: ~ 1--[1'
.../
~
V
v
,.
v
~~
t:--.~
6
~~ l-" f+
5 ~ ~ A"
r/* 10
N"
./ N ........
'X
""
I",);:;; R 1\
/ j...A
(J
Ic I"- f'.-.. 6
1"-
l'-
V. ~ rer i'- iI'-
P
~
'Fll.LER %
6,. - 85
0,1- 80
0,.- 75
Figure 8.25(b) Complex viscosity and dynamic storage modulus vs. frequency at
220C for 75, 80 and 85 wt% ferrite-filled polyester elastomer (solid lines indicate
kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
Through these plots, Saini and Shenoy [61] suggest estimation of the
parameters at higher filler loading by bold extrapolation. Generally, such
bold extrapolation is normally not recommended as it can be misleading.
But since they were particularly dealing with magnetic polymer
composites, the commercial values of the product would be realized only
at 87 to 94 wt% of filler whose rheology is almost impossible to measure
on conventional equipment without causing irreparable damage due to
BARIUM FWITE FIllED

LOW DENSITY POLYEIHYLENE
~E UNITS
rl"'- PASEC
G' - PASCALS
W- RAD/SEC
,..............
220C
~
..
.;..
c,.,
, ~
....
,. --
"* f". i'.:t ~

-~
~ If
~-
"S ..- :;..<
f-.- ~ I-
] r- ...
......,.
~
~ ~ ')
r/*
4
10 '" G'
"-
~
"" "1SI..,
0"
{: ....... P"-
b'-- ~:>r-- i'-
FILLER '10
.c. - 85
0.1- 80
0 . - 75
- -
Figure 8.25(c) Complex viscosity and dynamic storage modulus vs. frequency at
220C for 75, 80 and 85 wt% ferrite-filled low density polyethylene (solid lines indicate
kind permission from Society of Plastics Engineers Inc., Connecticut, USA)
the abrasive nature of the ferrites. Hence an estimated value that is, at
least, reasonably accurate is often more than welcome, even if it means
that one has to have recourse to some bold extrapolation. This approach
can be followed by those who are interested in highly filled systems
and hence this approach has been presented here.
In Figures 8.25(a)-(c), it can be seen that all three compositions in each
of the matrices exhibit a yield stress when compared with the unfilled
lable 8.5 Model parameters for barium ferrite filled polymer systems in equations
(8.2) and (8.5)
Wt% filler K n' n" m"
8-1-8 75 9.4 x 103 0.41 0.59 0.63

80 1.2 x 104 0.38 0.54 0.82
85 2.3 x 104 0.32 0.46 0.92
Polyester elastomer 75 4.2x104 0.54 0.56 0.79
80 8.0 x 104 0.45 0.48 0.78
85 2.7 x 105 0.30 0.32 0.87
LDPE 75 2.0 x 104 0.24 0.38 0.78
80 2.2x104 0.18 0.37 0.87
85 3.3 x 104 0.14 0.36 0.98
Source: Rel. 61 (reprinted with kind permission Irom Society 01 Plastics Engineers Inc.,
Connecticut, USA).
system at frequencies below 1 radi sec as observed from the complex

viscosity vs. frequency curves. This is due to the tendency of the
partieIes to agglomerate into network structure due to their small size
of 3 ~m and their anisotropie platelet-shaped form. The presence of
agglomerates would naturally increase the flow resistance especially at
low frequencies wherein the deformation rates are not high enough to
12
IBARIUM FElUUTE FIllED POLYMERS I
11
1.0
0.9
m"
0.8
0.7
A - LOW DENSITY POLYETHYLENE

0.6 o- S-I-S BLOCK COPPOLYMER
o - POLYESTER F.LASTOMER
0.5
70 80 90 100
w % FILlER
Figure 8.26(a) Variation of the adjustable parameter m" with filler concentration.
(Reprinted from Re!. 61 with kind permission from 80ciety of Plastics Engineers Inc.,
Connecticut, U8A.)
106
I BARIUM FElUUTE FlllED POLYMERS I
UNIT5
K- PA,SEC
o - POLYESTER ELASTOMER
... - LOW DENSITV POLYETHYlENE
3 0 - 515 BLOCK COPPOLY.ME.R
10 L _____--'-_~========::::::J
70 80 90 100
w % FILLER
Figure 8.26(b) Variation 01 the parameter K with liller concentration. (Reprinted Irom
Re!. 61 with kind permission Irom Society 01 Plastics Engineers Inc., Connecticut,
USA.)
0.7
IRARIUU F1!RRITB P1LI.1!D POLnmRS I
0.6 0- S.I.S BLOCK COl>POLYMBR
CI - POLYBSl'D. ELAS'l'OlQ.
c
0.5 .... - LOW DllNSlTY POLYEI'HYlENE
0.4
n'
0.3
0.2
0.1
70 80 100
w % FILL'Elt
Figure 8.26(c) Variation 01 the power law parameter n' with liller concentration.
(Reprinted Irom Rel. 61 with kind permission Irom Society 01 Plastics Engineers Inc.,
Connecticut, USA.)
0.8
IBAllIU)4 PEIW'l'R PII.LED POLnaiSl
0.7 o- S-I-S :SLOCK COPPOLnGi.
o - POlYES'IER. RLASl'OlIall
A - LOW DENSITY POLY!IHYI.ENl!
0.6
0.5
11"
0.4
0.3
0.2
0.1
10 80 90 100
w%FIU.D.
Figure 8.26(d) Variation 01 the power law parameter n" with Iiller concentration.
(Reprinted Irom Rel. 61 with kind permission Irom Society 01 Plastics Engineers Inc.,
Connecticut, USA.)
break the clusters. At high frequencies, however, the clusters are broken
down and the flow resistance is dominated by the effects of matrix-
filler affinity.
In order to understand the effect of the polymer matrix clearly, it is
important to observe the complex viscosity behavior of the three
matrices when they are unfilled as shown in Figure 8.27(a). It is seen
that 5-1-5 block copolymer has the highest complex viscosity while
Hytrel elastomer has the lowest. Low density polyethylene lies in
between and shows a far more decreasing complex viscosity trend with
frequency than the other two.
Figure 8.27(b) shows the relatively complex viscosity behavior when
each of these matrices is filled with a fixed volume of 57% (Le. 85 wt%)
of barium ferrite. The difference in the relative viscosity arises due to
the differences in shear level during the mixing operation on account of
the differences in the viscosities of the base matrix. This, of course, can
explain why the Hytrel polyester elastomer filled system shows the
highest relative viscosity. However, there are also other reasons for this,
based on the matrix-filler affinity. Since polyethylene is non-polar, it
has no affinity for the filler. On the other hand, since 5-1-5 is polar
because of the presence of polystyrene and polyisoprene blocks, it has a
1~~;;;;'~~~~--~~~~~--~~~~~
IUNPILI.I!D POLYMERS I
UNrrS
1'(- PASEC
W- RADISEC
I220C I
o SlS BLOCK COPOLYMElt

A LOW DENSITY POLYEl1rYI.ENE
Cl POLYESTEJ!. ELASTOMER.
Figure 8.27(a) Variation 01 the complex viscosity with Irequency lor unlilled polymers.
(Reprinted lrom Reis. 61, 82 with kind permission lrom Society 01 Plastics Engineers
Inc., Connecticut, USA and Gull Publishing Co., Houston, Texas, USA.)
better filler affinity. This affinity for the filler provides a greater force to
break filler-filler bonds as the polymer tends to pull the filler particles
away during shear mixing. This would assist in getting a better
dispersion and can result in a lower viscosity. At the same time, when
the matrix-filler affinity is high, the system would behave like a bead-
spring structure wherein the filler particles are the beads and the
polymer acts as springs. This sort of structure would always be
exemplified by higher level of viscosity. Thus the final rheological
response is the sum total of the response due to a better dispersion and
the restrained deformation behavior due to the bead-spring structure.
Though a filled polymer melt is regarded as a two-phase system, the
classical concepts of phases in a material as having clearly distinguish-
103 r----,----,--,-"""""'~,...,..,..----.-__..:IB=ARIUM::::::::::FERRITE===F1Il.ED::::::':::::=:pO::L::;YMEItS:;:::::::;:;::J1
Iw~~cl
I220C I
r(r
10
o S-I-S BLOCK cOPOLYMEl

'" lOW DENSII'Y POLYETHYLENE
o POLYESTER ELASTOMER.
IL-_L-~-LLLL~_~~-L~~LL_~~~-WWLU
10- 1
Figure 8.27(b) Variation of the relative complex viscosity with frequency for 57vol%
barium ferrite filled polymers. (Reprinted fram Ref. 82 with kind permission fram Gulf
Publishing Co., Houston, Texas, USA.)
able interfaces is not truly valid. There exists a certain transitionallayer

(interphase) whieh includes a layer of the polymerie component altered
under the influence of the filler surface (adsorption layer) and a surface
layer of the filler whieh is affected by the polymer matrix [62] as shown
in Figure 8.28. Whereas the properties of the matrix and filler are
known before they are compounded, the interphase layer is formed by
their interaction and depends largely on their matrix-filler affinity for
each other.
Shenoy and Saini [62] used dynamie viscoelastic melt data for
quantitative estimation of matrix-filler interaction and postulated that
an equation of the following form may be used:
. .
":. -. o-

Figure 8.28 Schematic model of a filled polymer system: (1) polymer, (2) filler, and
(3) interphase layer. (Reprinted from Ref. 62 with kind permission from Society of
Plastics Engineers Inc., Connecticut, USA.)
(8.10)
where G~ and G; are the dynamic loss moduli for the filled and unfilled
polymer melts, respectively; <P is the volume fraction of the filler. The
parameter B is related to the filler geometry and the effective thickness
~R of the interfacial region as follows [93]:
B= (1 + D2~R)3 for spheres (8.11)
B = (1 + 2~Rr (1 + 2tR) for rods (8.12)
B = (1 + 2~R) 2 (1 + 2~R) for platelets (8.13)
Where D = diameter of the sphere, rod or platelet, Ip = length of the

rod-shaped particle, X = thickness of the platelet-shaped particle. The
postulated matrix immobilization at the interphase of the filler given by
~R is shown schematically in Figure 8.29.
From equation (8.10) it is evident that a plot of (1 - G;/G~) vs. <p on a
log-log scale must yield a straight line, from which the exponent n can
be evaluated as the slope and the parameter B from the intercept. ~R
can then be estimated by using the appropriate choice from equations
(8.11)-(8.13).
Using the data from Figure 8.25(a) and the concepts of the simple
model presented through equations (8.10)-(8.13), a plot of 1 - G;/G~ vs.
NO 1N'I'iRACl'ION
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _
0:
IN'l1!RACTION
I
I
I
i+---AR._
I I
____ G:
I
(R)
Figure 8.29 Postulated matrix immobilization at the interface of a dispersed filler with
the dynamic complex modulus G* shown as a function of r, the distance from the
center of the filler. fl.R is the effective thickness of the interfacial layer, G; and G~ are
the complex modulus of filler and polymer matrix, respectively. (Reprinted fram Ref.
62 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
4J on a log-log scale is drawn for four typical frequencies (0.1, I, 10, 100
rad/sec) as shown in Figure 8.30. The estimated values of n and Bare
tabulated in Table 8.6. Values of B greater than 1 suggest an interaction
and the higher the magnitude then the greater the interaction. It is seen
from Table 8.6 that interaction decreases as frequency increases. This
stands to reason because at higher frequencies the dynamic
deformations weaken the interphase between the polymer and the filler
and hence result in a lesser number of interactions.
Shenoy and Saini [62] have shown that a correlation between the
interaction parameter in the melt state and that in the solid state exists
at comparable frequency of deformation so that the matrix-filler affinity
at any temperature of interest could be estimated. Figure 8.31 shows the
dynamic mechanical data in terms of the loss modulus Eil at a frequency
of 11 Hz for the same ferrite-filled S-I-S systems over a temperature
range from -100 to Oe. Variation of the storage modulus E' and the
(J.l-R..ADISEC
x - 0.1
... -1.0
UNITS _ 10.0
Gi>.G'c- PASCALS -100.0
10"1 L _ _ _ _ -======::::::::.-=====::!.J
Figure 8.30 Variation of 1 - G~/G~ with filler volume fraction 4> at four different
frequencies. (Reprinted from Ref. 62 with kind permission from Society of Plastics
Table 8.6 Values of the parameters in equation (8.10);

temperature = 220C
Frequency w (rad/sec) 8
0.1 0.46 1.76

1.0 0.67 1.31
10.0 0.77 1.13
100.0 0.91 1.03
Source: Ref. 62 (reprinted with kind permission from Society of

Plastics Engineers Inc., Connecticut, USA).
loss tangent b with temperature are not included in the figure as they
are not needed in developing the matrix-filler affinity correlation.
However, the same is available elsewhere [94] and may be referred to
in case one is interested.
In the case of filled polymer composites, Ziegel and Romanov [95]
have suggested that the interaction parameter B can be evaluated by
comparing the loss moduli of the filled and unfilled system through the
following equation.
~~ = [1 - (4)B)"r 1 (8.14)
p
10
10
BARIUM FEWTE FII.l.ED STYRENE-ISOPRENE-STYRENE 1
UNITS
E" - PASCALS
T - DEGREES KELVIN
&
,..- ...... .. ~
~
"'~
...... "... ""
\
'~ ......
'10 \
/'
.... - ..... 11
,
11 ,j,
I
E'
-- ,. ,.

.~
.... ,
,.,
t \ ~
'+
.~'+- .".
....
\ ., I.-
\ ...........
\
It
FmITEW% I " .....

.- ....-
A- 85 I
.- 80
75
.....
- UNFIllED
I I I I I
m 193 213 233 253 273
Figure 8.31 Variation of dynamic loss modulus EH with temperature for various levels
of ferrite loadings (0, 75, 80 and 85wt%) in S-I-S block co polymer. (Reprinted from
Ref. 62 with kind permission fram Society of Plastics Engineers Inc., Connecticut,
USA.)
where E~ and E; are the loss moduli of the filled and unfilled systems,
respectively, as evaluated through solid state dynamic oscillatory
studies. Using equation (8.14), the interaction parameter B was deter-
mined [62] at three different temperatures namely, -100, -70 and
-40C and tabulated in Table 8.7.
It is seen that the interaction parameter B is strongly dependent on
temperature and hence Shenoy and Saini [62] sought a correlation
Table 8.7 Values 01 the parameters in equation (8.14);

Irequency = 11 Hz
Temperature C/K B
-100/173 3.00 1.81

-70/203 2.75 1.71
-40/233 1.40 1.56
Source: Re!. 62 (reprinted with kind permission Irom Society 01

Plastics Engineers Inc., Connecticut, USA).
between the interaction parameter in the solid state and that in the melt
state because a change of state merely implies a temperature shift. In
order to make a comparison, a plot of B vs. I/T on ordinary sc ale was
drawn as shown in Figure 8.32. The B values at three different
temperatures (-100, -70 and -40C) taken from Table 8.7 were plotted
alongside the B value at 220C for a frequency of 10 rad/sec as taken
from Table 8.6. It is seen that a linear relationship exists between the
interaction parameter in the solid state and melt state when compared
at nearly equivalent frequencies. It can be seen that among the four
values of B used in Figure 8.32, three were determined using loss
modulus data from shear mode measurements. Ideally speaking, it
would have been preferable to use loss modulus data generated for the
solid as well as the melt using the same mode of operation. The only
possible mode of oscillation for the melt is torsional or shear; whereas
one can use either tensile or torsional mode for the solid to generate the
viscoelastic functions. However, it is seen from Figure 8.32 that an
excellent correlation exists between the interaction parameter B in the
solid state with that in the melt state despite the fact that the data for
the solid state were genera ted using tensile mode while that for the
melt were generated using the shear mode. It is, undoubtedly, a better
idea to generate the loss modulus data for the solid and the melt in the
shear mode based on the suggested approach for quantitative
estimations of matrix-filler interactions in order to minimize errors.
From the above discussion, it is clear that it is possible to generate
dynamic data in the melt state for quantitatively estimating the matrix-
filler interaction and then extrapolating the affinity behavior to the
solid-state. All that needs to be done is to genera te the plot as given in
Figure 8.32 by using B values determined only from the melt data at
different temperatures and then extrapolating to lower temperatures.
Compounding and grinding steps are needed to generate melt
rheological data whereas, solid-state dynamic da ta require an extra
step of molding the sampies in a standard form. This extra time
consuming step may induce further thermomechanical history which
Effect of matrix additives 387
B 1.5
1.0 L...-_ _ _...L-_ _ _....I-_ _ _-J....._ _ _--l
20' 3.0 4.0 5.0 6.0

10'0'0'
T
Figure 8.32 Variation of B with reciprocal temperature in kelvins. (Reprinted fram

Ref. 62 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA)
can be avoided by generating the matrix-filler interaction information

directly from melt data as shown above.
8.8 EFFECT OF MATRIX ADDITIVES

One method of changing the polymer's interaction with the filler is by
the addition of small quantities of matrix additives. Typical examples of
these types of additives are the phthalates, fatty acid ester, metallic
soaps, paraffin waxes, etc., as shown in Table 1.6. The main function of
most of these additives is to alleviate the attractive forces between the
polymer molecules by annulling the dipole-dipole interactions, hydro-
gen bonding, and other forces existing between polymer molecules.
When the intermolecular attractions are disrupted, the polymer
molecules flow more easily over each other. This does have an effect on
the rheological properties of the filled polymer system.
Figure 8.33 shows the effect of different types of additives on the
viscosity of alumina-filled polyethylene [45,96]. The lower viscosity is
also accompanied by a decrease in the dynamic storage modulus, as
. ..
IALUMINA FII.LED LOW DENSITY POLYETHYJ..ENEI
'" UNlTS
9.", '" rt- PASEC
'"
.D I,"'", W- RAD/SEC
o ,.'"
"" '"
~!'"0 0 0 ' .;''''",
",
ff'"
.t4 0 0 . . . '"
. . . "'",
- tOO
0& 0
.... "'",
.... '"
o.!. 0.... '"

O.!< 0 .... '"
O.!< 0.... '"
o A: 0.1 .."
o lh 0 ~ "'.."
- X'ff "'",
0;& 0 '"
00 00
z I.
o 0
00 ",,+0 . -
o ",,+0
OO""~~
o ""
00""""
I- 00""
0""
0
'" - NO .ADDITIVE
... - !NT.S4 (AXEL)
- W90S (Bi'X.MAI.LlNCICRODT)
- E-WAl( (BASF)
- - W900 (BYKMALLINCICRODT)
o - lNT.33.UDKH (AXEL)
"" - lNT.EQ.6 (AXEL)
+ - Kl!MAMIDEE (HOMKO SHEFFIELD)
o - W910 (BYK-MALLINCKRODT)
w
Figure 8.33 Variation 01 complex viscosity with Irequency showing the effect 01
wetting agents on the rheology 01 alumina-lilled polyethylene. (Reprinted Irom Rel.
45.)
shown in Figure 8.34. It is important when making a choice of the

additive to use one that is compatible with the polymer matrix.
Incompatible additives can be identified by a sud den drop in the
storage modulus at higher frequencies resulting from the migration of
the additive to the measuring tool surface [44,45] as can be seen from
Figure 8.35. Incompatibility often occurs when the matrix and the
additive have levels of polarity. As these additives are introduced
under the influence of heat and are effective at high temperatures, the
molecular atlractive forces within the polymer get increasingly restored
as the system cools down to room temperature. Hence, in many cases,
the additive gets forced out of the system when there is a large polarity
difference between the polymer and the additive.
Effect of matrix additives 389
IALUMrN'A FlllED LOW DEN'SITY POLYETHYI..ENEI

UNITS
G' - PASCALS
W - RAD/SEC
'0000000000000
~oooooo
00 0000 0
CJCJog<><> 000 00 000000 0
CJ CJCJg~~tf>CJOCJ8&gt~<6
o NO ADDITIVE
o INT-33-UDKH (AXEL)
(> INT-EQ-6 (AXEL)
CJ W-910 (BYK-MAlLINCKRODTJ
103
Figure 8.34 Variation of storage modulus with frequency showing the effect of three
of the most effective wetting agents on the rheology of alumina-filled polyethylene.
IALUMINA FIIl.ED LOW DENSITY POLYETHYLENE I

UNITS
---
.....
G' - PASCALS
- ~
W- RAD/SEC
00
000 i '1,- ~
G' ~~ 0 0 000 0000

-
I 0 INT.33.UDKH (AXEl.) I
INTEQ6 (AXEl.)
I I I
Figure 8.35 Variation of storage modulus with frequency showing the effect of
incompatible additives on the rheology of alumina-filled polystyrene. (Reprinted from
Ref.45.)
REFERENCES
1. Aral, B.K. and Kalyon, D.M. (1997) Viscoelastic behavior of filled polymers,
Paper 5-A presented at the 13th international meeting of the Polymer
Processing Society Oune 10-13).
2. Chapman, F.M. and Lee, T.5. (1970) Effect of talc filler on the melt rheology
of polypropylene, SPE Journal, 26, 37-40.
3. Mills, N.J. (1971) The rheology of filled polymers, J. Appl. Polym. Sei. 15,
2791-805.
4. Nazem, F. and Hill, c.T. (1974) Elongational and shear viscosities of bead-
filled thermoplastic, Trans. Soc. Rheol., 18, 87-101.
5. Han, C.D. (1974) Rheological properties of calcium carbonate-filled
polypropylene melts., J. Appl. Polym. Sei., 18, 821-9.
butadiene and butadiene-styrene copolymer, J. Appl. Polym. Sei., 18,
1013-38.
20,501-23.
Part I: Rheological and mechanical properties, Polym. Engg Sei., 17, 657-64.
Polym. Engg Sci., 17, 715-18.
626-31.
reinforcement, Plastic Compounding, 1, 26-36 (Nov IDec).
extrusion and injection molding characteristics of polyethylene and
polystyrene melts, Polym. Engg Sei., 18, 268-72; (1978) A fundamental study
18. Monte, S.J. and Sugerman, G. (1979) A new generation of age and water-
Engg Sei., 19, 617-24.
References 391

