Advances in Urethane Science and Technology

Advances
in Urethane
Science and
Technology
Editors:
D. Klempner
K.C. Frisch
Advances in
Urethane Science
and Technology
Daniel Klempner
and
Kurt Frisch
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2001 by

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©2001, Rapra Technology Limited
All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
ISBN: 1-85957-275-8
Typeset by Rapra Technology Limited

Printed and bound by Lightning Source UK
Dedication
In memory of Kurt C Frisch

One of the founding Fathers of polyurethanes
January 15th 1919 to October 21st 2000

Contents
1 Dimensional Stabilising Additives for Flexible Polyurethane Foams ................ 3

1.1 Introduction ............................................................................................. 3
1.2 Experimental Procedures .......................................................................... 6
1.2.1 Materials ....................................................................................... 6
1.2.2 Handmix Evaluations .................................................................... 8
1.2.3 Machine Evaluation ...................................................................... 9
1.3 TDI - Flexible Moulded Additives .......................................................... 15
1.3.1 Dimensional Stability Additives for TDI ...................................... 16
1.3.2 Low Emission Dimensional Stability Additives ............................ 42
1.4 MDI Flexible Moulded Foam Additives ................................................. 63
1.4.1 Dimensional Stability Additives for MDI .................................... 64
1.4.2 Low Emissions Dimensional Stability Additives in MDI.............. 67
1.5 TDI Flexible Slabstock Low Emission Additives ..................................... 73
1.5.1 Reactivity .................................................................................... 74
1.5.2 Standard Physical Properties ........................................................ 74
1.5.3 TDI Flexible Slabstock Foam Review .......................................... 74
1.6 Foam Model Tool Discussions ................................................................ 75
1.6.1 TDI and MDI Moulded Foam Model .......................................... 75
1.6.2 TDI Flexible Slabstock Foam Model ........................................... 78
1.7 Conclusions ............................................................................................ 81
2 Demands on Surfactants in Polyurethane Foam Production with

Liquid Carbon Dioxide Blowing .................................................................... 85
2.1 History of Polyurethane Foams .............................................................. 85
2.1.1 Environmental Concerns in Relation to Flexible Foam Density ... 86
i
Advances in Urethane Science and Technology
2.2 Current Liquid Carbon Dioxide Technologies for Flexible Slabstock .........
Polyether Foam Production .................................................................... 88
2.2.1 Machinery ................................................................................... 88
2.2.2 The Foaming Process ................................................................... 90
2.2.3 Additional Tasks of Silicone Surfactants in Flexible Slabstock
Foam Production ......................................................................... 95
2.2.4 Chemistry of a Silicone Surfactant in Flexible Slabstock
Foam Production ......................................................................... 99
2.2.5 A Surfactant Development Example .......................................... 101
3 Polyurethane Processing: Recent Developments ........................................... 113

3.1 Industrial Solutions for the Production of Automotive Seats
Using Polyurethane Multi-Component Formulations ........................... 113
3.1.1 Market Requirements ................................................................ 113
3.1.2 Dedicated Solutions: Metering Equipment ................................ 114
3.1.3 Dedicated Solutions: Mixing Heads........................................... 116
3.1.4 Dedicated Solutions ................................................................... 121
3.2 ‘Foam & Film’ Technology - An Innovative Solution to Fully
Automate the Manufacture of Automotive Sound Deadening Parts ..... 130
3.2.1 The Problem .............................................................................. 131
3.2.2 The Approach to a Solution ...................................................... 131
3.2.3 The Film .................................................................................... 133
3.2.4 Industrial Applications .............................................................. 135
3.2.5 Applications .............................................................................. 137
3.2.6 Advantages ................................................................................ 138
3.3 InterWet - Polyurethane Co-injection ................................................... 138
3.3.1 Glass-Reinforced Polyurethanes, a Well-Known Technology ..... 139
4 Recent Developments in Open Cell Polyurethane-Filled Vacuum Insulated

Panels for Super Insulation Applications ...................................................... 157
4.1 Introduction ......................................................................................... 157
4.2 Some General Properties of Open Cell PU Foams for Vacuum
ii
Contents
Insulated Panels .................................................................................... 158

4.3 Vacuum Issues in the Selection of VIP Components .............................. 163
4.3.1 Vacuum Properties of the Open Cell Foams .............................. 163
4.3.2 Vacuum Properties of the Barrier Film ....................................... 167
4.3.3 The Getter Device ...................................................................... 179
4.4 Vacuum Panel Manufacturing Process and Characterisation ................ 188
4.4.1 Some Manufacturing Issues ....................................................... 188
4.4.2 Characterisation of Vacuum Panels ........................................... 191
4.5 Insulation Performances of Open Cell PU-Filled Vacuum Panels .......... 196
4.6 Examples of VIP Applications and Related Issues................................. 199
4.6.1 Household Appliances ............................................................... 199
4.6.2 Laboratory and Biomedical Refrigerators .................................. 203
4.6.3 Vending Machines ..................................................................... 204
4.6.4 Refrigerated/Insulated Transportation ....................................... 205
4.6.5 Other Applications .................................................................... 206
4.7 Near Term Perspectives and Conclusions.............................................. 206
5 Modelling the Stabilising Behaviour of Silicone Surfactants During the

Processing of Polyurethane Foam: The Use of Thin Liquid Films ................. 213
5.1 Introduction ......................................................................................... 213
5.2 Film Drainage Rate: Reynold’s Model and Further Modifications ........ 216
5.2.1 Rigid Film Surfaces .................................................................... 216
5.2.2 Mobile Film Surfaces ................................................................. 217
5.2.3 Surface Viscosity ........................................................................ 217
5.2.4 Surface Tension Gradients ......................................................... 218
5.3 Experimental Investigation of Model, Thin Liquid Polyurethane
Films and the Development of Qualitative and Semi-Quantitative
Models of Film Drainage ...................................................................... 219
5.3.1 Experimental Details ................................................................. 221
5.3.2 Qualitative Description of Polyurethane Films .......................... 223
iii
5.3.3 Quantitative Measurement of Film Drainage Rates:

Bulk and Surface Effects ............................................................ 226
5.4 The Development of Theoretical Models of Vertical, Draining
Thin Liquid Model PU Films ................................................................ 236
5.4.1 Rigid-Surfaced Collapsing Wedge Model ................................... 236
5.4.2 Deforming Film Models ............................................................ 239
5.4.3 Tangentially-Immobile Films ..................................................... 242
5.4.4 Finite Surface Viscosity .............................................................. 245
5.4.5 Adding Surfactant Transport ..................................................... 249
5.5 Summary .............................................................................................. 254
6 Synthesis and Characterisation of Aqueous Hybrid Polyurethane-Urea-

Acrylic/Styrene Polymer Dispersions ............................................................ 261
6.1 Preface .................................................................................................. 261
6.2 Introduction ......................................................................................... 261
6.2.1 General Considerations ............................................................. 261
6.2.2 Acrylic Dispersions and Polyurethane Dispersions (DPUR) ....... 264
6.2.3 Hybrid Acrylic-Urethane Dispersions ........................................ 266
6.3 Concept of the Study ............................................................................ 268
6.3.1 Selection of Starting Materials ................................................... 268
6.3.2 Assumptions for Synthesis of Hybrid Dispersions ..................... 269
6.4 Methods of Testing ............................................................................... 276
6.4.1 Dispersions ................................................................................ 276
6.4.2 Coatings .................................................................................... 277
6.4.3 Films .......................................................................................... 278
6.5 Experimental results ............................................................................. 279
6.5.1 Characterisation of Starting Dispersions Used for Synthesis
of MDPUR ................................................................................ 279
6.5.2 Synthesis of MDPUR and MDPUR-ASD ................................... 288
6.5.3 Investigation of the Effect of Various Factors on the
Properties of Hybrid Dispersions ............................................... 290
iv
Contents
6.5.4 Additional Experiments ............................................................. 312

6.6 Discussion of results ............................................................................. 320
6.6.1 Estimation of the Effect of Various Factors on the Properties
of Hybrid Dispersions and Films and Coatings Made
from Them ................................................................................ 320
6.6.2 Mechanism of Hybrid Particle Formation ................................. 326
6.7 Summary ................................................................................................ 330
7 Adhesion Behaviour of Urethanes ................................................................ 335

7.1 Introduction ......................................................................................... 335
7.2 Surface Characteristics of PU Adhesive Formulations ........................... 335
7.2.1 Experimental ............................................................................. 336
7.2.2 Results and Discussion .............................................................. 338
7.2.3 Conclusions ............................................................................... 347
7.3 Acid/Base Interactions and the Adhesion of PUs to Polymer Substrates 347
7.3.1 Experimental ............................................................................. 348
7.4 The Effectiveness of Silane Adhesion Promoters in the Performance
of PU Adhesives .................................................................................... 355
7.4.1 Experimental ............................................................................. 356
7.4.3 Conclusions ............................................................................... 364
8 HER Materials for Polyurethane Applications ............................................. 369

8.1 Introduction ......................................................................................... 369
8.2 Experimental Conditions ...................................................................... 370
8.2.1 Chain Extenders ........................................................................ 370
8.2.2 Prepolymers ............................................................................... 370
8.2.3 Preparation of Cast Elastomers ................................................. 372
8.2.4 Physical and Mechanical Properties Determination ................... 372
8.3 HER Materials Synthesis and Characterisation .................................... 373
v
8.4 Cast Poly(Ether Urethanes) ................................................................... 375

8.4.1 Pot Life Determination .............................................................. 375
8.4.2 Polyurethane Castings ............................................................... 376
8.4.3 Calculation of Hard and Soft Segment Contents ....................... 376
8.4.4 Hard Segment Versus Hardness ................................................. 378
8.4.5 Tensile Properties ....................................................................... 378
8.4.6 Tear, Compression Set and Rebound Properties......................... 380
8.4.7 Differential Scanning Calorimetry ............................................. 381
8.4.8 Dynamic Mechanical Analysis ................................................... 383
8.5 Cast Poly(Ester Urethanes) ................................................................... 390
8.5.1 Pot Life Determination .............................................................. 390
8.5.2 Tensile Properties ....................................................................... 390
8.5.3 Tear, Fracture Energy, Compression Set and
Rebound Properties ................................................................... 390
8.5.4 Differential Scanning Calorimetry Analysis ............................... 393
8.6 Cast Polyurethanes from HER/HQEE Blends ....................................... 397
8.6.1 Freezing Point Determination of HER/HQEE Blends ................ 397
8.6.2 Cast elastomers and Their Properties......................................... 398
8.7 High Hardness Cast Polyurethanes ....................................................... 401
8.7.1 Cast Elastomers and Their Hard and Soft Segment Contents .... 401
8.7.2 Hardness, Tensile, Tear, Compression Set and
Rebound Properties ................................................................... 401
8.7.3 FT-IR Analysis of Cast Polyurethanes ........................................ 403
8.7.4 Differential Scanning Calorimetric Analysis .............................. 405
8.8 High Thermal Stability Polyurethane with Low Heat Generation ........ 405
8.8.1 Hardness Measurements ............................................................ 408
8.8.2 Tensile Measurements ................................................................ 408
8.8.3 Differential Scanning Calorimetric Analysis .............................. 410
vi
Contents

8.9 Conclusions .......................................................................................... 416
9 Ultra-Low Monol PPG: High-Performance Polyether Polyols

for Polyurethanes ......................................................................................... 421
9.1 Introduction ........................................................................................... 421
9.2 MDI/BDO Cured Elastomers Based on Ultra-Low Monol PPG Polyols . 424
9.2.1 Effect of Monol Content on 4,4´-Methylene Diphenylmethane
Diisocyanate (MDI)/1,4-Butanediol (BDO) Cured Elastomers... 424
9.2.2 Processability and Property Latitude of Elastomers Based on
Ultra-Low Monol PPG Polyols .................................................. 429
9.2.3 Processing Latitude Improves by Incorporating
Oxyethylene Moieties ................................................................ 434
9.3 One-Shot Elastomer System Based on EO-Capped, Ultra-Low
Monol PPG Polyols .............................................................................. 436
9.3.1 Effect of Primary Hydroxyl Concentration on One-Shot
Elastomer Processability ............................................................ 436
9.3.2 Effect of Monol Content on One-Shot Elastomer Processability
and Properties............................................................................ 438
9.3.3 Processability and Property Latitude of Elastomers Based
on EO-Capped, Ultra-Low Monol Polyols ................................ 440
9.4.1 MDI/BDO Cured Elastomers: Acclaim Polyol 3205 Versus .............
PTMEG-2000 ............................................................................ 445
9.4.2 Enhanced Elastomer Properties Utilising Ultra-Low Monol
PPG/PTMEG Blends .................................................................. 447
9.5 Polyol Molecular Weight Distribution Effect on Mechanical
and Dynamic Properties of Polyurethanes ............................................ 449
9.5.1 TDI Prepolymers Cured with Methylene Bis-(2-Chloroaniline)
[MBOCA] .................................................................................. 450
9.5.2 Moisture-Cured TDI Prepolymers ............................................. 454
9.5.3 Aqueous Polyurethane/Urea Dispersion Coatings ...................... 456
9.5.4 MDI Prepolymers Cured with BDO .......................................... 459
9.6 Conclusions .......................................................................................... 461
vii
APPENDIX........................................................................................................ 465
Laboratory Preparation of 2,4-TDI and 4,4´-MDI Prepolymers ................... 465
Laboratory Casting of 4,4´-MDI Prepolymers Cured with BDO .................. 465
Laboratory Casting of One-Shot Elastomers Based on Carbodiimide-
Modified MDI, Polyol, and BDO ................................................................. 465
Laboratory Casting of 2,4-TDI Prepolymers Cured with MBOCA .............. 466
Laboratory Moisture-Curing of 2,4-TDI Prepolymers ................................. 466
Laboratory Preparation of Aqueous Polyurethane/Urea Dispersions
using the Prepolymer Mixing Process ........................................................... 466
Abbreviations .................................................................................................... 469
Contributors ...................................................................................................... 473
Author Index ..................................................................................................... 477
Main Index ........................................................................................................ 483
viii
Preface
This is a landmark issue of ‘Advances in Urethane Science and Technology’. Not

only is this the first volume of the new millennium, but it is the first to be published
by Rapra Technology.
On a more solemn note, one of the editors, Kurt C. Frisch, passed away shortly
before publication. Dr. Frisch, founder of the University of Detroit Mercy’s Polymer
Institute, was one of the pioneers of polyurethanes and was responsible for the
successful introduction of polyether polyurethane flexible foams into commerce in
the mid-1950s. Let us not only mourn the loss of, but also celebrate the life of this
great scholar by continuing to further the frontiers of urethane science and
technology. This volume is a good example of this progress.
Polyurethanes continue to be one of the most versatile of all polymers, finding

applications in foams (flexible, rigid, and in-between), elastomers, coatings, sealants,
adhesives, paints, textiles, and films. This volume presents some of the major
advances in polyurethanes, both from the materials and research side of things as
well as processing and applications, and includes studies on foams (additives,
vacuum panel applications, blowing and processing), elastomers, adhesion
behaviour and new urethane raw materials.
I would like to take this opportunity to express my gratitude to the authors who
contributed to this book and to the University of Detroit Mercy for its
encouragement of this effort.
I would also like to thank the staff of Rapra, in particular, Frances Powers, Claire
Griffiths and Steve Barnfield.
Daniel Klempner, Ph. D.
Polymer Institute,University of Detroit Mercy

July, 2001
1
2
1
Dimensional Stabilising Additives for Flexible
Polyurethane Foams
Gary D. Andrew, Jane G. Kniss, Mark L. Listemann, Lisa A. Mercando,
James D. Tobias and Stephan Wendel
1.1 Introduction
The issues that an automotive seat manufacturer faces when formulating and producing
seats are escalating. Physical properties such as tensile and tear strengths, compression
set and wet set are critical when meeting specific mechanical performance requirements
as defined by the original equipment manufacturer (OEM). As new requirements for
comfort and durability are instituted, tests such as dynamic creep testing, long term
vibration characterisation and repeated compression tests under various atmospheric
and load conditions have been used to characterise foam performance for comfort.
Comfort properties are best controlled by the polyols used to produce the polyurethane
foam cushion. Significant changes in polyol technology to meet these dynamic comfort
properties have had an impact on the processing of polyurethane foam and on physical
properties. Increased tightness of the foam article resulting from changes in these raw
materials has focused more attention by foam producers on crushing methods. Flexible
moulded polyurethane foam requires some type of mechanical crushing to prevent
shrinkage and ultimately maintain part stability.
With recent changes made to polyol technology, mechanical methods of crushing do not
always provide the consistency required to produce a part that is dimensionally stable.
Additionally, producers of polyurethane articles are continually building more complexity
into their seat designs to meet the aesthetic values required by today’s consumers. These
complex seat designs place more emphasis on crushing capability due to the nature of
the designs. With all these changes, additives needed to be developed which provide a
wider processing latitude and increased breathability to the polyurethane article. Wider
processing latitudes should reduce scrap and repair rates on the foam production line
and improve economics for the polyurethane producer [1].
The formation of moulded foam is a complicated chemical process which involves several
reactions occurring simultaneously. There are rapid volume and temperature increases
and the concurrent development of phase separated polymer networks. To understand
how foam properties can be affected by catalyst and surfactant chemistries several
techniques are used to identify key performance benefits and issues. A force to crush
3
(FTC) detection device was used to measure the force required to crush a part to 50% of
its thickness for determination of cell openness. Mass-loss/rate-of-rise was run to
understand rate of rise and height measurements, weight loss from carbon dioxide
generation and temperature profiles. A scanning electron microscope (SEM) was used to
determine differences in cell structure and cell distribution caused by changes in the
catalyst and surfactant chemistries. Physical properties were also tested using ASTM test
methods for flexible cellular polyurethane. A novel chemical reaction foam modelling
technique was also used to determine the selectivity of the catalyst packages, compared
to industrial standard controls [2].
In the past it was thought that the cell structure of polyurethane foam is controlled by
the type and amount of surfactant used. Dabco DC5043 (Air Products and Chemicals,
Inc.) was developed to enhance cell wall drainage to better enable cell opening during
crushing cycles. It was also thought that surfactant technology was the best way to
provide improved crushing techniques; therefore, catalyst technology was ignored [3].
As mentioned earlier, with new polyol technology development more emphasis was placed
on crushing. New additive technology needed to be developed that would open cells
during the foam formation and reduce the requirement and criticality of the crushing
processes. The technology had to go beyond providing easier cell opening at crush to
providing more open cells during the polyurethane formation.
The real challenge in polyurethane foam formation is to control the chemical and
physiochemical processes up to the point where the material finally sets. The sequence
and the rate of the chemical reactions are predominately a function of the catalyst and
the reactivity of the basic raw materials, polyol and isocyanate. The physiochemical
contribution to the overall stability and processability of a system is provided by the
silicone surfactants. Optimum foaming results will be achieved only if the correct
relationship between chemistry and physics exists [4].
Another rapidly increasing environmental concern is over the emission of volatile

organic compounds (VOC) during and following the production of industrial and
consumer goods. This has stimulated a great deal of effort within the chemical industry
to reduce and/or control the ways in which such emissions may occur. In the
polyurethane foam industry, efforts to reduce VOC emissions have greatly impacted
the technologies used in manufacturing processes, especially for the use of organic
auxilliary blowing agents such as chlorofluorocarbons. In addition, the ultimate fate
of additional foaming additives, including surfactants and catalysts, is now coming
under increased global scrutiny. As a result, foam manufacturers have expressed a
desire for polyurethane additives that, among other things, do not exhibit the degrees
of fugitivity common to many of the additives that are currently used in polyurethane
foam production today.
4
Dimensional Stabilising Additives for Flexible Polyurethane Foams
Polyurethane foams are prepared from the simultaneous reactions of diisocyanate with
water and with polymeric diols and/or triols to form hydrogen-bonded urea (hard)
segments and polyurethane networks (soft segments). The commercial production of
polyurethanes via isocyanate poly-addition reactions requires the use of one or more
catalysts. Tertiary amines are widely accepted in the industry as versatile polyurethane
catalysts. Amine catalysts are generally stable in the presence of standard polyurethane
formulation components and can have an impact on both the blowing (water-isocyanate)
and gelling (polyol-isocyanate) reactions. Although the use of catalysts in the
manufacturing of polyurethane foam both speeds the production of the foamed article
and, through the judicious choice of catalyst package, allows control of the physical
properties of the product, there are some problems associated with the use of these
additives. A number of commonly used tertiary amine catalysts can volatilise under certain
conditions. Release of tertiary amines during foam processing and from consumer products
is generally undesirable. Therefore, identifying alternatives to standard tertiary amine
catalysts which have no or low volatility, yet exhibit the same type of activity in isocyanate
poly-addition reactions, is desirable.
The non-fugitive catalysts reported in this chapter address the problems associated with
the use of polyurethane catalysts by reducing the odour and volatility of these materials
and by eliminating the ability of these additives to escape from finished foam products.
One strategy has involved functionalising the catalysts to render the species reactive
toward isocyanates, thereby covalently attaching the catalysts to the polymer network.
This strategy not only renders the catalytic material non-fugitive in the final product, but
also reduces the odour and volatility of the catalyst through increases in molecular weight
and polarity. These non-fugitive catalysts also provide equivalent or improved physical
properties when compared to industry standards, whereas conventional reactive amine
catalysts as well as metal catalysts cannot always meet todays ever increasing manufacturer
and consumer performance requirements.
These increasingly evolving requirements have led to the development of both novel
non-fugitive catalysts and new cell-opening non-fugitive catalysts for flexible foam. These
new low emission additives have been developed to meet the challenge of optimised
foaming and result in little or no emissions. Several of the non-fugitive catalysts possess
cell-opening capability. This new technology allows the manufacturer of polyurethane
foam to optimise their system to achieve the best processing latitude for their foam process.
These new additives maintain, or in some cases, improve key physical properties while
providing a more open foam.
5
1.2 Experimental Procedures
Data presented herein was derived from a combination of handmix and high pressure
impingement-mixing machine produced foam. Foams were prepared using several general
types of formulations for toluene diisocyanate (TDI) and two general types of formulations
for methylenediphenyl diisocyanate (MDI) which are representative of currently utilised
formulations in the automotive interior component industry. In addition, an all water
blown formulation was used to represent the flexible slabstock industry.
1.2.1 Materials
The materials used are shown in Table 1.1.
Table 1 Materials used in experimental work

Trade name Formulation Manufacturer
Dabco 33LV 33% TEDA in DPG APCI
Dabco BL-17 Delayed action tertiary amine blowing catalyst. APCI
Dabco BL-53 Newly developed tertiary amine, which provides APCI
blowing and cell opening capabilities.
Dabco B-16 Tertiary amine surface cure catalyst. APCI
Polycat 15 (PC-15) Balanced reactive amine catalyst. APCI
Dabco BLV Dabco 33-LV/Dabco BL-11 in a 3:1 catalyst blend. APCI
Dabco T-9 Stannous octoate catalyst. APCI
Dabco NE1060 Newly developed non-fugitive gelling catalyst for APCI
flexible moulded applications.
XF-N1085 Newly developed non-fugitive cell opening APCI
blowing catalyst.
Dabco NE500 Newly developed non-fugitive gelling catalyst for APCI
flexible slabstock foam from APCI.
Dabco NE600 Newly developed non-fugitive intermediate APCI
blowing catalyst for flexible slabstock
applications.
Dabco NE200 Newly developed non-fugitive intermediate APCI
blowing catalyst for flexible slabstock
applications.
6
Table 1 Continued
Trade name Formulation Manufacturer
XF-O11006 Newly developed non-fugitive cell opening APCI
gelling catalyst.
Dabco DC5169 Silicone copolymer surfactant for cold cure systems. APCI
Dabco DC5043 Silicone copolymer surfactant for TDI cold cure APCI
systems.
Dabco DC2585 Silicone copolymer surfactant for MDI cold cure APCI
systems.
Dabco DC2517 Silicone copolymer surfactant. APCI
XF-N1586 Newly developed silicone copolymer surfactant, APCI
which promotes open cells.
XF-N1587 Newly developed silicone copolymer surfactant, APCI
which promotes open cells.
DEOA-LF Diethanolamine Liquid Form APCI
(Dabco) (85% DEOA: 15% water)
Arcol E848 Conventional polyol with an OH# of 31.5 Lyondell
Chemical
Arcol E851 43% solids copolymer polyol with an OH# of 18.5 Lyondell
Chemical
NC-630 Polyol with an OH# of 31.4 Dow Chemical
NC-700 41% solids copolymer polyol with an OH# of 21.0 Dow Chemical
Voranol 3512 Polyether polyol with an OH# of 48.3 Dow Chemical
Polyol A High functionality triol with an OH# of 32.5 Dow Chemical
Polyol B 41% solids copolymer triol with an OH# of 23.8 Dow Chemical
Polyol C Polyether polyol with an OH# of 28 Dow Chemical
Polyol D Cell opening polyol
PRC-798 Solvent-based release agent Chem-Trend
APCI: Air Products and Chemicals, Inc.
DEOA: Diethanolamine
DPG: Dipropylene glycol
TEDA: Triethylene diamine
7
1.2.2 Handmix Evaluations
1.2.2.1 Flexible Moulded Foam Handmix Procedure
Handmix experiments were carried out using the following procedure. Formulations
were blended together for approximately 10 minutes using a mechanical mixer
equipped with a 7.6 cm diameter, high shear, mixing blade, rotating at 5000 rpms.
Premixed formulations were maintained at 23 ± 1 °C using a low temperature
incubator. Mondur TD-80 (Bayer; a blend of 2,4-TDI and 2,6-TDI isomers in the
ratio of 4:1) or modified MDI was added to the premix at the correct stoichiometric
amount for the reported index for each foam. The mixture was blended together
with a Premier Mill Corporation Series 2000, Model 89, dispersator for approximately
five seconds. The foaming mixture was transferred to an Imperial Bondware #GDR-
170 food container or ‘chicken’ bucket and allowed to free rise in order to obtain the
processing data.
1.2.2.2 Flexible Slabstock Foam Handmix Procedure
Handmix experiments were carried out using the following procedure. A premix
consisting of polyol, surfactant and water was prepared by blending the components
in a shaker for approximately 20 minutes. The premix was allowed to stand for 2
hours prior to making the foam to allow for degassing of the mixture. A measured
amount of premix was poured into a 1.9 litre paper cup; the required stoichiometric
amounts of amine and tin catalysts were added to the contents of the cup and mixed
for 20 seconds using a Premier Mill Corporation dispersator equipped with a 5.5 cm
diameter, high shear, mixing blade, rotating at 6,000 rpm. The corresponding amount
of Mondur TD-80 to provide for a 110 index (isocyanate index, which is the amount
of isocyanate used relative to the theoretical equivalent amount [5]) was measured
into a 400 cm3 beaker. Methylene chloride in the correct proportion was added to
the beaker containing the Mondur TD-80; the beaker was carefully swirled for 4 or
5 seconds and the contents poured into the paper cup. The mixture was blended
together for 6-7 seconds and the foaming mixture poured into a paper bucket for up
to 12 seconds and allowed to free rise with the processing data being recorded.
Reactivity profiles were determined from hand-mix foams prepared in 5.68 litre paper
buckets. Foams for physical properties were prepared in 35.6 x 35.6 x 25.4 cm
cardboard boxes. Identical procedures were followed for both reactivity and physical
property experiments.
8
1.2.3 Machine Evaluation
1.2.3.1 TDI Flexible Moulded Foam Procedure
Machine runs for the TDI flexible moulded foam were carried out on a Hi Tech SureShot
MHR-50 (Hi-Tech Industries, Inc.), cylinder displacement series, high pressure machine.
Fresh premixes, consisting of the appropriate polyols, water, crosslinker, surfactants and
catalysts for each formulation were charged to the machine. Mondur TD-80 was used
throughout the entire study. All chemical temperatures were held at 23 ± 2 °C via the
machine’s internal temperature control units. The foam was poured into an isothermally
controlled, heated aluminium mould maintained at 71 ± 2 °C. The mould was a typical
physical property tool designed with internal dimensions of 40.6 cm x 40.6 cm x 10.2
cm. The mould has five vents, each approximately 1.5 mm in diameter, centred 10.0 cm
from each edge and the geometric centre of the lid. The mould was sprayed with a
solvent-based release agent, Chem-Trend PRC-798, prior to every pour and allowed to
dry for one minute before pouring. The foam premix was puddle poured into the centre
of the mould with a wet chemical charge weight capable of completely filling the mould
and obtaining the desired core density. Minimum fill requirements were established for
each formulation evaluated. The foam article was demoulded at 240 seconds after the
initial pour. After demoulding, the foam was placed through a mechanical crusher, tested
for FTC measurements, or left uncrushed and set aside for 24 hour shrinkage
measurements described in Section 1.2.3.2c.
All foams to be tested in each catalyst set were mechanically crushed 1 minute after
demoulding using a Black Brothers Roller crusher set to a gap of 2.54 cm. Crushing was
carried out three times on each part, rotating the foam 90 degrees after each pass through
the roller. All parts produced for physical testing were allowed to condition for at least
seven days in a constant temperature and humidity room (23 ± 2 °C, 50 ± 2% relative
humidity).
Three to four specimens were produced for any given set of conditions. Four test specimens
were die-cut from each foam pad and evaluated for each physical property listed in
subsequent data tables. All results were included in calculating averages and standard
deviation. Each test was carried out as specified in ASTM D3574 [5].
For each formulation evaluated, duplicate free rise ‘chicken’ buckets were poured at the
same shot size to determine overall reactivities and foam shrinkage. Data recorded were
cream time (the time between the discharge of the foam ingredients from the mixing
head and the beginning of the foam rise [5]), top-of-cup (TOC; the time between the
discharge of the foam ingredients from the mixing head and when the centre of the foam
reaches the same height as the top of the chicken bucket), string gel (the time between
9
pouring of the mixed liquids and the time that strings of viscous material can be pulled
away from the surface of the foam when it is touched with a tool [5]), full rise time and
final height. The free rise buckets were again tested for final heights after 24 hours.
Measurements of height were made using a Mitutoyo height gauge. In addition to all the
standard tests, several more unique tests were performed where indicated, and are
described in Section 1.2.3.2.
1.2.3.2 Tests
1.2.3.2a Maze Flow Mould Test Description
A common type of isothermally heated mould was used to determine the flowability of
formulations with each of the catalyst candidates. This maze mould is shown in Figure 1.1.
Machine foam was poured into the mould at the top left corner of the open cavity as
indicated by ‘pour spot’ on the figure. The lid was then closed and clamped tightly. Foam
was allowed to free flow consecutively through each of the five gates for the standard 4
Figure 1.1 Diagram of Maze Flow Mould (Top View)
10
minutes prior to demould. Minimum fill was first determined by completely filling the
cavity with little or no extrusion through the vent at the end of the fifth gate. Mathematical
reduction of the shot size was performed to obtain the first of three systematically scaled
down foam fill weights. This first foam should have a fifth leg (the foam in gate 5 of the
maze flow mould, see Figure 1.1) which barely touches the front cavity wall. The second
reduction in foam fill weight produced a foam that flowed approximately halfway through
the fifth gate. The third reduction in foam fill weight was equivalent to the step change
from foam 1 to foam 2. Shot times were held constant for each of the three foam fill
weights as compared to the control determined standard shot time in any given solids
level formulation. These three foams were weighed for total foam pad and fifth leg weight,
and measured for fifth leg length to obtain a range of flow values for each of the
experimental catalysts compared to the control additives.
1.2.3.2b Dimensional Stability Test
Foam dimensional stability is essentially the result of a balance between external and
internal forces. The external forces are defined as the ambient pressure along with any
additional applied loads. The internal forces are the strength of the polymer matrix and
the internal cell pressure [6]. Basically, if the sum of the internal forces is greater than the
external forces, the foam will expand. Consequently, if the sum of the external forces is
greater than the internal forces the foam will shrink. Any expansion or shrinkage will
impact on the internal and/or external forces until an equilibrium is obtained. It is the
internal forces, i.e., cell pressure and strength of the polymer matrix as defined by ‘green
strength’ or cure, which will have an impact on the dimensional stability performance of
the moulded polyurethane.
Dimensional stability can be measured on a freshly demoulded part by determining the

amount of force required to open cells, as measured by FTC. FTC measurements were
made thirty seconds after demoulding. The foam pad was removed from the mould,
weighed and placed in the FTC apparatus. The force detection device is equipped with a
2.2 kg capacity pressure transducer mounted between the 323 cm2 circular plate cross
head and the drive shaft. The actual force is shown on a digital display. This device
mimics the ASTM D3574, Indentation Force Deflection Test [6] and provides a numerical
value of the freshly demoulded foam’s initial hardness or softness. The foam pad was
compressed to 50 percent of its original thickness at a cross head velocity of 275 mm per
minute with the force necessary to achieve the highest compression cycle recorded in
whole Newtons. Several compression cycles were completed. A cycle takes approximately
30 seconds to complete. Values are reported as the FTC value for the foam based on the
assumption that the lower the FTC values the better the dimensional stability of the
foam. This test requires the foam to be fully cured at demould. A dimensionally stable
11
foam will exhibit little or no tendency to shrink after demoulding. Poor dimensional
stability can result in numerous defects of the polyurethane article, such as lack of fit of
a polyurethane piece to the substrate. These defects will ultimately cause loss of revenue
to the polyurethane manufacturers because of increased repair and/or scrap rates.
Additionally the degree of cell openness of polyurethane foam can be measured directly
by the air flow physical properties of the polyurethane part. Higher air flow values
measured for a particular foam would indicate that the foam has less of a tendency to
shrink and therefore be more dimensionally stable as compared to a foam with lower air
flows. Additionally, higher air flows may also indicate that the foam was much easier to
crush-out thereby breaking many of the cell windows. Dimensionally stable foam should
reduce scrap and rework by allowing the foam to conform to near its original moulded
shape or at least return to its original shape after being crushed.
1.2.3.2c Shrinkage Test
An additional dimensional stability evaluation was done with a shrinkage template

apparatus (Figure 1.2).
Figure 1.2 Diagram of Shrinkage Template Apparatus
12
It was designed to measure the average foam pad shrinkage of an uncrushed foam. This
apparatus consists of two 432 mm long x 432 mm wide x 6.35 mm thick, plexiglass
plates, mechanically pinned in each corner with threaded bolts to maintain the plates at
a constant 102 mm spacing. The single uncrushed foam from each of the catalyst sets
was aged 24 hours prior to being placed between the two plates. Both top and bottom
plates each contain 5 mm diameter holes evenly spaced, diagonally from corner to corner,
25 mm apart in an X-shaped pattern. Nineteen holes are contained in each leg of the X,
for a total of 37 holes per plate. Measurements were made with a digital caliper by
inserting the end down through each hole to just touch the foam surface with the indicated
value being recorded. All measurements were normalised to discount the plexiglass plate
thickness and subsequently averaged to a single mould cavity and lid value.
1.2.3.2d Time Pressure Release Test
Time Pressure Release (TPR) is the opening of the mould during the curing cycle to
release the internal pressure and then re-closing for the duration of the cure time [8]. The
sudden release of the internally generated pressure bursts the cell windows, thereby
improving the crushability of the foam. The tool is opened only a few millimetres and
for a specific time. TPR can be applied at any time during the curing cycle, however, care
must be taken not to perform the operation too early or too late since surface quality
issues may occur.
A ‘simulated’ TPR process was carried out during this study, whereby the tool lid was
opened approximately 1.5 mm for a three second duration. TPR was applied at various
time intervals throughout the evaluation. Two mechanical clasps affixed to the top and
bottom halves of the tool precisely controlled the gap opening. These clasps were manually
opened and closed at the desired TPR time interval.
1.2.3.2e Pail Test
Another test was devised to evaluate foam bulk stability in a free-rise mixed foam.
Foams prepared from TDI formulations were poured directly from the machine head
into a large open pail (the pail is a common high density polyethylene plastic with
approximate dimensions of 365 mm high and 290 mm in diameter) at a targeted mass.
Several pours were carried out to ensure equivalent catalyst activity amongst each
formulation. Foams were allowed to stand for 24 hours prior to removal from the pail.
Each foam was weighed to obtain total individual mass. Subsequently, a 25 mm slice
was cut directly through the geometric vertical centre of the foam. Foam slices were
examined for cell structure.
13
1.2.3.2f Dynamic Fatigue Test
Dynamic Fatigue Constant Pounding testing was carried out using standard testing
procedures outlined in ASTM D3574-95 [6]. A 60 minute recovery time and 80,000
cycles were used for each test sample.
1.2.3.2g Fogging Test
Gaseous foam emissions were compared in the standard fogging test procedure outlined
in SAE J1756 [9]. A standard 7.6 cm thick piece of foam was preconditioned for 48
hours, then tested in the Hart fogging apparatus at 100 °C for 3 hours. Glossmeter
readings of the foam were taken after 60 minutes at room temperature.
1.2.3.2h Headspace Analysis Test
Foam emissions were also evaluated by cutting equivalent portions, approximately 1 gram,
of foam from the geometric centre of the moulded foam articles 60 minutes after demoulding.
Each sample was inserted into a 20 cm3 Kimble glass crimp top vial with a Teflon seal.
Several vials were sealed without foam to be used as blanks to ensure all emissions had
eluted through the gas chromatograph prior to the injection of a second gas sample. All
vials were loaded into a Tekmar 7000 Headspace Autosampler tray for sequential heating
for 1 hour at 54 °C. After heating and temperature equilibration, the headspace of the vial
was sampled and directly injected within a closed loop system onto a Hewlett Packard
5890 Series II Plus gas chromatograph containing a HP-5 (5%-diphenyl/95%-
dimethylsiloxane copolymer) stationary phase column (30 m, 0.25 mm internal diameter,
1.00 mm film thickness). A standard oven heating profile was used to separate the gas
components for detection with a Hewlett Packard 5972 Series Mass Selective Detector.
Elution peaks were individually identified by comparison to standard libraries.
1.2.3.3 MDI Flexible Moulded Foam Procedure
Machine runs for the MDI flexible moulded foam were conducted on a Krauss-Maffei,
cylinder displacement series, high pressure machine. Fresh premixes, consisting of the
appropriate polyols, water, crosslinker, surfactants and catalysts for each formulation were
charged to the machine. Modified MDI was used throughout the entire study. All chemical
temperatures were held at 25 °C ± 2 °C via the machine’s internal temperature control
units. Foam pours were made into an isothermally controlled heated aluminium mould
maintained at 60 °C ± 2 °C. The mould was a typical physical property tool designed with
14
internal dimensions of 40.6 cm x 40.6 cm x 10.2 cm. The mould has two vents each
approximately 1.0 mm in diameter centred 10.0 cm from each edge and the geometric
centre of the lid. The mould was sprayed with a solvent-based release agent prior to every
pour and allowed to dry for one minute before pouring. The foam premix was puddle
poured 15 cm away from the geometric centre of the mould with a wet chemical charge
weight capable of completely filling the mould with the appropriate core density. Minimum
fill requirements were established for each formulation evaluated. The foam article was
demoulded at 300 seconds after the initial pour. Upon demoulding, the foam was placed
through a mechanical crusher or tested for FTC measurements.
The foams were mechanically crushed 1 minute after demoulding using a roller crusher set to
a gap of 3.0 cm. Crushing was carried out three times on each part. All parts produced for
physical testing were allowed to condition for at least seven days in a constant temperature
and humidity room (23 °C ± 2 °C, 50% ± 2% relative humidity). Three to four parts were
produced for any given set of conditions. Four test specimens were die-cut from each pad
and evaluated for each physical property listed. All results were included in calculating the
averages and standard deviation. Each test was conducted as specified in ASTM D3574 [5].
For each formulation evaluated, free rise cup foams (see Section 1.2.2.1) were poured to
determine reactivities and foam shrinkage. Data recorded were gel time, full rise time and
final height. The free rise cup foams were tested for final heights and free rise density after 24
hours. Height measurements were carried out using a Mitutoyo height gauge. All experimental
formulations reported in this work were matched by rise profile to each control formulation.
FTC measurements were conducted 90 seconds after demoulding. The foam pad was removed
from the mould, weighed and placed in the FTC apparatus (Instron 4502). The force detection
device is equipped with a 5.0 kN capacity pressure transducer. The actual force is shown on
a digital display. This device mimics the ASTM D3574, Indentation Force Deflection Test
and provides a numerical value of freshly demoulded foams initial hardness or softness. The
pad was compressed to 70 percent of its original thickness at a cross head velocity of 380 mm
per minute with the force necessary to achieve the highest compression cycle recorded in
Newtons. Values are reported as the FTC value for the foam based on the assumption that
the lower the FTC values the better the dimensional stability of the foam.
1.3 TDI - Flexible Moulded Additives
The automotive industry has placed increased pressures on OEM suppliers to improve
their productivity, quality and cost of the polyurethane articles which they produce.
Styling changes, complex designs and OEM productivity demands for automotive seats
have necessitated the need to produce more open foam in all-water blown TDI- and
15
MDI-based systems. Furthermore, changes in polyol technologies designed to improve

seat comfort factors can have a negative impact on foam openness and dimensional
stability. Specifically, the comfort of high resilience foam may be related to the degree of
dimensional stability or foam openness.
Flexible moulded polyurethane foam requires mechanical crushing to open foam cells,
which in turn prevents shrinkage and improves overall dimensional stability. Current
mechanical methods for cell opening consist mainly of roller crushing, vacuum rupture
and TPR. However, mechanical methods do not always result in complete or consistent
cell opening and require a flexible moulded foam producer to invest in additional
machinery. Additionally, if the polyurethane article is not crushed properly, dimensional
stability suffers which can cause an increase in repair and scrap rates resulting in a negative
impact on the cost of production. A chemical method for cell opening would be preferred.
1.3.1 Dimensional Stability Additives for TDI
When producing flexible high resilience foam, it is important to provide a wider TPR
window to expand processing latitude and at the same time maintain or improve physical
properties. This should result in reduced scrap and/or repair rates, providing improved
economics for the polyurethane producer.
The most commonly used catalyst and surfactant package for all water blown TDI-
based moulded foam production is a blend of Dabco 33-LV and Dabco BL-11, coupled
with Dabco DC5043 silicone surfactant. Additionally, the acid-blocked counterparts of
these two catalysts, Dabco 8154 and Dabco BL-17, can also be used for the production
of high resilience moulded foam. A combination of Dabco 33LV and Dabco BL-17 is
used to facilitate a short delay in the reactivity of the polyurethane foaming process. A
combination of silicone surfactants, Dabco DC5043 and Dabco DC5169, are utilised to
provide good foam stabilisation, improve cell regulation and cell wall drainage. These
combinations of catalysts and surfactants served as the control additives to which the
experimental additives were compared and contrasted.
A newly developed cell opening catalyst, Dabco BL-53, was evaluated to determine its
impact on dimensional stability and general processability. Dabco BL-53 affords all the
benefits of Dabco BL-11 or Dabco BL-17, with the added advantage of cell opening and
slightly delayed initiation times. Dabco BL-53 is not a chemical equivalent for Dabco
BL-11 or Dabco BL-17; however, it will provide similar performance. For rapid
demoulding systems, it is recommend that Dabco BL-53 be used at 0.12 to 0.22 pphp,
with the optimum level at 0.16 to 0.19 pphp, in combination with a Dabco 33-LV level
at 0.30 to 0.32 pphp.
16
As polyurethane seating design changed from the relatively simple configurations of

the early 1990s to the more complex designs of today, the need to improve cell opening
or dimensional stability has intensified. Accordingly, silicone surfactants providing
improved foam stabilisation, cell regulation and cell wall drainage were needed to
enable polyurethane manufacturers to achieve their production goals. Two experimental
silicone surfactants, X-N1586 and X-N1587, were developed to provide open foam
and promote dimensional stability.
A TDI cushion formulation, with a density of 45 kg/m3 and a TDI back formulation,
with a density of 35 kg/m3 were used in the TDI automotive study. All of these
formulations were modified accordingly with the appropriate crosslinker, water, and
additive levels for the chosen density range. These formulations are shown in
Tables 1.2 and 1.3.
Table 1.2 ~45 kg/m3 cushion formulation

Formulation Control BL53 Exp. SSF BL53/Exp. SSF
Identification I II III IV
Components pphp pphp pphp pphp
Polyol A 68.00 68.00 68.00 68.00
Polyol B 32.00 32.00 32.00 32.00
Water 2.77 2.77 2.77 2.77
Dabco 33LV 0.30 0.30 0.30 0.30
Dabco BL-17 0.18 - 0.18 -
Dabco BL-53 - 0.20 - 0.20
Dabco DC-5043 0.75 0.75 - -
Dabco DC-5169 0.25 0.25 - -
X-N1586 - - 0.3 0.3
X-N1587 - - 0.7 0.7
Dabco DEOA-LF 1.53 1.53 1.53 1.53
TDI (100 index) 37.3 37.3 37.3 37.3
Exp. SSF: experimental silicone surfactant
pphp: parts per hundred polyol
17
Table 1.3 ~35 kg/m3 back formulation

Formulation Control BL53 Exp. SSF BL53/Exp. SSF
Identification V VI VI I VIII
Polyol A 80.00 80.00 80.00 80.00
Polyol B 20.00 20.00 20.00 20.00
Water 3.27 3.27 3.27 3.27
Dabco 33LV 0.30 0.30 0.30 0.30
Dabco BL-17 018 - 0.18 -
Dabco BL-53 - 0.20 - 0.20
Dabco DC-5043 0.75 0.75 - 0.75
Dabco DC-5169 0.25 0.25 - -
X-N1586 - - 0.3 0.3
X-N1587 - - 0.7 0.7
Dabco DEOA-LF 1.53 1.53 1.53 1.53
TDI (100 index) 42.2 42.2 42.2 42.2
1.3.1.1 Reactivity
1.3.1.1a Handmix Mass-Loss/Rate-of-Rise
Formulations used in the mass-loss/rate-of-rise are summarised in Tables 1.2 and 1.3.
Surfactant and catalyst additives were changed according to the formulation being studied.
Foams were run at the optimum index as they were during the machine study. All experiments
were duplicated. Each mixed formulation was poured into a ‘chicken’ bucket equipped with
a thermocouple positioned at the centre of the bucket resting on a Mettler PM 30,000 balance.
The centre height of the rising foam was recorded every second using a DAPS QA Model
#2500 rate-of-rise apparatus. Knowing the foam mass, the rate-of-rise and using the ideal
gas law, it is possible to calculate the carbon dioxide generated or trapped over time [10, 11].
Figures 1.3 and 1.4 show height versus time achieved for the cushion and back formulations
using the control formulations I and V, as well as the experimental formulations II, III, IV,
VI, VII and VIII. The foam height versus time graphs clearly indicate higher rates for
control formulations I and V in both cushion and back formulations. Cushion and back
18
Figure 1.3 Foam Height versus Time - Cushion Formulation
Figure 1.4 Foam Height versus Time - Back Formulation
formulations, which contained the new additives in formulations II, III, IV, VI, VII and
VIII did not achieve the same foam height when compared to the control formulations.
Several things could cause the differences observed in the foam heights. First, reactivity
rates for control formulations might be faster than the experimental catalyst or surfactants.
Second, overall foam stability could be compromised for the experimental catalyst and
surfactants. Lastly, carbon dioxide might be diffusing from the reacting polyurethane foam
19
at an accelerated rate. All of these possibilities were explored. Data generated and
observations will be reported which demonstrate how these new additives promote
dimensional stability through increased carbon dioxide diffusion.
Temperature profiles for control formulations I and V indicate reaction temperatures

which fall in the middle of the temperature profiles compared to the new additives denoted
in Figures 1.5 and 1.6. These temperature profiles clearly demonstrate that carbon dioxide
Figure 1.5 Temperature versus Time - Cushion Formulation
Figure 1.6 Temperature versus Time - Back Formulation
20
conversion is occurring at the same rate in the control as in the experimental formulations.
The fact that carbon dioxide conversion is occurring at the same rates would not account
for the lower foam heights observed in Figures 1.3 and 1.4.
In the control formulations, I and V, the amount of carbon dioxide diffused was less than the
amount of carbon dioxide diffused using the new additives. Figures 1.7 and 1.8 were generated
using the ideal gas law from data generated with the mass-loss/rate-of-rise apparatus. Diffusion
Figure 1.7 Carbon Dioxide Trapped versus Time - Cushion Formulation
Figure 1.8 Carbon Dioxide Trapped versus Time: Back Formulation
21
of carbon dioxide from cells as they form in the free rise reaction apparently keeps the
reacting foam from reaching the same foam height when using these experimental additives.
Reactivity profiles for these three new additives are essentially the same. Data discussed
later in Section 9.3.1.1b, Tables 1.4 and 1.5, further supports the fact that there is no
Table 1.4 Machine mix free rise reactivity comparison using cushion formulation
Control BL53 Exp. SSF BL53/Exp. SSF
Formulation I II III IV
Cream (Seconds) 4. 7 4.6 4.9 4.9
Top of Cup (Seconds) 24.1 23.6 23.9 23.4
String Gel (Seconds) 55.4 53.7 54.3 54.2
Full Rise (Seconds) 100.4 103.8 105.3 105.6
Rise: Gel Ratio 1.81 2.01 1.94 1.94
Final Height (mm) 278.4 279.6 280.8 272.6
24 Hour Height (mm) 263.4 265.5 265.5 257.6
% Shrinkage 5.4 5.0 5.4 5.5
Table 1.5 Machine mix free rise reactivity comparison using back formulation
Control BL53 Exp. SSF BL53/Exp. SSF
Formulation V VI VII VIII
Cream (Seconds) 4.8 4.5 4.8 4.8
Top of Cup (Seconds) 23.5 22.9 25.4 26.5
String Gel (Seconds) 53.2 52.1 55.6 55.9
Full Rise (Seconds) 109.5 108.7 111.9 111.2
Rise/Gel Ratio 2.06 2.08 2.02 1.99
Final Height (mm) 273.6 275.7 268.3 270.1
24 Hour Height (mm) 245.6 246.9 236.1 235.9
% Shrinkage 10.2 10.4 12.0 12.7
22
significant change in reactivity when comparing the control formulations to the

experimental formulations.
1.3.1.1b Machine Free Rise Reactivity
The machine mix free rise reactivity comparison of all formulations are shown in
Tables 1.4 and 1.5. This experimental data illustrates that the overall free rise foam
reactivity for both the cushion and back formulations remains relatively the same for
the beginning of the reaction. The full rise reactivities in cushion formulations II, III
and IV and back formulations VII and VIII start to deviate slightly from the control
reference formulations I and V.
Percent shrinkage remains fairly consistent within the cushion formulations, I, II, III and
IV. Increased foam shrinkage was observed with back formulations VII and VIII. This
could be attributed to better cell wall drainage efficiency, providing more open foam
and/or an overall increased carbon dioxide diffusion through the polymer network.
1.3.1.2 Foam Physical Properties
1.3.1.2a TPR Effect on Machine Run Moulded Foam FTC
When producing polyurethane, manufacturers use some type of mechanical crushing to open
cells and insure the polyurethane article does not lose dimensional stability. Several techniques
can be used to provide the needed mechanical cell opening. Manufacturers will use TPR,
which has been described in Section 1.2.3.2d, along with mechanical roller crushing. Some
producers will rely exclusively on the roller crushing and vacuum crushing techniques to
provide the mechanical cell opening required. In both cases reducing FTC values and improving
foam openness is important for producing polyurethane articles that are dimensionally stable.
If TPR is carried out too soon during the polyurethane moulding cycle, the article will
collapse (blowout) as indicated in Figure 1.9. This is indicative of the foam being
insufficiently cured or lacking enough green strength when TPR was applied. If TPR is
conducted too late in the manufacturing process scalloping (concave surface areas on the
foam article) and tight foam (insufficient number of open cells within the foam article
that causes the hot gas to be trapped and upon cooling forces the entire foam part to
shrink) may also occur. When scalloping occurs the foam article must be repaired or
scrapped. When tight foam occurs dimensional stability will suffer and there will be a
negative impact on physical properties as denoted in Figure 1.10. The foam pad in Figure
1.10 was produced at a 140 second TPR without crushing using formulation V.
23
Figure 1.9 Example of a Collapse/Blowout Moulded Foam

(Reproduced with permission from APCI)
Figure 1.10 Example of Tight Foam with Shrinkage

(Reproduced with permission from APCI)
24
To understand the benefits of these new additive technologies that provide reduced FTC
values, a TPR range from 70 to 150 seconds was run for each of the formulations in
Tables 1.2 and 1.3. At a 70 second TPR all formulations suffered blowout since the foam
was not sufficiently cured and thus lacked green strength. At an 80 second TPR, no
formulations evaluated experienced blowouts or collapse; however, slight distortions
and imperfections were evident on the foam surfaces to varying degrees of severity. To
complete the TPR window, TPR cycle times were continually ramped up in this fashion
to determine the upper limit at which TPR could be applied for each formulation. The
upper limit is reached for a given formulation when the foam displays the obvious signs
of scalloping and/or ‘dishing’ (concave surface areas of the foam). When this occurs the
foam is usually very tight and cannot be used as a functional part. Additionally, parts
were produced without utilising TPR during the production cycle in order to compare
the difference in foam crushability when TPR is used.
1.3.1.2b Cushion Formulation Machine Evaluation Utilising TPR
Cushion control formulation I, which is listed in Table 1.2, was evaluated at a 90-100
second TPR. Initial FTC values of 156 N/323 cm2 for a 90 second TPR and 165 N/323
cm2 for an 100 second TPR were observed. These values were acceptable and produced
foam parts of good quality. The new additives in formulations II, III and IV produced
maximum initial FTC values of 160 N/323 cm2 at TPR of 90 to 100 seconds. Foam
produced at an 80 second TPR for the control formulation I and formulations II, III and
IV containing the new additives resulted in minor problems with foam quality, i.e.,
scalloping. At a 70 second TPR, control and experimental formulations failed because of
severe blowout. Figures 1.11 and 1.12 show no significant difference of FTC for all
formulations evaluated.
When TPR values were increased to 120 seconds for control formulation I, initial values
increased to 623 N/323 cm2 and scalloping or foam quality suffered (Figure 1.13).
However, increasing the TPR time for cushion formulations II, III and IV to 120 seconds,
produced maximum initial FTC values of 205 N/323 cm2 (Figure 1.13). Foam surface
quality was very good. Increasing the TPR to 140 seconds increased initial FTC values to
a maximum of 543 N/323 cm2 and 534 N/323 cm2 for formulations II and III, respectively
(Figure 1.14). Foam quality was still very good. Formulation IV, which utilises a
combination of both surfactant and catalyst technologies, achieved a lower initial FTC
value at a 140 second TPR of 191 N/323 cm2. This was only slightly higher than the FTC
values of the control formulation at a 90 second TPR. Figures 1.11, 1.12, 1.13, and 1.14
show the results of FTC through the entire TPR range applied in this study. These figures
clearly demonstrate that use of the new additives can reduce FTC values and maintain
dimensional stability over the applied TPR range.
25
Figure 1.11 FTC at 90 TPR - Cushion Formulation
26
27
Figures 1.15, 1.16, and 1.17 further demonstrate the reduction of FTC values that can
be achieved when the new catalyst and surfactant technologies are utilised. These figures
clearly show a large difference achieved from plotting initial FTC to the final FTC cycle
versus increasing TPR cycle times. Moreover, the lower delta FTC values obtained indicate
an improved crush-out capability. The optimum TPR range for control formulation I is
90-100 seconds, while the optimum range for formulations II and III is increased to 120
Figure 1.15 Initial FTC versus TPR Time - Cushion Formulation
Figure 1.16 Delta Difference of 1st to 3rd FTC versus TPR Time - Cushion Formulation
28
Figure 1.17 Delta Difference of Initial to Final FTC versus TPR Time - Cushion Formulation
seconds. Formulation IV provided reduced FTC values up to a 140 second TPR.