poly(ethylene terephthalate) and blends, Polyrn. Engg Sei., 19, 638-50.
764-9.
19,671-3.
24. Crowson, RJ., Folkes, M.J. and Bright, P.F. (1980) Rheology of short glass
fiber-reinforced thermoplastics and its applications to injection molding I.
Fiber motion and viscosity measurement, Polyrn. Engg Sei., 20, 925-33.
reinforced thermoplastics and its application to injection molding 11. The
effect of material parameters, Polyrn. Engg Sei., 20, 934-40.
26. Goel, O.c. (1980) Effect of polymerie additives on the rheological properties
of talc-filled polypropylene, Polyrn. Engg Sei., 20, 198-20l.
27. Tanaka, H. and White, J.L. (1980) Experimental investigations of shear and
elongational flow properties of polystyrene melts reinforced with calcium
carbonate, titanium dioxide and carbon black, Polyrn. Engg Sei., 20, 949-56.
28. Czamecki, I. and White, J.L. (1980) Shear flow rheological properties, fiber
reinforced polystyrene melts, J. Appl. Polyrn. Sei., 25, 1217-44.
polymer melts, Rubber Chern. rech., 53, 823-35.
II. J. Polyrn. Sei. (Polym. Chem. Edn), 18, 3211-17.
31. Knutsson, B.A., White, J.L. and Abbas, K.A. (1981) Rheological and
Polym. Sei., 26, 2347-62.
32. Cope, O.E. and Linnert, E. (1980) The lowdown on loading down resins
using hydrophobie encapsulation, Plastie Engg, 37-9 (June).
relative viscosity of polymer melts filled with various inorganic fillers, Rheol.
Acta, 20, 207-9.
34. Han, C.O., Van der Weghe, T., Shete, P. and Haw, J.R (1981) Effect of
properties of filled polypropylene, Polyrn. Engg Sei., 21, 196-204.
36. 5harma, YN., Patel, RO., Ohimmar, I.H. and Bhardwaj, 1.5. (1982) 5tudies
of the effect of titanate coupling agent on the performance of
polypropylene-calcium carbonate composite, J. Appl. Polyrn. Sei., 27, 97-104.
37. Nakatsuka, T., Kawasaki, H., Itadani, K. and Yamashita, 5. (1982) Phosphate
coupling agents for calcium carbonate filler, J. Appl. Polyrn. Sei., 27, 259-69.
38. Lee, W.M., Abe, O.A., Chipalkatti, M.H. and Liaw, T.F. (1982) Rheological
properties of particulate-filled linear low density polyethylenes, Proe. Ann.
Conf Reinf Plast. Cornpos. Inst. Soe., Plast. Ind., 37 (120), 7.
polypropylene reinforced with glycerol-treated miea, Can. J. Chern. Engg, 60,
334-41.
Polyrn. Cornposites, 3, 193-211.
42. White, J.L. (1982) Rheological behavior of highly filled/reinforced polymer
melts, Plastics Cornpounding, 47-64 Oan/Feb).
43. Bigg, D.M. (1982) Rheological analysis of highly loaded polymerie
composites filled with non-agglomerating spherical filler particles, Polyrn.
Engg Sei., 22, 512-18.
Polyrn. Engg Sei., 23, 206-10.
ness of filler surface treatments, Plastics Cornpounding, (March/ April).
46. Lern, K.W. and Han, CD. (1983) Rheologieal behavior of concentrated
263-88.
47. Daley, L.R. and Rodriguez, F. (1983) Flow properties of ethylene-propylene
terpolymer filled with silica modified by silane coupling agents, Ind. Eng.
Chern. Prod. Res. Dev., 22, 695-8.
48. Mutsuddy, B.C (1983) Influence of powder characteristics on the rheology
of ceramic injection molding mixtures, Proc. Brit. Cerarn. Soc., 33, 117-37.
49. Chaffey, C.E. (1983) Reinforced thermoplastics: through flow to use, Ann.
Rev. Mater. Sci., 13, 43--65.
50. Shenoy, A.V., Saini, D.R. and Nadkami, V.M. (1983) Rheograms of filled
polymer melts from melt-flow index, Polyrn. Cornposites, 4, 53-63.
51. Shenoy, A.V. and Saini, D.R. (1983) Interpretation of flow data for
multieomponent polymerie systems, Colloid Polyrn. Sei., 261, 846-54.
coating of calcium carbonate on the rheologieal properties of its suspension
in molten polystyrene, J. Appl. Polyrn. Sei., 28, 1481-501.
53. Luo, H.L., Han, C.D. and Mijovie, J. (1983) Effects of coupling agents in the
rheologie al behavior and physical mechanical properties of filled nylon 6,
J. Appl. Polyrn. Sei., 28, 3387-98.
Proc. IX Intl. Congress on Rheology in Mexico, Adv. in Rheology, 3, 429-37.
Acta, 23, 20-30.
56. Kitano, T., Kataoka, T. and Nagatsuka, Y. (1984) Dynamic flow properties of
408-16.
57. Suetsugu, Y. and White, J.L. (1984) A theory of thixotropie plastie
viscoelastic fluids with a time-dependent yield surface and its comparison
to transient and steady state experiments on small particle filled polymer
polymer melts, Chern. Engg Cornrn., 36, 211-21.
References 393
59. Bretas, RES. and Powell, RL. (1985) Dynamie and transient rheologieal
60. Saini, D.R, Shenoy, A.V. and Nadkarni, V.M. (1985) Effeet of surfaee
treatment on the rheologieal and meehanieal properties of ferrite-filled
polymerie systems, Polym. Engg Sei., 25, 807-1l.
61. Saini, D.R and Shenoy, A.V. (1986) Viseoelastie properties of highly loaded
62. Shenoy, A.V. and Saini, D.R (1986) Quantitative estimation of matrix filler
63. Saini, D.R, Shenoy, A.Y. and Nadkarni, V.M. (1986) Melt rheology of highly
64. Shenoy, A.V. and Saini, D.R (1986) Wollastonite reinforeed polypropylene
composites: Dynamie and steady state melt flow behavior, J. Reinf Plastics
Comp., 5, 62-73.
65. Mute!, A.T. and Kamal, M.R (1986) Characterization of the rheological
66. Edirisinghe, M.J. and Evans, J.RG. (1987) Rheology of ceramie injeetion
67. Sacks, M.D., Khadilkar, es., Scheiffele, G.w., Shenoy, A.V., Dow, J.H. and
Cera mies, 24, 495-515.
68. Dow, J.H., Sacks, M.D. and Shenoy, A.V. (1988) Dispersion of ceramic
particles in polymer melts, Ceram. Trans. (Ceram. Powder Sei. IIA), 1, 380-8.
69. Hunt, K.N., Evans, J.RG. and Woodthorpe, J. (1988) The influence of mixing
route on the properties of ceramie injection moulding blends, Br. Ceram.
Trans. J., 17-2l.
characteristic in the alumina/thermoplastic resin system, J. Am. Ceram. Soc.,
17, 1093-99.
71. Poslinski, A.J., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Freehette, F.J.
(1988) Rheologieal behavior of filled polymer systems 1. Yield stress and
72. Poslinski, A.J., Ryan, M.E., Gupta, RK., Seshadri, S.G. and Frechette, F.J.
(1988) Rheologieal behavior of filled polymerie systems 11. The effect of a
bimodel size distribution of particulates, J. Rheol., 32, 751-7l.
73. Ishigure, Y., Nagaya, K., Mitsumatsu, F., Otabe, S., Hayashi, K., Sobajima,
A. and Murase, 1. (1989) Relationship between the flow characteristics of
highly filled alumina or zirconia-organie binder and the properties of
sintered products in injection mol ding processing, Rep. Gifu Pref Ind. Res.
74. Dow, J.H., Sacks, M.D. and Shenoy, A.V. (1990) Dispersion of alumina
431-42.
75. Edirisinghe, M.J., Shaw, H.M. and Tomkins, K.L. (1992) Flow behavior of
ceramic injection moulding suspensions, Ceramies Int., 18, 193-200.
76. Nielsen, L.E. (1974) Mechanical Properties of Polymers and Composites, Mareel
77. Han, C.D. (1976) Rheology in Polymer Processing, Academie Press, New York,
7,182-8.
133-57.
York, 1, Ch. 7, 295-352.
Publishers, Moscow 380-402.
81. Han, C.D. (1981) Multiphase Flow in Polymer Processing, Academie Press,
New York.
Encyclopedia of Fluid Mechanics, (ed. N.P. Cheremisinoff), Gulf Publishing,
Houston, TX, 7, 667-701.
polymers, in Encyclopedia of Fluid Mechanics, (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, TX, 9, 243-76.
85. Advani, S.G. (ed.) (1994) Flow and Rheology in Polymer Composites Manu-
facturing, Elsevier Science BV.
86. Carreau, P.J. (1972) Rheologieal equations from molecular network theories,
Trans. Soc. Rheol., 16, 99-127.
87. Wagner, M.H. (1976) Analysis of time-dependent non-linear stress-growth
data for shear and elongational flow of a low-density branched polyethylene
melt, Rheol. Acta, 15, 136-42.
88. Wagner, M.H. (1977) Prediction of primary stress difference from shear
viscosity data using a single integral constitutive equation, Rheol. Acta, 16,
43-50.
89. Chong, JS., Christiansen, E.B. and Baer, AD. (1971) Rheology of con-
centrated suspensions, J. App/. Polym. Sei., 15, 2007-21.
90. Allen, T. (1981) Partic/e Size Measurement, Chapman & Hall, London.
91. Kalyon, D. (1988) Mixing in continuous processors, in Encyclopedia of Fluid
Mechanics, (ed. N.P. Cheremisinoff), Gulf Publishing, Houston, TX, 7,
887-926.
92. Dow, JH. (1992) PhD Thesis, University of Florida, Gainesville.
93. Ziegel, K.D. (1969) Role of the interface in mechanical energy dissipation of
composites, J. Colloid Interf Sei., 29, 72-80.
94. Saini, D.R, Shenoy, AV. and Nadkarni, V.M. (1984) Dynamic mechanical
properties of highly loaded ferrite filled thermoplastic elastomer, J. Appl.
Polym. Sei., 29, 4123-43.
95. Ziegel, K.D. and Romanov, A (1973) Modulus reinforcement in elastomer
composites. 1. Inorganic fillers, J. Appl. Polym. Sei., 17, 1119-31.
96. Bigg, D.B. (1984) Interrelation among feedstock form, product requirement,
equipment type, and operating parameters in polymer mixing processes,
Polym. Plast. Techno/. Eng., 23, 133-68.
Extensional flow
properties 9
The bulk of the extensive literature on the rheology of filled polymer

systems [1-85] is focused on the flow behavior in shear. The exten-
sional flow properties have been treated in a rather limited manner
[1,4,14,27,29,86,87], despite the fact that knowledge of the rheology in
shear mode generally does not allow prediction of the behavior in
extension [88]. The reason for this is because steady extensional
viscosity is in general difficult to measure, and also because filled
polymers go less into applications involving the film blowing, fiber
spinning and flat-film extrusion processes wherein the extensional flow
is of importance.
Extensional flow occurs when the material is not in contact with solid
boundaries, as is the ca se during drawing of filaments, films, sheets or
inflating bubbles. Converging flows at the inlets of dies are also
extensional in nature. In extension, the material is stretched continually
in a particular direction as already explained in section 2.1.3. The
principal axis of strain keeps doubling in length at equal intervals of
time during a steady extensional flow. For example, a circular filament
having a length 10 initiallY and 1 at time t undergoes steady extensional
flow when 1 = 10 exp(i:t) where i: is the extensional rate. There are a few
different ways in which extensional flow can be measured as discussed
in section 3.3. However, it is often difficult to keep the apparatus
running for long enough time to achieve steady state extensional flow
conditions for sure. Where such steady flows are achievable then the
ratio of the tensile stress along the filament, to the extensional rate i:
gives the extensional viscosity rJE; or else, the ratio that results from
such measurements basically depends in a rather complicated manner
on the transient viscoelastic properties.
The limited information on the extensional flow properties of filled
polymer systems does not leave much room for extensive discussion on
this subject. Thus, this chapter is rather restricted and though the

396 Extensional flow properties
intention was to discuss the effects of various factors on the extensional

flow properties as was done earlier for the shear flow properties in the
preceding three chapters, the same could not be done due to lack of
available information. Certain subcategories are absent and even in the
subcategories that are covered in this chapter, the discussion is quite
concise.

The experimental studies of White et al. [29] illustrate the effect of the
filler type on the extensional flow properties of filled systems. Though
nine fillers were covered as given in Table 6.1 when studying shear
flow properties, the extensional flow studies were restricted only to
three of them, namely, titanium dioxide (Ti02 ), carbon black (CB) and
calcium carbonate (CaC03 ). The filled systems were prepared using a
fixed grade of polystyrene Dow Styron 678U and the loading level was
fixed at 30 vol%. The extensional viscosity measurements were done
using an extensional rheometer developed in house by Ide [89].
Figure 9.1 shows the variation of extensional viscosity with exten-
sional rate for the three filled polystyrene systems containing Ti0 2, CB
and CaC03 . A comparison between Figure 9.1 and Figure 6.1 indicates
the fillers appear in the same sequence when their levels of increases
are considered. The highest viscosity increase occurs in CaC03 filled
system, the lowest in Ti02 filled system and the medium in CB filled
system both in extensional as wen as shear flow. This naturally leads to
the conclusion that the effect of filler type on the extensional viscous
properties would be qualitatively akin to the effect on the shear viscous
properties.
Even though the available information on the effect of filler type on
the extensional flow properties is not as extensive as in shear, it
provides a sufficient premise to draw reasonable conclusions due to the
qualitative behavioral similarity. Thus, the extent of extensional
viscosity increase would always be lowest for three-dimensional
spherical fillers, higher for two-dimensional platelet fillers and highest
for one-dimensional fibrous fillers. Also when considering rigid and
flexible fillers, the increase in the level of steady extensional viscosity
would be more for rigid fillers than for flexible fillers because the rigid
fillers would resist deformation to a greater extent.
Where extensional flow occurs due to converging flow fields through
dies, then orientation of the filler, particularly the one-dimensional
fiber, and, to some extent, the two-dimensional platelet types, affects
the extensional flow behavior. Theory for the flow of concentrated
dispersions of chopped fibers in polymer melts in different extensional
flow situations is available [90,91] and the equilibrium fiber orientation
.~
~
IFIllED POLYSTYRENEI
~
UNITS
f1E - PASEC
.
e - SEC
-1
-
0
0
i
i 1180 0 cI

0
0
0
!
0
0
I-
0 0
0 0 0
~ CaC03
.CB
o Ti02
o PS
I I
.
e
Figure 9.1 Variation of steady state extension al viscosity with extension al rate for
filled polystyrene melts at 30vol% of various types of fillers as indicated. (Reprinted
from Ref. 29 with kind permission from American Chemical Society, Washington OC,
USA.)
can be calculated. The limitation of the approach [90,91] is that the

polymer matrix is considered as a second order fluid and only two-
dimensional flow has been considered. It has been shown elsewhere
[92] that extensional strain is more effective than shear strain for
aligning fibers.
In capillary rheometers, when short fiber filled polymer melt enters
the die [93-96], the fibers get aligned due to the extensional strain and a
partial plug flow is at times observed [94,96,97]. Alternatively, the
migration effect [98,99] is observed because the flow front is found to
be deficient in polymer for the glass bead filled low density poly-
ethylene in a spiral mold test [98] and for glass filled epoxy systems
flowing in a rectangular seetion end-gated mold [99]. Observations of
fiber orientation under conditions of converging, diverging and
shearing flows are available [24].
Convergent flow results in higher fiber alignment along the flow
direction, whereas diverging flow causes the fibers to align at 90 to the
major flow direction. It was also observed [24] that shear flow, on the
other hand, produces a decrease in alignment parallel to the flow
direction and the effect is pronounced at low flow rates.
Contact microradiography was used [24] to study extrudates pro-
duced using a Davenport constant volume flow rate capillary rheometer.
A variety of dies of different diameters was used, and in each case the
entry angle was 180 Contact microradiographs were made at various
0

flow rates and the fiber orientation was found to depend strongly on
flow rate. Figure 9.2 shows contact microradiographs of sections cut
parallel to the cylinder axis in extrudates obtained from 2 mm diameter
dies for a commercially available glass fiber-filled polypropylene pro-
duced by ICI (Propathene HW60GR/20). This material was in the form
of roughly spherical granules, containing 20% by weight of well-
dispersed glass fibers having a diameter of 10 11m and modal length of
500 11m.
Figure 9.2(a) shows an extrudate collected at a shear rate of 1.5 sec- 1
from a die of 100 mm length. The fibers show little sign of alignment
and appear to form a fairly random tangled mesh. In Figure 9.2(b) the
shear rate is 24 sec- 1 from the same die. The fibers are more highly
aligned along the flow direction at this flow rate. Figure 9.2(c) shows an
extrudate collected at a shear rate of 24 sec- 1 from a 2mm diameter die
of length 0.3 mm, and the alignment in the flow direction is more
pronounced than for the 100 mm die. Figure 9.2(d) shows a section cut
from the extrudate at a shear rate of 1430 sec- 1 from a die of length
0.3 mm, and in this ca se the fibers are aligned almost completely in the
flow direction. From these contact microradiographs it appears that fiber
alignment increases with flow rate, but decreases with die length.
In order to improve the tensile properties of low-density polyethylene,
Mead and Porter [100] added high density polyethylene fibers and film
strips. This resulted in an increase in the extensional viscosity and
consequently, the tensile modulus of the composite was increased by a
factor of 10. The effect of different mineral fillers (e.g. tale, mica, day,
dolomite) on the rheological properties of low density polyethylene
films was studied by Arina et al. [17]. It was found that the fillers
increased the extensional viscosity of a polymer matrix in concurrence
with the earlier observations of Han and Kim [86] as weH as Mead and
Porter [100].
Nakajima et al. [101] studied the viscoelastic behavior of butadiene-
acrylonitrile copolymer fiHed with carbon black. Capillary extrusion
measurements with an Instron and dynamic oscillatory measurements
with a Rheovibron suggested the occurrence of 'strain hardening' in
fiHed elastomer due to tensile extension causing structural changes in
the carbon black filled elastomer. It is possible that the structure built
by the carbon black in the elastomer increasingly jams against
(a) (c)
""'~ -.
!. lmm I I ~I
(b) (d)
Figure 9.2 Contact microradiography of extrudate from a capillary rheometer of commerciaily available glass fiber filled polypropylene
produced by ICI (Propathene HW60GR/20). Extrudate was obtalned at 210 a C dies of 2 mm diameter: (a) 100 mm long die, shear
rate = 1.5 sec- 1 ; (b) 100 mm long die, shear rate = 24 sec- 1 ; (c) 0.3 mm long die, shear rate = 24 sec- 1 ; (d) 0.3 mm long die, shear
rate = 1430 sec- 1 . (Reprinted from Ref. 24 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
extension until finally the structure yields and, thereafter, the sampie
breaks.
The effect of adding carbon black in styrene-butadiene rubber (SBR)
compounds has received the attention of Cotten and Thiele [102]. It was
shown that, in extensional flow, the stress in carbon black filled SBR
compounds continues to grow with increasing strain up to the point of
rupture. Cotten and Thiele [102] evaluated their data using the Denn-
Marrucci equation (2.66b) given in section 2.3.5. It was concluded that
whenever stiffening of SBR compounds during extension was desired,
low structure carbon black with high surface area ought to be used.
Fedors and Landel [103] pointed out that stress-strain behavior of
swollen elastomers can be determined experimentally more conveniently
by measurements in uniaxial compression than uniaxial extension. In
extension, strains of the order of a few hundred percent are required
whereas, in compression, strains of the order of only a few percent
provide sufficient data for analysis. SBR-glass bead composites cured
by means of dicumyl peroxide were used for stress-strain measure-
ments to estimate the concentration of the effective network chains per
unit volume of the whole rubber. It was found that with decreasing
volume fraction of the composite, the effective network density
decreased linearly at first and then rather rapidly in an unexpected and
inexplicable manner.

When the extensional viscosity is plotted as a function of the applied
tensile stress [27] as shown in Figure 9.3, the effect of filler size becomes
obvious. It is seen that filled polystyrene systems containing the two
fillers Ti02 and CB at the same loading level of 30 vol% show the
existence of the yield stress during extensional flow. This behavior is
identical to that observed for steady shear viscosity in Figure 6.1 for the
same two systems. In fact, it is seen that the higher yield stress value is
observed for CB filled system and the lower for Ti02 filled system for
both shear and extensional flow.
A look at the particle size of these fillers in Table 6.1 indicates that
though both have small particle sizes, CB is the smaller of the two by a
factor of 4. The smaller the particle size, the higher the yield stress, as
was concluded in section 6.2, happens to hold for extensional viscosity
as weH. The sm aller size fillers, especially those below a diameter of
O.5llm would have strong particle-particle interactions which would
aid in forming a network of finite strength and manifest this by a
display of yield stress.
The yield stress values in shear and extensional flows have been given
[29] in Table 9.1 for filled polystyrene systems containing three different
1~ r-----------------~==========~
IFILLED POLYSTYRENE I
UNITS
17E - PASEC
1:: 11 - PA.SCA.LS
I180C I
1::21
105~__________~__________~________~
103 105
""Cl 1
Figure 9.3 Variation of steady state extensional viscosity with tensile stress for filled
polystyrene melts at 30vol% of two types of fillers as indicated. (Reprinted from Ref.
27 with kind permission fram Society of Plastics Engineers Inc., Connecticut, USA.)
labia 9.1 Elongational and shear flow yield values for some filled polystyrene
systems at 180C
Filler Loading Y. x 10- 3 Ys X 10- 3 Y.IY,

(vol%) (Pa) (Pa)
Carbon black 20 ~4.5 2.5 ~1.8

Carbon black 30 17 9 ~1.9
Titanium dioxide 20 ~1.6 ~1.0 ~1.6
Titanium dioxide 30 4 2.2 ~1.9
Calcium carbonate 20 ~5.0 3.0 ~1.7
Calcium carbonate 30 22 12 ~1.8
(untreated)
Calcium carbonate 30 ~0.7 ~0.4 ~1.75
(treated)
Source: Reis 27 and 29 (reprinted with kind permission Irom Society 01 Plastics Engineers Inc.,
Connecticut, USA and American Chemical Society, Washington OC, USA).
types of filler - CB, Ti0 2 and CaC03 at a loading level of 20 vol%. The
yield value in extension is seen to be 1.6 to 1.9 times greater than that
measured in shear [27]. This is very elose to the von Mises criterion [104]
of 1.73 or approximately equal to the J3 suggested [105] for plastic
yielding, which is referred to as a critical distortion strain energy in the
interpretation by Hencky [106,107]. The existence of a von Mises criterion
equivalent to a critical distortional strain energy seems reasonable to

explain the breakup of particle network structures formed due to
interparticle forces. The yield stress in extension and shear can thus be
understood to relate to the particle-particle interaction energy per unit
volume, especially in the ca se of small size particles.
Filled systems with larger particles would be non-interacting and
hence would show no yield stress. In fact, their response to deformation
is determined by hydrodynamic interaction and not by particle-particle
interaction. Extensional viscosity measurements on styrene acrylonitrile
(SAN) melts with large glass beads have been reported by Nazem and
Hill [4]. They found that extensional viscosity is equal to three times the
zero shear viscosity, thereby endorsing the fact that there is no particle-
particle interaction when dealing with larger particles, especially at
volume fractions of less than 20%. However, at higher volume fractions
of 36%, it was found that the ratio of extensional viscosity to shear
viscosity dropped to 1.7.