Formulation I did not provide acceptable foam surface quality above 100 second TPR.
Formulations II, III and IV provided good surface quality and acceptable physical
properties throughout the entire TPR range.
1.3.1.2c Back Formulation Machine Evaluation Utilising TPR
Back formulation evaluations were carried out in the same manner as the cushion
formulation study. Because of lower solids and higher water content necessary to obtain
specific densities and physical properties, this system was more sensitive to processing
and TPR range than the cushion formulation.
Back formulations V, VI, VII and VIII found in Table 1.3, were all run at TPR times of
70-150 seconds and no TPR. Collapsed foam was encountered at TPR times of 70 seconds
for all formulations. FTC values for the back control formulation V had an initial FTC
value of 138 N/323 cm2 at a 90 TPR and 160 N/323 cm2 at a 100 second TPR time.
Formulations VI, VII and VIII produced a maximum initial FTC value at a 90 and 100
second TPR of 138 N/323 cm2. Control formulation V and experimental formulations
VI, VII and VIII provided acceptable FTC values at 90 and 100 second TPR times (Figures
18 and 19). No significant difference in FTC was realised with these formulations at
these TPR times. The foam quality at this TPR range was also very good. When TPR
times were increased to 120 seconds for control formulation V, initial FTC increased to
645 N/323 cm2. Experimental formulations VI, VII and VIII maintained acceptable initial
29
Figure 1.18 FTC at 90 TPR - Back Formulation
Figure 1.19 FTC at 100 TPR - Back Formulation
FTC values of 334 N/323 cm2, 245 N/323 cm2 and 156 N/323 cm2, respectively, (Figure
1.20). At a 120 second TPR, control formulation V exhibited scalloping while the
experimental formulations VI, VII and VIII continued to produce parts with good foam
quality. Initial FTC values for the control formulation V increased to 1,045 N/323 cm2
at a 140 TPR and severe shrinkage was observed. FTC values for formulations VI and
VII reached maximum values of 649 N/323 cm2, respectively, and 627 N/323 cm2 at a
30
Figure 1.20 FTC at 120 TPR - Back Formulation.
Figure 1.21 FTC at 140 TPR - Back Formulation.
140 second TPR (Figure 1.21). Foam produced for these two formulations at a 140
second TPR still produced acceptable quality foam. Formulation VIII achieved lower
FTC values than any of the back formulations evaluated at a 140 second TPR range. The
initial FTC value for formulation VIII was 405 N/323 cm2 with foam surface quality
maintained (Figure 1.21). Figures 1.18, 1.19, 1.20, and 1.21 show the results of FTC
values through the entire TPR range utilised in this study.
31
Figures 1.22, 1.23, and 1.24 further demonstrate the reduction of FTC values that can
be achieved in the back formulations when the new catalyst and experimental silicone
surfactant technologies are utilised. At a 90 and 100 second TPR, control formulation V
produces good quality foam. When the TPR is increased above 100 seconds foam tightness
and surface quality issues arise with the control formulation. Formulations VI, VII and
VIII yield good quality foam at all TPR cycle times used in this study. As in the cushion
formulation, these lower FTC delta values demonstrate how these newly developed
additives enhance crush-out capabilities. Furthermore, this effectively illustrates that the
TPR window can be extended as compared to the control formulation.
Figure 1.22 Initial FTC versus TPR Time - Back Formulation
Figure 1.23 Delta Difference of 1st to 3rd FTC versus TPR Time - Back Formulation
32
Figure 1.24 Delta Difference of Initial to Final FTC versus TPR Time - Back Formulation
1.3.1.2d Cushion and Back Formulation Machine Evaluation Without TPR
Several polyurethane manufactures do not utilise TPR in their production process. The
formulations evaluated in this study were designed to utilise TPR when producing
polyurethane articles. However, indications of reduced force required to crush a pad
using roller crushing and/or vacuum rupture can be understood from the data generated
when TPR is not applied to the process. The initial FTC values recorded for the control
cushion and back formulations I and V were 1,379 N/323 cm2 and 1,299 N/323 cm2,
respectively. Using formulations II, III, VI and VII, FTC values were reduced to 1,152 N/
323 cm2 and 1,090 N/323 cm2 for the cushion formulation and 1036 N/323 cm2 and
1023 N/323 cm2 for the back formulation. Only minimal shrinkage was observed with
the surface quality being maintained. Using formulations IV and VIII, FTC values could
further be decreased to 1032 N/323 cm2 and 943 N/323 cm2, respectively. Again, foam
surface quality was good with only minimal shrinkage being observed. Figures 1.25 and
1.26 show the FTC values obtained when no TPR was applied during this study.
1.3.1.2e Machine Physical Property Data Comparisons of Various TPR Times
Physical properties were evaluated for all the formulations found in Tables 1.2 and 1.3
with TPR being applied at various times throughout the moulding cycle as previously
discussed. Additionally, physical properties were evaluated with no TPR being applied.
The 90 second TPR time was chosen to be the minimum time to perform TPR for all
formulations. Physical property pads were produced at this TPR time. Extended TPR
33
Figure 1.25 FTC at No TPR - Cushion Formulation
Figure 1.26 FTC at No TPR - Back Formulation
times were achieved with the experimental formulations. Physical property pads for
physical testing were produced at these extended times.
Various TPR windows were identified for the formulations outlined in Tables 1.2 and 1.3.
The control formulations I and V both had an upper TPR range of 100 seconds. At a 110
second TPR both formulations I and V had scalloping and surface distortion issues (see
Section 1.3.1.2a). Thus the effective TPR range for formulations I and V is 90 to 100
34
seconds. This provides a very narrow process range when utilising TPR with these specific
formulations. However, when using the Dabco BL-53 catalyst, or X-N1586/X-N1587
experimental silicone surfactants, both cushion and back formulation TPR times can be
extended well beyond the 100 second TPR upper limit of the control formulations I and V.
1.3.1.2f Physical Property Comparison at 90 Second TPR
Tables 1.6 and 1.7 provide the physical property comparison for all formulations I-VIII
at a 90 second TPR time. The data clearly demonstrates that physical properties are
maintained, and in several cases improved, compared to the control formulations. For
example, airflow can be improved by as much as 20% as compared to both cushion and
back control formulations, when using Dabco BL-53 and experimental silicone surfactants
Table 1.6 Physical properties at 90 TPR: cushion formulation

Physical Property Control BL53 Exp. SSF BL53/
Exp. SSF
I II III IV
ILD (N) AVG SD AVG SD AVG SD AVG SD
25% 175 2.2 181 1.5 185 3.1 184 2.8
65% 455 3.5 468 2.1 492 2.4 487 4.1
25% Return 154 1.5 159 1.8 160 1. 5 163 1.8
Ball Rebound (%) 61 (1.5) 63 0.6 61 0.9 62 0.6
Airflow (SLM) 38 5.8 47 4.2 50 5.1 57 6.2
3
Density (kg/m ) 44 0.8 44 0. 4 43 0.8 44 0.7
Tensile (kPa) 179 8.4 183 3.1 187 5.4 180 3.2
Tear (N/m) 254 12.1 261 8.9 291 13.3 292 9.4
Elongation (%) 176 7.2 182 6.1 182 5. 8 179 5.1
Wet Set (%) 22 (1.2) 21 0.9 20 0.9 18 1.7
50% Compression Set 5 0.3 5 0.2 5 0.3 4 0.1
50% Humid Aged 12 0.9 10 0.4 9 0.3 8 0.5
Compression Set
SD: Standard Deviation
ILD: indentation load deflection
SLM: standard litres per minute
35
Table 1.7 Physical properties at 90 TPR: back formulation

Physical Properties Control BL53 Exp. SSF BL53/
Exp. SSF
V VI VII VIII
25% 125 3.0 134 3.6 144 1.8 155 1.7
65% 35 4 3.9 370 5.8 396 5.9 422 6.0
25% Return 10 8 1.7 116 2.9 122 1.7 128 3.1
Ball Rebound (%) 60 2.1 60 0.9 60 1.2 60 1.2
Airflow (SLM) 37 2.5 48 1.2 49 4.1 50 3.8
3
Density (kg/m ) 35 0.6 36 1.2 36 1.2 36 1.2
Tensile (kPa) 137 6.3 145 5.1 155 9.7 163 10.1
Tear (N/m) 245 9.6 254 10.5 268 11.5 275 11.8
Elongation (%) 165 8.2 176 4.7 170 8.9 178 10.5
Wet Set (%) 24 1.1 22 1.1 18 1.2 19 1.2
50% Compression Set 8 0.5 8 0.2 4 0.2 4 0.5
50% Humid Aged 14 1.2 10 0.3 10 0.4 9 0.5
Compression Set
SD: Standard Deviation
ILD: indentation load deflection
SLM: standard litres per minute
X-N1586/X-N1587 in combination (formulations IV and VIII). Furthermore, Japanese

wet set values [6] can be improved by 5 to 8% with the Dabco BL-53, and experimental
silicone surfactants X-N1586 and X-N1587. Wet set values are improved nearly 20%
when the two additives are utilised in combination as evidenced by Formulations IV and
VIII. Equally important, humid aged compression set, tensile and tear physical properties
display a positive improvement trend as compared to the control formulations.
36
1.3.1.2g Physical Property Comparison at 130 and 150 Second TPR
Tables 1.8 and 1.9 illustrate the physical properties for selected formulations at TPR
times of 130 and 150 seconds. Control physical properties were not evaluated at these
extended TPR times since the control formulations I and V had visual surface distortions
and severe scalloping. The data in Tables 1.8 and 1.9 demonstrate that the TPR window
can be extended by using these newly developed additives without negative impact to the
physical properties. In fact, the data indicates that several of the physical properties for
the experimental formulations exceed the control formulation properties at the 90 second
TPR time. For example, airflow measurements are improved when utilising the extended
TPR times. Improvements are greater than 10% with the Dabco BL-53 catalyst and
experimental silicone surfactant combinations. Additional improvements are also observed
with wet set and 50% humid aged compression set values.
Table 1.8 Physical properties at 130 TPR and 150 TPR: cushion formulation
Physical Properties 130 TPR 150 TPR
BL53 Exp. SSF BL53/Exp. SSF
II III IV
ILD (N) AVG SD AVG SD AVG SD
25% 175 1.8 164 3.5 174 1.1
65% 434 2.5 457 1.0 467 4.5
25% Return 138 1.8 143 1.5 152 1.1
Ball Rebound (%) 61 0.5 62 0.5 61 0.4
Airflow (SLM) 43 3.2 46 4.7 53 7.4
3
Density (kg/m ) 43 0.8 42 0.8 43 0.7
Tensile (kPa) 174 4.1 180 5.1 170 3.5
Tear (N/m) 255 7.4 274 10.5 279 12.1
Elongation (%) 180 3.9 180 3.5 173 3.3
Wet Set (%) 21 1.5 19 1.3 19 0.3
50% Compression Set 5 0.5 5 0. 1 4 0 .3
50% Humid Aged 10 0.8 10 0.8 8 0.3
Compression Set
37
Table 1.9 Physical properties at 130 TPR and 150 TPR: back formulation
Physical Properties 130 TPR 150 TPR
BL53 Exp. SSF BL53/ BL53/
Exp. SSF Exp. SSF
VI VII VIII VIII
25% 111 2.1 145 4.2 156 0.7 155 1.2
65% 344 5.1 396 3.5 435 8.0 430 3.0
25% Return 96 2.2 123 2.2 132 0.6 129 2.1
Ball Rebound (%) 59 1.4 59 1.5 62 0.7 60 0.2
Airflow (SLM) 49 5.5 45 2.3 49 1 .8 52 2.1
3
Density (kg/m ) 35 0.8 36 1.0 36 0.8 36 0.2
Tensile (kPa) 136 5.1 148 5.4 152 7.9 147 6.1
Tear (N/m) 254 9.1 261 8.0 248 8.0 239 5.8
Elongation (%) 170 9.3 166 5.3 163 5.6 175 4.9
Wet Set (%) 22 1.1 19 0.8 19 0.5 19 0.8
50% Compression Set 9 0.2 5 0.3 4 0.2 4 0.6
50% Humid Aged 10 0.5 10 0.6 9 0.5 9 0.8
Compression Set
1.3.1.2h Physical Property Comparison with No TPR
Tables 1.10 and 1.11 illustrate the physical property performance of all formulations I
through VIII without utilising TPR. Given that the specific formulations were designed
to be used with the TPR process, foam pads produced under these conditions were very
tight upon demoulding. Mechanical crushing at 30 seconds after demould was required
instead of the one minute time frame; otherwise, irreversible shrinkage may have occurred
prior to placing the foam through the roller crusher. The data in Tables 1.10 and 1.11
indicate that utilising Dabco BL-53 catalyst and/or the experimental silicone surfactants
X-N1586 and X-N1587, have a positive influence on the physical properties even when
no TPR is applied. Moreover, if the properties of the new additives are compared to the
control formulations I and V at the 90 second TPR time (Tables 1.5 and 1.6), physical
properties are not adversely affected. In some instances the properties are still maintaining
their improvement over the control formulations. Control formulations run at no TPR
exhibited surface quality distortions.
38
Table 1.10 Physical properties at no TPR: cushion formulation

Exp. SSF
I II III IV
25% 145 0.5 150 1.2 157 0.5 157 2.1
65% 395 0.5 407 2.2 428 3.0 428 4.2
25% Return 127 0.5 131 1.1 136 0.5 138 2.1
Ball Rebound (%) 60 0.7 61 1.4 61 1.0 62 0.7
Airflow (SLM) 34 2.6 42 2.5 47 6.2 49 1.3
3
Density (kg/m ) 42 0.8 42 0.5 41 0.6 41 0.6
Tensile (kPa) 159 5.3 160 5.4 175 3.5 169 4.5
Tear (N/m) 241 6.7 252 6.7 269 10.6 268 11.1
Elongation (%) 174 4.1 180 4.2 174 4.5 174 4.3
Wet Set (%) 24 0.6 22 0.9 22 0.2 20 0.3
50% Compression Set 6 0.2 5 0.1 5 0.2 5 0.2
50% Humid Aged 12 0.2 10 0.1 10 0.7 9 0.1
Compression Set
1.3.1.2i Physical Property Review
All of the physical property data generated at the higher TPR cycle times illustrates that the
window for TPR can be extended when using Dabco BL-53 catalyst and X-N1586, X-
N1587 experimental silicone surfactants. Physical properties were not adversely affected
when compared to the control samples. By extending the effective TPR window, polyurethane
moulders who utilise this process will enjoy a greater latitude for their processing, providing
more freedom to troubleshoot difficult tooling and moulding operations. Additionally,
polyurethane manufacturers that do not practice the TPR process can also benefit with
improvements realised for physical properties and dimensional stability, as illustrated by
many of the physical properties enhancements found in Tables 1.9 and 1.10.
Finally, the question remains whether the stability, especially shear stability, suffers from the
significantly improved breathability and dimensional stability provided with these new
additives. Examination of cellular structures of the machine mixed free rise ‘chicken’ bucket
39
Table 1.11 Physical properties at no TPR: back formulation

Exp. SSF
V VI VII VIII
25% 103 0.5 113 2.1 127 0.7 138 5.0
65% 297 5.0 330 7.7 355 0.6 386 8.4
25% Return 89 0.5 98 2.5 107 0.6 115 3.5
Ball Rebound (%) 58 0.7 61 0.1 61 0.1) 61 1.4
Airflow (SLM) 39 1.1 46 3.1 47 5.1 46 3.8
3
Density (kg/m ) 35 0.5 35 0.8 35 0.8 35 0.8
Tensile (kPa) 123 4.9 135 8.8 132 5.7 140 9.9
Tear (N/m) 235 6.5 245 6.3 252 11.6 239 5.9
Elongation (%) 161 8.2 175 7.0 165 6.1 170 9.2
Wet Set (%) 23 1.8 22 1.6 19 0.2 21 1.0
50% Compression Set 9 1.0 9 0.4 6 0.4 5 0.3
50% Humid Aged 14 1.8 11 0.5 11 0.6 10 0.6
Compression Set
foams demonstrated no evidence of elongated cells or side shear in the outer edges of the cup.
Furthermore, when the TPR ramp study was being carried out it was determined that all
formulations had similar lower limit TPR times of approximately 90 seconds. Essentially,
this early TPR time would mimic a poorly sealed mould so that the shear forces become
obvious in and around the gap or space created by opening the mould. The foam mixture, if
not sufficiently stabilised or adequately cured, would be accompanied by a pressure relief
which leads to significant mechanical stress, causing collapse. The fact the Dabco BL-53
catalyst, X-N1586 and X-N1587 experimental silicone surfactants did not have blowouts or
shear collapses at the 90 second TPR illustrates shear stability is not compromised.
1.3.1.3 Scanning Electron Microscopy
A scanning electron microscopy study of moulded foam parts was carried out to understand
what affect the additives might have on the morphology of the foam cell structure. It is
clear from the SEM photomicrographs in Figures 1.27, 1.28 and 1.29 that there is no
40
Figure 1.27
Formulation I, Control
(Reproduced with permission
from APCI)
Figure 1.28
Formulation II, BL-53
from APCI)
Figure 1.29
Formulation III, Exp. SSF
from APCI)
41
visual effect on the cell structure of foam produced with the new additives as compared to
the control. The additives did not appear to have an affect on the cell morphology of a
crushed foam. However, it was not possible to determine differences in cell morphology
from an uncrushed part, since the parts were mechanically crushed to prevent normal
distortion from foam shrinkage. Formulations I, II and III were used for the SEM study.
1.3.2 Low Emission Dimensional Stability Additives
Another emerging need in the automobile market segment is for lower and ultimately no
emissions of polyurethane foam additives into the environment. Current efforts revolve
around automotive passenger compartment air quality improvements by reduction of
the emissions typically from the current migratory additives used to produce interior
foam components. These emissions can cause a variety of problems in the final application
of the foam, ranging from odour to vinyl staining and window fogging. The migratory
nature of current additives is accelerated by sunlight and heat. Thermally induced
dehydrohalogenation of the foam/covering interface is assisted by the migration of fugitive
tertiary amine catalysts causing vinyl staining (colour change). Breakdown of the vinyl
clad covering subsequently releases other chemical compounds, such as plasticisers, which
then contribute to window fogging. Consumers and automakers are becoming more
conscious of automotive interior air quality, interior vinyl degradation and film formation
(windshield fogging) [12].
This section of the chapter reports on the development of non-fugitive gelling and blowing
polyurethane catalysts to address the aforementioned emission issues. These catalysts
chemically bind to the polyurethane foam matrix (contain active hydrogens) rendering
them incapable of migrating back out of the foam after the reaction is complete, while
still producing a quality product. Equivalent or improved physical properties such as
airflow, compression set and crushability, must be maintained as compared to the industry
standards used in TDI-, MDI-based systems, and TDI/MDI blend systems. Presented in
this section is work using these non-fugitive catalysts in a variety of flexible polyurethane
foam applications, including MDI and TDI automotive and flexible slabstock
formulations. The results show that these new additives can give dimensional stability
and processability to the foam, while providing non-fugitive and non-fogging benefits.
Additionally, improvements to the physical properties of the polyurethane article when
using the new additives, occurs.
Accordingly, these non-fugitive catalysts provide good to excellent foam stabilisation,

cell regulation and cell wall drainage and are needed to enable polyurethane manufacturers
to maintain their standard production goals. Two experimental non-fugitive catalysts,
XF-N1085 and XF-O11006 were developed to provide open foam and promote
42
dimensional stability. During the development of non-fugitive catalysts, it was observed

that TDI formulations, in general, tend to be more closed cell with the use of these
catalysts compared to MDI systems. Therefore, the technology was advanced to
incorporate non-fugitivity and cell opening characteristics within a single catalyst.
XF-N1085 is a novel cell opening blowing, non-fugitive catalyst which affords all the
benefits of the well known Dabco BL-11, with the added advantage of cell opening and
no foam emissions. XF-N1085 is not a drop in replacement for Dabco BL-11. For rapid
demoulding of TDI systems, it is recommended that XF-N1085 be used at 0.2 to 0.4
php, with the optimum level at 0.25 to 0.35 pphp, in combination with an XF-O11006
level at 0.6 to 0.9 pphp. XF-O11006 is a novel cell opening gelling non-fugitive catalyst
which gives all the benefits of the well known Dabco 33-LV, with the added advantage of
cell opening, low volatility and no foam emissions. XF-O11006 is not a drop in
replacement for Dabco 33-LV.
Several representative industry cushion and back formulations, listed in Tables 1.12-
1.15, were utilised to compare multiple additives. Dabco NE200 was compared against
Table 1.12 ~45 kg/m3 TDI Lyondell cushion formulation

Formulation IX X XI XII
identification
Arcol E848 50.00 50.00 50.00 50.00
Arcol E851 50.00 50.00 50.00 50.00
Water 2.34 2.34 2.34 2.34
Dabco 33LV 0.25 - - -
Dabco BL-11 0.10 - - -
Dabco NE1060 - 0.08 0.53 -
Dabco NE200 - 0.64 - -
XF-N1085 - - 0.26 0.26
XF-O11006 - - - 0.68
Dabco DC5043 0.75 0.75 0.75 0.75
Dabco DEOA-LF 1.76 1.76 1.76 1.76
TDI (100 index) 32.74 32.74 32.74 32.74
43
Table 1.13 ~35 kg/m3 TDI Lyondell back formulation

Formulation Identification XIII XIV XV XVI
Arcol E848 70.00 70.00 70.00 70.00
Arcol E851 30.00 30.00 30.00 30.00
Water 3.24 3.24 3.24 3.24
Dabco 33LV 0.25 - - -
Dabco BL-11 0.10 - - -
Dabco NE1060 - 0.08 0.53 -
Dabco NE200 - 0.64 - -
XF-N1085 - - 0.26 0.26
XF-O11006 - - - 0.68
Dabco DC5043 1.00 1.00 1.00 1.00
Dabco DEOA-LF 1.76 1.76 1.76 1.76
TDI (100 index) 41.87 41.87 41.87 41.87
Table 1.14 ~45 kg/m3 TDI Dow cushion formulation

Formulation identification XVII XVIII XIX XX
NC-630 46.00 46.00 46.00 46.00
NC-700 54.00 54.00 54.00 54.00
Water 2.34 2.34 2.34 2.34
Dabco 33LV 0.25 - - -
Dabco BL-11 0.10 - - -
Dabco NE1060 - 0.22 0.70 -
Dabco NE200 - 0.64 - -
XF-N1085 - - 0.27 0.25
XF-O11006 - - - 0.80
Dabco DC5164 1.0 1.0 1.0 1.0
Dabco DC5169 0.5 0.5 0.5 0.5
Dabco DEOA-LF 1.76 1.76 1.76 1.76
TDI (100 index) 32.70 32.70 32.70 32.70
44
Table 1.15 ~35 kg/m3 TDI Dow back formulation

Formulation identification XXI XXII XXIII XXIV
NC-630 68.00 68.00 68.00 68.00
NC-700 32.00 32.00 32.00 32.00
Water 3.24 3.24 3.24 3.24
Dabco 33LV 0.25 - - -
Dabco BL-11 0.10 - - -
Dabco NE1060 - 0.27 0.58 -
Dabco NE200 - 0.52 - -
XF-N1085 - - 0.32 0.24
XF-O11006 - - - 0.77
Dabco DC5164 0. 2 0.2 0.2 0.2
Dabco DC5169 0.6 0.6 0.6 0.6
DEOA-LF 1.76 1.76 1.76 1.76
TDI (100 index) 41.92 41.92 41.92 41.92
Dabco BL-11 for equivalent blowing efficency. Dabco NE1060 was compared against
Dabco 33LV for equivalent gelling efficiency. Required blow:gel ratios are listed in each
table. Additionally, XF-N1085 and XF-O11006 were specifically developed as
dimensional stability/cell opening additives and they are also compared here.
1.3.2.1 Reactivity
Tables 1.16 and 1.17 illustrate that the overall free rise foam reactivity for both the cushion
and back formulations remains relatively the same for the entire foaming reaction. This
was achieved by balancing the experimental catalyst levels, blow:gel ratios, and matching
them to the control Dabco BL-11 and Dabco 33LV levels in IX, XIII, XVII and XXI.
45
Table 1.16 Machine mix free rise reactivity comparison using TDI
cushion formulations
Formulation IX X XI XII XVII XVIII XIX XX
Cream 4.9 4.8 4.8 4.5 3.5 3.8 4.5 4.9
(Seconds)
Top of Cup 37 36 39 35 32 35 36 37
(Seconds)
String Gel 56 55 56 53 53 53 55 56
(Seconds)
Full Rise 83 81 84 78 71 75 81 83
(Seconds)
Table 1.17 Machine mix free rise reactivity comparison using TDI
back formulations
Formulation XIII XIV XV XVI XXI XXII XXIII XXIV
Cream 3.8 3.8 3.8 3.4 4.2 3.2 3.2 3.2
(Seconds)
Top of Cup 30 33 32 31 32 37 36 37
(Seconds)
String Gel 58 56 59 57 54 55 57 56
(Seconds)
Full Rise 82 85 94 91 75 86 85 88
(Seconds)
1.3.2.2 Flexible Moulded Foam Machine Physical Property Data
To understand the benefits of these new additive technologies that provide low volatility,
no amine emissions, no fogging and, in some cases, cell opening, all TDI moulded
formulations were run on the Hi Tech machine. Several foams were produced for each
catalyst combination and formulation to obtain physical property pads, FTC pads,
shrinkage pads, and flow evaluations.
46
1.3.2.2a Standard Physical Properties
Tables 1.18 to 1.21 provide the physical property comparison for the TDI flexible moulded
formulations IX-XXIV. The data clearly demonstrates that physical properties are
maintained, and in several cases improved, compared to the control formulations,
depending on the formulation and the use of experimental cell-opening catalysts. For
example, ILD properties were comparable or improved over the control in both low and
high solids formulations, especially in the Dow polyol system. This is attributed to the
slightly different polymer matrix resulting from non-fugitive catalysis which can produce
higher load properties. In almost all cases, the support factor was comparable to the
control. Tensile values in the Dow system were matched to the control using XF-N1085
in combination with Dabco NE1060, formulations XIX and XXIII. Dry and humid
compression sets (50% dry, 50% humid aged, and 75% humid aged) were, in many
formulations, slightly elevated, with the Dabco NE1060/XF-N1085 catalyst combination
(XIX and XXIII) closest to the control. The compression set data illustrates that this
Table 1.18 Physical properties for Lyondell TDI cushion formulations

Physical Property IX X XI XII
25% 180 - 170 - 182 - 181 -
65% 534 - 486 - 522 - 517 -
25% Return 157 - 150 - 160 - 158 -
Ball Rebound (%) 64 1.0 65 0.8 64 1.2 65 0.7
Airflow (SLM) 48 5.7 45 8.5 62 11.3 40 2.8
3
Density (kg/m ) 42 1.3 44 0.5 43 1.0 44 1.0
Tensile (kPa) 143 10.1 136 66.7 163 7.8 176 6.5
Tear (N/m) 193 12 186 7 217 23 193 7
Elongation (%) 98 7.0 102 6.3 97 6.1 102 10.6
Wet Set (%) 18 1.0 20 1.2 20 0.9 22 1.4
50% Compression Set (%) 5 0.4 8 1.1 6 0.1 7 0.7
50% Humid Aged 9 0.2 16 0.8 6 0.5 17 1.2
Compression Set (%)
Hysteresis (%) 19 0.1 18 0.1 19 0.1 20 0.4
Support Factor 3.0 - 2.9 - 2.9 - 2.9 -
47
Table 1.19 Physical properties for Lyondell TDI back formulations

Physical Property XIII XIV XV XVI
25% 103 - 97 - 99 - 103 -
65% 315 - 287 - 289 - 310 -
25% Return 87 - 84 - 86 - 89 -
Ball Rebound (%) 62 0.8 64 0.56 64 1.1 62 0.7
Airflow (SLM) 65 5.7 62 8.5 71 11.3 59 2.8
Density (kg/m3) 31 1.0 30 0.9 31 1.3 30 0.9
Tensile (kPa) 104 4.5 119 6.8 112 8.7 121 4.4
Tear (N/m) 243 19 224 21 259 16 259 19
Elongation (%) 93 5.7 97 7.6 100 4.2 100 7.4
Wet Set (%) 27 0.9 25 0.9 26 1.0 26 0.9
50% Compression Set (%) 6 0.7 8 0.4 7 0.53 8 0.4
50% Humid Aged 16 0.6 20 1.2 20 1.1 17 1.0
Compression Set (%)
Hysteresis (%) 21 0.1 18 0.2 20 0.2 20 0.1
Support Factor 3.1 - 3.0 - 2.9 - 3.0 -
property is very system dependent when using non-fugitive catalysts. For performance
optimisation, one may want to consider reformulation to produce the desired physical
properties. The use of XF-N1085 and XF-O11006 will improve or maintain physical
properties compared to the control for TDI systems. The Japanese wet set data was
determined to be comparable or, in the case of the Lyondell back formulation, slightly
improved when compared to the control foam.
The use of cell opening non-fugitive catalysts was found to improve wet sets in the
Lyondell high solids formulation. In addition, the cell opening catalysts were also found
to decrease hysteresis and increase tensile strength in the back formulations using Lyondell
polyol compared to the control formulation.
48
Table 1.20 Physical properties for Dow TDI cushion formulations

Physical Property XVII XVIII XIX XX
25% 106 - 180 - 180 - 193 -
65% 321 - 51 3 - 518 - 551 -
25% Return 92 - 155 - 156 - 166 -
Ball Rebound (%) 56 0.6 55 1.9 56 0.8 57 0.8
Airflow (SLM) 17 2.8 23 5.7 17 2.8 20 2.8
Density (kg/m3) 45 0.4 44 0.6 44 0.8 44 0.7
Tensile (kPa) 215 14.3 176 6.8 205 4.0 171 13.7
Tear (N/m) 210 11 210 16 235 18 221 14
Elongation (%) 100 7.0 93 6.6 89 6.9 103 5.8
Wet Set (%) 16 0.2 21 1.4 20 0.6 17 0.6
50% Compression Set (%) 6 0.6 9 0. 1 8 0.3 8 0.3
50% Humid Aged 13 0.5 17 0.8 20 2.6 18 0.7
Compression Set (%)
Hysteresis (%) 21 0.1 21 0.1 21 0.6 22 0.1
Support Factor 3.1 - 2.9 - 2.9 - 2.9 -
1.3.2.2b Dynamic Fatigue Results
Table 1.22 shows the dynamic fatigue test results for Lyondell and Dow cushion foams
tested for 80,000 cycles and 60 minute recovery time. Results indicate that equivalent
dynamic fatigue values are obtainable with use of the new non-fugitive and cell opening
catalysts, based on nominal test error of ± 3.
1.3.2.2c FTC Results
In both the Lyondell cushion and back formulations IX through XVI listed in Tables
1.11 and 1.12, addition of XF-N1085 and XF-O11006 result in a reduction in FTC
values (Tables 1.22 and 1.23) throughout the initial several repetitions of the crushing
cycle illustrated in Figures 1.30 and 1.31. At the end of the ten complete repetitions, all
three experimental catalyst packages, resulted in the same final FTC value. Without the
49
Table 1.21 Physical properties for Dow TDI back formulations

Physical Property XXI XXII XXIII XXIV
25% 108 - 100 - 110 - 115 -
65% 315 - 299 - 313 - 311 -
25% Return 94 - 87 - 95 - 100 -
Ball Rebound (%) 63 0.8 60 1.7 60 1.9 63 0.8
Airflow (SLM) 48 2.8 62 8.5 45 5.7 59 5.7
Density (kg/m3) 33 1.0 33 0.4 33 0.9 32 0.3
Tensile (kPa) 145 5.4 127 7.4 141 5.8 139 4.8
Tear (N/m) 249 9 242 4 247 16 263 23
Elongation (%) 106 11.0 98 8.0 109 12.7 105 4.9
Wet Set (%) 21 0.9 16 1.3 22 1.7 19 1.9
50% Compression Set (%) 5 0.4 7 0.6 8 0.6 7 0.4
50% Humid Aged 15 0.9 31 2.1 21 0.2 26 1.8
Compression Set (%)
Hysteresis (%) 19 0.1 18 0.2 20 0.1 19 0.2
Support Factor 2.9 - 3.0 - 2.9 - 2.7 -
Table 1.22 Dynamic fatigue ASTM D3574-95 [5] (80,000 cycles)

Original 40% Final 40% % Change (%)
Deflection Deflection
Force (N) Force (N)
IX 282 244 13.4
X 258 207 19.9
XI 273 222 18.6
XII 272 238 12.7
XVII 302 228 24.4
XVIII 261 206 20.9
XIX 264 200 24.3
XX 280 297 29.5
50
Table 1.23 FTC values for TDI cushion in Lyondell system

Lyondell High Solids (N)
Frequency FTC Value FTC Value FTC Value FTC Value
IX X XI XII
1 767 923 738 698
2 356 540 345 349
3 242 316 234 249
4 198 236 189 205
5 167 193 162 178
6 149 167 160 171
7 140 151 158 167
8 138 145 156 160
9 138 140 158 160
10 133 127 156 160
Figure 1.30 FTC Graph for TDI Cushion in Lyondell System

(Ref. Table 1.22)
51
Figure 1.31 FTC Graph for TDI Back in Lyondell System

(Reference Table 1.23)
use of these cell opening catalysts, the Dabco NE1060/Dabco NE200 non-fugitive catalyst
package tightens the foam resulting in slightly elevated values during several initial FTC
footplate depressions.
In the cushion Dow formulations XVII through XX, the XF-N1085 and XF-O11006
show similar trends to the Lyondell formulations with reduced FTC (Figure 1.32 and
Table 1.24), thereby producing a more dimensionally stable foam. In contrast, for the
low solids back formulations XXI through XXIV, all catalyst combinations exhibited
no significant difference to the control catalyst (Figure 1.33 and Table 1.25). Inherent
tightness in this particular back formulation did not allow the same degree of catalyst
differentiation to occur in these foams. Adjustment to the catalyst loading levels would
be required to demonstrate the same reduced FTC performance as previously described
in other formulations.
Figures 1.34 and 1.35 further demonstrate the reduction of FTC values that can be
achieved with these new catalyst technologies. The graphs indicate the results achieved
by plotting the delta of the initial and third FTC value for every formulation. Moreover,
lower delta values illustrate an improved crush-out capability.
52
Figure 1.32 FTC Graph of TDI Cushion in Dow System

Table 1.24 FTC values for TDI back in Lyondell system

Lyondell Low Solids (N)
XIII XIV XV XVI
1 830 858 698 683
2 474 558 427 409
3 294 360 251 245
4 196 236 169 165
5 151 182 129 129
6 118 136 107 105
7 100 11 6 91 91
8 85 96 80 80
9 76 85 76 71
10 73 80 69 64
53
Figure 1.33 FTC Graphs for TDI Back in Dow System

Table 1.25 FTC values for TDI cushion in Dow system

Dow High Solids (N)
XVII XVIII XIX XX
1 1014 1234 959 843
2 654 885 620 516
3 471 641 454 383
4 369 503 360 309
5 314 414 305 267
6 274 347 280 240
7 254 298 256 225
8 236 247 229 211
9 216 249 207 196
10 207 220 187 191
54
Table 1.26 FTC values for TDI back in Dow system

Dow Low Solids (N)
XXI XXII XXIII XXIV
1 936 881 901 905
2 500 505 516 500
3 309 311 311 298
4 227 231 211 209
5 171 178 158 167
6 138 140 127 138
7 116 111 107 118
8 100 96 93 105
9 87 82 82 98
10 80 69 76 89
Figure 1.34 Delta Difference Graph of First and Third FTC Values in Lyondell System
55
Figure 1.35 Delta Difference Graph of First and Third FTC Values in Dow System
1.3.2.2d Pail Test Results
Visual examination of the foam slice’s cellular structure showed no evidence of

elongated cells or side shear collapse near the outer edges. The appearance of these
elongated cells or side shear collapse is a phenomenon created by the frictional drag
of the plastic pail (see Section 1.2.3.2e) on the rising foam. Each slice was measured
for maximum height, normalised by weight and displayed in Figure 1.36 for
comparison of final foam recession to the control. It is evident from the data that no
significant difference exists in bulk stability when using any of the cell opening or
non-fugitive catalysts.
1.3.2.2e Maze Mould Test Results
Data in the Lyondell system, formulations IX through XVI, generated using the
previously described maze flow mould is summarised in Tables 1.27 and 1.28 and
56
Figure 1.36 Graph Comparing 24 Hour Pail Height
Table 1.27 Maze flow mould data for Lyondell TDI cushion formulations IX - XII
Formulation Identifier Pad wt. (g) Flow past 5th gate (g) % of Total pad wt.
MINIMUM 5th Gate
IX 405 30 8.0
X 404 30 8.0
XI 405 35 9.5
XII 409 30 7.9
MEDIAN 5th Gate
IX 474 101 27.1
X 472 104 28.3
XI 478 109 29.5
XII 479 105 28.1
MAXIMUM 5th Gate
IX 524 150 40.1
X 526 160 43.7
XI 531 161 43.5
XII 528 155 41.6
57
Table 1.28 Maze flow mould data for Lyondell TDI back formulations XIII-XVI
MINIMUM 5th Gate
XIII 619 92 17.5
XIV 617 102 19.8
XV 615 108 21.3
XVI 616 107 21.0
MEDIAN 5th Gate
XIII 667 143 27.3
XIV 666 153 29.8
XV 665 160 31.7
XVI 668 156 30.5
MAXIMUM 5th Gate
XIII 718 193 36.8
XIV 715 202 39.4
XV 716 206 40.4
XVI 718 208 40.8
shown graphically in Figure 1.37. The graph utilises a xy scatter plot with linear
regression trendlines and R2 values (coefficient of determination) reported for each
formulation group. It compares estimated and actual y-values and ranges in value
from zero to one. Since these values are very close to one, there is a near perfect
correlation in the samples. However, if the coefficient of determination approaches
zero, the regression equation is not helpful in predicting a y-value. The data trends
suggest that increasing part weight, regardless of formulation type, shows no significant
penalty in flow compared to the control formulations IX and XIII.
Similar maze flow mould results are also obtained with the Dow cushion and back
formulations summarised in Tables 1.28 and 1.29 and shown graphically in Figure 1.38.
In these Dow formulations, XVII through XXIV, the data suggests slightly improved
linear regression trendlines and R2 values. Again, no significant penalty in flow is observed
as compared to the control formulations XVII and XXI.
58
Figure 1.37 Maze Flow Mould Graph for Formulations IX-XVI
Table 1.29 Maze flow mould data for Dow TDI cushion formulations XVII-XX
MINIMUM 5th Gate
XVII 404 40 11.0
XVIII 403 36 9.8
XIX 399 34 9.3
XX 404 25 6.6
MEDIAN 5th Gate
XVII 457 93 25.6
XVIII 457 92 25.2
XIX 458 100 27.9
XX 453 69 18.0
MAXIMUM 5th Gate
XVII 509 149 41.4
XVIII 508 140 38.0
XIX 508 149 41.5
XX 513 136 36.1
59
Table 1.30 Maze flow mould data for Dow TDI back formulations XXI-XXIV
MINIMUM 5th Gate
XXI 568 65 12.9
XXII 566 70 14.1
XXIII 565 64 12.8
XXIV 569 83 17.1
MEDIAN 5th Gate
XXI 617 122 24.7
XXII 616 120 24.2
XXIII 614 112 22.3
XXIV 618 132 27.2
MAXIMUM 5th Gate
XXI 668 168 33.6
XXII 665 172 34.9
XXIII 666 164 32.7
XXIV 670 183 37.6
Figure 1.38 Maze Flow Mould Graph for Formulations XVII-XXIV
60
1.3.2.2f Shrinkage Test Results
Shrinkage results displayed in Figures 1.39 and 1.40 were generated with the shrinkage
apparatus previously described in the experimental section. Overall, the cavity shrinkage is
much greater as compared to the lid shrinkage, evidenced in both Lyondell and Dow polyol
systems. The use of Dabco NE1060/Dabco NE200 produced foams with more shrinkage
than the control catalysts. However, utilising non-fugitive cell opening catalysts, XF-N1085
and XF-O11006 resulted in shrinkage comparable to the control and in some cases even less.
As expected, less shrinkage was observed in both Dow and Lyondell cushion formulations
due to the increased solids loading as compared to their respective back formulations.
Figure 1.39 Uncrushed Foam Shrinkage for Lyondell System
Figure 1.40 Uncrushed Foam Shrinkage for Dow System
61
9.3.2.2g Fogging Test Results
Several machine foam samples were tested in accordance with fogging test method SAE
J1756-94 [9]. Results are listed in Table 1.31. The results obtained in the Lyondell polyol
system showed improved percentage reflectance over the control indicating reduced
emissions from the foam. Comparable results were obtained in all the Dow polyol system
samples regardless of catalyst use.
Table 1.31 Fogging results

System Identifier % of Reflectivity
IX 87
X 97
XI 98
XII 96
XVII 93
XVIII 92
XIX 93
XX 93
1.3.2.2h Headspace Analysis and Vinyl Staining Test Results
Headspace analysis in series with gas chromatography and mass spectrometry has
indicated no emissions from the experimental non-fugitive catalysts mentioned in this
paper. Emissions from the fugitive control catalysts were measured and identified. These
results support the fact that these experimental catalysts will result in no VOC emissions
which will ultimately yield no amine fogging and no vinyl staining from the final
polyurethane foam article. Additional volatility measurements have indicated that these
experimental catalysts volatilise 3 to 10 times less than the current industry standards
(Dabco 33LV and Dabco BL-11) in the temperature range of 0 °C to 150 °C.
Vinyl staining tests using commercial formulations and various grades and types of vinyl
have indicated that the experimental catalysts mentioned in this chapter do not contribute
to vinyl staining. Compared to industry standard amine catalysts, use of these experimental
non-fugitive catalysts will result in significant reduction (ΔE of less than 2) in staining
measurements [12]. DE is the numerical total colour difference, using lightness and
chromaticity factors, between a sample and a known colour standard.
62
1.3.2.2i TDI Flexible Moulded Foam Review
The most commonly used catalyst packages for all water blown TDI flexible foam
production are blends of Dabco 33LV and Dabco BL-11 at a typical ratio of approximately
3:1. These new non-fugitive catalysts, Dabco NE1060, Dabco NE200, XF-N1085, and
XF-O11006 are recommended for TDI formulations at various gel:blow ratios depending
upon the selectivity desired. Ratios from 2:1 to 8:1 can be used to tailor the reaction
profile to the preferred selectivity for optimisation of physical properties and adaptation
to various processing conditions. The physical properties obtained with these new non-
fugitive catalysts are similar to the physical properties generated with standard industry
catalysts. However, slight formulation adjustments may be necessary to improve dry and
wet compression set values in certain instances. Improved crush-out capability can also
be achieved when incorporating the new cell-opening non-fugitive catalysts, XF-N1085
and XF-O11006. Complementary methods of emission analysis, headspace and fogging,
both suggest reduced emissions from the foam with these new non-fugitive catalysts.
1.4 MDI Flexible Moulded Foam Additives
The current trend toward lower foam densities, faster demould times, and the increased
use of complex metal and plastic insert frames in the construction of automobile interior
components has increased the difficulty of controlling the numerous process and chemical
variations a polyurethane manufacturer encounters on a daily basis. To successfully
produce moulded high resilience polyurethane foam, the manufacturer must maintain a
critical balance between foam over stabilisation, resulting in foam shrinkage, and under
stabilisation, resulting in internal defects, such as basal cell formation and shear collapse.
This often difficult to achieve balance is referred to as processing latitude. Variations on
either side of the processing latitude can result in costly increases for the producer in
scrap and repair rates. To help minimise production losses, polyurethane manufacturers
are essentially forced to over stabilise their foam formulations on a regular basis.
Subsequently, the closed cells which normally result from this over stabilisation are opened
via standard mechanical crushing techniques [13].
New surfactant technologies have been developed which promote improved cell wall
drainage and contribute to the final level of cell openness of the foam product without
causing any of the aforementioned negative attributes typical to a foam process. Due to
this unique cell opening action of these new additive technologies, the foam crushing
portion of the process can be greatly simplified or potentially eliminated.
Figure 1.41 shows a variety of flexible moulded Dabco surfactants which can be utilised
in TDI and/or MDI formulations. Using Figure 1.41, proper selection of the surfactant
can be made, enabling polyurethane formulators to expand their processing latitude, cell
openness, and bulk stability of the foam article in their critical formulations.
63
Figure 1.41 Flexible Moulded Surfactant/Property Relationships
1.4.1 Dimensional Stability Additives for MDI
An increasing North American trend in the moulded polyurethane foam industry today
is the use of MDI. While the advantages and disadvantages of MDI versus TDI are still
being debated, the fact remains that most polyurethane producers are using MDI in at
least part of their daily flexible foam production. The surfactant requirements for MDI-
based formulations can vary dramatically, dependent upon the type of MDI and polyols
being used. Most MDI formulations are inherently quite stable; therefore minimal
stabilising contributions are necessary from the surfactant. Conventional TDI high
resilience moulded surfactants are far too potent for MDI formulations. For example,
utilisation of Dabco DC5043 or Dabco DC5164 in an MDI seating formulation may
result in over stabilisation and significantly contribute to the shrinkage of the foam article.
To demonstrate the effectiveness of these dimensional stabilising additives, Dabco DC2517

and Dabco DC5244, several moulded high resilience foam experiments were carried out
using the formulation illustrated in Table 1.32, to compare with two non-cell opening
surfactants Dabco DC2585 and an additional surfactant (control). Much of the work
described next utilises proprietary formulations and only a general description of some
of the components can be disclosed.
64
Table 1.32 MDI flexible moulded formulation

Components pphp
Polyether polyol, diol/triol blend 100
Water 3.5
Diisopropanol amine 2.0
Dabco 33LV 0.3
Dabco BL-11 0.25
Dabco B-16 0.3
Surfactants 1.0
MDI prepolymer (2.3 functionality, 26% NCO) 100 Index
1.4.1.1 Reactivity - Handmix Rate of Rise
Data generated in the rate-of-rise comparison tests are summarised in Table 1.33. Foams
were run at an optimum index of 100 and all experiments were duplicated. Each mixed
formulation was poured into a ‘chicken’ bucket equipped with a thermocouple positioned
at the centre of the bucket resting on a Mettler PM 30 balance. The centred height of the
rising foam was recorded in millimetres every second using a DAPS (data acquisition
and plotting system) QA Model #2500 rate-of-rise aparatus. Reactivity profiles for these
new additives are essentially the same. Data discussed next further supports the fact that
there is no significant impact on reactivity or physical properties when comparing the
control to the Dabco DC2517 and Dabco DC5258 formulations.
Table 1.33 Handmix rate of rise reactivity comparison

Formulation Profile
Top of Cup 1 (seconds) 12.4
Top of Cup 2 (seconds) 48.1
String Gel (seconds) 53.4
Full Rise (seconds) 101.8
Full Rise Height (mm) 395.1
65
1.4.1.2 Standard Physical Properties
To understand the benefits of these new additive technologies that provide low volatility
and cell opening, all MDI moulded formulations were run in handmix foam to demonstrate
performance. Several foams were produced for each surfactant formulation to obtain
physical property pads, FTC pads, shrinkage pads, and flow evaluations.
Table 1.34 illustrates moulding foams at a density of 47-48 kg/m3; similar physical
properties are obtained for ILD, resilience, airflow, 50% dry sets and extensive properties.
However, slight nominal improvements in 50% humid aged compression sets (HACS)
and wet sets are achieved with Dabco DC2517 and Dabco DC5258.
Table 1.34 Physical properties for MDI moulded formulations

Physical Property Control DC2517 DC2585 DC5258
25% 302 3.4 295 4.5 292 5.2 300 1.8
65% 764 9.9 762 8.2 759 7.2 753 1.3
25% Return 223 3.5 213 4.7 212 3.9 219 1.0
Ball Rebound (%) 44.3 0.4 43.7 0.7 43.7 0.7 44.0 0.5
Airflow (SLM) 22.5 2.1 24.3 9.1 23.3 5.0 28.1 10.4
Tensile (kPa) 165 5.1 171 9.8 165 11.7 167 8.6
Tear (N/M) 305 11.5 303 15.7 309 11.2 330 19.8
Elongation (%) 95 7.4 94 5.5 93 6.8 97 4.5
Wet Set (%) 18.5 1.3 16.6 2.6 19.1 0.2 16.4 0.6
50% Compression Set 10.1 1.1 10.2 1.1 10.4 0.9 9.1 0.8
50% HACS 28.0 0.2 26.6 1.2 25.7 0.7 24.3 1.6
1.4.1.3 FTC Results
The FTC graph shown in Figure 1.41 illustrates an approximate 14% decrease in initial
FTC values and continues throughout the remaining FTC cycles. This improvement in
FTC represents foam articles that will shrink less immediately after demoulding when
cooling of the trapped gas begins, allowing more time to complete the post crushing
66
procedure or potentially eliminating the procedure all together. Several foams were
prepared with each surfactant and allowed to cool for 24 hours in an uncrushed state, to
confirm the relationship between FTC and foam shrinkage. Foams prepared with Dabco
DC2517 and Dabco DC5258 showed significantly less shrinkage, approximately 10-
15% less, as compared to the control and Dabco DC2585. This is readily comparable to
the differences in FTC values shown in Figure 1.42.
Figure 1.42 FTC Graphs for MDI Dimensional Stability Additives
1.4.2 Low Emissions Dimensional Stability Additives in MDI
The control catalyst combination for the MDI seating is a standard commercial catalyst
package. The balanced non-fugitive catalyst package Dabco NE1060/Dabco NE200 and
the low emission catalyst package Dabco NE1060/Dabco BL-11 use levels were set in
order to match performance to the commercial catalyst control package for the MDI
formulations. The silicone surfactant control was Dabco 2525. Cell opening non-fugitive
catalysts were not needed for this application based on the reported FTC values discussed
later in this chapter.
An MDI formulation, with a density of 40 kg/m3 and an MDI formulation, with a density
of 55 kg/m3 were used in the MDI automotive study with the formulations shown in
Table 1.35. For rapid demoulding of non-fugitive MDI systems, it is recommended that
Dabco NE1060 be used at 0.5 to 2.0 pphp, with the optimum level at 1.0 to 1.5 pphp
with 0.3 to 0.7 pphp of Dabco NE200. For low emission systems the authors recommend
Dabco NE1060 be used at 1.0 to 2.0 pphp, with the optimum level at 1.0 to1.6 pphp
with 0.03 to 0.1 pphp of Dabco BL-11.
67
Table 1.35 Flexible moulded MDI formulations

Formulation XX- XX- XX- XX- XX- XX- XX- XX- XX- XX-
Identification V VI VII VIII IX X XI XII XIII XIV
Components pphp pphp pphp pphp pphp pphp pphp pphp pphp pphp
Polyol C 100 100 100 100 100 100 100 100 100 100
Polyol D 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Water 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Control Catalyst 0.70 - - - - 0.70 - - - -
Package
Dabco BL-11 - 0.08 - 0.05 - - 0.08 - 0.05 -
Polycat 15 - 0.30 0.30 - - - 0.30 0.30 - -
Dabco NE1060 - 1.00 0.55 1.50 1.20 - 1.00 0.55 1.50 1.20
Dabco NE200 - - 0.60 - 0.40 - - 0.60 - 0.40
Dabco DC2525 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Crosslinker 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60
Modified MDI 90 90 90 90 90 105 105 105 105 105
Index
1.4.2.1 Low Emissions Moulded Foam Machine Standard Physical Properties
For complete comparison of these new additive technologies that provide low volatility, no
amine emissions and no fogging, all moulded formulations were run on a Krauss-Maffei
machine. Several foams were produced for each catalyst combination and formulation to
obtain physical property pads and FTC pads, shown in Tables 1.36 to 1.41.
Tables 1.36 and 1.37 provide the physical property comparison for the ~46 kg/m3 MDI
flexible moulded formulations XXV-XXXIV. The data clearly demonstrates that physical
properties are maintained, and in several cases improved, compared to the control
formulations, depending on the formulation and the use of experimental cell-opening
catalysts. For example, the data in Table 1.36 illustrates that at an index of 90, all
physical properties are comparable to the control formulation. When the index is increased
to 105, ball rebound and airflow are improved, with a slight decrease in indentation
force deflection (IFD) properties when the non-fugitive catalyst (XXXIV) is compared to
the control formulation (XXVI). When Dabco NE1060/Dabco NE200 is used (XXIX),
the physical properties are equal to the control at an index of 90. Improved Japanese wet
sets (see Section 1.3.1.2f) and slightly decreased IFD values are observed at an index of
105 compared to the control formulation (XXX).
68
Table 1.36 Physical properties for 46 kg/m3 MDI moulded formulations at an index of 90
Physical Property XX V XXVI XXVII XXVIII XXIX
ILD (N) AVG SD AVG SD AVG SD AVG SD AVG SD
25% 159 - 159 - 14 9 - 15 5 - 15 5 -
65% 459 - 450 - 43 6 - 45 0 - 44 8 -
25% Return 127 - 126 - 11 9 - 12 3 - 12 3 -
Ball Rebound (%) 51 0.6 51 0.6 51 0.6 51 0.6 51 1.2
Airflow (SLM) 22.4 7.6 24.4 6.5 29 7.4 34 7. 9 17 5.0
Density (kg/m3) 46 3.4 44 1.0 43 2.4 46 3.7 45 0.9
Tensile (kPa) 129 10.6 298 14.4 125 6.7 133 5.9 127 9.9
Tear (N/m) 212 12 201 16 197 12 217 16 205 20
Elongation (%) 114 9.9 118 6.1 112 4.6 120 1.3 118 9.3
Wet Set (%) 13 0.6 16 1.2 10 0.5 13 0. 4 13 1.3
50% Compression 9 1.6 10 1.0 9 1.6 10 0.5 10 0.8
Set (%)
50% Humid Aged 13 0.5 13 2.0 13 1.5 12 1. 3 14 1.0
Compression Set (%)
Physical Property XX X XXXI XXXII XXXIII XXXIV
25% 275 - 260 - 264 - 261 - 251 -
65% 768 - 731 - 739 - 738 - 71 6 -
25% Return 209 - 197 - 201 - 198 - 190 -
Ball Rebound (%) 43 0.6 45 1.2 45 0.0 45 1. 0 47 1.2
Airflow (SLM) 40.8 8.5 31.4 7.1 38 27.2 33 9.9 46 8.5
Density (kg/m3) 46 1.1 47 4.4 45 0.6 46 3.2 44 1.3
Tensile (kPa) 176 9.8 409 19.2 173 6.8 168 6.3 169 11.7
Tear (N/m 263 8 252 4 25 6 12 279 16 244 12
Elongation (%) 105 4.2 109 4.1 102 6.7 105 4.3 103 6.2
Wet Set (%) 15 0.8 15 0.4 11 0.2 9 0. 7 17 0.2
50% Compression 8 0.6 9 1.3 8 0.3 10 0.9 9 1.0
Set (%)
50% Humid Aged 13 2.0 13 1.8 12 1.0 14 1. 7 14 1.0
Compression Set (%)
69
Physical Property XXV XXVI XXVII XXVIII XXIX
25% 235 - 238 - 218 - 26 0 - 23 5 -
65% 637 - 636 - 59 7 - 731 - 64 1 -
25% Return 188 - 190 - 17 4 - 197 - 18 7 -
Ball Rebound (%) 46 0.6 44 1.0 46 0.6 45 1.2 42 0.6
Airflow (SLM) 21 4.0 35 11.9 35 5.4 31.4 7.1 27 12.5
Density (kg/m3) 53 3.4 50 3.6 50 3.5 47 4. 4 52 1.9
Tensile (kPa) 148 24.7 164 8.0 161 3.2 149 19.2 162 11.0
Tear (N/m 207 12 220 12 197 4 252 4 20 5 12
Elongation (%) 117 6.0 116 7.9 120 1.7 109 4.1 118 4.1
Wet Set (%) 11 1.4 13 0.9 15 1.3 15 0. 4 10 0.3
50% Compression 8 0.9 7 1.5 9 1. 0 9 1. 3 9 0.4
Set (%)
50% Humid Aged 11 1.5 14 2.1 13 1.3 13 1.8 12 0.9
Compression Set (%)
Physical Property XXX XXXI XXXII XXXIII XXXIV
25% 398 - 38 0 - 38 8 - 38 3 - 381 -
65% 1066 - 1029 - 1039 - 1042 - 1032 -
25% Return 303 - 288 - 295 - 289 - 289 -
Ball Rebound (%) 46 1.0 43 0.6 44 0.6 43 0.6 45 1.2
Airflow (SLM) 54 17.3 62.9 21.8 48 15.0 67 9.3 48 4.5
Density (kg/m3) 52 3.7 52 1.2 54 0.7 54 0. 4 55 0.5
Tensile (kPa) 217 17.0 218 7.0 207 12.9 217 6.6 223 10.5
Tear (N/m) 299 12 283 24 307 24 29 9 16 315 16
Elongation (%) 105 4.2 108 1.4 102 1.1 111 4.1 109 2.1
Wet Set (%) 14 1.4 12 0.7 13 0.7 11 0. 6 15 0.9
50% Compression 6 1.1 8 0.8 8 0. 6 9 1. 1 9 0.4
Set (%)
50% Humid Aged 14 1.9 14 0.8 13 0.9 12 1. 2 14 0.8
Compression Set (%)
70
Tables 1.38 and 1.39 provide the physical property comparison for the ~55 kg/m3 MDI flexible
moulded formulations XXV-XXXIV. The data clearly demonstrates that physical properties
are maintained, and in several cases improved, compared to the control formulations, depending
on the formulation. For example, the data in Table 1.38 illustrates that all physical properties
are matched to the control formulation (XXV) at an index of 105 with the exception of a
slightly lower ball rebound for the full non-fugitive catalyst package. At an index of 105, all
physical properties for the experimental non-fugitive catalysts formulations were determined
to be similar to the control (XXX). When Dabco NE1060/BL-11 is used as a low emission
catalyst package (XXXIII), all physical properties at the index of 105 are comparable to the
control foam. At an index of 105 (XXXIII), airflow, elongation and Japanese wet sets and
HACS are improved over the control (XXX) and 50% dry compression sets are slightly elevated.
1.4.2.2 FTC
Tables 1.40 and 1.41 show numerical values which are shown graphically in Figures
1.43 and 1.44. FTC values are dramatically improved versus the control (XXV), shown
Table 1.40 FTC values for MDI formulations at an index of 90

Formulation FTC (N/323cm2) FTC (N/323cm2)
46 kg/m3 55 kg/m3
XXV 52 76
XXVI 14 24
XXVII 35 63
XXVIII 8 13
XXIX 4 12
Table 1.41 FTC values for MDI formulations at an index of 105

Formulation FTC (N/323cm2) FTC (N/323cm2)
46 kg/m3 55 kg/m3
XXX 2.6 4.5
XXXI 1.3 1.9
XXXII 1.9 3.2
XXXIII 1.9 3.2
XXXIV 1.3 1.9
71
Figure 1.43 FTC at an Index of 90 for MDI Formulations
Figure 1.44 FTC at an Index of 105 for MDI Formulations
in Figure 1.43, for the foams with an index of 90. FTC values for all of the formulations
at an index of 105 are very similar to the control (error is ± 6.4 N/323cm2), as illustrated
in Figure 1.44.
72
1.4.2.3 MDI Flexible Moulded Foam Review
The non-fugitive catalyst package Dabco NE1060/Dabco NE200 and the low emission
catalyst combination Dabco NE1060/Dabco BL-11 closely match the entire reactivity
profile demonstrated by the standard control catalysts typically used in MDI flexible
foam. Additionally, the Dabco NE1060/Dabco NE200 combination demonstrates a higher
selectivity towards the blowing reaction as compared to a standard 2.5:1 ratio of Dabco
33LV to Dabco BL-11. This higher blowing selectivity can help improve cell opening and
produce a more dimensionally stable polyurethane article. These non-fugitive catalysts
also provide a reduction in the force necessary to crush freshly demoulded foam without
adversely affecting the remaining physical properties of the foam in MDI formulations
over a range of formulation indices.
1.5 TDI Flexible Slabstock Low Emission Additives
Handmix rate of rise comparison tests were performed using the same equipment and
process as described for TDI and MDI hand mix foam. The formulations used are
listed in Table 1.42 and the rate of rise data reported in Table 1.43. Dabco BLV with
Dabco T-9 was used as the industry standard catalyst control for the water blown
flexible slabstock foam formulations. The silicone surfactant used in the reported flexible
slabstock formulations was DC5160. All water blown formulations were made at
densities of 23 kg/m3.
Table 1.42 Flexible slabstock formulations

Formulation XXXV XXXVI XXXVII
Identification
Components pphp pphp pphp
Voranol 3512 100 100 100
Water 4.60 4.60 4.60
Dabco BLV 0.12 — —
Dabco NE500 — 0.06 0.16
Dabco NE600 — 0.12 —
Dabco T-9 0.25 0.25 0.26
Dabco DC5160 0.90 0.90 0.90
TDI (100 index) 57.4 57.4 57.4
73
Table 1.43 Hand mix free rise reactivity comparison using

flexible slabstock formulations
Formulation XXXV XXXVI XXXVII
Cream (Seconds) 13 12 13
Top of Cup (Seconds) 25 24 24
String Gel (Seconds) 67 67 64
Full Rise (Seconds) 112 1 11 109
1.5.1 Reactivity
Formulations from Table 1.42 were used in rate of rise catalyst comparisons and the
results are summarised in Table 1.43. The data suggests there is no significant change in
reactivity when comparing the control formulation (XXXV) to the experimental
formulations.
1.5.2 Standard Physical Properties
Table 1.44 lists the physical property data for the flexible slabstock formulations. The
experimental non-fugitive catalyst Dabco NE500 can be used with a slight increase in
Dabco T-9 catalyst level (shown in Table 1.42, formulation XXXVII). Formulation
XXXVII compares very well to the control (XXXV). Formulation XXXVI illustrates the
use of Dabco NE500 and Dabco NE600 balanced non-fugitive catalyst combination, to
match a Dabco BLV control. In this case, all physical properties were also matched, with
the exception of slightly decreased airflow and improved ILD properties. Overall, either
the non-fugitive catalyst combination Dabco NE500/Dabco NE600 or the use of Dabco
NE500 with increased Dabco T-9 can replace Dabco BLV in all water blown flexible
slabstock formulation.
1.5.3 TDI Flexible Slabstock Foam Review
Dabco NE600 in combination with Dabco NE500 or Dabco NE600 as a sole amine
catalyst used with increased levels of T-9 provides for equal or improved performance
compared to Dabco BLV in all water-blown flexible slabstock foam. In all cases, these
catalyst combinations can completely replace Dabco BLV and eliminate amine emissions
from the flexible slabstock foam.
74
Table 1.44 Physical properties for flexible slabstock foam

Physical Property XXXV XXXVI XXXVII
ILD (N) AVG SD AVG SD AVG SD
25% 198 - 211 - 200 -
65% 401 - 421 - 401 -
25% Return 126 - 134 - 128 -
Ball Rebound (%) 41 0.1 40 0.1 40 0.1
Airflow (SLM) 108 5.3 72 6.0 94 6.8
Density (kg/m3) 22 0.3 22 0.4 22 0.2
Tensile (kPa) 71 0.6 73 0.5 75 0.5
Tear (N/m) 200 - 200 - 200 -
Elongation (%) 97 7.5 106 6.7 104 6.1
90% Compression Set (%) 6 0.5 7 0.5 6 0.5
1.6 Foam Model Tool Discussions
Details of the TDI and MDI foam model systems have been previously published [2].
The models require the use of mono-functional reactants that are quantitatively analysed
to correlate structure-activity relationships for various classes of catalysts. A realistic
thermal profile is produced through the imposition of an external exotherm. Urethane,
urea, allophanate and biuret reaction products are quantified by liquid chromatographic
analysis of quenched reaction samples. The models effectively account for such non-
ideal conditions as reactant depletion at variable rates, temperature and concentration-
dependent catalyst activity, and catalyst selectivity as a function of isocyanate distribution.
1.6.1 TDI and MDI Moulded Foam Model
The information below highlights the features characteristic of the TDI and the MDI
flexible moulded models. Table 1.45 illustrates the conversion of the formulations from
Tables 1.12-1.15 into a TDI model system. Table 1.46 illustrates the conversion of the
formulations from Table 1.35 into an MDI model system.
Since the TDI and MDI automotive polyols are highly ethylene oxide (EO) tipped the
reactive hydroxyl group can be represented by a primary alcohol. The electronic effect of
75
Table 1.45 TDI flexible moulded foam model system

Formulation Mass Model Compounds Mass
(g) (g)
Polyether Polyols 100 Diethylene glycol methyl ether 10.43
CH3OCH2CH2OCH2CH2OH
Diglyme 95.89
CH3OCH2CH2OCH2CH2OCH3
Diethanolamine 1.74 Dibutylamine 2.14
(water free basis)a
Water 4.20 H2O 4.20
Surfactant No surfactant required for model
Catalyst Package 0.35 Catalyst Package 0.35
TDI 80 Index 105 40 mole% PhNCO Varied
60 mole% o-TolylNCO
a
Diethanolamine hydroxyls included with diethyleneglycol methyl ether mass.
Table 1.46 MDI flexible moulded foam model system

Formulation Mass Model Compounds Mass
(g) (g)
Polyether Polyol 100 Diethylene glycol methyl ether 7.51
CH3OCH2CH2OCH2CH2OH
Diglyme 93.54
Diisopropanolamine 0.85 Dibutylamine 0.81
(water free)a
Water 2.90 H2O 2.90
Dabco DC-2525 1.00 No surfactant required for model
Catalyst Package 1.60 Catalyst Package 1.60
Mondur MR Index 95 80 mole% PhNCO Varied
20 mole% o-TolylNCO
a
Diisopropanolamine hydroxyls included with diethyleneglycol methyl ether mass.
76
the ether two carbons away from the alcohol is accounted for by using an ether alcohol.
Thus both stearic and electronic effects on the reaction kinetics can be accurately reflected
in the model compound. The unreactive polyether backbone of the polyol can be
represented by the dimethyl ether of diethylene glycol. Dipropylene glycol dimethyl ether
would be more representative of the polyether backbone of a typical EO-tipped propylene
oxide (PO) polyol, but the rate and selectivity measurements are minimally affected by
the choice of model polyol backbone. Note the sum of the masses of the model alcohol
and the diglyme slightly exceeds 100 grams, the total polyol mass, since the hydroxyls
from the alkanolamine crosslinkers are included in the model alcohol mass. Nonetheless,
the concentration of reactive groups is comparable to that in the actual foam. Water and
catalysts are the same for both formulation and model. The model system does not
require a surfactant however, since a foam is not actually produced. TDI 80 and Mondur
MR are represented by 40:60 mole% and 80:20 mole% mixtures of phenyl and ortho-
tolyl isocyanate, respectively. Phenyl isocyanate represents the 4-position in 2,4-TDI or
4,4´-MDI, and tolyl isocyanate represents the more sterically hindered 2- and 6-positions
in the 2,4- and 2,6-TDI, or the internal rings of MDI oligomers. It is important to include
both isocyanate types because using only the more reactive phenyl isocyanate significantly
overestimates the reactivity of the system.
Detailed procedures for an individual model run can be found in the literature [14]. For
these runs a masterbatch mixture containing the alcohol, ether, water, catalyst and the
3,3´-dimethylbiphenyl internal standard was prepared in advance. The masterbatch
mixture was charged to a 50 cm3 roundbottom flask equipped with a glass thermocouple
well, septum, and jacketed mechanical stirrer with gas inlet and a septum. For the TDI
model the flask was placed under a slow argon purge in a sand bath capable of raising
the internal temperature from 60 °C to 120 °C in 4 minutes in the absence of any reactions.
The isocyanate was added via a syringe when the internal temperature reached 60 °C.
For the MDI runs the flask was wrapped with insulation but not otherwise heated
externally, and the isocyanate was added at 25 °C. Samples were then withdrawn via a
syringe at 30 second intervals for eight minutes. The samples were quenched with
dibutylamine and analysed by liquid chromatography to determine the yields of the urea
and urethane reaction products as well as the unreacted isocyanates, analysed as the
dibutyl ureas.
The flexible moulded chemical foam model provides a detailed look at the performance
of the industry standard catalyst package Dabco 33LV/Dabco BL-11 compared to the
non-fugitive catalyst packages Dabco NE1060/Dabco NE200 and Dabco NE1060/XF-
N1085. The foam results presented previously can be explained in terms of the overall
catalyst performance. The catalysts were characterised with a model system because
urea, urethane and isocyanate can be quantified as a function of time, so this approach
provides the highest level of detail. However, a model system is only relevant to the
77
extent that it accurately reproduces the environment in an actual foam. The mixing in
the model systems is less energetic, so this may influence the relative rates of catalyst
hydrolysis versus reaction with isocyanate. However, if catalysts are compared under a
consistent set of conditions, the relative performance differences should be meaningful.
The most convenient way to compare catalyst performance is to use blow to gel selectivity.
Selectivity as a function of time (t), is defined next.
Normalised blowing rate = (% yield of ureas at time, t) / (limiting urea yield)

Normalised gelling rate = (% yield of urethanes at time, t) / (limiting urethane yield)
Blow to gel selectivity = (Normalised blowing rate) / (Normalised gelling rate)
Catalyst selectivity is defined as the ratio of the normalised amount of blowing (urea
formation) to the normalised amount of gelling (urethane formation). A selectivity of
1.0 means that the normalised amounts of blowing and gelling are equal at that point in
the reaction. A selectivity substantially below 1.0, for example about 0.3, is indicative of
a strong gelling catalyst. A selectivity greater than 1.0 is indicative of a blowing catalyst.
However, it has been shown that a catalyst with a blow-to-gel selectivity greater than 0.8
can still serve to balance a strong gelling catalyst such as TEDA, and a good quality foam
can be produced [14].
Note the limiting urea and urethane yields are simply the molar equivalents of water and
alcohol, respectively, from Tables 1.45 and 1.46. Selectivities are plotted as a function of
isocyanate conversion in Figures 1.45 and 1.46.
1.6.2 TDI Flexible Slabstock Foam Model
Details on the development and use of foam model systems for flexible moulded foam
have been published [14]. In this section the features characteristic of slabstock foams
will be highlighted. Table 1.47 illustrates the conversion of the formulations from Table
1.42 into a model system.
Since the Voranol 3010 polyol is fully PO tipped, the reactive hydroxyl group can be
represented by a secondary alcohol. The unreactive polyether backbone of the polyol
can be represented by the dimethyl ethers of dipropylene glycol and diethylene glycol.
The diglyme represents the wt% EO incorporation into the polyol. Note the sum of the
masses of the model alcohol and the two dimethyl ethers equals 100 grams, the total
polyol mass. This ensures that the concentration of reactive groups is comparable to that
in the actual foam. Water and catalysts are the same for both formulation and model.
78
Figure 1.45 TDI Flexible Foam Model Selectivity versus NCO Conversion
Figure 1.46 MDI Flexible Foam Model Selectivity versus NCO Conversion
79
Table 1.47 Slabstock foam model system

Formulation Mass (g) Model Compounds Mass (g)
Voranol 3010 100 1-Methoxy-2-propanol 9.01
CH3OCH2CH(CH3)OH
Dipropyleneglycol dimethyl ether 82.99
(CH3O(CH3)CHCH2)2O
Diglyme 8.0
Water 2.00-6.00 H 2O 2.00-6.00
Dabco DC5160 0.75 No surfactant required for model
Dabco BLV 0.20 Dabco BLV 0.20
Dabco T-9 0.50 Dabco T-10 0.50
TDI 80 Index 90, 105, 120 40 mole% PhNCO Varied
60 mole% o-Tolyl NCO
Once again the model system does not require a surfactant, since a foam is not actually
produced. As noted previously, TDI 80 is represented by a 40:60 mole% mixture of
phenyl and ortho-tolyl isocyanate.
Detailed procedures for an individual model run can be found in the literature [14]. For
these runs a masterbatch mixture containing the alcohol, ethers, water, Dabco BLV catalyst
and the 3,3´-dimethylbiphenyl internal standard was prepared in advance. The masterbatch
mixture was charged to a 50 cm3 roundbottom flask equipped with a glass thermocouple
well, septum, and a jacketed mechanical stirrer with gas inlet. The flask was placed under
a slow argon purge in a sand bath capable of raising the internal temperature from 50 °C
to 120 °C in 4 minutes in the absence of any reactions. Isocyanate was added via syringe
when the internal temperature reached 50 °C, and the T-9 was injected from a microliter
syringe immediately afterwards. Samples were then withdrawn via the syringe at 30 second
intervals for eight minutes. The samples were quenched with dibutylamine and analysed
by liquid chromatography to give yields of the urea and urethane reaction products as well
as the unreacted isocyanates, analysed as the dibutyl ureas.
The chemical flexible slabstock foam model provides a detailed look at the performance
of the industry standard catalyst Dabco BLV compared to the non-fugitive catalysts Dabco
NE500 and the Dabco NE500/Dabco NE600 package, keeping the Dabco T-9 level
constant. Selectivity and conversion can be calculated as described previously. Note that
80
the limiting urea and urethane yields are simply the molar equivalents of water and
alcohol, respectively, from Table 1.47.
Dabco 33LV is considered to be a strong gelling catalyst, but under slabstock conditions
it is actually more of a blowing catalyst, with an initial selectivity near 2. This reflects the
difficulty of catalysing the secondary alcohol-isocyanate reaction in competition with
the water-isocyanate reaction. Tertiary amine catalysts are highly sensitive to stearic
hindrance near the reaction site. Secondary alcohols actually become less reactive than
water, even in the presence of a strong gelling catalyst. This is why tin catalysts are
critical in flexible slabstock formulations because they are less sensitive to stearically
hindered reactions. Dabco BLV contains some bisdimethylaminoethyl ether (Dabco BL-
11), which is a very strong blowing catalyst. Thus the initial selectivity is even higher,
near 4. The non-fugitive catalysts give selectivities comparable to that of Dabco BLV.
Note that the non-fugitive catalyst packages are more blowing selective than both the
TDI and MDI controls. Modern polyol technology tolerates and in some cases even
benefits from higher initial blowing selectivity because of the reduced levels of monol
and diol relative to triol. Thus network formation is more efficient, and correspondingly
less gelling is required to produce a superior urethane network. Higher blowing selectivity
can promote improved cell opening, which is now more critical in the face of improved
network formation. In a sense the control formulations are over gelled, but older
formulations could tolerate high gelling due to weaker urethane networks and the frequent
use of Dabco BL-11, which is a potent blowing catalyst.
Although the selectivity curves are different, the catalyst packages are still rate matched.
Rate matching in foam is usually accomplished by comparing rise profiles, which are
largely determined by the blowing rate. Thus the non-fugitive catalyst packages provide
blowing comparable to the controls, but provide a lower extent of urethane formation
early in the foaming process.
1.7 Conclusions
Incorporation of these newly developed additives in the production of polyurethane foam

results in polyurethane articles that give dimensional stability, low emissions and wider
processing latitude. These dimensional stability additives provide a significant reduction
in the force necessary to crush freshly demoulded foam without adversely affecting the
physical properties of the foam. As increasing demands are placed on the foam producers
to meet specific comfort and durability requirements, physical properties and
environmental concerns, the need for these additives will continue to be a key criterion
for polyurethane manufacturers.
81
Acknowledgments
The authors would like to thank and acknowledge the efforts and support of the following
people at Air Products and Chemicals, Inc.: Mark A Eckert, Steven E Robbins for physical
property testing of foams generated in this study, and Ilean S Ruhe for preparation and
editing of this work. We would also like to thank Air Products and Chemicals, Inc., for
support of this work and permission to publish it.
References
1. J. D. Tobias, G. D. Andrew, Presented at the SPI Polyurethanes Expo ‘98, Dallas,

TX, 1998, p.445.
2. M. L. Listemann, A. C. L. Savoca and A. L. Wressell, Journal of Cellular Plastics,

1992, 28, 4, 360.
3. R. G. Petrella and S. A. Kushner, Presented at the SPI Polyurethanes ‘90

Conference, Orlando, FL, 1990, p.186.
4. G. Burkhart and M. Klincke, Presented at the SPI Polyurethanes ‘95 Conference,

Chicago, IL, 1995, p.297.
5. Flexible Polyurethane Foam, The Dow Chemical Company.
6. ASTM D3574-95
Standard Test Methods for Flexible Cellular Materials - Slab, Bonded, and
Molded Urethanes Foams.
7. L. J. Gibson and M. F. Ashby, Cellular Solids, Structure and Properties,

Pergamon Press, Oxford, 1988, Chapters 5 and 6.
8. K. D. Cavender, Presented at the SPI, Magic of Polyurethane Conference, Reno,

NV, 1985, p.314.
9. SAE J1756
Test Procedure to Determine the Fogging Characteristics of Interior Automotive
Materials, 1994.
10. M. S. Vratsanos, Presented at the SPI, Polyurethanes ’92 Conference, New

Orleans, MS, 1992, p.248.
11. K. F. Mansfield, Air Products & Chemicals, Inc., unpublished results.
82
12. R. G. Petrella and J. D. Tobias, Presented at the SPI Polyurethanes ‘88

Conference, Philadelphia, PA, 1988, p.28.
13. D. G Battice and W. I. Lopes, Presented at the SPI Polyurethanes: Exploring New
Horizons Conference, Toronto, Canada, 1986, p.145.
14. M. L. Listemann, K. R. Lassila, K. E. Minnich and A. C. L. Savoca, inventors;

Air Products and Chemicals, Inc., assignee; US Patent 5,508,314, 1996.
83
84
2
Demands on Surfactants in Polyurethane Foam
Production with Liquid Carbon Dioxide Blowing
Andreas Weier and Georg Burkhart
2.1 History of Polyurethane Foams
The history of polyurethane foams and of polyurethanes in general is not that long for a
plastic material. It has been characterised by one special feature: the consistent changes
of the industry.
When Otto Bayer started his research on this new class of plastic material built from the
addition reaction of isocyanates and hydroxyl containing materials in the years 1936/1937
he envisioned a plastic material which could be tailored to many different applications by
the broad variety of acidic hydrogen containing compounds already available.
But there were also setbacks to this concept. The first major drawback was the fact that
the necessary diisocyanates were not available on an industrial scale and large scale
synthesis of these compounds seemed to be a rather high hurdle.
A second major point was an obstacle that Bayer and his group faced again and again.
When they tried to make the polyurethanes they envisioned in solid form, like films, etc.,
they always ended up with gas bubbles in their plastics. That was due to the inefficiency
of the methods available to synthesise pure water free material. After encountering this
effect for nearly four years Bayer made a bold move in line with the concept ‘use what
you cannot prevent’ – in this case the formation of gas bubbles [1, 2]. Thus Bayer’s group
started to make polyurethane foams.
Although these new lightweight porous materials were envisioned as supportive materials
as well as insulative materials in the base patents [3, 4] their market development remained
slow. This can be seen by the fact that even in 1952 polyisocyanates, mainly toluene
diisocyanate (TDI), were available worldwide in quantities of less than 100 tonnes. After
this rather hesitant start of polyurethane history and the first major switch from solid
materials to porous foamed plastics, the industry has been characterised by significant
changes in concept and the resulting industrial application of these switches.
The first major switch resulted from the basic research enabling the technical production
of soft polyurethane foams in the early 1950s. This technology was mostly focused on
polyester polyols as raw materials. About five years later polyether polyols entered the
85
market as yet another major change within the polyurethane foam industry. Since the
early 1950s the foaming machines for the industrial production of polyurethane foams
had been discontinuous machines. With the use of polyalkyleneglycols as polyols, the
importance of continuous foam production grew significantly, for both performance
and commercial reasons. In the early 1950s, the necessary stabilisers for the production
of polyurethane foams had been silicone oils, with the major suppliers being Bayer, Dow
Corning, General Electric and ICI. In the late 1950s the picture changed with the broad
application of the continuous process, first with prepolymers, then the one-shot-process.
For this type of polyurethane foam production a different class of stabilisers was needed:
the new silicone-polyether copolymers.
The larger variability of the available polyetherpolyols laid the foundation for a significant
broadening of the performance range of polyurethanes – and all this with lower costs
than before. The growth of polyurethanes after this chemical change was fast [5]. Even
in 1960 more than 45,000 tons of flexible polyurethane foam were produced. Besides
its major application as insulation materials and comfort products in furniture
applications, new usage areas have been continuously identified and tailor-made
polyurethane materials have been supplied. Nowadays the range covers very high density
contour parts as well as very low density packaging foams, flexible foams as well as
semi-rigid and rigid foams, thermoplastic polyurethanes as well as integral skin foams or
reaction injection moulded (RIM) materials [6]. In the beginning of the 1990s an estimated
500,000 people had jobs in the polyurethane industry, either within production of raw
materials or in the conversion to final products [7].
2.1.1 Environmental Concerns in Relation to Flexible Foam Density
By definition the production of a foam depends on the formation and stabilisation of gas
bubbles in a liquid. That is true even for polyurethane foam when the additional curing
of the liquid results in an elastic or rigid solid material. One of the central questions is
how the gas bubbles are generated and how long this generation takes.
The basic chemical gas forming process in polyurethane foaming is the very exothermic
reaction of water and isocyanate, resulting in the generation of carbon dioxide, urea and
heat. This method as the sole method to generate the gas bubbles of a polyurethane foam
is limited to the production of a rather small range of density/hardness combinations.
The achievable minimum density is limited by the tolerable heat in a foam bun before
scorching or even self-ignition occurs. Increasing water levels lead to the generation of
increasing amounts of carbon dioxide and therefore to lower densities. Increasing water
levels will also result in higher hardness as more urea is generated. During reaction the
urea appears in a variety of associated forms before it will ultimately separate as a solid
in flexible slabstock polyether foams [8, 9, 10].
86
Demands on Surfactants in Polyurethane Foam Production…
During the history of polyurethane flexible slabstock foam production the accessible density/
hardness range was continuously broadened with a wide variety of techniques. The most
obvious one was the use of a physical blowing agent to generate the gas volume necessary to
expand or generate gas bubbles without generating additional heat during the process. Due
to its inert character and its low biological toxicity, CFC-11 (Freon) was the liquid blowing
agent of choice for many years in Europe, North America and Asia. That changed after
recognition of the fact that CFC-11 had both a high global warming potential (GWP) and a
high ozone depletion potential (ODP). The result was the inception of the Montreal Protocol
and subsequently the exploration of a broad variety of alternative blowing agents (ABA),
including hydrochlorofluorocarbons (HCFC), acetone, cyclopentane and methylene chloride.
With the use of ABA, both the available densities and the available foam hardnesses
were lowered in comparison to the purely water blown foams, as in these cases gas
volume was produced without generation of urea. Softening of foam was also achieved
chemically, either with the use of an additive to change the urea morphology [13] or with
the use of crosslinkers in combination with a low isocyanate index [14].
A few years later machinery modifications enabled foamers to produce low density foams
by the use of increased water levels while reducing traditional blowing agent levels. This
reaction preferentially utilises the reaction generating carbon dioxide as a blowing agent.
When the water in the formulation is increased, the foam bun temperature can become
too high for safe processing. This problem has been tackled by forced cooling equipment
generating an air exchange in the foam bun directly after production and thereby cooling
the bun to prevent scorch or fire problems. There is a variety of technologies for the
forced cooling of foams, including Envirocure [13, 14], Rapid Cure [15], Reeves Brothers
[16] and lateral cooling [17]. For the production of very soft foam grades some physical
blowing agent is still needed. Also there are always some safety concerns over possible
equipment malfunctions when making these hot foam grades.
A safer way to control flexible foam density and hardness is the variation of production
pressure. Making high as well as low pressures available in the foam production
environment can give access to higher density hard grades as well as to low density
foams without the use of physical blowing agents. The two commercial processes
addressing this approach are Variable Pressure Foaming (VPF) and Foam One. As foam
production is done in a closed chamber, volatile materials can be trapped rather efficiently.
This creates the possibility of a clean and safe, as well as ABA free foam production. A
setback is the high capital investment cost, especially for a VPF unit. Therefore this
equipment only becomes cost effective in very high volume production plants.
Review of the many production techniques reveals that the production of a broad range
of flexible foam qualities with reduction of environmental hazards (ODP as well as GWP)
is possible by numerous options. All of these current technologies offer benefits, but
provide no clear economical solution for total ABA elimination.
87
Within all the blowing agents available today, carbon dioxide probably offers the best
combination of zero ODP, low GWP and low price. As it is abundant, it doesn’t have to
be generated. For capturing and transporting only a minor amount of energy is needed.
Merely the point of emission is changed. On top of all that it is also non-flammable,
which minimises safety concerns in the foam plant.
Therefore many attempts have been made to produce polyurethane foams with carbon
dioxide that is not generated by a chemical reaction during the foaming process. The
difficulty is that carbon dioxide is a gas at room temperature under atmospheric pressure.
The only way to utilise carbon dioxide not generated chemically is to mix the carbon
dioxide under pressure or in a liquid state with the chemical components of the foam
formulation. Then the pressure is subsequently released causing the frothing or pre-
expansion. Carbon dioxide as a non-reactive blowing agent in the frothing technique
has been suggested for quite some time already [18, 19]. The pressurised reaction mixture
is ejected at atmospheric pressure causing a turbulent vaporisation of the blowing
agent. This allows the manufacture of a foam with reduced density, but the cell structure
is of very inconsistent quality due to irregular shaped and oversized cells or bubbles
being present.
2.2 Current Liquid Carbon Dioxide Technologies for Flexible Slabstock

Polyether Foam Production
2.2.1 Machinery
The situation changed when Cannon introduced liquid carbon dioxide foaming technology
for the industrial production of polyurethane flexible foams with its CarDio process. This
process was introduced to the polyurethane foam production industry in 1994. Today foam
manufacturers worldwide consider liquid carbon dioxide as a blowing agent and make this
process available for the industry. The major point of this technology is the control of the
frothing that occurs as soon as the pressurised liquid carbon dioxide as part of the foam
formulation leaves the pressurised equipment and the liquid foam mixture is released into
atmospheric pressure. The controlled release of the mixture into the comparatively low
atmospheric pressure conditions is essential to all the liquid carbon dioxide foaming techniques.
In the CarDio process this is accomplished with the specifically designed lay down device
[20, 21] which is called a ‘Gate Bar’ (see Figure 2.1). The gate bar essentially consists of
a metal bar with a pressure drop slot connecting the outside with a feeding tube inside
the bar. Through a liquid mix injection point formulation components with the pressurised
liquid carbon dioxide enter the gate bar.
88
Figure 2.1 Cannon Gate Bar Principle
The frothing mixture flows along the frothing cavity and through an outlet aperture
acting as a pressure drop zone onto a substrate, e.g., the moving belt of the foam machine.
A variation of the original gate bar design was introduced with the CarDio 2000 featuring
a pressure adjustable lay down device [22]. It allows adjustment of the slot width in
response to the output and the liquid carbon dioxide percentage (see Figure 2.2).
Figure 2.2 CarDio Froth laydown
89
Another patented technology for liquid carbon dioxide foaming is the NovaFlex process
developed by Hennecke and Bayer [23]. The NovaFlex process uses a creamer dispensing
the froth on to the machine. It focuses on the same task of pressure reduction as the
CarDio gate bar, except dispensing the froth occurs at one single spot on the belt and is
not distributed over nearly the whole belt width. The same is true with the third version
of liquid carbon dioxide machinery, the Beamech CO-2 equipment. Obviously, both the
NovaFlex as well as the Beamech CO-2 process use pressure reduction devices different
from the gate bar of the CarDio process as they are said to show a different response to
the use of fillers or generally solid particles within the foam formulations. One modification
of the original NovaFlex process is the MultiStream configuration. It allows the use of
liquid carbon dioxide with a range of polyol types in all different ratios by utilising one
liquid carbon dioxide addition point in one high pressure polyol stream which is then
combined with additional polyols by pass streams [24, 25].
2.2.2 The Foaming Process
2.2.2.1 A Comparison of Rise Profiles
A comparison of the foaming profile found in a standard flexible slabstock foam

production with the one seen during liquid carbon dioxide foaming clearly shows a large
difference in the rise profiles, especially at the lay down (Figure 2.3).
Figure 2.3 Foaming profiles of standard flexible foam production and

liquid carbon dioxide foaming.
90
In standard foam production, a mixture of liquid materials is dispensed and the gas bubbles
within the foam structure are only generated by a rather slow chemical reaction. In the case
of liquid carbon dioxide foaming the mixture is already dispensed in a two-phase process.
No matter which particular pressure drop system is utilised, the pressure drop is very
fast due to the large flow speeds in the system. The fast pressure drop between the mixing
head and the dispensing compresses this time span for bubble formation to fractions of
a second. As all the gas bubbles resulting in foam cells of the final foam have to be
generated in this short instant, clearly the nucleating powers of the formulation ingredients
are challenged severely. This is especially true when looking at the foam stabilisers used
as they are the main formulation ingredients determining the nucleation.
2.2.2.2 The Nucleation of Gas Bubbles
As early as 1969, Kanner and Decker [26] showed by photomicrography that self-nucleation
is essentially absent in a polyurethane foam system. Their results indicate that bubbles are
introduced by the process of mixing and that the presence of a silicone surfactant increases
the volume of air bubbles introduced during the mixing. Nucleation in this context means
the formation of gas bubble cores on which a bubble might grow above its critical bubble
radius. The critical bubble radius is the smallest bubble radius for which the addition of
more gas will result in a net decrease in free energy. A bubble which is smaller than the
critical radius will not spontaneously grow in size because the addition of more gas results
in a net increase in free energy. Obviously a decrease in the surface tension of a foaming
mixture by the silicone surfactant would decrease the energy needed to generate bubbles of
the necessary critical radius. Even under conditions of a supersaturation pressure of 2.03
MPa carbon dioxide in a liquid with a surface tension of 0.025 N/m and a temperature of
25 °C, the critical bubble radius is 2.4 x 10-5 cm. It has been proven that silicone surfactant
can aid nucleation by lowering surface tension [27].
However the surface tension lowering of a silicone surfactant might just be one effect
helping to induce new bubble formation by liquid carbon dioxide. The surfactant is
entirely soluble in the liquid and therefore cannot act as a heterogeneous nucleating
agent. Besides that other surfactants like fluorocarbons can also lower the surface tension
but still don’t act like a silicone surfactant does in polyurethane foam production. A
possible explanation of this difference might be related to the exceptional solubility of
oxygen and nitrogen in silicones as demonstrated by Arkles [28, 29]. It is well known in
the polyurethane industry that insufficient air loading of raw materials like the polyols
results in coarse cell structures even in the conventional foaming process. Obviously a
sufficient amount of nitrogen and/or oxygen is needed for good nucleation. As silicones
show a high permeability and solubility for these gases, it is reasonable to assume that
91
the ease of formation of nuclei for gas bubbles is higher in silicone-like surroundings
provided along the siloxane backbone of a silicone surfactant.
An effect not accessible to Kanner and Decker, and therefore not a subject of their
experimental work, was the high nucleation demand found in the new liquid carbon
dioxide foaming technologies. Their finding that bubbles are introduced during the process
of mixing by the shear energy of the mixer might reflect the observation that the amount
of nuclei generated during mixing has always been sufficient for a standard polyurethane
foaming process. The rather large timescale between mixing and appearance of gas bubbles
large enough to be visually detectable obviously gave carbon dioxide molecules sufficient
time to diffuse to a nucleation site as they were only generated slowly within the foam
formulation. With the new liquid carbon dioxide foaming technologies, a significantly
higher number of nucleation sites is needed for the carbon dioxide to find a gas bubble
or a gas bubble core during the short time frame of the pressure decrease in the pressure
reduction area within the equipment used.
Whereas the former trend in some polyurethane (PU) markets has been to sacrifice more
and more of a surfactant’s nucleating power to gain higher and higher activity, liquid
carbon dioxide foaming has led to a new description of the needed performance profile.
This is recognising the fact that quite a number of the very high active surfactants used at
the time of the introduction of the liquid carbon dioxide processes resulted in unacceptable
foam structures. Irrespective of the liquid carbon dioxide system, the high activity
surfactants generated coarse foams. That is in contrast to the findings of Kanner and
Decker in standard foam systems. Obviously under these conditions the mixing energy
of the machine system has not been high enough to generate sufficient nuclei or gas
bubbles to guarantee a regular fine celled foam structure. Obviously under these conditions
the main quality issue of a surfactant is its nucleation power, and not the stabilisation
activity. Not surprisingly a well established medium active surfactant was used during
the development of the first commercial liquid carbon dioxide process, the CarDio process.
It provided a good balance between nucleation and processing as well as activity. Therefore
this type of surfactant was still the number one choice for processes even four years after
the introduction of commercial liquid carbon dioxide foaming. Still, due to the high
demands in nucleation, the broad variety of foam grades and the flame retardant (FR)
demands of some markets a desire for optimising the different surfactant performance
aspects could clearly be seen. It also provided a focus of interest for the flexible slab
polyurethane community for quite a few years.
2.2.2.3 Emulsification of Raw Materials
In addition to nucleation, there is one further objective to be fulfilled or at least supported

by the silicones used. That is the emulsification of the raw materials used in the foam
92
formulation. An obvious example for this performance aspect is the chemical reaction of
water and isocyanate, i.e., the formation of carbon dioxide and urea. The different polarities
of isocyanate and water should normally prevent their reaction with each other in the
short time frame of a PU foam reaction and even the use of polyols as the major formulation
component will not always help to overcome the tendency for phase separation.
Even the polyols used in some special foam types can give rise to a number of problems.
One of the challenges for the emulsification power of silicone surfactants in flexible
slabstock foam production for example is the combination of a standard polyol with a
hypersoft polyol. The consistency of the foaming results and the cell structure obtained
can be severely influenced by the choice of silicone surfactant used. It can be easily
rationalised that the rise profile and physical foam properties like tensile strength and
elongation will be influenced by tendencies for phase separation after the mixing and
dispensing of the formulation ingredients.
2.2.2.4 Stabilisation of the Foam During Foam Rise
Probably the most obvious task of any silicone surfactant in flexible polyurethane foam
production is to stabilise the foam during the foam rise. If the surfactant used is
contaminated or is in too low a concentration, settling of the foam or even foam collapse
will occur. Two possible reasons for the foam instability during the rise time are discussed
in the literature, and lead to different theories on the roles of silicone surfactants used.
The first explanation of the role of silicone surfactants in flexible polyurethane foam is
based on the fact that as soon as the volume fraction of the gas bubbles exceeds 74%, the
spherical bubbles will distort into multi-sided polyhedrals. This means that cell windows
with Gibb’s plateau borders are formed (a polyhedral foam consists of cell windows and
struts. Another term for struts is Gibb’s plateau borders). A pressure difference due to
capillary pressure will cause liquid in the cell window to drain into the struts since the
pressure inside the plateau borders is lower than that in the cell windows. Without adding
silicone surfactants this drainage rate will be very fast, so that film rupture and bubble
coalescence occur rapidly. It has been shown that due to the surface tension gradient
generated by a silicone surfactant the cell window drainage rate is lower [30]. Therefore
different surface structures do have different effects on cell window drainage. That has
been said to result in a distribution of different cell window thicknesses at the time of cell
opening [31]. The critical factor in this picture is the surface elasticity. It is known to be
caused by a surface tension gradient along the cell window upon expansion and it will
retard the cell window drainage rate. This effect is called Gibbs-Marangoni effect and is
reviewed by Scriven and Sternling [32]. Owen and co-workers also studied the dynamic
surface tension of a series of surfactant solutions and stressed the importance of surface
elasticity [33]. Similar work has been performed by Zhang and co-workers [34].
93
A different view point of the mechanism of flexible polyether polyurethane foam stabilisation
by silicone-based surfactants has been published by Rossmy and co-workers [8, 9, 10]. The
authors investigated the urea precipitation phenomenon in polyurethane foams in greater
detail. By adding a defoaming agent to a foam formulation they showed that urea precipitation
turned a clear foam mix opaque. They also noted that the cell rupture always occurred just
after urea precipitation. In light of this observation the hypothesis is that precipitation of
polyurea destabilises the foam mix and leads to cell opening. The surfactant then aids in
stabilising the foam by incorporating the urea precipitate in the foam matrix, adding integrity
to the foam. Today it is not doubted any more that there really are urea domain structures in
polyurethane foams and they have been subject to intensive research [35, 36].
2.2.2.5 Control of Blow Off
Another major point of consideration is obviously the processing latitude of silicone

surfactants. This phrase describes the variability of catalyst concentration without running
into either closed, dead foam or observing first signs of foam instability indicated by
splits in the foam. Not only will a different silicone surfactant result in a different
processing window, e.g., amount of stannous octoate variation between the two extremes,
but also the position of the processing window might be different.
Figure 2.4 shows the remaining fragments of a cell window after cell opening as found in
the fully cured foam. It is very obvious that the opening of a flexible PU foam is not a
Figure 2.4 Opening of a cell window
94
pressure induced rupture of a foam bubble. Otherwise there would be no explanation

why the cell opening process clearly starts at a number of locations around the periphery
of the cell window. Obviously weak points in the cell window offer starting points for
the opening of the liquid film. Then drainage occurs, as can be seen by the thin strings
remaining between the opened areas in the cell window. The actual timing of this opening
process is critical as it determines the physical properties of the foam and the foam
economics. As the viscosity of the liquid material is rising very sharply due to crosslinking
at the end of the foaming profile, there is only a very short time frame in which the
material is crosslinked enough to support the foam without a high settling once the gas
bubbles have opened and no internal gas pressure is supporting the foam anymore. On
the other hand a further delay in gas bubble opening would lead to an incomplete recession
of the material into the foam struts so that the foam will be showing a rather low air
flow or even shrinkage.
2.2.3 Additional Tasks of Silicone Surfactants in Flexible Slabstock

Foam Production
2.2.3.1 Influence on burn performance of the foam
As soon as the foam is produced and cured the silicone surfactants used are not needed
or desired any more. One exception might be the production of hydrophilic or hydrophobic
foams where a surface active material like a silicone will in some cases have a recognisable
influence. But with standard foams as well as with liquid carbon dioxide blown foams,
additional performance aspects besides the stabilisation during the foam rise might be
important for surfactant selection. These criteria therefore have to be addressed as well
and deserve some consideration as they might also affect the number of key additives a
foam operation has to handle. An effect clearly seen in the final foam is the undesirable
effect the silicone surfactant has on the burn performance of the resulting foam. Especially
in liquid carbon dioxide foaming, suitable conventional (or non-FR) surfactants have
been available right from the beginning. But the development of optimised universal or
non-FR-surfactants for liquid carbon dioxide foaming took considerable effort and time.
To understand the effect of the silicone surfactant on burning it is interesting to have a
look at a theory for flame spread development.
The simplified illustration in Figure 2.5 shows that the heat decomposes the organic
material at the surface during an endothermic procedure. Pyrolysis products are created
and because of an exothermic reaction with oxygen at the boundary layer of the flame,
the formation of even higher reactive decomposition products takes place. These aggressive
radicals are responsible for an accelerated degradation of the polymeric surface. As long
as the result of the energy is positive, there is thermal feedback to the endothermic process
95
Figure 2.5 General assumption about flame spread
at the surface and the combustion keeps going. It is believed that the formation of hydrogen
radicals and hydroxyl radicals from the organic material are the key factors initiating
and supporting the combustion phenomena. The working mechanisms of FR address
these phenomena.
The effect of a silicone surfactant on the burning behaviour of the polyurethane foam
can be quite significant even though they normally represent less than 1% of the plastic
material. It is due to the fact that in any case the decomposition of a polyurethane foam
starts at the surface. Because of the surface activity of the foam stabilisers it is easy to
rationalise their enrichment on the surface and it is the surface that is the most influential
part of the polymer regarding flame spread development.
This point can be further highlighted if we look at the influence of surfactants on the
FR-performance of a polyurethane foam with 1 weight percent of surfactant externally
applied (Figure 2.6). To characterise the burn performance in this case, a horizontal
burn test was used and the burn length was measured. Surfactants A, B, C and D are
rigid foam surfactants with different structural parameters in the silicone as well as in
the polyether chains. It can be seen in Figure 2.6 that all the different types of silicone
surfactants used do have a negative influence on the burn performance of the foam.
The reason for this behaviour can be mainly attributed to the structure of the siloxane
backbone within the siliconepolyethercopolymers [37]. To characterise the effect of
the polydimethylsiloxane (PDMS) chain used as the backbone of such a
siliconepolyethercopolymer, interesting tests have been made by external application
of pure PDMS in different weights as well as the use of molecules of different average
chain length (Figure 2.7).
96
Figure 2.6 Influence of surfactants on FR-performance - external application

of 1% surfactant
Figure 2.7 Effect of 1% PDMS - applied externally
Not only do increasing amounts of externally applied PDMS lead to increasing burn
length in, but more astonishingly, this effect is obviously correlated to the average
chain length of the applied siloxane. It can be seen that with longer chain length of the
PDMS, the detrimental effect on the FR-performance of the foam increases. This effect
far out balances the pure weight effect that would explain why a higher amount of
PDMS leads to higher burn length value due to the larger amount of materials supporting
the decomposition.
To address the question of whether the different volatility of the different PDMS
chains is the main reason for this effect, an additional test with silica was carried
97
out. It is easy to expect that solid materials, especially if inorganic, will have a positive
effect on the FR-performance of the foam and that they will lead to a decreasing
burn length in a burn test. Depending on the chemical nature they could be either
expected to be a heat sink, a material to catch free radicals, to char the burn front of
the foam or to liberate non-gaseous products to dilute the oxygen at the burn front.
Astonishingly, silica, a chemically inert material, under these conditions increased

the burn length of the foam (Figure 2.8). The assumption here is that on the surface
of the silica-particles either catalytic effects on the heat initiated oxidation processes
take place or the silica particles themselves act like a wick in a candle, providing a
means to transport melted organic material from the surface and increase the diffusion
flame front. If the formation of silica-particles on the burn front is indeed the major
detrimental effect of the silicone containing polymer, it should be helpful to decrease
the average length of any unmodified PDMS chain part between any two modifying
groups. Although in practice this is also an efficient tool to improve the burn
performance of the resulting foam, it negatively affects the nucleation power of the
silicone surfactant. Therefore this way of addressing FR-performance behaviour is
detrimental to the nucleation efficiency of any surfactant for liquid carbon dioxide
foaming [38]. That is the main reason why conventional (non-FR) silicones for the
liquid carbon dioxide processes were available before their optimised universal or
even pure FR-counterparts.
Figure 2.8 Addition of solid material
98
2.2.4 Chemistry of a Silicone Surfactant in Flexible Slabstock Foam Production
As outlined previously the main reason for the interest in optimised surfactants for the
liquid carbon dioxide processes lies in their role as nucleation promoters.
The silicone surfactants can be viewed as PDMS-polyether-copolymers which are mainly

based on a combination of just three structural units: the methyl substituted siloxane
backbone as well as a sophisticated ratio and arrangement of ethylene oxide and/or
propylene oxide forming the attached polyethers and, in some cases, additional
modifications.
A typical structure of a silicone surfactant is shown in Figure 2.9.
Figure 2.9 Building blocks of a surfactant
The molecules generally have a siloxane backbone formed by dimethylsiloxane units,

substituted methylsiloxane units and some endgroups. Polyether groups and/or additional
modifications can be attached to the siloxane backbone. Not only are a wide variety of
those additional modifications possible but also the polyether groups can vary in quite a
number of ways. Although they mostly consist of ethylene oxide and propylene oxide units
they obviously can be different in chain length, i.e., their molecular weight. They can also
have the different monomers distributed along the polyether chain in an either random or
a blockwise fashion as well as with alternating blocks. The polarity can be either evenly or
unevenly distributed. A more polar side could be either close to the attachment point to the
siloxane or far away from it. As this is true for each of the polyethers used and flexible
99
slabstock surfactants generally have more than one type of polyether attached, this gives
rise to virtually millions of different combinations for surfactant molecules. Also, in most
foaming applications the pendant polyethers have to be unreactive to isocyanates so that
they do not act like crosslinkers which would lead to tight or shrinking foam.
In addition there are two general ways to link the polyethers to the siloxane chains (see
Figure 2.9). This opens the basis for two separate product lines, each having its special
advantages over the other.
2.2.4.1 Si-C-Surfactants Versus Si-O-C-Surfactants
The Si-O-C products resulting from the reaction of chlorosiloxanes and hydroxyl
groups of polyethers provide an extremely good processing and superior consistency
combined with being hydrolytically stable under the water-amine conditions found
in polyurethane foaming. The Si-C products offer a more beneficial access to high
activity and lead to an easier production of flame retardant foams. These products
are derived from the addition of an Si-H functionality at the siloxanes to a double
bond, a process called hydrosilylation.
Examples of how this variety of structural parameters affects the development of silicone
surfactants especially for liquid carbon dioxide blown foams, are many [39, 40, 41, 42]
and this latest drive in surfactant development provides good examples of the important
performance issues and how they can be addressed.
Figure 2.10 Synthesis of Si-C and Si-O-C linked siloxane-polyether-copolymers
100
2.2.5 A Surfactant Development Example
In surfactant developments for liquid carbon dioxide PU foaming, the described

complexity of structural parameters in a surfactant led to the desire to characterise
nucleation performance of a surfactant without the need to judge the final, cured foam.
One important reason is the fact that a coarse or even irregular cell structure in the
final foam does not necessarily indicate the reason for such a ‘bad’ cell structure. It
could arise from a deficiency in nucleation performance so that the number of gas
bubbles formed at the beginning of the foaming reaction was not sufficient (lack of
nucleation). Another possible scenario could be that the initial number of bubbles
formed was rather high, but many of the gas bubbles were lost during the foam rise
due to gas bubble coalescence. That would mean that the stabilising power of the
surfactant would be insufficient and had to be improved.
One of the first published attempts to get an indication of the nucleation performance of
a silicone surfactant was the froth test [39, 40, 41]. In this test polyol and surfactant are
stirred in a reproducible fashion and the resulting froth density as well as the time needed
for the foam to collapse is measured. After some experience with industrial surfactants
used in the market these products with known performance in industrial liquid carbon
dioxide foaming were subjected to the froth test. No direct correlation could be found
between the obtained data and the performance of the products on industrial machines
(Figure 2.11).
Figure 2.11 Performance of surfactants (Tegostab B 8228 and B 8220) in the froth test
Comp.: competitive surfactant; EP-H-18: experimental product
101
As can be seen from Figure 2.11, both products Tegostab B 8228 and Tegostab B 8220
show nearly identical performance in this mixing test although industrial experience has
shown that Tegostab B 8220 results in significantly finer cell structure than Tegostab B
8228, even if both of them yield a very regular cell structure.
Even more confusing is the picture resulting from the comparison of a widely used
surfactant and an experimental product called EP-H-18 by Burkhart and co-authors
[42]. Both of the products again resulted in identical values in the froth stability test,
but differed significantly on an industrial production machine. Whereas the competitive
material resulted in a coarse cell structure, the experimental product yielded a fine and
regular foam.
A (30 s) B (30 s) C (30 s)
A (150 s) B (150 s) C (150 s)
bad good better
Figure 2.12 Video images of foam formulations with commercial surfactants of

different performance in liquid carbon dioxide processes
102
Because of these results a video microscopy check on the homogeneity of the gas bubbles
in the liquid mixture was performed. For this test the ingredients of a standard foam
formulation were mixed and immediately poured onto a polished metal plate. The
creaming of the foam was then filmed by a video camera with a 10x magnification.
Thirty and 150 seconds after the stirring commenced, a video printout was made and the
number of formed gas bubbles as well as their size homogeneity was characterised (see
Figure 2.12). This procedure is referred to as the video test.
2.2.5.1 Possible Silicone Structures
Not taking cyclic molecules into account, the general structures of industrial silicone
surfactants for flexible slabstock foam production can be seen in Figure 2.13. The main
building blocks of these materials are a PDMS backbone and attached polyethers based on
ethylene oxide and propylene oxide addition products. The siloxane backbones can either
be linear or branched and can have their polyether substituents attached in an either pendant
or terminal location. These four general structures are outlined in Figure 2.13).
Figure 2.13 General structures of silicone surfactants (schematic depiction)
103
The simplest type of the possible structures is a linear A-B-A-copolymer with a straight
siloxane backbone and polyether chains at the termini. This type of structure is described
as ST (for straight, terminal). With a straight siloxane backbone there is also the possibility
of attaching polyether groups as pendant chains. This combination is denoted SP (straight,
pendant). If the siloxane is branched as well it could have polyether groups attached as
terminal or as pendant groups (BT and BP). These four types of structures gave different
results in the video imaging test (see Figure 2.14).
The ST type of structure resulted in only a small number of gas bubbles being formed in the
early stages of the reaction. Somewhat better was the combination of branched silicone with
pendant polyether groups. The best video imaging results were reported with the branched
siloxane, combined with terminal polyether groups followed closely by the SP type of molecule.
ST SP
– +
BT BP
+(+) o
Figure 2.14 Video imaging test, comparison of different silicone structures

-, o, +, +(+) are a non numerical quality rating of degree of nucleation. - is poor
and +(+) is very good
104
These results matched, more or less, with industrial experience. Whereas the ABA type
of copolymer (ST-structure) is known to be a rather poor performing surfactant for
polyurethane production, the SP and the BT type of structures are commonly used. The
structure that performed best in the video imaging test (the BT type structure) is the
standard structural type that can be found in commercial SiOC-PDMS copolymers
obtained by the reaction of a chlorosubstituted PDMS with the hydroxyl group of
polyether (see previously). Although these SiOC products (named after the silicone-oxygen-
carbon bond linking the PDMS and the polyether side chain) provide a very good
combination of broad processing, good nucleation and consistent quality, their main
disadvantage is their very recognisable negative effect on the burning behaviour of the
produced polyurethane foam.
Therefore these types of products are commonly denoted as conventional or non-FR-silicones.
In contrast, the second best type of structure seemed to be the SP type. These structures
are the fundamental means to build SiC-products which are used as universal
surfactants, for example in North America. Although SP structures seemed to be the
obvious choice to build FR or universal type of surfactants (having a less negative
effect on FR-performance) they did not seem to show as good a nucleation as the BT
type of molecules.
The fourth structural type, BP products, no known experience or industrial application

was recognised, and due to the combination of not extremely good nucleation (according
to the video test) and the complicated synthesis necessary to make them, no reported
work was undertaken with these types of molecules.
Besides the type of branching in the siloxane backbone and the attachment points of
the polyether side groups, another factor characterising the siloxanes is the number
of unmodified PDMS groups for each of the modified methylsiloxane groups in the
molecule. This ratio is often denoted as the P-value and is especially important in
regards to the burn performance of the resulting foams (see Figure 2.10 and discussion
above). As that is another variable that has to be taken into account when
characterising a silicone surfactant for polyurethane foam production, this factor
was screened for as well.
As can be seen from the video test results, there seems to be a slight improvement in the
nucleation efficiency with increasing P-value. However the drawback is that the higher
P-values result in surfactants which will lead to a considerably negative effect on the
burn performance of the resulting foam [43].
The summary of the data at this point seemed to indicate that the combination of good
nucleation efficiency with the BT-structures and the advantage of high P-values seem to
105
P-value
Figure 2.15 Video imaging test; nucleation efficiency with increasing P-value
correlate with the fact that, especially based on SiOC type of chemistry, it is easier to
build a non FR-surfactant structure than to build a universal or true FR-silicone surfactant
for liquid carbon dioxide foaming.
In the case of good FR-surfactants therefore, a compensation for the unavailability

of high P-values had to be found in regard to nucleation efficiency of the molecule.
Because of a suggestion in the literature [44] that the high solubility of carbon dioxide
in certain aromatic solvents might be due to interaction between the molecules, the
influence of aromatic structures in surfactant molecules was screened. Whereas the
standard siloxane backbone in PU surfactants is normally consisting of a PDMS
chain between the substituted silicon atoms, high temperature silicone resins are
used with phenylmethylsiloxane groups within the chain. Although these types of
molecules seemed to be viable candidates for testing, they did not seem to be attractive
options for industrial use due to the complicated synthesis and the high costs associated
with them.
Another option to incorporate aromatic structures in organomodified silicones has been

the use of styrene oxide as a monomer for the synthesis of the polyether side chain within
the copolymer structure [45] (see Figure 2.16).
Comparison of structural siliconepolyether analogues with and without styrene oxide

incorporation in surfactant test molecules showed an indication of a positive trend in the
video test regarding the nucleation efficiency of those aromatic group substituted silicone
polyether copolymers.
Surprisingly enough in a real foam test these molecules performed rather badly, resulting
in a considerably coarser foam than the reference (see Figure 2.17).
106
Figure 2.16 Aromatically substituted polyether
Surfactant
without aromatic groups with aromatic groups
Cell structure in foam test:

10 cells/cm 8 cells/cm
Figure 2.17 Comparison of standard and aromatically substituted siliconepolyether
That observation was rationalised with the following assumption. If indeed aromatic
rings would increase the solubility of carbon dioxide then these types of structures would
be more soluble in a liquid carbon dioxide containing environment. This would result in
a decreased tendency to move to the surface of a such a liquid phase. The obvious result
would be a decrease of surface activity, so the net result could very well be a higher
nucleation efficiency combined with a lower activity during the rise time of the foam,
leading to gas bubble coalescence.
107
If that is true, the polarity and therefore solubility of the molecule would have to be
adjusted to lower values. As explained previously the increase of the P-value was not an
option for the generation of a surfactant with good FR-performance.
Therefore to further decrease the solubility of a surfactant in a formulation for flexible

slabstock PU-foam, the polarity of the surfactant molecule was decreased by lowering
the polarity of the polyether side chain with the use of higher alkylene oxides to have
more non-polar groups along the polyether chain (Figure 2.18). This would lead to a
higher carbon:oxygen ratio in the polyether side chain. Since it has been known for more
than 30 years [46] that the polyether polarity affects the cell size distribution of flexible
slabstock PU foams that is a very good method for fine-tuning surfactants. Foaming tests
showed that the carbon:oxygen content had a significant impact on the overall activity
of the surfactant, resulting in decreasing foam height with increasing carbon:oxygen
ratio, especially when a carbon:oxygen ratio of about 2.6 was exceeded.
Figure 2.18 Influence of carbon to oxygen ratio in polyether side chains
The utilisation of the outlined principles and the continuous work with the many possible
variables by all the additive suppliers again and again has brought new high performance
surfactants, supporting the continuously changing demands in the innovative polyurethane
industry and most probably will continue to do so. Therefore this industry has all the
fascination that comes from the interaction of chemistry and physics, industrial application
and theoretical interest, commercial importance and environmental awareness. So even
more than 50 years after its beginning it will remain an area of new challenges and
performance oriented efforts.
108
References
1. No inventor; I.G. Farben AG, assignee; German Patent 728,981, 1937.
2. A. Höchtlen and W. Droste, inventors; Farbenfabriken Bayer AG, assignee;

German Patent 913,474, 1941.
3. P. Hoppe, inventor; Farbenfabriken Bayer, assignee; German Patent 851,851, 1948.
4. W. Droste and A. Höchtlen, inventors; Farbenfabriken Bayer, assignee; German

Patent 860,109, 1952.
5. Chemical and Engineering News, 1961, 39, 11, 62.
6. K. Moser, Kunststoffe, 1983, 73, 12, 764.
7. F. K. Brochhagen in Handbook of Environmental Chemistry, Vol. 3, Part G, Ed.,

O. Hutzinger, 1991, Springer Verlag, Berlin, p.73.
8. G. Rossmy, H. J. Kollmeier, W. Lidy, H. Schator and M. Wiemann, Journal of

Cellular Plastics, 1981, 17, 6, 319.

10. G. Rossmy, W. Lidy, H. Schator, M. Wiemann and H J. Kollmeier, Journal of

11. G. Burkhart, H-H. Schlöns and V. Zellmer, inventors; Th. Goldschmidt AG,
assignee; US Patent 5 132 333, 1992.
12. R. Ricciardi, Presented at the Polyurethane Foam Association conference in

Scotsdale, AZ, 1996.
13. M. A. Ricciardi, D. J. Smudin, R. D. Wagner, M. Pcolinsky and J. E. Chaya,

inventor; no assignee, US Patent 3,890,414, 1975.
14. M. A. Ricciardi and D. G. Dai, inventors; Crain Industries, Inc., assignee, US

Patent 5,171,756, 1992.
15. H. Stone, inventor; PMC, Inc., assignee, US Patent 5,128,379, 1992.
16. A. A. Grizwold, inventor; Reeves Brothers, Inc., assignee; US Patent 4,537,912,

1985.
109
17. J. L. Drye and G. C. Cavenaugh, inventors; Trinity American Corporation,

assignee, US Patent 5,188,792, 1993.
18. P. Merriman, inventor; Dunlop Rubber Co., Ltd., assignee; US Patent 3,184,419,
1965.
19. E. N. Doyle and S. Carson, inventors; no assignee, US Patent 5,120,770,1992.
20. C. Fiorentini, M. Griffith and A. Charles, inventors; Krypton International SA,

assignee; European Patent 0645226A2, 1995.
21. C. Fiorentini, M. Taverna and T. Griffiths, Journal of Cellular Polymers, 1994,

13, 5, 361.
22. CarDio Newsletter No.4, September 1997, Article no. 97037.
23. R. G. Eiben, Presented at Utech ’96, The Hague, The Netherlands, 1996, Paper
No.31.
24. Innovations, 1998, October, 801, 15.
25. Novaflex Multistream, Hennecke leaflet PI125, October 1998.
26. B. Kanner, T. G. Decker and G. Thomas, Journal of Cellular Plastics, 1969, 5, 1,

32.
27. B. Kanner, W. G. Reid and I. H. Petersen, Industrial Engineering Chemistry,

Product Research & Design, 1967, 6, 2, 88.
28. B. Arkles, Silanes & Silicones catalogue, Petrach Systems, Bartram Road, Bristol,
PA, 19007, USA, 1987, p 87.
29. B. Arkles, Chemtech, 1983, 13, 542.
30. X. D. Zhang, C. W. Macosko, H. T. Davis, A. D. Nikolov and D. T. Wasan,

Journal of Colloid and Interface Science, 1999, 215, 2, 270.
31. K. Yasunaga, R. A. Neff, X. D. Zhang and C. W. Macosko, Journal of Cellular

Plastics, 1996, 32, 5, 427.
32. L. E. Scriven and C. V. Sternling, Nature, 1960, 187, 186.
33. M. J. Owen, T. C. Kendrick, B. M. Kingston and N. C. Lloyd, Journal of Colloid

Interface Science, 1967, 24, 2, 141.
110
34. X. D. Zhang, C. W. Macosko and H. T. Davis in Polymeric Foams, Ed., K. C.