One of the effects of increasing filler concentration is that constant
extensional viscosities, namely, steady-state conditions are reached
more easily and earlier in the filled systems than in unfilled systems
and the values decrease with increasing extensional rate. This point has
been brought out in the work of Lobe and White [19] who studied the
influence of carbon black on the rheological properties of a polystyrene
melt.
Figure 9.4 shows the extensional viscosity vs. time curves for unfilled
polystyrene melt at different extensional rates. It was found [19] that
the extensional viscosity may tend to become constant at very low
deformation rates, but become unbounded at higher and higher
deformation rates. With filler concentration at low loading levels of 5
and 10% of carbon black filler, it was found [19] that the plots
resembled those in Figure 9.4. However, at higher filler concentrations,
constant extensional viscosities were achieved with time and these
values were found to decrease with increasing extensional rate as
shown in Figures 9.5 and 9.6 for 20 and 25 vol% carbon black loading.
The extensional behavior of a polymer system containing particulate
filler was studied experimentally by Han and Kim [86]. It was found
that, at a fixed extension rate, the extensional viscosity increased with
increasing filler concentrations because the solid particles of calcium
carbonate did not deform under stretching and hence exerted more
resistance to the flow of the molten threadline with an increase in
concentration.
It is natural that the effect of filler concentration on steady-state
Y/E -PASEC
t - SEC
-1
e -SEC
Inooc I
~
0-00063
~ -0.0200
0-0.0630
0-0.2000
Figure 9.4 Variation of extensional viscosity with time at different extensional rates
for unfilled polystyrene melt at 170 D G. (Reprinted from Ref. 19 with kind permission
from Society of Plastics Engineers Inc., Gonnecticut, USA.)
extensional viscosity is qualitatively not any different from that on

steady shear viscosity [27,86]. From Figures 9.7-9.9, it can be seen that,
as expected, extensional viscosity increases with increases in loading
level and decreases rapidly with increasing extensional rate.
In Figures 9.7 and 9.8, the data were generated using an in-house
developed rheometer [89], while in Figure 9.9, the data were obtained
using a melt spinning apparatus [86]. It should be noted that the melt
spinning apparatus does not provide steady extensional flow conditions
and hence the extensional viscosities determined from such an instru-
IGARBON BLACK FILLED POLYSTYlUlNE I

UNITS
I'/E -PASEC
t - SEC
-1
- SEC
InoOc I
~
0-00063
6 -00200
0-00630
c -0.2000
104 L..---L.-..1....I....J..J..J..L.I.l.--.l..--L-JL....L..Ju..L.1..I..----1.-L....L-L..L..L.L..LJ
10- 1
Figure 9.5 Variation of extensional viscosity with time at different extensional rates
for 20vol% carbon black filled polystyrene melt at 170C. (Reprinted from Ref. 19 with
kind permission from Society of Plastics Engineers Inc., Connecticut, USA)
ment are at times referred to as spinning viscosities indicating the

unsteady state conditions.
In general, the relative influence of different kinds of particulate
fillers on the extensional viscosity at the same loading level is the same
as that of the shear viscosity [27]. In the case of fiber-filled polymer
systems, the same comment cannot be made as can be seen from Figure
9.10. For unfilled high density polyethylene (HDPE), '1E/'1o is 3 at low
extensional rates, while it is much higher for glass fiber filled HDPE
[14]. This result can be explained qualitatively through the theoretical
..j,.,foI
25 % C.ARBON BI.ACK
I FIU.lID POLYS'I'YRENE
P UNITS
11E
16 .... t
-PASEC
-SEC
-1
.If I"" E -SEC
V 1>
~ "V
J'1~~Ob
,/
I!f .&...
00.0063
60.0200
... V o 0.0630
Cl 0.2000
6. } V
10
5 II J
Figure 9.6 Variation of extension al viscosity with time at different extensional rates
for 25vol% carbon black filled polystyrene melt at 170C. (Reprinted from Ref. 19 with
kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
arguments put forth by Batchelor [108]. However, what is unusual in

Figure 9.10 is that the values of rJE/3rJO are much higher for the melt
containing 20 wt% of glass fibers than for the one containing 40 wt% of
glass fibers [14]. Chan et al. [14] attribute this peculiar behavior to the
small aspect ratios of the fibers used by them. They also found that
using the theoretical expressions of Batchelor [108] gave them values
which were far too large compared to their experimental data. Further,
since the theory did not predict a decreasing trend for extensional
viscosity with increasing extensional rate, it is not truly appropriate to
seek explanations based on such theory.
9.4 EFFECf OF FILLER SURFACE TREATMENT

There is enough evidence, at least in the case of shear viscosity, that
any increase due to filler addition can be significantly reduced through
filler surface treatment. The same effect can be expected for extensional
viscosity as weIl. In the case of shear viscosity, there have been a
number of studies to support conclusions drawn on the effect of various
107 I---~~~::;;~~~::;;~~~;l
ICARBON :aI.A.CK FILLED POLYSTYRENEI
UNITS
I1E -PA SEC
1
-SEC
106
I1E
lOS
CB
.30%
(120%
(I) I()%
0 0%
104
I 3
Figure 9.7 Variation 01 steady state extensional viscosity with extensional rate lor
carbon black li lied polystyrene melt at 180C with different levels 01 Iiller loading as
indicated. (Reprinted Irom Rel. 27 with kind permission lrom Society 01 Plastics
I1ITANIUM DIOXIDE FllI.ED POLYSTYllNEI

UNTI'S
I1E -PASEC
1
OE - SEC
I180C I
Ti0 2
.30%
(I 20%
o 0%
lf~====--L-_--_L-_--~
10'3
Figure 9.8 Variation 01 steady state extensional viscosity with extensional rate lor
titanium dioxide lilled polystyrene melt at 180C with different levels 01 liller loading as
indicated. (Reprinted Irom Rel. 27 with kind permission Irom Society 01 Plastics
5
4 ICALCIUM CARBONATE FILLED POLYPROPYLENEI
3 UNITS
11E -PA'SEC
2 -1
-SEC
!2000C!
Ir?
9
TI:; 8
7
6
5
4
CaC03
3
o 15.4 %
v 6.4%
2
;:. 2.9%
00%
104
0.05 0.1 0.2 0.3 0.4 0.5 0.7 1.0
Figure 9.9 Variation of apparent extensional viscosity with extensional rate for
calcium carbonate filled polypropylene at 200C with different levels of filler loading
as indicated. (Reprinted from Ref. 86 with kind permission from John Wiley & Sons,
Inc., New York, USA)
surface treating agents. However, in the case of extensional viscosity,

the available information is limited [27].
Figure 9.11 shows the effect of surface treatment on extensional
viscosity for 30% calcium carbonate filled polystyrene [27]. The data are
presented in two forms, namely steady state extensional viscosity vs.
extensional rate in Figure 9.11(a) and steady state extensional viscosity
vs. tensile stress in Figure 9.11(b). Irrespective of the type of data
representation, it is seen that surface treated calcium carbonate reduces
the level of extensional viscosity and brings it closer to that of the
unfilled polymer. The yield stress value is reduced considerably though
the va lues of the ratio of yield stress in extension to that of shear is still
maintained nearer to the von Mises value of 1.73 as can be seen from
Table 9.1. Surface treatment tends to modify the forces of particle-
particle interaction and hence show reduced yield stress va lues due to
lowering of the interaction forces [2,27].
The effects of titanate coupling agents on the rheological properties of
particulate filled polyolefin melts were studied by Han et al. [15]. Experi-
10
'IoGF
7'/E
6 .. 40
37'/0 D 20
o 0
4
2
..
0
I 3
Figure 9.10 Variation of relative extensional viscosity with extensional rate for glass
fiber filled high density polyethylene at 180C with different levels of filler loading as
indicated. (Reprinted from Ref. 14 with kind permission from John Wiley & Sons, Inc.,
New York, USA)
107 I-----r~=;:;=:=;:;:::=:===:=il
I.
CALCIUM CARBONAIE FllUllI.
POLYSTYUNIl
UNII'S
1la -PA' SEC
. .1
e- SEC
o 0 0
UNTREAl'JID (30% CaC0 3 )
TREAl'JID (30% CaC0 3)
4 0 UNFILLED
\0 L-______~____~==~========~
Figure 9.11(a) Variation of steady state extensional viscosity with extension al rate
for calcium carbonate filled polystyrene containing 30% untreated and treated filler.
Connecticut, USA)
References 409
107
UNITS
1\ - PASEC
106 "C 11 - PASCALS

1\
1~
t:JN'IlW>JEI) (30% CaCO)l

1'REATED ClO'I. C.CO)l
10 4
3
10 104 105
'C II
Figure 9.11(b) Variation of steady state extension al viscosity with tensile stress for
calcium carbonate filled polystyrene containing 30% untreated and treated filler.
(Reprinted fram Ref. 27 with kind permission fram Society of Plastics Engineers Inc.,
Connecticut, USA)
ments were carried out with systems like calcium carbonate-filied

polypropylene and fiber glass-filled polypropylene with the addition of
titanate coupling agents, and an increased extension of the filled
systems was observed in the presence of these additives. In fact
addition of titanate coupling agents to calcium carbonate-filied
polypropylene decreased the extensional viscosity to such an extent that
it almost equalled the extensional viscosity of pure polypropylene.
Effect of the additives on fiber glass-filled polypropylene was the
same but the decrease in extensional viscosity was to a much lesser
extent.
REFERENCES
1. Wagner, A.H., Kalyon, D.M., Yazici, R. and Fiske, Tl (1997) Extensional
flow of engineering plastics with glass fibers, Paper 8-D, presented at the
13th international meeting of the Polymer Processing Society Gune 10-13).
2. Chapman, F.M. and Lee, T.S. (1970) Effect of tale filler on the melt rheology
of polypropylene, SPE J., 26, 37-40.
3. Milis, N.J. (1971) The rheology of filled polymers, J. Appl. Polym. Sei., 15,
2791-805.
4. Nazem, F. and Hili, C.T. (1974) Elongational and shear viscosities of bead-
filled thermoplastic, Trans Soc. Rheol., 18, 87-101.
5. Han, CD. (1974) Rheological properties of calcium carbonate-filled poly-

propylene melts., J. Appl. Polym. Sei., 18, 821-9.
butadiene and butadiene-styrene copolymer, J. Appl. Polym. Sei., 18, 1013-38.
20,501-23.
Part I: Rheological and mechanical properties, Polym. Engg Sei., 17, 657-64.
partic1e filled polymer melts, Rheol. Acta, 17, 149-55.
626-31.
13. Copeland, JR and Rush, O.W. (1978) Wollastonite: short fiber filler/reinforce-
ment, Plastic Compounding, 1, 26-36 (Nov./Dec.).
extrusion and injection molding characteristics of polyethylene and poly-
styrene melts, Polym. Engg Sci., 18, 268-72; (1978) A fundamental study
15. Han, CD., 5andford, C and Yoo, H.J. (1978) Effects of titanate coupling
18. Monte, 5.J. and 5ugerman, G. (1979) A new generation of age and water-
Engg Sei., 19, 617-24.
21. Kataoka, T., Kitano, T., Oyanagi, Y. and 5asahara, M. (1979) Viscous
22. Kitano, T., Kataoka, T., Nishimura, T. and Sakai, T. (1980) Relative viscosities
of polymer melts filled with inorganic fillers, Rheol. Acta, 19, 764-9.
23. Kitano, T., Nishimura, T., Kataoka, T. and 5akai, T. (1980) Correlation of
19,671-3.
24. Crowson, R.J., Folkes, M.J. and Bright, P.F. (1980) Rheology of short glass
fiber-reinforced thermoplastics and its applications to injection molding 1.
Fiber motion and viscosity measurement, Polym. Engg Sei., 20, 925-33.
References 411
reinforced thermoplastics and its application to injection molding 11. The
effect of material parameters, Polym. Engg Sei., 20, 934-40.
26. Goel, D.C (1980) Effect of polymerie additives on the rheologieal properties
of talc-filled polypropylene, Polym. Engg Sei., 20, 198-201.
27. Tanaka, H. and White, J.L. (1980) Experimental investigations of shear
calcium carbonate, titanium dioxide and carbon black, Polym. Engg Sei.,
20,949-56.
28. Czamecki, I. and White, J.L. (1980) Shear flow rheologieal properties, fiber
reinforced polystyrene melts, J. Appl. Polym. Sei., 25, 1217-44.
polymer melts, Rubber Chem. Tech., 53, 823-35.
11. J. Polym. Sei. (Polym. Chem. Edn), 18, 3211-217.
31. Knutsson, B.A., White, J.L. and Abbas, K.A. (1981) Rheological and extrusion
characteristics of glass-fiber reinforced polycarbonate, J. Appl. Polym. Sei., 26,
2347-62.
using hydrophobie encapsulation, Plastic Engg, 37-9 (June). .
Acta, 20, 207-9.
coupling agents on the rheological properties, processing and mechanieal
properties of filled polypropylene, Polym. Engg Sei., 21,196-204.
35. Stamhuis, J.P. and Loppe, J.P.A. (1982) Rheological determination of polymer-
filler affinity, Rheol. Acta, 21, 103-5.
36. Sharma, YN., Patel, RD., Dhimmar, I.H. and Bhardwaj, I.S. (1982) Studies of
the effect of titanate coupling agent on the performance of polypropylene-
calcium carbonate composite, J. Appl. Polym. Sei., 27, 97-104.
coupling agents for calcium carbonate filler, J. Appl. Polym. Sci., 27, 259-69.
38. Lee, W.M., Abe, D.A., Chipalkatti, M.H. and Liaw, T.P. (1982) Rheological
Con! Rein! Plast. Compos. Inst. Soc., Plast. Ind., 37(12D), 7.
polypropylene reinforced with glycerol-treated miea, Can. J. Chern. Engg, 60,
334-41.
auf das fliessverhalten von kunststoff-schmelzen, Rheol. Acta, 21, 491-3.
Polym. Composites, 3,193-211.
42. White, J.L. (1982) Rheologieal behavior of highly filled/reinforced polymer
melts, Plastics Compounding, 47-64 (Jan./Feb.).
43. Bigg, D.M. (1982) Rheological analysis of highly loaded polymerie composites
filled with non-agglomerating spherical filler particles, Polym. Engg Sci., 22,
512-18.
Polym. Engg Sei., 23, 20&-10.
ness of filler surface treabnents, Plastics Compounding (March/April).
263-88.
terpolymer filled with siliea modified by silane coupling agents, Ind. Eng.
Chem. Prod. Res. Dev., 22, 695-8.
48. Mutsuddy, B.C (1983) Influence of powder characteristics on the rheology
of ceramic injection molding mixtures, Proc. Brit. Ceram. Soc., 33, 117-37.
49. Chaffey, CE. (1983) Reinforced thermoplastics: through flow to use, Ann.
Rev. Mater., Sei., 13, 43-65.
50. Shenoy, A.V., Saini, D.R and Nadkami, V.M. (1983) Rheograms of filled
polymer melts from melt-flow index, Polym. Composites, 4, 53-63.
51. Shenoy, A.V. and Saini, D.R (1983) Interpretation of flow data for multi-
component polymerie systems, Colloid Polym. Sei., 261, 846-54.
52. Suetsugu, Y. and White, J.L. (1983) The influence of partic1e size and surface
in molten polystyrene, J. Appl. Polym. Sei., 28, 1481-501.
53. Luo, H.L., Han, CD. and Mijovic, J. (1983) Effects of coupling agents in the
rheological behavior and physical mechanieal properties of filled nylon 6,
J. Appl. Polym. Sei., 28, 3387-98.
Proc. IX Intl. congress on Rheology in Mexico, Adv. in Rheology, 3, 429-37.
Acta, 23, 20-30.
408-16.
57. Suetsugu, Y. and White, J.L. (1984) A theory of thixotropie plastic visco-
elastic fluids with a time-dependent yield surface and its comparison to
transient and steady state experiments on small particle filled polymer
polymer melts, Chern. Engg Comm., 36, 211-21.
59. Bretas, RES. and Powell, RL. (1985) Dynamie and transient rheological
60. Saini, D.R, Shenoy, A.V. and Nadkami, V.M. (1985) Effect of surface
treabnent on the rheologieal and mechanical properties of ferrite-filled
61. Saini, D.R. and Shenoy, A.V. (1986) Viscoelastic properties of highly loaded
62. Shenoy, A.V. and Saini, D.R (1986) Quantitative estimation of matrix filler
systems, Polym. Composites, 7,96-100.
63. Saini, D.R, Shenoy, A.V., Nadkami, V.M. (1986) Melt rheology of highly
References 413
64. Shenoy, A.V. and Saini, D.R. (1986) Wollastonite reinforced polypropylene
composites: dynamic and steady state melt flow behavior, J. Reinf Plastics
Comp., 5, 62-73.
65. Mutei, A.T. and Kama!, M.R. (1986) Characterization of the rheological
behavior of fiber-filled polypropylene melts und er steady and oscillatory
Composites, 7,283-94.
66. Edirisinghe, M.J. and Evans, J.R.G. (1987) Rheology of ceramic injection
67. Sacks, M.D., Khadilkar, CS., Scheiffele, G.w., Shenoy, A.V., Dow, J.H. and
Sheu, R.S. (1987) Dispersion and rheology in ceramic processing, Adv. in
Ceramics, 24, 495-515.
68. Dow, J.H., Sacks, M.D. and Shenoy, A.V. (1988) Dispersion of ceramic
partic1es in polymer melts, Ceram. Trans. (Ceram. Powder Sei. I1A), 1, 380-8.
69. Hunt, KN., Evans, J.R.G. and Woodthorpe, J. (1988) The influence of mixing
route on the properties of ceramic injection moulding blends, Br. Ceram.
Trans. J., 17-21.
70. Takahashi, M., Suzuki, 5., Nitanda, H. and Arai, E. (1988) Mixing and flow
characteristic in the alumina/thermoplastic resin system, J. Am. Ceram. 50c.,
17,1093-9.
71. Poslinski, A.J., Ryan, M.E., Gupta, R.K, Seshadri, S.G. and Frechette, F.J.
(1988) Rheological behavior of filled polymer systems 1. Yield stress and
shear-thinning effects, J. Rheo/., 32, 703-35.
72. Poslinski, A.J., Ryan, M.E., Gupta, R.K, Seshadri, S.G. and Frechette, F.J.
(1988) Rheological behavior of filled polymerie systems TI. The effect of a
73. Ishigure, Y., Nagaya, K, Mitsumatsu, F., Otabe, 5., Hayashi, K, Sobajima,
A. and Murase, 1. (1989) Relationship between the flow characteristics of
highly filled alumina or zirconia-organic binder and the properties of
sintered products in injection mol ding processing, Rep. Gifu Pref Ind. Res.
74. Dow, J.H., Sacks, M.D. and Shenoy, A.V. (1990) Dispersion of alumina partic1es
in polyethylene melts, Ceram. Trans. (Ceram. Powder Sei. III), 12, 431-42.
ceramic injection moulding suspensions, Ceramics Int., 18, 193-200.
76. Nielsen, L.E. (1974) Mechanical Properties of Polymers and Composites, Marcel
77. Han, CD. (1976) Rheology in Polymer Processing, Academic Press, New York,
7,182-8.
133-57.
79. Pau!, D.R. and Newman, S. (1978) Polymer Blends, Academic Press, New
York, 1, Ch. 7,295-352.
Publishers, Moscow, 380-402.
81. Han, C.D. (1981) MuItiphase Flow in Polymer Processing, Academic Press,
New York.
82. Shenoy, A.V. (1988) Rheology of highly filled polymer melt systems, in
Encyclopedia of Fluid Mechanics (ed. N.P. Cheremisinoff), Gulf Publishing,
Houston, TX, 7, 667-701.
83. Yanovsky, Yu.G. and Zaikov, G.E. (1990) Rheologieal properties of filled
polymers, in Encyclopedia oj Fluid Meehanies (ed. N.P. Cheremisinoff), Gulf
Publishing, Houston, TX, 9, 243-276.
Proeesses in Bubbles, Drops and Particles (eds RP. Chhabra and D. Dekee),
85. Advani, S.G. (ed.) (1994) Flow and Rheology in Polymer Composites Manujae-
tu ring, Elsevier Scienee BV.
86. Han, C.D. and Kim, Y.W. (1974) Studies on melt spinning. A. Elongational
viseosity and spinnability of two phase systems, f. Appl. Polym. Sei., 18,
2589-603.
87. Nieoderno, 1. and Nieolais, 1. (1974) Viseosity of bead suspensions in
polymerie solutions, f. Appl. Polym. Sei., 18, 2809-18.
88. Astarita, G. and Marrueci, G. (1974) Prineiples oj Non-Newtonian Fluid
Meehanies, p. 299, MeGraw-Hill, London.
89. Ide, Y. and White, J.1. (1978) Experimental study of elongational flow and
failure of polymer melts, f. Appl. Polym. Sei., 22, 1061-79.
90. Lockett, F.J. (1972) National Physieal Laboratory Report No. 25, Division of
Materials Applieations, Teddington, England.
91. Johnson, A.F. (1973) National Physieal Laboratory Report No. 26, Division
of Materials Applieations, Teddington, England.
92. Modlen, G.F. (1969) Re-orientation of fibres during meehanieal working, f.
Mater. Sei., 4, 283-9.
93. Nieoderno, 1., Nieolais, 1. and Aeierno, D. (1973) Orientation of short
fibers in polymerie materials resulting from eonverging flow, Ing. Chim.
Ital., 9, 113-16.
94. Bell, J.P. (1969) Flow orientation of short fibre eomposites, f. Comp. Mater.,
3,244.
95. Murty, K.N. and Modlen, G.F. (1977) Experimental characterization of the
alignment of short fibers during flow, Polym. Engg Sei., 17, 848-53.
96. Lee, W.K. and George, H.H. (1978) Flow visualization of fiber suspensions,
97. Newman, S. and Trementozzi, Q.A. (1965) Barus effect in filled polymer
melts, f. Appl. Polym. Sei., 9, 3071-89.
98. Kubat, J. and Szalanczi, A. (1974) Polymer-glass separation in the spiral
mold test, Polym. Engg Sei., 14, 873-7.
99. Goettler. 1.A. (1973) Ultimate tensile properties and composite structure of
flow-molded short fiber composites, 31st ANTEC, Teeh. Papers, 559-62.
100. Mead, W.T. and Porter, R.S. (1978) The preparation and tensile properties
of polyethylene eomposites f. Appl. Polym. Sei., 22, 3249.
101. Nakajima, N., Bowerman, H.H. and Collins, E.A. (1978) Nonlinear
viseoelastic behavior of butadiene-acrylonitrile copolymers filled with
carbon black, Rubber Chem. Teeh., 51, 322-34.
102. Cotten, G.R. and Thiele, J.1. (1978) Influence of carbon blaek on processi-
bility of rubber stocks III. Extensional viscosity, Rubber Chem. Teeh., 51,
749-74.
103. Fedors, R.F. and LandeI, RF. (1978) Determination of network density of
composites eontaining inert fillers from stress-strain measurements in the
swollen state, Polymer, 19, 1189-94.
104. von Mises, R (1913) Naehr. Ces. Wiss. Coettingen, Math.-Phys. KI., p. 532.
References 415
105. White, J.L. (1979) A plastic-viscoelastic constitutive equation to represent

the rheological behavior of concentrated suspensions of small particles in
polymer melts, J. Non-Newtonian Fluid Mech., 5, 177-90.
106. Hencky, H. (1924) Zur theorie plastischer deformatimen und der hierdurch
im material herrorgerufenen nachspannungen, ZAMM, 4, 323-34.
107. Reiner, M. (1948) Deformation and Flow, Lewis, London.
108. Batchelor, G.K. (1971) The stress generated in a non-dilute suspension of
elongated particles by pure straining motion, J. Fluid Mech., 46, 813-29.
Concluding remarks 10
This final chapter of the book is meant to provide a forum for

recapitulation of some of the matters of importance discussed in all the
preceding chapters.
Chapter 1 introduced the various materials which go into the making
of filled polymer systems. The polymer could be a thermoplastic,
thermoset or elastomer. Further, it could be linear, branched, amor-
phous, crystalline or semi-crystalline. At the same time, it may fall into
the category of a homoploymer, copolymer, or liquid crystalline
polymer. Any type of such a polymer could be compounded with fillers
to form filled polymer systems.
The fillers, on the other hand, include those solid materials that are
added as reinforcing agents to provide strength or mere extenders to
reduce cost. There are various reasons for the use of fillers besides
increasing stiffness, strength, toughness, impact strength or reduction in
cost. They may be included to get better dimensional stability, increased
heat deflection temperature, reduced permeability to gases or liquid,
and to modify electrical/magnetic properties of the polymer matrix into
which they are incorporated.
Available fillers are of various types and forms, namely, rigid,
flexible, spherical, ellipsoidal, flakes, platelets, fibers or whiskers. They
may be organic or inorganic in nature. All varieties of fillers have been
tried in polymers in order to impart various advantageous benefits. The
presence of the fillers in the polymer matrix alters the rheological
properties of the polymer.
Rheological measurements are often used as an effective tool for
quality control of raw materials, manufacturing process/final product
and predicting material performance. The rheological properties of the
filled polymers are dictated, not only by the type of the filler, but also
by its size, size distribution and amount. A key factor in the use of
fillers without adversely affecting material properties is the stress

transfer at the filler-matrix interface. The physieo-chemieal interactions

between the filler and matrix then achieve a great deal of importance.
The interfacial adhesion can be substantially enhanced through use of
a surface modifying agent which is capable of adhering well to both the
matrix and filler particles. Not all surface modifying agents can couple
at both ends of their chemical moieties. In fact, some surface modifiers
attach only to the filler, others react only with the polymers and some
others do not react at all. In all these ca ses, they may be treated as
lubrieants. Only those surface modifiers which react with filler and
polymer can be termed coupling agents, though in most available
literature this term has been loosely used to describe any surface
modifying agent.
Chapter 2 discusses the fundamentals of rheology and classifies flow
as shear and extensional. Definitions of various rheological parameters
under the three subheadings of steady simple shear flow, unsteady
simple shear flow and extensional flow are given. The important
material parameters that burgeon out of the discussion are the steady
shear viscosity, the normal stress difference, complex viscosity, dynamie
viscosity, storage modulus, loss modulus and extensional viscosity. This
chapter sets the platform for rheologieal discussions that are under-
taken in Chapters 6, 7, 8, and 9 to study the effect of different
parameters related to filler and polymer on the rheology of the filled
polymer systems.
Basie description of non-Newtonian fluids is provided so that
concepts of shear rate dependent viscosities with or without elastie
behavior, yield stress with or without shear rate dependent viscosities
and time dependent viscosities at fixed shear rates get classified. The
filled polymer systems fall into the category of pseudoplastie fluids
with or without yield stress and also often depict the behavior of
thixotropie fluids. Their viscoelasticity may give rise to various
anamolous effects that are discussed in Chapter 2, such as the
Weissenberg effect, extrudate swell, drawn resonance, melt fracture and
so on.
Rheologieal models have been described for steady shear viscosity
function, normal stress difference function, complex viscosity function,
dynamic modulus function and the extensional viscosity function. The
variation of viscosity with temperature and pressure is also discussed.
Chapter 3 deals with rheometry which is the method of measurement
of the various rheological parameters described in Chapter 2. The
rheometers may be of the rotational type or the capillary type for shear
flows and the shear free type for extensional flows.
Chapter 4 deals with constitutive theories and equations for
suspensions and lays down the foundations for understanding the
basies of filled polymer rheology. Starting from the simplest dilute
418 Concluding remarks
suspensions for spherical particles to the complex concentrated