Khemani, Chapter 9, ACS Symposium Series 669, American Chemical Society,
Washington DC, 1997.
35. J. P. Armistead, G. L. Wilkes and R. B. Turner, Journal of Applied Polymer

Science, 1988, 35, 3, 601.
36. M. W. Creswick, K. D. Lee, R. B. Turner and L. M. Huber, Presented at the SPI

31st Annual Technical/Marketing Conference, Philadelphia, PA, 1988, p.11.
37. A. Weier, G. Burkhart, M. Klincke, Presented at Industrial Applications of

Surfactants IV, Suffolk, UK, 1998, p.260.
38. G. Burkhart, R. Langenhagen and A. Weier, Presented at the Polyurethanes Expo

’98, Dallas, TX, 1998, p.129.
39. S. B. McVey, B. L. Hilker and L. F. Lawler, Presented at the Polyurethanes Foam

Association conference, San Antonio, CA, 1995.
40. S. B. McVey, B. L. Hilker and L. F. Lawler, Presented at Utech 96, The Hague,
Paper No.38.
41. G. Burkhart, V. Zellmer and R. Borgogelli, Presented at the SPI Polyurethanes

Expo ’96, Las Vegas, NV, 1996, p.144.
42. G. Burkhart, R. Langenhagen and A. Weier, Presented at the Polyurethanes Expo

’98, Dallas, TX, 1998, p.129.
43. A. Weier, G. Burkhart and V. Zellmer, Presented at the SPI, Polyurethanes ’94
Conference, Boston, MA, 1994, p.202.
44. J. H. Hildebrand, J. M. Prausnitz and R. L. Scott, Regular and Related Solutions:

the Solubility of Gases, Liquids and Solids, Van Nostrand Reinhold Co., New
York, 1970.
45. No inventors; Th. Goldschmidt AG, assignee; German Patent 19, 726, 653, 1999.
46. R. J. Boudreau, Modern Plastics, 1967, 44, 5, 133.
111
112
3
Polyurethane Processing: Recent Developments
Max Taverna
This chapter highlights three aspects of manufacturing technology, which have recently brought
significant benefits to the producers of automotive seats, reinforced parts and generic moulded
items. These different manufacturing areas have been grouped here under a single title in
order to cover a wider spectrum of reader’s interests and to illustrate the broad area of
improvement and innovation that can still be found in this steady-growing segment of industry.
3.1 Industrial Solutions for the Production of Automotive Seats Using

Polyurethane Multi-Component Formulations
Cannon has developed complete systems for the manufacture of moulded polyurethane
automotive seating elements made with varying combinations of several raw materials.
The resultant cushions – although produced in a random sequence on the same moulding
line - are characterised by mechanical properties tailored to the specific application of
each part [1].
This section describes the components of this technology which are:
• dedicated multi-component, high-pressure metering machines with closed-loop control

of both the output and pour pressures
• dedicated mixing heads capable of processing six components (all with high-pressure
recirculation), including low-viscosity toluene diisocyanate (TDI) and water-based additives
• dedicated mould-handling systems for a flexible manufacturing concept based on

just-in-time methods
3.1.1 Market Requirements
A recent analysis (internal Cannon Report) of the automotive seat-manufacturing market

segment, to identify the future needs and trends of this group highlighted a number of
interesting considerations for a producer of polyurethane processing equipment.
113
First, the number of suppliers is getting smaller and smaller, due to the extensive merger
and acquisition campaign run in recent years by the two largest players (Lear Co., and
Johnson Controls). This concentration creates an opportunity for making strategic choices
regarding the ‘make or buy’ decision with respect to manufacturing solutions. These
large manufacturers have grown significantly thanks to their own successful development
of both chemical formulations and moulding plants. Providing them with new machinery
sometimes means accepting their request to manufacture a concept that was developed
by their own engineering department.
The second aspect concerns the growing demand for simpler, high-efficiency plants, with
a reduced number of operators and a high degree of operating flexibility. It must be
possible to produce several different parts on the same moulding line so that, in the case
of a sudden change in production plans, complete projects can be switched from one
production line to another within a very short time frame. This increased flexibility
requires careful design of the metering equipment, mix heads and mould carriers because
they must be able to perform very different tasks in sequence or by project. A specific
request involves the potential to process multi-component formulations, where a wide
range of foams can be produced on one machine.
The third aspect, potentially in conflict with the previous concept, involves the development
of families of formulations based on specific chemicals: all diphenylmethane diisocyanate
(MDI), MDI/TDI in various percentages, all TDI and special polyols. This means dealing
with very different demould times and moulding conditions, that render a generic ‘seat
plant’, that was still so useable just a few years ago, obsolete. In this case, specific packages
must be available, which conflicts with the concept of high flexibility expressed above.
3.1.2 Dedicated Solutions: Metering Equipment
A high-pressure multi-component metering unit was designed for automotive seating

producers, with a pump-dosing system capable of precisely dosing TDI and other low-
viscosity components. Output adjustment on-the-fly and closed-loop control, easy to
obtain with piston-driven metering units, were engineered for pump-driven machines as
well. The number of main components (polyols and isocyanates) can be set, as necessary,
since the design is modular: each dosing line includes a dedicated tank, its temperature
control system, high- and low-pressure filters, recirculation valves, a dosing pump and
motor and a portion of the control panel (see Figure 3.1).
The modular design of this unit allows for easy addition of further components to a
formulation. Storage, metering, temperature-time control modules and feed lines are
assembled in modules and can be added as needed. Computerised process control easily
integrates the new chemicals in the formulation.
114
Figure 3.1 A high-pressure multi-component metering unit
Two methods were used to enable fast, precise changing of the output and to ensure
closed-loop control of the machine, which is essential to guarantee continuous, accurate
output of low-viscosity chemicals:
• via an inverter mounted on the pump motor

• via a programmable step-by-step motor that changes the setting of the pump.
The output control on the closed-loop machine operates continuously, comparing the set
output value of the inverters with the real output as measured by the volumetric flow
transducers. The system enables pouring only when the parameter is within the limits set
by the operator via the keyboard and when it is possible to change the pump speed in less
than half a second.
The unit also includes maintenance and alarm menus. Through the maintenance menu,
it is possible to set limitations on the following parameters:
• number of shots
• material consumption
• working hours
115
Once these set values are reached, the corresponding warning message informs the operator
to perform the required maintenance operation.
The programmable stepping device is very precise - the pump can be set at 256 discrete
positions - and can be easily programmed through the machine programme logic controller
(PLC). Since the switching time between formulations can be as low as 0.6 of a second,
multiple ratios can be set within the same pour program to produce multi-hardness and
multi-density foams with repetitive results.
3.1.3 Dedicated Solutions: Mixing Heads
Cannon has designed a new mixing head, capable of mixing six components, each with
individual recirculation control. The new mixing head was specifically designed to meet the
needs of the automotive seat producers who wished to mould TDI-based flexible foams with
a maximum of flexibility in their formulation. Several pure ingredients are kept separate up
to the point of injection and it is possible to operate each stream on demand, provide high-
pressure recirculation and avoid the contamination of components (see Figure 3.2) [1, 2].
Figure 3.2 The new Cannon Ax Head, specifically designed for multi-component
polyurethane formulations. It can mix up to six chemicals all with a high-pressure
recirculation feature.
116
Although this solution is currently available on the market, competitive mix heads are
limited to four streams, their dimension and weight require heavy-duty pour robots while
providing speed and pour pattern limitations during operation and they have complex
pressure set-up and regulation procedures.
3.1.3.1 Multi-Component Operation
The innovative aspect of this mixhead is that TDI - and eventually a TDI-compatible
sixth component - are fed axially into the mixing chamber through the small piston that
cleans the mixing chamber. The other four components, polyols, other catalysts, additives,
flame retardants, are fed radially into the mixing chamber. A seal on the small piston
provides a permanent separation between the polyol and TDI feeding areas so that any
crossover of the low-viscosity components is avoided.
The main advantage of the new mixing head is its reliability. It can operate for millions
of shots because of the remote position of the TDI feeding area. TDI is fed in at a pressure
of only 1 MPa, with perfect mixing efficiency (see Figures 3.3, 3.4 and 3.5).
Figure 3.3 Section of the mixing-chamber’s cleaning piston. Four chemicals are fed radially
in the mixing chamber, while two are fed through a hole drilled in the cleaning piston.
117
Figure 3.4 During the high-pressure recycle phase all six components flow
in the grooves carved in the mixing chamber’s piston and return to their
storage tanks.
Figure 3.5 When the injection signal is received, the mixing chamber’s piston
retracts, the four components fed radially meet the two that are fed axially
through the mixing chamber’s piston. The mixed blend reaches the discharge duct,
which is positioned at an angle of 90° to the mixing chamber and leaves the head
through the pouring hole.
118
Defining ‘Formulation #1’ as being composed of polyol #1 and isocyanate and ‘Formulation
#2’ as polyol #2 and isocyanate, an example of a working sequence is as follows:
1. Pour ‘Formulation #1’: polyol #1 and isocyanate recycle through the mixing chamber’s
piston grooves and are poured in the open mould
2. ‘Formulation #2’ remains dormant since polyol #2 continues to recirculate through a

high-pressure nozzle positioned close to the mixhead
3. The formulation change is implemented by:

• closing the mixing chamber’s piston (the self-cleaning piston is kept open)
• opening the polyol #2 high-pressure nozzle and closing the polyol #1 nozzle
• re-opening the mixing chamber’s piston with the new ‘Formulation #2’
The maximum response time, which occurs between two consecutive shots with different
formulations, is 0.6 seconds.
3.1.3.2 Pour Pressure Control
The pressure control of the component injectors, which is very important for ensuring the
proper mixing of the different liquid streams, has been achieved via three different approaches:
• closed-loop control of the injection pressure via hydraulic servo valves and feed-
back control from the pressure gauges
• open-loop control via hydraulic servo valves
• fixed-position control via various hydraulic valves, preset at different values
The package supplied with the head to achieve pressure control (see Figure 3.6) includes:
• hydraulically-operated nozzles to be installed on the mixhead for the components

that are fed radially; each nozzle has a double function:
- selection of the component to be used in the specified formulation
- control of the re-circulation/injection pressure during the pour
• hydraulic unit for operation of nozzles
• valves for control of the oil flow; each valve has three positions (off, injection pressure
#1 and injection pressure #2)
119
Figure 3.6 Scheme of the circuit used to guarantee a closed-loop control of the pouring
pressure of each chemical.
• high-performance recycle stream distributors with relevant pressure control to

maintain non-specified components in high-pressure recirculation, ready to be injected
within 0.6 seconds
• one set of high-pressure flexible hoses to connect the proportional valves to the
injector nozzles
• appropriate controls
3.1.3.3 Variable Geometry Mixhead

To ensure proper mixing conditions for a wide range of formulations - which can differ
in chemical composition, viscosity, ratio and output - it is important to provide appropriate
backpressure in the mixing area. This can be obtained with the adjustable geometry
regulation of the mixing area: the mix head’s larger piston can be mechanically set to
partially block the outlet of the mixing chamber when it is fully retracted. This occlusion
increases the turbulence in the mixing area, causing more efficient mixing to be obtained.
120
3.1.3.4 Advantages
A very compact design: its outside dimensions of 40 x 20 cm and 22 kg weight translate

into a high degree of manoeuvrability.
• The pour pattern can be defined very precisely, according to the design of the mould
and the position of any inserts.
• The pouring operation can be executed in an open mould without fear of collision
with the upper mould half.
• The robot carrying the head can achieve high acceleration and speeds without
mechanically stressing the moving elements.
The large number of chemical components that can be handled simultaneously provides
a high degree of flexibility in formulations, allowing for optimum use of the moulding
line. Several different parts can be produced on the same moulding line and different
types of foam can easily be produced in random sequence without forcing the operator
to use pre-defined sequences of moulds.
3.1.4 Dedicated Solutions
3.1.4.1 Foaming Robots
The basic features of a typical Cannon double-arm pour robot, normally supplied to
carry two heads (see Figure 3.7), are:
• two-axes Cartesian robot with two arms moving independently of each other,
• arm movements (along the ‘X’ and ‘Y’ axes) achieved via a rack-and-pinion system
driven by electronic variable-speed motors,
• racks fitted with position encoders to detect the relevant ‘X’ and ‘Y’ coordinates.
The Technical Specifications include:

- maximum speed for X axis: 2.4 m/s
- maximum speed for Y axis: 2.4 m/s
- maximum acceleration: 3.5 m/s2
- maximum load on the arm: 120 kg
- maximum ‘X’-axis stroke: 250 cm
- maximum ‘Y’-axis stroke: 115 cm
- minimum distance between 2 arms: 55 cm
- available working area: 307 x 115 cm
121
Figure 3.7 A double-arm Cartesian robot, designed to perform multi-hardness PU

foaming in open-mould pouring processes for automotive seat moulding.
3.1.4.2 Mould Carriers
The concept of the dedicated flexible foam moulding line relies on a mould carrier having
a simple solid structure, with a minimum number of mechanical parts, which require
maintenance. It consists of two upper and two lower sections linked by means of a
hooking system. The presence of two separate lower platens allows the operator to
compensate for any difference in mould thickness without incurring any problem by
mounting two moulds on the same carrier (see Figure 3.8). Insertion, centring and fixation
of various moulds within the mould carrier are achieved by means of tensioning screws.
Each mould carrier is usually provided with two pneumatic cylinders for opening and
closing. Upon demand, the closing system can be actuated hydraulically or mechanically.
Mould carrier tilting, for optimum evacuation of air during the filling phase, is
accomplished with a cam system. Each mould carrier can have two tilting positions:
either horizontal or frontally inclined by 20 degrees (see Figure 3.9). It is possible to
programme different angles of opening and tilting to correspond with the type of mould
currently being used.
Mould identification – necessary in order to transmit the appropriate mould/formulation

information to the dosing system - is achieved with a code reader. The electrical controls
122
Figure 3.8 Independently-moving lower platens allow for the use of different thickness
of moulds as a double mould carrier.
Figure 3.9 A different degree of tilting can be obtained for each mould carrier, to
optimise the evacuation of air from the moulds during the filling/
polymerisation phase.
123
for the moulding line are interfaced to the metering system controls in order to co-
ordinate all the working processes.
The typical working sequence can be defined as follows:
• mould identification: the control system on the moulding line reads the code coming
from the field
• pour programme selection: inside the mixhead manipulator control unit, a schedule
- assigning a specific pour programme to the different moulds - has to be loaded
• pour programme execution: the manipulator control unit sends the input to the
machine control unit; when the mould under consideration requires multi-hardness
foaming, both mix heads are activated, while in the case of a single-hardness seat,
only one mixhead is activated
Stroking of the Platens
As stated previously, the lower half of the mould carrier is composed of two independent
platens. They are fitted with a guiding system to ensure maximum parallelism between
the platens.
In order to ensure equal clamping pressure and complete closure of the moulds over the
entire parting line, pneumatically inflated tubes stroke each platen. They are inflated
after the mould carrier has been closed and deflated just before opening. The total stroke
is a few centimetres. The clamping force afforded by this system is 12,700 kg, using a
working pressure for the air bags of 0.3 MPa.
Mould Temperature Control System
Individual thermoregulator units are used, one for each press. They are mounted on the
rear of each mould carrier. This solution affords complete autonomy to each press, making
it possible to control the temperature of the moulds prior to being placed on the production
line. Subsequently, when a press is placed on the moulding line, it is ready to commence
production.
The thermoregulators work in a closed circuit; the relevant refilling has to be performed
off-line. The control panel for each thermoregulator is mounted on the operator side for
easier access.
124
Mould Carrier Exchange
The mould carrier concept for fixing and centring is designed for quick mould carrier
removal or exchange.
The mould carrier can be removed as follows:
• disconnect the electrical plug (positioned on the operator side)

• disconnect the air by removing the relevant joint mounted on the mould carrier
• remove the complete mould carrier (with its thermoregulator) using a fork lift
The estimated time to perform this operation is less than five minutes.
Service Station
A dedicated station where service operations on moulds and mould carriers can be
performed, without disturbing the production cycle, is foreseen for each moulding line
(see Figure 3.10).
Figure 3.10 All maintenance and setting operations on moulds and mould-carriers can
be executed off-line, in a dedicated service station that performs all the line’s
movements and operative functions.
125
The service station comes with one complete mould carrier on its freestanding frame. It
is equipped with a dedicated thermoregulator for warming of moulds destined to be
inserted on the moulding line, along with all the required safety fences/light barriers,
controls, and connections for air, water and electrical power.
3.1.4.3 Transport Systems
Cannon provides different mould-carrying systems, each customised to meet the customer’s
needs. The most common solutions are conveyors and turning tables. In the last part of
this section some innovative concepts, which provide a more compact layout, a minimised
investment requirement and a maximum degree of flexibility in a changing manufacturing
scenario, are presented.
Oval Conveyor
The conveyor is made of a central steel frame, which is positioned on the floor. It is
composed of a series of straight-line modules with a curved module at each end and
comes complete with a number of carriages running on an oval steel track (also mounted
on the floor). On each carriage, mainly composed of a rigid steel frame positioned on
four pivoting wheels, a single lid mould-carrier is mounted. Four idle wheels, running
along a central guide plate, maintain the system on its set path (see Figure 3.11).
Continuous movement is achieved by means of one drive system being placed between
every two carriages. Each driving system has two entrainment wheels running along the
guide plate. The entrainment wheels – operated via an AC motor – are maintained in
traction along the guide plate by a spring. An inverter is used to adjust the speed from 4
m to a maximum of 9 m/min, while the AC motor is fitted with a brake so that, in case
of an emergency, the plant can stop within a few centimetres of travel.
This system can easily be expanded to incorporate any new business obtained for that
range of moulded products. Extensions are achieved by fitting an even number of new
carriers to the line and extending the supporting frame accordingly.
Mould Carrying Systems: FlexiDrum
Developed in the early 1980s as a revolutionary tool for the production of foamed
refrigerator doors, the well-known concept of the rotary polymerisation system is now
being proposed as a compact and simple mould-carrying system for the production of
automotive seats (see Figure 3.12).
126
Figure 3.11 A modular oval conveyor for flexible foam moulding. It can be easily extended,
adding modules of track and pairs of mould carriers, when higher productivity is required.
Figure 3.12 Flexidrum, a compact moulding line for medium-low volume of

automotive seat production.
1a Service station: demoulding, cleaning, insert positioning, release agent application;
1b Open mould view of 1a; 2 Foaming station, with robot on a platform;
3-6 Polymerisation stations; 7 Six arm rotating structure to support mould carriers; 8 Central
collector of signals, air and warm water; 9 Supporting structure (and rotor, not shown)
127
Six or more mould carriers can be fixed on the surfaces of a wheel that rotates vertically –
similar to a Ferris wheel, rather than horizontally, as with a merry-go-round. The opening
and closing movements can be hydraulic or pneumatic. Mould conditioning can be
accomplished using a rotating collector that feeds each mould carrier with water at the
desired temperature. Manual service operations are performed on the lower mould half in
the first station. Foaming is achieved in the subsequent station using a platform-mounted
robot. Polymerisation takes place in the remaining four (or more) elevated stations as they
are passed through a compact suction hood that removes the escaping fumes. Several
advantages can be highlighted for this new version of mould carrying system:
• simplified mechanical construction that does not incorporate wheels which roll
along the floor picking up and transporting scrap foam and/or dirt
• optimised layout which will work even when space is limited
• reduced power cost thanks to its vertical layout which minimises the suction area,
requiring only one fan for extraction of the fumes
• limited number of operators required
Carousel for In Situ Foaming
A number of dedicated moulding lines have been designed for the production of in situ
moulded foams. In situ moulding technology adds a delicate operation to the list of
conventional operations (mould cleaning, release agent spraying, insert positioning,
foaming and demoulding) that must be executed to mould a standard foamed item: the
manual positioning of the textile container into which the foam will be dispensed. This is
a delicate operation that requires some time, yet should not penalise the cycle.
A practical solution consists of a carousel line with a row of service positions where the
operators can work on moulds that have been temporarily taken off-line (see Figure 3.13).
When the press leaves the curing area, it passes in front of the first free operator and is
automatically disengaged by the dragging system. The moulds can be serviced, taking all
the time required, then, when the textile inserts have been positioned, the carrier can be re-
inserted in the first available position in the line.
Multi-Hardness and Multi-Density Foams with Natural Carbon Dioxide
The availability of multi-component mixheads with variable geometry opens the path to
another interesting option: the addition of natural carbon dioxide for expansion of the
128
Figure 3.13 Oval moulding line with 16 double mould carriers, designed for in situ
foaming of textiles.
1 to 4 Service stations, where mould carriers are taken temporarily off-line for
mould service; 5 Spare station; 6 Foaming station; A Pouring robot; B Metering
equipment, on mezzanine; 7 to 16 Polymerisation stations; C Mould carrier
changing station; D Suction hoods
foam with an environmentally friendly blowing agent and reduction of the foam density
by as much as 20-25%. With this new mixhead, it is possible to use two different
approaches to add natural carbon dioxide to the formulations:
• CannOxide [3-12] - a technology developed to meter natural carbon dioxide at the

point of injection, at the desired percentage, into one of the polyol streams
• EasyFroth [1, 2, 4, 11, 12, 13,14] for carbon dioxide – a technology that allows the
premixing of given percentages of blowing agent in one of the two components,
usually the isocyanate.
Both methods are currently in industrial production, each having operating and
investment ‘pro’s and con’s’ that must be evaluated according to the production volumes
and flexibility required. For example, a car seat with three different hardnesses can be
produced using two different formulations for the hard and soft parts - (see areas ‘A’
and ‘B’ in Figure 3.14) - and incorporate some natural carbon dioxide to decrease the
seat density below the thighs (area ‘C’).
129
Figure 3.14 Triple hardness automotive seat

A – Soft foam; B – Hard foam; C – Soft and lower-density foam, blown with natural
carbon dioxide
3.2 ‘Foam & Film’ Technology - An Innovative Solution to Fully

Automate the Manufacture of Automotive Sound Deadening Parts
Until now, one of the major limitations in the polyurethane moulding process has been
the necessity to interrupt the working sequence between each moulding, to remove foam
scrap and apply release agent prior to foaming. The introduction of ‘Foam & Film’
technology makes manual intervention unnecessary, removing the one factor that has
always been a major weakness when working with polyurethanes in comparison to other
injected or extruded plastics [15-19].
The main idea behind this new approach consists of thermoforming a thermoplastic
or polyurethane film as part of the moulding sequence. By using a vacuum effect,
this film adheres perfectly and smoothly to the mould cavity, without any creases or
wrinkle formation. The mould is equipped with a dedicated frame device, specifically
designed to hold the film. A heating system ensures that the film reaches the desired
temperature prior to the thermoforming phase and subsequent injection of
polyurethane into the mould.
130
Several industrial applications have been found and a number of fully automated plants
currently incorporate this technology. The manufacture of sound deadening parts for
the automotive industry represents one of the most exciting applications for this
innovative technology.
3.2.1 The Problem
Mould cleaning is required because of the chemical nature of the polyurethane process.
The objective in developing the ‘Foam & Film’ technology was to eliminate the tedious,
time-consuming manual operations, which must be performed on the moulds as part of
a discontinuous polyurethane foaming process.
The need to properly vent the mould, to avoid air entrapment, often results in a thin
flash of polyurethane being formed around the moulded part, which needs to be manually
removed afterwards via a simple trimming operation. These manual operations involve
both cleaning of the mould and spraying of the release agent.
It is necessary to demould parts in the shortest possible time, when the foam is not yet
fully polymerised, because the thin cross-section of the flash makes them very fragile
during the first few minutes following the demould. Often small pieces of flash will
break off when the part is extracted, falling back onto the mould. If they are not removed
from the mould surface, they could mar the surface of the subsequent parts or they could
allow rising foam to leak from the mould if left along the seal. More extensive cleaning
operations are required every few shifts in order to remove deposits of release agent
from the mould surface and there require production to be stopped.
Various technologies have been applied to minimise the required downtime, but so far a
valid solution has not been found. The adhesive force between polyurethane and metal
(either aluminum or steel) requires a release agent to be sprayed onto the moulds every
single cycle (or every few cycles) to enable easy removal of the part. In addition, various
internal mould release technologies are available, but they do not apply to all formulations.
As stated previously, these operations take a long time, are expensive and are typically
executed manually and it is impossible to have a fully automated line without getting rid
of them. To create a fully automated line, both the need to manually clean the mould and
the need to spray release agents on it had to be eliminated.
3.2.2 The Approach to a Solution
The new approach to polyurethane moulding is to introduce a thermoplastic or

polyurethane film thermoforming process on one or both halves of the mould as part of
131
the overall sequence. By using a vacuum, this film adheres perfectly and smoothly to the
mould cavity, without any creases or wrinkle formation.
The system’s key concept is a specially designed and patented frame, integrated into the
mould, which is specifically designed to hold the film in position during this thermoforming
process. This frame can be either two or three dimensional, to better follow the shape
and the cavities of the mould (see Figure 3.15).
Figure 3.15 ‘Foam and Film’ concept

1. Unrolling and cutting plastic film to required length; 2. Infrared (IR) heating of film
on holding frame; 3. Thermoforming the film in the mould cavity; 4. The same process
(1-3) is carried out in the other half of the mould at the same time; 5. Robotised foam
deposition in mould; 6. Mould closed for expansion/polymerisation. Parts are removed
‘wrapped’ in the film.
The frame receives the film after it is unrolled by pinchers and cut dimensionally. It
then moves it in front of an infrared lamp for several seconds to heat it to the required
temperature. A control system ensures that the film reaches the desired temperature
prior to the thermoforming phase. Special infrared heaters, Cannon’s MVL heaters,
are used to ensure high efficiency and very low thermal inertia. Once the film is heated,
the frame moves into the mould where the film, held in place along its four edges, is
vacuum-formed onto it. The use of the frame during the vacuum forming prevents the
film from folding or wrinkling (see Figure 3.16).
132
Figure 3.16 A patented frame holds the releasing film in position so that when
thermoformed over the mould, it is kept under tension and does not form wrinkles.
3.2.3 The Film
There are two different types of ‘Foam & Film’ processes available, based on the different
types of film used: adhesive and releasing.
• In the adhesive type, the film sticks to the part and is unloaded with it, granting an
aesthetic finish and a waterproof covering (see Figure 3.17).
• The releasing film, on the contrary, remains vacuum-formed to the mould for several
shots (5-15, dependent upon the process and the materials utilised) and it is then
replaced when it begins to wear.
Obviously, with the adhesive type, the film has a high adhesion coefficient with polyurethane,
while in the releasing version the poorer the adhesion, the better. In both cases, the film
prevents the mould from ever being put in contact with the polyurethane foam. That is
why both cleaning and spraying are no longer necessary and all operations can be automated.
133
Figure 3.17 Two shock absorbing inserts for automotive doors moulded in semi-rigid EA-
foam with the ‘Foam & Film’ technology as they appear immediately after demoulding. The
film protects the foaming against moisture and degradation. No release agents or mould
cleaning operations are needed to produce this part in a highly automated moulding plant.
3.2.3.1 Adhesive Film Solution

Basically, three types of film can be used in the adhesive Foam & Film process:
• Thermoplastic polyurethane (TPU)

• Polyethylene (PE)
• Thermoplastic film (TP)
TPU is a good film for both cold and hot processes, providing good adhesion to the foam
and excellent mechanical properties but the cost is high (around 0.65 US$ per square
metre). PE film can only be used in cold processes, it requires a special treatment for
perfect adhesion and it gives an overall poorer performance but it has the advantage of
being very inexpensive. TP film is only suitable for hot processes, it requires no treatment,
and it guarantees good adhesion at a low cost (less than 0.2 US$ per square metre).
This last type of film is what has been developed in depth, obtaining very good tear and
impact resistance, flexibility, elongation and welding ease. This is the solution that has
been used for most automated Foam & Film plants supplied so far. Using this film,
General Motors makes sound-deadening parts with fully automated equipment that has
a productivity of 8000 parts/day, running 24 hours per day with zero operators [17, 18].
3.2.3.2 Releasing Film Solution

The second type of film, the releasing one, sticks to the mould and not to the polyurethane
part. In the releasing Foam & Film technology, there are two main types of film that can be
134
used: PE and TP. PE, once again, is very common and inexpensive, but gives poor release
from the foam, which minimises the benefits of this technology. TP film provides an easy
process with good release from the foam for several shots at a very reasonable price.
3.2.4 Industrial Applications
A good example of such a continuous moulding process that incorporates ‘Foam &
Film’ technology is a system developed for the production of industrial vehicle carpets.
These products are usually made out of a sandwich of two or more layers of different
materials. Individually, they provide different features: aesthetics and function (a textile
carpet or a synthetic mat), sound deadening (a layer of polyurethane foam) and protective
(a cheap layer to protect the foam from moisture and degradation).
INSOTEC, a technology designed by Cannon for the manufacture of sound-deadening

automotive components, offers a variety of manufacturing alternatives that provide
significant benefits such as improved quality parts, reduced costs, shorter process times,
as well as regular and consistent production cycles (see Figure 3.18).
Figure 3.18 A large full-automated production plant for truck floor-covering mats
using the ‘Foam & Film’ technology. The parts are made of thermoformed PVC (or
thermoplastic elastomer) foam-backed with PU, which is kept separate from the
mould with a film (adhesive type).
135
These excellent results have recently been improved with the introduction of the new
‘Foam & Film’ technology. The technology makes manual intervention unnecessary,
removing the one factor, which has always been a major weakness with polyurethane
processing and added a significant cost to the parts that are perceived to be an economical
component of a vehicle. These components have a surface area of about 3 m2 and consist
of a surface layer of polyvinyl chloride (PVC) or thermoplastic elastomer (referred to as
the ‘heavy layer’), an intermediate sound-deadening layer of flexible, medium-to-low
density polyurethane foam and a lower thermoplastic film. The film is designed to prevent
the formation of flash during the moulding process, eliminate permanent residue usually
left in the mould, and to act as a release agent (once the part is in the vehicle, this film
inhibits water absorption, which is a very frequent problem with industrial vehicles). In
the past, polyurethane films, which were strong mechanically and performed well but
were quite expensive were used. With the new ‘Foam & Film’ technology, it is possible
to replace this polyurethane film with a thinner, less costly thermoplastic one, resulting
in high quality production at a lower cost.
The system is composed of two shuttle-bed clamps served by one metering unit, which
dispenses the pre-heated heavy layer in the mould. Pre-heating is carried out using a
special infra-red heater, which incorporates easily adjustable, special low thermal-inertia
resistances. When a vacuum is applied to the mould, the material adheres to the lower
mould half, taking on its shape and embossed design.
The protective film is automatically unrolled from an overhead source using a vertical
traversing frame with pinchers that pulls an appropriate length of film over the frame
and cuts it to length. The frame is positioned over the edge of the mould. Another bank
of heaters slides laterally in front of the mould and warms the film to the correct forming
temperature; a vacuum is applied at the end of the heating phase to conform the film to
the mould.
The use of two presses, as opposed to one, means that slack periods are eliminated and
use of the cycle time is maximised. While the film and heavy layer are being placed in one
of the moulds and pre-heated, foaming and polymerisation are taking place on the other.
The polyurethane dosing and foaming section of this plant is equipped with a moulding
technology that allows chlorofluorocarbon (CFC) blowing agents to be replaced with
liquid carbon dioxide. This helps reduce the density of the polyurethane considerably
and thus saves on material costs.
The overall production time is just two and a half minutes per part. Being a two-
station plant, this equipment can produce close to 50 finished parts per hour – without
a dedicated operator.
136
3.2.5 Applications
This technology has already been used on turnkey plants for sound insulation parts,
carpet back foaming and seat cushions. No limitations for this technology are foreseen
and, actually, ‘Foam & Film’ can be implemented in almost every kind of polyurethane
process needing either release agent or a cover/surface film.
The system requires the presence of an open mould where the film-holding frame can be
inserted to position the film prior to the vacuum-forming phase. Obviously, this technology
is more easily applied to new equipment and new moulds since, most of the time, existing
moulds must be modified to provide the vacuum and hold the frames. When one surface
of the part is covered by an aesthetic or functional layer (carpet, plastics, etc.), obviously
the film is only applied to the opposing side where the foam would be in contact with the
mould (see Figure 3.19).
Figure 3.19 Turnkey installations using the ‘Foam & Film’ technology are producing
numerous parts for the automotive industry.
137
3.2.6 Advantages
‘Foam & Film’ offers significant benefits, such as quality parts, reduced costs, shorter
process times, as well as regular and consistent production cycles.
• operator intervention is no longer required for mould cleaning and application of

release agent; consequently this leads to increased productivity, uniformity and the
cycle regularity which comes with a completely automatic line - a fully automated
foaming process is now possible.
• polyurethane or TP film can be used, the latter being thinner and cheaper but giving
the same performance.
• films which adhere to the product can be used, becoming an integral part of the finished
component; this can be a very useful feature for non-aesthetic parts that are to be
mounted in hidden positions and will benefit from this extra protection against humidity,
oil, aggressive chemicals and foam-aging agents such as oxygen or other gases.
• films, which adhere to the mould, can be re-used several times as a substitute for
release agent.
• the availability of a wide range of film sizes means no dimensional limitations on the
parts to be moulded.
To summarise, ‘Foam & Film’ Technology:
• automates the production of polyurethane moulded parts,
• eliminates mould cleaning,
• eliminates spraying of release agent, saving its cost plus those of all the relevant
dispensing equipment and special fume extraction systems (although regular fume
extraction must be maintained for the polyurethane process),
• offers a low operating cost.
3.3 InterWet - Polyurethane Co-injection
The combined use of polyurethane and reinforcing agents or fillers has been common
practice for a long time. A recently introduced technology - simultaneously injecting
foam and glass fibre in open moulds - did not give satisfactory results, according to some
of the early users. Cannon has developed an industrial solution - named InterWet - that
138
improves both manufacturing performances and mechanical properties of moulded parts

[20-27]. In addition, it allows for the use of other reinforcing fibres (natural and synthetic)
and opens the way to the easy addition of powder and granulate fillers.
3.3.1 Glass-Reinforced Polyurethanes, a Well-Known Technology
Glass-reinforced polyurethane has been used for many years, utilizing different
technologies: reinforced reaction injection moulding (RRIM), open-mould pouring over
a flat mat (LD-SRIM), closed-mould injection on preformed glassmat-sandwiches (SRIM).
Cannon has for many years dealt with glass-handling polyurethane technologies,
developing in the early 1970s a special RRIM mixing head able to mix formulations
containing high percentages of milled fibre, and launching in the 1980s the HE metering
machines, closed-loop electronically-controlled piston-metering systems able to cope with
the abrasion deriving from glass and mineral charges. Later in the 1980s the Compotec
preformers were introduced, for the production of preformed glass mats required by
SRIM - structural-moulding applications.
A new technology has been introduced by Krauss-Maffei, long fibre injection (LFI) [28],
that simultaneously pours polyurethane and chopped glass roving on the surface of open
moulds; after the shot the press is immediately closed to allow for the expansion of the
foam, which surrounds all the fibres and produces a lightweight, resistant composite
panel. Most recently, Hennecke has introduced FipurTec [29, 30], a technology where
the fibre is chopped outside the head and projected into the flow of reacting chemicals,
where this touches the surface of the mould.
In essence these systems carry out a job similar to that performed for very many years
in the polyester ‘chop-and-spray’ applications, the only differences being that
polyurethane has a different profile of reactivity and viscosity build-up than polyester
and that, at least in one case, the glass roving is conducted through the mixing device
instead of being fed outside of it.
The interest behind this technology lies in the fact that a thin, resistant composite part
can be moulded in only one operation. Using preformers requires more equipment, space,
investments, etc. In addition, glass roving costs roughly half that of glass mat, and this
can represent a considerable saving when producing large, highly reinforced parts.
3.3.1.1 Practical Problems That Needed to be Addressed
A few practical problems have been identified in this technology, mainly deriving from
the design of the mixing equipment currently available. In one case the chopped fibre is
139
fed through a pipe that is co-axially positioned in a conventional ‘L-shaped’ head and
then the mixed resin is conveyed around the pipe that feeds the chopped fibre. In the
other case the fibre is projected separately from the polyurethane; in this case the glass
meets the polyurethane only at the end of the head’s final discharge duct. The separation
of the fibre and polyurethane before the exit of the head results in wetting of the fibres
not being optimal; this is visible during moulding, where part of the glass gets stuck
vertically into the base of rising foam, visibly dry.
The main problem comes from the dry chopped glass that - leaving the nose of the head
still not wet - flies everywhere near the mould surface. This results in negative effects on
workers, on cleaning and maintenance operations, and on part quality. This problem
can seriously hinder the application of this technology.
3.3.1.2 The Cannon Approach
Cannon started looking into this technology in the summer of 1997, at the urging of
some car parts producers who were unsatisfied with the performances of the existing
ones. The main objectives of the project were:
• To supply in the shortest possible time a reliable solution for the injection of glass-
reinforced polyurethane foams:
with as little as possible an impact on the working environment,
with the best possible quality,
• To provide the lightest possible mixing/dispensing equipment, in order to reduce the

investment in head-carrying robots,
• To design a multi-purpose solution, not limiting the choice of charge to glass roving only,
but including a wider range of natural and artificial fibres, as well as pulverised fillers,
• To provide maximum flexibility in charge feed, so that products with different content
of charges - in the same moulding or between subsequent moulds - can be produced,
• To provide maximum number of automatic checks on the charge’s feeding line, to

avoid the troubles experienced during automatic production cycles.
Due to the short delivery time required, it was not realistic to conceive totally new
equipment for this application, and it was decided to concentrate on the use of existing,
proven pieces of hardware. Performance of the foaming section had been optimised in
previous years, and the main obstacle was the proper handling of glass and other fillers.
140
3.3.1.3 The Technologies Involved
The project was split into three parallel lines of development, to speed up results and make
use of the experience of various existing specialists for the specific engineering tasks:
• Charge/Reinforcement (handling, dosing and feeding)

• Polyurethane (dosing, mixing and laydown)
• Robotics.
Handling Reinforcements and Charges
This project required a multi-functional solution, able to accommodate various types of

fibres, fillers and charges; accordingly, the design of the whole handling section would have
had to respect this future necessity. Since the most urgent need called for the use of glass
roving, the first development focused on the design of a simple, reliable device to store, meter
and chop conventional type glass-roving rolls. A proper technical specification was drafted
to provide optimum handling of the types of glass most suitable for this peculiar application.
Various qualities of roving are available on the market for different end-uses: the diameter
of the basic threads (bunches of individual glass fibres) and of the final roving (the rope
made with various threads) define the weight and the field of application, while the type
of coating (a thin layer of special resin applied on the fibres after the glass-extrusion
phase) determines the best compatibility of the roving with the polymeric matrix.
A specific type of Owens Corning Fibreglass (OCF) roving was selected as the reference,
having a 2400 Tex specific weight, i.e., the roving weighs 2,400 grams per kilometre, with
high ‘softness’ of the thread. Other types would have been easier to cut (or to be broken,
since a fibre of glass is not shear-cut - it is bent beyond its critical radius until it breaks), but
their individual fibres were more agglomerated in the thread and would have been more
difficult to wet. All parts were designed to cope with a wider range of roving.
The glass-feeding device was conceived to be installed over the polyurethane mixing
head, and its design was made in strict cooperation with the team in charge of designing
the head. It is basically composed of:
• A pulling/cutting device: two opposed rolls that rotate and trap between them one or
more roving, pulling them from their storage. A blade - held in one of the two rolls -
forces the fibres to bend beyond their critic radius until they break;
• A conducting system: a flow of compressed air that pushes the chopped fibre from
the cutting place to the mixing head.
141
A few interesting technical features characterise this roving feeding-chopping section:
• A hydraulic motor, to drive the glass-roving pulling rolls, was chosen to provide
proper speed, torque and easy variation of the driving speed. Its high power/weight
ratio made it preferable to an electric motor;
• A special cutting device was conceived, based on a rotating blade-holder (very easy
to access and maintain) capable of accommodating up to four blades. By fixing more
than one blade in the proper holders one can chop the roving in different lengths, the
longer size being that equal to the circumference of the rotating blade-holder. The
part had to be dimensioned to resist the very high operating speed, up to 5,000 rpm,
without suffering from the presence of glass debris around rotating shafts. This design
proved useful later, in the further development of a variable-length chopping system;
• A glass-guide system using compressed air was designed to take away all the cut
roving from the chopping device and bring it through the mixing head down onto
the mould, with the additional task of providing a final purge of the discharge duct.
The Mixing Head
Most of the development work was concentrated in designing a mixing head able to wet
all the solid components before they left, to ensure the projection of a very well wetted
mixture rather than a blend of liquid only coupled with a dry, flying filler. The mechanism
which could ensure a thorough wetting of high percentages of solid fillers with a mixture
of polyurethane is to provoke high turbulence in the mixing head’s area where liquid and
solid meet, and then reduce the turbulence to allow for splash-free open-mould distribution
of the blend obtained. It was in fact observed that, with heads where the junction between
liquid and solid was in a turbulence-free zone, the wetting was not optimal.
By using the Cannon FPL head, an existing, two-decades-proven, piece of hardware it

would have been possible to obtain the best available mixture of the polyurethane component
with a turbulence-free laydown in the mould. Its internal geometry is L-shaped, with two
cylindrical chambers of different diameters connected at a 90º angle. The turbulent flow
created by impinging of two components in the small mixing chamber is quickly converted
into a smooth laminar flow as the chemicals are diverted through 90 degrees downwards
into a large discharge duct and then leave the head. At the end of the pour the smaller
mixing chamber is sealed and automatically cleaned using a hydraulic piston.
By using the original mixing chamber for the liquid components and boring a hole through
the main cleaning piston - the plunger - so that a solid component could be fed through it,
a wide range of fillers can be used (see Figure 3.20). When the mixing operation begins, the
142
Figure 3.20 The Cannon FPL head used for InterWet incorporates in its upper section
the glass cutting mechanism and relevant safety checks.
main piston is retracted until it clears the discharge duct at the junction of the two cylindrical
chambers. In a controlled sequence, the small piston sealing the mixing chamber retracts
and the two chemical components are fired at high pressure against each other through
injectors in the mixing chamber before leaving it through the discharge duct.
The metering and feeding operation of the solid component from the head’s upper part is
controlled mechanically, assisted by an intense flow of compressed air. Its feed is
synchronised with the arrival of the liquid blend from the mixing chamber. The solid
component meets the liquid blend and together they are co-injected into the mould.
Following co-injection, the small piston seals the mixing chamber, the large piston seals
and cleans the discharge duct and the feed of solid component is interrupted, although
the flow of air is maintained for a short time in order to clean any residual polyurethane
- which could interfere with the next pouring operation - from the nose of the head.
143
Figure 3.21 Open-mould co-injection of PU and glass fibre is executed at high speed
and in a clean working environment, with an InterWet machine.
The innovative concept in this solution is that the solid component meets the liquid
formulation just in front of the mixing chamber, where the turbulent flow of the mixture
is directed through a 90° angle downwards creating a laminar flow. In this way, the
kinetic energy from the pressurised liquids is used to wet the stream of solid component
thoroughly and efficiently at a point just 20-25 mm from the point of impingement. The
blend of polyurethane and filler leaves the head already well blended, and there is no
evidence of ‘flying glass’ out of the head (see Figure 3.21).
This special design and technique ensures that the solid component is thoroughly internally
wetted, hence its name, InterWet.
144
Robotics
The development of a proper device to carry the mixing head during the pouring operation
over open moulds required relatively short time. Basic requirements were multi-axes
capacity, speed, precision and easy programming.
The designers concentrated on the use of commercial polar robots, operating up to 6

axes at high speed and precision (see Figure 3.22).
The limited weight of the Cannon FPL mixing head allowed for the selection of a medium-
sized model able to carry on the wrist 125 kg of payload at up to 2 m/s, with acceleration
of 3 m/s2. This robot was fitted with two storage boxes for the roving, mounted on the
elbow area (actually this model allows to install there up to 3 glass-roving rolls, for a
maximum 60 kg payload). This is a very convenient glass-storage solution for laboratory
and small production applications. When high quantities of glass are required, a solution
able to reduce rolls-replacement times must be provided. A proper device has been designed
to accommodate the 1,000 kg of glass demanded for industrial heavy-duty tasks. In this
case the glass rolls - that could be cascade-joined one another - must be positioned the
closest possible to the head, so that the way the roving must take to reach the chopper is
not restrained by long guides.
Figure 3.22 One of Cannon’s R&D units devoted to the development of

InterWet technology.
145
First Results
The assembly of the pieces of hardware was completed in less than eight weeks from the
beginning of the project, and immediately trials were scheduled in the laboratory using a flat
test-plate mould.
A conventional Cannon HE - a piston-driven, electronically closed-loop controlled dosing

unit available in the laboratory - was connected to a new mixing head, that had been fitted to
the wrist of the robot by means of proper flanges.
The glass was carried from its storage to the chopper by means of flexible plastic pipes, and
the path was designed so that there would be no obstructions and friction for the roving.
Glass roving X900A, a 2400 Tex, very soft roving with average attitude to the cut, was
supplied by Owens Corning Fibreglass.
A chemical formulation supplied by Dow, characterised by cream time of 12 seconds, gel

time of 40 seconds, demoulding time of 3 minutes and free rise density of 50-55 kg/m3
was used.
The first tests were run using approximately 30 parts of glass over 100 parts of polyurethane.
Surprisingly, the results were extremely satisfactory from the very beginning (see Figure 3.23).
Figure 2.23 Homogenous wetting of all fibres was obtained since the very first trials
with InterWet, thanks to the interval geometry of the mixing head.
146
After fixing minor problems with the cutting control, an optimum distribution of blend
was obtained, and the glass fibres were all wet (this was clearly visible because
polyurethane was pigmented in black, and absolutely no white spot of dry glass was
shown at the end of an open-mould pouring operation). Being all wet, the fibres did not
tend to stick vertically in the rising foam, therefore less possibility remained for the air to
remain trapped in the mixture: the moulded parts were, in fact, totally free of air bubbles.
A number of trials were satisfactorily run using thin, transparent polyethylene film as
liner for both mould halves, so that when the liner was peeled off it was possible to
evaluate the quality of the compound and its surface (see Figure 3.24).
The second series of trials was run on a mould for production of automotive door panels
where a layer of expanded or compact PVC sheet was unrolled on the lower mould-half
and cut to measure, its edges were blocked with a frame and it was vacuum-formed to
perfectly adhere to the mould surface. After this operation the blend of polyurethane
and glass was poured on the rear side of the PVC liner, and the mould carrier closed for
polymerisation. On this occasion - since the first results were very encouraging - the
Figure 3.24 No holes are visible in this InterWet non-presses laboratory sample,
photographed against a strong light. The diffuser-mounted on the InterWet provides a
very distribution of material all over the mould.
147
percentage of glass was increased to 35% of the total blend, i.e., approximately 60 parts
of glass to 100 parts of polyurethane. Again, very nice parts were obtained at the early
stages (see Figure 3.25).
Figure 3.25 Nice parts, free from air entrapments between reinforced PU and outer
skin were obtained at a very early stage of the InterWet development work.
First Improvements
• Improved distribution [25]
One aspect of the laydown - the width of the pouring path - was worth immediate
attention; since the reactive blend leaving the head covered only a few centimetres of
mould at each pass, a rather high number of passes was required to properly cover the
whole surface which forced use of the robot at very high speed to complete the whole
pattern before creaming started. To avoid the overlapping of two contiguous layers of
mixture, sometimes a narrow gap remained between the layers. This did not create
problems but the distribution of glass in those thin strips was probably different than in
the other areas of the mould.
148
To overcome these problems, a specially-designed pneumatic device was added at the

exit of the mixing head, that deviates, under controlled conditions, the flow of mixture
from its natural, vertical direction and distributes it over a wider pattern and, consequently,
in a thinner section. By doing so it is irrelevant if two contiguous layers do overlap (since
the layers are thinner the effect is negligible) and fewer passes are required to cover the
same surface. The robot can be used at lower speed (or a simpler, less expensive robot
can be used) or more parts can be made in the same unit of time. This could be relevant
thinking to carousel-based operations, where the robot would have to perform different
pouring patterns in a sequence, on different moulds.
Another advantage derived from this pneumatic distributor is that the jet of air pushes
even further down the fibres, which results in a very thin layer of mixture applied on the
mould surface. This means that the male half of the mould - when closing over the
female part - does not ‘wash down’ the vertical walls from the layer of reacting foam and
glass which covers them, since this layer is quite thin and does not constitute an obstacle
for the lowering plug. Parts as thin as 1.5 mm can be moulded with optimum surface
aspect and homogeneous distribution of glass across the whole surface.
• Variable fibre length, with ‘on-the-fly’ change
The first fibre-cutting device, as stated above, had the possibility of accommodating
more blades. Therefore, the length of cut fibre obtained was equal to the circumference
of the cylindrical blade-holder when only one blade was installed, or half of its
circumference with two blades, or one-quarter of it with four blades. Since this was
foreseen in the original wish list, the option of allowing the user to vary the length of
glass fibre at will, even ‘on-the-fly’ on the same moulding, was soon taken into
consideration. A simple, sturdy mechanical device was designed to allow for this variable
cutting. This mechanism which operates via an impulsion given by the robot’s programme
at a given point of the pouring pattern, cuts the roving in shorter sections; this variable-
length cutter provides different cuts of fibre: from L to L/12, where L is the longest
possible choice and the combinations depend on the use of the 12 blades installed on the
holder.
• Variable glass fibre output
Operated by a hydraulic motor, the pulling device (two opposed rolls that rotate and
trap between them one or more roving, pulling them from their storage) is able to provide
variable output of glass. By electronically controlling an inverter or a proportional valve
it is quickly possible to vary the motor speed, providing more or less fibre in different
149
parts of the moulding. The motor can be even stopped (thus feeding only polyurethane
foam) or left running after the end of the polyurethane shot (providing dry, unblended
glass fibre over some areas of the mould where an extra reinforcement would be desired).
• Extended safeties
The main concerns in operating this kind of plant derive mostly from the irregular feed
of glass to the head. For this reason the latest InterWet machines have been equipped
with detectors able to command an immediate stop to the machine in case of:
• Empty storage of glass roving

• Roving blocked in its roll
• Roving blocked somewhere along the feeding line
• Roving not properly fed into the head after the cutter and forming a ‘birds nest’
• Malfunction of a single blade.
3.3.1.4 Advantages of the InterWet Process
These new developments have resulted in a higher degree of flexibility for the InterWet
machines whose advantages versus the existing and available similar methods can be
summarised as follows:
• Optimum overall mechanical properties, due to an optimum glass fibre wetting with
PU, because of the mix-head design
• Better distribution of the mechanical properties of the moulded part, i.e., no areas
without or with little glass, due to a more homogeneous glass fibre distribution in
the mould, because of the special distribution system.
• Programmable variation of mechanical properties on the same part, since the

distribution of the composite’s mixture on the surface of the mould is fully
programmable. One can have in different areas of the same part:
• PU and glass in fixed proportion
• PU and a varying proportion of glass
• PU only
• Extra glass over an already filled area.
150
• Easy operation because it uses a standard (modified) FPL mix-head with obvious
consequences in terms of simplicity of maintenance, reliability in use and availability
of spare parts when required.
• Flexibility in operation because it is designed for more than one type of additive
component: it can easily be converted to process fillers or fibres or chopped scrap
foam. Its range of application includes continuous reinforcing fibres, natural fillers
(mineral or organic), pulverised plastics, etc.
• All the operational advantages deriving from the use of a light mixing head (robot
size, speed, productivity, etc).
• Economics, because - being based on commercially available components - its

mechanical parts can be less expensive than specially developed ones.
When compared with other glass-reinforcing technologies the following advantages must
be added:
Versus some RRIM applications:
• Economics, since it is no longer necessary to carry out the expensive dispersion of

solids in the polyol component - now, by adding them directly in the mixing head, it
is possible to eliminate all the traditionally associated problems, i.e., possible
absorption of polyol into the filler with the resulting slow release of reactive
components in the polymer matrix, abrasion, clogging of lines and tanks, fluctuating
percentages of filler in the liquid, etc.
Versus some mat applications:
• Economics:
in glass (roving costs less than mat)
in equipment (one more machine, storage, handling, floor space, etc.)
in scrap (preformed parts - although optimised - require punch-cutting that produces

scrap trim)
in stock (stored preforms can be damaged by sunlight, dust, moisture, and often
must be thrown away)
in manpower (to handle, position, punch, etc.)
151
• Quality (foam mixes better when co-injected with glass roving rather than when
injected into a pressed mat preform)
• Flexibility: it’s easy to mount on a carousel various moulds and produce small series
exploiting the flexible properties of the robot.
It is evident that there are applications where both RRIM and mat preforms are still
preferred because of their specific advantages. InterWet has been conceived to fill the
gap between the two technologies, and allow for more extended use of reinforcements
and fillers in applications where neither RRIM nor mat preforms could be used [31].
3.3.1.5 Applications
When this technology was first introduced it immediately appealed - for the above
mentioned reasons – to automotive and transportation end users. Volumes, cycle times
and final properties meet this market segment’s requirements, but until the currently
available solutions address some of the above-illustrated problems this industry would
not select it for mass production.
A market segment where this application would be really interesting is the manufacture
of special sanitary-ware parts, for at least three different purposes. The quickest to
understand for its immediate advantages is the combination of an outer plastic shell -
with either aesthetic or functional purposes - back-foamed with reinforced polyurethane;
examples include whirlpool tubs, bath tubs, shower trays, and vertical elements for shower
cabins integrated with accessories. These products are characterised by medium-small
production series, wide range of models, and large surfaces. The high operating flexibility
allowed by the programmable robot is very adaptable for the production of this type of
moulding: the larger the part, the more advantages can be found in this technology.
Medium-deep-draw shaped parts can be easily thermoformed from large thermoplastic
sheets (even in medium-small series) and immediately reinforced in an integrated
production line including thermoformer, foaming station and curing area. Dimensions,
productivity and investment must be tailored to the project’s requirements.
Another area of interest for this new technology is the re-use of chopped foam scrap,
either flexible or rigid; the design of the solid component’s feeding device - as foreseen in
the project’s objectives - has been made in a way that, using an appropriate volumetric-
feeding mechanism, powders, granulates and recycled foams can be dosed in the mixing
chamber through the same channel bored in the mixing head’s cleaning plunger. It is
possible to add roughly pulverised scrap foam to the virgin formulation directly in the
mixing head. This would solve a recycling problem, as well as lowering the cost of
152
Figure 3.26 In addition to glass roving a number of other materials can be co-injected
with PU using the InterWet technology, scrap PU foams, sand, ground cork and other
fillers that would be difficult to add in the component tank.
formulation. Positive trials have been made in a development phase, with filler loading
as high as 10% of the final part’s weight (see Figure 3.26).
Another interesting potential application is the use of continuous fibres, cut in medium-
long size, to reinforce thin pads and cushions moulded with flexible foams. The continuous
development of lighter, thinner parts - where weight-reduction and volume-exploitation
is the object of intense development - requires the use of formulations characterised by
very high mechanical properties that unreinforced foam cannot meet. The use of long
natural or synthetic fibres to reinforce these flexible mouldings had applied for a long
time, but only under the form of textile inserts manually inserted in the mould prior to
the foaming operation. Being able to co-inject foam and long fibres - applying longer or
shorter sizes according to the mechanical properties required - represents an advantage
that comes at a very attractive investment cost.
Note: The Cannon FPL Mixing Head is covered by several international patents.
153
References
1 M. Taverna and B. Pile, Presented at the Polyurethanes Expo ’99 Conference,

Orlando, FL, USA, 1999, p.37.
2 Modern Plastics International, 1999, 29, 3, 127.
3 M. Taverna, Presented at the Recycle ’94 Conference, Davos, Switzerland, 1994,

Paper No.35.
4 L. White, Urethanes Technology, 1995, 12, 2, 3.
5 Plastics and Rubber Weekly, 1995, No.1612, 10.
6 D. Smock, Plastics World, 1995, 53, 11, 20.
7 British Plastics and Rubber, 1995, November, p.10.
9 M. Taverna, Presented at the Utech Asia ’97 Conference, Suntec City, 1997,
Paper No.12.
11 C. Fiorentini, M. Taverna and J. Luca, Presented at the Polyurethanes ’95

Conference, Chicago, IL, USA, 1995, p.476.
12 Plastiques Flash, 1998, 304/5, 92.
13 M. Taverna, P. Corradi and B. Biondich, Presented at the Polyurethanes ’95,

1995, Chicago, IL, p.484.
14 M. Taverna and P. Corradi, Presented at the Utech Asia ’96 Conference, The
Hague, 1996, Paper No.10.
15 P. Mapleston, Modern Plastics International, 1997, 27, 8, 30.
16 Plastics and Rubber Asia, 1997, 12, 72, 34.
17 British Plastics and Rubber, 1997, July/August, 19.
18 Plastics and Rubber Weekly, 1997, No.1687, 17.
154
19 M. Taverna, Presented at the Polyurethanes Expo ’98 Conference, Dallas, TX,

USA, 1998, p.685.
20 P. Mapleston, Modern Plastics International, 1997, 27, 11, 41.
21 Plastics Rubber Weekly, 1998, No.1729, 13.
22 Macplas International, 1998, February, 46.
23 G. Graff, Modern Plastics International, 1998, 28, 11, 38.
24 British Plastics and Rubber, 1998, November, 20.
25 M. Taverna and A. Bonansea, Presented at the Polyurethanes Expo ’98, 1998,

Dallas, TX, 687.
26 European Plastics News, 1999, 26, 4, 48.
27 Composites – French/English, 1999, 36, 50.
28 J. Stark and F. Peters, Presented at the Utech ’99 Conference, 1999, Singapore,
Paper No.6.
29 Plastics and Rubber Asia, 1997, 12, 70, 34.
155
156
4
Recent Developments in Open Cell
Polyurethane-Filled Vacuum Insulated Panels
for Super Insulation Applications
Paolo Manini
4.1 Introduction
Rigid polyurethane (PU) foam is the preferred insulator material in a wide range of
applications encompassing household, industrial and commercial appliances (refrigerators,
freezers, display cases, vending machines), transportation (refrigerated trucks and reefers,
shipping containers), insulation in buildings and in industrial plants.
The replacement of chlorofluorocarbons (CFC) with environmentally more benign

chemicals, as recently mandated by the Montreal Protocol and subsequent revisions, has
caused a reduction of the insulation efficiency of the PU foams, since the new blowing
agents available, like hydrocarbons, hydro-fluorocarbons (HFC) or carbon dioxide have
worse gas thermal conductivity properties.
In applications, the lower insulation efficiency of the CFC-free foams generally leads to
higher energy consumption levels unless specific compensation actions are taken.
This issue is particularly severe for the household appliance industry, which has also
been called upon over the past years to progressively reduce the energy consumption
of their products.
With the energy efficiency targets getting more and more demanding and only marginal
improvement obtainable from the optimisation of conventional technologies, the appliance
manufacturers are seriously looking at alternatives which may provide additional benefit
in terms of energy savings.
The appliance industry is not the only one involved in the debate on energy consumption
reduction. The growing attention to the global warming issue is forcing policy makers to
take actions to cut carbon dioxide emissions and minimise the greenhouse effect. With
this in mind, the Kyoto Conference has posed ambitious targets for energy saving, the
achievement of which calls for improvements in many fields, from transportation, to
refrigeration and building insulation.
The ban on CFC and the demand for a more efficient use of energy, both issues coming from
environmental concerns, are therefore posing serious challenges to the Industry as a whole.
157
Vacuum Insulated Panels (VIP), having a thermal conductivity three to five times lower
than conventional PU foams, allow the achievement of superior insulation performance.
They can be used to partially replace the conventional insulation materials to provide
a more efficient insulation structure, which allows energy saving without the need to
increase the insulation thickness. Alternatively, VIP can be used in those applications
where it is important to reduce the insulation thickness to a minimum value without
loosing thermal performances.
A VIP is obtained by packaging a microporous low conductivity filler material inside a

highly impermeable gas barrier bag. The filler is then evacuated to a proper vacuum level
and the bag sealed. A gas adsorbent, normally referred to as a getter, inserted in the bag
before sealing, is also necessary in most panel designs to ensure the proper vacuum level
during the lifetime of the panel.
Several fillers have been proposed in the past, either in the form of compressed powders
or fibres, however all have some disadvantages in terms of cost, process complexity and/
or weight. This has prevented VIP technology from finding widespread acceptance in
most applications. The recent development of open cell rigid foams, first introduced into
the market in the early 1990s has sparked off new interest in this technology. However,
in order to fully exploit the unique properties of these insulating materials, the re-
evaluation and re-design of the other key elements of a vacuum panel, i.e., the barrier
film, the gas adsorbent and the manufacturing cycles, has also been necessary. This process,
which is still ongoing and has potential for further improvements, has required the
commitment of several sectors of the industry in the last five to six years.
In this chapter, the present status of the open cell PU foam-filled vacuum panel technology
is discussed and some recent developments in film, getter and processing technologies
are reviewed. Special focus is given to the vacuum issues, which are key for the proper
selection and treatment of the VIP components. Some specific aspects, related to the
manufacturing, characterisation and practical use of vacuum panels, as well as the
achievable benefits, are also considered. Examples of applications where this technology
is finding its place in the market and areas where further work is necessary to make
vacuum panels more cost effective are presented.
4.2 Some General Properties of Open Cell PU Foams for Vacuum

Insulated Panels
Vacuum panels have been studied as a means to improve thermal insulation for a long
time. Several insulating fillers, such as silica and perlite powders [1, 2, 3], fibre glass [4,
5], and aerogels [6, 7, 8] have been proposed as core materials for VIP, each of them
158
Recent Developments in Open Cell Polyurethane-Filled Vacuum Insulated Panels…
having specific advantages and disadvantages in term of weight, thermal conductivity,

handling, processing, vacuum properties and cost.
To overcome some of the drawbacks associated with the use of these materials, new
families of fillers, based on PU [9, 10, 11, 12] and, more recently, polystyrene (PS) [13]
open cell foams, have been developed and proposed to the market. Both open cell PU
and polystyrene foams are now being considered as interesting options due to their
moderate outgassing, good thermal insulation values, low weight, ease of handling
and cost effectiveness.
This chapter will focus on the open cell PU foams, even though many general aspects and
recent developments of the technology, dealing with films, getters and manufacturing
processes, can be also applied, with minor changes, to other micro porous fillers.
The thermal conductivity, or λ factor (mW/m-k), for some of the most popular filler
materials is shown in Figure 4.1 as a function of pressure (Pa). The thermal conductivity
of cyclopentane (CP) blown closed cell PU foam is also given for comparison.
Figure 4.1 Thermal conductivity as a function of pressure for some filler materials
159
Regardless of the type of filler, all curves have a similar behaviour, with a low pressure
region, where the λ factor is constant, followed by a region where the λ factor increases
with increasing pressure.
This common trend can be explained considering that the total apparent thermal
conductivity in micro porous materials is the sum of four physical contributions, i.e., the
thermal conductivity through the solid, λs , the thermal conductivity through the gaseous
phase, λg, the thermal conductivity by thermal radiation, λr and by gas convection, λc:
λ = λs + λr + λg + λc (1)
The last term of Equation (1) can be neglected for core material with cell size smaller than 1 mm.
An extensive treatment of the above physical mechanisms and their role in heat transfer
in low density closed cell foams has been provided by Glicksman [14].
In the case of the open cell PU foams detailed expressions for the first two terms of
Equation (1) have been given by Kodama and co-workers [9].
Both terms are independent of pressure and strictly related to the foam density and
morphology (cell size, structure and degree of anisotropy).
In particular, λs is directly proportional to the thermal conductivity Ks of the foam and

inversely proportional to the cellular anisotropy η according to the formula [9]:
[( ) ]
λ s = 1 − Vg2 / 3 K s / η (2)
where Vg is the fraction of foam volume occupied by the gaseous phase.
To reduce the heat transfer through the solid it is therefore necessary to increase the
cellular anisotropy and to lower the thermal conductivity of the polymer structure.
Following Kodama and co-workers, the heat transfer by radiation is given by:
λ r = 2 / 3 Vg1/ 3 H r d (3)
where d is the cell size and Hr is the coefficient of thermal conduction by radiation which
depends on the emissivity of the polymer and the morphology of the cell. To minimise
the λr contribution, the cell size and Hr have to be reduced. The former can be achieved
by adjusting the formulation of the foam, the latter by reducing the opening size of cell
membranes to make radiation transmission through the cellular windows less efficient.
160
The heat transfer by gas conduction, λg, becomes progressively more important as the
pressure increases, as shown by the following set of equations [15]:
( )
λ g = λ goΠ / (1 + 2L / d) (4)
where λgo is the thermal conductivity of air at atmospheric pressure, Π is the porosity of
the foam and L is the mean free path of air, linked with pressure P by:
L = (kT ) / ⎛ 2 π P σ 2 ⎞ (5)
⎝ ⎠
where T is the absolute temperature, k the Boltzmann constant and σ the collision diameter
of air (about 4 x 10-10 m2).
The λg contribution vanishes for L>>d. For currently available foams, having an average
cell size in the 100-200 μm range, this means that pressure has to be kept at 1.0 Pa or
below to completely eliminate the heat transfer by gas conduction.
To ensure this condition the foam has to be properly evacuated and all gas sources
deteriorating the vacuum during the panel life effectively compensated by a suitable
adsorbent, or getter, having sufficient gas capacity and efficiency.
As shown by Equations (1-5), the insulation properties of an open cell foam depend on
a complicated interplay of different parameters such as the PU thermal conductivity,
foam density, cell size and cell size distribution, cell morphology and anisotropy, which
have to be optimised during the foam preparation to obtain the best trade-off among the
three thermal conductivity contributions, λs, λr and λg.
In this process, the mechanical properties of the foam cannot be neglected, being essential
to ensure structural stability of the vacuum panel.
In fact, after sealing, the vacuum panel is exposed to the hydrostatic load of the
atmospheric pressure and has to withstand it for a long time, which can be 15-20 years
or even more depending on the application.
Dimensional stability tests carried out on open cell PU foam-filled vacuum panels showed
that creep problems should not occur for properly prepared panels, provided the open
cell foam preparation has been optimised [15].
The open cell PU cores are produced according to various preparation technologies,
such as lamination and block foaming. In both cases, after the foam has been grown, a
cutting operation is usually necessary to remove the outer skin of the material, which
161
contains a high percentage of closed cells, and to slice the PU into slabs of the proper size
and thickness. The removal of the outer skin may be a labour intensive process which
produces waste, lowers the process yield and increases the overall production costs, this
issue being particularly important in the case of the lamination process. Great attention
is therefore now being paid to design and the open cell foam production process, to
reduce waste and increase productivity.
A different approach to making open cell foam slabs has been proposed recently [11],
which is based on the use of the PU fluff obtained from the recycling of used refrigerators
(Recycled Urethane Fluff, or RUF panel).
During the recycling process, the rigid insulation foam contained in the old refrigerators
or freezers is mechanically ground into a fine powder, to completely separate and recover
the CFC present in the foam. The resulting fluff, composed of completely open cells, is
dried and introduced into a binding machine where it is sprayed with a certain amount
of isocyanate (15-20% by weight) and thoroughly mixed. The blend is then transferred
to a mould, heated at 120 °C and compressed at 0.5 MPa for 10 minutes to consolidate
it and remove residues of the process. After de-moulding and curing, the RUF panel can
be used as core material in a VIP.
The fluff obtained from recycling one single refrigerator can be used to produce enough
vacuum panels to insulate a new appliance, thus generating a virtual recycling loop.
Due to the use of very fine compressed powder, the density of this open cell foam is three
to four times higher than those produced by lamination or block foaming.
Selected physical properties of some open cell PU foams are listed in Table 4.1.
162
Table 4.1 Some physical properties of open cell PU foams

Ref. [56] Ref. [56] Ref. [9] Ref. [12] Ref. [11]
Production Lamination Block - Block RUF
process foam foam
Density (kg/m3) 60-64 52-58 52 60-65 180-200
Cell size(μm)
Average 100 130-170 140 - -
Perpendicular - - 75 - -
Parallel - - 205 - -
Thermal 7 5.5-7.5 4.5-5 7 8-10
conductivity
(mW/m-K) @ 5 Pa
Compressive strength (MPa )
Average 0.25 0.23-0.35 0.26 - -
Parallel - - 0.383 - -
Perpendicular - - 0.133 - -
Pre-treatment 120 °C 120 °C 140 °C 120 °C 120 °C
x 30 min x 30 min x 1 hour x 30 min x 30 min
Open cell content 100 100 10 0 100 100
(%)
4.3 Vacuum Issues in the Selection of VIP Components
4.3.1 Vacuum Properties of the Open Cell Foams
To fully exploit the insulating performances of the open cell PU foams, pressure in the
panel has to be kept preferably below 1.0 Pa during its life. To achieve this demanding
target, the foam must be 100% open celled and with a very low outgassing rate.
In spite of the increasing use of open cell PU foam, data from the literature on its vacuum
properties are quite scarce.
To estimate the outgassing contribution, specific tests can be carried out using high vacuum
benches equipped with a quadrupole mass spectrometer.
163
Figure 4.2 Scheme of the stainless steel high vacuum bakeable bench equipped with
mass spectrometer for outgassing tests on vacuum components. IG: ionisation gauge.
To quantify the relatively small amounts of gas species released from the sample, it is
necessary to use very clean, bakeable, high or ultra-high vacuum systems made with stainless
steel and/or glass components. This ensures better leak-tightness and a negligible gas emission
from the bench. A sketch of a typical experimental apparatus, having two separate pumping
groups and base pressure at 1 x 10-6 Pa or lower, is shown in Figure 4.2.
A practical technological implementation of the scheme shown in Figure 4.2 is illustrated

in Figure 4.3.
The sample to be analysed is mounted in a glass bulb which is connected to the test
bench and evacuated for 10 minutes with a turbo and a rotary pump to a final pressure
of 10-4 Pa. The bulb is then isolated from the pumps and the total pressure increase, due
to the sample outgassing, is monitored with a capacitance manometer for some days.
The use of the capacitance manometer avoids changes in the gas composition which
might occur if a hot filament pressure gauge is used. From time to time a small amount
of gas is sampled from the test volume, through valves V4 and V6, and passed to the
mass spectrometer for partial pressure measurement. Before running the outgassing tests
164
Figure 4.3 A stainless steel outgassing bench equipped with a quadrupole mass
spectrometer and an external oven for vacuum bake-out
(Reproduced by courtesy of SAES Getters SpA, Italy).
on the PU sample, a blank run has to be carried out. The result of the blank run is then
subtracted from the outgassing test to get the actual gas emission from the PU sample.
The use of two distinct pumping groups is essential to minimise the system contamination
(mainly water vapour) which occurs when the bulb is opened to the air, to mount the
specimen. In fact, during this operation, valve, V4, is kept closed, reducing the surface
area of the bench which can absorb water and atmospheric gases.
Before being used in a vacuum panel, the open cell PU foam needs a preliminary heat
treatment in air, generally carried out at 120-150 °C for 10-60 minutes to remove water
and other volatile species which otherwise would desorb and rapidly cause the vacuum
to deteriorate. The result of a typical outgassing test carried out at 23 °C on a foam
sample baked at 120 °C for 30 minutes is shown in Figure 4.4 for all desorbed gases but
water. Water is difficult to quantify since it sticks to the walls of the system and only
partially reaches the mass spectrometer. Water can be estimated as the difference between
the total absolute pressure and the sum of the partial pressures of the other gas species,
which can be accurately quantified with the mass spectrometer.
165
Figure 4.4 Outgassing rate for an open cell PU foam. Water is not shown.
For each gas species, the amount released by the sample at a given time is obtained by
simply multiplying the test volume (V) by the gas partial pressure (qi(t) = Pi V, qi(t) is the
outgassing rate (Pa-l/h) at time t, Pi being the measured i-th partial pressure).
The experimentally determined qi value for each gas species can be interpolated over
time according to the semi-empirical law quoted in the literature [16]:
q i (t) = q0i (t − αi ) (6)
where qi(t) and q0i are the outgassing rate (Pa-l/h) at time t (hour) and the desorbed
amount (Pa-l) after 1 hour of the i-th gas species, respectively. The dimensionless parameter
αI is related to the desorption mechanism of the i-th gas species, its value usually ranging
from 0.5 to 1, depending on the gas species and the material considered [16, 17].
Integration over time of Equation (6), provides an estimate of the PU sample outgassing
load Qi for each gas species after a given time. As an example, the estimated gas released
after 1 to 20 years for the sample of Figure 4.4 and for a 50 x 50 x 2 cm3 panel size is
given in Table 4.2. The main gases, besides water, are carbon dioxide, nitrogen, carbon
monoxide and hydrogen. It is interesting to note that, given the nature of the desorption
166
Table 4.2 Outgassing parameters and estimated gas load Qi (Pa-l) after 1, 5
and 20 years for a 50 x 50 x 2 cm VIP
Gas q0i (Pa-l/h) αi Qi (1) (Pa-l) Qi (5) (Pa-l) Qi (20) (Pa-l)
CO2 8 x 10-3 1 22 25 27
CO 2 x 10-3 1 54 64 75
N2 9 x 10-3 1 10.8 12.8 15
-5
H2 5 x 10 0.5 2.3 6.2 13
process (Equation (1)), most of the gas is given off during the initial period of operation
of a VIP.
Results shown in Figure 4.4 and Table 4.2 can vary from sample to sample depending on
the open cell PU foam preparation technique, its microstructure and density and the
pre-treatment.
Since desorption is a thermally activated process [18], the outgassing rates increase as
the temperature increases. The outgassing contribution has therefore to be carefully
evaluated in all those applications where the vacuum panels operate continuously at
temperatures higher than room temperature, e.g., 60-80 °C, or have to withstand high
temperature peaks, for example 100 °C, even for a relatively short period of time. Examples
of such applications are presented and discussed in Section 4.6.
An additional factor which may have an impact on the vacuum properties is the closed
cell content of the PU foam. All the open cell PU foams so far presented in the literature
for VIP applications are quoted to be 100% open cell based on pycnometric measurement.
On the other hand, the accuracy of this test method is generally close to ± 0.2% [15], so
that the possibility of a small fraction of closed cells cannot be completely ruled out and
has to be considered as an additional potential source of pressure build-up in the panel.
Closed cells might be present due to a non optimal foam preparation or to the incomplete
skin removal.
4.3.2 Vacuum Properties of the Barrier Film
The barrier film plays an important role in vacuum panel technology since it has the task
of minimising air and moisture penetration into the vacuum core. The barrier must be
167
durable and able to resist to puncturing and abrasion. It must be functional over a wide
temperature range and retain its physical properties, such as dimensional stability,
flexibility and sealability for years.
Thermal conductivity of the skin should also be very low to minimise the heat transfer
through the panel edges which can partially reduce the insulation efficiency of the
evacuated panel (‘edge effect’, see Section 3.2.1). These properties have to be coupled
with very low gas permeation and outgassing rates.
Gas permeation through the barrier envelope is one of the most important factors
responsible for the pressure increase in a panel during its life.
Depending on the structure of the barrier film and the materials used, gas ingress can
preferentially take place through the whole surface of the barrier film (permeation
through the surface) or through the heat-sealed plastic VIP flanges (permeation at the
edges), or both.
4.3.2.1 Gas Permeation Through the Surface
Several types of barrier materials, having different structures and gas transmission rates,
are commercially available from the food, packaging and electronic industry. Gas barrier
requirements for vacuum panels are however much more demanding.
Composite plastic films, obtained by laminating several polymeric sheets have been
proposed in the past for precipitated silica-filled panels, where pressures as high as 500-
1000 Pa can be tolerated without excessive degradation of the thermal conductivity. In
the case of open cell PU-filled panels, requiring much lower pressure values, this barrier
structure is generally inadequate, if a lifetime exceeding one to two years is needed.
To improve the permeation properties, barrier materials, such as aluminium and silicon
oxide, can be vacuum deposited on the polymer surface in the form of a thin film (0.01-
0.05 μm thick) [19].
However, most commercially available metallised samples do not provide enough barrier
properties for long term applications, mainly due to water transmission through the large
density of pin holes and micro-defects present in the sputtered aluminium layers [20].
To overcome this problem, barrier films obtained by laminating a thicker continuous

metal foil with various polymeric sheets, such as polyethylene terephthalate (PET),
Nylon and polyester (PE) have been proposed to the appliance industry some years ago
and are now commercially available [15, 21]. Aluminium is the preferred choice for
168
the metal, mainly due to its good workability, which allows production and lamination
of virtually pin hole-free foils having thickness of 6 μm or less [21]. The presence of
the aluminium foil dramatically improves the gas barrier property of the film, well
beyond the sensitivity limits of the analytical techniques commercially available for
the measurement of gas permeation.
In the case of water, which is one of the most important permeating species, two standard
methodologies are at present widely used to measure its transmission rate through a material,
as described by ASTM E96-00 [22]. According to the first procedure (‘the desiccant method’)
the barrier sample is sealed to the open mouth of a test plate, which is cylindrical in shape,
in which the desiccant is placed, and the assembly kept in a humidity and temperature
controlled environment. The permeation of water through the sample is measured by the
weight increase of the assembly. In the second procedure (‘water method’) the test plate
contains water and the transmission rate through the barrier sample into the controlled
environment is measured by the weight decrease of the assembly.
A variation of the first method, frequently used in practice, is based on periodically

weighing vacuum panels, containing of desiccant, and kept in a given temperature and
humidity-controlled environment.
Another very common technique is based on the use of an infrared sensor as described
by ASTM F1249-90 [23]. The barrier sample is sealed between a dry and a wet chamber
kept at known temperature and relative humidity. The two chambers make up a diffusion
cell which is placed in a test station where the dry chamber and the top of the barrier are
flushed with dry air.
Water vapour which penetrates through the barrier film blends with the dry air and is
transported to a pressure-modulated infrared sensor. The infrared radiation is absorbed by
the water molecules and the sensor produces an electrical signal which is proportional to the
concentration of water in the gas phase. The intensity of the signal is then compared with the
signal generated by measurement of a sample having a known water transmission rate. This
allows the determination of the water transmission rate through the test specimen. The
detection limit for water transmission generally quoted for commercially available instruments
based on this principle is in the 0.01 g/m2 day range (at 90% relative humidity and 23 °C).
These techniques are generally more than adequate for many plastic or standard quality
metallised films but can hardly discriminate between samples containing aluminium foil,
which generally have water transmission rates much lower than this value.
To better estimate gas permeation for high quality barriers a novel technique has been
developed [24, 25], which is based on the measurement with a quadrupole mass
spectrometer of the helium transmission rate through the sample.
169
Figure 4.5 Scheme of the experimental bench for the helium permeation test.
A sketch of the experimental bench is shown in Figure 4.5.
A picture of the bench is shown in Figure 4.6.
The bench is a stainless steel ultra-high vacuum apparatus equipped with rotary, turbo-
molecular and non-evaporable getter (NEG) pumps. The sample, a circular coupon of
about 30 cm2 area, is mounted between two flanges and the helium pressure is applied
(generally in the 0.0001-0.1 MPa range) on one side of the sample, the other side being
in view of the quadrupole mass spectrometer. A variable conductance C (l/s) is mounted
between the mass spectrometer and the evacuation group, so that the helium flow rate F
(Pa-l/s) through the conductance can be measured with the mass spectrometer according
to the equation:
170
Figure 4.6 High vacuum bench for helium permeation tests

(Reproduced by courtesy of SAES Getters SpA, Italy).
F = C (P1 - P2) (7)
where P1 and P2 are the pressures before and after the conductance C, respectively.
Under equilibrium conditions, which can be reached after some minutes or some hours,
depending on the nature of the sample, the gas flow, F, provides the helium transmission
rate. A typical graph showing the achievement of steady state conditions is given in
Figure 4.7.
171
Figure 4.7 Achievement of the equilibrium condition in a helium permeation test for a
laminated film composed of 15 μm Nylon, 12 μm PET, 6 μm aluminium, 50 μm high
density polyethylene (HDPE) (or Nylon 15 μm/PET 12 μm/Al 6 μm/HDPE 50 μm).
The use of the mass spectrometer ensures very high sensitivity for helium, better than
10-11 Pa-l/(s m2 Pa), mainly due to the negligible presence of helium as a constituent of
the gas background. Due to its high sensitivity and the relatively short measuring time,
this technique can be used effectively to support the development of improved laminates
and also for quality control in a production environment.
The estimation of the transmission rates for gases other than helium can also be obtained,
provided a preliminary calibration is carried out. This is particularly important for water,
which is the main gas permeating through the barrier skin. To run the calibration
procedure, the helium transmission rate is measured for various samples having different
and known permeation rates for water. The linear correlation between helium and water
transmission rates is then established, as shown in Figure 4.8.
The correlation factor for water was found to be close to 500 for most of the PE/PET/
Nylon-based films analysed by the authors, either metallised or incorporating an
aluminium foil [26]. It was then possible to estimate the order of magnitude of the water
172
Figure 4.8 Experimental determination of the correlation factor between helium and
water transmission rates.
transmission rate for an unknown low permeation rate sample by simply measuring the
helium transmission rate and multiplying it by 500.
Table 4.3 provides a comparison between the helium permeation rates in two films, a
laminate incorporating a 6 μm aluminium foil, PET 12 μm/Aluminium 6 μm/HDPE 50 μm
(Film B) and a multi-layered barrier composed of four aluminium-sputtered PET sheets
laminated onto a 50 μm PE (Film A). Tests were run at 24 °C. From the measurement of
Table 4.3 Helium and water permeation rates through films

Sample Permeation rate (MPa s-1cm-2 Pa-1) Estimated water
amount in a VIP
helium water after 15 years
Film A 910 x 10-12 460 x 10-9 100 g
-15 -13
Film B 130 x 10 670 x 10 0.02 g
173
Table 4.4 Thermal conductivity of some materials used as gas barriers and/or
structural layers in barrier films.
Material Thermal conductivity Typical thickness
(μ /m-K) (μm)
PET 0.15 10-15
HDPE 1.05 40-60
PVDC 0.13 10-20
Nylon 0.43 10-20
Aluminium 273 6-7
PVDC: Polyvinylidene chloride
the permeation rates, the quantity of water permeating in 15 years in a 50 x 50 x 2 cm3

vacuum panel has been estimated.
The metallised barrier here considered cannot be used for long term applications, where
10-15 years or more are targeted, since the amount of desiccant necessary to compensate
for the water transmission would be too large.
A much lower permeation rate is provided by Film B, which is therefore well suited for
long term applications.
In spite of the extremely good gas barrier properties, VIP prepared with such a film
suffers from an intrinsic limitation, i.e., the high thermal conductivity of the aluminium
foil, as shown in Table 4.4.
A fraction of the heat flow is, in fact, transferred from the hot to the cold panel surface by the
aluminium foil through the panel flanges, rather than through the core material (so called
‘edge effect’). As a result, the average insulation value of the panel is less than the expected
value based on the actual insulating properties of the core material (centre of the panel
thermal conductivity), this difference being more remarkable the smaller the panel size.
The edge effect can be evaluated, as a function of the panel size, the laminate structure and
the aluminium thickness, by numerical methods, such as the Finite Element Analysis (FEA).
Results of such an analysis are given in one specific example in Figure 4.9, where the
average thermal conductivity of a vacuum panel using a PET 12 μm/Aluminium 6 μm/
HDPE 50 μm laminate is plotted against the panel area.
174
Figure 4.9 Thermal conductivity versus panel area.
The thermal conductivity and the thickness of the PU core material considered here are
6 mW/m-K and 2 cm, respectively.
Figure 4.9 shows that the panel thermal conductivity approaches the value of the core
material only for a sufficiently large panel area (≈ 1-10 m2). For very small panels, the
insulating properties of the core material are spoiled by the edge effect and the energy
savings in the real application may be minimal.
For this reason, efforts are now being made to improve the aluminium–based laminates
and/or to develop products not containing the aluminium foil but still having sufficiently
good gas barrier properties, so as to achieve an acceptable trade-off between energy
saving performances and acceptable lifetime. This challenging objective can be addressed
by selecting and properly combining together suitable polymers having improved gas
barrier properties.
A typical example of this process, recently reported by Lamb and Zeiler [27], is given in
Table 4.5, which shows how significant improvements can be obtained in non aluminium-
foil containing skins working on the film structure.
175
Table 4.5 Oxygen transmission (OTR) and water (WTR) transmission rates for
some film structures [27]
Film structure OTR x 10-10 m2 day (STP) WTR g/m2 day
PET 34.8 43.4
PET + PVDC 2.3 9.3
PET + PVDC + metallised 0.04 0.62
layer
Mylar 200RSBL300 0.00015 < 0.15
STP: Standard, temperature, pressure
A comparison of some different types of improved metallised and aluminium foil-

containing barriers, also including a preliminary investigation of the effect of temperature
on the gas transmission rates, has been recently reported by Bonekamp [28].
Due to the still developmental nature of most of these barriers, more work is necessary
to assess their usability for long term applications. Extensive characterisation of the
mechanical, sealability and stress resistance properties are also important issues to consider.
4.3.2.2 Gas Permeation Through the Flanges
The permeation of atmospheric gases through the polymeric sealed flange of a vacuum
panel can be an important contribution to the pressure increase in a VIP for long term
applications. The gas permeation rate depends on the pressure gradient across the vacuum
panel, the type of polymer used as a sealant, the flange geometrical parameters (exposed
surface and width) and temperature. Polyethylene is at present one of the preferred sealing
materials due to the good trade-off achieved among sealability, mechanical properties,
gas permeation, outgassing rates, reliability and cost.
Gas permeability values quoted in the literature for PE are scattered over an order of
magnitude, depending on the actual density of the sample and the gas considered [29,
30, 31]. Typical permeability values corresponding to medium and high density PE are
shown in Table 4.6.
Results of the calculation for argon, nitrogen, oxygen and water and the total pressure,
are given in Figure 4.10 and show the role of permeation in deteriorating the vacuum
level in the panel. The width and height of the PE flange here considered are 10 and 0.1
mm, respectively and the environment is air at 21 °C and 50% relative humidity.
176
Table 4.6. Permeation rates for gases (cm3/m2d, STP) and water (g/m2d)
in a 25 μm thick PE sheet
Gas MDPE x 10-10 HDPE x 10-10 Temperature °C
N2 387 96.75 21
O2 1548 425.7 21
Ar 3096 774 21
H2O 10.85 4.65 38, 90% RH
MDPE: medium density PE; RH: relative humidity
Figure 4.10 Pressure increase due to gas permeation at the panel PE flanges.
In the case of panels which are encapsulated, i.e., surrounded by a closed cell PU foam,
as happens for panels in household refrigerators, freezers or vending machines (see Section
4.6), the picture is more complicated. The gas environment surrounding the vacuum
panel will depend on the type of encapsulating foam and will change with time as a
consequence of the gas out-diffusion from the closed cells and the progressive air
penetration from the outside, thus making predictions more difficult. This ageing process
177
will also depend on the temperature and the hermeticity of the case surrounding the
encapsulating foam as shown in various papers [32, 33]. Permeation of blowing agents
through the seals, even though not a major contribution, has also to be considered.
The use of a different PE grade or a different sealant polymer will provide different
pressure build-up curves in the panel both in terms of total and partial gas pressures.
High barrier polymers, such as polyvinylidene chloride (PVDC), polyacrylonitrile (PAN),

polyester, acid copolymers and ionomers have been proposed and are under evaluation
as a replacement for PE. However, they present some drawbacks in terms of sealability
and/or mechanical properties and/or outgassing rates. Cost of these polymers is also
generally higher.
4.3.2.3 Outgassing Properties of the Film
In general, very little data have been published on the outgassing properties of the skins
for vacuum panels, even though they can contribute, in some cases, in a non-negligible
way to the deterioration of the pressure inside the VIP. This can be due to the outgassing
properties of the materials used as barrier layers and/or the lamination process, which
may introduce volatile substances or trap gases in between the various sheets.
The outgassing properties of a barrier sample can be measured using the same experimental
equipment shown in Figure 4.2 and have to be taken into account to estimate the total
gas load in the panel. For the same film having the barrier property in Table 4.3, the
extrapolation of the outgassing experimental data to 20 years in a 50 x 50 x 2 cm3 size
panel is shown in Table 4.7. Water, which is also given off by the barrier, was not quantified
in this test.
Table 4.7 Outgassing parameters and gas load for a barrier incorporating
a 6 μm aluminium foil
Gas q0 (Pa-l/h) α Q (Pa-l)
H2 35 x 10-4 0.5 29
-1
N2 43 x 10 1.3 133
178
4.3.3 The Getter Device
As discussed in the previous sections, gas desorption from the surfaces exposed to the
vacuum (filler and barrier) and gas permeation through the bag contribute to increase
the pressure in a VIP during its life.
These contributions, as well as the residual gases left in the panel after the exhaust and
seal-off process, have to be taken into account to provide an accurate estimation of the
pressure increase in a VIP as a function of time. Figure 4.11 shows the total pressure
increase, not including water, for some panel sizes, when data from Tables 4.2, 4.3, 4.6
and 4.7 are used.
Figure 4.11 Estimated total pressure increase in some open cell foam-filled VIP as a
function of time. The additional pressure increase due to water vapour is not
considered in this calculation.
179
For given temperature and environmental conditions, the pressure build-up depends on
the specific size of the panel, and in particular on the ratio between the perimeter and the
thickness, the lower the latter the higher the pressure increase. A barrier film incorporating
an aluminium foil and a panel seal-off pressure of 5 Pa have been here considered. In this
example, water has been assumed to be completely absorbed by a proper amount of
desiccant and not to contribute to the pressure increase.
In the case of a typical 50 x 50 x 2 cm3 size VIP, the pressure build-up exceeds 100 Pa
after a few years and even not considering water, the total pressure after 20 years exceeds
250 Pa.
The deterioration of the thermal conductivity for such a panel, a direct consequence of
the increase of the internal pressure, is shown in Figure 4.12, for a PU foam following
the curve of Figure 4.1.
Due to the nature of the thermal conductivity versus pressure curve, the deterioration of
the λ factor is negligible at the beginning but increases steadily with time.
Figure 4.12 Increase of the thermal conductivity in a vacuum following the pressure
build-up as per Figure 4.11. Water is supposed to be absorbed by a desiccant and not
contribute to the pressure rise.
180
In some applications, such as in domestic refrigerators and freezers, an additional gas

burden may be also generated in the panel during the appliance manufacturing process
or by the appliance operating conditions, which may even accelerate the deterioration of
the thermal conductivity.
These examples show that for medium and long term applications (> 2-3 years) a simple
desiccant is not enough and specific getter materials have to be added to sorb the extra
amount of gases generated in the panel.
The wide spectrum of gases present in a panel, including carbon dioxide, carbon monoxide,
hydrogen, nitrogen, oxygen and water, as well as traces of blowing agents, also calls for
an absorption system having high sorption capacities and adequate pumping speed for
all these gases.
Zirconium-based NEG alloys, which are widely used in a variety of vacuum applications
[34, 35, 36, 37] cannot be used in plastic evacuated panels due to their limited sorption
capacity at room temperature and the need to be heat activated at relatively high
temperature (> 350 °C) prior to their use, this process being clearly not compatible with
the panel polymeric components.
Very large area physical adsorbents, like molecular sieves, zeolite or activated charcoal
[38, 39] have very good efficiency for water and some organics but present serious limitations
in sorbing carbon monoxide, hydrogen, nitrogen and oxygen at the temperature and pressure
conditions typically encountered in VIP applications. Therefore, they have beneficial effects
during the very initial life of the VIP without being able to ensure long lifetime, as required,
for example, by the appliance industry. They are also sensitive to the sorption temperature,
i.e., the higher the temperature the lower the sorption performance, which spoils sorption
performances in high temperature applications, e.g., 60-100 °C.
Physical adsorbents have also a second drawback which is related to their treatment,
when mass production quantities have to be handled. To fully take advantage of their
sorption capacity, in fact, a relatively high temperature pre-treatment process which cleans
the surface by promoting gas desorption is required. However, after this treatment, the
adsorbents are exposed again to the ambient environmental conditions during the
subsequent handling and mounting operations. Due to their reactivity, they will rapidly
sorb some gases from the environment and this will reduce their capacity in a poorly
reproducible way, critically dependent on the environmental conditions, temperature
and exposure time. Fluctuations in their sorption performances as well as in the VIP
insulating efficiency could be the final result.
To eliminate the above problems and address the lifetime issues posed by the appliance
industry, a novel getter device, the COMBOGETTER, has been recently proposed [40].
181
At the heart of this device is a barium-lithium alloy, in a 1 to 4 atomic ratio [41], able to
efficiently chemically absorb a large amount of nitrogen at room temperature, up to
more than 2500 Pa-l (N2)/g (alloy) [42].
This very specific feature allows the getter to compensate for the air inlet coming from
permeation, thus ensuring long lifetime requirements.
High efficiency calcium oxide and a metal oxide are also added to barium-lithium to
absorb moisture, hydrogen and some of the most common blowing agents, such as R141
b and cyclopentane which could permeate through the VIP during its life. All these
materials are prepared according to proprietary processes, which confer upon them unique
properties in terms of sorption efficiency and capacity. The active powders are compressed
in a stainless steel cup according to a configuration which allows optimum sorption
performances and ease of use (Figure 4.13).
The getter device does not need to be heat activated or pre-treated before being used in
VIP and can be handled in air for a reasonable period of time (several minutes), during
the panel manufacturing process, without affecting its sorption capacity.
Mounting can be accomplished by inserting the getter in a recess cut in the filling material.
Alternatively, if the filler is sufficiently soft, as is the case for open cell PU, the getter can
be simply pressed into it.
Figure 4.13 Picture of the COMBOGETTER device for VIP.
182
Table 4.8 Gas sorption capacity of the

COMBOGETTER
Gas type Gas capacity, Pa-1
Air 530
CO/CO2 800
H2 9300
H2O 80000
Blowing Agents 130
Gas capacity data for the getter are summarised in Table 4.8.
A typical sorption curve for nitrogen at room temperature is given in Figure 4.14 (sorption
throughput, Pa-l/s, as a function of the sorbed amount, Pa-l).
Figure 4.14 Sorption curve for nitrogen for the COMBOGETTER (at room temperature)
183
Figure 4.15 Sorption curve for nitrogen for the COMBOGETTER

(in the 20-70 °C range)
This throughput is adequate to compensate for the relatively slow gas inlet rate occurring
during the VIP lifetime. The effect of the temperature on the sorption performance is
shown in Figure 4.15 in the range 20-70 °C.
These data show that the getter is effective also at relatively high temperatures, where
physical adsorbents become less efficient.
The getter in VIP technology has several roles, as demonstrated by the following examples:
a) Life insurance
Permeating and outgassed species (carbon dioxide, carbon monoxide, hydrogen,

nitrogen, oxygen, water) which can significantly increase the pressure are irreversibly
fixed by the getter, as shown by tests of actual panels (Figure 4.16).
Pressure in VIP has been recorded by means of a viscous pressure gauge, as explained
in Section 4.4.2.2. The resulting thermal conductivity of gettered panels is therefore
much lower in the long term, as shown in Figure 4.17, which compares the λ factor
in gettered and ungettered panels after almost 3 years of ageing.
184
Figure 4.16 Measurement of the pressure in two vacuum panels

(with and without getter)
Figure 4.17 Measurement of the thermal conductivity in two panels (with and
without COMBOGETTER) aged at room temperature
185
b) VIP manufacturing process
The ability of the getter to sorb air can be also used to reduce the evacuation time in
panels, this contribution being particularly interesting for medium and large size
panels, e.g., > 0.5 m2, where achieving base pressure in the low 1 Pa can be time
consuming for open cell foams with very small cell openings, which limit the evacuation
efficiency. For each application, a trade-off between the getter capacity needed to
reduce the evacuation time and that necessary to ensure long lasting service
performance has to be found.
A typical example of the getter’s ability to act as a chemical ‘in situ’ pump to sorb
residual gases after the evacuation process is shown in Figure 4.18, which compares
the pressure trend in panels with and without the getter immediately after the
evacuation and seal-off.
Figure 4.18 Pressure decrease in a VIP due to the in situ pumping effect
of the COMBOGETTER.
186
c) Process yield and heavy duty conditions
The COMBOGETTER normalises the vacuum level in the production cycle by

compensating for fluctuations in the quality of the VIP components and the
manufacturing process.
It can also compensate for the gases generated in the panel during ageing or heat
treatment, as happens during storage in the warehouse, the foaming process in a
refrigerator cabinet or the high temperature operating conditions required by
several specific applications. Experimental data on vacuum panel performances
under these conditions are presented and discussed in Section 4.6.
For some specific VIP sizes and short term applications (for example one to two
years) a getter for air may not be necessary, since the permeation contribution is
less relevant here. In these cases water is usually the most important gas to be
sorbed and the use of a simple dryer is sufficient to keep the pressure at the
required 10 Pa value. Calcium oxide is one of the preferred desiccants due to its
availability, low cost, good environmental features and large water sorption
capacity. The production process influences the calcium oxide physical structure
(particle size, porosity and morphology) and thus the water sorption efficiency
may be actually an important parameter to consider in short-term applications
(for example in shipping containers, where lifetimes as short as a few months or
less, can be of interest). A comparison between a commercially available product
and a highly efficient calcium oxide, prepared by SAES according to a proprietary
process is given in Figure 4.19.
Also physical absorbents, like molecular sieves and silica gel or activated carbon,
can be used for short-term applications.
187
Figure 4.19 Water sorption test on two calcium oxide samples. Samples were exposed
at 100-200 Pa water partial pressure at 23 °C. Sample A was prepared by SAES
according to a proprietary process to increase material surface area and porosity.
4.4 Vacuum Panel Manufacturing Process and Characterisation
4.4.1 Some Manufacturing Issues
Before being inserted in the barrier bag, the open cell foam needs preliminary pre-
treatment in air to remove water and the residue of the foam production process.
Volatile materials are in fact used to blow the foam chemicals and remain partially
trapped in the foam matrix or condense as a liquid on the foam surface after the cells
have been opened.
Even though part of these volatile substances will desorb at room temperature, the
remaining quantity will generate an unacceptable pressure build-up in the panel [43].
The baking process is also necessary to remove the water absorbed by the PU foam
when exposed to humid air (about 1.8 % by weight, at 23 °C, 50% relative humidity),
this being particularly effective to reduce the evacuation time, as shown by tests of
actual panels [44]. Pre-treatments generally range from 150 °C for 10 minutes to 120
°C for up to a few hours [9, 12, 43], depending on the foam type.
188
Figure 4.20 Water re-absorption curve of a small PU sample after baking.
After the foam has been thoroughly baked, it is important to reduce its exposure time to
the working environment to avoid significant moisture re-absorption, which takes place
when PU foam cools down. As an example, the weight increase due to water re-absorption
during cooling to room temperature is shown in Figure 4.20 for a small PU sample, dried
at 150 °C for 20 minutes and then exposed to 50% relative humidity.
These data indicate the need to design the production process and equipment in such a
way that the foam is exposed to air for a very short time, not exceeding a few minutes. A
limited exposure is also beneficial to reduce the evacuation time of the panel, which
strongly depends on the desorption rate of physisorbed water. To further minimise re-
absorption of water on the foam it is advisable to process the PU in a dry or humidity-
controlled area. The water content picked-up by the foam can be measured in the finished
panel by means of residual gas analysis (RGA) with the mass spectrometer, as described
in Section 4.4.2.2. In general, the proper pre-treatment of the foam followed by adequate
handling ensures better initial insulation performance and shorter evacuation cycles which
also mean higher productivity and lower costs per panel.
The open cell foam slabs are generally easier to handle and process than powder-based
core materials like precipitated silica or perlite. However, precautions have to be adopted
189
during handling of the foam to avoid powder generation which could have an impact on
the quality and reliability of the seals. Care also has to be taken during the production
process to ensure adequate VIP flatness, which is an important factor for the subsequent
proper mounting of the panel in various applications.
Appropriate film handling and processing is also the key to produce reliable and good
quality panels.
Gas barrier properties of films, in fact, mainly depend on the number of defects, such as
cracks and pinholes, present in the layered structure. This number increases as a
consequence of the mechanical stresses the film undergoes during its handling. Moreover,
the high load applied by the atmospheric pressure on the vacuum panel, this value being
particularly high in the corners and along the edges, stretches the layers and locally
increases the defect density.
A preliminary investigation of these effects has been carried out by Sugiyama and co-
authors [21] for some laminated plastic films incorporating a 6 μm aluminium foil.
Films have been analysed as such and after having been twisted to simulate handling
conditions. VIP have also been prepared and samples cut from the flat surface of the
panel, the edges and the corners to check for any local increase of the permeation rate.
Tests were carried out at 23 °C on samples of 2.5 x 10-3 m2 area applying 0.0505 MPa
helium pressure. The structure of the analysed films was Nylon 15 μm/vacuum metallised
PET 12 μm/aluminium 6 μm/HDPE 50 μm. The results, shown in Table 4.9 clearly indicate
that the twisting process is responsible for significantly larger permeation rates. Samples
cut at the corners also show higher permeation rates, which confirms that stress conditions
in these areas increase the local pin-hole density in the aluminium foil.
Table 4.9 Helium permeation rates through barrier films submitted to different
mechanical treatments
Sample number Type of sample He permeation rate
(Pa-l/s) x 10-11
1 Reference film (no treatment) <7
2 Sample cut from the flat surface of 7
the vacuum panel
3 Sample cut from the corner of the 450
vacuum panel
4 Sample mechanically twisted 230
190
Even though the total permeation rate is still acceptable, data suggests that suitable
precautions have to be adopted to limit as much as possible stress and film deterioration.
Similar behaviour is also expected for metallised films and has to be addressed accordingly.
4.4.2 Characterisation of Vacuum Panels
The rapid development of the open cell foam-filled vacuum panel technology has required
parallel development and improvements of the analytical techniques necessary to assess
VIP performance and reliability. This latter aspect is key for the widespread adoption of
the technology. The selection of the best components, foam, bag and adsorbent, as well
as the careful control of the manufacturing cycle, minimises the chance of having poorly
performing insulating panels. However, since the potential risk of defective seals or micro-
leaks cannot be completely ruled out, several techniques have been developed to either
support and establish the VIP manufacturing cycle or to assess their quality after
production.
In the following sections, some techniques to check the insulating performance of vacuum
panels are illustrated, a few of them also being able to be used as a tool for Quality
Assurance (QA) and Quality Control (QC) for the manufacturing process.
4.4.2.1 Measurement of the VIP Thermal Conductivity
The direct measurement of the thermal conductivity or λ factor is one of the most common
ways to check the quality of a vacuum panel. Several test methods are available, such as
the heat flow meter [45], guarded hot-plate and guarded-calibrated hot box [46, 47]
procedures, which measure the heat transferred under steady state conditions through
the sample whose surfaces are kept at two different given temperatures.
The last two techniques are absolute methods since they do not require the use of reference
or calibration specimen. However they are relatively expensive and time-consuming and
difficult to adapt to rapid testing.
In the heat flow meter technique, the sample is placed between two plates controlled at
different temperatures. Thermocouples placed just below the plate surfaces measure the
temperature drop across the sample. One (or more) heat flow transducers mounted on
the plate measures the voltage which is proportional to the heat flow through the sample.
Knowing the relationship between the voltage signal of the transducer and the heat flow
through it, which can be obtained by calibrating the transducer to a known thermal
conductivity standard, the thermal conductivity for the specimen can be obtained.
191
Heat flow meter test results generally agree well with those generated by absolute methods.
The technique, which is easier to use and is a universally recognised standard test procedure
[45], is also usable either for high accuracy measurements to support VIP analytical
modelling/development or for fast tests for QA/QC programs.
This latter requirement is becoming more and more important as VIP technology moves
closer to the market. Recent improvements have been based on the use of a novel dual
heat flow transducer design and a tight control of plate temperatures [48].
They allow a pass/fail test on a vacuum panel to be completed within a few minutes, thus
providing the possibility for an extensive quality check during the manufacturing cycle.
This is particularly important not only for VIP manufacturers but also for the final users,
to verify continued panel integrity after handling and transportation and before mounting.
Another relatively novel development in thermal conductivity measurement equipment

is based on a transient modified hot wire (MHW) heat reflectance technique [49]. In this
technique, heat is generated by a constant electrical current in an element that has one
side in contact with the surface of the specimen and the other side in contact with a
backing material. The temperature at the interface is measured and the rate of temperature
rise is related to the thermal conductivity of the sample. Quantitative data can be obtained
by calibrating the instrument with known standards in a given environment (pre-set
temperature and relative humidity). Preliminary investigations by Dixon and Mathis
[50] suggest that the MHW method has the potential to discriminate between panels
having different vacuum levels, at least in the 100 and 1000 Pa range.
Thanks to the short measuring time (~5 minutes are required between two measurements),
this technique also seems promising as a pass/fail test for QA/QC applications.
4.4.2.2 Measurement of the Pressure
Since the thermal performance of the panel is dependent on its internal pressure, an
alternative approach is to measure the pressure evolution as a function of time.
The spinning rotor gauge (SRG) technique [51], which is based on the measurement of
the deceleration rate caused by gas friction on a freely spinning spherical metallic ball, is
particularly well suited to monitor the pressure in sealed-off devices and has been proposed
in the recent years also for vacuum panel applications [5, 40, 52, 53].
The ball, or rotor, is suspended by magnetic forces between two mutually attracting
permanent magnets and additional coils provide the rotating magnetic field to spin it.
192
After the rotor has been accelerated and has achieved constant speed, the powering coils
are switched off, allowing the rotor to slow down.
A correlation between the deceleration rate and the pressure can be drawn, provided the
density and the radius of the rotor and the mean velocity of the gas molecules impinging
the rotor surface is known. Positive features of this technique are the wide pressure
range covered, from 10-4 to 105 Pa, the low-cost sensor and the possibility of operating
several sensors with a single electronic unit.
The sensor can be connected to the VIP using a high vacuum compatible resin, as shown
in Figure 4.21.
In the advanced SRG models, such as the SAES Getters SpiroTorr unit [54], the
instrument can operate basically at any spatial orientation on both the sensor and the
gauge head.
Figure 4.21 Diagram of the VIP mounting the spinning rotor gauge. Vacuum tightness
is ensured by a high vacuum epoxy resin.
193
In particular, by mounting the sensor horizontally in the panel it is then possible to

combine the pressure readings with thermal conductivity measurements on the same
specimen.
The measuring equipment is shown in Figure 4.22.
Pressure readings are not very much dependent on the gas type for pressure in the range or
below 10 Pa, so that the precise knowledge of the gas composition is not strictly necessary
to get a fairly accurate pressure measurement. For higher pressures, the ball (which is
suspended by the magnetic field) deceleration rate becomes more dependent on the gas
species and a precise reading requires the knowledge of the main gases involved [55].
Typical results obtained using the SRG are shown in Figure 4.16 and Figure 4.18.
Figure 4.22 Picture of the SAES Getters SpiroTorr SRG connected to a vacuum panel.
194
Due to the need to mount the sensor, this technique cannot be used as a quality control
method. Its role is more in the area of basic investigation and technology assessment.
Another way to measure the pressure is by puncturing the panel and analysing the gas
atmosphere with a mass spectrometer. The sample is connected to the analytical bench
of Figure 4.3 by a glass tube which is sealed with a high vacuum epoxy resin, as in
Figure 4.23.
The tubing is then evacuated, the panel punctured, using for example a metallic hammer,
and the internal atmosphere expanded to the mass spectrometer for the residual gas
analysis.
This approach allows measurement of both total and partial pressures in the panel, thus
providing useful information on the gas ratios, this being useful as an R&D tool or to
monitor and improve the manufacturing process. However, since this is a destructive
and relatively time-consuming test it can only be used for one-off samples. A non-
destructive technique to measure total pressure in a vacuum panel has been proposed
recently, which is based on the use of a laser beam source coupled to a detection system.
Figure 4.23 Pictorial view of the method used to connect the analytical bench to the
vacuum panel for RGA analysis.
195
The panel is placed in a vacuum chamber and the laser beam impinging on the panel
surface is reflected by the laminate and recorded by the detector. The chamber is then
slowly pumped down. When the pressure in the chamber is lower than the internal pressure
in the panel, the volume of the bag increases by gas expansion, thus causing the laminate
surface to move and deflect the laser beam in a different direction. This will generate an
electrical feedback signal which is recorded by the equipment as the internal pressure of
the vacuum panel. Present sensitivity of such types of equipment, although not well
established, is around some hundreds of Pa. It is likely that this value can be lowered by
calibrating the laser sensor against an absolute pressure gauge. This measuring technique
is quite fast (about one panel per minute) and can therefore be used as a QC/QA tool in
a manufacturing line.
4.5 Insulation Performances of Open Cell PU-Filled Vacuum Panels
The actual insulation efficiency of PU-based vacuum panels depends on the intrinsic core
material conductivity, the vacuum level, the type of barrier envelope, the panel size and
arrangement in the insulating structure.
All these aspects have to be optimised to get full benefits from VIP technology. As
previously discussed, laminates incorporating a continuous aluminium foil provide, at
present, the best gas barrier properties for VIP. Their main drawback is the loss of
insulation properties at the panel flanges due to the relatively high thermal conductivity
of the aluminium foil which reduces the overall insulating performance, this effect being
directly related to the panel size and the aluminium foil thickness.
The influence of the edge effect on the insulating performance of the panel in actual
applications can be better appreciated by introducing the ECR (Energy Consumption
Reduction) factor:
ECR = (Kpu – Kvip )/ Kpu (8)
where Kpu and Kvip (W/m) are the thermal conductivity of the conventional closed cell
foam and of the vacuum panel, respectively.
The ECR factor provides the percentage increase in the insulation efficiency obtained by
completely replacing the conventional foam with a vacuum panel having given thermal
conductivity Kvip. Calculation of Kvip is not easy, since it is a complicated function of the
size of the panel, its geometry, the thermal conductivity of the core material and the
thermal conductivity of the laminate (which is basically the aluminium foil, due to its
high thermal conductivity). The heat flow through the laminate and through the open
cell foam, both necessary to get Kvip, can be calculated by FEA.
196
Figure 4.24 ECR values as a function of the aluminium thickness for VIP of
different sizes.
Once Kvip is known, the ECR factor is obtained by Equation (8). The result of the ECR
calculation is shown in Figure 4.24 as a function of the aluminium thickness for some
different panel sizes.
It is clear from Figure 4.24 that high ECR values can only be obtained by reducing the
aluminium thickness as much as possible and using relatively large vacuum panels, i.e., >
0.5 m per side.
If the panel is encapsulated, as actually happens in several applications, the conventional

foam surrounding it also has to be taken into account in the ECR calculation, since it
may contribute to heat dissipations, its effect being particularly important around the
VIP flanges.
The ECR values for encapsulated panels of different sizes prepared with a laminate
incorporating a 6 μm aluminium foil (Table 4.3, Film B) are given in Table 4.10. The
calculation has been made assuming a foam thermal conductivity of 6 mW/m K and a
thickness of 0.5 cm of additional PU foam (thermal conductivity of 20 mW/m K) for a
total thickness of 0.025 m.
197
Table 4.10 ECR values in encapsulated VIP of different sizes

VIP size (cm) ECR (%)
40 x 40 x 2 16.5
50 x 50 x 2 26.7
50 x 100 x 2 36.7
100 x 100 x 2 46.1
The ECR values achievable with the aluminium foil-based laminates are very interesting
for large size panels, where the edge effect is not severe. For small panels, which are also
important, since they can be easily adopted in a variety of applications, from household
appliances to shipping containers, the improvement in the insulation efficiency is not as
remarkable.
The energy consumption reduction in two refrigerator cabinets, each using one panel,
100 x 50 x 2 cm3 large, covering 40% and 60% of the total surface is shown in Table
4.11. The same assumptions used in Table 4.10 have been made for the PU thermal
conductivity and thickness of the barrier foil.
Table 4.11 ECR values for two refrigerators with varying VIP coverage
VIP size (cm) Refrigerator/freezer ECR
surface coverage
100 x 50 x 2 60% 22%
100 x 50 x 2 40% 14.7%
In general, for household appliances, depending on the surface coverage of the cabinet
and the panel thickness, energy savings from 10% to 30% have been reported using
open cell PU foam-filled panels packaged in a 6 μm aluminium foil-based barrier [12,
15, 52, 56].
198
The influence of the vacuum panel thickness to the total insulation thickness ratio as
well as the change in performance, by increasing the foam λ value, has been determined
by Hamilton [54]. In general, results can be optimised by adjusting the VIP size and
thickness to provide the most cost effective option.
Further improvements can be obtained by decreasing the aluminium foil thickness or

using a metal foil-free barrier and/or decreasing the thermal conductivity of the foam.
The latter can be achieved by careful control of the foam microstructure and in particular
the cell shape, orientation and size, which play an essential role in determining the foam
thermal conductivity and its dependence on gas pressure. Conductivity values close to 5
mW/m K have been quoted for properly prepared open cell foam samples [9].
4.6 Examples of VIP Applications and Related Issues
4.6.1 Household Appliances
Refrigerators and freezers account for about 20% of the total electricity consumption of
household appliances. For this reason the appliance industry is under pressure to improve
the energy efficiency of their products to cope with the need to reduce carbon dioxide
emissions, as recently mandated by the Kyoto Conference. This objective has to be achieved
without penalising product performance. Several options to decrease the energy
consumption are under evaluation, ranging from high efficiency compressors to the
adoption of intelligent electronic devices [57, 58, 59].
Improvement of the insulation through the use of vacuum insulated panels filled with
silica powder or glass wool as core materials has been evaluated, and adopted in limited
amounts, by most refrigerator manufacturers [60, 61, 62], cost being the main obstacle
to large sales of these products. The lower cost of the open cell foams, combined with the
low density and good handling properties, has generated renewed interest for this
technology as an environmentally friendly option to energy consumption reduction. A
second driving force for the appliance industry is the possibility of increasing the internal
volume of refrigerators and freezers without increasing the outer dimensions. This aspect
is particularly important in Europe and Japan, where the built-in appliance market is an
important segment and space constraints play a role.
Adoption of PU-based vacuum panels in refrigerators and freezers requires the proper
handling of the foaming process, which may influence the structural and vacuum properties
of the panel.
199
In fact, during the appliance manufacturing cycle, the panels are glued to the cabinet
walls and then foamed in place with a conventional closed cell PU foam, this process
being necessary to further improve the overall structural and thermal insulating properties
of the cabinet. To allow a better flowability of the injected chemicals, the cabinets are
generally pre-heated at about 45 °C for some minutes. The presence of the panels, which
reduces the free flow and expansion of the foam, requires special care to avoid generation
of air-filled void volumes which would deteriorate the insulation performance [56]. To
prevent this, and provide the best integration between VIP and conventional PU foams,
specific systems have been recently developed to be used in conjunction with VIP [10].
As a combined effect of the cabinet pre-heating and the exothermicity of the foaming
reaction, temperatures even higher than 100-120 °C can be reached on the VIP surface,
leading to temperature-enhanced gas desorption. A typical result using a 50 x 50 x 2 cm3
panel is shown in Figure 4.25.
Figure 4.25 Measurement of the temperature increase experienced by the two panel
surfaces during the foaming process.
200
This gas contribution has to be evaluated case by case since it depends strictly on the
actual foaming conditions, such as the chemicals used, the process variables, the
refrigerator design and VIP geometry. However, under some circumstances, the pressure
increase can be a measurable fraction of the maximum acceptable level, thus causing a
deterioration of the VIP thermal insulation properties from the very beginning of the
refrigerator life.
As an example, Figure 4.26 shows the effect of a thermal treatment carried out at 50, 70
and 90 °C on a VIP prepared with an open cell foam and an aluminium foil-containing
laminate. The foam was pre-baked at 150 °C for 20 minutes and no absorbent was used.
After the preparation, the panel was put in a oven and kept at the indicated temperature
for 15 to 20 minutes. The panel was then removed and the total pressure measured as a
function of time. To allow the continuous monitoring of the pressure, a SpiroTorr spinning
rotor gauge was mounted in the panel as shown in Figure 4.21.
Desorbed gases after the thermal treatments are only partially reabsorbed by the foam
and generate a measurable pressure build up in the VIP.
Figure 4.26 pressure evolution in a panel submitted to various heat treatments.