suspensions of fibrous fillers, the various relationships between relative
viscosity with volume fraction are highlighted. The effect of filler shape,
concentration, size, size distribution on the viscous behavior is
discussed. The migration of particles towards the tube axis and the
consequences of the wall effect on the rheological properties are
described. Particle rotation is also shown to affect the rheology and
result in an apparent display of increased viscosity. The effect of
flocculation is seen to increase the viscosity of suspension rather
sharply. The effect of the suspending medium and its interaction with
the suspended particles results in an increase in effective particle size
and decrease in molecular mobility. Similarly, the effect of physical
processes such as crystallization and chemical processes such as
polymerization modify the viscosity of suspensions with time. There is
considerable effect of the electrostatic field and displays of increased
viscosity due to the combined effect of the first, second and third
electroviscous effects.
Extensional viscosity is modified by the presence of suspended
particles. Particularly long slender particles have a drastic effect on the
extensional viscosity of suspensions as seen from the constitutive
equations provided for these systems.
Chapter 5 describes methods for the preparation of filled polymer
systems. The quality of the mixture resulting from any compounding
action of filler with polymer must be evaluated as there are various
mixing mechanisms involved. The effidency of the dispersive and
distributive mixing determines the goodness of mixing. The com-
pounding techniques that are used are the traditional two-roll mills or
interna I mixers and the modern-age single or twin-screw extruders. The
techniques vary considerably in their method of operation and results.
When setting up a compounding operation, it is important to use
proper selection criteria to decide whether batch or continuous mixers
are appropriate and pay attention to the dump criteria. It is known that
the physical properties of the compounded filler system vary con-
siderably with the selected compounding techniques. The goodness of
mixing is best adjudged by the determination of the rheological
properties of the filled polymer systems.
There are a number of compounding/mixing variables that affect the
final quality of the mix. Variables affecting the compounding operations
could be machine variables or operating variables. The mixer type,
rotor geometry, mixing time, rotor speed, ram pressure and chamber
loadings (in the case of internal mixers), as well as the mixing
temperature all have a considerable effect on the goodness of the final
mix. It is important to understand the sensitivity to these variables so
that the mixing can be carried out under optimum conditions.
The rheological properties of the filled polymer systems are discussed

under various headings, namely, steady shear viscous properties,
steady shear elastic properties, unsteady shear viscoelastic properties
and extensional flow properties, in Chapters 6, 7,8 and 9, respectively.
The effect of filler type, size, concentration, size distribution,
agglomerates, surface treatment and polymer matrix on the rheology of
the filled systems is discussed in detail in most cases. Only where
information is lacking, such as in the case of extensional flow properties
in Chapter 9, are some of the effects missing, and the discussion is
concise on the treated effects.
In general, steady shear viscosity and extensional viscosity be ar very
similar results when the effects of the various parameters are
considered. Addition of fillers increases the viscosity of the base
polymer. The extent of viscosity increase is the lowest for 3-dimensional
spherical fillers, higher for 2-dimensional platelet fillers and the highest
for I-dimensional fibrous fillers. Rigid fillers show greater increases in
the level of viscosity than flexible fillers.
The size of the filler determines whether the filled systems would
show unbounded viscosity buildup at low shear / extensional rates
during shear and extensional flows, respectively. The smaller the
partiele size, the greater the yield stress. The ratio of the yield stress in
extension to that in shear, is approximately quite elose to the value of
the von Mises criterion for plastic yielding of 1.732 or J3.
Polydispersity reduces the viscosity of filled systems at a fixed
loading level. For dilute suspensions having a volume fraction of solids
less than 0.2, the effect of the variation of partiele size on filled system
viscosity is normally minimal. However, at high loading levels, the
viscosity can be reduced drastically when the particle size modality is
increased.
Agglomerates occlude liquid in their interparticle voids, thereby
increasing the relative viscosity value at any given solids loading.
With increasing number of agglomerates, the maximum possible filler
loading is decreased. ThUS, for highly filled polymer systems, it is
important to reduce the degree of agglomeration to a minimum level,
in order to decrease the system viscosity for easier processing and also
to increase the extent of filler loading if desired.
With increasing concentration of filler, the interparticle interactions
increase weakly at first and then rather strongly as the concentration
becomes higher and higher. The concentration at which particle-particle
interactions begin depends mainly on the geometry and surface activity
of the filler. High aspect ratio fillers would begin to interact at much
lower concentrations, while non-agglomerated large size spherical
particles do not interact even up to 20 vol%. Use of surface modifiers
helps to decrease partiele-partiele interaction as the surface treatment
helps the polymer to wet the filler better. However, the action of the
surface modifiers is system-specific and hence, it is very difficult to
predict the performance of the surface modifiers apriori for any filler-
polymer combination. Thus, most often a surface modifier is selected
rather empirically for the particular filler-polymer combination of
interest. The amount of surface modifier should be small but adequate
because too Httle of it does not give the desired effects and too much of
it does not improve rheological or product properties to more than a
certain extent besides adding extra cost to the product. The optimum
surface modifiers to be used are most often in the range of 0.6-0.8% by
weight of the filler. The method of surface treatment also affects the
performance. Pretreatment is more efficient in iJnparting favorable
improvements in rheological properties but adds to the cost due to the
extra step of pretreatment. Direct addition of surface modifier during
the filler-polymer compounding process saves on the cost of pre-
treatment but requires a greater amount of surface modifiers which
offsets this cost benefit. Proper evaluation of which is more apposite for
a particular situation must be done before opting for the preferred
method of surface treatment.
The chemical nature and the viscoelastic characteristics of the
polymer matrix do have an effect on the final rheological properties of
the filled polymer system. This is because the original characteristics of
the polymer determine the level of the shear imparted during the shear
mixing when the filled polymer systems are being prepared. Higher
viscosity polymer would develop higher shear stress and may be able
to break agglomerates better during mixing. Depending on the chemical
nature of the polymer, the matrix-filler affinity would also control the
level of the force to break filler-filler bonds during high shear mixing.
Polymers with greater filler affinity would provide greater force. Such
polymers, if they also have reasonably high viscosity which is not
highly shear-thinning, would probably help the most in getting the best
filler dispersion.
It has been shown that the steady shear viscosity vs. shear rate flow
curves of filled polymer melts at various temperature and filler
loadings can be unified when plotted on a log-log scale in terms of a
reduced viscosity parameter (1] x MFI) vs. a reduced shear rate
parameter (y /MFI). The unified curves are independent of the filler
type and shape, but depend on the polymer matrix. Thus, separate
unification is achieved for each generic type of polymer. They do
depend on the filler size and loading level. In cases wherein particle-
particle interaction gives rise to yield stress, the master curve would
not be unique in the low shear region. However, in the higher shear
rate region beyond 10-1 S-1, the master curve would be unique
irrespective of the filler type, size, and amount as well as surface
modifier and amount. In fact, in this region, the master curve for the
filled polymer system is not different from the unfilled polymer
system. The master curves can be used to estimate the flow curves in
the higher shear rate region at the temperature of interest, merely from
the knowledge of MFI and the glass transition temperature of the
specific system.
There are certain precautions which should be borne in mind when
determining the MFI of filled polymer systems. The filler particle size
and shape may warrant modification of the MFI apparatus, and
possible yield stress characteristics of the filled polymer system may
demand a change from the standard ASTM temperature and load
conditions given in Appendix A. Whatever changes are done in order
to obtain reliable MFI data for the filled polymer systems, it is
important that these values are converted to those at standard
temperature and load conditions using equations from section 6.8
before using them in the master rheograms.
During normal stress measurement of filled polymer systems, there
are certain difficulties due to the abnormal effects of interactions
between the measuring equipment and the yield stress of the filled
systems. Further, there is always a problem of gap setting of the cone-
n-plate viscometer due to the high residual stresses which do not relax
for a long time and also due to the filler particle size or agglomerates
which may interface with the gap. Hence generating normal stress data
is often quite difficult. Nevertheless, reliable steady shear elastic data
are available in the literature which has obviously been generated with
great care.
It is seen that spherical fillers like glass beads do not affect the
normal stress difference. Particulate fillers like titanium dioxide,
calcium carbonate and carbon black, reduce the normal stress difference
whereas fibrous fillers like aramid, glass and cellulose fibers, increase it.
The large increase in normal stresses of fiber filled polymer systems is
explained on the basis of the hydrodynamic particle effect, associated
with orientation in the flow direction. Of course, if the fiber diameter is
very small then the increase in normal stresses is small and at times
may even show a decrease.
It is important to make plots of normal stress difference N1 vs. shear
stress '12 rather than vs. shear rate y if correct data interpretation is
intended. The former plots are independent of temperature and
molecular weight of the polymer matrix (though not its distribution)
and the rheological behavior is correctly interpretable by analogous
comparison with the steady state compliance Je'
It is obvious that the mobility of polymer chains under the influence
of an applied stress is reduced by the presence of the filler, thereby
decreasing the elastic response of particulate filled polymer systems
with increasing concentration. However, it was shown that a plot of

t/l1.r = Nj(c!>. y)/Nj(O. y) vs. c!>l4>m was unique and independent of shear
rate but an increasing function of filler concentration. This approach of
presenting the normal stress difference vs. filler concentration may be
acceptable for data representation but not for data interpretation.
Using a filler size distribution, the normal stress difference of the
filled polymer system can be altered. The relative primary normal stress
coefficient is reduced when a bimodal distribution is used and gives the
lowest values at about 10-30% volume fraction of the small particles.
With increasing number of filler agglomerates for particulate fillers,
the normal stress difference is lowered. The extent of lowering of the
normal stress difference depends on the amount of occluded liquid
by the agglomerates, the average number of particles in each
agglomerate and hence the size of the agglomerates. When an
agglomerate is formed or is present, it is as though the particle size
of the filler has increased throughout the system. Larger particles in
an unagglomerated system would lower the normal stress difference
less. By analogy then, with increasing number of particles in the
agglomerates, the extent of normal stress difference lowering decreases.
Contrary to this, if more liquid is occluded in the interparticle voids of
the agglomerates, then the extent of normal stress difference lowering
increases. These two opposing factors determine the eventual extent of
normal stress difference lowering due to agglomerates formed by
particulate fillers.
Agglomerates of fiber also would tend to decrease the normal stress
difference. But, since unagglomerated fibers are known to increase
normal stress difference, the extent of this increase would be reduced
due to presence of agglomerates as the fibers which form the
agglomerates are restrained and cannot orient during flow.
Use of surface modifiers often helps to reduce the number of
agglomerates, thus increasing the values of N j as against that of the
untreated system of a fixed filler loading at the same level of shear
stress. The behavior is system-specific, and changing the filler or the
polymer or the type of surface modifier can accentuate or reduce the
effect that the surface treatment has on the normal stress difference.
Viscoelastic properties of filled polymer systems under shear can also
be studied through unsteady state data. Small amplitude oscillations for
getting dynamic rheological data are truly appropriate when handling
highly filled systems because they keep the sampIes in the gap of the
measuring instrument intact. Ouring dynamic data generation, it is
important to use a low amplitude because the effect of strain on the
rheological response is quite strong. Unsteady shear data in terms of
thixotropic sweep responses and stress relaxation behavior also provide
a good insight into the dispersion level of the filler in the polymer.
The complex viscosity vs. frequency behavior on different types of

filler is qualitatively the same as that of shear viscosity vs. shear rate.
Only the extent of the viscosity increases due to the filler addition
would be different for the unsteady and steady state because the Cox-
Mertz rule is known to fail for filled polymer systems.
When storage modulus vs. frequency plots for different types of filler
are considered, it is revealed that all fillers increase storage modulus at
any frequency. On the other hand, the storage modulus for spherical
fillers is known to decrease with increasing frequency.
With increasing filler concentration, the complex/ dynamie viscosity
as well as storage/loss moduli show a continually increasing trend.
However, the viscous response dominates the elastic response with
increasing filler concentration. The storage and loss moduli begin to
depiet more solid like behavior at higher concentrations and show
independence with respect to frequency.
Using a filler size distribution, the filler loading can be increased. In
fact, if changes in filler size distribution are made, a good method of
tracking the packing arrangements is by observing the differences in
the storage modulus-frequency response of the filled polymer systems
during dynamie measurements in the low strain region. Bimodal
distributions are more effective than broadly distributed powders in
achieving higher filler loadings.
Presence of filler agglomerates can be detected by using the torque
vs. mixing time curves and the dynamie data in conjunction with each
other. By tracking the maximum torque, it can be deduced whether the
mixing was done under high shear stress conditions. When the peak
torque is high, the shear force is strong enough to break agglomerates
and this gets reflected in the dynamic viscosity and storage modulus
being lower.
Effect of filler surface treatment is quite dramatic, whether it is
through the use of surface modifiers or by heat treatment of the
filler. It is good to back up the dynamie data with other unsteady
measurements like the thixotropie sweep and stress relaxation
measurements and the torque curve when handling surface treated
fillers. This is because the effect of surface treatment is quite
complex and system-specific. Where the torque peak is high, while
the complex viscosity and storage modulus are low and the stress
relaxation time is short for a treated filler system when compared
with the untreated one, then it is definite that the surface treatment
has helped in dispersing the filler. This is because the high peak
torque shows that high shear forces broke down the agglomerates
and the surface treatment prevented any chance of their reformation
because the dynamie data and stress relaxation measurements
indicated so.
Effect of filler-matrix affinity can be quantitatively estimated through

dynamic viscoelastic data. An interaction parameter has been defined
which gives a measure of the postulated matrix immobilization at the
interphase of the filler. It has been shown that there is a correlation
between the interaction parameter in the melt state and the solid state
at comparable frequency of deformation. Thus, it is possible to genera te
dynamic data in the melt state for quantitatively estimating the matrix-
filler interaction and then extrapolating the affinity behavior to the solid
state.
Rheology is a powerful tool for studying the dispersion level of the
filler and the matrix-filler affinity. The various methods that can be
used to understand the rheological behavior of filled polymer systems
have been elucidated in this book and it is hoped that it will serve as a
useful guide when indulging in further research areas related to filled
polymer systems in future.
Appendix A Glossary
Addition polymerization is a chemie al reaction in whieh simple

molecules (monomers) are added to each other to form long chain
molecules (polymers) without the formation of byproducts.
Amorphous polymer is one that has no crystalline component and
there is no order or pattern to the distribution of the molecules.
Apparent viscosity is the ratio of shear stress by shear rate whieh has
not been corrected for entrance length effects in a capillary rheometer.
Barus effect or die swell or extrudate swell is the increase in diameter
of the polymerie melt extrudate upon emergence from the die.
Branched polymer is one in whieh the main chain in the molecular
structure is attached with side chains, that is in contrast to a linear
polymer.
Complex modulus consists of the real and imaginary part of the
modulus. The real part is called the storage modulus and the imaginary
part is called the loss modulus.
Compounding involves the process in which polymers are softened,
melted and intermingled with solid fillers and other liquid additivesto
form filled polymer systems.
Condensation polymerization is a chemieal reaction that takes place
between the polyfunctional molecules with the possible elimination of a
small molecule such as water.
Consistency is a rheologieal property representing the viscous behavior
of a non-Newtonian material.
Constitutive equation is an equation relating stress, strain, time and
sometimes other variables, such as temperature or pressure.
426 Appendix A Glossary
Couette flow is the shear flow in an annular gap between two coaxial
cylinders in relative rotation.
Crystalline polymer is one that has an ordered structural arrangement
of molecules.
Deborah number is defined as the ratio of characteristic time (or in
other words, the relaxation time) of the material to the scale of
deformation to whieh it is subjected (i.e. the duration of observation).
Die swell or extrudate swell or Barus effect is the increase in diameter
Dielectric constant is a dimensionless factor derived by dividing the
parallel capacitance of the material by that of an equivalent volume of
vacuum.
Dispersive mixing is defined as an operation whieh reduces the
agglomerate size of the minor constituent to its ultimate particle size.
Distributive mixing is defined as an operation whieh is employed to
increase the randomness of the spatial distribution of the minor
constituent within the major base with no further change in size of that
minor constituent.
Dump criteria is the standard taken in judging the moment when the
mixing is deemed as complete.
Dynamic viscosity is the ratio of the stress in-phase to the rate of strain
under sinusoidal conditions.
Elasticity represents a reversible stress-strain behavior.
Elastomer is a rubbery polymer that deforms upon the application of
stress and reverts back to the original shape upon release of the applied
stress.
Equation of state or constitutive equation is an equation relating
stress, strain, time and sometimes other variables, such as temperature
or pressure.
Extensional strain is the relative deformation in strain due to
stretching.
Extensional viscosity is the ratio of tensile stress to the extensional rate.
Extra stress tensor is the difference between the stress tensor and the
isotropie pressure contribution.
Extrudate swell or die swell or Barus effect is the increase in diameter
Filled polymer system is the softened or melted polymerie mass in

which one or more fillers have been dispersed.
Filler is the inert solid material added as cost reducing or reinforcing or
property modifying agent to a polymer without significantly affecting
the molecular structure of the polymer.
Flexural modulus is the term relating to stiffness of the material and
basically represents the force required to break a sampie by bending or
flexing.
Flexural strength is the ability of a material to resist forces that tend to
bend it.
Flow activation energy is the energy required to activate the viscous flow.
Flow curve or rheogram is a curve relating shear stress or viscosity to
shear rate.
Glass transition temperature is the temperature at which increased
molecular mobility results in significant change in properties.
Heat distortion temperature is the temperature at which a material
bends by a predetermined amount under a given load.
Hysteresis is a material characteristic which results in different values
of the responses for the same values of corresponding stress or rate of
strain when applied in increasing and decreasing order.
Impact strength is the ability of a material to resist forces that tend to
break it when dropped or struck by a sharp blow.
Incompressible fluid is one that does not undergo a volume change,
i.e. it is density preserving.
Interface is the contacting surface where two materials meet.
Interphase is the region separating the filler from the polymer and
comprises of the area in the vicinity of the interface.
Loss modulus is the imaginary part of the complex modulus.
Melt Flow Index (MFI) is the weight of the polymer in grams extruded
in ten minutes through a capillary of specific diameter and length by
press ure applied through dead weight und er prescribed temperature
conditions as per set international standards.
Melt flow indexer is the apparatus used for measuring MFI.
Melt fracture is the irregular distortion of a polymerie melt extrudate
upon passing through a die due to improper melt or process
characteristics.
428 Appendix A Glossary
Mixing describes the process of intima te intermingling of polymers

with fillers/additives or two polymers without any specific
restrictions.
Model is an idealized relationship of behavior expressible in mathe-
matical terms.
Molecular weight is a measure of the chain length of the molecules that
make up the polymer.
No-slip condition at asolid boundary implies that the molecules in the
thin fluid layer adjacent to the solid surface move at the same velocity
as that of the surface.
Normal stress coefficient is the ratio of the normal stress by the square
of the shear rate.
Normal stress difference is the difference between the normal stress
components.
Paraffin wax is a chemical substance obtained as a residue from the
distillation of petroleum and is made up of higher homologues of
alkanes with a melting range of 50 to 90e.
Plasticizer is a material generally of low molecular weight that is
incorporated into a thermoplastic melt to improve its workability
during processing and flexibility in the finished product.
Power-Iaw model is behavior characterized by apower (n) relationship
between shear stress and shear rate.
Relaxation time is the time taken for the stress to decrease to an
exponentially inverse of its initial value under constant strain.
Rheology is concerned with the description of the deformation of the
material under the influence of stresses.
Rheogram or flow curve is a curve relating shear stress or viscosity to
shear rate.
Rheometry is an instrumental technique for measuring rheological
properties.
Steady flow is the flow in which the velocity at every point is the same.
Storage modulus is the real part of the complex modulus.
Suspension is a system in which denser particles, that are at least
microscopically visible, are distributed throughout a less dense fluid
and settling is hindered either by the viscosity of the fluid or by the
impact of its molecules on the particles.
Tensile strength is the ability of a material to withstand forees tending

to pull it apart.
Thermoplastic is a polymer that ean be made to soften and take on
new shapes by the applieation of heat and pressure.
Thermoset is a polymerie material that has undergone a ehemical
reaetion, known as euring in A, Band C stages depending on the
degree of eure by the applieation of heat and eatalyst.
Vortices are intense spiral motions in a limited region of .a flowing
fluid.
Weissenberg effect is an effeet exhibited by eertain non-Newtonian
fluids and involves the climbing of the fluid up a rod rotating in it.
Yield stress is the stress eorresponding to the transition from elastie to
viseous deformation of the flow eurve.
Appendix B ASTM conditions
and specifications for MFI
lable B1a Standard testing conditions 01 temperature and load as per *ASTM
01238 and tASTM 03364
Condition Temp. Load Approximate pressure Shear stress

(0C) piston + (x10 5 dynes/cm 2 )
weight (kg) (kg/cm 2 ) (psi)
*A 125 0.325 0.46 6.50 0.3

*B 125 2.160 3.04 43.25 1.97
*C 150 2.160 3.04 43.25 1.97
*0 190 0.325 0.46 6.50 0.3
*E 190 2.160 3.04 43.25 1.97
*F 190 21.600 30.40 432.50 19.7
*G 200 5.000 7.03 100.00 4.6
*H 230 1.200 1.69 24.00 1.1
*1 230 3.800 5.34 76.00 3.5
*J 265 12.500 17.58 250.00 11.4
*K 275 0.325 0.46 6.50 0.3
*L 230 2.160 3.04 43.25 1.97
*M 190 1.050 1.48 21.00 0.96
*N 190 10.000 14.06 200.00 9.13
*0 300 1.200 1.69 24.00 1.1
*P 190 5.000 7.03 100.00 4.6
*Q 235 1.000 1.41 20.05 0.91
*R 235 2.160 3.04 43.25 1.97
*S 235 5.000 7.03 100.00 4.6
*T 250 2.160 3.04 43.25 1.97
t 175 20.000 28.12 400.00 18.4
Note: An asterisk (*) denates ASTM 01238 and a dagger (t) denates ASTM 03364.
Appendix B ASTM conditions and specifications for MFI 431
Table B1b Testing conditions for commonly used polymers
Polymer Condition
*Acetals E, M
*Acrylics H, I
*Acrylonitrile-butadiene-styrene G
*Cellulose esters D, E, F
*Nylon K,Q,R,S
*Polychlorotrifluoroethylene J
*Polyethylene A, B, D, E, F, N
*Polyterephthalate T
*Polycarbonate o
*Polypropylene L
*Polystyrene G, H, I, P
tPoly(vinyl chloride)
*Vinyl acetal C
Note: An asterisk (*) denotes ASTM 01238 and a dagger (t) denotes ASTM
03364.
Table B1c Test temperature summary
Test temperature CC) Condition
*125 A,B
*150 C
t175
*190 D, E, F, M, N, P
*200 G
*230 H, I, L
*235 Q,R,S
*250 T
*265 J
*275 K
*300 o
Note: An asterisk (*) denotes ASTM 01238 and a dagger
(t) denotes ASTM 03364.
432 Appendix B ASTM conditions and specifications for MFI
Table B1d Test load summary
Load (kg) Gondition
*0.325 A,D,K
*1.000 Q
*1.050 M
*1.200 H,O
*2.160 B,G, E, L, R, T
*3.800 I
*5.000 G,P,E
*10.000 N
*12.500
t20.000
*21.600 F
Note: An asterisk (*) denotes ASTM 01238 and a dagger

Cf) denotes ASTM 03364.
Table B1e ASTM specifications for piston and die dimensions
Piston Die
Diameter *, t (0.3730 0.0003 in *, t (0.0825 0.0002 in

= 9.474 0.007 mm) = 2.095 0.005 mm)
Length *, t (0.250 0.005 in (0.315 0.0008 in
= 6.35 0.13 mm) = 8.00 0.02 mm)
t (0.916 0.0008 in
= 23.26 0.02 mm)
Note: An asterisk (*) denotes ASTM 01238 and a dagger (t) denotes ASTM 03364.
Appendix C Data details and
sources for master rheograms
Table C1 Details of data used for master rheograms of filled polymers in Figures 6.32-6.39 (Source: Ch. 6 Refs [50) and [149])
Polymer Grade Filler type, amount Coupling MFI (temp.oC/ Data No. of data Data
agent, load condition, tempo points (shear source
amount kg) c rate Ch.6
range, sec- 1 Ref.
LDPE P 1 4.9 c (220/2.16) 220 5(630-12000) [16)