Pressure readings are taken by means of a SpiroTorr SRG (see Figure 4.3).
201
Table 4.12 Residual Gas Analysis in encapsulated panels with and

without the getter
Encapsulated VIP Total Pressure Partial Pressure (Pa)
(Pa) Air CO/CO2 H2O H2
Without getter 40 6 29 5 0.1
With getter 0.7 0.3 0.01 0.3 0.1
The effect of the temperature increase resulting from the foaming process, on the vacuum
level in a panel can also be seen in Table 4.12 which shows the result of an RGA carried
out on two test panels encapsulated by an appliance manufacturer. In the getterless panel,
the pressure immediately after the foaming is already exceeding the 10 Pa target value
and close to the maximum acceptable value (generally set at 50 Pa).
The deterioration of the vacuum during the foaming process has been recently addressed
by Kücükpinar and co-workers who ran specific tests aimed at quantifying this effect in
open cell foam-filled VIP with and without getters [53].
As shown in this study, the COMBOGETTER was able to compensate for the extra gas
load generated during the foaming process, thus confirming the results in Table 4.12.
Further specific outgassing studies are necessary to understand the mechanisms of gas
generation during the foaming process, even though this investigation presents several
difficulties because of the large number of parameters involved.
The foaming process may also stress the laminate due to the combined effect of temperature
and applied pressure on critical areas such as the panel edges and the corners. Defects
generated here may in turn increase the gas diffusion inside the panel, reducing the designed
lifetime.
Another important issue in refrigerator/freezer applications is longevity, since 15 to 20

years lifetime is targeted by most manufacturers.
Durability tests on panels are therefore necessary to assess VIP reliability and performance
over time. Figure 4.27 shows the pressure values in some encapsulated panels, as measured
by RGA. Panel A, containing a COMBOGETTER, was aged at room temperature for
some weeks and then kept at 40 °C for more than 30 months. Panels B and C did not
have any adsorbent. The latter was aged at 40 °C for about 3 months, while the former
was unaged.
202
Figure 4.27 Residual gas analysis in panels encapsulated and aged for different times.
Panel A contains one COMBOGETTER, panels B and C are without.
The pressure in panel A is well below the 10 Pa target value as compared to panel C
whose pressure is one order of magnitude higher. Pressure in panel B, which was just
encapsulated, was slightly lower than in panel C. For comparison, the calculated pressure
increase in the panel, as predicted based on the model discussed in Section 4.3, is also
shown. This result confirms the role of the getter to compensate for the encapsulation
process and to ensure VIP longevity and also supports the gas load model previously
described.
Still, a better assessment is necessary through longer term tests and, possibly, through
accelerated tests able to provide experimental data within a shorter time. Activity is
ongoing in SAES Getters Laboratories, as well as in various other research centres to
provide such an assessment.
4.6.2 Laboratory and Biomedical Refrigerators
This is very special equipment designed to operate at very low temperatures, e.g., from
-30 °C to -86 °C, to age samples or to store valuable and perishable goods, like organs
and tissues, biological and medical samples or vaccines. Vacuum panels are used mainly
to increase the internal storage volume without increasing the energy consumption.
203
Since the conventional insulation must be very thick to ensure the achievement of such
low temperatures, a partial replacement of the conventional insulator with VIP
contributes significantly to increase the internal volume, from 20% up to 40% or
more in specific models.
As a second advantage, panels provide an overall superior passive insulation, which

means that the temperature rise in the case of power failure is less steep and more time
is necessary before a given critical temperature is reached. This provides extra-safety
for delicate articles which may rapidly deteriorate when their temperature exceeds a
given value.
Due to the generally higher insulation thickness, the foaming process here may be even
more exothermic than in domestic appliances. Means have therefore to be taken to keep
the VIP temperature as low as possible during the encapsulation.
Ultra-low temperature freezer models using foam filled vacuum panels were successfully
placed on the market by a leading company some years ago and other companies are
expected to follow soon.
4.6.3 Vending Machines
Vending machines are especially popular in Japan, Korea and the Far East. It is estimated
that in Japan about 2.5 million of these appliances are in the field with a replacement
market of about 0.4 million pieces/year.
VIP are finding widespread use in vending machines since most manufacturers are
extensively using one or two panels to separate the hot and cold beverage compartments.
Also in this case, the main driving force for VIP adoption has been the possibility to
increase the internal volume for the storage of beverages, rather than the improvement
in energy efficiency.
Vending machines are quite a demanding application for VIP, since the panel operating
temperature is cycled between room temperature and 60-70 °C and the lifetime is 5
years. As already discussed, the high temperature promotes higher diffusion and outgassing
rates and provides additional mechanical stress to the envelope.
Ageing tests have been carried out by vending machines manufacturers to assess VIP
usability and reliability in this application.
Results obtained in SAES Getters Laboratories for 50 x 50 x 2 cm3 panels aged for
several months at 60 °C are shown in Figure 4.28.
204
Figure 4.28 Measurement of the thermal conductivity as a function of time for panels
aged at 23 and 60 °C, with and without the COMBOGETTER.
Again, the deterioration of the thermal conductivity, due to the pressure increase, is quite
dramatic in the getterless panels both at 23 and 60 °C. As expected, the thermal conductivity
increase is much more rapid for the panels aged at 60 °C than for the panel kept at room
temperature. Only minimal differences are measured in the panels containing the
COMBOGETTER, which could compensate for the increased gas load at both temperatures.
4.6.4 Refrigerated/Insulated Transportation
Large vacuum insulated containers, ships and trucks are under evaluation by various
companies, mainly in Europe and Japan.
The main advantages offered by using VIP are space saving and better insulation, so as
to keep the temperature increase rate as low as possible even in the absence of a power
source. The lifespan is generally from 10 to 15 years.
Since very large VIP, e.g., 2-3 m2 size are considered for this application, the edge effect
(see Section 4.3.2.1) is here a marginal issue.
205
Small commercial shipping containers to store and deliver pharmaceuticals, frozen food
and valuable temperature-sensitive products is also another interesting area for the use
of VIP.
Long lifespan is not a problem, since most of these shipping containers have a projected
life of the order of weeks or months. Therefore, it is even possible to use the VIP more
than once, the specifications on the permeation properties of the barrier film are less
tight and the getter not necessary. A specific dryer, to adsorb water, may be used in most
cases. The small size VIP and the limited projected life suggest the possibility of using
metallised barriers for the skin of the panel in these applications, at least on one side, so
as to overcome the edge effect, which, in this case is very critical.
4.6.5 Other Applications
A variety of other potential applications exist for VIP, from cold stores to insulation in
buildings and in industrial plants, e.g., industrial reactors or liquid natural gas tanks.
Also super insulation at relatively high temperature applications for water heaters, heat
pipes or boiling pots have been considered and are under evaluation. The key issue of the
adoption of VIP in this last family of applications is the possibility to bend the open cell
PU filled VIP into a round or cylindrical shape. The combination of high temperature
and bending provides additional challenges to VIP technology and further improvements
in the material selection and processing might be required.
4.7 Near Term Perspectives and Conclusions
The open cell PU foam is a very promising filler material for VIP. It shows good vacuum
compatibility, thermal conductivity, light weight, ease of handling and processing and
moderate cost. To allow its use, significant improvements have been made recently in the
barrier and getter technology, as well as in the panel manufacturing and testing procedures.
Laminated barriers, incorporating a 6 μm continuous aluminium foil, are providing a

reasonable trade-off between permeation properties and energy saving, especially in large
size panels (~1 m2), where the edge effect is less important. These films can therefore be
used in applications such as refrigerators, freezers, vending machines and insulated
transportation, where 10-20 years lifetime and relatively large panels are required.
Traditional metallised or multilayered plastic barriers, even though more appealing from
the energy saving point of view, are not advisable in long term applications, due to their
poorer gas barrier properties. However, the need to improve performance and VIP cost
effectiveness is pushing the film industry to further improve their products either by
206
reducing the aluminium foil thickness to 5 μm and below or developing aluminium-free

composite barriers. If successful, this latter solution would dramatically increase the
vacuum panel insulation efficiency. New families of improved metallised products have
been developed very recently and proposed for testing and are under evaluation in several
laboratories.
The outgassing and permeation data, on both components and finished panels, and the
use of models quoted in the literature, allow the evaluation of the total gas load and the
pressure increase in a vacuum panel as a function of time, size and operating conditions.
This in turn is beneficial for designing the most suitable solution for the absorbent.
A high capacity getter system, the COMBOGETTER, capable of adsorbing air, moisture
and the other gases of interest without the need for any pre-treatment has been specifically
developed for VIP application. Its roles are many since it chemically absorbs residual,
outgassed and permeating species and provides the means to shorten the evacuation
process and increase the manufacturing yield.
Mass production technologies to manufacture high quality open cell foam panels are on
the market. Several techniques are also becoming available for the fast measurement of
the thermal conductivity. This is a very important issue to build a QA/QC system able to
ensure the quality and the reliability of the products, not only after production but also
immediately before use.
As far as the applications are concerned, open cell PU foams are finding their place in the
market for both low and high temperature appliances, from refrigerators to vending
machines. Present production volumes are still limited but near term perspectives are
encouraging, especially in Asia and Europe. The strong push for energy reduction and
the parallel continuous refinement of the technology should provide further motivation
to VIP adoption.
Cost is still the main obstacle to the widespread adoption of this technology. A preliminary
qualitative cost comparison between silica and open cell PU, which includes raw material,
panel manufacture and panel installation costs [10] shows that a cost reduction of about
one-third over silica could be achieved. This has to be improved to bring the cost of the
vacuum panel down further, so as to really interest more segments of the insulation
industry.
Very recent breakthroughs in the foam mass production technologies seem to indicate
that this target is reachable.
Even though far from being complete, the material presented in this chapter shows that
significant technological achievements have been obtained during the last few years.
207
Thanks to this, vacuum panel technology is becoming a technically viable and cost effective
solution to the need to reduce energy consumption in household appliances and in
commercial and industrial applications. To successfully achieve this target, additional
efforts are necessary to further improve the component quality and reliability (foam,
film and adsorbent), to optimise panel production and to reduce costs.
Acknowledgements
The author would like to thank Dr. Paolo della Porta, President and CEO of SAES Getters
SpA, for his continuous support and long lasting commitment to VIP technology. The
author also acknowledges Dr. Bruno Ferrario, Corporate R&D Director, for fruitful
discussions and suggestions.
Special thanks are given to Dr. Roberto Caloi and Dr. Enea Rizzi for their valuable
technical support in the development of theoretical models and in running experimental
measurements on VIP components and finished devices.
References
1. H. A. Fine, Journal of Thermal Insulation, 1989, 12, 183.
2. D. W. Yarbrough, R. S. Graves, F. J. Weaver and D. L. McElroy, presented at ORNL/

CON-215, Oak Ridge National Laboratory, Oak Ridge, TN, Sept. 1986, p.1.
3. L. R. Glicksman and N. Solomou, Presented at the SPI Polyurethanes Conference,

Boston, MA, 1994, p.182.
4. H. M. Strong, F. P. Bundy and H. P. Bovenkerk, Journal of Applied Physics,

1960, 31, 1, 39.
5. B. Veltkamp and P. Hoogendoorn, Vuoto, 1999, 28, 1-2, 27.
6. J. Fricke, Presented at the 13th European Conference on Thermophysical

Properties, Lisboa, Portugal, 1993, p.207.
7. R. L. Tabor, Presented at the SPI Polyurethanes Conference, Boston, MA, 1994,

p.288.
8. G. Biesmans, D. Randall, E. Francais and M. Perrut, Presented at the

Polyurethanes World Congress ’97, Amsterdam, The Netherlands, 1997, p.294.
208
9. K. Kodama, K. Yuge, Y. Masuda and Y. Tanimoto, Presented at the

Polyurethanes World Congress, October 1993, p.140.
10. R. De Vos and I. D. Rosbotham, Cellular Polymers, 1994, 13, 2, 147.
11. K. W. Dietrich and D. W. McCullogh, Presented at UTECH 96, The Hague, The
Netherlands, 1996, Paper No.64.
12. W. H. Tao, W. F. Sung and J. Y. Lin, Journal of Cellular Plastics, 1997, 33, 3,
545.
13. P. Pendergast and B. Malone, Vuoto, 1999, 28, 1-2, 27.
14. L. R. Glicksman in Low Density Cellular Plastics: Physical Basis of Behaviour,

Ed., N. C. Hilyard and A. Cunningham, Chapman & Hall, London, 1994,
Chapter 5, p.104.
15. W. Wacker, A. Christfreund, D. Randall and N. W. Keane, Presented at the

Polyurethanes Expo ’96, Las Vegas, NV, 1996, p.35.
16. A. Roth, Vacuum Technology, North Holland Publishing Company, Amsterdam,

1982, 186.
17. F. Sciuccati, G. Gasparini and B. Ferrario, Vuoto, 1988, 17, 4, 345.
18. P. A. Redhead, Vacuum, 1962, 12, 203.
19. P. Mercea, L. Muresan and V. Mecea, Journal of Membrane Science, 1985, 24,
297.
20. T. A. Beu and P. V. Mercea, Materials Chemistry and Physics, 1990, 26, 309.
21. A. Sugiyama, H. Tada and M. Yoshimoto, Vuoto, 1999, 28, 1-2, 51.
22. ASTM Standard E96-00 Standard Test Methods for Water Vapor Transmission of
Materials.
23. ASTM Standard F 1249-90 (1995) Standard Test Method for Water Vapour
Transmission Rate Through Plastic Film and Sheeting Using a Modulated
Infrared Sensor.
24. P. Manini, inventor; Saes Getters SpA, assignee; WO 9803850A1, 1998.
25. P. Manini, Journal of Cellular Plastics, 1999, 35, 5, 403.
209
26. P. Manini and E. Rizzi, Poster presented at the European Workshop on Vacuum
Panel Technology for Super Insulation in Domestic Appliances and Industrial
Applications, Milano, Italy, 1998.
27. W. Lamb and R. Zeiler, Presented at the Vacuum Insulation Panel Symposium,
Baltimore, MD, 1999. Paper available from the SAES Getters web site, http://
www.saesgetters.com.
28. J. Bonekamp, Presented at the Vacuum Insulation Panel Symposium, Baltimore,

MD, 1999. Paper available from the SAES Getters web site, http://
www.saesgetters.com.
29. R. Juran, J. Covington and J. Carley, Modern Plastics Encyclopedia, McGraw

Hill, NewYork, 1987, 64, 10A.
30. Polymer Handbook, 3rd Edition, Ed., J. Brandrup and E. H. Immergut, John
Wiley and Sons, New York, 1989.
31. S. J. Adam and C. E. David, Presented at the 23rd International SAMPE

Technical Conference, New York, NY, 1991.
32. K. E. Wilkes, W. A. Gabbard and F. J. Weaver, ORNL/CP-95971, Oak Ridge

National Laboratory, TN, 1998.
33. G. Biesmans, R. De Vos and I. D. Rosbotham, Presented at the Polyurethanes

World Congress 1993, Vancouver, BC, 1993, 498.
34. A.Barosi in International Symposium on Residual Gases in Electron Tubes, Ed.,

T. A. Giorgi and P. della Porta, Academic Press, London, 1972, 221.
35. C. Boffito, B. Ferrario, P. della Porta and L. Rosai, Journal of Vacuum Science
and Technology, 1981, 18, 1117.
36. B. Ferrario, A.Figini and M.Borghi, Vacuum, 1984, 35, 13.
37. C. Boffito, B. Ferrario, L. Rosai and F. Doni, Journal of Vacuum Science and
Technology, 1987, A5, 3442.
38. D. W. Breck, Zeolite Molecular Sieves, R. E. Krieger Publishing Company,

Malabar, Florida, 1984, Chapter 8.
39. J. S. Mattson and H. B. Mark, Activated Carbon: Surface Chemistry and

Adsorption from Solution, Marcel Dekker, New York, 1971.
210
40. P. Manini, Vuoto, 1997, 27, 2, 45.
41. C. Boffito and A. Schiabel, inventors; Getters SpA, assignee; European Patent
0514348 A1, 1991.
42. R. M. Caloi, P. Manini, S. Valdrè, E. Magnano, J. Kovac, E. Narducci and M.

Sancrotti, Journal of Vacuum Science and Technology, 1999, A17, 2696.
43. R. De Vos, I. D. Rosbotham and J. Deschaght, Presented at the Polyurethanes

World Congress, 1994, Boston MA, p.194.
44. J. Akita, Vuoto, 1999, 28, 1-2, 59.
45. ASTM Standard C518-98, Standard Test Method for Steady-State Thermal
Transmission Properties by Means of the Heat Flow Meter Apparatus.
46. ASTM Standard C236-89 (1993) e1, Standard Test Method for Steady-State
Thermal Performance of Building Assemblies by Means of a Guarded Hot Box.
47. ASTM Standard C177-97, Standard Test Method for Steady-State Heat Flux
Measurements and Thermal Transmission Properties by Means of the Guarded-
Hot-Plate Apparatus.
48. S. Smith and C. Urso, Vuoto, 1999, 28, 1-2, 64.
49. N. E. Mathis, Measurement of Thermal Conductivity Anisotropy in Polymer

Materials, Chemical Engineering Department, University of New Brunswick,
Fredericton, NB, Canada, 1996, Ph.D. Thesis.
50. C. Dixon and N. Mathis, Presented at the Polyurethanes Expo ‘99, 1999, p.607.
51. J. K. Fremerey, Journal of Vacuum Science and Technology, 1985, A3, 3, 1715.
52. E. Kücükpinar, H. Güclü, A. S. Akkurt and F. Özkadi, Vuoto, 1999, 28, 1-2, 31.
53. E. Kücükpinar, F. Özkadi , A. Soyal and H. Güclü, Presented at the Polyurethanes

Expo ‘99, 1999, p.339.
54. C. Boffito, M. Moraja and G. Pastore, Journal of Vacuum Science and

Technology, 1997, 15, 4, 2391.
55. B. E. Lindenau and J. K. Fremerey, Journal of Vacuum Science and Technology,

1991, A9, 5, 2737.
211
54. A. J. Hamilton, Vuoto, 1999, 28, 1-2, 27.
55. H. A. Fine and J. Lupinacci, Energy-Efficient Refrigerator Prototype Test Results,

EPA-43D-R-94-011, June 1994.
56. E. A. Vineyard, J. R. Sand and R. H. Bohman, ASHRAE Transactions, 1995, 1,

1422.
57. E. A. Vineyard and J. R. Sand, presented at ORNL/CP-97450, Oak Ridge

National Laboratory, TN, 1998.
58. G. J. Haworth, R. Srikanth and H. A. Fine, Presented at the 44th Annual

International Appliance Technical Conference, Ohio, USA, 1993, p.1.
59. E. A. Vineyard, T. Stovall, K. E. Wilkes and K. W. Childs, ASHRAE Transactions,

1998, 104, 2.
60. T. F. Potter, D. K. Benson and L. K. Smith, Presented at ACEEE 1988,

Proceedings from the Panel on Appliances and Equipment,1998, 4, 4.86.
212
5
Modelling the Stabilising Behaviour of Silicone
Surfactants During the Processing of
Polyurethane Foam: The Use of Thin Liquid Films
Steven A. Snow, Udo C. Pernisz, Benjamin M. Nugent, Robert E. Stevens,
Richard J. Braun and Shailesh Naire
5.1 Introduction
The commercial production of polyurethane (PU) foam requires a tremendous diversity

of ingredients. Common ingredients include isocyanates, polyether polyols, water, catalysts
and stabilisers (surfactants). Most of the surfactants used in the foaming process are
silicone surfactants, the major suppliers being Th. Goldschmidt AG, Witco and Air
Products and Chemicals, Inc. Worldwide volume for silicone surfactants in polyurethane
foam has been recently estimated at 30,000 tonnes/year [1]. In practice, a wide range of
silicone surfactant structures are necessary to produce PU foam with a sufficiently broad
range of physical properties. This structural diversity also reflects the need for the
surfactant to perform many different tasks in foam formulations. The physical behaviour
of these surfactants in the PU foam formulation process [2] has recently been reviewed.
These roles of the surfactant include reducing surface (interfacial) tension [3-11], altering
surface viscoelasticity [5, 7, 11, 12-15], and modifying polymer reaction kinetics and
morphology [16-21]. The focus of this chapter is on the mechanism of PU foam
stabilisation and how it is affected by silicone surfactants.
In order to understand a complicated physical mechanism such as PU foam stabilisation,

one must first be concerned with the thermodynamics and kinetics of the process. As a
PU (or any) foam rises, energy is absorbed by the system and converted into a combination
of excess gravitational and surface energy. For PU foams, this excess energy is created by
both high-shear mixing and energy transfer from the chemical polymerisation reaction
(between isocyanates and either polyols or water). One function of the silicone surfactant
is to stabilise this foam until it is a self-supporting, gelatinous froth. This froth can
further harden, yielding elastomeric or rigid foam products. Once hardened, the foam
still contains excess gravitational and surface energy; however, the rate of dissipation of
this energy is extremely low. Therefore, when discussing foam ‘stability’, one is specifically
considering the rate of foam degradation.
Foam degradation involves both physical and energetic changes in the foam. Four physical
processes are commonly associated with PU foam degradation:
213
• a decrease in foam volume,

• a decrease in the number of bubbles (cells),
• an increase in average cell size, and
• a decrease in the dispersity of cell sizes.
These physical processes involve the release of excess gravitational and surface energy.
Excess gravitational energy is released during the drainage of liquid from the foam. The
liquid can drain from between the bubbles, thinning the liquid membrane known as the
lamella. The liquid can also drain from the plateau borders in the foam. These borders
are the relatively wide channels in the foam created at the intersection point of three
lamellae. Mysels, Frankel and Shinoda [22] estimated that, in aqueous foams, the amount
of gravitational energy released during degradation was five orders of magnitude less
than the amount of surface energy released. It is assumed that this estimation roughly
holds for the degradation of PU foams; therefore, the focus here will be on processes that
reduce the surface energy of PU foams.
Two processes, the diffusion of gas from small to larger bubbles (Ostwald Ripening) [23]
and bubble coalescence, reduce the surface area of the foam and, therefore, the surface
energy. Ostwald ripening involves the diffusive molecular transport of gas from small to
large(r) bubbles. Ostwald ripening in foams leads to the counterintuitive phenomena of
large bubbles in a foam expanding as smaller ones shrink. This process results both in a
reduction in the number of bubbles and in the dispersity of bubble sizes. However,
Owen [12] has demonstrated that Ostwald ripening plays only a minor role in PU foam
stability; therefore, this chapter will focus on the process of bubble coalescence.
Bubble coalescence involves the merging of two distinct bubbles into one, due to the
rupture and recession of the lamella. Early in the PU foaming process, the rupture of a
lamella at the edge of the PU foam will cause bubble collapse as the gas inside is lost to
the surrounding atmosphere. This process will reduce the number of bubbles present
and the foam volume. Lamella rupture within the interior of the foam will cause bubble
coalescence, decreasing the number of bubbles, increasing the average bubble size, but
not necessarily decreasing the foam volume. Later in the foaming process, as the PU gel
network sets up, the lamella may rupture but the two bubbles can retain their separate
identities. This process is known as cell opening. If many of the lamellae have ruptured
in this fashion, the object is more correctly called a sponge instead of a foam. In this
case, air can easily be pushed out of the sponge if it is loaded with weight (as for example
when one sits on PU foam padding on a car seat). Therefore, the mechanical properties
of the PU foam depend greatly on the degree of cell opening present. There is general
agreement that a strong stabilising effect from the surfactant is necessary early in the
214
Modelling the Stabilising Behaviour of Silicone Surfactants…
foam process. The stabilising role, if any, of the surfactant late in the foaming process
remains a controversial issue [2, 19-21, 23-27]. This chapter will focus on the earlier
stages of the foaming process, before the gelling of the liquid PU phase.
The mechanism of rupture depends upon the thickness of the lamella film. Ultra-thin
films, with thicknesses in the 1-20 nm range, are believed to rupture due to the
amplification of thermally-generated surface waves [28-30]. However, studies by Artavia
and Macosko [31] and Akabori and Fujimoto [32] demonstrated that most of the ruptured
lamellae in a PU foam are in the 200-1000 nm thickness range. Therefore, it is assumed
here that the mechanism of rupture of these thicker films is most important when
considering PU foam.
It has been extensively demonstrated that ‘thick’ liquid films rupture due to the
formation (nucleation) of a pinhole in the film which spreads outward radially until
the film is destroyed. The nucleation of the pinhole could result from either the presence
of fluid instabilities in the film (for example, Marangoni, Rayleigh-Taylor or Benard
instabilities) [33] or else by the presence of immiscible microphases which could serve
as nucleation sites.
For PU foams, it has been proposed that film rupture is nucleated by the phase separation
of polyurea segments [19-21, 24-26]. It was postulated that the phase separation process
could be retarded by the presence of silicone surfactants containing a high percentage of
polyoxyethylene. The polyoxyethylene segment of the surfactant could interact strongly
with polyurea via the formation of a hydrogen bonding network. However, in cases
where the silicone contains lesser amounts of polyoxyethylene, such as in many commercial
foam stabilisers, a direct effect of the concentration and structure of the silicone surfactant
on this phase separation process has not been found [2, 26].
Circumstantial evidence of the influence of Marangoni instabilities on PU foam stability,

and presumably film stability and the nucleation of pinholes, has been amply demonstrated
[34]. Marangoni instability in a fluid film refers to a situation where a gradient of surface
tension exists, stimulating compensating surface flows. For example, the stretching of
the film reduces the surface concentration and, therefore, increases the surface tension.
Furthermore, this stretched and thinned spot would be prone to rupture. However,
within a certain range of surfactant concentration, this thin spot can re-thicken due to
the diffusion/convection of surfactant and underlying bulk liquid to the thin spot
(Marangoni flow).
Once nucleated, the film hole can spread out radially at a rate inversely proportional to
the bulk viscosity of the film. Spreading can occur until the film is destroyed. For
example, in typical aqueous films, the rate of spreading is so high that high-speed
photography is necessary to capture the event. However, in a gelling PU foam, the rate
215
of spreading can be very low, and, in fact, films can have multiple holes in them without
being destroyed [24-26, 32].
Detailed investigations on the effect of silicone surfactants on the nucleation and growth
of holes in PU films have not been reported. Furthermore, that is not the topic of this
chapter which is specifically concerned with the effect of the silicone surfactant on the
rate of drainage of PU films. However, this topic is highly related to film rupture as it has
been shown that the probability of film rupture is an inverse squared function of the film
thickness [35]. The time-dependent film thickness is a function of the drainage rate of
the film.
5.2 Film Drainage Rate: Reynold’s Model and Further Modifications
5.2.1 Rigid Film Surfaces
Thin film drainage has been investigated in detail both theoretically and experimentally
[22, 28-30, 35]. An extensively applied physical model of a draining thin film is the one
of Reynold’s, a form of which is shown in Equation 1:
VRe = 2Fk3 3πμR 4 (1)
where VRe is the velocity of film thinning, F is the external force on the film (causing
drainage), k is the film thickness, μ is the dynamic viscosity, and R is the film radius.
The Reynold’s model assumes that:
• the liquid inside the film is Newtonian in its rheological behaviour.
• the surfaces of the film are circular, immovable, parallel plates; surface velocity equals
zero, surface viscosity is infinite.
• the flow inside the film is laminar.
• the flow inside the film is driven by gravity and/or pressure gradients and is resisted
by the bulk viscosity of the liquid.
The dependencies of drainage (flow) rate on the variables of film thickness, area and
bulk viscosity are quantified in Equation 1. For example, with decreasing film thickness
k, the drainage rate decreases in proportion with k3; furthermore the drainage rate
decreases with increasing viscosity.
216
Previous discussions [34] of PU film drainage rate (and ultimately foam stability and cell
opening) focused on the dependence of rate on bulk viscosity. Per Reynold’s model, factors
which increased the bulk viscosity, such as catalyst concentration and polyol reactivity,
presumably decreased film drainage rate and yielded a more stable, less porous foam.
5.2.2 Mobile Film Surfaces
The Reynold’s model and equation have also been modified to account for surface effects
on film drainage rate [29]. To accomplish this, the assumption (boundary condition) of
a surface velocity of zero must be relaxed. This change also decreases the surface viscosity
from an infinite to a finite value. This process yields Equation 2. Allowing for a finite
surface velocity increases the film drainage rate from that which would be expected
under the Reynold’s conditions.
V / VRe = 1 + 1 / e f (2)
Where V/VRe is the measured velocity of thinning divided by the velocity of thinning
under the conditions of the Reynold’s equation and ef is the surface mobility factor.
The surface mobility factor is analysed in detail in [36]. This analysis demonstrates that
two factors control the degree of surface mobility: the surface viscosity and the presence
of surface tension gradients.
5.2.3 Surface Viscosity
The rates of thinning of vertically-supported, thin liquid films of polyol solutions of

various silicone surfactants have been measured [37]. It was found that the rate for films
stabilised by a trimethylsilyl-capped polysilicate (TCP; a highly branched silicone not
containing polyethers), was much lower than that for the films stabilised by common
silicone polyether copolymer surfactants. The retardation of drainage rate was correlated
with an increase in surface viscosity. Furthermore, it was noted that PU foams prepared
using TCP were significantly more stable than those containing the commercial surfactants.
Surface viscosity scales directly with the surfactant surface concentration, the
intermolecular cohesion between the surface molecules and the intermolecular adhesion
between the surfactant molecules and the underlying bulk liquid layer.
Increasing the surface concentration decreases the average distance between molecules,
therefore increasing the sum value of the attractive molecular forces between them. In
217
many cases, high surface concentration yields a low film drainage rate and a highly
stabilised foam.
The intermolecular cohesion is the result of the balance of attractive (van der Waals,
polar bonding) and repulsive (ionic) intermolecular forces. The total cohesive energy is a
product of the total area of cohesion and the cohesive energy per unit area. For example,
the cohesion of the polyether chains of a typical silicone surfactant yields most of the
surface viscosity contribution in PU films and foams [38]. Although it has not been
investigated, one could speculate that the surface viscosity would scale with the length of
the polyether chain. Increasing the chain length increases the potential area of contact
between the chains.
The unit area cohesive energy is a function of the strength of the intermolecular bonds
present. For example, silicone surfactant molecules could possibly cohere via van der
Waals bonding of the methyl groups of the siloxane backbone or else via polar bonding
between the ethylene oxide units in the polyether chain. The van der Waals bonding
between methyl groups is known to be weak; consequently, the surface viscosity of
unsubstituted PDMS is close to zero [15, 38]. However, the polar bonding between the
polyether chains would be much stronger and, therefore, the source of surface viscosity
measured in silicone polyether copolymers.
Intermolecular adhesion between the polyether chains of a typical silicone surfactant

and the underlying ‘polyurethane’ liquid matrix could increase the surface viscosity
contribution in PU films and foams.
In order to maximise surface viscosity, and therefore minimise the drainage rate, the
surfactant concentration, the intermolecular cohesion and adhesion should all be high.
Later in the chapter evidence is presented correlating silicone surfactant concentration
and structure (which influences the intermolecular cohesion and adhesion) to surface
viscosity and film drainage rate.
5.2.4 Surface Tension Gradients
An idealised model of the surface of a thin liquid film is one of a monolayer of evenly-
distributed surfactant molecules. However, a more realistic model is one where the
molecules are not evenly distributed; therefore, the surface concentration depends on
surface position. The result of this heterogeneous distribution is that gradients of surface
concentration, and therefore surface tension, are present. One example of this was pointed
out in Section 5.1 on the effect of Marangoni instabilities on film rupture. Regarding
film drainage, a surface tension gradient exerts a surface stress that can either impede or
218
accelerate the underlying bulk flow (drainage). In thin films, these gradients typically
make the surface rigid, retarding flow and therefore decreasing, drainage rate. The
gradients can be relieved by the diffusion of surfactant from areas of high to low
concentration; the drainage rate of the film is proportionately increased.
Diffusive surfactant fluxes are functions of the intensity of the concentration gradient
and the diffusion coefficient of the surfactant. The intensity of the concentration gradient
depends upon the overall surfactant concentration. At low or high concentrations, these
gradients are relatively weak. At intermediate concentrations, they are quite strong.
The diffusion coefficient of the surfactant is a function of its size and shape. The most
simple and common case to analyse is where the surfactant assumes a spherical shape.
In this case, the diffusion coefficient of the surfactant scales inversely with the solvated
molecular volume (Stoke’s law).
Overall, to accelerate film drainage, it is useful to have a high concentration of surfactant

whose surface partition coefficient is also high. The surface partition coefficient is a
measure of the tendency of the surfactant to adsorb at the surface instead of remaining
in the bulk. In the case of silicone polyether surfactants, the coefficient scales with the
ratio of silicone to polyether. Under these conditions (high surfactant concentration,
high ratio of silicone to polyether) the flux of surfactant to the surface, relieving surface
tension gradients, will also be high. A large diffusion coefficient (for the surfactant
molecule, a small size and a compact shape) is also helpful. Later in this chapter
correlations of silicone surfactant concentration, partition coefficient, and diffusion
coefficient to film drainage rate will be discussed.
5.3 Experimental Investigation of Model, Thin Liquid Polyurethane

Films and the Development of Qualitative and Semi-Quantitative
Models of Film Drainage
This section begins with a qualitative description of thin liquid PU films. This initial
investigation had five goals in mind: to confirm that stable, vertically-oriented, thin liquid
films could be prepared using mixtures of ingredients designed to model a PU foam, to
study the hydrodynamic phenomena in the films, to compare the physical behaviour of
these films to the behaviour of the more common aqueous soap films, to observe specific
surfactant effects on the properties of these films, and to extrapolate conclusions about
the behaviour of these films to operational PU foam.
After this qualitative description, an accurate measurement of the drainage rates of these
films was sought in order to study the effect of bulk and surface variables on the rate. In
219
order to make an accurate measurement, a novel interferometric method was developed

and implemented. This method was validated by the discovery that film drainage rate
scaled with the reciprocal of bulk viscosity as predicted by Reynold’s equation.
Once this method was validated, the effect of silicone surfactant concentration and structure
on the drainage rate of the films was investigated. Generally, the drainage rate displayed a
maximum as a function of surfactant concentration. This maximum was consistent with a
physical model where the two major influences on drainage rate are surface tension gradients
and surface viscosity. As surfactant concentration increased, the retarding effect of gradients
decreased, and the film drainage rate increased. However, above a certain concentration, the
drainage retarding effect of surface viscosity overcame the gradient effect.
The dependence of film drainage rate on silicone surfactant molecular structure was also
systematically investigated. In order to understand this correlation, three physical
parameters of the film affected by surfactant structure must be considered. These
parameters are the surface partition coefficient, the surfactant molecular diffusion
coefficient and the degree of intermolecular cohesion within the surface layer. Specifically,
as the length of the polyether (solvophilic) portion of the surfactant increased, the surface
partition coefficient decreased, the diffusion coefficient decreased, and the degree of
cohesion increased. This resulted, at constant surfactant concentration, in a complex
effect on the film drainage rate.
A quantitative physical model of a draining vertical thin film was developed from first
principles. The starting point was the Navier-Stokes equation. The initial model featured
a fixed-surface, wedge-shaped vertical film, with immobile surfaces. This is essentially
the Reynold’s model modified to this film shape and orientation. Good agreement of the
predictions of this model with experimental data was obtained.
The next model relaxed the condition of fixed film shape (allowed for curvature in the
film surface) and analysed the effects of the menisci on the film drainage. Analysis of the
Navier-Stokes equation was simplified by the application of the lubrication approximation.
The results from this analysis agreed extremely well with experimental values both in
terms of film drainage rate and the changes in film shape with time. The development
and growth of bulges and waves on the bottom of the film were particularly intriguing.
This phenomenon was experimentally observed in these films.
Finally, models were developed where the condition of infinite surface viscosity was relaxed.
This allowed the analysis of surfactant effects on film drainage, in particular surface viscosity
and surface transport. Specifically, the model predicted the decrease in drainage rate as surface
viscosity increases, as expected from the qualitative models and measured experimentally.
The effect of surface transport was significantly less than that of surface viscosity.
220
5.3.1 Experimental Details
5.3.1.1 Film Formulation
Unless noted otherwise, the experimental work in this chapter involved a model flexible
slabstock PU foam formulation [39] at the instant of mixing (see below):
• 20.00 g VORANOL 3137 (3100 MW polyether copolymer, The Dow Chemical

Company),
• 5.46 g toluene,
• 0.20 g DABCO DC 198 (surfactant Air Products and Chemicals, Inc.)
For simplicity’s sake, chemical reactions were avoided. This was accomplished by
substituting toluene for toluene diisocyanate (TDI) in the formulation. This formulation
had a nominal viscosity of about 0.8 Pa-s.
5.3.1.2 Description of the Experimental Interferometer
The following experimental variables were addressed during the design and construction
of the interferometer:
• control of film area,
• control of the withdrawal rate of the film,
• control of spurious vibration potentially leading to film rupture,
• control of solvent evaporation,
• precise vertical alignment of the film,
• optical control of the interferometric measurement (illumination with plane parallel

light, use of monochromatic light, uniform illumination of the film surface),
• Imaging of the film including magnification, presentation on a video screen, and

video recording capabilities, and
• Precise measurement of film lifetimes.
221
Consideration of these points led to the experimental setup sketched in Figure 5.1.
The film is formed between two narrow blades set by 10 mm apart and supported in a
surrounding frame; a film of 20 mm height could be formed between the blades. The
frame was vertically clamped on an optical bench. A glass cuvette with rectangular
cross section was fabricated with a closely fitting lid through which the clamp rod fits
tightly in order to prevent evaporation of the solvent and at the same time to allow the
cuvette to be lowered and raised to adjust the bulk liquid level or to draw a film. The
cuvette stands on a small pedestal which was driven by a computer-controlled stepper
motor assembly allowing film size control at velocities of the receding or advancing
bulk liquid level up to 25 mm/s. The sample holder assembly was mounted on an
optical bench.
The two nearly plane-parallel surfaces of the film constitute a Fizeau interferometer
which produces interference fringes in the reflected light [40]. The fringes are lines
of constant film thickness. Film drainage data were acquired by generating
monochromatic light by means of an interference filter (λ = 505 nm) or with a HeNe
laser (λ = 632.8 nm).
Figure 5.1 Schematic of the thin liquid film interferometer.
222
Figure 5.2 Depiction of film formation. The film is formed within the boundaries of
the inner frame by the lowering of the liquid level at a controlled rate. The frame and
liquid are within the transparent walls of the enclosed glass cuvette.
5.3.1.3 Film Formation
The process of film formation is depicted in Figure 5.2. Films were formed by lowering
the sample liquid from a point where the vertical frame was completely immersed to a
point where it was only partially immersed. In most experiments, the vertical film so
formed was left in direct contact with the bulk liquid. Films were withdrawn from the
bulk liquid at a rate varying from 0.25 to 50 mm/s.
5.3.2 Qualitative Description of Polyurethane Films
In a typical experiment, stable, vertical, liquid films were formed from the model PU
formulation (see Section 5.3.1.1). These films were stable for two to five minutes. The
series of photographs in Figure 5.3 depicts many of the physical features of these films.
Thirty to sixty seconds after film formation, dark horizontal interference fringes were
observed that initially appeared at the top of the film and steadily moved downward.
Over time, the number of fringes decreased. Flow patterns, including eddy currents,
fingering patterns and swirls, appeared at the bottom and sides of the films and rose
upwards. The rate and amount of these flows decreased as the lifetime of the film increased.
Films were subjected to a rapid raising and lowering of the bulk liquid level. These
motions strongly stimulated the surface flows previously mentioned.
223
Figure 5.3 The visual sequence of a draining film. The first photograph in the
sequence is in the top left hand corner and the sequence of photographs proceeds
clockwise. Photograph 2: one minute after formation. The dark horizontal lines
faintly present are the interference fringes. Photograph 4: 3-5 minutes after film
formation. Fewer fringes are present and span the height of the film. The reduction
in the number of fringes versus Photograph 2 is consistent with a significant amount
of film drainage. Photograph 3: 8-12 minutes after film formation. Photograph 1:
approximately 15 minutes after film formation.
The pattern of horizontal fringes observed on the face of the films suggested a vertical
wedge shape, with the film thickness increasing as one descends the film. The wedge
shape of the vertical PU films has a number of implications for operational PU foam.
Any cell window in PU foam does not have uniform thickness. This non-uniformity has
been reported in at least two studies [24-26, 32]. In addition, it would be expected that
the rupture of the cell window would occur at its thinnest point [24-26, 32].
As seen in Figure 5.3, the interference fringes progress down the face of the film and the
distance between the fringes increases as the film continues to drain. This indicates a
decrease in the film thickness gradient during the drainage of the film. The drainage of
the wedge-shaped film can be visualised in that the sides of the wedge, intersecting at the
224
top of the film, pivot inwards as fluid drains out of the bottom. This is a collapsing
inwards of the wedge.
As the film is draining, interference fringes radiate outwards from the top centre of the
film (photographs 2-4 in Figure 5.3). This radiation suggests that both horizontal and
vertical flow processes are present. These flow processes are driven by both gravity (vertical
flow) and suction into the Plateau borders of the film (horizontal flow). Once the fluid
has entered the Plateau border, it flows down a relatively wide channel into the bulk
liquid. The Plateau borders in these films can be seen in Figure 5.3. They are the dark
regions between the film and the frame. The width of the Plateau channel increases as
one descends the face of the film, giving it roughly a triangular shape. Plateau borders
are also present in operational polyurethane foams. In fact, horizontally-aligned films
within these foams can only drain due to Plateau border suction. The individual Plateau
borders within the PU foam form a network which allows for liquid drainage down the
foam. Ultimately, this network becomes the structural ‘struts’ of the foam.
As reported in the literature, interference fringes in many vertical aqueous films are
horizontal with little curvature. These films also displayed ‘mobile’ surfaces, rapid and
extensive surface flows and rapid rates of drainage [22, 28-30]. These features were all
linked to the presence of a low surface viscosity. Based on our experimental observations,
the PU films stabilised by DABCO DC 198 have low surface viscosities. This conclusion
is supported by reports of measurements of low surface viscosities in polyol solutions
containing silicone polyether surfactants [12, 15, 38].
The phenomena of edge turbulence, fingering and upward flows in aqueous soap films
have been extensively investigated [22, 28-30, 41-46]. These hydrodynamic phenomena
have been defined as marginal regeneration and gravity convection. Marginal regeneration
refers to a process where, simultaneously, thick films are sucked into the Plateau border
and thinner films are pulled out. This exchange results in a net increase of material in
the Plateau border, essentially draining the film. Within the film, after the material
exchange, the new thin spots then migrate upward (gravity convection) until they reach
a height where their thickness equals the film thickness.
Instead of describing these phenomena in PU films as ‘gravity convection ‘, it is proposed

that this flow near the surface of the film is driven by surface tension gradients. These
are examples of Marangoni flows, and would proceed from an area of high surface
tension to one of low surface tension. Marangoni flows are extremely common and one
well-known example is the phenomenon of ‘tears’ in a glass of port wine or brandy. This
view is also gaining some acceptance in the field of aqueous thin liquid films. Stein [42-
44] recently proposed that the flows observed in mobile-surfaced, aqueous soap films
are Marangoni flows.
225
The surface tension gradients necessary to drive this type of flow can arise from three
different physical phenomena: surface tension gradients are necessary to support the
weight of the vertical film, flows in the film or the channel of the Plateau border impose
stresses on the surface monolayer which are balanced by a surface tension gradient, and
extension or compression of the surface layer can create transient surface tension gradients.
Regarding the cell windows of operational PU foam, it is apparent that surface tension
gradients are constantly present, due to all three mechanisms discussed previously. In
particular, the constant stretching of the bubbles during the process of foam growth acts
as a potent stimuli for these flows.
5.3.3 Quantitative Measurement of Film Drainage Rates: Bulk

and Surface Effects
5.3.3.1 A Method to Measure Film Drainage Rates: The ‘Collapsing

Wedge’ Model
The distribution of the interference fringes in a liquid film can be viewed as a contour
map of the film thickness, with each successive fringe representing a section of constant
film thickness (isopach). Therefore, the distance between fringes throughout the film
gives the gradient of film thickness. In order to precisely measure PU film drainage rates,
a physical model correlating the time change in the fringe density (ds/dt; the quantity
that can be measured in the laboratory) to the time change in volume (dV/dt, the film
drainage rate) of the film must be applied.
Qualitatively it appears that the drainage of the film collapsed the sides of the film wedge
inwards. During this collapsing process, the two sides of the wedge act as if they were
hinged together at the top of the film. With this geometric model of film shape, the
drainage rate of the film, dV/dt, can be expressed mathematically by Equation 3.
dV c ds
= WL2 (3)
dt 2 dt
Where V is the film volume, t is time, c is the change in film thickness per interference
fringe, W and L are the film width and height, respectively, and s is the fringe density.
If both sides of Equation 3 are divided by the cross-sectional area (WcsL) of the film at
the bottom Equation 4 is obtained:
226
(1/WScL) dV/dt = L/2s ds/dt (4)
The quantity on the left of Equation 4 is the flux. If it is assumed that the flux is a
hyperbolic function of time, namely,
(1/WScL) dV/dt = b/t + t0 (5)
where b is a drainage constant and t0 is the time where hyperbolic drainage begins.
Solving the differential equation for s yields Equation 6.
2b
s = k0 (t + t0 )
m
with m = − (6)
L
where k0 is the fringe density at t = t0
As Equation 6 shows, a log-log plot of fringe density versus time should be linear for t >
t0 with a slope of m (<0) and an intercept of logs0 = logk0 + mlogt0. This prediction was
realised experimentally with high degrees of precision and accuracy.
Therefore, the instantaneous film drainage rate is explicitly given by Equation 7.
c
dV / dt = WL2 ⋅ mk0 t m −1 = −cWLbk0 t m −1 (7)
2
5.3.3.2 The Effect of Bulk Dynamic Viscosity on Film Drainage Rate
The drainage rate measurement described in Section 5.3.3.1 was novel and required
experimental verification of its accuracy and precision. This was accomplished by
measurement of the dependence of film drainage rate on the reciprocal of bulk viscosity
(see Figure 5.4). The Reynold’s equation (Equation 1) predicts that this correlation should
be linear. As seen in Figure 5.4, a linear correlation was obtained. It should be noted that
this form of the Reynold’s equation assumed an infinite surface viscosity. This condition
was not able to be achieved in practice. However, it was assumed that the surface viscosity
was constant throughout the range of experiments and that Equation 1 was valid under
this condition.
The excellent correlation achieved between film drainage rate and reciprocal bulk viscosity
motivated the measurement of the correlations between drainage rate and surface variables.
227
Figure 5.4 The experimental dependence of film drainage rate on bulk viscosity. The
bulk viscosity was varied by varying the ratio of toluene to polyol in the formulation
5.3.3.3 The Effect of Surface Variables on Film Drainage Rate
5.3.3.3.1 Analysis of Commercial Silicone Surfactants
Initially, the drainage rates of PU films stabilised by various commercial silicone surfactants
were measured. These surfactants are applied in the marketplace to stabilise flexible
slabstock PU foam. These data are given in Table 5.1.
The surfactants listed in Table 5.1 span a range of drainage rates of 1.5 to 2. The
narrowness of this range is not surprising because the PU foam stability (in terms of
foam volume and porosity) achievable with these commercial surfactants does not vary
to a great extent. By comparison, as described in Section 5.3.3.3.2, rigid-surfaced films
have been observed which have drainage rates of less than 1% of those listed in Table
5.1. Within this context, the drainage rates in Table 5.1 are rather fast, consistent with
the previously discussed low surface viscosity of the films. This is also consistent with
228
Table 5.1 A comparison of commercial flexible slabstock PU

foam surfactants in PU thin liquid films (1 pph surfactant)
Surfactant dV/dt x 104 (mm3/min)
(Error ± 10%)
DC 198a 165
DC 5950a 190
a
DC 5039 170
b
L620 173
c
BF2370 107
DC: Dabco
a
Air Products and Chemicals, Inc.
b
Witco Specialties
c
Th. Goldschmidt AG
the consideration that these surfactants have been optimised to provide sufficient drainage
rate to produce porous, flexible slabstock PU foam.
Incidentally, one surfactant investigated (FC 171; 3M Company) gave a significantly

higher drainage rate (271 x 10-3 mm/min) than the surfactants shown in Table 5.1. This
surfactant, a non-ionic fluorocarbon-based material, is not sold as a stabiliser for PU
foam. Although foam tests were not attempted with this stabiliser, one must presume,
based on its high drainage rate, that these foams would be quite unstable.
5.3.3.3.2 The Effect of Surfactant Concentration on Film Drainage Rate
Physical models for the potential effect of surfactant concentration on film drainage rate
have been discussed in detail in Section 5.2. It was predicted that surface tension gradients
and surface viscosity affect film drainage rate. It was expected that the drainage rate would
increase with an increase in surfactant concentration due to the lessening of the intensity of
surface tension gradients. However, It was also expected that the drainage rate would
decrease as the surfactant concentration increased due to the increase of surface viscosity.
This correlation was examined for two different silicone surfactants as illustrated in Figure
5.5. These plots show a maximum in film drainage rate as a function of surfactant
concentration, consistent with the concept that the overall rate is the result of two opposing
229
Figure 5.5 The effect of surfactant concentration on film drainage rate: Comparison of
the two surfactants DC 198 (solid line) and DC 5950 (dotted line) 10 mm high films
were drawn from the standard PU film formulation at a rate of 0.25 mm/s
effects. At lower concentrations, the increase in drainage rate observed with increase in
surfactant concentration is consistent with a decrease in the intensity of surface tension
gradients in the film due to increased bulk-to-surface surfactant flux. The decrease in drainage
rate seen at higher surfactant concentrations is consistent with an increase of surface viscosity.
These conclusions are supported by several published experimental studies.
In their studies of three-phase capillary air slug (bubble) flow, Stebe and Maldarelli [47]
correlated surfactant concentration to equivalent flow rate invoking similar reasoning.
At a higher surfactant concentration, flow rate increased with surfactant concentration,
due to the relief of surface tension gradients at the air bubble surface. When using
protein-based surfactants, retardation of flow due to surface viscous effects (flow rate
decreased with an increase in protein concentration) was observed.
230
Following the work of Kanner and co-workers [37], the drainage of films stabilised by a
TCP was examined. As previously mentioned, they observed a significantly low film
drainage rate and attributed it to the high surface viscosity measured for these solutions.
In studies of high TCP concentrations, rigid-surfaced films with very slow drainage (as
detected by the movement of interference fringes) and surface flows were observed. At
low TCP concentrations, the films were mobile-surfaced and fast draining. These
observations are consistent with the concept that the surface viscosity increases with
surface concentration. Further reinforcement of this concept is given by the data in
Table 5.2. Assuming that surface viscosity is proportional to surfactant concentration,
the inverse dependence of film drainage rate on surface viscosity is quite apparent
from this data.
Table 5.2 The rate of film drainage of PU thin films

as a function of the concentration of TCP
[TCP] dV/dt
(ppm) x104 (mm3/min)
10 69 5
60 31 1
120 33
330 7
ppm: parts per million
Previously, in the literature, the ‘extremes’ of mobile and rigid surfaces were much
discussed without significant mention of ‘intermediate’ behaviour. Intermediate behaviour
was studied here by simple titration of the appropriate amount of TCP into the film
solutions. In this regime, the film drainage rates were intermediate between those of
mobile and rigid-surfaced films, as were the rate and extent of surface flows.
For both Dabco DC 198 and Dabco DC 5950 (Air Products and Chemicals, Inc.), the
surfactant concentration (approximately 1 pph) leading to maximal drainage rate, is
similar to that optimally used in manufactured PU foam. Presuming that the surfactant
concentration needed for effective film stabilisation is similar to that needed for effective
foam stabilisation, it appears that a maximal drainage rate aids in the optimal production
of flexible slabstock polyurethane foam.
231
5.3.3.3.3 The Effect of Surfactant Molecular Structure on Film Drainage Rate
Once the effect of surfactant concentration on film drainage rate had been measured, the
effect of molecular structure was investigated. It was hypothesised that the surfactant
structure would affect the intensity of surface tension gradients within the film and the
surface viscosity. Within this framework, the effect of molecular structure on the diffusion
and surface partition coefficients, and on the degree of intermolecular cohesion in the
surface layer was investigated.
For TCP mentioned in the previous section, an accurate structural characterisation of

the material was not available. However, it was known that it was a complex three-
dimensional siloxane structure, capped by Me3SiO- or -OH units.
By comparing the films prepared from TCP solutions to those from solutions of highly
purified (Me3SiO)8Si8O12, it was deduced that the source of the surface rigidity was the
OH (silanol) groups on TCP. These groups can hydrogen bond to each other, thus forming
a highly cohesive network at the surface and yielding a high surface viscosity. A similar
effect was also noted in aqueous films containing carbohydrate functional organic
surfactants [48]. The source of OH groups in these surfactants are the carbohydrate
functionalities.
These results motivated a more careful look at the specific effects of surfactant structure
on film drainage rate using traditional silicone PU foam stabilisers. In order to accomplish
this, the drainage rates of PU films stabilised by a series of surfactants of the general
molecular structure (Me 3 SiO)(SiMe 2 0) 100 (SiMeRO) 10SiMe 3 (R= -(CH 2) 3 (EO) x
(PO)xOC(O)Me, EO = ethylene oxide, PO= propylene oxide, X= 6, 12, 18, 21, 30) were
investigated. These five surfactants differed only in the length of the alkylene oxide
chains. Therefore, for the rest of this chapter, they will be referred to only by their X
value. Relevant measured physical properties are listed in Table 5.3. Film drainage rate
data is shown in Figure 5.6. Unfortunately, it was not possible to obtain accurate surface
viscosity data for these materials.
Analysis of the data in Table 5.3 and Figure 5.6 begins with four hypotheses regarding
the physical consequences, to a silicone/polyether copolymer, of an increase in polyether
length (X) at constant siloxane chain length. An increase in X leads to a copolymer with:
1) A higher ratio of solvophilicity (through the polyether portions) to solvophobicity

(through the silicone portion) and therefore, a higher solubility in the liquid (polyether/
toluene mixture) phase.
2) A larger solvated volume and therefore a lower diffusion (through the liquid phase)
coefficient.
232
Table 5.3 Characterisation data for silicone surfactants

X Γ∞ × A Kad D
10 2 2 17
(x 10 mol/cm ) (A ) x 10 (cm) x 10 (cm2/s)
11
6 1.76 94 33.2 723

12 1.26 132 22.3 574
18 0.98 169 12.8 424
21 NM NM NM 377
30 1.04 160 21.0 66
× = length of alkylene oxide chains
Γ∞ = surface concentration at surface saturation, also known as the surface adsorption
A = area per molecule at the surface
Kad = surface partition constant
D = diffusion coefficient
NM = not measured
Figure 5.6 Film drainage rate as a function of surfactant concentration and structure
(X = length of alkylene oxide chain)
233
3) A larger area at the liquid/air interface.
4) A larger area of polyether chain cohesion in the interfacial layer. This increase in
cohesion area should result in an increase in cohesion energy per molecule and
therefore, at surface saturation, a higher surface viscosity.
Generally, the experimental data in Table 5.3 are consistent with these hypotheses.
Firstly, the surface partition coefficient, Kad, is the ratio of the surface saturation
concentration (Γ∞) to the overall amount of surfactant needed to saturate the surface
(keeping in mind that a significant amount of the surfactant remains solubilised).
Therefore, at relatively constant Γ∞, Kad should decrease as the solubility of the
copolymer increases. This can be seen in Table 5.3. Secondly, the solvated volumes
were not directly measured; however, the diffusion coefficients were measured and
they decreased as X increased. It is generally known that the diffusion coefficient varies
as the inverse of the solvated volume [49]. From this relationship, one would conclude
that the solvated volumes of the copolymers increased with X. Thirdly, the interfacial
areas of the copolymers generally increased as X increased. Finally, we were not able
to measure the surface viscosities of these materials in solution. However, all of them
yielded mobile-surfaced films. This means that their surface viscosities were relatively
low, as expected.
It is unclear why the X = 30 copolymer did not give data consistent with the expected
trends in the data observed for X = 6-18. It would have been helpful to have had more
data on the X = 21 species; perhaps, the deviations observed for the X = 30 species
would have also been recognisable for the X = 21 data. For X = 30, one possible factor
which could have yielded non-compliant data would have been an unexpected
configuration of the polyether groups. After all, they are quite long (total of 60 monomer
units). Perhaps they assumed an unusual coiled or spiral configuration both in bulk
solution and at the interface. This would be consistent with an unexpected solvated
volume, degree of solvation, interfacial area and area of polyether cohesion. Previous
work with silicone polyethers has demonstrated unexpected results with exceptionally
long polyethers [50].
One goal of this study was to correlate the data in Table 5.3 with the experimental
drainage rate data for these surfactants, displayed in Figure 5.6. In order to interpret
these correlations, the following hypothesis were developed.
• Low values of X correspond to a high tendency of the surfactant to adsorb at the

surface (high Kad) and a large diffusion coefficient (D). This favours rapid relief of
surface tension gradients. Furthermore, the surface viscosity values should be
minimal under these conditions. Therefore, the films should drain rapidly and be
relatively unstable.
234
• As X increases, Kad and D should decrease, which decreases the efficiency of relieving
surface tension gradients. Also, the surface viscosity should increase. Both factors
should cause a relative decrease in film drainage rate and furthermore, an increase in
film stability.
The following conclusions can be made on analysing Figure 5.6.
The profile for X = 6 is rather complex. Ignoring the points at very low concentrations
(which are difficult to interpret), the profile has only the ‘first half’ of the expected
parabolic shape. At moderately low concentrations, the drainage rate increases with
concentration, consistent with the decrease in the intensity of surface tension gradients.
Incidentally, this decrease in gradient is also reflected in the fact that the film lifetimes
decrease in this range. In fact, above a certain concentration, films are too unstable to
allow for the measurement of the drainage rate. This high degree of (Marangoni)
instability, only observed for the X = 6 species, is consistent with an overly-efficient relief
of surface tension gradients in the film. This efficiency is due to the high bulk-to-surface
flux of this surfactant, which itself is due to its high values of Kad and D. At high surface
concentrations, the films could potentially be stabilised by a high surface viscosity.
However, for X = 6, the surface viscosity would be expected to be low, and this is borne
out by the experimental data, i.e., the films are so unstable that drainage rate measurements
could not be made.
The drainage rate for X = 6 should be the highest of any of the surfactants. This is not
confirmed by experiment. It is possible that the films where this would be demonstrated
(at higher surfactant concentrations) were simply too unstable to be investigated.
The expected parabolic shape of the drainage profile is observed for X = 12, and at a
relatively low concentration, as might be expected. These films were more stable than
those exhibited for X = 6, due to a less efficient relief of surface tension gradients. This
would be expected, as Kad and D should be lower than for X = 6. The decrease in drainage
rate at higher concentrations is due to the build up of surface viscosity. A higher surface
viscosity than for X = 6 would be expected, as the area of polyether cohesion has increased.
The drainage rate profile for X = 18 is at a lower value than either X = 6 or X = 12,
consistent with stronger surface tension gradients and higher surface viscosity. The fact
that film stabilities were higher than for either X = 6 or X = 12 is consistent with this
conclusion.
It is intriguing that, for X = 30, the ‘first half’ of the drainage profile is not observed at
all. Perhaps it could exist at very low surfactant concentrations, but these films prematurely
rupture. A sufficiently high concentration of surfactant is necessary at the surface to
allow for the presence of the surface tension gradients that stabilise films in this regime
235
(in other words, ‘high’ but not ‘too high’). These low gradients would result in a high
drainage rate and, a marginally stable film. As the concentration of this surfactant is
increased, the drainage rate is strongly retarded due to the build up of surface viscosity.
Viscous effects would be expected to be particularly strong in this system due to the long
polyether chains, and the resulting large area of cohesion.
Overall, the limitations of analysing these data in terms of simple, qualitative models
motivated the development of more refined, quantitative models of the draining film.
The development of these models is the topic for the next section.
5.4 The Development of Theoretical Models of Vertical, Draining Thin

Liquid Model PU Films
In quite a few of the experiments, there was an extension region in the upper part of the
film that was essentially two-dimensional. In particular, this occurred in the early part
of the experiments (typically several minutes, at least) and in the upper half to two-thirds
of the film for nearly the entire width. Under these circumstances, the interference fringes
were essentially horizontal and parallel. These were also the conditions under which the
exponent for the drainage rate was measured. This leads us to consider two-dimensional
models for film drainage; they can be considered as a cross-sectional slice down the
centre of the film perpendicular to the surface of the film. All of the theory described in
this section will be for this two-dimensional case.
To develop a quantitative model, the problem was approached in stages. The first
model assumed that the surface of the film was wedge-shaped; the narrowing with
time was predicted in the tangentially-immobile case [51]. The film was then modelled
with a deforming surface; the film still thins, but it takes on more complicated shapes
predicted by the solutions of non-linear partial differential equations. These
generalisations have resulted in a series of models that gradually incorporate more of
the experimental behaviour. A few details and some results from these models will
now be discussed.
5.4.1 Rigid-Surfaced Collapsing Wedge Model
The simplest model was a theoretical version of the collapsing film wedge. As discussed
previously (Section 5.3.3.1), the collapsing wedge geometry was imposed on the analysis
of the experimental data to generate instantaneous film drainage rates. Therefore, it
seemed reasonable to use this same shape in the development of the first theoretical
model [51]. This led to the condition that the shape of the film was invariant with
236
time. The other key assumptions applied in the construction of this model were that
all of the flow in the film was downward (parallel flow) and that the surface of the film
was tangentially immobile (infinitely large surface viscosity). Therefore, outside of
surface viscosity, there was no specific surfactant effects on the drainage rate of the
film. In fact, no surfactant transport or concentration gradient effects were incorporated
in the model.
A diagram of the model construction is shown in Figure 5.7. The film shape is represented
by the solid line; the wedge shape that replaces the deforming film shape is sketched with
the dashed line.
Figure 5.7 Schematic representation of the model film studied. The dashed-dotted line
is the centreline of the film; the film is assumed to be symmetric around it. The solid
curve is a sketch of the actual film surface; the dashed line is a wedge approximation
to the film shape. Differences are exaggerated to clarity.
237
Within the wedge, the momentum in the vertical direction is conserved by that component
of the Navier-Stokes equations:
∂w ∂p ∂2 w
ρ = ρg − +μ 2 (8)
∂t ∂z ∂c
To simplify matters, it is assumed that the flow is so slow and gradually changing that
the left hand side of the equation can be neglected. The flat sides of the wedge along
with the slow flow assumption allow the pressure gradient term to be neglected. The
differential equation for the velocity profile in the film is then obtained:
∂2 w ρg
+ =0 (9)
∂x2 μ
The solution to this equation is subject to ∂w/∂x = 0 in the centre of the film and ω = 0 on
the surface of the film, x = k (z, t). The velocity profile is given by
ρg 2
w( x, t ) =
2μ
(k − x2 ) (10)
and the average velocity of the film is then found to be
ρg k2
w= (11)
3μ 4
This equation clearly indicates that drainage of the film is accelerated by increasing
density and inhibited by increasing viscosity.
Further analysis of this model yields a prediction that the slope of the plot of log (fringe
density) against log (time) should be -0.5. These predicted results are in excellent
agreement with experimental results where a rigid-surfaced film was investigated;
experimental data gave a slope of -0.47. For the mobile-surfaced films investigated, the
value of the shape ranged from -0.6 to -0.92; the more negative the value, the faster the
film drainage.
At this point, theory could be developed only for the rigid case; the development of
theory for the mobile cases requires more complicated mathematical models, which are
described next.
238
5.4.2 Deforming Film Models

A schematic of the draining film useful for setting up the mathematical theory is given in
Figure 5.8. The free surface of the film, k(z, t), can now deform along its length with
time, and partial differential equations for this and other dependent variables of interest
will be developed.
The mathematical problems in this section are specified in the following way, unless stated
otherwise. The Navier-Stokes equations govern the motion of the incompressible,
Newtonian fluid inside the film [52]. The film is assumed to be symmetric about its vertical
centreline (the z-axis). On the free surface of the fluid, several equations must be satisfied:
the kinematic condition, and the normal and tangential stress conditions [53, 54]. An
equation governing the transport of surfactant in the free surface by both advection (fluid
Figure 5.8 Schematic representation of the model studied
239
motion) and diffusion also holds [55, 56]. The surface tension, σ (in mks units: N/m), of
the film-air boundary is assumed to vary linearly with the surface concentration, Γ:
∂σ
σ = σm + Γm (Γ − Γm ) (12)
∂Γ
The subscript m denotes the reference values of σ and Γ; these reference values are chosen
for convenience in matching up with experiments. The additional parameters that show
up in the boundary conditions on the free surface are the surface shear viscosity and
surface dilatational viscosity, represented by μs and κs, respectively, and the surface
diffusivity of the surfactant denoted by Ds.
No fluid can enter or exit through the wire frame at the top, and the film surface is
pinned there. At the bottom, the film drains into the bath (or pool) in the cuvette, from
which the film is drawn. The bath is otherwise inert, and it is assumed that the film
shape tends to a static meniscus shape over the bath. This assumption will allow boundary
conditions over the bath to be specified. The details of the mathematical specification of
the problem appear elsewhere [57-60]; in this section, the focus is on simplified models
and comparing results from them with the experimental results discussed previously.
The equations mentioned above will be made dimensionless with the length scales
μV0 σ
d= , D= and l = d1 / 3 D2 / 3 (13)
ρg ρg
d, D and l are the film thickness, the static meniscus radius, and an intermediate scale,
respectively.
The horizontal length scale is d, while the length scale along the film is l . Of particular
importance is that, for the PU solvent of interest here, the ratio of the lengths d/ l is a
small quantity. The ratio
δ 2 ≡ d / l << 1 (14)
is used to reduce the original mathematical fluid dynamics problem to a simpler set of
partial differential equations; the mathematical method is a multiple scale analysis, and
when it is applied to thin fluid layers, it is called lubrication theory. For recent reviews of
this type of approach, see references [29, 61]. We choose
ρgd 2
V0 = (15)
μ
240
as the velocity scale; in mks units, V0 is in m/s. The time scale is l / V0 and the pressure
scale is based on viscous shear, μV0 / ( lδ 4 ). The surface concentration is made
dimensionless with the reference value, Γm.
Several dimensionless groups appear in the non-dimensional equations; these are given
in Table 5.4. These non-dimensional groups serve to highlight the relative importance of
the myriad parameters in the problem; the interpretation of these groups in terms of
ratios of physical forces are also given in Table 5.4. These parameters will be referred to
as appropriate in the following sections.
For the typical experiment of interest, the Reynolds number is very small; this will help
make the simplifications that follow valid. The Péclet number (P) is large; it may be as
large as 104 at the start of some experiments, according to our estimates. In all the
computations presented here, P = 102 will be used. The typical value of δ is 0.1 to 0.2;
the capillary number is then smaller than 10-4. The other quantities will be varied in the
results to follow.
Table 5.4 Table of non-dimensional parameters and their interpretations. The

third column gives an interpretation of the physical forces represented in the
numerator compared to the physical forces represented in the denominator
(Note that in our scalings C = σ6)
Number Definition Comparison of forces
ρV0 l Inertial
Reynolds ℜ=
μ Viscous shear
Modified (κ + μ) V0 / l2 Surface viscous shear

S=
Boussinesq μV0 / d Viscous shear
μV0 Viscous shear

Capillary C=
σm Surface tension
∂σ
Γm Γm δ 2 Shear from concentration gradients
Marangoni M= ∂Γ
Viscous shear
μV0
V0 l Advective transport
Péclet p=v
Ds Diffusive transport
241
5.4.3 Tangentially-Immobile Films
For high concentrations of some TCP in PU, the surfactant develops structure on the
film surface and the surface of the film still deforms but doesn’t move tangentially. This
‘rigid’ case [22] is the slow draining limit of the experiment. In that case, the tangential
stress condition may be replaced by the condition that the tangential velocity component
is zero. We have been able to show mathematically that this case is achieved in the limit
of large surface viscosity [59, 60] or S → ∞; this will be discussed further in the next
section.
When lubrication theory is used in this context, a single, nonlinear partial differential
equation for the film shape k(z,t) is obtained. In one approach, which is called the
‘whole film’ model, the equation obtained is:
⎡k ⎤
kt + ⎢ 3 (κ z + 1)⎥ = 0 (16)
⎣3 ⎦z
which holds over the domain 0 < z < L. The subscripts t and z denote partial
differentiation; for example κz = δk/δz. Here
kzz
κ=
(1 + δ k ) (17)
3 /2
4 2
z
is the curvature of the film. At the top of the film, z = 0, the film is pinned (k(0,t) = 1)
and no fluid leaves or enters, by requiring that
κ z = −1 (18)
At the bottom of the film, we specify the slope, kz(L,t) = C, and the second derivative is
specified via
⎛ 1 ⎞
kzz (L,t ) = 2⎜ 2 −
C
( )
3 /2
⎟ 1+ δ C ≡ s1
4 2
(19)
⎝δ 1+ δ C ⎠
4 2
This approach is based on methods for including the static meniscus in film models that
have been developed by Ruschak [62] and Kheshgi and co-workers [63]; equation (12) is
a first integral of the equation for the static meniscus that is the surface of the bath.
242
The initial condition used for all calculations was a linear shape for k. This was a
convenient shape, and for later times in the computations, the results are rather
insensitive to the initial conditions. This problem is readily solved using numerical
methods described in references [57].
Numerical results are given in Figure 5.9; one can see in the figure that distinct regions of
the film developed: (i) a meniscus at the top of the film (at the wire frame); (ii) a long flat
middle region where effects from the average surface tension were negligible; (iii) a region
where bumps and dips developed near the bottom of the film and (iv) a static meniscus at
the bottom of the film where it joined the bath.
Figure 5.9 Film shapes k(z,t) versus z with L = 37.5, h = 0.05, kz(L) = 5 and δ = 0.2.
The initial slope of the film was 0.23
243
Figure 5.10 Computed thickness for models without and with surface tension, solid and
dashed lines, respectively, at t = 15 on the right and t = 231.9 on the left;
here δ = 0.25. The case with surface tension is computed with kz(L,t) = 0 and neglecting
all terms with d in equations (17) and (using C = 0 in Equation (19)); see [57] for details
A number of interesting possibilities arise. The bumps and dips at the bottom of this
film could be the precursor to complicated three-dimensional behaviour observed at the
bottom of films in experiments. Only further work will verify this conjecture, and we are
currently pursuing that line of inquiry.
The long middle region of the film offers the possibility of still further simplification. If
one rescales the variables in the problem again, a much simpler equation for the (rescaled)
free surface shape K(Z,T) arises, which we shall call the ‘flat film’ model. This model is
244
KT + K 2 K z = 0 (20)
with the single boundary condition specifying K(0,T). Here Z =z/δ and T =t/δ are the
rescaled space and time variables, respectively. Solutions found numerically for the film
shapes from Equation (20) and a more complicated model for the film shape [57] are
given in Figure 5.10. As time increases, the agreement between the approximations
improves. In the middle part of the film, no matter which simplification is used, the
numerical results indicate that the film is flattening out with t-1/2 behaviour at long times.
This simple equation also has an exact solution, which has similarity behaviour for long
times given by K = Z / T [57, 61]. Similar solutions have been found by Mysels and
co-workers [22] and Moriarty and co-workers [64]. In this way, it can be found
analytically that the rate of flattening of the film is proportional to t-1/2 for long times, in
good agreement with the slowest-draining experimental case of t-0.47.
Based on that success, this kind of simplification will be attempted with more complicated
models to see if similar results can be achieved.
5.4.4 Finite Surface Viscosity
When there is finite surface viscosity, the surface of the film is mobile. Lubrication theory
for our vertical draining film gives a system of two partial differential equations describing
the evolution of the film surface k(z,t) and the velocity of the fluid at the surface w(S)(z,t).
These equations are
⎡ k3 ⎤
kt + ⎢ kw( s ) +
3
(1 + κ z )⎥ = 0 (21)
⎣ ⎦z
k
wzz( s ) +
NS
(1 + κ z ) = 0 (22)
Here
1
N≡ (23)
1 + δ 4 kz2
The boundary conditions at the top are
k(0, t) = 1, κ z (0, t) = −1 and w ( s ) (0, t) = 0 (24)
245
and at the bottom are
kz (L,t) = C, kzz (L,t) = s1 and w ( s ) (L,t) = 0 (25)
Here C is the specified slope and a consistent s1 can be calculated with the first integral
of the equilibrium meniscus shape [62, 63], as in the rigid case discussed above. In
Equations (21) and (24), κ is the curvature of the film given in Equation (27).
Previous work [62, 63] has shown that it is possible to keep the full curvature in
the normal and tangential stress conditions and integrate the partial differential
equation for the free surface k through the matching region (where the film meets
the bath) onto the static meniscus; this model relies on those results. While we do
not rigorously apply matched asymptotic expansions in this work, the equations
contain all of the terms necessary to match the film onto a static meniscus (for the
bath surface) and it has been shown that the terms neglected are uniformly small
for δ<<1 [65].
By introducing surface velocity, w(S) (z,t), as a dependent variable in the model, we

avoid computing a fifth order derivative of k. This formulation greatly simplifies
our task; a complete description of the above derivation can be found in references
[58, 60, 65]. During this work such a formulation was applied in a similar situation
[66, 67].
Some computed results are shown in Figures 5.11 and 5.12. For large S, the film
drains slowly; the downward parabolic shape in the middle region (Figure 5.11; free
surface shapes for varying S) agrees with the typical rigid film profiles given in Chapter
III of Mysels and co-workers [22]. In the limit of S → ∞, w(S) approaches zero along
the whole film and the free surface shapes tend to that of the tangentially-immobile
case [57]. It is also found that for very large S, the film thickness in the middle
region tends to decrease with the power law t -0.5 as before; this is very close to the
experimental rate of t-0.47 obtained at Dow Corning [68] for their most rigid film and
agrees with results from Mysels and co-workers [22]. As S decreases, drainage is
much faster and the film thins more rapidly (Figure 5.11); free surface shapes for
smaller S, take on the typical shapes for mobile films given in Chapter IV of Mysels
and co-workers [22]. In the limit of small S, t-1 thinning in the middle of the film is
found which agrees well with the maximum experimental rate of t-0.92. This model is
able to span the film drainage behaviour from rigid to mobile films.
If the simplification for the flat middle part of the film is pursued. In that case, the
simplified equations become
246
Figure 5.11 Film shape at t = 16 for several values of S (shown in the upper right).
The film is much thinner for small values of S because the free surface is mobile. For
large values of S, the free surface becomes tangentially immobile.
⎡ K3 ⎤
KT + ⎢ KW ( s ) + ⎥ =0 (26)
⎣ 3 ⎦z
( s) K
Wzz + =0 (27)
S
Once again the capitalised variables are rescaled versions of those in Equations (25-29)
[60]. These are subject to the boundary conditions:
247
Figure 5.12 w(s) with t = 16 and kz(L,t) - 10 varying S shown in the upper right. The
surface velocity decreases as S increases
K = W ( s ) = 0, at Z = 0 (28)
and WZ( s ) = 0, at Z = L (29)
The initial condition for K is
K(Z, 0) = 1 + 0.23Z (30)
and a consistent W(s)(Z,0) is found from its equation. The consistent value of W(S)(Z,0)
is required for the numerical solution of the problem [60].
248
By studying these equations for large and small S, the slow and fast draining limits of the
experiment have been obtained using analytical expressions [60]. For large S, solutions
of the following form are found:
f1 (Z) f (Z)
K≈ 1 /2
, and W ( s ) ≈ 2 1 / 2 (31)
T T
where f1(Z) and f2(Z) satisfy ordinary differential equations. The solutions approximate
computed solutions for the rigid film case very well. In this way the rigid case for large
surface viscosity within lubrication theory is analytically recovered. For small S, we can
find solutions of the form
f3 (Z) f (Z)
K≈ , and W ( s ) ≈ 4 (32)
T T
where f3(Z) and f4(Z) also satisfy ordinary differential equations. In this way, the fast
draining limit of the experiments, where the measured exponents for the fastest thinning
case are -0.92, is analytically recovered.
Surfactant transport will now be included in the model, in an effort to obtain intermediate
thinning rates as observed experimentally.
5.4.5 Adding Surfactant Transport
Surfactant transport is also important in the vertical draining film; surfactant concentration
gradients may develop, which may in turn strongly affect the fluid flow via the Marangoni
effect. When surfactant transport is considered, lubrication theory then gives three
nonlinear partial differential equations for the free surface shape k(z,t), the surface velocity
w(S)(z,t) and the surface concentration of surfactant Γ(z,t). The mathematical problem
to be solved for these dependent variables is:
⎡ k3 ⎤
k2 + ⎢ kw( s ) + (1 + κ z ) ⎥ = 0 (33)
⎣ 3 ⎦z
k M
wzz( s ) + (1 + κ z ) + 2 Γz = 0 (34)
NS N S
249
⎡ 1 ⎤
Γt + N 2 ⎢Γw ( s ) − N 2 Γz ⎥ = 0 (35)
⎣ P ⎦z
inside the film. Boundary conditions are, at the top:
k(0, t) = 1, w ( s ) (0, t) = Γz (0, t) = 0, κ z (0, t) = −1 (36)
and at the bottom:
kz (L,t) = C, kzz (L,t) = s1 and w ( s ) (L,t) = Γz (L,t) = 0 (37)
where L is the lower end of the computational domain; C is specified and a consistent s1
can be calculated with the first integral of the equilibrium meniscus shape [62, 63], as
discussed previously.
Some normalisation factors in the surface transport equation for G that ordinarily would
become unity in lubrication theory at leading order have also been retained. While we
do not rigorously apply matched asymptotic expansions in this work, the equations
contain all of the terms necessary to match the film onto a static meniscus (for the bath
surface) and it has been shown that the terms neglected are small for δ<<1 [65].
Marangoni effects have a substantial impact for smaller values of S, retarding surface
drainage and enhancing film thickness; Figure 5.13 shows free surface shapes for several
M with S = P = 102 and δ = 0.1. For a small M, the Marangoni effect is too weak to retard
drainage and the film thins rapidly. As M increases, the Marangoni effect become more
prominent, retarding drainage and the film is considerably thicker at the same time in
the computation. As M → ∞, w(S) → 0 all along the film and the surface becomes rigid.
A rigid fluid surface associated with a large Marangoni number was observed in a levelling
problem [69] and in a similar geometry to this work.
Interesting free surface shape features are shown in Figure 5.14, for M = -10, S = 102
with varying t. There are parts of the free surface shape that appear to be draining
rapidly, as if they are mobile, and other parts that drain slowly, as if they were rigid-
surfaced. Concave-out profiles above an upward-propagating wave indicate a mobile
surface while an essentially downward-parabolic profile following the wave indicates a
rigid surface. These assertions are supported by the thinning rates of t-1 above the wave
and t-1/2 below it. The wave that separates the two regions is driven by surface tension
gradients that are shown in Figure 5.15. The localised gradient of the surfactant
concentration on the surface is sufficient to drag fluid up the film; the gradient is preserved
250
Figure 5.13 Film shape at t = 16 with S = 102 fixed for several values of M (shown
in the upper right). The film is much thinner for small values of M. For large values
of M, Marangoni effects are stronger, drainage is retarded and the free surface
becomes tangentially immobile.
because the Péclet number is large, and so it is not smeared out by diffusion. The associated
surface velocity profiles are shown in Figure 5.16; the negative surface velocity clearly
shows that fluid is moving up the film on its surface, as a result of the Marangoni effect.
The wave seen in Figure 5.14 propagates up the entire length of the film. Similar behaviour
is seen in the experiments of Snow and co-workers [70, 71] with PU films, where what
appears to be bumps propagate up the edges of the film. On that basis, it is believed that
the wave observed may be related to those structures observed in the three-dimensional
films. Work is currently being done to verify this conjecture.
251
Figure 5.14 Film shape with S = 102 and M = -10 fixed for several values of time t
(shown in the upper right). A wave driven by surface tension gradients propagates up
the film. Thinning proportional to t-1 and concave-out profiles above the propagating
wave indicate a mobile surface; below the wave, t1/2 thinning and the downward
parabolic shape indicate a rigid surface.
If S < 102, it is found that the film drainage is typically too rapid to allow for much effect
from surface tension gradients (and thus Marangoni stresses). For S > 104, we find that
the films behave, in large part, as if they were rigid [70]. It is clear that the maximum
impact of the Marangoni effect occurs at an intermediate value of the surface viscosity.
These results lend support to the assertion that the greatest foam stability occurs when
the Marangoni and surface viscous effects are at intermediate value, as given in the first
section of this chapter.
252
Figure 5.15 Surfactant distribution with S = 102 and M = -10 fixed for several values
of time t (shown in the upper right). The surface tension gradients driving the wave up
the film are easily seen.
253
Figure 5.16 Surface velocities with S = 102 and M = -10 fixed for several values of
time t (shown in the upper right). Negative values indicate flow up the film, and flow
up the film is caused by the surfactant concentration gradients.
5.5 Summary
The stabilising behaviour of silicone surfactants during the formation of PU foam can be
investigated in detail, both experimentally and theoretically by the use of a foam model
system, specifically vertical, thin liquid PU films. These films were investigated by a
combination of direct observation and interferometric measurements. The formation and
temporal evolution of structures on the surface of the film, including fingering patterns, was
a result of the Marangoni effect. Experimentally, these films demonstrate a wedge shape and
the gravity-driven drainage of these films causes a collapsing inwards of the wedge.
The evolution of structures and the drainage of these films were functions of the
concentration and molecular structures of the surfactants. The two film physical
254
parameters correlated to film structures, film drainage and the properties of the surfactant
are: (1) the strength and lifetime of surface tension gradients, (2) the surface viscosity.
Two extremes of film behaviour were identified. Firstly, a rigid-surfaced film where the
rate of drainage and structural evolution were low. Secondly, a mobile-surfaced film
where the rate of drainage and structural evolution were high. Intermediate cases were
also detected and measured.
The theoretical and numerical model for vertical liquid film drainage that has been
developed reproduces a number of features described in these experiments. These features
include film shapes and thinning rates.
Complex, time-dependent, three-dimensional structures were observed in the region where

the film meets the bath (away from the edges of the film). It is also believed that the
localised bumps and dips at the bottom of the film in these two-dimensional results, may
be the precursor of those observed motions in the experiments; this notion is currently
being investigated.
Future work will include adding intermolecular forces that act across the film and
extending our work to three-dimensions in order to make closer comparison with
experiment. Furthermore we endeavor to obtain accurate independent measurements of
surface viscosity and correlate them to both film properties and surfactant parameters.
Acknowledgements
RJB and SN gratefully acknowledge support from Dow Corning Corporation for this work.
RJB is also grateful for the support of the National Science Foundation via grants DMS-
9623092 and DMS-9631287.
SAS and UCP would like to thank Ben Vesper, Mike Owen, Andy Goodwin, John Frey,
Randy Hill, Dave Battice, Mike Stanga, Kathy Goudie, Joan Sudbury-Holtshlag, Mike
Reuter, and Gloria Lyon for many helpful discussions and their support.
References
1. D. Reed, Urethanes Technology, 1995, 11, 6, 22.
2. S. A. Snow and R. E. Stevens in Silicone Surfactants, Surfactant Sciences Series,

#86, Ed., R. M. Hill, Marcel Dekker, New York, 1999, Chapter 5.
255
3. B. Kanner, W. G. Reid and I. H. Petersen, Industrial Engineering Chemistry,

Product Research & Design, 1967, 6, 2, 88.
4. R. J. Boudreau, Modern Plastics, 1967, 44, 5, 133.
5. E. G. Schwarz in Applied Polymer Symposia #14: Silicone Technology, John

Wiley and Sons, New York, 1970, p.71.
6. B. Kanner, E. D. Goddard and R. D. Kulkarni, Presented at the SPI and FSK

Conference on Cellular and Non-cellular Polyurethanes, Strasbourg, France,
1980, p.647.
7. B. Kanner, and T. G. Decker, Journal of Cellular Plastics 1969, 5, 1, 32.
8. T. E. Lipatova, S. H. G. Vengerovskaya, A. E. Feinerman and L. S. Sheinina,

Journal of Polymer Science: Polymer Chemistry Edition, 1983, 21, 7, 2085.
9. T. C. Kendrick, B. M. Kingston, N. C. Lloyd and M. J. Owen, Journal of Colloid

and Interface Science, 1967, 24, 2, 135.
10. T. C. Kendrick and M. J. Owen, Presented at the Chimica Physica Applied

Practical Ag. Surfactant C.R. Congress International Detergents, 1968, 2, 1, 571.
11. E. G. Dubyaga, A. B. Komarova and O. G. Tarakanov, Colloid Journal of the

USSR, 1986, 4, 881.
12. M. J. Owen and T. C. Kendrick, Journal of Colloid and Interface Science, 1968,
27, 1, 46.
13. M. Dahm, Publication No.1462 of the National Academy of Science, National

Research Council, 1966, 52.
14. M. J. Owen, T. C. Kendrick, B. M. Kingston and N. C. Lloyd, Journal of Colloid

and Interface Science, 1967, 24, 2, 141.
15. J. Ritter, J. E. Dubjaga and A. B. Komarowa, Plaste und Kautschuk 1979, 26, 11,
624.
16. L. I. Kopusov and V. V. Zharkov, International Polymer Science and Technology,

1981, 8, 3, T34.
17. G. Rossmy, G. Sanger and H. Seyffert, VDI-Berichte, 1972, 182, 173.
18. H. Hamann and J. Ritter, Plaste und Kautschuk, 1983, 30, 7, 364.
256



22. K. J. Mysels, K. Shinoda and S. P. Frankel in Soap Films-Studies of their Thinning

and a Bibliography, Pergamon Press, New York, 1959.
23. D. F. Evans and H. Wennertröm, The Colloidal Domain, VCH Publishers, New
York, 1994, p.55.
24. R. Neff, Reactive Processing of Flexible Polyurethane Foam, University of

Minnesota, USA, 1995, [Ph.D Thesis].
25. X. Zhang, Role of Silicone Surfactant in Polyurethane Foaming Process,

University of Minnesota, USA, 1998, [Ph.D Thesis].
26. K. Yasunaga, R. A. Neff, X. D. Zhang and C. W. Macosko, Journal of Cellular

Plastics, 1996, 32, 5, 427.
27. S. A. Snow, W. N. Fenton and M. J. Owen, Journal of Cellular Plastics, 1990, 26,
2, 172.
28. J. S. Clunie, J. F. Goodman and B. T Ingram, Surface and Colloid Science, 1971,
3, 167.
29. I. B. Ivanov, in Thin Liquid Films, Surfactant Science Series No.29, Marcel
Dekker Inc., New York, 1988.
30. R. J. Pugh, Advances in Colloid and Interface Science, 1996, 64, 0, 67.
31. L. D. Artavia, A Model for Low Density Foams, University of Minnesota, USA,
1991, [Ph.D Thesis].
32. K. Akabori, and K. Fujimoto, International Progress in Urethanes, 1980, 2, 41.
33. C. A. Miller and P. Neogi, Interfacial Phenomena, Surfactant Science Series,

Volume 17 Marcel Dekker, Inc., New York, 1985, p.196 and p.243-262.
257
34. R. M. Herrington, and R. B. Turner, Advances in Urethane Science and

Technology, 1992, 11, 1.
35. A. J. De Vries, Recueil, 1958, 77, 383.
36. I. B. Ivanov, in Thin Liquid Films, Surfactant Science Series No.29, Marcel
Dekker Inc., New York, 1988, p.419.
37. B. Kanner, B. Prokai, C. S. Eschbach and G. J. Murphy, Journal of Cellular

Plastics, 1979, 15, 6, 315.
38. M. J. Owen, Industrial Engineering Chemistry, Product Research and

Development, 1980, 19, 67.
39. R. Herrington, K. Hock, Flexible Polyurethane Foams, Dow Plastics, Midland,

MI, 1991, 9.
40. Photonics Dictionary, Volume 3, The Photonics Design & Applications

Handbook, in the chapter on ‘Interpretation of Interferograms’. Laurin
Publishing Co., Oakbrook Terrace, IL, 1991.
41 J. B. M. Hudales and H. N. Stein in The Structure, Dynamics and Equilibrium

Properties of Colloidal Systems, Eds., D. M. Bloor and E. Wyn-Jones, Kluwer
Academic Publishers, The Netherlands, 1990, 549.
42. J. B. M. Hudales and H. N. Stein, Journal of Colloid and Interface Science, 1991,
138, 2, 354.
43. H. N. Stein in Surfactants in Solution, Volume 11, Eds., K. L. Mittal and D. O.

Shah, Plenum Press, New York, 1991, 481.
44. H. N. Stein, Advances in Colloid and Interface Science, 1991, 34, 175.
45. K. Koczo, J. K. Koczone and D. T. Wasan, Journal of Colloid and Interface

Science, 1994, 166, 1, 225.
46. J. B. M. Hudales and H. N. Stein, Journal of Colloid and Interface Science, 1990,
137, 2, 512.
47. K. J. Stebe and C. Maldarelli, Journal of Colloid and Interface Science, 1994,
163, 1, 177.
48. S. A. Snow, B. M. Nugent and F. L. Baines, Unreported observations.
258
49. Principles of Colloid and Surface Chemistry, 2nd Edition, Ed., P. C. Heimenz,
Marcel Dekker, Inc., New York, 1986, p.65 and p.83.
50. T. E. Gentle and S. A. Snow, Langmuir, 1995, 11, 2906.
51. U. C. Pernisz and S. A. Snow, The Drainage of Liquid Polyurethane Films, Dow
Corning Corporation Research Report, 1999, 1999-I000-46182, Midland, MI.
52. G. K. Bachelor, An Introduction to Fluid Dynamics, Cambridge University Press,

Cambridge, 1987.
53. D. A. Edwards, H. Brenner and D. T. Wasan, Interfacial Transport Processes and

Rheology, Butterworth-Heinemann, Boston, 1991.
54. J. C. Slattery, Interfacial Transport Phenomena, Springer-Verlag, New York,

1990.
55. H. A. Stone, Physics of Fluids A, 1990, 2, 1, 111.
56. H. Wong, D. Rumschitzki and C. Maldarelli, Physics of Fluids, 1996, 8, 11,

3203.
57. R. J. Braun, S. A. Snow and U. C. Pernisz, Journal of Colloid and Interface

Science, 1999, 219, 2, 225.
58. S. Naire, R. J. Braun and S. A. Snow, Dow Corning Corporation Research

Report, 1999, 1999-I0000-47199.
59. S. Naire, R. J. Braun and S. A. Snow, Journal of Colloid and Interface Science,
2000, 230, 1, 91 .
60. S. Naire, R. J. Braun and S. A. Snow, SIAM Journal on Applied Mathematics,

2000, 61, 3, 889.
61. A. Oron, S. H. Davis and G. B. Bankoff, Reviews of Modern Physics, 1997, 69,
931.
62. K. J. Ruschak, AIChE Journal, 1978, 24, 705.
63. H. S. Kheshgi, S. F. Kistler and L. E. Scriven, Chemical Engineering and Science,

1992, 47, 683.
64. J. A. Moriarty, L.W. Schwartz and E.O. Tuck, Physics of Fluids A, 1991, 3, 5,
733.
259
65. S. Naire, R. J. Braun and S. A. Snow, An Insoluble Surfactant Model for a

Vertical Draining Free Film II. Film Plus Meniscus in preparation, 2000.
66. L. W. Schwartz and R. V. Roy, Journal of Colloid and Interface Science, 1999,
218, 309.
67. O. E. Jensen, Physics of Fluids, 1994, 6, 3, 1084.
68. S. A. Snow, B. M. Nugent and U.C. Pernisz, Dow Corning Corporation Research
Report, 1996, 1996-I0000-42699.
69. L. W. Schwartz, R. A. Cairncross and D. E. Weidner, Physics of Fluids, 1996, 8,

7, 1693.
70. S. A. Snow, U. C. Pernisz and R.E. Stevens, Dow Corning Corporation Research
Report 1995, 1995-I0000-40859.
71. S. A. Snow, U. C. Pernisz and R. E. Stevens, Presented at the Polyurethanes Expo

‘98, Dallas, TX, 1998, p.217.
260
6
Synthesis and Characterisation of Aqueous
Hybrid Polyurethane-Urea-Acrylic/Styrene
Polymer Dispersions
Janusz Kozakiewicz, Anita Koncka-Foland, Jan Skarzynski
and Izabella Legocka
6.1 Preface
Because of several limitations in using solvent-based systems worldwide, there is a growing

demand for new types of aqueous polymer dispersions for a wide application range (coatings,
adhesives, leather or textile finishing compounds). Especially interesting seems to be combining
the excellent application properties of vinyl/acrylic polymer and copolymer dispersions such
as adhesion, suitable viscosity, high solids content and surface wettability with excellent
properties of films made of polyurethane dispersions (DPUR) such as mechanical strength,
elasticity, solvent resistance and abrasion resistance. Since blending of both types of dispersions
did not result in truly positive effects, the solution of choice must be synthesis of combined
(hybrid) dispersion systems containing both polymers. This chapter will be devoted to a
description of methods of synthesis and a discussion of the structure/properties relationships
of such systems, especially when applied as coatings.
6.2 Introduction
6.2.1 General Considerations
There are strict ecological limitations relating to allowable volatile organic compounds
(VOC) content in coatings introduced in many regions and countries, e.g., the California
Rule of 1995 [1] or special provisions in the EU, and which force the manufacturers to
search for new, more environment-friendly formulations for particular products which
usually requires replacing of the substantial binder (polymer or resin). Undoubtedly the
products for which the development has been the most significant in the field of coatings
over the last few decades are aqueous dispersion-based and powder coatings. In the
former group, DPUR, which are presently being widely used as binders for coating
formulations have already taken a leading position [2-5] and compete successfully with
acrylic dispersions despite the distinctly higher market prices. Both blends of DPUR and
acrylic dispersions [6], and (recently) hybrid acrylic-urethane dispersions [7-12], obtained
by synthesis, and not simple blending are now available. The latter products are much
261
more interesting from both a scientific and practical point of view since the synthesis of
a hybrid system may lead to new polymer architectures which may result in considerable
improvement of properties. Especially attractive is the possibility of synthesising
interpenetrating polymer network (IPN) systems based on polyurethanes and acrylic
polymers using this principle since it has been shown that in such systems synergistic
effects may occur [12], i.e., the properties of a hybrid may be better than those of a blend
of its components. At the same time, hybrid dispersion particles usually have quite complex
morphology (in most cases a ‘core-shell’ type) which affects properties of dispersions
and films and coatings made of them [13].
If a comparison were made between hybrid dispersion systems taking into account the
kind of dispersion particles they contain, it would appear that the best properties should
generally be observed for systems obtained by synthesis for which the particles have a
uniform structure (they may be called ‘true hybrid’ particles) and the worst – for simple
blends of the two dispersions [14] (see Figure 6.1).
Obviously, both types of dispersion particle morphology presented in Figure 6.1 (‘core-
shell’ and ‘true hybrid’) should be considered as idealised cases. In practice, a variety of
different particle morphologies may be observed. Three of them are shown in Figure 6.2.
The most important factor that affects the morphology of hybrid dispersion particles
seems to be the method of preparation of such hybrids.
Generally, the methods of preparation of aqueous hybrid polymer dispersions may be

classified into four groups [17]:
1) blending of two dispersions

(a) addition of polymer A dispersion to polymer B dispersion
(b) addition of polymer B dispersion to polymer A dispersion
2) synthesis of polymer A in a dispersion of polymer B
3) synthesis of polymer B in a dispersion of polymer A
4) ‘in situ’ preparation of hybrid dispersions

(a) co-emulsifying of polymers A and B in water
(b) co-emulsifying the mixture of polymers A and B
(c) co-emulsifying the system consisting of polymers A and B:
• IPN composed of polymers A and B (or a precursor of such IPN)
• chemically linked polymers A and B (or a precursor of such system)
262
Synthesis and Characterisation of Aqueous Hybrid Polyurethane-Urea…
a) Blend of dispersions
⇓
no synergistic effect
• poor stability
• matte and hazy films and coatings
• always two Tgs
• poor mechanical properties of films
b) ‘Core-shell’ c) ‘True-hybrid’
⇓ ⇓
synergistic effect possible synergistic effect probable
• good stability • excellent stability
• usually matte and hazy films and • usually glossy and transparent films
coatings and coatings
• usually two Tgs • usually one Tg
• good mechanical properties of films • excellent mechanical properties of films
Figure 6.1 Comparison of hybrid dispersion systems obtained by (a) blending, (b) and
(c) by synthesis, taking into account particle type.
263
‘engulfed’ or ‘englued’ ‘gradient’ morphology [15] ‘fruit-cake’ morphology

morphology [15] (the (there is a gradient of [16] (particles of one
particles of one polymer concentration of one polymer are distributed
are ‘glued’ to the polymer in the other in the in a matrix of the other)
particles of the other) hybrid particle)
Figure 6.2 Examples of different particle morphologies of hybrid dispersions obtained

by synthesis (such morphologies may be considered intermediate between ‘core-shell’
and ‘true hybrid’ morphology shown in Figure 6.1).
In practice, methods (2) and (3) seem to be the most commonly used. Recently, yet
another method of preparation of hybrid polymer dispersions, called an ‘active blending’
has been reported [18]. The components of such ‘active blends’ or ‘active mixtures’
remain inactive when in the presence of water, and cross-react during film formation.
The other factors that may influence hybrid dispersion particle morphology will be
discussed in detail in Section 6.3.2 of this Chapter.
6.2.2 Acrylic Dispersions and Polyurethane Dispersions (DPUR)
Aqueous acrylic dispersions have been used as binders for coatings for over 60 years.
Their main advantages include: low cost and excellent tolerance of additives or pigments;
however, they have several drawbacks such as the presence of relatively large amounts of
water-sensitive additives (protective colloids, emulsifiers, etc.) and the need to use
coalescing agents when a continuous film is desired.
Aqueous DPUR appeared on the market much later (in the 1960s), and after only a couple of
years achieved the quality that allowed them to be widely applied as coating binders. Substantial
advantages of DPUR include excellent mechanical properties and solvent resistance. Their
drawbacks are relatively high cost and poor tolerance of additives and pigments.
264
(a)
(b)
- polyol chain
- hydrophilic moiety
- hard segment (urethane or urea)
Figure 6.3 Main structures of polyurethane or polyurethane-urea chain in DPUR.

(a) Hydrophilic groups are not incorporated into the polymer chain (are present as
pendant groups); (b) Hydrophilic groups are incorporated into the polymer chain
Methods of preparation of aqueous acrylic dispersions are well known [19] and will
not be discussed here. Emulsion polymerisation of acrylic monomers is usually carried
out using a water-soluble initiator or a ‘redox’ system. In this process, relatively high
levels (up to several %) of emulsifiers and protective colloids are used. The dispersed
polymer generally has a linear structure and a high molecular weight (MW). The
properties of dispersions and films are mostly affected by the kind of monomer(s)
used [20].
DPUR can be prepared in many ways [21, 22], which eventually lead to one of the structures
(polyurethane or polyurethane-urea) shown in Figure 6.3.
In practice, the structures shown in Figure 6.3 are partly or fully crosslinked. The two
main methods which lead to these structures are the ‘acetone process’ (historically older)
[23] and the ‘prepolymer-ionomer process’ [24] that is commonly used to manufacture
DPUR at present. A combination of these two methods can also be used.
In the ‘acetone process’, the first step is the synthesis of NCO-terminated urethane
prepolymer which is then dissolved in acetone and reacted with a di-hydroxy or di-
amino compound containing groups which are the precursors of ionic groups, e.g., -SO3,
-COOH, N≡. The next steps are the emulsification of the resulting product in water
combined with the formation of ionic groups and distillation of acetone.
265
In the ‘prepolymer-ionomer process’, the compound which contains the moieties which
are the precursors of ionic groups is incorporated in the polymer chain already at the
stage of urethane prepolymer formation. Then they are neutralised, which results in the
formation of a ‘prepolymer-ionomer’ which is emulsified in water and eventually
crosslinked. In this process, the prepolymer-ionomer is usually dissolved in a small amount
of water-miscible solvent of high boiling point, e.g., N-methylpyrolidone, which plays
the role of coalescing agent in the process of film formation. It is then possible to obtain
DPUR which contain either ‘cationic DPUR’ with a pH of less than 7 (cationic moieties
are attached to the polyurethane or polyurethane-urea chain) or ‘anionic DPUR’ with a
pH of greater than 7 (anionic moieties are attached to the polyurethane or polyurethane-
urea chain). If non ionic hydrophilic moieties are attached to or incorporated in the
polyurethane or polyurethane-urea chain, then a ‘nonionic DPUR’ may be obtained.
Properties of DPUR depend on several factors. The most important are structure of the
polyurethane or polyurethane-urea chain, degree of crosslinking and the amount of
coalescing agent [25].
6.2.3 Hybrid Acrylic-Urethane Dispersions
Information on the preparation of hybrid acrylic-urethane dispersions by synthesis,

published so far is quite scarce. More detailed data on this process are available only in
the patent literature.
The basic process was first patented by Inmont, USA, in 1982 [9]. They simply claimed
polymerisation of vinyl polymers in DPUR. In 1986, a patent for another method of
preparation of hybrid acrylic-urethane dispersions (diluting of prepolymer-ionomer with
monomers, emulsifying the resulting solution in water and polymerisation) was granted
to Witco, USA [26].
In subsequent years the number of patents dealing with hybrid acrylic-urethane dispersions
increased rapidly, and approximately 30 patents have been granted so far worldwide,
the majority in Japan.
Despite the large number of patents, at the time acrylic-urethane hybrid dispersions entered
the market (in about 1990), their properties, and specifically their structure/properties
relationships and particle morphology, had not been described in the scientific literature
until 1992, when Gruber from Air Products presented a paper at the ACS Meeting in San
Francisco [27] that dealt with the general characterisation of such dispersions. In 1996,
Hegedus and Kloiber (also from Air Products) published an important paper [28] where
they presented the properties not only of dispersions but also of coatings made on their
basis. However, there was no information on composition and chemical structure of products
266
referred to in their article. To prepare hybrid dispersions, they diluted a prepolymer-ionomer

with acrylic monomers, emulsified them in water and carried out emulsion polymerisation
of the monomers. They found, amongst other things, that unlike films obtained from blends
of acrylic dispersion and DPUR, the film obtained from the hybrid dispersion showed only
one glass transmission temperature (Tg), but no information on the particle morphology
was given. Some data on particle morphology was presented in 1997 in two publications
by Zeneca [29, 30] who described the properties of hybrid acrylic-urethane dispersions
crosslinked by formation of azomethine groups from the reaction between carbonyl groups
present as pendant groups in the polyurethane-urea chain and amino groups from the
polyamine used for crosslinking the dispersion by reaction with free NCO groups of the
prepolymer-ionomer.
In one of these articles [30] the properties of this kind of dispersion were compared with
the properties of its analogue crosslinked additionally by oxidation of double bonds
present in polyurethane-urea chain (air-drying) and it was concluded that the former
resulted in higher coating hardness. The authors of both publications presented their
schematic drawings showing the ‘core-shell’ morphology of their dispersion particles,
but did not reveal any experimental evidence that would confirm such morphology.
Another interesting paper dealing with hybrid vinyl/acrylic-urethane dispersions was published
in 1996 by Cytec [31]. They prepared hybrid dispersions by swelling DPUR particles with
monomers at a polyurethane:vinyl component ratio of 3:1 (w/w) and then carrying out
emulsion polymerisation. The resulting hybrid dispersions were additionally crosslinked by
the reaction of epoxy groups (when glycydyl methacrylate was used as one of the monomers)
with carboxylic groups attached to the polyurethane-urea chain or by using TMI (unsaturated
aliphatic isocyanate; Cytec industries, USA) as one of the monomers. The authors suggested
that IPN structures were formed in these reactions. The paper contains very good photographs
of dispersion particles, but no information on particle morphology is given.
The effect of type of diisocyanate and polyol used in synthesis of hybrid PU/acrylic polymer
dispersions was recently reported by authors from Lamberti [32].
A recently published patent [33] from Zeneca described in detail the methods of
preparation of hybrid polyurethane/vinyl polymer dispersions but neither discussed the
effect of various factors on the properties of the hybrid dispersions nor provided any
information on their particle morphology.
Based on this brief literature survey, it seems quite clear that not all features of the hybrid
acrylic-urethane dispersions have been studied so far. The purpose of the present study is
to clarify the effect of various factors on the properties of acrylic/styrene-urethane
dispersions. Some results of preliminary investigations of the particle morphology will
also be revealed.
267
6.3 Concept of the Study
6.3.1 Selection of Starting Materials
It was decided that synthesis of DPUR would be carried out according to the ‘prepolymer-
ionomer’ method generally described in Section 6.2. The scheme of the reactions leading
to DPUR is presented in Figure 6.4.
Step I - polyaddition
Step II - neutralisation
Step III - emulsifying + crosslinking
Figure 6.4 Schematic representation of the reactions leading to DPUR using the
‘prepolymer-ionomer process’
For the synthesis of DPUR, a cycloaliphatic diisocyanate, isophorone diisocyanate (IPDI) from
Hüls, was used since unlike aromatic isocyanates, it does not result in yellowing of the coatings
and films. The polyols used were polytetramethylene glycol (PTMG) with a MW of 2000
268
supplied by BASF and commercially available polyesterdiols commonly used in coatings (Bester
190 and 195, supplied by Polychimica) with hydroxyl numbers equal to 32 and 122, respectively.
Polyesterdiol containing double bonds (Irpurate 240Tz from InterRokita, Poland, with hydroxyl
numbers equal to 276) was also used in some experiments. Both polyether- and polyester-diols
were used to look at the effect of structure of the polyurethane-urea chain on the properties of
the dispersions, films and coatings. N-methylpyrrolidone (NMP) from Sidaco was used as co-
solvent (coalescing agent) and 2,2´-dimethylolpropionic acid (DMPA) from Angus was used as
the source of pendant carboxylic groups in the polyurethane-urea chain.
Polymerisation of acrylic monomers was carried out according to the standard procedure
using two different initiating systems:
(a) Water-soluble initiator – potassium persulphate
(b) ‘redox’ system – cumene hydroperoxide (CHP) + Rongalit with the structure:
Rongalit
The choice of initiating systems was made by considering their possible effect on particle
morphology (see section 6.3.2). The other additives (emulsifiers, protective colloids) were
standard materials commonly used in emulsion polymerisation of acrylic monomers.
It was assumed that three monomers would be used in this study: methyl methacrylate,
butyl acrylate and styrene. The possiblity of using styrene seemed to be especially interesting
because of its very low cost compared to the other monomers. The other two monomers
were selected for the significant differences in their polarity and solubility in water that
might affect the particle morphology and the Tg of poly(methyl methacrylate) and poly(butyl
acrylate). Difunctional acrylate monomer (1,4-butanediol dimethacrylate) was also used
in some experiments since it encouraged the formation of an IPN structure.
6.3.2 Assumptions for Synthesis of Hybrid Dispersions
6.3.2.1 General Considerations
Based on the literature survey (see Section 6.2) and the author’s preliminary experiments
the following methods of synthesis of hybrid dispersions (after this point in the chapter
they will be called modified DPUR (MDPUR)) were selected:
269
1) radical polymerisation of monomers in DPUR obtained as presented in Figure 6.4

and then diluted with water.
a) with continuous feeding of monomers
b) after swelling of DPUR particles with monomers for 20 hours
2) using the monomers as active diluents (co-solvents) of prepolymer-ionomer followed

by their polymerisation after emulsifying the prepolymer-ionomer in water
3) emulsifying the prepolymer-ionomer in diluted acrylic-styrene dispersion (ASD)
It was assumed that the method of MDPUR synthesis would have be the major factor
that would determine particle morphology. In Figures 6.5-6.7, the methods (1) – (3)
applied in this study are presented schematically.
Hybrid dispersions obtained by polymerisation, i.e., according to methods 1a, 1b and 2,

will be designated as MDPUR-ASD and hybrid dispersions obtained by synthesis of PUR
in ASD, i.e., according to method 3, will be designated as MDPUR.
Figure 6.5 Method 1 (radical polymerisation of monomers in DPUR
270
Figure 6.6 Method 2 (using the monomers as active diluents for prepolymer-ionomer)
Figure 6.7 Emulsifying the prepolymer-ionomer in diluted ASD
271
6.3.2.2 Analysis of the Process of MDPUR Synthesis Using Dispersion

Particle Morphology
• Method 1: Polymerisation of monomers in DPUR
Before the polymerisation starts, the system will consist of the following components:
(a) DPUR particles that will be only slightly swelled with monomers (in Method 1a –
continuous feeding of the monomers) or fully swelled with monomers (in Method 1b
– swelling of DPUR particles before polymerisation)
(b) Monomer droplets which will be obviously more numerous in Method 1a
(c) Monomer dissolved in water
~ ~~~
~~~ ~~
~~~~~~~~
~~ ~ ~
(d) Micelles of emulsifier
272
When the process is carried out according to Method 1a it may be assumed that the kind
of initiating system (water-soluble initiator or redox system) does not have any significant
effect on the morphology of hybrid dispersion particles since the polymerisation proceeds
mainly on the surface of DPUR particles and monomer droplets and in the micelles of
emulsifier. In the case of water-soluble initiator (potassium persulphate) the polymerisation
starts in water where the ion-radicals are formed from the monomer molecules dissolved
in water. These ion-radicals can diffuse to DPUR particles, monomer droplets and
emulsifier micelles. After this happens the system will consist of:
(a´) DPUR particles partly swelled with monomer, with adsorbed ion-radicals
~ ~~~~
~ ~~ ~~ ~
~ ~~~ ~
~~ ~ ~
(b´) monomer droplets of the size much smaller than before polymerisation and with the
adsorbed ion-radicals
~ ~
(c´) micelles of emulsifier with the adsorbed ion-radicals
273
After polymerisation is completed both acrylic/styrene polymer particles (a) and the hybrid
particles (b1 and b2) may be formed:
(a)
Hybrid particles of uniform structure (‘true hybrid’) (b1) or hybrid particles of ‘core-
shell’ structure where the core is composed of polyurethane-urea (b2):
(b1) (b2)
Obviously, other morphologies of dispersed particles are also possible (see Section 6.2).
The factor which probably has quite a significant effect on formation of separate particles
of the acrylic/styrene polymer is concentration of initiator. The higher it is, the higher is
the probability that polymerisation would proceed in monomer droplets. If it is relatively
low, this chance is diminished since monomer droplets diffuse into DPUR particles.
Probability of formation of hybrid particles of more uniform structure increases with
increase in solubility of monomer in water since longer-lived ion-radicals may be formed
and their adsorption on DPUR particles is easier. The second important factor affecting
the hybrid particle morphology is solubility of monomer in polyurethane-urea which
constitutes the particles of DPUR. If it is higher, swelling of DPUR particles with monomer
is easier and the probability of formation of hybrid particles of more uniform structure is
higher.
When polymerisation is carried out after initial swelling of DPUR particles in monomers
(Method 1b), then formation of separate particles of acrylic/styrene polymer is also possible,
but much less probable since the amount of monomer present in the system as monomer
droplets is very low in this case (assuming that the amount of monomer used to swell
DPUR particles was not higher than the maximum amount resulting from the equilibrium
swell curve (see Section 6.5.4)). It can be anticipated that in this method of MDPUR synthesis
many more hybrid particles of much more uniform structure will be formed than when the
monomers are continuously added to the reaction system (Method 1a), especially when a
274
‘redox’ type of initiating system is used. Furthermore, formation of hybrid particles of

reversed morphology (core – acrylic/styrene polymer, shell – polyurethane-urea) cannot be
excluded, especially when the polarity of monomer will be low:
If this happens, then gelling of the whole reacting system becomes very probable.
• Method 2: Using monomers as active diluents for prepolymer-ionomer
In this case it can be assumed that polymerisation will proceed in a similar way as described
previously for Method 1b. The only difference may be that both structure and size of
DPUR particles formed from the prepolymer-ionomer diluted with monomers will differ
from the ‘standard’ case, i.e., when NMP is used as diluent for prepolymer-ionomer.
Moreover, some fraction of the monomer molecules may be so closely ‘trapped’ in the
crosslinked polyurethane-urea structure in DPUR particles that their participation in
polymerisation will be difficult. This may lead to a decrease in average MW of acrylic/
styrene polymer which will be formed inside DPUR particles.
• Method 3: Emulsifying prepolymer-ionomer in diluted acrylic/styrene dispersion
In this case, the course of MDPUR synthesis seems to be much simpler than in Methods
1 and 2 because no polymerisation of monomers will proceed in the system. Before the
process starts, only ASD particles are present in the system:
After addition of prepolymer-ionomer and crosslinking it with polyamine some of these

particles may remain untouched, but both new hybrid ‘core-shell’ particles where acrylic/
styrene polymer will constitute the core and polyurethane-urea will form the shell:
275
as well as DPUR particles:
will appear in the system.
It may be assumed that the factors that would decide the course of the process and the
fraction of hybrid particles would be:
(a) Difference in surface tension of prepolymer-ionomer and the emulsifier used in

synthesis of ASD. If the surface tension of the former is higher, then formation of
‘core-shell’ hybrid dispersion particles is also higher since adsorption of prepolymer-
ionomer on acrylic/styrene polymer dispersion particles is easier. If the surface tension
of the latter is higher, then adsorption is more difficult and a greater number of
separate DPUR particles may be formed.
(b) Polarity of acrylic/styrene polymer. If it is high, then formation of ‘core-shell’ hybrid

particles is less probable because of difficult adsorption of prepolymer-ionomer. If it
is low, then it is expected that formation of hybrid dispersion particles will be easier.
6.4 Methods of Testing
6.4.1 Dispersions
The viscosity of prepolymer-ionomers and dispersions was determined at 25 °C using a

Hoppler Rheoviscometer. The NCO content of the prepolymer-ionomer was measured
by titration. MW was determined by gel permeation chromatography (GPC) according
to ISO/TC61/ISC5 using tetrahydrofuran (THF) as solvent and Shimadzu CR 4A
276
Chromatopac apparatus. Free monomer content in the dispersions was measured by gas
chromatography (GC) (Giede 18.3 apparatus)
Mechanical stability of dispersions was determined using a laboratory centrifuge with

rotational speed of 3700 rpm. Particle size, particle size distribution and zeta potential
of the dispersions was determined using Malvern Zeta Sizer 4 equipment. Minimum
film formation temperature (MFFT) was measured using a Coesfeld apparatus.
To produce photographs of dispersion particles, transmission electron microscopy

(TEM) was used. Photographs were taken at the Lomonosov University, Moscow, (see
Figures 6.12, 6.16 and 6.23-6.25) and the Institute of Chemical Physics of the Russian
Academy of Sciences in Moscow), see Figures 6.31-6.33. A special method developed
in this Institute was used for investigating dispersion particle morphology. According
to this method, a drop of dispersion (very diluted, 0.5-1.0%) and stained with osmium
tetroxide) was placed between the ‘thermal electrodes’ of a ‘thermodiffusion’ apparatus
constructed at the Institute. The temperature gradient between the electrodes was 35
°C and the time taken to settle the dispersion particles was 30-40 minutes. The substrate
with the settled particles was then washed with water and dried. Photographs were
taken using a TEM-EM 301 apparatus (Philips). It was shown in previous studies [34]
that the substrate does not affect the dispersion particle morphology.
The maximum degree of swelling of DPUR particles with monomers was determined
using the equilibrium swelling method described in Section 6.4.3.
6.4.2 Coatings
Coatings were made from dispersions by applying them onto degreased glass plates with
a 120 μm gap applicator. The resulting coating was dried at room temperature for 72 h
(for hardness and adhesion tests) and at 40 °C (for water resistance test).
Water resistance was determined by examination of the coating after 24 hours immersion.
It was designated by numbers (1-4) and letters (A-D) where the higher number means a
higher number of bubbles and the ‘higher’ letter means a higher dissipation of bubbles
on the plate [35]. Adhesion was determined by a ‘double-cutting knife’ method and
designated by numbers (1-4). Higher numbers mean lower adhesion. For determination
of hardness the pendulum method (Persoz) was applied [36].
The drying time of the coatings was determined according to the relevant Polish standard
(corresponding to DIN 53150 [37]). Times needed to achieve 1° of hardness (touch dry)
and 3° of hardness (hard dry) were measured.
277
6.4.3 Films
Films were obtained from dispersions by casting them onto glass Petri dishes and allowing
them to dry for 14 days at room temperature. Mechanical properties, i.e., tensile strength
(dr), stress at 100% elongation (d100), elongation at break (er) and Shore A hardness were
determined according to ISO 527 [38] (strip type specimens were tested).
Percentage swell in water, methylethylketone (MEK) and xylene was determined for
square specimens (25 x 25 mm) after 2 weeks of immersion at room temperature and
calculated from the following equation:
3
⎛ L⎞
% swelling = 100 ⋅ ⎜ ⎟ − 100
⎝ 25 ⎠
where L is maximum length.
The Tg was determined by differential scanning calorimetry (DSC) according to ASTM