P 1 Quartz powder, 33 phr 16.7c (220/2.16) 220 4(630-12000) [16)
P 1 Quartz powder, 100 phr 3.0 c (220/2.16) 220 4(630-12000) [16)
P 1 Quartz powder, 11 phr 2.2 c (220/2.16) 220 4(630-12000) [16)
P 1 Calcium carbonate I, 33 phr 2.1 c (220/2.16) 220 4(630-12000) [16)
P 1 Calcium carbonate I, 66 phr O.4 c (220/2.16) 220 4(630-12000) [16)
P 1 Calcium carbonate 11, 33 phr 5.4 c (220/2.16) 220 4(630-12000) [16)
P 1 Calcium carbonate 11, 66 phr 2.0c (220/2.16) 220 4(630-12000) [16)
PP 10-2626 Tale, 66 phr 3.3" (200/2.16) 200 6(10-500) [157)
10-2626 Tale, 66 phr 5.5 b (230/2.16) 230 6(10-500) [157)
10-2626 Tale, 66 phr 8.7" (250/2.16) 250 6(10-500) [157)
E115 5.4 c (200/2.16) 200 4(5-40) [5)
E115 CaC03 , 11 phr 3.0c (200/2.16) 200 5(5-40) [5)
E115 CaC03 , 25 phr 2.3 c (200/2.16) 200 5(4-40) [5)
E115 CaC03 , 66 phr 0.85 c (200/2.16) 200 5(1-40) [5)
E115 CaC03 , 230 phr 0.18c (200/2.16) 200 5(0.3-40) [5)
Profax 6523 15.7c (240/2.16) 240 3(1-100) [18)
Profax 6523 CaC0 3 , 230 phr KR-TTS, 0.5 phf 7.6 c (240/2.16) 240 4(0.1-100) [18)
Profax 6523 CaC03 , 230 phr KR-TTS, 1.5 phf 44 c (240/2.16) 240 3(1-100) [18)
Profax 6301 Mica, 66 phr 30c (220/2.16) 220 3(3-60) [9)
Profax 6301 Mica, 66 phr Z-6032, 0.5 phf 108c (220/2.16) 220 4(2-10) [9)
Table C1 (continued)
Polymer Grade Filler type, amount Coupling MFI (temp.oC/ Data No. of data Data
agent, load condition, tempo points (shear source
amount kg) C rate Ch.6
range, sec- 1 Ref.
PS STYRON 678 U 1.5" (180/5) 180 6(0.01-100) (27)

STYRON 678 U Carbon black, 11 phr 0.93c (180/5) 180 6(0.01-50) (27)
STYRON 678 U Carbon black, 25 phr 0.55c (180/5) 180 7(0.01--0.5) (27)
STYRON 678 U Carbon black, 43 phr 0.16c (180/5) 180 6(0.01--0.5) (27)
STYRON 678 U Ti02 , 11 phr 0.83c (180/5) 180 4(0.01--0.4) (27)
STYRON 678 U Ti0 2 ,25phr 0.53c (180/5) 180 4(0.01--0.4) (27)
STYRON 678 U Ti0 2 ,43phr 0.44c (180/5) 180 3(0.01--0.4 ) (27)
STYRON 678 U Glass fiber, 25 phr 0.73c (180/5) 180 4(0.01-100) (14)
STYRON 678 U Glass fiber, 66 phr 0.36c (180/5) 180 4(0.01-100) (14)
STYRON 678 U CaC0 3 , 50 phr 0.27c (180/5) 180 4(0.01--0.4) (18)
STYRON 678 U CaC0 3 , 50 phr Treated 2.0 c (180/5) 180 4(0.01--0.4) (18)
PET PET 1 49c (275/2.16) 275 4(10-5000) (20)
PET 1 Glass fiber, 33 phr 11.3c (275/2.16) 275 5(6-5000) (20)
PET 1 Glass fiber, 66 phr 4.9 c (275/2.16) 275 5(6-5000) (20)
PC Makroion 2805 6.1 c (290/1.2) 290 3(10-1000) (31)
Makroion 9410 Glass fiber, 10 phr 3.3 c (290/1.2) 290 4(1-1000) (31)
Makroion 8035 Glass fiber, 30 phr 1.4c (290/1.2) 290 4(1-1000) (31)
Nylon Zytel 40c (288/2.16) 288 3(50-6700) [158)
Zytel 49c (291/2.16) 291 4(10-10000) [158)
Zytel Glass fiber, 15 phr 29.4 c (291/2.16) 291 4(10-1000) [158)
Zytel Glass fiber, 50 phr 12.8c (288/2.16) 288 3(10-4400) [158)
Zytel Glass fiber, 50 phr 15.7c (291/2.16) 291 4(10-10000) [158)
Maranyl A100 113c (280/2.16) 280 5( 100-10000) [25)
Maranyl A190 Glass fiber, 50 phr 22 c (280/2.16) 280 5(100-1000) [25)
PEI ULTEM 1000 19.81 c (360/5) 360 5(5-5000) [136)
ULTEM 1000 Glass fiber, 11 phr or 10 w% 5.9c (360/5) 360 5(5-5000) [136)
ULTEM 1000 Glass fiber, 25 phr or 20w% 3.96c (360/5) 360 5(5-5000) [136)
ULTEM 1000 Glass fiber, 43 phr or 30 w% 2.45 c (360/5) 360 5(5-5000) [136)
PEEK PEEK 45G 1.9c (380/5) 380 5(0.1-1000) [159)
PEEK 4530A Carbon fiber, 43 phr or 30w% 16.7c (380/5) 380 5(0.01-1000) [159)
PEEK 4530GL Glass fiber, 43 phr or 30 w% 2.96 c (360/5) 360 7(15-1000) [159)
PEEK 4530A Glass fiber, 43 phr or 30 w% 4.2c (395/5) 395 7(15-1000) [159)
a MFI value calculated trom equation (6.30) knowing the MFI value as per tootnote b.
b MFI value given by manutacturer or measured under ASTM test conditions.
C MFI value read out trom t vs. y curve using equations (6.26) and (6.27) by the method discussed in section 6.8.
Appendix C Data details and sources for master rheograms 437
Table C2 Parameters of the filled polymer systems covered in the data analyzed for
master rheograms of filled polymers in Figures 6.32-6.39 (Source: Ch. 6 Refs [50] and
[149])
Matrix Filler type Amount (phr) Coupling agent Shape
LOPE Quartz powder I 33 100 200 Particulate

Quartz powder II 11 33 Particulate
Calcium carbonate I 33 66 Prismatic
Calcium carbonate 11 33 66 Prismatic
PP Talc 66 Platelet
Calcium carbonate 11 25 66 230 Prismatic
Calcium carbonate 230 0.5 to 1.0 phf Prismatic
titanate
Mica 66 Platelet
Mica 66 0.5 phf silane Platelet
PS Carbon black 11 25 43 Particulate
Titanium dioxide 11 25 43 Particulate
Glass fiber 25 66 Fibrous
Calcium carbonate 50 Treated Prismatic
Calcium carbonate 50 Untreated Prismatic
Nylon Glass fiber 15 50 Fibrous
PC Glass fiber 10 20 30 40 Fibrous
PET Glass fiber 33 66 Fibrous
PEI Glass fiber 11 25 43 Fibrous
PEEK Carbon fiber 43 Fibrous
Glass fiber 43 Fibrous
438 Appendix C Data details and sources for master rheograms
Table C3 Details of unfilled polymer data used for master rheograms in Figures 6.32-
6.39 (Source: eh. 6 Refs [50] and [149])
Polymer Grade MFI (temp.oC/ Temperature NO.of data pOints Oata

load condition, at which data (shear rate source
kg) generated (OC) range, sec- 1 ) Ch.6
Ref.
LOPE Indothene 22FA002 0.2 b (190/2.16) 190 9(0.01-1000) [144]

Indothene 24FS040 3.0" (175/2.16) 175 10(0.01-1000) [144]
Indothene 24FS040 4.0" (190/2.16) 190 10(0.01-1000) [144]
Indothene 24FS040 5.0" (205/2.16) 205 10(0.01-1000) [144]
Indothene 26MA200 20 b (190/2.16) 190 10(0.01-1000) [144]
PP 10-6016 39" (210/2.16) 210 6(10-500) [157]
10-6016 6.5 b (230/2.16) 230 6(10-500) [157]
10-6016 10.3" (250/2.16) 250 6(10-500) [157]
PS Styrene 666 U 7.5 b (200/5) 200 10(5-5000) [160]
Styrene 666 U 37.0" (220/5) 220 10(5-5000) [160]
Styrene 666 U 130" (240/5) 240 10(5-5000) [160]
H 5M 15.4" (210/5) 210 6(10-500) [157]
H 5M 47.7" (230/5) 230 5(20-500) [157]
H 5M 121" (250/5) 250 6(10-500) [157]
Nylon Plaskon 8201 5.0c (231/2.16) 231 4( 10--4000) [161]
Plaskon 8201 13.7c (260/2.16) 260 4(10-1000) [161]
Plaskon 8201 29.5c (288/2.16) 288 4(10-10000) [161]
Nylon 610 235c (280/2.16) 280 4(10-10000) [162]
PET Fiber grade IV = 0.57 54' (275/2.16) 275 9(1-5000) [163]
Fiber grade IV=0.57 64c (285/2.16) 285 9(1-5000) [163]
Fiber grade IV=0.57 86c (295/2.16) 295 9(1-5000) [163]
Fiber grade IV = 0.57 103c (305/216) 305 9(1-5000) [163]
Bottle g rade IV = 1.044 1.5c (275/2.16) 275 8(1-1000) [163]
Bottle grade IV = 1.044 1.6c (285/2.16) 285 8(1-1000) [163]
Bottle grade IV = 1.044 1.77' (295/2.16) 295 8(1-1000) [163]
Bottle grade IV = 1.044 1.96' (305/216) 305 8(1-1000) [163]
PC Lexan 141 1.3' (250/1.2) 250 4(20-300) [164]
Lexan 141 3.5c (270/1.2) 270 4(20-300) [164]
Lexan 141 6.1' (290/1.2) 290 4(20-300) [164]
PEI ULTEM 8.34 c (355/5) 355 3(200-7000) [165]
ULTEM 22.08 (375/5) 375 3(200-10000) [165]
ULTEM 39.25' (395/5) 395 3(200-10000) [165]
PEEK PEEK 951GV 10Sc (360/5) 360 4(15-1000) [159]
PEEK 951GV 22.6' (395/5) 395 4(4-1000) [159]
" MFI value calculated from equation (6.30) knowing the MFI value as per footnote b.
b MFI value given by manufacturer or measured under ASTM test conditions.
c MFI value read out from r versus y curve using equations (6.26) and (6.27) by the method
discussed in section 6.8.
Appendix D Abbreviations
STANDARDS
ASTM American Society for Testing and Materials
BS British Standards
DIN Deutsches Institut fr Normung
ISO International Standards Organisation
JIS Japanese Industrial Standards
POLYMERS
ABS Acrylonitrile-butadiene-styrene
C-ester Cellulose ester
C-ether Cellulose ether
EVA Ethylene-vinyl acetate
HOPE High density polyethylene
HIPS High impact polystyrene
LOPE Low density polyethylene
LLOPE Linear low density polyethylene
PA Polyamide
POM Polyacetal
PAr Polyarylate
PAS Polyaryl sulfone
PBT Poly(butylene terephthalate)
PC Polycarbonate
PE Polyethylene
PEEK Polyether ether ketone
PEI Polyetherimide
PES Polyether sulfone
PET Poly(ethylene terephthalate)
PI Poly(isobutylene)
PMMA Poly methyl methacrylate
440 Appendix D Abbreviations
pp Polypropylene
PPO Poly phenylene oxide
PPS Poly phenylene sulfide
PS Polystyrene
PVA Poly(vinyl akohol)
PVB Poly(vinyl butyral)
PVC Poly(vinyl chloride)
PVDF Poly(vinylidene fluoride)
SAN Styrene acrylonitrile
SBR Styrene butadiene rubber
SBS Styrene-butadiene-styrene
SIS Styrene-isoprene-styrene
SMA Styrene-maleic anhydride
TPE Olefinic-type thermoplastic elastomer
UHMWPE Ultra high molecular weight polyethylene
VCVA Vinyl chloride-vinyl acetate
Appendix E Nomenclature
Table E1
Symbol Description Units Equation

1 2 3 4
a Volume Iraction 01 component 'A' in (5.2a), (5.3b)

a mixture
Bo Hall width 01 channel (3.18)
a1 Empirical coefficient whose value lies - (4.2)
between 1 and 2
BMF1 MFI ratio (6.15)
a Model parameter (2.53)-(2.56)
A Surlace area 01 plate in Figure 2.1 m2
Ao Frequency term depending on the Pa sec (2.69)
entropy 01 activation lor Ilow
AS Constant (2.74)
Ao Constant (2.73)
AH Hamaker's constant (6.5a), (6.6)
Ap Adjustable parameter (4.12b)
An Constant dependent on the nature (6.12), (6.13)
01 the continuous phase
b Volume Iraction 01 component 'B' in (5.2b), (5.3c)
a mixture
bo Hall thickness 01 channel (3.17)
12 Overall width 01 the residence time m (5.14)
distribution curve in Figure 5.28
B Filler-polymer interaction parameter (8.10)-(8.14)
B'0 Constant (2.74)
Bi' Bi, Coefficients (4.27)
BMJ, n) Function dependent on volume (6.3)
Iraction and power-Iaw index
B2(</>, n) Function dependent on volume (6.3)
Iraction and power-Iaw index
442 Appendix E Nomenclature
Table E1 (continued)

1 2 3 4
c Arbitrary adjustable parameter (2.57)

C1.C2.C3 Constants (2.63)
C Positive constant representing the (6.5a), (6.6)
total number of nearest
neighbors of each sphere
C; Constant (2.68)
c; Constant (2.68)
dp Particle diameter in Figure 4.4 m
Ci Particle diameter in Figure 4.5 m
0 Diameter of sphere, rod or platelet- m (6.5a), (6.6),
shaped particle (8.11 )-(8.13)
Da Average diameter of different sizes of m (6.17)-(6.20)
particulates
i
00
Diameter of the ith component
Orifice diameter
m
m
(6.17)-(6.21 )
OE Extrudate diameter m
0p1. 0p2. Op, Average diameter of suspending m (4.22), (4.23),
particles 1, 2 and ith fraction, (4.25)
respectively
Ope Projection circumscribing diameter in J.tm
Table 8.4 from section 8.6
TDR Diameter of tube or pipe

Draw ratio
m (4.22), (4.23)
QRe Critical value of draw ratio

TI Symmetric part of the gradient or sec- 1 (2.3), (2.4),
deformation tensor (2.23), (2.28),
(2.30)
e e
Exponential (where = 2.71828)
Ei Independent parameter (2.57)
ev Parameter contributing the (4.32)
electroviscous effects
eV1 , ev2 ' ev3 Coefficients corresponding to each (4.31)
of the three electroviscous effects
E Activation energy for viscous flow kJ/mole (2.69), (2.70)
Ec Coulombic interaction energy J (6.2)
Ev van der Waals interaction energy J (6.2)
E,n1 Interaction energy J (6.1)
e!,,, Viscous dissipation energy for matrix J (6.1), (6.3)
EviS Viscous dissipation energy for filled J (6.1), (6.3)
system
Eo Activation energy of the flow process kJ/mole (6.8), (6.10)
for unfilled polymer system
Eoo Activation energy of the flow process kJ/mole (6.9), (6.10)
for filied polymer system containing
4J volume fraction of filler

1 2 3 4
E, Value of E determined under kJ/mole (2.71 )

constant shear stress conditions
Ej Value of E determined under kJ/mole (2.72)
constant shear rate conditions
E"c Dynamic loss modulus for filled Pa (8.14)
polymer in solid state
E"p Dynamic loss modulus for unfilled Pa (8.14)
polymer in solid state
M Difference between the activation kJ/mole
energy for viscous flow of filled
and unfilled polymer system
f Force in Figures 2.1, 2.3,2.4 Newtons (2.2)
f( ep,) Function of the volume fraction of (4.28)
the floccules in a suspension
f(T,O) Free volume of the continuous m3 (6.13), (6.14),
phase at temperature T but (6.15)
without the presence of any other
dispersed phase
f(T, ep) Free volume of the multi-component m3 (6.12), (6.14)
system at temperature T
containing ep weight fraction of the
dispersed phase
f1 Number fraction of the ith (6.17)-(6.19)
component defined by eq. (6.21)
F Force exerted by the test load L on Newtons (6.24)
the polymer in the melt flow indexer
Fmax Maximum force tending to divide a Newtons (5.11 )
dumbbell shaped agglomerate in
a fluid
G Apparent melt shear modulus Pa (3.16b)
Gc , Gmo Storage moduli for the filled and (6.23)
unfilled polymer, respectively
G' Dynamic storage modulus Pa (2.15)
G'(O, w) Dynamic storage modulus at Pa (8.7a)
frequency of w for unfilled
polymer system
G'(ep, w) Dynamic storage modulus at Pa (8.7a)
frequency of w for filled polymer
system containing ep volume
fraction of filler
G', Relative dynamic storage modulus Pa (8.9)
defined as the ratio of the
dynamic storage modulus for the
filled to unfilled polymer system
G" Dynamic loss modulus Pa (2.16)

1 2 3 4
G"(O, w) Dynamic loss modulus at frequency Pa (8.7b)

of w for unfilled polymer system
G"(</>, w) Dynamic loss modulus at frequency Pa (8.7b)
of w for filled polymer system
containing </> volume fraction 01
liller
GI' Dynamic loss modulus for filled Pa (8.10)
c
polymer melt
GI'p Dynamic loss modulus for unfilled Pa (8.10)
polymer melt
G* Complex modulus Pa (2.21)
H Gap between two parallel discs of m (3.7)
viscometer
Intensity of segregation (5.10)
Je Steady state compliance Pa-' (2.50)
k Constant power index (6.16)
ke Thickness of the electrostatic (6.5a)
interaction layer
k, Hydrodynamic interaction coefficient - (4.25)
ko Constant (2.75)
K Consistency index whose values are g/cm sec 2 - n (6.35), (6.36)
tabulated in Tables 6.8 and 6.9 (g/10 min)"
Ko Rate constant for volume increase of - (4.30)
the crystals
~J, Coefficient (2.49), (2.50)
K Consistency index kg/m sec 2 - n (2.39), (2.40),
(2.44a), (4.29),
(6.31)
Variable length 01 cylindrical rod in m
Figure 2.3
10 Initial length of cylindrical rod m (2.26)
IN Length 01 nozzle m (6.24)
Ip Length of rod-shaped particle m (8.12)
L Test load, i.e. dead weight + piston kg (6.26)
weight
L, Test load 1 kg (6.32)
L2 Test load 2 kg (6.32)
m Damping constant (2.47), (2.48)
m Number of thread starts per screw (5.13)
m' Adjuslable parameter (2.60)
m" Adjustable parameter (2.61 )-(2.63)
M Total number of components in a (4.27)
blend of suspended particles
MFI Melt Ilow index g/10min

1 2 3 4
MFI(T,O) Melt flow index of the continuous g/10 min (6.13)

phase at temperature T but
without the presence of any other
dispersed phase
MFI(T, cp) Melt flow index of the multi- g/10 min (6.12)
component system at temperature
T and containing cp volume
fraction of the dispersed phase
MFI, Melt flow index determined under g/10 min (6.32)
test load 1
MFI 2 Melt flow index determined under g/10min (6.32)
test load 2
MFI T , Melt flow index at ASTM g/10 min (6.30)
recommended test temperature
MFI T2 Melt flow index at required g/10 min (6.30)
temperature
m"m, Mixing index (5.7)
Mw Weight average molecular weight (2.49), (2.50),
(2.75)
Mw, Critical weight average molecular (2.75)
weight
Mz z average molecular weight (2.49), (2.50)
n Power-Iaw index whose values are
given in Tables 6.8 and 6.9
n' Power-Iaw index (2.52b), (2.62b)
n" Power-Iaw index (2.52b),2.62b)
7i Power index (8.10), (8.14)
N Power index in the Carreau model (2.42), (2.43),
(2.48), (2.52a),
(2.62a), (6.33)
N, Primary normal stress difference Pa (2.7)
N2 Secondary normal stress difference Pa (2.8)
NF Normal force Newtons (3.4)-(3.6)
N' Number of particles in sampie
N', Number of ultimate particles of the (5.1)
major component
N'2 Number of ultimate particles of the (5.1)
minor component
N'r Number of floccules (4.28)
N" Number of sam pies of same size (5.4)-(5.6)
N Speed of rotation rpm (3.1),(5.12),
(5.13)
P Pressure Pa (2.3)
PH Pressu re hole error Pa
Pm Measured pressure Pa

1 2 3 4
P Power-index in the General (2.44), (6.36)

Rheological model whose values
are given in Table 6.9
P" PI Particle size frequency lunction 01 (4.26)
the ith and jth particle
P(XA ) Probability distribution lor finding XA (5.3a)
concentration in a sam pie
IJ,.Pdi Pressure drop in extrusion die Pa (3.10)-(3.12) ,
(3.14), (3.15)
0 Volumetric flow rate m3 /sec (5.12), (5.13),
(5.15), (6.25)
Oe Leakage flow rate between screw m3 /sec (5.13)
llight and other screw
Of Leakage Ilow rate between screw m3 /sec (5.13)
Ilight and barrel wall
OL Leakage flow rate m3 /sec (5.13)
Os Leakage Ilow rate between flanks m3 /sec (5.13)
perpendicular to the plane
through screw axis
Ot Leakage flow rate between Ilanks 01 m3 /sec (5.13)
screw II ig hts
Oth Theoretical flow rate m3 /sec (5.13)
Radial position m (3.1 )
r1 Radius of particle 1 in an m (5.11 )
agglomerate
r2 Radius of particle 2 in an m (5.11 )
agglomerate
r. Ratio 01 length 01 diameter 01 a rod- (4.15), (4.16),
shaped particle (4.18), (4.19),
(4.33)-( 4.36)
r. Ratio 01 the semi-axis of the ellipsoid - (4.14a), (4.14b)
of rotation
R Gas constant = 8.314 J/mol K (2.69)-(2.72)
R(r) Coeflicient 01 correlation (5.9)
RN Radius 01 nozzle m (6.24), (6.25)
Rp Radius 01 piston m (6.24)
R Radius 01 disc or cone 01 viscometer m (3.2)-(3.9)
. Sell-cleaning time sec (5.14)
S Standard deviation 01 composition 01 - (5.6), (5.7)
spot sam pies
Ef Variance 01 composition of spot (5.5)
sampies
SL Scale 01 segregation (5.8)
SR Elastic strain recovery (2.38), (3.15),
(3.16a)
Table E1 (eontinued)
Symbol Deseription Units Equation

1 2 3 4
Sw Die swell ratio 01 extrudate diameter (2.37)

to die diameter
Time see
t Average residenee time see (5.14), (5.15)
tanb Loss tangent= G"/G' (2.17)
tr 15 Traee 01 the delormation tensor (2.5)
T Polymer melt temperature C
T, ASTM reeommended test K (6.30)
tem pe ra tu re
T2 Temperature at whieh MFI is K (6.30)
required
Tg Glass transition temperature 01 K
polymers
Tg" Tgo Charaeteristies glass transition K (6.23)
temperature lor lilled eomposite
and unlilled polymer
Ts Standard relerenee temperature K (2.68), (2.70),
equal to Tg + 50 (6.30)
T Measured torque Newtons (3.2), (3.3)
T Symmetrie Cauehy stress tensor Pa (2.3)
Vi Volume Iraetion 01 the ith (6.21 )
eomponent
V" V2 , V3 Veloeity eomponents along x" x2 , x3 m/see
axis
Vc Volume 01 C-shaped ehannel m3 (5.13)
between Ilanks 01 sueeessive
Ilights
VI Free volume m3 (5.15)
Vs Volume 01 sam pie m3 (5.3e)
.!'{ Distanee between the points 01 m (5.14)
inlleetion on the residence time
distribution eurve in Figure 5.28
X1 ,X2 ,X3 Distances along the x" x2 , x3 axis m
XI' Xi Weight proportion 01 the ith and jth (4.27)
eomponent in ablend 01
suspended particles
x Positional veetor m (2.4)
X Thiekness 01 platelet-shaped particle m (8.13)
XA Coneentration 01 eomponent 'A' in a (5.3a)
sampie
XA, Measured value 01 XA lor the ith (5.4), (5.5)
sam pie
X'A, Coneentration 01 eomponent 'A' at (5.9)
point 1 in the ith sampie

1 2 3 4
Concentration of component 'A' at (5.9)

point 2 in the ith sampie
Actual mean concentration of (5.4)-(5.6)
component 'A' in a sampie
Z Quantity calculated for checking (5.6)
mixing quality
Zo Degree of flocculation (4.19)
Z(a) Model parameter (2.53)-(2.56)
Appendix F Greek symbols
Table F1 Greek symbols

1 2 3 4
(1. Ultimate particle size of component A (5.3c)

(1.0 Rate of energy dissipation within the (4.29)
neighbourhood of a typical sphere
in a suspension
(1.1' (1.2' (1.3 Coefficients (4.5)
(1.c Coefficient in the crowding factor (4.8), (4.18)
expression
(Xli Crowding factor coefficient (4.26)
(1.r1 Function of the axis ratio re (4.13), (4.14b)
(1.r2 Function of the axis ratio re (4.13), (4.14b)
(1.E Einstein's constant (4.1), (4.4), (4.15),
(4.17)
,
(1. Ellis model parameter (2.41), (6.34)
,
(1.c Adjustable factor (4.21). (4.22)
(1.c " Adjustable factor (4.21), (4.23)
Ci Constant (5.12)
[! Coefficient (4.17)
Term defined by equation (6.18) (6.17)
(T) Difference between free volumes of m3 (6.14), (6.15)
the polymer and the filled polymer
system
o Rate constant for the equilibrium (4.19)
between free filler particles and
floccules
Constant (5.12)
y Shear rate sec- 1 (2.1), (6.23), (6.27),
(6.29)
450 Appendix F Greek symbols
Table F1 Continued

1 2 3 4
1'0 Amplitude 01 the sinusoidal variation (2.12), (2.13),

01 shear rate (2.15), (2.16)
1'a Shear rate at outer radius 01 disc sec- 1 (3.7)
Ym Amplitude 01 oscillation in the
maximum (or effective) shear rate
(Ym)
1'w Wall shear rate sec- 1 (3.13)
Y~s Interlacial energy between liquid- J (1.1 )
solid phase
Y~v Interlacial energy between liquid- J (1.1 )
vapour phase
Y~v Interlacial energy between solid- J (1.1 )
vapor phase
b Phase angle (2.14)-(2.17)
bs Diameter ratio 01 small particle to
large particle in Figure 6.18(b)
e Void Iraction or porosity
e Dielectric constant (6.5)
ef Degree 01 lill m2 /sec (5.15)
e Uniaxial extensional rate sec- 1 (2.22)-(2.26),
(2.66a), (2.66b),
(3.19), (3.20)
es Biaxial extensional rate sec- 1 (2.27), (2.28)
,
ec Critical extension al rate sec- 1
ep Plan ar extensional rate sec- 1 (2.29), (2.30)
Capillary entrance end effect (3.12), (3.14)-(3.16)
correction lor viscous effect
~ Steady shear viscosity Pa.sec
~(Y) Steady shear viscosity lunction Pa.sec (2.9)
~a Apparent viscosity 01 a Iluid in Pa.sec
Figure 4.5
~A Viscosity value read Irom intersecting Pa. sec (2.44b)
asymptotes
~c Viscosity 01 the li lied composite Pa.sec (6.22)
material
~E Uniaxial extension al viscosity Pa. sec (2.31), (2.66a),
~E(t) Extensional viscosity as a lunction 01 Pa. sec (2.66b)
time
~ES Biaxial extensional viscosity Pa.sec (2.32)
~EP Plan ar extensional viscosity Pa.sec (2.33)
~f Viscosity 01 a homogeneous Pa.sec (4.28)
suspension 01 Iloccules
~mc Viscosity 01 the polymer matrix Pa. sec (6.22)
~mo Viscosity 01 the unallected polymer Pa. sec (6.22)
Table F1 Continued

1 2 3 4
'1N Viscosity 01 lilled polymer system in Pa.sec (2.45b)

the Newtonian plateau region
'1r Relative steady shear viscosity which Pa.sec (6.11 )
is the ratio 01 viscosity 01 lilled to
unlilled polymer system
('1r)y Relative viscosity at lixed shear rate (6.7)
t'Jrmlx Relative viscosity 01 a mixture of two (4.21)
suspended particles
'15 Viscosity 01 a dilute suspension 01 Pa. sec (4.29)
spheres
'1r Trouton's viscosity in uniaxial Pa.sec (2.65)
stretching
'1v Volume viscosity Pa.sec (2.3)
'10 Zero shear viscosity; also viscosity 01 Pa.sec (2.34), (2.36),
the suspending medium (4.22), (4.23),
(4.28), (4.33)-
(4.36)
'10.T Steady shear viscosity 01 unfilled Pa.sec (6.8), (6.10)
polymer system at a temperature T
'10.TR Steady shear viscosity 01 unlilled Pa.sec (6.8), (6.10)
polymer system at a relerence
temperature TR
'1<P.T Steady shear viscosity 01 lilled Pa.sec (6.9), (6.10)
polymer system containing </>
volume Iraction 01 liller at a
temperature T
'1 <P.T R Steady shear viscosity 01 lilled Pa. sec (6.9), (6.10)
polymer system containing 4>
volume Iraction 01 liller at a
temperature TR
,
'1 Dynamic viscosity Pa.sec (2.18)
'1; Relative dynamic viscosity delined as (8.8)
the ratio 01 dynamic viscosity 01
lilled to unlilled polymer system
'1 " Imaginary part 01 complex viscosity Pa. sec (2.19)
'1* Complex viscosity Pa.sec (2.20), (2.51),
(2.52a), (2.52b)
'1~ Zero-Irequency viscosity lunction Pa. sec (2.52a)
'1*(</>, y) Viscosity lunction dependent on Pa. sec (6.5b)
volume fraction and shear rate
'1 00 Shear viscosity value at very high Pa.sec
shear rate
e Spherical coordinate giving the
orientation 01 the rod as shown in
Figure 4.2
452 Appendix F Greek symbols
Table F1 Continued

1 2 3 4
(Jo Cone angle in Figure 3.1 radians (3.1)

(j' Contact angle radians (1.1 )
(J Half angle of convergence of stream radians (2.67)
line at the entrance of die
A Relaxation time; also time constant sec (2.42), (2.43),
and model parameter (2.48), (2.56),
(2.62a), (6.33)
A1 , A2 Parameters of the Oldroyd model sec (2.66a)
Ac Characteristic time sec
As Time scale of deformation sec
I(4)) Function of 4> (4.3)
J..i Mean of composition of a random (5.2a), (5.3b)
homogeneous mixture
II Interaction parameter (4.19)
v Kinematic viscosity m2 /sec (5.15)
v Constant (4.28)
P Polymer melt density kg/m 3
Po Density of the suspending medium kg/m 3 (4.22), (4.23)
(J Standard deviation of composition of (5.7)
a random homogeneous mixture
(J2 Variance of composition of a random (5.2b), (5.3c)
homogeneous mixture
(J1' (J2 Upper and lower limits of the (4.26)
dimensionless radius, respectively
Average extensional stress Pa (2.67a)
,
(JE
Shear stress Pa (2.36), (2.39)
'w Wall shear stress Pa (3.11), (3.12)
'y Yield stress Pa (2.45), (6.5a), (6.6)
'1/2 Special value of shear stress when Pa (2.41), (6.32)
steady shear viscosity is half the
zero shear viscosity
,g1 Amplitude of the sinusoidal variation Pa (2.14)-(2.16)
of shear stress
'12' '21 Shear stress components of the Pa (2.2), (2.6), (2.9)
stress ten so r
'11' '22' '33 Normal stress components of the Pa (2.6)-(2.8)
stress tensor
'11 - '22 Primary normal stress difference Pa (2.10)
'22 - '33 Secondary normal stress difference Pa (2.11 )
f Extra stress tensor Pa (2.3), (2.6), (2.34)
4> Volume fraction of the suspended
particles or fillers
4>' Weight fraction of filler in Figures
6.17(a), 6.17(b) and 6.31
Table F1 Continued

1 2 3 4
1>0 Initial volume 01 the crystals m3 (4.30)

1>,. 1>2' 1>3 Volume concentration 01 suspended (4.21), (4.24)
particles lor 1, 2 and ith size
Iraction, respectively
1>cr Critical concentration below wh ich (4.16)
the interaction between the rods
can be neglected
1>, Volume Iraction 01 Iloccules in the (4.28)
suspension
1>L Volume Iraction ollarger particles
1>m Maximum attainable concentration 01
lillers defined as 1 - e or maximum
packing Iraction
1>~ Maximum packing 01 spheres 01 (6.18)
unilorm size r
1>5 Volume Iraction 01 smaller particles
t/J Spherical coordinate giving the
orientation 01 the rod as shown in
Figure 4.2
t/Jo Surlace potential of particulates J (6.5a)
t/J,. t/J2 Primary and secondary normal stress kg/m
coefficients
t/J,CY) Primary normal stress coefficient kg/m (2.10), (2.46),
lunction (2.47)
t/J2(Y) Secondary normal stress coefficient kg/m (2.11 )
lunction
t/J '.y Relative normal stress difference (7.1)
coefficient defined as the ratio 01
normal stress 01 filled to unfilled
polymer system at the same shear
rate
'1', Enclosed angle for a curved fiber in
Figure 4.4
w Frequency 01 oscillations or angular rad/sec (2.12)-(2.21 )
Irequency
Qmlxed Probability (5.1)
Author Index
Abbas, K.A. 41, 49, 243, 292, 305, 312, Arina, M. 41, 48, 243, 259, 304, 312,
313, 315, 331, 334, 338, 391, 395, 333,338,390,395,398,410,414
411 Armstroff, O. 208, 240
Abdel-Khalik, 5.1. 83-5, 107, 108 Armstrong, RC 55, 59, 60, 67, 79, 104,
Abe, D.A. 41, 49, 243, 273, 305, 312, 105
334,338,391,395,411 Arrhenius, S. 140, 171
Acierno, D. 9,44, 166, 174,397,414 Ashare, E. 85, 108
Acrivos, A. 136, 142, 170, 171,247, Astarita, G. 67, 79, 81, 84, 105, 107,
308 108,395,414
Adams, E. F. 266, 309 Ayer, J.E. 26fr8, 309
Adams, J.w.C 117, 133, 267
Adams-Viola, M. 136, 168 Bachmann, J.H. 18, 45
Adler, P.M. 136, 170 Baer, A.D. 142, In, 257, 265, 267, 269,
Advani, S.G. 41, 51, 243, 308, 312, 337, 308,346,394
338,394,395,414 Bagley, E.B. 72, 74, 105, 106, 121, 133
Agarwal, PK 98, 109 Baily, E.D. 117, 133
Aggarwal, S.L. 8, 44 Baird, D.G. 9, 44, 331, 337
Agur, E.E. 194,239 Baker, F.S. 113, 132, 136, 169
Ahu, CW. 262, 263, 309 Ballenger, T.F. 85, 108
Akay, G. 74, 106 Ballman, RL. 100, 110, 128, 131, 134,
Alfrey, T., Jr. 140, 171 135
Allen, P.W. 1,44 Balmer, J. 74, 106
Allen, T. 357, 394 Bamane, sv. 81, 82, 86, 87, 107, 301,
Allport, D.C 8, 44 302,311
Alter, H. 18, 45 Bandyopadhyay, G. 41,52
Althouse, L.M. 41, 49, 243, 273, 306, Bares, J. I, 44
312,335,338,360,361,387,388, Bames, H.A. 41, 47, 67, 79, 84, 105,
392,394,395,412 107, 136, 170
Anderson, P.C 136, 168 Barringer, E.A. 266, 267, 309
Andres, U.T. 138, 170 Bartenev, G.M. 14,41,45,285,310
Andrews, RD. 117, 133 Batchelor, GK 136, 164-ti, 170, 174,
Angerer, G. 121, 133 405,414
Aoki, Y. 117, 133 Bauer, L.G. 136, 168
Arai, E. 41, 51, 243, 307, 312, 336, 338, Baumann, DK 189,238
393,395,413 Baumann, G.F. 104, 111
Aral, BK 338, 390 Bayliss, M.D. 136, 153, 169
456 Author Index
Becker, E. 67, 79, 105 Bowen, H.K. 262, 263, 266, 267, 272,
Beek, W.1. 194, 239 309,310
Belcher, H.V. 100, 109 Bowerrnan, H. H. 398, 414
Bell, J.P. 166, 174, 397, 414 Bradley, H.B. 35, 46
Benbow, J.J. 74, 75, 106 Brandrup, J. 1,44
Bennett, K.E. 131, 135 Brauer, G.M. 136, 169
Berger, S.E. 35, 46 Braun, D.B. 136, 169
Beris AN. 88, 90, 108 Brede, H.L. 140, 171
Berlarnont, J. 136, 168 Brenner, H. 136, 170
Bemier, R 136, 169 Bretas, RES. 41, 50, 243, 306, 312, 335,
Bersted, B.H. 74, 106 338, 393, 395, 412
Berstein, B. 72, 85, 106 Bright, P.F. 41, 48, 243, 305, 312, 334,
Bestul, A.B. 100, 109 338,391,395,397,398,410,414
Bhardwaj, 1.S. 41, 49, 243, 273, 277, Brodnyan,J. 147, 172
278,305,312,334,338,391,395, Broutrnan, L.J. 17, 45
411 Browned, W.E. 136, 169
Bhattacharya, S.K. 41, 52, 266, 268, 310 Bruch, M.312,332
Bhavaraju, S.M. 136, 168 Brydson, J.A. 41, 47
Bierwagon, G.P. 19,45 Bulkley, R 83, 107, 247, 308
Bigg, D.M. 41, 47, 49, 50, 196,219,225, Bungenberg de Jong, H.G. 140, 171
236, 237, 239, 241, 243, 273, 277, Burgers, J.M. 145, 172
278, 290, 304, 306, 312, 333, 335, Burke, J.J. 8, 44
338-40,349,350,354,360,361,
387,388,390,392,394,395,410-12 Carneron, G.M. 36, 46
Billrneyer, Jr. F.w. 1, 43, 44 Carley, J.F. 103, 110, 196, 239
Binding, D.M. 98, 109, 131, 135 Carr, R 136, 167
Birchall, J.D. 190,238 Carreau, P.J. 41, 51, 74, 81, 85, 106-8,
Bird, RB. 55, 59, 60, 65, 67, 79-81, 243,284,287,308,312,337,338,
83-5,97,104,105,107-9 341, 394, 395, 414
Birks, A.M. 74, 106 Carruthers, J.M. 113, 132,222,241
Blake, W.T. 125, 134 Carter, RE. 113, 132, 136, 169
Blanch, H.w. 136, 168 Caso, G.B. 136, 169
Blankeney, W.R 146, 147, 172 Castillo, C. 136, 168
Bludell, D.J. 103, 110 Cengel, J.A. 139, 171
Blyler, L.L. 118, 126, 133, 134 Cessna, L.C 16,45
Boger, D.V. 113, 131, 136, 170, 312, Chaffey, CE. 41, 47, 49, 50, 243, 273,
337 275-7,292,304-6,312,333-5,338,
Bogue, D.C 85, 91, 108, 117, 133 390,392,395,410-2
Bohn,E.10,44,262,263,309 Chan, CF. 79, 107
Boiesan, V. 102, 110, 140, 171 Chan, F.S. 163, 173
Boira, M.5. 41, 47, 243, 273, 275-7, 292, Chan, Y. 41,48, 163, 166, 173,243,292,
304,312,333,338,390,395,410 304,312,315,333,338,390,395,
Boonsrra,B. B. 226,241 405,410
Booth, F. 163, 173 Channis, CC 18, 45
Booy, M.L. 208, 240 Chaprnan, F.M. 41, 47, 115, 132, 151,
Borghesani, A.F. 136, 168 172, 243, 246, 303, 312, 332, 338,
Botsaris, G.D. 136, 168 390, 395, 407, 409
Boudreaux, Jr. E. 75, 106 Charles, M. 124, 134, 136, 168
Bourne, R 299, 311 Charley, RV. 74, 106
Bowen, B.D. 10, 44 Charrier, J.M. 166, 174
Author Index 457
Chartoff, R.P. 118, 133 Cracke!, P.R. 136, 168

Chattopadhyay,S.290,299,310 Craig, R.G. 136, 169
Chen, I.J. 85, 108, 117, 133 Crawley, R.L. 72, 105
Chen, S.J. 179, 237 Cross, M.M. 81, 107, llS, 132
Chen, Y.R. 136, 169 Crowder, J.W. 14,41,45,85, 108,243,
Cheng, D.C-H. 136, 170 304,312,319,333,338,390,395,
Cheremisinoff, N.P. 67, 79, 105, 136, 410
169,189,194,238,239 Crowson, R.J. 41, 48, 243, 292, 305,
Chhabra, R.P. 81, 107 312,334,338,391,395,397,398,
Chipalkatti, M.H. 41, 49, 243, 273, 305, 410,411,414
312, 334, 338, 391, 395, 411 Cuculo, J.A. 75, 106
Chong, JS. 142, 171,257,265,267,269, Czamecki, I. 41,48,49,243,244, 305,
308,346,394 312,313,315,334,338,344,391,
Christiansen, E.B. 142, 171,257,265, 395,396,400,411,414
267,269,308,346,398
Chung, c.I. 194,239 Daane, J.H. 126, 134
Chung, J.T. 67, 105, 125, 126, 134 Daley, L.R. 41, 50, 243, 306, 312, 335,
Chung, K.H. 194,239 338, 392, 395, 412
Churchill, R.W. 81, 82, 107 Danckwerts, P.V. 175, 181, 183, 237,
Churchill, S.W. 81, 82, 107 238
Clark, ES. 86, 108,316, 337 Danforth, S.c. 88, 90, 108
Clarke, B. 140, 145-7, 150, 171 Darby, R. 43, 52, 67, 79, 105, 136, 168,
Clegg, D.w. 43, 52 170
Clegg, P.L. 72, 75, 105 Daroux, M. 81, 107
Code, R. K. 136, 168 Davis, J.H. 19,45
Cogswell, F.N. 41, 47, 65, 76, 98, 103, Davis, P.K. 136, 168
104, 107, 109, 110, 113, 130, 131, De Boojs, J. 140, 171
135 De Brujin, H. 139, 171
Cohen, L.B. 273, 277, 310 De Cindio, B. 166, 167, 174
Cohen,M. 103, 110 De Kee, D. 81, 107, 136, 168
Cokelet, G.R. 136, 167 De Simon, L.B. 113, 132, 136, 169
Coleman, B.D. 43, 52, 66, 104 De Waele, A. 80, 107
Coleman, G.N. 92, 109, 136, 168 Dealy, J.M. 41, 43, 47, 53, 65, 104, 113,
Collins, E.A. 1,44, 103, 110,398,414 130, 132, 135
Collyer, A.A. 9, 43, 44, 52 Den Otter, J.L. 117, 124, 133, 134
Colwell, R.E. 43, 53, 113, 132 Denn, M.M. 73, 97, 106, 109, 142, 171,
Connelly, R.W. 113, 132,222,241 312,337
Conway, B.E. 162, 173 Denson, C.D. 130, 135
Cook, J. 17,45 Derjaguin, B. 247, 308
Cooper, E.R. 8, 37, 44, 47 Deryagin, B.V. 186, 238
Cooper, S.L. 8 Dhimmar, I.H. 41, 49, 243, 273, 277,
Cope, D.E. 41, 49, 243, 273-5, 305, 312, 278,305,312,334,338,391,395,
334,338,391,395,411 411
Copeland, J.R. 30-33, 46, 243, 273, 304, Dibenedetto, A. T. 285, 286, 310
312,333,338,390,395,410 Dillon, R.E. 74, 106, 120, 133
Cotten, G.R. 14,45,226,241,319,337, Dintenfass, L. 136, 167
400,414 Dobry, A. 162, 173
Cox, W.P. 86, 108 Dobry-Duclaux, A. 162, 173
Crabbe, P.G. 113, 131 Donovan, R.c. 194,239
Crabtree, J.D. 36, 46 Doolittle, A.K. 257, 308
458 Author Index
Doraiswamy, D. 88, 90, 108 Fiekhman, V.D. 97, 109

Dougherty, T.J. 151, 153, 173 Fielding, J.H. 118, 133
Dow, J.H. 41, 51, 136, 154, 157, 160, Fikentscher, H. 140,171
168, 173,229,232,236,237,241, Fikham, V.D. 128, 135
243,266,307,312,336,338,349, Filymer, Jr., W.G. 136, 168
357,360,367,369-71,393-5,413 Fink,J\.10,44,262,263,309
Driol, E. 36, 46 Finnigan, JW. 139, 171
Droste, D. H. 285, 286, 310 Fisa, B. 41, 49, 243, 305, 312, 334, 338,
Duffey, H.J. 72, 105 392, 395, 411
Dufresne, A 286,287,310 Fischer, EX 151, 173
Dulik, D. 136, 169 Fiske, T.J. 395, 409
Flory, P.J. 1, 43
Edirisinghe, M.J. 41, 51, 52, 189, 238, Folkes, M.J. 9,41,44,48,243,292,305,
243,266,268,307,310,312,336, 312,334,338,391,395,397,398,
338, 393, 395, 413 410,411,414
Eguiluz, M. 162, 173 Ford, RG. 41, 52
Eilers, H. 141, 171 Ford, T.F. 139, 141, 171
Einstein, A 137, 140, 170, 247, 308 Forger, G. 15, 45
Eise, K. 186, 238 Fox, T.G. 104, 111
Eisenlauer, J. 155, 173 Frados, J. 1, 44
Eisenschitz, R 121, 133 Franked NA 142, 171, 247, 308
Epstein, N. 10, 44, 262, 263, 309 Frechette, F.J. 41, 51, 83, 107, 143, 171,
Erdmenger, R 208, 240 243, 250, 255, 257, 264, 269, 307,
Erenrich, E.H. 136, 168 308,312,316,319,321,336-8,
Erickson, p.w. 35, 37, 38, 46, 47 345-8,353,355,393,395,413
Erwin, L. 196,215,240 Fredrickson, AG. 66, 104
Espesito, R 200, 240 Freestone, ARI. 113, 131
Ester, G.M. 8, 44 French,K.W.41,52
Evans, J.R.G. 41, 51, 52, 189, 238, 243, Friedrich, C. 312, 332
266, 268, 307, 310, 312, 336, 338, Fryling, CF. 162, 173
393, 395, 413 Fujita, H. 257, 308
Evans, RL. 136, 167, 223, 224, 241 Fu-Iung, L. 136, 167
Everage, AE. 131, 135 Fukase, H. 194,239
Eveson, G.F. 264, 309 Fukusawa, Y. 118, 133
Eyring, E.M. 141, 171
Eyring,H. 99, 109, 141, 171,255,308 Galgoci, E.C 41, 52
Garcia, RR 272, 310
Fan, L.T. 179,237 Gatner, F.H. 71, 105
Farooqui, 5.1. 136, 169 Gaskins, F.H. 100, 109, 113, 122, 124,
Farris, RJ. 265, 309 131,134
Faruqui, AA 139, 171 Geisbusch, P. 41, 48, 243, 292, 304, 312,
Faulkner, D.L. 41, 47, 123, 124, 134, 333,338,390,395,410
243, 304, 312, 333, 338, 345, 390, George, H.H. 166, 174,397,414
395,410 German, RM. 41, 52, 266, 268, 310
Fedors, R F. 400, 414 Gerson, Ph.M. 194, 239
Feldman, D. 102, 110, 140, 171 Gibson, J\.G. 98, 109, 131, 135
Fenner, RT. 196,239 Gillespie, T. 151, 173, 264, 309
Ferguson, J. 100, 109, 136, 153, 169 Glasscock, 5.D. 72, 105
Ferraro, CF. 151, 173 Glazman, Yu. M. 136, 168
Ferry, J.D. 41, 47, 99, 109 Goddard, J.D. 165, 166, 174
Author Index 459
Godfrey, J. 200, 240 Hatshek, E. 138, 170

Goel, D.C 41,48, 151, 172,243,305, Hauwink, R 140, 171
312,334,338,391,395,411 Haw, J.R 41, 49, 243, 273, 276, 277,
Goettler, L.A 166, 174, 397, 414 305,312,313, 319, 323, 334, 338,
Gogos, CG. 180, 183-5, 194,237 391, 395, 411
Goldman, A 266, 267, 309 Haward, RN. 100, 109
Goldsmith, H.L. 150, 172 Hayashi, K. 41, 51, 243, 266, 307, 312,
Goodrieh, J.E. 126, 134 336,338,393,395,413
Gordon, J. 17, 45 Heath, D. 136, 155, 169
Goring, D.A. 163, 173 Heertjes, P.M. 136, 169
Govier, G.W. 151, 173 Heneky, H. 401,414
Graessley, W.W. 72, 105 Henderson, CB. 265, 309
Grateh, S. 104, 111 Henderson, D. 141, 171
Greener, J. 113, 132, 222, 241 Herriek, J. 22, 46
Groto, H. 264, 309 Hersehel, W.H. 83, 107,247,308
Gruver, J.L. 104,111 Heywood, N.!. 136, 151, 169
Gunberg, P. F. 226, 241 Higashitani, K. 77, 107
Gupta, RK. 41, 51, 83, 107, 143, 171, Highgate, D.J. 154, 173
243, 250, 255, 257, 264, 268, 269, Hildebrand, J. H. 103,110
307,308,310,312,317,319,321, Hill, CI. 41,47, 145, 172,243,304,
336-8,345-8,353,355,393,395, 312,333,338,390,395,402,409
413 Hill, J.w. 65, 104
Gurland, J. 248, 308 Hinkelmann, B. 41, 49, 50, 243, 305,
Guth, E. 140, 143, 171, 172 306,312,334,335,338,392,395,
411,412
Hagler, G.E. 85, 108 Hlavaeek, B. 74, 106
Hallouche, M. 201, 240 Hlavaeek, V. 262, 263, 309
Hamaker, C 247, 308 Hodgetts, G.B. 113, 131
Han, C.D. 41, 47-51, 91, 108, 115, 124, Hoffman, D.J. 103, 110
132, 134, 243, 273, 276-8, 292, Hofman-Bang, N. 117, 133
304-7,312,313,315,316,319,323, Hold, P. 175, 179, 180, 189, 190, 195,
332-8, 361, 390-2, 394, 395, 398, 215,217,237,238,240
402,403,407,410-4 Holderle, M. 312, 332
Haneoek,M. 41,48, 243, 305,312, 334, Holdsworth, P.J. 103,110
338, 391, 395, 411 Holmes, L. A. 85, 108
Hanks, RW. 136, 168 Honkanen, A 41, 48, 243, 259, 304,
Hanna, RD. 16, 45 312, 333, 338, 390, 395, 398, 410,
Happel, J. 138, 170 414
Harbard, E.H. 140, 171 Hooper, RC 37, 46
Harmsen, G.J. 163, 173 Hope, P.S. 9, 44
Harper, J.C 151, 172 Hopper, J.R 14,45,319,337
Harris, J. 43, 52 Hori, Y. 74, 106
HaITis, S.L. 194,239 Horie, M. 113, 131
Hartlein, RC 29,36,38,46,47 Hornsby, P.R 224, 241
Hartnett, J.P. 84, 107 Howards, AJ. 190,238
Harwood, J.A.c. 38, 47 Howland, C 215, 240
Hashimoto, AG. 136, 169 Hsieh, H.P. 149, 172
Hashin, Z. 147, 172 Hu, R 84, 107
Hassager, O. 55, 59, 60, 67, 79, 83-5, Huang, CR 115, 124, 132
104, 105, 107, 108 Hudson, N.E. 136, 153, 169
460 Author Index
Huget, E.F. 113, 132, 136, 169 Kambe, H. 138, 170

Hugill, H.R 266, 267, 309 Kanno, T. 152, 173
Hunt, KN 41, 51, 223, 224, 241, 243, Kasajima, M. 103, 110
266, 307, 312, 336, 338, 393, 395, Kataoka, T. 41,48-50, 115, 132, 142,
413 143, 171,223,241,243,246,248,
Huppier, J.D. 85, 108 249,255,257,304-6,308,312,
Hutton, J.F. 41, 43, 47, 52, 67, 79, 105 333-5,338,346,390-2,395,
Hylton D.C 130, 135 410-2
Katz, HS. 10, 44
Ide, Y. 130, 135,396,403,414 Kawasaki, H. 41,49,243,273, 305, 312,
Immergut, E.H. I, 44 334,338,391,395,411
Insarova, N.l. 165, 174 Kearsley, E. 72, 85, 106
Irving, H.F. 198, 240 Kendall, K 190,238
Ishida, N. 118, 133 Khadilkar, CS. 41, 51, 136, 154, 157,
Ishigure, Y.41, 51, 243, 266, 307, 312, 168,173,232,236,237,241,243,
336,338,393,395,413 266,307,312,336,338,393,395,
Itadani, K 41, 49, 243, 273, 305, 312, 413
334,338,391,395,411 Killman, E. 155, 173
Ito, K 103, 110 Kim, D.H. 243, 303
Kim, KU. 115, 124, 132
Jacobsen, P.H. 113, BI, 136, 169 Kim, K.Y. 43, 53, 113, 132
Jakopin,S. 186, 193, 196,202,227,238 Kim, WS. 208, 240
James, AE. 81 44, 136, 169 Kim, Y.W. 395,398,402,403,414
Janacek,J.286,310 King, KD. 136, 168
Janeschitz-Kriegl, H 41, 47, 117, 124, King, RG. 115, 132
133,134 Kirkwood, RB. 136, 167
Janssen, L.P.B.M. 74, 106,202,214,240 Kishimoto, J. 257, 308
Jarzebski, G.J. 247, 250, 308 Kitano, T. 41, 48-50, 115, 132,
Jastrzebski, Z. 151, 172 142, 143, In, 223, 241, 243, 246,
Jeffrey, D.J. 136, 170 248,249,255,257,304-6,308,312,
Jeffrey, J.B. 143, 172 333-5,338,346,390-2,395,
Jepson, CH. 175, 196, 237 410-2
Jerdrzejczyk, H. 136, 167 Kitchner, J.A. 156, 173
Jewmenow, S.D. 208,240 Kizior, T.E. 165, 174
Jinescu, V.V. 103, 110, 136, 170 Klein, 1. 194, 196,238
Johnson, AF. 396, 397, 414 Knappe, W. 121, 134
Johnson, CF. 41,51 Knudsen, J.G. 139, 171
Johnson, J.F. 100,101,104,109,111 Knutsson, B.A. 41, 49, 243, 292, 305,
Johnson, RO. 41, 50, 279, 292, 310 312,313,315,331,334,338, 391,
Jung, A 103, 110 395,411
Juskey, V.P. 41,49,243,273,305,312, Kohan, M.l. 292, 311
334,338,392,395,411 Kolarik, J. 286, 310
Kondo, A 124, 134
Kaghan, W.S. 100, 110 Kondu, AJ. 76, 107
Kaloni, P.N. 67, 79, 105 Koran, A 136, 168
Kalousek, G.L. 113, 131, 136, 168 Kom, M. 155, 173
Kalyon, D.M. 189, 193, 201, 238, 240, Kosinski, L.E. 113,132,222,241
338,357,390,394,395,409 Kossen, N.W.F. 136, 168
Kamal, M.R41, 50, 243, 307, 312, 336, Kraus, G. 18,45,104,111
338,393,395,413 Kremesec, V.J. 153, 173
Author Index 461
Krieger, I'M. 151, 153, 162, 173, 262, Litovitz, T.A. 103, 110
264,309 Lobe, V.M. 41, 48, 115, 132, 243, 246,
Krotova, N.A 186, 238 304,312,313,317,333,338,390,
Krurnbock,E. 121,134 395,402,410
Kruyt, H.R 140, 171 Lockett, F.J. 396, 397, 414
Kubat, J. 397, 414 Lodge, AS. 43, 52, 66, 72, 77, 104, 107
Kurnins, CA 38, 47 Loh, J. 136, 168
Kunio, T. 194, 239 Loppe, J.P.A. 41, 49, 143, 172, 243, 305,
Kuno, H. 264, 309 312, 334, 338, 391, 395, 411
Kurgaev, E.F. 138, 170 Lornsten, J.M. 98, 109, 130, 135
Kwei, T.K. 38, 47 Loshach,S. 104,111
Luebbers, RH. 148, 172
Lacey, P.M.C 179, 180, 237 Luo, H.L. 41, 50, 243, 273, 306, 312,
Lakdawala, K 282, 310 335,338,361,392,395,412
Larnb, P. 74, 75, 106 Lyons, J.W., 43, 53, 113, 132
Larnoreaux, R H. 103, 110
Lande!, RF. 14,45,99, 109, 153, 173, Macdonald, I.F. 85, 108
400,414 Macedo, P.. 103, 110
Laskaris, A 22, 46 MacGarry, F.J. 37, 46
Lau, H.C 121 Mack, W.A. 189, 193,238
Laude, RF. 36, 46 Macosko, CW. 130, 135
Lee, B.L. 115, 118, 132 Maddock, B.H. 194,239
Lee, D.1. 264, 265, 309 Maheshri, J.C 208, 240
Lee. KJ. 243, 303 Maine, F.W. 16,45
Lee, M.CH. 236, 241 Malkin, AY. 14,41,45,47, 117, 133,
Lee, T.5. 41, 47, 115, 132, 151, 172, 243, 243,307,312,319,337,338,394,
246,303,312,332,338,390,395, 395,413
407,409 Mallouk, RS. 196, 239
Lee, W.K 98, 109, 166, 174,397,414 Mangels, J.A. 41, 51, 52, 266, 267, 309
Lee, W.M. 41, 49, 243, 273, 305, 312, Manley, RSt.J. 140, 171
334,338,391,395,411 Mannei!, W.R 136, 168
Lefebvre,J. 136, 168 Mark,H. 140, 171
Leitlands, V.V. 130, 135 Markovitz, H. 43, 52, 66, 92, 104, 109
Lern, K.w. -41, 49, 243, 306, 312, 335, Maron, S.H. 255, 308
338,392,395,412 Marrucci, G. 67, 79, 97, 105, 109, 142,
Lenk, RS. 41, 47 171,395,414
Lens, W. 140, 171 Marsden, J.G. 35, 36, 46
Leonard, M.H. 14,45 Martelli, F. 204, 240
Leonov, AI. 121, 134 Maschrneyer, RO. 145, 172
Lerner, I. 37,46 Mason, S.G. 140, 146, 150, In, 172
Lewellyn, M.M. 136, 168 Masuda, T. 86, 108
Lewis, H.D. 266, 267, 309 Matijevic, E. 262, 308
Liaw, T.F. 41, 49, 243, 273, 305, 312, Matsurnoto, S. 149, 172
334,338,391,395,411 Matthews, G. 175, 237
Lightfoot, E.N. 136, 168 Maxwell, B. 103, 110, 118, 133
Lin, Y.H. 121, 134 McCabe, CC 14,45
Linnert, E. 41, 49, 243, 273-5, 305, 312, McGeary, RK 139, 171
334, 338, 391, 395, 411 McGrath, J.E. 8, 44
Lipatov, Yu. S. 286, 310 McHale, E.T. 265, 309
Lippe, RJ. 113, 131 McIntire, L.V. 120, 133
462 Author Index
McKeIvey, J.M. 180,194,196,237, Mount III, E.M. 194,239

239 Muchmore, CB. 136, 168
Mead, VV. T.398,414 MuelIer, N. 14,45
Meares, P. I, 43 Mujumdar, A.N. 88, 90, 108
MedaIia, A.I. 14,45,319,337 Mullins, L. 14,38,45,47, 140, 171
Meissner, J. 55, 96, 100, 104, 109, 113, Munro, J.M. 136, 168
115, 128, 130, 132, 135 Munstedt, H. 117, 130, 133, 135
Meister, B.J. 91, 108 Murase, I. 41, 51, 243, 266, 307, 312,
Mendeison, R.A. 100,109 336,338,393,395,413
Menges, G. 41, 48, 243, 292, 304, 312, Murty, K.N. 397, 414
333,338,390,395,410 Mute!, A.T. 41, 50, 243, 307, 312, 336,
Mennig, G. 41, 50, 121, 133, 243, 306, 338,393,395,413
312,335,338,392,395,412 Mutsuddy, B.C 41, 50, 52, 243, 266,
Mertz, E.H. 86, 108 306,312,335,338,392,395,412
Metz, B. 136, 168
Metzner, A.B. 71, 79, 88, 90, 98, lOS, Nadim, A. 136, 170
107-9,136,165,170,174,332, Nadkami, V.M. 11, 12, 41, 44, 50, 236,
337 237, 241, 243, 251, 252, 266, 273,
Mewis, J. 136, 165, 170, 174, 332, 337 276-8,284,287,290,292,299,306,
Middieman, S. 41, 47, 67, 79, 103, lOS, 307,310-2,330,335,336,338,384,
110,196,239 392-5,412
Mijovic, J.41, 50, 243, 273, 306, 312, Nagatsuka, Y. 41, 50, 243, 306, 312,
335,338,361,392,395,412 335,338,392,395,412
Milewski, J.V. 10,44,268,310 Nagaya, K. 41, 51, 243, 266, 307, 312,
Millman, R.S. 17, 45 336,338,393,395,413
Mills, N.J. 41, 47, 117, 133, 243, 246, Nakajima, N. 72, lOS, 398, 414
303,312,332,338,345,390,395, Nakatsuka, T. 41, 49, 243, 273, 305,
409 312,334,338,391,395,411
Minagawa, N. 41, 47, 115, 132, 243, Napper, D.H. 154, 156, 173
246,277,304,312,315,317,319, Nazem, F. 41, 47, 243, 304, 312, 333,
333,338,390,395,410 338,390,395,402,409
Minoshima, VV. 86, 108, 316, 337 Nevin, A. 117, 133
Missavage, R.J. 136, 168 Newman, S. 123, 124, 134, 243, 307,
Mistry, D.B. 160, 173 312, 336, 338, 394, 395, 397, 413,
Mitsumatsu, F. 41, 51, 243, 266, 307, 414
312,336,338,393,395,413 Newnham, R.E. 41, 52
Mizoguchi, M. 194, 239 Nguyen, Q.D. 136, 170
ModIen, G.F. 397, 414 NichoIs, R. 213, 215, 240
Mohr, VV.D. 175, 181, 183, 196, 237 Nicoderno, L. 153, 166, 167, 173, 174,
Mokube, V. 264, 309 395,397,414
Molau, G.E. 8, 44 Nicoiais, L. 36, 46, 153, 166, 167, 173,
Monte, S.J. 41, 48, 243, 273, 275-8, 292, 174,286,310,395,397,414
304,310,312,333,338,390,395, Nieisen, L.E. 14,41, 45, 47, 51, 137,
410 147, 170, 172, 243, 257, 269, 307,
Mooney, M. 118, 133, 141, 149, 171 308, 312, 336, 338, 393-5, 413
Morawetz, H. 1,44 NikoIayeva, N.E. 14,45, 117, 133, 319,
Moreland, C 148, ISO, 172 337
Morgan, R.}. 158, 173 Nishijima, K. 41, 48, 115, 132, 142, 143,
Morley, }.G. 17,45 171,243,246,304,312,333,338,
Morrison, S.R. 151, 172 390, 395, 410
Author Index 463
Nishimura, T. 41, 48, 243, 246, 248, Pinder KL. 113, 131
249,255,257,304,308,312,333, Pinto, G. 196,240
338,346,390,391,395,410 Pipkin, A.C 97, 109
Nissan, A.H. 71, 105 Pisipati, R 331, 337
Nitanda, HAI, 51, 243, 307, 312, 336, Platzer, N.A.J. 8, 44
338, 393, 395, 413 Plotnikova, E.P. 14,45,117,133,319,
Noll, W. 43, 52, 66, 67, 79, 104 337
Nomura, A 194,239 Plueddemann, E.P. 35, 36, 38, 46, 47,
Noshay, A 8, 44 273, 277, 279, 310
Pokrovskii, V.N. 138, 143, 170, 172
Oda, K 86, 108, 316, 337 Pollett, W.F.O 115, 132
~ama, T. 103, 110 Porter, RS. 100,101,103,104,109-11,
Okubo, S. 74, 106 126,134,299,311,398,414
Onogi, S. 86, 108 Poslinski, AJ. 41,51,83, 107, 143, 171,
Opsahl, D.G. 136, 167 243, 250, 255, 257, 264, 269, 307,
Orenski, P.l. 35, 46 308,312,317,319,321,336-8,
Ostwald, W. 80, 107 345-8,353,355,393,395,413
Oswald, G.E. 136, 168 Powell, RL. 41, 50, 243, 306, 312, 335,
Otabe, S. 41, 51, 243, 266, 307, 312, 336, 338, 393, 395, 412
338,393,395,413 Powers, J.M. 136, 169
Ouchiyama,N.268,310 Pritchard, J.H. 299, 311
()verbeek,J. 163,173 Prokunin, AN. 130, 135
Oyanagi, Y. 41, 48, 75, 106, 163, 166,
173,243,248,249,255,292,304, Rabinowitsch, B. 121, 133
312, 315, 333, 338, 390, 391, 395, Radushkevich, B.V. 97, 109, 128, 135
405,410 Raible, T. 130, 135
Rajaiah, J. 247, 308
Padget, J.C 292, 311 Rajora, P. 74, 106
Palmgren, H. 183, 238 Ramamurthy, AV. 121, 134
Pao, Y.-H. 91, 108 Ramney, M.W. 35, 46
Papkov,S. 140,171 Rauwendaal, CI. 189,200,202,214,
Parish, M.V. 272, 310 238,240
Park, CS. 243, 303 Reddy, KR 73, 106
Park, H.J. 243, 303 Reiner, M. 54, 80, 104, 138, 141, 170,
Parkinson, C 149, 172 401,414
Patel, RD. 41, 49, 243, 273, 277, 278, Revankar, V.v.S. 262,263,309
305,312,334,338,391,395,411 Rhi-Sausi, J. 130, 135
Paul, D.R 75, 106, 243, 307, 312, 336, Richardson, CJ. 98, 109
338,394,395,413 Richardson, J.F. 136, 151, 169
Payne, AR 38, 47 Richardson, P.CA 113, 131, 136, 169
Pearson, J.RA. 43, 52,72,106,200,240 Rideal, G.R 292,311
Penwell, RC 103, 110 Rieger, J.M. 166, 174
Petrie, CJS. 43, 52, 65, 73, 104, 106, Riseborough, B. E. 16,45
130,135 Rodriguez, F. 41, 50, 243, 306, 312, 335,
Pett, RA 266, 268, 309 338,392,395,412
Peyser, P. 286, 310 Roff, W.J. 1, 44
Philippoff, W. 100, 109, 113, 122, 124, Rogers, B.A 136, 168
131, 134 Rogers, M.G. 126, 134
Pickthall, D. 36, 46 Romanov, A 384, 394
Pierce, P.E. 255, 308 Rosen, M.R 67, 79, 105
464 Author Index
Rosevear, J. 41, 49, 243, 305, 312, 334, Scheffe, RS. 265, 309
338,391,395,411 Scheiffele, G.W. 41, 51, 136, 154, 157,
Roteman, J. 38,47 168, 232, 236, 237, 241, 243, 266,
Rubio, J. 156, 173 307,312,336,338,393,395,413
Ruckenstein, E. 74, 106 Schenkel, G. 207, 240
Rudd, J.F. 100, 110 Schmidt, L.R 41, 47, 123, 124, 134, 243,
Rudraiah, N. 67, 79, 105 304,312,333,338,345,390,395,
Rumpf, H. 272, 310 410
Runt, J.P. 41, 52 Schmitz, AO. 125, 134
Rush, O.w. 30-33, 46, 243, 273, 304, Schooten, JV 163, 173
312,333,338,390,395,410 Schott, H. 100, 110, 120, 133
Russel, W.B. 136, 170 Schowalter, W.R 43, 52, 67, 79, 105,
Russell, RJ. 71, 105 121, 134
Rutgers, LR 138, 170 Schrader, M.E. 37, 46
Ryan, M.E. 41, 51, 83, 107, 143, 171, Schramm, G. 67, 105, 113, 132
243,250,255,257,264,269,307, Schreiber, H.P. 72, 74, 105, 106
308,312,317, 319, 321, 336-8, Schubert, H. 272, 310
345-8,353,355,393,395,413 Schultz, J.M. I, 43
Schurtz, J.F. 41, 52
Saarnak,J\. 136, 169 Schwartz, H.5. 20, 45
Sabia, R 100, 110 Schwartz, RT. 20,45
Sabsai, O.Yu 14.45,117,133,319,337 Scott, J.R 1,44
Sacks, M.D. 41, 51, 136, 154, 157, 158, Scott Blair, G.W. 43, 52
168, 173,229,232,236,237,241, Sebastian, D.H. 194, 239
243,266,307,312,336,338,349, Segre,G. 150, 172
357,370,371,393,395,413 SeIlers, J.w. 18,45
Saechtling, H. I, 44 Sergeeva, L. M.286,310
Saini, D.R 11, 12, 41, 44, 47, 50, 82, 87, Seshadri, S.G. 41, 51, 83, 107, 143, 171,
90,92,93,100-2,108-10,115,126, 243,250,255,257,264,268,269,
132,134,236,237,241-3,251,252, 307, 308, 310, 312, 317, 319, 321,
257,258,266,273,276-8,284,287, 336-8,345-8,353,355,393,395,
290, 292, 300, 301, 306-8, 310-2, 413
330,335,336,338,340-3,372,373, Severs, E.T. 41,47, 141, 171
375,381,383-5,392-5,412,413 Seyer, F.J\. 165, 174
Saito, N. 140, 171 Shaheen, E.L 148, 172
Sakai, T. 41, 48, 243, 248, 249, 255, 257, Sharrna, Y.N. 41,49,243,273, 277, 278,
304,308,312,333,338,346,391, 305,312,334,338,391,395,411
395,410 Shaw, H.M. 41, 51, 243, 266, 307, 312,
Sakamoto, K. 118, 133 336,338,393,395,413
Salovey, R 282,310 Shenoy, AV. 11, 12,41,44,47,50, 51,
Sanchez, LC. 103, 110 81,82,86,87,90,92,93,100-2,
Sandford, C. 41, 48, 243, 273, 276-8, 107-10,115,126, 132, 134, 136,
292, 304, 312, 315, 333, 338, 390, 154, 157, 168, 229, 232, 236, 237,
395, 407, 410 241-3,251,252,257, 258, 266, 273,
Sarrniento, G. 113, 131 276-8, 284, 287, 290, 292, 299,
Sasahara, M. 41, 48, 115, 132, 142, 143, 300-2,306-8,310-2,330,335-8,
171,243,246,248,249,255,304, 340-3,349,357,370-3, 375, 381,
312,333,338,390,391,395,410 383-5,392-5,412,413
Saxton, RL. 175, 196, 198,237,240 Shenoy, U.V. 81, 82, 86, 87, 107, 301,
Schaart, B. 214, 240 302,311
Author Index 465
Sherman, P: 136, 149, 168, 172 Swanborough, A 189,190, 193,238

Shete, P. 41, 49, 243, 273, 276, 277, 305, Sweeny, K.H. 265, 269, 309
312,313,319,323,334,338,391, Szalanczi, A. 397, 414
395,411 Szczesniak, AS. 136, 168
Sheu, RS. 41, 51, 136, 154, 157, 168,
232, 236, 237, 241, 243, 266, 307, Tadmor, Z. 59, 104, 180, 183-5, 194,
312, 336, 338, 393, 395, 413 196,217,237-40
Shida, M. 72, 105 Tadros, Th.F. 136, 154--6, 169, 173
Shinya,S.194,239 Tager, A. 1, 43
Shirata, T. 41, 49, 142, 143, 171,243, Takahashi, M. 41, 51, 86, 108, 243, 307,
305,312,334,338,391,395,411 312,336,338,393,395,413
Silberberg, A 150, 172 Takano,M. 166, 174
Simha, R 138-41, 147, 170-2 Takserman-Krozer, R 166, 174
Simon, RH.M. 100, 110 Tammela, V. 41, 48, 243, 259, 304, 312,
Siskovic, N. 115, 124, 132 333,338,390,395,398,410,414
Skatschkow, W.w. 208, 240 Tan, CG. 10, 44, 262, 263, 309
Skelland, A.H.P. 67, 79, 105 Tanaka, H. 41, 48, 49, 243, 244, 246,
Slattery, J.C 153, 173 247, 248, 268, 292, 305, 308, 310,
Smilga, V.P. 186, 238 312,313,315,317,323,334,337,
Smith, J.H. 136, 167 338,344,391,395,396,400,403,
Smits, CT. 136, 169 404,407,411,414
Smoluchowsky,M. 163, 173 Tanford, C. 1, 43
Snyder, J.w. 14,45 Tanner, RI. 43, 52, 67, 72, 73, 79, 97,
Sobajima, A 41, 51, 243, 266, 307, 312, 104, 105, 106, 109
336,338,393,395,413 Taylor, R 118, 133
Somcynsky, T. 138, 139, 171 Taylor, N.H. 292, 311
Soni P.L. 103, 110 Teutsch, E.O. 41, 50, 279, 292, 310
Soppet, F.E. 266-8, 309 Theberge, J. E. 16, 45
Southern, J.H. 75, 103, 106, 110 Thiele, J. L. 400,414
Spencer, RS. 74, 106, 120, 133 Thomas, D.G. 138-42, 170
Spriggs, T.W. 91, 92, 97, 108, 109 Thomson, J.B. 16, 45
Spruiell, J.E. 86, 103, 108, 111, 316, 337 Thurgood, J.R 136, 168
Stade, K. 189,201,238 Thurston, G.B. 136, 167
Stamhuis, J.E. 41, 49, 143, 172,243, Ting, AP. 148, 172
305,312,334,338,391,395,411 Tiu, C. 81, 107
Steingiser, S. 104,111 Tobolsky, AV. 8, 44, 117, 133
Stephenson, S.E. 130, 135 Todd, D.B. 189, 208, 228, 238, 240
Sterman, S. 35, 46 Tolstukhina, PS. 14,41,45
Stevenson, J.P. 128, 135 Tomkins, K.L. 41, 51, 243, 266, 307,
Stober, W. 10,44,262,263,309 312,336,338,393,395,413
Stover, B.J. 141, 171 Tordella, J.P. 73, 75, 106, 120, 133
Studebarker,M. L. 14,45 Travers, A. 22, 46
Suetsugu, Y. 41, 50, 243, 246, 273, 306, Trela, W. 41, 52, 266, 267, 309
312,335,338,392,395,412 Tremayne, P. 41, 49, 243, 305, 312, 334,
Sugerman, G.T. 41,48,243,273,275-8, 338, 391, 395, 411
292, 304, 310, 312, 333, 338, 390, Trementozzi, Q.A. 123, 124, 134, 397,
395,410 414
Sund strom, D.M. 194,239 Trottnow, R 72, 106
Suzuki,S. 41, 51,243,307,312,336, Trouton, P.T. 93, 109
338, 393, 395, 413 Truesdell, C 66, 67, 79, 104
466 Author Index
Tsao,I. 88,90, 108 Warren, RC 113, 132, 136, 169

Tsutsui, M. 103, 110 Wasiak, A 103, 110
TuR, P. 113, 131 Waston, W.F. 18,45
Turcotte, G. 136, 168 Watson, CA 179,237
Turetsky, S. B. 226, 241 Watson III, J.G. 194,239
Turnbull, O. 103, 110 Weidenbaum, S5. 180,237
Tusim, M.H. 194,239 Weill, A 74, 106
Weinberger, CB. 165, 174
Uebler, E.A. 79, 107 Weiss, Y. 8,44
Uhland, E. 74, 106, 121, 133 Weissenberg, K. 71, 105, 115, 121, 132,
Uhlherr, P.H.T. 81, 107, 113, 131 133
Umeya, K. 152, 173 Werner, H. 208,240
Usagi, R 82, 107 Westman, AE.R 266, 267, 309
Utracki, L.A 41, 43, 49, 52, 103, 110, Westover, RF. 299, 311
136,170,243,305,312,334,338, Whalen, T.J. 266, 268, 309
392,395,411 Whelan, J.P. 41, 51, 292, 299, 311
White, J.L. 14,41,45,47-50, 75, 76, 85,
Van Buskirk, P. R 226,241 86,103, 106-8, 111, 115, 118, 120,
VanderWeghe, T. 41, 49, 243, 273, 276, 124,130,132-5,163,166,173,243,
277,305,312,313,319,323,334, 244,246-8,273,277,292,304-6,
338, 391, 395, 411 308,312,313,315-7,319,323,331,
Van Ooren, RE. 136, 168 333-5,337,338,344,390-2,395,
Van Suijdam, J.C 136, 168 396,400-5,407,410-2,414
Van Wazer, J.R 43, 53, 113, 132 Whiting, R 113, 131, 136, 169
Vand, V. 140, 171 Whitmore, RL. 148, 150, 172,264,309
Veal, CJ. 136, 168 Whittaker, RE. 38, 47
Vermeulen, J.R 194,239 Whorlow, RW. 43, 53, 113, 132, 154,
Vermilyea, S.G. 113, 132, 136, 169 173
Verreet, G. 136, 169 Wigotsky, V. 200, 240
Vervoom, P.M.M. 136, 169 Wildemuth, CR 143, 172
Vinogradov, G.Y. 14,41,45,47,97, Wilkinson, W.L. 67, 79, 104
109, 117, 128, 133, 135, 243, 307, Willard, H. 136, 167
312,319,337,338,394,395,413 Willermet, P.A. 266, 268, 309
Virbsom, L. 217, 240 Williams, O.J.A. 136, 169
Vlachopoulos,J.194,239 Williams, M.C. 136, 143, 168, 172
Volpe, AA 37, 47 Williams, M.L. 99, 109
Von Mises, R 401,414 Williams, RM. 41, 52, 266, 267, 309
Willmouth, F.M. 103, 110
Wagner, AH. 395, 409 Winning, M.O. 151, 173
Wagner, M.H. 84,85, 108,343,394 Winter, H.H. 131, 135
Wagnes, M.P. 18,45 Wissbrun, K.F. 41,47,98, 109, 299, 311
Wales, J.L.S. 117, 121, 124, 133, 134 Withers, V.R 136, 168
Walk, C 215, 240 Wolf, RF. 18,45
Walker, J. 66, 104 Wong, W.M. 41,49,243,273,306, 312,
Wall, O.R 136, 168 335,338,360,361,387,388,392,
Walters, K. 41, 43, 47, 52, 53, 67, 71, 394,395,412
79,84, 105, 107, 113, 116-8, 132 Wood, R 189,238
Wang, RH. 179,237 Woodthorpe, J. 41, 51, 223, 224, 241,
Warburton, B. 160, 173 243,266,307,312,336,338,393,
Ward, S.G. 148, 150, 172,264,309 395,413
Author Index 467
Wright, B. 100, 109 Young, CC 194, 239

Wright, CH. 139, 171 Youngblood, E.L. 136, 168
Wu, S. 41, 48, 243, 292, 304, 312, 333,
338,391,395,410 Zahorski, S. 43, 52
Wyman, CE. 208, 240 Zaikov, G.E. 41, 51, 243, 308, 312, 337,
338,394,395,414
Yarnada,~.299,311 Zakharenko, N.V. 14,41,45,285,
Yarnashita, S. 41,49,243,273,305,312, 310
334,338,391,395,411 Zapas, L. 72, 85, 106
Yanovsky, YU.G. 41, 51, 243, 308, 312, Zhao, G.y. 262,263,309
337,338,394,395,414 Ziabicki, A. 103, 110, 166, 174
Yao, J. 215, 240 Ziegel, K.D. 147, 172,384,394
Yazici, R. 395,409 Ziernanski, L.P. 35, 46
Yoo, H.J. 41, 48, 243, 273, 276-8, 292, Zingel, U. 41, 48, 243, 292, 304, 312,
304,312,315,333,338,390,395, 333, 338, 390, 395, 410
407,410 Zisrnan, W.A. 19,45
Subject Index
Activation energy 100-2 polystyrene 245, 295, 314, 324, 397,

Alumina filled 407-9
polyethylene 349-51, 353, 358-9, Carbon black filled
362-8,370-3,388-9 polyethylene 287
Amorphous polymer polystyrene 245, 260, 283, 295, 314,
definition 5 316,397,401,404-6
Antistatic agent 23 Carbon fiber filled
Aramid fiber filled polyethylene 249
polystyrene 245, 314 Cauchy stress tensor 57
Arrenhius-Eyring equation 99 Cellulose fiber filled
Azidosilanes 26, 28 polystyrene 245, 314
Central tube effect 150
Bagley correction 121-3 Characteristic time 54
Barium sulfate filled Chemical bonding theory 37
polyethylene 274 Chemical additives 160
Barium ferrite filled Chlorinated paraffins 28
polyester elastomer 253 Chrome complexes 25
polyethylene 253, 286, 374, 377-9, 381 Commodity plastics 6
polyurethane thermoplastic Complex viscosity 60
elastomer 253 Complex modulus 61
styrene-isoprene-styrene block Compounding
copolymer 254, 277, 286, 374, definition 175
377-9,381,384,385,387 process tasks 188
Batch mixers 189-92 techniques 175
Biaxial variables 221-37
extension 64 chamber loadings 231
extensional viscosity 65 mixer type 223-4
Blending mixing temperature 232--6
definition 175 mixing time 225-8
Block copolymer 7 order of ingredient addition
Branched polymer 3 236-7
ram pressure 229-31
Calcium carbonate filled rotor geometry 224-5
polyethylene 249-50, 274, 293 rotor speed 229
polypropylene 249, 259, 274, 276, Constitutive equation 57
282,294,319,325-6,328 Constrained recoil 62
470 Subject Index
Contact angle 19, 20 Effect of fiBer size distribution

Continuous compounders steady shear
192-218 elastic 321
Copolymer viscous 262-71
definition 7 unsteady shear
Coupling agent viscoelastic 350-6
characteristics 29 Effect of fiBer surface treatment
mechanism 35 extensional 405-9
Cox-Mertz method or rule steady shear
86-9 elastic 323-9
Creep compliance 62 viscous 273-9
Creep 61 unsteady shear
CrystaBine polymer viscoelastic 360-72
definition 5 Effect of fiBer type
extensional 396-400
Deborah number steady shear
definition 54 elastic 313-5
Deformable layer theory 37 viscous 244-6
Dilatant behavior 152 unsteady shear
Dispersive mixing 184 viscoelastic 344
Distributive mixing 183 Effect of matrix additives
Dolomite fiBed unsteady shear
polyethylene 262 viscoelastic 387-9
Draw resonance 73 Effect of polymer matrix
Dump criteria 218-21 steady shear
Dynamic elastic 330-2
loss modulus 60 viscous 279-87
storage modulus 60 unsteady shear
viscosity 60 viscoelastic 372-87
Einstein equation 138
Effect of fiBer agglomerates Elastic solid
steady shear description 39, 54
elastic 321-3 Elastic energy 122
viscous 272-3 Elastomers
unsteady shear definition 2
viscoelastic 35fr60 examples 2, 6
Effect of fiBer concentration Electroviscous effect 163
extensional 402-5 EBipsoidal particles 143
steady shear Engineering thermoplastics
elastic 317-21 examples 7
viscous 248-62 Entry flow 75
unsteady shear Extension
viscoelastic 345-9 biaxial64
Effect of fiBer size planar 65
extensional 400-2 uniaxial62
steady shear Extensional viscometer
elastic 315-7 extrusion method 130-1
viscous 246-8 filament stretching 128-130
unsteady shear Extensional viscosity
viscoelastic 344-5 biaxial65
Subject Index 471
planar 65 Glass bead/ sphere filled

uniaxial65 polypropylene 123, 327, 340
Extensional rate polystyrene 245, 314
biaxial64 Glass transition temperature
planar 65 definition 5
uniaxial63 Glass bead/sphere filled
Extensional flow 55, 62, 65,164 polybutene 256, 270-1, 318, 322,
Extra stress tensor 57 347-8,355-6
Extrudate swell 71 styrene acrylonitrile 123-4
thermoplastic polymer 251-2, 256,
Filled polymer 318,347-8
definition 11, 13 Glass fiber filled
examples 13 nylon 280, 296, 330
Filled polymer rheology polycarbonate 261, 281, 298, 331
definition 54 polyether ether ketone 300
Filler polyetherimide 281, 299
cost-effectiveness 15 polyethylene 249, 408
definition 9 polyethylene terephthalate 261, 280,
ellipsoidal 10, 11 297
fibrous 10, 11 polypropylene 187, 249, 329
flexible 10 polystyrene 245, 295, 314, 317, 322
geometry 19 Graft copolymer 7
inorganic 11
organic 11 Homopolymers 6
platelike 10, 11 Hooke's law in shear 122
rigid 10
selection 13 Intensity of segregation 181
spherical 10, 11 Interface
surface 19 definition 16
surface treatment 21 Interfacial
types 10-12 energy 20
Filler-polymer interactions 16, 17 region 16
Finishes 22 Internal mixers 190-2
Flocculation 151 Interphase
Flow curve definition 16
ideal unfilled 40
filled 42 Liquid crystalline polymer 9
Flow Loss tangent 60
curve 40, 42 Lubricant 23
entry 75
extensional 55, 62 Matrix additives
shear 55 examples 43
Fluids Melt flow index 127
Newtonian 66, 67,77,78 Melt flow indexer 126-8
non-Newtonian 66-8, 77, 78 Melt fracture 73-5
pseudoplastic 67, 68 Melting temperature
thixotropie 67, 68, 70 definition 5
viscoelastic 67-9, 77, 78 Mica filled
Franklin fiber filled polyethylene 263
polystyrene 245, 314 polypropylene 275, 294
472 Subject Index
Mica filled (contd) Plasticizer 23

polystyrene 245, 314 Plate separation 77
Mixing Poly (vinyl chloride)
definition 175 fine partic1es filled 103
goodness 175 Polybutene
index 179-80 glass bead/sphere filled 256,270-1,
mechanisms 183 318,322,347-8,355-6
temperature 232~ Polycarbonate
Mixing glass fiber filled 261, 281, 298, 331
devices in single-screw systems Polyester elastomer
198 barium fernte filled 254, 286, 374,
dispersive 184 377-9,381
distributive 183 unfilled 285, 380
pins 198 Polyether ether ketone
seetions 199 glass fiber filled 300
time 225-8 Polyetherimide
variables 221-37 glass fiber filled 281, 299
Modulus Polyethylene
complex 61 alumina filled 349-51, 353, 358-9,
dynamic loss 60 362-8,370-3,388-9
dynamic storage 60 barium ferrite filled.253, 286, 374,
Molecular weight 377-9,381
description 39 barium sulfate filled 274, 286
distribution 39 calcium carbonate filled 249-50, 274,
293,359~0
Network polymer 3, 4 carbon black filled 287
Newtonian fluids carbon fiber filled 249
behavior 77, 78 dolomite filled 262
description 66 glass fiber filled 249, 408
generalized 67 mica filled 263
Non-Newtonian fluids quartz filled 258, 293
behavior 77, 78 silica filled 359~0
description 66, 67 silicon filled 89
Normal stress steel sphere filled 340-2, 353
components 58 talc filled 262
difference titanium dioxide filled 320
cone and plate 117 unfilled 285, 293, 380
definition 59 zirconia filled 354
parallel-disk 118 Polyethylene terephthalate
Nylon glass fiber filled 261, 280, 296
glass fiber filled 280, 296, 330 Polymerie esters 27, 28
Polymerization
Open milIs 189-90 addition 1
condensation 1
Packing of filler 139 Polypropylene
Partic1e size distribution 147 calcium carbonate filled 249, 259,
Partic1e surface effect 150 274,276,282,294,319,325~,
Planar 328
extension 65 glass bead/sphere filled 123,327,
extensional viscosity 65 346
Subject Index 473
glass fiber filled 187,249,294,329 power-Iaw 80

mica filled 275, 294 steady shear viscosity 79-84
talc filled 249, 294 Rheology
unfilled 294 definition 39
Polystyrene Rheometer (see also Viscometer)
aramid fiber filled 245, 314 capillary type 113, 114, 118-28
calcium carbonate filled 245, 295, definition 112
314,324,397,407-9 rotational-type 113-8
carbon black filled 245, 260, 283, types 114
295,314,316,397,401,404-6 Rheometry
cellulose fiber filled 245, 314 definition 12
Franklin fiber filled 245, 314 Rod-shaped particles 144
glass bead filled 245, 314 Rotational viscometer 113
glass fiber filled 245, 295, 314, 317,
332 Scale of segregation 181
mica filled 245, 314 Scale of scrutiny 183
titanium dioxide filled 245, 260, 295, Segregation
314,316,320,397,401,406 intensity 181
unfilled 403 scale 181
Polyurethane thermoplastic elastomer Self-cleaning time 228
barium ferrite filled 253 Semi-crystalline polymer
Pressure hole error 77 definition 5
Purely elastic solid Shear flow
definition 54 extensional 55
Purely viscous liquid steady simple 55
definition 54 unsteady simple 55, 59
Shear stress
Quartz filled capillary 124
polyethylene 258, 293 components 58
Shear rate
Rabinowitsch-Weissenberg correction capillary 124
121 cone and plate 116
Random copolymer 7 definition 56
Residence time 227-8 Silanes 25-7
Resitols 4 Silica filled
Resols 4 polyethylene 359-60
Restrained layer theory 37, 38 Silicon filled
Reversible hydrolyzable bond theory polyethylene 89
38 Single screw extruders
Rheological models conventional 193-8
Carreau 81 modified 198-200
complex viscosity 86-90 Single screw kneaders 201
dynamic modulus 90-3 Small-amplitude oscillatory flow 59,
Ellis 80 60
extensional viscosity 93-8 Specialty polymers
general 81 examples 7
Herschel-Bulkley 83 Spherical particles 137
modified Carreau 86, 87 Steady state compliance 86
modified Herschel-Bulkley 83 Steady shear viscosity unification
normal stress difference 84 287-303
474 Subject Index
Steady simple shear flow 55 Thermoplastics

Steel sphere filled definition 1
polyethylene 340--2, 353 examples 2
Stick-slip phenomenon 121 Thermosets
Stress relaxation 61 definition 2
Stress examples 2
growth 61 Time
normal 58 characteristics 54
relaxation 61 residence 227-8
shear 56, 58 scale of deformation 54
Striation thickness 181, 196 self-cleaning time 228
Styrene acrylonitrile Titanates 26, 28
glass bead filled 123-4 Titanium dioxide filled
Styrene-isoprene-styrene block polyethylene 320
copolymer polystyrene 245, 260, 295, 314, 316,
barium ferrite filled 254, 277, 286, 320, 397, 401, 406
374,377-9,381,384-5,387 Trouton viscosity 95
unfilled 285, 380 Tubeless siphon 78
Surface wettability theory 37 Twin screw extruders 202-15
Surface modifiers classification 205
effects 160 intermeshing
examples 26, 27 co-rotating 207-11
mechanism 35 counter-rotating 21-4
silane treated non-intermeshing
alumina 362-5, 367 counter-rotating 214-5
barium ferrite 277 Two-roll mill189-90
calcium carbonate 325-{;
glass beads 327 Uebler effect 79
mica 275, 294 Uniaxial
suggested 34 extension 62
titanate treated extensional viscosity 65
alumina 362-4, 366-72 Unification of steady shear viscosity
barium ferrite 277-8 287-303
calcium carbonate 276, 294, 328 Uniform copolymer 7
glass fibers 329 Unsaturated polyester
Surface treatment day filled 274
effect 30--3 mica filled 274
method 24, 25 silica filled 274
Suspension talc filled 274
concentrated 139-143 wollastonite filled 274
definition 136 Unsteady simple shear flow 55
dilute 137-8
rheology 136 Viscoelastic fluid behavior 77, 78
Viscoelastic effects 71
Talc filled Viscoelasticity
polyethylene 262 description 54
polypropylene 249, 294 Viscometer (see also Rheometer)
Thermoplastic polymer cone and plate 115-7
glass/sphere filled 251-2, 256, 318, extensional 128
347-8 parallel-disc 117-8
Subject Index 475
Viscometric functions 59 Wall slip (see Stick-slip

Viscosity phenomenon)
complex 60 Wall effect 150
definition 59 Weissenberg effect 71
dynamic 60 Wettability 19
extensional 65 Wetting 185
function 59 Wollastonite filled
shear 57, 58 polyethylene 274
Viscous liquid polypropylene 87, 88, 94-7
description 39, 54
Zirconia filled
W-L-F equation 99 polyethylene 354

Aroon v. Shenoy (Auth.) - Rheology of Filled Polymer Systems-Springer Netherlands (1999)

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Aroon v. Shenoy (Auth.) - Rheology of Filled Polymer Systems-Springer Netherlands (1999)

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Rheology of Filled

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2 Basic rheological concepts 54

2.2 Non-Newtonian flow behavior 66

4 Constitutive theories and equations for suspensions 136

4.2.7 Effect of adsorbed polymers 154

5 Preparation of filled polymer systems 175

6 Steady shear viscous properties 243

7 Steady shear elastic properties 312

7.7 Effect of polymer matrix 330

8 Unsteady shear viscoelastic properties 338

9 Extensional flow properties 395

10 Concluding remarks 416

Appendix A Glossary 425

Author index 455

Polymerie materials have been replacing other conventional materials

backgrounds, a concerted effort has been made to provide the initial

included to recapitulate the irnportant aspects discussed in the

1.1.1 THERMOPLASTICS, THERMOSETS AND ELASTOMERS

A. V. Shenoy, Rheology of Filled Polymer Systems

Table 1.1 Some candidate polymers used in the formation of filled

Thermosets Elastomers Thermoplastics

Epoxies Neoprenes Nylons

Thermosets are materials that have undergone a chemical reaction,

1.1.2 LINEAR, BRANCHED OR NETWORK POLYMERS

LOW PRESSURE H DPE

HIGH PRESSURE LDPE

LOW PRESSURE LLDPE

Figure 1.1 Comparison 01 structures 01 HDPE, LDPE, and LLDPE.

ethylene (LOPE) has a branched structure and a density :::::;0.92g/cm3 ,

The last stage of the heating process results in the formation of

It should be noted that the structure of phenolics is much more

1.1.3 CRYSTALLINE, SEMI-CRYSTALLINE OR AMORPHOUS POLYMERS

1.1.4 HOMOPOL YMERS

When X == H, the resulting polymer is polybutadiene; when X == CH3 ,

A~ -L- NH --- R~! -t or ~- NH --- R'_ NH _! - R"-!_t

When R == (CH 2 h, the resulting polymer is polyamide: nylon-6; when

1.1.5 COPOLYMERS AND TERPOLYMERS

Copolymerization is often used to alter the properties of homo-

possible. Acrylonitrile imparts chemical resistance while butadiene

1.1.6 LIQUID CRYSTALLINE POLYMERS

Table 1.2 Examples of rigid and flexible fillers

Aluminum oxide ASbestos fiber

1.2.1 RIGID OR FLEXIBLE FILLERS

1.2.2 SPHERICAL, ELLIPSOIDAL, PLATELIKE OR FIBROUS FILLERS

Table 1.3 Filler classification by physical form

1.2.3 ORGANIC OR INORGANIC FILLERS

1.3 FILLED POLYMERS

Table 1.5 Some typical examples of lilled polymer systems

Thermoset: Phenol-formaldehyde resin Wood flour/cotton flock

strength and prevented cracking of the resin by reducing the exotherm in

Table 1.6 Reasons lor the use 01 lillers in thermoplastics

1. To increase stiffness, strength and dimensional stability

in the case of high-impact polystyrene or polypropylene, deformable

1. Cost and availability

Table 1.7 Predominant function of some typical fillers

Function Typical fillers

Cost savings Wood flour, saw dust, cotton flock

worst is able to be resuspended with mlllimum mixmg. Thermal

1.4 FILLER-POL YMER INTERACTIONS

weak fi11er-polymer interface, on the other hand, results in increased