D3418-82 [39].
Surface free energy was calculated from experimental values of dynamic contact angle
determined using a tensiometer constructed in the Institute of Chemical Physics of the
Russian Academy of Sciences.
The degree of crosslinking was calculated from the maximum degree of swelling determined
according to the following procedure: samples of film weighing approximately 0.1 g each
were immersed in toluene and the degree of swelling was calculated from the equation:
m(τ) − m0
α(τ) =
m0
where m(τ) – mass of the sample after time τ

α(τ) – degree of swelling, and
m0 – initial mass of the sample.
After the maximum degree of swelling was reached (determined graphically), the sample
was weighed and dried to constant solids content (mc). Content of the soluble fraction of
the sample (S, %) was calculated according to the equation:
m0 − mc
S=
m0
278
Crosslinking density (j) was calculated from the equation:
1
j=
S+ S
and fraction of active chains (V ), from the equation:

S
Vs = (1 − S)2 (1 − 2jS)(1 + js)
6.5 Experimental results
6.5.1 Characterisation of Starting Dispersions Used for Synthesis of MDPUR
Table 6.1 shows the properties of DPUR used for synthesis of MDPUR (MDPUR-ASD)
together with the properties of prepolymer-ionomers used as intermediates in their
preparation.
Figures 6.8 and 6.9 show the MW distribution for standard prepolymer-ionomers used
in DPUR synthesis, obtained from polyetherdiol (MW = 2000) and a mixture of
polyesterdiols (MW = 920 and 3190), respectively. The weight average MW (Mw) and
number average MW (MN) of these prepolymer-ionomers were (not counting free IPDI):
- using polystyrene standard
MN MW MW/MN
Polyetherdiol-based 6083 13604 2,24
Polyesterdiol-based 6619 16010 2,41
- using polyethylene glycol (PEG) standard
MN MW MW/MN
Polyetherdiol-based 5215 11153 2,1
Polyesterdiol-based 6999 16811 2,40
For DPUR the MW distribution could not be determined by GPC as the films did not
dissolve completely.
279
Table 6.1 Properties of DPUR used as starting materials for MDPUR-ASD obtained according to methods 1a and 1b
280
(see Section 6.3.2) and of the prepolymer-ionomers (diluted with NMP or acetone) used in their preparation. Properties of
prepolymer-ionomers diluted with monomers (designated as PPUR) used as intermediates in synthesis of MDPUR-ASD
according to method 2 have also been included in this table.
Properties of prepolymer-
Properties of DPUR
ionomers
Designationa NMP
Average Zeta
of DPUR Polyol Content
NCO, % Mechanical Particle Particle potential MFFT
(PPUR) % Viscosity Solids Viscosity
pH Stability, size size mV °C
mPa-s % mPa-s
minutes distribution
Theor. Pract. nm nm
DPUR 237 37-55

PTMG-2000 0 3.23 2.59 7,500 30.9 20 7.9 >90 58.3 -54.6 <0
(240, 244, 332) 75-130
DPUR 258b PTMG-2000 15.3 2.75 2.15 4,720 36.1 315 7.0-7.3 >90 120-420 161.8 -21.2 <0
PPUR 288 PTMG-2000 3.2 2.50 2.68 - - - - - - - - -

PTMG-2000
PPUR 289 3 3.66 3.96 - - - - - - - - -
and Irpurate
PPUR 333 PTMG-2000 0 2.75 2.48 - - - - - - - - -
DPUR 345 PTMG-2000 17.8 2.74 2.32 38 0 35.9 200 7.6-7.9 >9 0 110-1,200 211.1 -7.9 <0
DPUR 346 PTMG-2000 3 3.24 3.04 7,500 31.5 20 7.6 60 75-770 215.5 -4.5 <0
Bester 190,
DPUR 354 0 4.32 4,72 6,300 39.0 108 7.1-7.4 >90 30-140 56.2 -60.6 <0
195 Irpurate
PTMG-2000
DPUR 356 4 4.53 4,23 3,800 28.4 15.5 7.1-7.4 >9 0 30-850 75.1 -98.8 <0
and Irpurate
a the numbers refer to the laboratory sample number

b different crosslinking polyamine was used
Figure 6.8 MW distribution of prepolymer-ionomer synthesised from polyetherdiol

(PTMG 2000, MW = 2000) as determined by GPC
Figure 6.9 MW distribution of prepolymer-ionomer synthesised from a mixture of

polyesterdiols (Bester 190 and 195, MW 920 and 3190, respectively)
Particle size distribution and zeta potential determined for one of the DPUR from Table
6.1 are shown in Figures 6.10 and 6.11, respectively. TEM photographs of the particles
of the same dispersion are shown in Figure 6.12.
Properties of films and coatings made from DPUR included in Table 6.1 are shown in
Tables 6.2 and 6.3, respectively.
DSC thermogram for a typical DPUR from Table 6.1 (DPUR-237) is presented in Figure 6.13.
Properties of ASD used as starting materials in synthesis of MDPUR according to method

3 are presented in Table 6.4.
281
Figure 6.10 Particle size distribution for typical DPUR synthesised in this study (DPUR
268 = DPUR 237 from Table 6.1)
Cell type AZ104 Cross Beam Mode

F(ka) = 1.50 (Smoluchowsky)
Data taken on 20/11/96 at 14:48:58
Cell voltage 138.1 V Current 0.1 mA
Conductivity 0.03 mS Temperature 24.8
Viscosity 8.95 x 10-4 Pa-s Dielectric Constant 79.0
Count rate 491761.9 pH 3.91
f(ka) 1.50 Cell position 85.40
Zeta Potential -54.6 mV StDev 5.7
Zeta Intensity Zeta Intensity Zeta Intensity

-150.0 0.0 -50.0 43.8 50.0 0.0
-137.5 0.0 -37.5 12.1 62.5 0.0
-125.0 0.0 -25.0 0.1 75.0 0.0
-112.5 0.0 -12.5 0.0 87.5 0.0
-100.0 0.0 -0.0 0.0 100.0 0.0
-87.5 0.0 12.5 0.0 112.5 0.0
-75.0 5.1 25.0 0.0 125.0 0.0
-62.5 38.8 37.5 0.0 137.5 0.0
Peak 1 mean -54.6 width 5.7
Figure 6.11 Zeta potential for typical DPUR synthesised in this study
(DPUR 268 = DPUR 237 from Table 6.1)
282
Synthesis and Characterisation of Aqueous Hybrid Polyurethane-urea…
Figure 6.12 Particles of typical DPUR synthesised in this study

(DPUR 237 from Table 6.1). Photograph was taken using TEM technique.
Reproduced with permission from Professor I. A. Grickova at Lomonosov
University, Moscow.
Table 6.2 Properties of films from DPUR used as starting materials for synthesis
of MDPUR-ASD according to methods 1a and 1b.
Properties of films
Designation
δ 100 δr εr % swell Tg
of DPUR Appear.
MPa MPa % H2O MEK Xylene °C
DPUR 237 T 3.2 19.0 680 Wh, Pieces Pieces -79.1
(240, 244, 332) Pieces
DPUR 345 T 7.05 7.9 130 Nt1 174.4 130 -71.6
Wh Br Br
DPUR 346 T, OrP Nt1 Nt1 Nt1 Nt1 Nt1 Nt1 -71.1
DPUR 354 T, - - - - - - -15.7
Cracks
DPUR 356 T, El - 16.3 27 12 199 109.7 <0
T, Br T, Br
T - transparent, El - elastic, Br - brittle, Wh - white, OrP - orange peel, Nt1 - not tested because of too
high adhesion to substrate
283
Table 6.3 Properties of coatings from DPUR used as starting materials for
synthesis of MDPUR-ASD according to methods 1a and 1b.
Properties of coatings
Designation
Drying time, min Hardness Water
of DPUR Adhesion
Hardness (1°) Hardness (3°) (Persoz) resistance
DPUR 237 10 15 0.12 4 No bubbles
(240, 244)
DPUR 345 180 340 0.164 1 1D
DPUR 346 25 50 0.178 3 Nt2
DPUR 354 25 25 0.25 None -
DPUR 356 40 60 0.36 4 1C, does not
whiten
Nt2 - not tested because of uneven surface
See section 6.4.2 for an explanation of water resistance codes
Figure 6.13 DSC thermogram for the film obtained from a typical DPUR synthesised
in this study (DPUR 237 from Table 6.1).
284
Table 6.4 Properties of ASD used as starting materials for synthesis of MDPUR according to method 3
Properties of ASD
Design Mech Free Particle Average Zeta
Monomer Initiator Solids, Viscosity MFFT Tg
of ASD pH stability monom., size distr part size potential
% mPa-s °C °C
min % nm nm mV
ASD 15 BA/MM/S K2S2O8 24.2 20 6.2 45 0.04/0.1/ 40-145 39.7 -12.9 >+50 +58. 0
(1/1.32/ 0.1
1.64)
ASD 17 MM K2S2O8 24.9 14 4.0-5.0 45 1.00 35-85 54.0 -43.4 >+50 +123.1
ASD 17 BA K2S2O8 24.9 6 4.0-5.0 45 0.53 30-140 59.7 -41. 3 -88.0
ASD 20 S K2S2O8 23.3 5 5.0-5.3 45 0.24 40-180 79.5 -55.5 >+50 +98.0
ASD 264 BA/MM/S CHP/ 22.5 5 6.2-6.5 >90 Nt Nt Nt Nt >+50 nt
(1/1.32/ Rongalit
1.64)
ASD 266 As above K2S2O8 21.4 6 6.2-6.5 >90 Nt Nt Nt Nt >+50 nt
BA: butyl acrylate
S: styrene
MM: methyl methacrylate
Nt: not tested
285
In Figures 6.14, 6.15 and 6.16 the particle size distribution, zeta potential and TEM
micrograph of dispersion particles of typical ASD from Table 6.3 (ASD sample number
15) are presented.
Figure 6.14 Particle size distribution for typical ASD synthesised in this study (ASD 15
from Table 6.3).
286
Figure 6.15 Zeta potential for typical ASD synthesised in this study
(ASD 15 from Table 6.3).
Figure 6.16 TEM micrograph of dispersion particles of ASD (see Table 6.3).
Reproduced with permission from Professor I. A. Grickova at Lomonosov
University, Moscow.
287
6.5.2 Synthesis of MDPUR and MDPUR-ASD

Hybrid polyurethane-urea-acrylic/styrene polymer dispersions were prepared according
to methods ‘1a’, ‘1b’, ‘2’ and ‘3’ described in Section 6.3.2. Dispersions designated as
MDPUR-ASD were made by polymerisation of monomers in DPU according to the
methods 1a, 1b and 2 while dispersions designated as MDPUR were made by synthesis
of DPUR in ASD according to method 3. In all syntheses the ratio of polyurethane-urea
to acrylic/styrene polymer in the hybrid was 2:1.
Tables 6.5, 6.6, 6.7 and 6.8 show the compositions of MDPUR-ASD prepared according
to methods 1a, 1b, 2 and 3, respectively.
Table 6.5 Composition of MDPUR-ASD prepared according to method 1a

(polymerisation of monomers in DPUR with continuous feeding of the monomers)
Designation of Designation of Monomer Coalescent (NMP)
MDPUR-ASD starting DPUR content in MDPUR-
(see Table 6.1) ASD, %
MDPUR-ASD 22 DPUR 240 MM 0
MDPUR-ASD 23 DPUR 244 BA 0
MDPUR-ASD 24 DPUR 244 BA, MM, S 0
MDPUR-ASD 14 DPUR 244 S 0
MDPUR-ASD 300 DPUR 354 MM, S 0
MDPUR-ASD 307 DPUR 356 BA, MM, S 3.3
MDPUR-ASD 309 DPUR 356 BA, MM, S 3.3
Table 6.6 Composition of MDPUR-ASD prepared according to method 1b

(polymerisation of monomers in DPUR after swelling DPUR particles with monomers)
Designation of Coalescent (NMP)
Designation of
starting DPUR Monomer content in MDPUR-
MDPUR-ASD
(see Table 6.1) ASD, %
MDPUR-ASD 270 DPUR-346 BA, MM, S 2
MDPUR-ASD 272 DPUR-346 BA, MM, S 2
MDPUR-ASD 304 DPUR-356 BA, MM, S 3.2
288
Table 6.7 Composition of MDPUR-ASD prepared according to method 2 (diluting of the prepolymer-ionomer
in monomers, polymerisation and crosslinking of prepolymer-ionomer). Properties of starting prepolymer-
ionomers are also included.
Designation of Coalescent Properties of starting prepolymer-ionomer
starting (NMP)
Designation of
prepolymer- Polyol Monomer content in NCO, % Viscosity at
MDPUR-ASD
ionomer MDPUR-ASD 25 °C, mPa-s
(PPUR) % Theoret. Pract.
MDPUR-ASD PPUR 288 PTMG-2000 BA,MM,S 3 2.50 2.68 760
97
98
102
MDPUR-ASD PPUR 333 PTMG-2000 BA,MM,S - 2.75 2.48 Nt
198 Irpurate
Nt – not tested
Table 6.8 Compositions of MDPUR prepared according to method 3 (synthesis of DPUR in ASD).
Properties of starting prepolymer-ionomers are also included
Coalescent Properties of starting prepolymer-ionomer
Designation of Polyol Designation of
(NMP) Content NCO, % Viscosity at
MDPUR starting ASD
in MDPUR, % theoret. Pract. 25 °C, mPa-s
MDPUR 243 PTMG-2000 11.6 ASD 15 2.74 2.64 4000
MDPUR 245 PTMG-2000 11.6 ASD 17 2.74 2.34 4500
MDPUR 247 PTMG-2000 11.6 ASD 18 2.74 2.24 4200
MDPUR 250 PTMG-2000 11.6 ASD 20 2.74 2.51 4000
MDPUR 347 PTMG-2000 3.6 ASD 264 3.12 2.85 5700
MDPUR 348 PTMG-2000 3.6 ASD 266 3.12 2.79 5000
289
6.5.3 Investigation of the Effect of Various Factors on the Properties of

Hybrid Dispersions
6.5.3.1 Method of Hybrid Dispersion Synthesis and Kind of

Initiating System
The results of investigations of the effect of method of hybrid dispersion synthesis

(1a, 1b, 2 or 3 – see Section 3.2) on the properties of dispersions as well as of films
and coatings made from them are presented in Tables 6.9 to 6.11 (dispersions
prepared using water-soluble initiator) and in Tables 6.12 to 6.14 (dispersions
prepared using ‘redox’ initiating system). In all dispersions the chemical structure
of the polyurethane-urea and acrylic/styrene polymer component was the same (see
relevant tables in Section 6.5.2). All the dispersions contained a similar low level
(2-3.6%) of NMP.
Particle size distribution and zeta potential of a typical hybrid dispersion obtained using
a water-soluble initiator are presented in Figures 6.17 and 6.18, respectively.
290
Table 6.9 Properties of hybrid dispersions of the same chemical composition prepared according to different
methods using a water-soluble initiator (K2S2O8)
Properties of dispersions
Method Designation
of of hybrid Mechanical Free Average
Viscosity Particle size Zeta pot MFFT
Synthesis dispersion Solids, % pH Stability monomer, part size
MPa-s distribution MV °C
Min BA/MM/S, % nm
MDPUR-
1a 30.7 9 7.1-7.4 15 Nt 30-230 61. 9 -18.4 <0
ASD 268
MDPUR-
1b 34.2 10 6.8-7.1 15 Nt 50-670 9 4. 4 -39.1 <0
ASD 270
MDPUR- 0.7/0.02/
2 31.4 10 6.8-7.1 15 50-120 108.4 -60.7 <0
ASD 97 0.015
MDPUR
3 41.6 200 7.4-7.7 15 Nt 55-520 115.4 -23.0 <0
348
Nt – not tested
Table 6.10 Properties of films made from hybrid dispersions of the same chemical composition prepared
according to different methods using water-soluble initiator (K2S2O8)
Method Designation Properties of films
of of Hybrid δ100 δr εr % swell
Synthesis Dispersion Appear. Tg °C
MPa MPa % H2O MEK Xylene
MDPUR-A-
1a T, El 8.2 10.8 164 13 Wh, El 347 T, Br 198 T, Br -73.4
SD 268
MDPUR-A-
1b T, El 9.2 13.3 180 0 Wh, El 347 T, Br 224 T, Br -73.4
SD 270
MDPUR-A-
2 T, El 6.5 10.0 210 13 Wh 341 T, G 310 T, G -56.6
SD 97
MDPUR
3 M, El 14.1 14.5 117 13 Wh, El 198 T, Br 198 T, Br -75.7
348
T- transparent, El - elastic, M - Mat, Wh - white, Br - brittle, G - gelatinous
291
Table 6.11 Properties of coatings made from hybrid dispersions of the same chemical composition prepared
292
according to different methods using a water-soluble initiator (K2S2O8)
Method of Designation of hybrid
Drying time, min Hardness
Synthesis Dispersion Adhesion Water resistance
1° 3° (Persoz)
1a MDPUR-ASD 268 30 50 0.22 4 1A whitening disappears after 1 h
1b MDPUR-ASD 270 25 45 0.20 4 2C whitening disappears after 1 h
2 MDPUR-ASD 97 35 60 0.12 4 2B whitening disappears after 1 h
3 MDPUR- 348 20 25 0.20 1 2A whitening disappears after 1 h
Table 6.12 Properties of hybrid dispersions of the same chemical composition prepared according to different
methods using a ‘redox’ initiator
Method Designation Free
of of hybrid Mechanical Average Zeta
Viscosity monomer, Particle size MFFT
Synthesis dispersion Solids % pH Stability part size potential
MPa-s BA/MM/S distribution °C
Min nm MV
%
MDPUR-
1a 29.7 7 6.8-7.1 15 Nt 35-310 68.0 -39.3 <0
ASD 274
MDPUR-
1b 29.3 10 7.1-7.4 15 Nt 85-650 90.4 -32.6 <0
ASD 272
<0.02/
MDPUR-
2 31.4 8 6.8-7.1 15 <0.008/ 105-165 130.6 -39.0 <0
ASD 98
<0.001
MDPUR
3 32.5 48 7.6-7.9 15 Nt 60-260 141.7 -25.4 <0
347
Nt – not tested
Table 6.13 Properties of films made from hybrid dispersions of the same chemical composition prepared
according to different methods using a ‘redox’ initiator
Properties of films
Method of Designation of Hybrid
δ100 δρ
δρ εr % swell Tg
Synthesis Dispersion Appear.
1a MDPUR-ASD 274 T, El 6.3 11.2 250 26 El 445 T, Br 374 T, Br -68.7
1b MDPUR-ASD 272 T, El 7.6 12.0 210 0, Wh, El 280 T, Br 280 T, Br -72.2
2 MDPUR-ASD 98 T, El 5.3 10.6 285 40 Wh, El 374 T, G 409 T, Br -70.6
3 MDPUR 347 M, el 12.5 15.0 187 0 Wh, El 130 T, Br 174 T, Br -77.2
T- transparent, El - elastic, M - Mat, Wh - white, Br - brittle, G - gelatinous
Table 6.14 Properties of coatings made from hybrid dispersions of the same chemical composition prepared
according to different methods using a ‘redox’ initiator.
Method of Designation of hybrid
Drying time, min Hardness
Synthesis dispersion Adhesion Water resistance
1° 3° (Persoz)
1a MDPUR-ASD 274 25 45 0.18 3 2D
whitening disappears after 1 h
1b MDPUR-ASD 272 25 50 0.16 4 3C
2 MDPUR-ASD 98 40 120 0.08 1 1A
3 MDPUR 347 30 40 0.19 1 4A
293
Figure 6.17 Particle size distribution for a typical polyurethane-urea-acrylic/styrene

hybrid dispersion synthesised in this study (MDPUR-ASD 97 from Table 6.7 prepared
according to method 2 using a water-soluble initiator).
Figure 6.18 Zeta potential for a typical polyurethane-urea-acrylic/styrene hybrid

dispersion synthesised in this study (MDPUR-ASD 97 from Table 6.7 prepared
according to method 2 using a water-soluble initiator)
294
The DSC thermogram of the film obtained from a typical hybrid dispersion obtained
using a water-soluble initiator is presented in Figure 6.19.
Particle size distribution and zeta potential of a typical hybrid dispersion obtained using
a ‘redox’ initiator are presented in Figures 6.20 and 6.21, respectively.
The DSC thermogram of the film obtained from a typical hybrid dispersion obtained
using ‘redox’ initiator is presented in Figure 6.22.
Figure 6.19 DSC thermogram for typical hybrid polyurethane-urea-acrylic/styrene

dispersion synthesised in this study (MDPUR-ASD 97 prepared according to method 2
using water-soluble initiator)
295
Figure 6.20 Particle size distribution for typical polyurethane-urea-acrylic/styrene

hybrid dispersion synthesised in this study (MDPUR-ASD 98 from Table 6.7 prepared
according to method 2 using a ‘redox’ initiator)
Figure 6.21 Zeta potential for typical polyurethane-urea-acrylic/styrene hybrid

dispersion synthesised in this study (MDPUR-ASD 98 from Table 6.7 prepared
according to method 2 using a ‘redox’ initiator)
296
Figure 6.22 DSC pattern for typical hybrid polyurethane-urea-acrylic/styrene

dispersion synthesised in this study (MDPUR-ASD 98 prepared according to method 2
using a ‘redox’ initiator)
6.5.3.2 Concentration of Coalescing Agent (NMP)
The properties of hybrid dispersions prepared using different methods (1a, 2 and 3 – see
Section 6.3.2) and different levels of coalescent (NMP) as well as of films and coatings
made from these dispersions are presented in Tables 6.15 to 6.17. In all dispersions the
chemical structure of the polyurethane-urea and acrylic/styrene polymer component was
the same (see relevant Tables in Section 6.5.2). All dispersions were prepared using a
water-soluble initiator.
297
298
Table 6.15 Properties of hybrid dispersions of the same chemical composition differing only in the
concentration of coalescent (NMP)
Content Properties of dispersions
Method Designation
of Solids Viscosity pH Mechanical Free monomer Particle size Average Zeta MFFT
of of hybrid
NMP % mPa-s Stability %, BA/MM/S distribution particle size potential °C
synthesis dispersion
% Min nm nm mV
MDPUR- <0.02/0.001/
1a 0 34.3 63 6.5-6.8 45 24-688 134.5 -42. 2 <0
ASD 241 0.008
MDPUR-
1a 2.0 30.7 9 7.1-7.4 15 Nt 30-230 61.9 -18. 4 <0
ASD 268
MDPUR-
1a 11.6 - - - - - - - - -
PUM 259a
MDPUR- <0.02/0.005/
2 0 38.3 21 6.2-6.5 15 30-290 261.3 -63.6 <0
ASD 198 0.008
MDPUR- 0.7/0.02/
2 3.0 31.4 10 6.8-7.1 15 50-120 108.4 -60. 7 <0
ASD 97 0.015
MDPUR
3 3.6 41.6 200 7.4-7.7 15 Nt 55-520 115.4 -23.0 <0
348
MDPUR Nt 0.1/0.17/
3 11.6 35.1 7.6 45 33-133 59.4 -14.4 Nt
243 (settling) 1.64
a
dispersion gelled during synthesis
Nt - not tested
Table 6.16 Properties of films made from hybrid dispersions of the same chemical composition differing only
in the concentration of coalescent (NMP).
Properties of films
Method Designation Content
of of Hybrid of NMP δ100 δr εr Swelling Tg
Synthesis Dispersion % Appearance
T, El
MDPUR-A- 0 T, G T, G
1a 0 Partly 9.5 15.8 215 -60.8
SD 24 T Pieces Pieces
cracked
MDPUR-A- 13 347 198
1a 2.0 T, Br 8.2 10.8 164 -73.4
SD 268 Wh, Br T, Br T, Br
MDPUR-A-
1a 11.6 - - - - - - - -
SD 259a
MDPUR-A- 0 280 374
2 0 T, El 5.6 11.2 255 -59.0
SD 198 Wh, E T, G T, G
MDPUR-A- 13 341 310
2 3.0 T, El 6.5 10.0 210 -56.6
SD 97 Wh T, G T, G
MDPUR 13 198 198
3 3.6 M, El 14.1 14.5 117 -75.2
348 Wh, E T, Br T, Br
M, El
MDPUR 12 300 251
3 11.6 Film not Nt Nt Nt -66.3
243 Wh, Br T, Br T, Br
even
a
dispersion gelled during synthesis
T- transparent, El - elastic, M - Matte, Wh - white, Br - brittle, G - gelatinous
Nt - not tested
299
300
Table 6.17 Properties of coatings made from hybrid dispersions of the same chemical composition differing
only in the concentration of coalescent (NMP)
Content
Method of Designation of Drying time, min
of NMP Hardness
Synthesis Hybrid Dispersion Adhesion Water resistance
% Hardness Hardness (Persoz)
(1°) (3°)
2C
1a MDPUR-ASD 24 - 30 50 0.14 4
1A
1a MDPUR-ASD 268 2.0 30 50 0.22 4
nt
1a MDPUR-ASD 259 11.6 nt nt nt nt

1B
2 MDPUR-ASD 198 - 35 45 0.12 3
2B
2 MDPUR-ASD 97 3.0 35 60 0.12 4
3 MDPUR 348 3.6 20 25 0.20 1 2A
nt
3 MDPUR 243 11.6 120 165 0.14 1
surface not even
nt - not tested
6.5.3.3 Chemical Structure of the Polyurethane-Urea Portion of the Hybrid
(a) Effect of polyol type
In Tables 6.18 to 6.20 the properties of two hybrid dispersions prepared using the same
method 1a (see Section 3.2) and having the same structure of the acrylic/styrene part of
the hybrid but based on different polyols, as well as of films and coatings made from
them are presented. Neither dispersion contained coalescent (NMP)
(b) Effect of introducing double bonds to the polyurethane-urea part of the hybrid
Properties of hybrid dispersions prepared according to the different methods (1a, 1b and
2 - see Section 6.3.2) and based on the same polyol (PTMG 2000), but differing in the
presence or absence of double bonds in the polyurethane-urea part of the hybrid, as well
as of films and coatings made of them, are presented in Tables 6.21 and 6.22. All
dispersions have a similar low level (2.0-3.3%) of coalescent and have the same structure
of the acrylic/styrene part of the hybrid. ‘Redox’ initiator was used in the synthesis of
dispersions according to the method 2, and in all other dispersions presented in these
tables a water-soluble initiator was applied.
301
Table 6.18 Properties of hybrid dispersions differing only in the structure of the polyurethane-urea
302
part of the hybrid
Designation Solids Viscosity pH Mechanical Free Particle size Average Zeta MFFT
of hybrid Polyol % MPa-s Stability monomer, distribution particle pot °C
Dispersion Min BA/MM/S nm size mV
% nm
MDPUR-ASD Polyetherdiol 34.3 63 6.5-6.8 45 <0.02/0.0- 24-688 134.5 -42.2 <0
24 (PTMG-2000) 01/0.008
MDPUR-ASD Polyesterdiol (Bester
39.5 18 6.5-6.8 15 Nt 78-197 175.6 -62.8 +18
300 190 + Bester 195)
Nt – not tested
Table 6.19 Properties of films made from hybrid dispersions differing only in the structure of
polyurethane-urea part of the hybrid
Properties of films
Designation of
Polyol Appear. δ100 δr εr Swelling Tg
hybrid Dispersion
MPa MPa % H2O MEK Xyl e n e °C
Polyetherdiol T, G,
MDPUR-ASD 24 T, El 9.5 15.8 215 0.9 0.8 pieces -60.8
(PTMG-2000) pieces
Polyesterdiol (Bester
MDPUR-ASD 300 T, pieces - - - - - - -
190 + Bester 195)
T- transparent, El - elastic, M - matte, Wh - white, Br - brittle, G - gelatinous
Table 6.20 Properties of coatings made from hybrid dispersions differing only in the structure of the
Designation of hybrid Drying time, min
Polyol Hardness
Dispersion Adhesion Water resistance
Hardness Hardness (Persoz)
(1°) (3°)
MDPUR-ASD 24 Polyetherdiol (PTMG-2000) 30 50 0.14 4 2C whitening disappears after 1 h
Polyesterdiol
MDPUR-ASD 300 25 25 0.3 2 1B no whitening
(Bester 190 + Bester 195)
Table 6.21 Properties of hybrid dispersions differing only in the presence of double bonds in the
Double bonds Properties of dispersions
Method Designation
in Solids Viscosity pH Mechanical Free monom. Particle size Average Zeta MFFT
of of hybrid
polyurethane- % mPa-s Stability %, distribution particle size potential °C
synthesis dispersion
urea Min. BA/MM/S nm nm mV
MDPUR-A-
1a - 30.7 9 7.1-7.4 15 - 43.8-174.4 61.9 -18.4 <0
SD 268
MDPUR-A-
1a + 35.3 24 6.5-6.8 15 - 35-180 81.7 -31.2 <0
SD 307
MDPUR-A-
1b - 34.2 10 6.8-7.1 15 - 66.8-422.1 94.4 -39.1 <0
SD 270
MDPUR-A-
1b + 34.4 18 6.5-6.8 15 - 30-70 32.5 +0.7 <0
SD 304
MDPUR-A- <0.02/<0.008/
2 - 31.4 8 6.8-7.1 15 105-165 130.6 -39.8 <0
SD 98 <0.001
MDPUR-A- <0.02/<0.008/ <0
2 + 33.6 9 5.9-6.2 >9 0 25-190 66.9 -33.1
SD 102 <0.001
303
304
Table 6.22 Properties of films made from hybrid dispersions differing only in the presence of double bonds
in the polyurethane-urea part of the hybrid
Properties of films
Method Designation Double bonds in
of of Hybrid polyurethane- δ100 δr εr Swelling Tg
Synthesis Dispersion urea Appearance
MDPUR-ASD 13 347 198
1a - T, El 8. 2 10.8 164 -73.4
268 Wh, El T, Br T, Br
MDPUR-ASD
1a + T, Cracks - - - - - - -54.1
307
MDPUR-ASD 0 347 224

1b - T, El 9.2 13.3 180 -73.4
270 Wh, El T, Br T, Br
1b + T, El - 11.0 63 -63.2
304 Wh, Br T, Br T, Br
2 - T, El 5. 3 10.6 285 -70.6
98 Wh, El T, G T, G
MDPUR-ASD 26 T, G 174
2 + T, E l - 17.5 95 -51.3
102 Wh, El 224 T, El
T - transparent, El - elastic, M - matte, Wh - white, Br - brittle, G - gelatinous
Table 6.23 Properties of coatings made from hybrid dispersions differing only in the presence of double
bonds in the polyurethane-urea part of the hybrid
Method Double Bonds in
Designation of Drying time, min
of polyurethaneurea Hardness
Hybrid Dispersion Adhesion Water resistance
synthesis % Hardness Hardness (Persoz)
(1°) (3°)
1A, whitening disappears
1a MDPUR-PUM 268 - 30 50 0.22 4
after 1 h
1C, whitening disappears
1a MDPUR-PUM 307 + 15 40 0.42 4
after 1 h
1b MDPUR-PUM 270 - 25 45 0.19 4
after 1 hr
1b MDPUR-PUM 304 + 20 40 0.38 4
after 1 h
1A, whitening disappears
2 MDPUR-PUM 98 - 40 120 0.08 1
after 1 h
2 MDPUR-PUM 102 + 25 60 0.16 1
after 1 h
305
6.5.3.4 Chemical structure of the acrylic/styrene part of the hybrid

The properties of hybrid dispersion prepared according to two different methods (1a
and 3 – see Section 3.2) and having the same chemical composition and differing only in
the chemical structure of the acrylic/styrene polymer component are presented in Tables
6.24 to 6.26. All dispersions were synthesised using a water-soluble initiator. Dispersions
prepared according to method 1a did not contain any coalescent while dispersions
prepared according to method 3 contained 11.6% of NMP.
TEM photos of the particles of two hybrid dispersions prepared using less hydrophobic
and more hydrophilic monomer prepared according to method 1a are presented in Figures
6.23 and 6.24. A TEM micrograph of the particles of a hybrid dispersion prepared
according to method 3 using more hydrophobic monomer is presented in Figure 6.25.
6.5.3.5 Crosslinking of the Acrylic/styrene Part of the Hybrid

The properties of hybrid dispersions prepared using method 1a (see Section 6.3.2), having
the same chemical composition and differing only in the presence or absence of partial
crosslinking of the acrylic/styrene polymer component are presented in Tables 6.27 to
6.29. Dispersions contained 3.3% of NMP.
Figure 6.23 Particles of hybrid polyurethane-urea-acrylic/styrene dispersion prepared

according to method 1a using less hydrophobic monomer and water-soluble initiator
(MDPUR-ASD 22). Photograph was taken using TEM.
Reproduced with permission from Professor I. A. Grickova, Lomonosov University, Moscow.
306
Table 6.24 Properties of hybrid dispersions differing only in the chemical structure of the acrylic/styrene
part of the hybrid
Method Designation
of of hybrid Monomer Solids Viscosity pH Mechanical Free monom. Particle size Average Zeta MFFT
synthesis dispersion % mPa.s Stability %, distribution particle size potential °C
Min. BA/MM/S nm nm mV
1a MDPUR- BA 32.6 75 6.2-6.5 45 0.3/-/- 15-450 93.7 -27.6 <0
ASD 23
1a MDPUR- MM 34.5 70 7.1-7.4 45 -/1.15/- 18-360 83.7 -19.3 <0
ASD 22
1a MDPUR- S 34.0 13 6.2-6.5 45 -/-/0.02 16-525 96.3 -26. 6 <0
ASD 14
1a MDPUR- BA/MM/S 34.3 63 6.5-6.8 45 <0.02/0.001/ 24-688 134.5 -42.2 <0
ASD 24 1/1.32/1.64 0.008
3 MDPUR BA 35.1 40 8.2-8.5 45 0.09/-/- 40-270 73.8 -31.3 <0
247
3 MDPUR MM 35.6 44 8.2 45 -/0.92/- 35-130 61.1 -31.6 nt
245
3 MDPUR S 35.2 36 7.3-7.6 90 -/-/0.11 40-250 87.1 -27.9 <0
250
3 MDPUR BA/MM/S 35.1 nt 7.6 45 0.1/0.17/1.64 33-133 59.4 -14.4 nt
243 1/1.32/1.64 (settling)
nt - not tested
307
308
Table 6.25 Properties of films made from hybrid dispersions differing only in the chemical structure of
the acrylic/styrene part of the hybrid
Properties of films
Method Designation
of of Hybrid Monomer δ100 δr εr Swelling Tg
Synthesis Dispersion Appear.
MDPUR- 13 347 409 - 57.6
1a BA T, El 3.5 4.2 136
ASD 23 Wh, El T, G T, G +79.6
MDPUR- - 59.8
1a MM T, Pieces nt nt nt nt nt nt
ASD 22 +71.4
MDPUR- - 54.0
1a S Wh Pieces nt nt nt nt nt nt
ASD 14 +72.1
BA/MM/
MDPUR- 0
1a S1/1.32/ T, El 9.5 15.8 215 T, G T, G -60.8
ASD 24 T
1.64
13 483 341 - 77.37
3 MDPUR 247 BA T, El 4.3 6.7 230
Wh T, G T, G - 47.38
- 66.6
3 MDPUR 245 MM T, Pieces nt nt nt nt nt nt
+77.0
26 224 251
3 MDPUR 250 S Wh, El 10.4 14.5 201 - 67.7
Wh, El T, Br T , Br
AB/MM/ M, El
12 310 251
3 MDPUR 243 S1/1.32/ Uneven nt nt nt - 66.3
Wh, Br T, Br T , Br
1.64 film
T - transparent, El - elastic, M - Matte, Wh - white, Br - brittle, G - gelatinous
nt - not tested
Table 6.26 Properties of films made from hybrid dispersions differing only in the chemical structure of
the acrylic/styrene part of the hybrid
Method
Designation of Drying time, min
of Monomer Hardness
Hybrid Dispersion Adhesion Water resistance
synthesis Hardness Hardness (Persoz)
(1°) (3°)
1a MDPUR-ASD 23 BA 35 50 0.09 1 2C
1a MDPUR-ASD 22 MM 35 50 0.27 4 1B
1D
1a MDPUR-ASD 14 S 35 50 0.12 1
BA/MM/S 2C
1a MDPUR-ASD 24 30 50 0.14 4
1/1.32/1.64 whitening disappears after 1 h
MDPUR 2B
3 BA 35 60 0.06 4
247 whitening disappears after 1 h
nt
3 MDPUR 245 MM nt nt nt nt
Cracks
1D
3 MDPUR 250 S 40 50 0,14 4
BA/MM/S
3 MDPUR 243 120 16 5 0.14 1 nt
1/1.32/1.64
nt - not tested
309

according to method 1a using more hydrophobic monomer and water-soluble initiator
(MDPUR-ASD 14). Photograph was taken using TEM.

according to method 3 using more hydrophobic monomer and water-soluble initiator
(MDPUR 250). Photograph was taken using TEM.
310
Table 6.27 Properties of hybrid dispersions differing only in the presence or absence of crosslinking of the
acrylic/styrene part of the hybrid
Crosslinking
Designation of Mechanical Particle size Average
of Acrylic/ Solids Viscosity Zeta pot MFFT
hybrid Dispersion pH Stability distribution particle size
styrene % MPa-s mV °C
Min nm nm
MDPUR-ASD 307 - 35.3 24 6.5-6.8 15 35-200 81.7 -31.2 <0
MDPUR-ASD 309 + 35.6 17 6.8-7.1 45 25-150 50.0 -64.5 <0
Table 6.28 Properties of films made from hybrid dispersions differing only in the presence or absence of
crosslinking of the acrylic/styrene part of the hybrid
Properties of films
Designation Crosslinking of
of Hybrid Acrylic/styrene δ100 δr εr Swelling Tg
Dispersion part of hybrid Appear.
MDPUR-
- T, cracks - - - - - - - 54. 1
ASD 307
MDPUR- 56 Nt 130
+ T, El - 11.1 53 - 57.5
ASD 309 Wh, Br Pieces T , Br
T - transparent, El - elastic, M - matt, Wh - white, Br - brittle, G - gelatinous
Nt - not tested
311
Table 6.29 Results of investigation of degree of crosslinking of hybrid

dispersions using the equilibrium swelling test. Results obtained for the starting
DPUR and ASD dispersions are also included for comparison
Designation Method Soluble Crosslinking Fraction of
Designation of αmax
of starting of hybrid fraction, S, density, active
hybrid dispersion %
dispersion synthesis % j chains, Vs
MDPUR-ASD 22 DPUR 240 1a 230 41.0 0.95 0.11

MDPUR-ASD 23 DPUR 244 1a 310 0 ∞ 1.00
MDPUR-ASD 24 DPUR 244 1a 170 86.0 2.8 0.49
MDPUR-ASD 14 DPUR 237 1a 320 7.5 2.9 0.59
MDPUR 243 ASD 15 3 220 4.0 4.2 0.71
MDPUR 245 ASD 17 3 1320 25.5 1.3 0.25
MDPUR 247 ASD 18 3 290 25.0 1.8 0.25
MDPUR 250 ASD 20 3 75 21.5 1.5 0.29
- DPUR 237 - 140 41 0.95 0.11
- ASD 15 - 210 30 1.0 0.19
- ASD 17 - D D D D
- ASD 18 - D D D D
- ASD 20 - D D D D
D - film dissolved in toluene
6.5.4 Additional Experiments
Additional experiments were performed in order to better clarify the mechanism of the process
of formation of hybrid dispersions and the effect of various factors on their properties.
6.5.4.1 Investigations of the Course of Swelling of DPUR Particles with Monomers
This experiment was designed in order to further clarify the mechanism of hybrid
dispersion particles formation. In this experiment, monomer was continuously added to
DPUR (of the composition corresponding to DPUR-237 – see Section 6.3.1) at a rate of
1 ml/h. After each hour, samples of the dispersion were taken and the following parameters
were determined: particle size, particle size distribution and zeta potential. Changes of
particle size distribution in the course of swelling are shown in Figure 6.26, and changes
of average particle size and zeta potential in Figure 6.27.
312
After 5 h
Initial sample
After 2 h
After 1 h
After 9 h
After 3 h
Figure 6.26 Changes of particle size distribution in the course of swelling of DPUR
particles with monomer
313
Taking advantage of the capabilities offered by the Malvern Zeta Sizer apparatus the
computer analysis of total volume of smaller and bigger particles (it may be noticed that
on the curves showing particle size distribution in Figure 6.26 that there are two peaks
visible). Results are:
Volume of small Volume of big

Time of sampling particles (peak 1) particles (peak 2)
Initial sample 100%
After 1 h 98% 2%
After 2 h 94% 6%
After 3 h 66% 34%
After 4 h 40% 60%
After 5 h 50% 50%
Figure 6.27 Changes of average particle size and zeta potential during addition of
monomer to DPUR
314
6.5.4.2 Determination of the Maximum Degree of Swelling of DPUR Particles
This experiment was aimed at clarifying what is the maximum amount of monomer that
would be able to swell polyurethane-urea, i.e., would be able to take part in the formation
of hybrid dispersion particles, assuming that enough time is allowed to achieve equilibrium.
Films made from DPUR 258 were used in this experiment. The following results were
obtained:
Monomer Maximum degree of swelling αmax, %

MM 88.14
Styrene 88.21
MM/Styrene = 1/1 89.0
The changes of the mass of polyurethane-urea film in the course of swelling with monomers
is shown in Figures 6.28 to 6.30.
Figure 6.28 Change of the mass of polyurethane-urea film (made from DPUR 258) in
the course of swelling with MM
315
the course of swelling with styrene
the course of swelling with MM/S = 1/1 (w/w) mixture
316
6.5.4.4 Investigation of the Effect of the Method of Synthesis of Hybrid

Dispersions on their Degree of Crosslinking
The degree of crosslinking of the starting dispersions (DPUR and ASD) and the hybrids
was determined using the equilibrium swelling test described in Section 4.3. The following
parameters were calculated based on the results of this experiment:
• Maximum degree of crosslinking, amax (%)

• Content of soluble fraction, S (%)
• Crosslink density (number of crosslinks per polymer molecule), j
• Fraction of active chains (composed of segments linked with crosslinks at both ends), Vs
The results are shown in Table 6.29
6.5.4.5 Investigation of Hybrid Dispersion Particles Morphology
The morphology of dispersion particles was investigated using the method described
in Section 6.4.1. Examples of different morphologies of particles of hybrid dispersions
synthesised in this study according to methods 1a, 1b and 3 are presented in Figure
6.31 in comparison with particles of the starting dispersion of BA/MM/S copolymer.
The contrast was selected so that in pictures ‘d’ and ‘c’ white colour represents the
polyurethane-urea part of the hybrid and in picture ‘b’ the same colour represents the
acrylic/styrene part of the hybrid.
The morphology of particles of hybrid dispersion synthesised according to method 2

using water-soluble and ‘redox’ initiators is presented in Figures 6.32 and 6.33,
respectively. Both pictures show both the single particles and the coalesced particles to
demonstrate what happens to the particle morphology in the process of film formation.
White colour represents the polyurethane-urea part of the hybrid.
6.5.4.6 Determination of Surface Free Energy of Films Made from Hybrid

Dispersions
The surface free energy of films made from hybrid dispersions was determined in order
to look at the values of its non-polar and polar component which could provide some
information on whether polyurethane-urea or acrylic/styrene polymer is on the film surface
(see Table 6.30).
317
(a) (b) (c) (d)
Figure 6.31 Examples of different morphologies of particles of hybrid polyurethane-

urea-acrylic/styrene dispersions synthesised in this study. Micrographs were taken
using TEM.
(a) ASD dispersion (BA/MM/S) (shown for comparison); (b) hybrid MDPUR-ASD dispersion (the
same monomers) prepared according to method 1b (see section 3.2); (c) hybrid MDPUR-ASD
dispersion (the same monomers) prepared according to method 1a (see Section 3.2); (d) hybrid
MDPUR-ASD dispersion (the same monomers) prepared according to method 3 (see Section 3.2)
Reproduced with permission from Professor A. E. Czalych, Institure of Chemical Physics of
the Russian Academy of Sciences, Moscow.
Figure 6.32 Morphology of particles of hybrid polyurethane-urea-acrylic/styrene hybrid

dispersion prepared according to method 2 (See Section 6.3.2) using water-soluble initiator
(MDPUR-ASD 97). Micrograph was taken using TEM. Both single particle and coalesced
particles are shown. Reproduced with permission from Professor A. E. Czalych, Institure of
Chemical Physics of the Russian Academy of Sciences, Moscow.
318
Figure 6.33 Morphology of particles of hybrid polyurethane-urea-acrylic/styrene hybrid

dispersion prepared according to method 2 (See Section 6.3.2) using ‘redox’ initiator
(MDPUR-ASD 98). Micrograph was taken using TEM. Both single particle and coalesced
particles are shown. Reproduced with permission from Professor A. E. Czalych, Institure of
Chemical Physics of the Russian Academy of Sciences, Moscow.
Table 6.30 Surface free energy (γ) and its polar (γp) and non-polar (γd)
components of films made from hybrid dispersions prepared according to
method 3. Results obtained for films made from DPUR and starting
acrylic/styrene dispersions are also shown for comparison
Designation of Acrylic/styrene part of γ γp γd
hybrid dispersion the hybrid mJ/m2 mJ/m2 mJ/m2
MDPUR 243 BA/MM/S 1/1.32/1.64 35.4 4.0 31.4
MDPUR 245 MM 34.7 3.3 31.4
MDPUR 247 BA 31.3 6.3 25.0
MDPUR 250 S 36.7 0.7 36.0
ASD 15 BA/MM/S 1/1.32/1.64 22.5 18.0 4.5
ASD 18 BA 23.0 1.8 21.2
DPUR 258 - 33.7 2.3 31.4
319
6.6 Discussion
6.6.1 Estimation of the Effect of Various Factors on the Properties of Hybrid

Dispersions and Films and Coatings Made from Them
6.6.1.1 Method of Hybrid Dispersion Synthesis and Type of Initiator
• Properties of dispersions
When the properties of hybrid dispersions having the same composition but prepared
according to different methods using water-soluble and ‘redox’ initiator (Tables 6.9 and
6.12) are compared with the properties of starting DPUR and ASD (Tables 6.1 and 6.4)
it can be noted that:
a) The type of initiator does not affect the properties of hybrid dispersions significantly
except for free monomer content which is distinctly lower when a ‘redox’ initiator is
used. This suggests that the mechanism of hybrid particle formation is similar in
both cases. This is strongly supported by the direct evidence that there is no difference
in morphologies of particles of hybrid dispersions obtained according to method 2
(see Section 6.3.2) using water-soluble or ‘redox’ initiator (compare Figures 6.32
and 6.33).
b) Neither method of synthesis nor type of initiator have any influence on mechanical
stability, viscosity or MFFT of hybrid dispersions. However, the following observations
can be made:
• mechanical stability of all hybrid dispersions is slightly lower than that of the
starting dispersions, but nevertheless it is good enough for successful application
of hybrid dispersions in practice (there was no settling of dispersions during
storage). Relatively high negative values of zeta potential observed for all hybrid
dispersions confirm that their stability should be good. For all hybrid dispersions
MFFT is < 0 °C (just as for starting DPUR) which should undoubtedly be
considered as their great advantage when compared to ADS.
• the viscosity of all hybrid dispersions is quite low and similar to the starting DPUR
a) The average particle size of hybrid dispersions depends strongly on the method of
synthesis (regardless of the initiator). The lowest values of average particle size are
observed for MDPUR-ADS prepared according to method 1a, i.e., with continuous
feeding of monomers to DPUR, and the highest for MDPUR prepared according to
method 3, i.e., emulsifying of prepolymer-ionomer in ASD followed by crosslinking
320
with polyamine. This result is in good correlation with the assumptions concerning
the mechanism of hybrid particles formation presented in Section 6.3.2. If the
dispersion is prepared according to method 1a, smaller ASD particles can be formed
along with bigger hybrid particles which may have various morphologies. If the
dispersion is prepared according to method 3, only bigger ‘core-shell’ particles can
be formed. Detailed comparison of the size of particles of starting DPUR (DPUR
346) and hybrid dispersions prepared from it according to method 1a (MDPUR-
ASD 268 and MDPUR-ASD 274) confirms this assumption that the average particle
size for starting DPUR is higher than for hybrid dispersions prepared from it.
b) The particle size distribution observed for hybrid dispersions is the lowest for MDPUR-
ASD prepared according to method 2, i.e., diluting prepolymer-ionomer with monomers,
emulsifying this solution in water, crosslinking with polyamine and polymerisation of
monomers. This can be explained by the fact that in this method, formation of hybrid
dispersion particles proceeds ‘in situ’, i.e., both prepolymer-ionomer (precursor of
polyurethane-urea component of the hybrid) and the monomers (precursors of acrylic/
styrene component of the hybrid) are emulsified at the same time, which means that
the chance of formation of hybrid dispersion particles having similar morphology and
size is very high. Higher uniformity of the whole system in the case when the hybrid
dispersions are prepared according to method 2 is also confirmed by the higher negative
values of zeta potential observed for these dispersions.
• Properties of films
From a practical point of view it is very important that, regardless of the type of initiator
and method of synthesis, the films made from hybrid dispersions are transparent (this
proves that their structure is quite uniform), strong, elastic and resistant to water (very
good resistance) and organic solvents (good resistance).
When the properties of films made from hybrid dispersions having the same composition
but prepared according to different methods using water-soluble and ‘redox’ initiator
(Tables 6.10 and 6.13) are compared with the properties of films made from the starting
DPUR (Table 6.2) it can be noted that:
a) Type of initiator practically does not have any influence on mechanical properties,
water resistance or solvent resistance of films made from hybrid dispersions. Slightly
higher values of elongation at break observed for films made from hybrid dispersions
prepared using ‘redox’ initiator (regardless of the method of synthesis) can result
from the fact that less grafting (or crosslinking) proceeds in the course of
polymerisation.
321
b) The effect of method of synthesis on the mechanical properties, water resistance and
solvent resistance of the films can be clearly seen when the results obtained for the
films made from hybrid dispersions prepared according to method 3 and according
to other methods are compared. In the cases where method 3 has been applied, the
films are distinctly stronger, less elastic and better resistant to water and organic
solvents. It is also interesting that their Tgs are lower (closer to the one observed for
DPUR). The explanation of this phenomenon is not clear since taking into account
the assumed hybrid particles formation mechanism presented in Section 6.3.2 one
could rather expect that not only Tg, but also the mechanical properties of the films
made from hybrid dispersions prepared according to method 3 would resemble those
of films made from DPUR (high elasticity and water/solvent resistance) more than
the properties of the films made of dispersions prepared according to the other
methods. Nevertheless, when this problem is more deeply analysed, it can be
anticipated that the reason for this phenomenon is the very high (much higher than
in dispersions prepared according to the other methods) number of particles of ‘pure
core-shell’ structure in dispersions prepared according to method 3. In the film made
of hybrid dispersion prepared according to this method, a very regular heterogeneous
structure is formed during coalescence of particles. In such a structure, acrylic/styrene
polymer (which constitutes the core in dispersion particles) is the dispersed phase
while polyurethane-urea (which constitutes the shell in dispersion particles) is the
matrix. Acrylic/styrene polymer then plays the role of toughener while polyurethane-
urea increases the water and solvent resistance of the film and provides its low Tg.
The second Tg corresponding to acrylic/styrene polymer, should also be detected in
this particular system, but DSC does not have the resolution which would be needed
here. However, when the torsion pendulum method was applied we were able to
spot this second Tg quite easily. We believe that this particular hybrid system is very
interesting and requires further studies to explain the mechanisms of both hybrid
particles and film formation.
• Properties of coatings
Regardless of the initiator and method of synthesis, all coatings made from hybrid
dispersions show very short drying time, reasonable hardness and water resistance. Based
on the results presented in Tables 6.11 and 6.14 it can be concluded that the best properties
of coatings have been achieved with dispersions prepared according to method 3, i.e., by
emulsifying the prepolymer-ionomer in ASD, and the worst – for dispersions prepared
according to method 2, i.e., by diluting the prepolymer-ionomer with monomers. The
properties of coatings made from hybrid dispersions are generally much better than those
of coatings made from starting DPUR (starting ASD dispersions did not form coatings
since they did not contain any coalescent).
322
6.6.1.2 Concentration of Coalescent in Hybrid Dispersions
As can be seen in Table 6.15, concentration of coalescent has a significant effect on the
properties of hybrid dispersions, regardless of the method of synthesis. Very high levels
of coalescent lead to gelling in the course of polymerisation (see MDPUR-ASD prepared
according to method 1a) or partial settling of dispersion during storage (see MDPUR
243 prepared according to method 3). It can also be noted that for dispersions prepared
without coalescent according to methods 1 and 2, average particle size is distinctly higher
and particle size distribution broader than when the process is carried out in the presence
of coalescent. This phenomenon can be explained by the positive influence of small
amounts of coalescent on the process of hybrid particle formation in the course of
polymerisation. It can be assumed that the particles of starting DPUR are partly swelled
by coalescent which helps the monomers to diffuse into them. When hybrid dispersions
have been prepared according to method 3, the reverse effect is observed. Here, increasing
the coalescent concentration results in diminishing both the average particle size and
particle size distribution range. The reason for this may be easier formation of separate
DPUR particles at lower levels of coalescent.
The effect of coalescent on the properties of films made from hybrid dispersions seems to
be not quite significant (see Table 6.16) which is strange when taking into account the
important role of coalescent in the process of film formation. The only observation that
can be made here is that, as has already been stated in Section 6.6.1.2.1, high levels of
coalescent cannot be recommended in preparation of hybrid dispersions.
Here, the effect of coalescent is clearly visible (see Table 6.17), but only if the coalescent
content is high (MDPUR 243). Then, drying time increases and coating hardness decreases.
However, no differences can be observed between the properties of coatings made from
hybrid dispersions which do not contain any coalescent and those which contain only
small amounts of coalescent.
323
6.6.1.3 Chemical Structure of the Polyurethane-Urea Component of the Hybrid
6.6.1.3a Substituting Polyetherdiol for Polyesterdiol
As can be seen from Table 6.18, the chemical structure of the polyurethane-urea part of
the hybrid does not affect the properties of hybrid dispersions, obviously not counting
the MFFT which is much higher if polyesterdiol has been used as a starting material for
the prepolymer-ionomer synthesis (compare MDPUR-ASD 300 and MDPUR-ASD 24).
Here, the effect of chemical structure of the polyurethane-urea part of the hybrid is, of
course, substantial (see Table 6.19). For hybrid dispersion synthesised without coalescent
using polyesterdiol as a starting material for the prepolymer-ionomer, the Tg is so high that
films cannot be obtained. On the other hand, if polyetherdiol is applied as a starting material
in the synthesis of the same dispersion, films of very good mechanical properties are obtained.
This was the reason for using polyetherdiol rather than polyesterdiol as the starting material
for synthesis of dispersions in this study.
It can be clearly seen from Table 6.20 that the hybrid dispersion prepared using polyesterdiol
(MDPUR-ASD 300) forms faster-drying coatings of better hardness, adhesion and water
resistance. This information may be important from the practical point of view.
6.6.1.3b Introducing Double Bonds to Polyurethane-Urea
As can be seen from Table 6.21, introducing double bonds into the polyurethane-urea
component of the hybrid does not affect the properties of hybrid dispersions regardless
of the method used for their synthesis.
Based on the data contained in Table 6.22 it can be concluded that the effect of introducing
double bonds to polyurethane-urea on the properties of films made from hybrid dispersions
324
is exceptionally strong. Regardless of the method of hybrid dispersion synthesis, the presence
of double bonds in polyurethane-urea results in a distinct increase in Tg and a drastic
increase in film stiffness (decrease in film elasticity), and, an increase in resistance to water
and organic solvents. This may mean that grafting or even crosslinking takes place during
polymerisation and/or crosslinking via oxidation of double bonds suggested earlier [29],
proceeds during air-drying of the films.
The presence of double bonds in polyurethane-urea has very significant effects on the
properties of coatings made from hybrid dispersions (see Table 6.23). It leads to drastic
(two-fold) increase in coating hardness and to distinct shortening of drying time. However,
there is no effect of double bonds in polyurethane-urea on adhesion or water resistance
of the coatings.
Generally, based on the results shown above, it can be concluded that introducing double
bonds into polyurethane-urea is undoubtedly one of the ways to obtain coatings of
excellent properties based on hybrid polyurethane-urea-acrylic/styrene dispersions.
6.6.1.4 Chemical Structure of the Acrylic/styrene Part of the Hybrid
Table 6.24 shows that the chemical structure of the acrylic/styrene part of the hybrid has
no effect on the macroscopic properties of hybrid dispersions, although the appearance
of the dispersion particles may be quite different (compare Figures 6.23 and 6.24).
Difference in the appearance of particles may result from the degree of hydrophobicity
of the monomer (this effect is explained in Section 6.3.2.1).
The chemical structure of the acrylic/styrene part of the hybrid has a substantial effect on
the properties of films made from hybrid dispersions (see Table 6.24). When the monomers
that form polymers of high Tg (styrene or MM) are used and the synthesis is carried out
according to method 1a, no film is obtained. For the same monomers but a different method
of dispersion synthesis (method 3), a film was obtained only for styrene and only when a
high level of coalescent was applied. In this case, the mechanical properties, water and
solvent resistance of the film were quite good, but the film was not transparent, which
325
indicated that the uniformity of the system, i.e., the compatibility of polystyrene with
polyurethane-urea was rather poor. Based on the results of investigations of the effect of
styrene on the morphology of the model polyurethane-urea-acrylic/styrene hybrid systems
[41] this assumption can be proved.
When BA or a mixture of monomers (BA/MM/S) was used for synthesis of hybrid

dispersions, transparent films of very good mechanical properties and water resistance
were obtained (the best properties were obtained when the dispersions were prepared
according to method 3). Solvent resistance was good only for films made from the
dispersion prepared according to method 3.
Using data presented in Table 6.26 it can be concluded that the type of monomer used in
the synthesis of hybrid dispersions has no effect on the drying time of coatings made
from these dispersions, but has a significant effect on coating hardness. The highest
hardness can be achieved with coatings made from dispersions prepared using MM as a
starting monomer, if it is possible to make a coating (compare MDPUR-ASD 22 and
MDPUR 245 in Table 6.26). It is noteworthy that it was not possible to make any
coating from MDPUR 245 (prepared according to method 3), despite the fact that it
contained a high level of coalescent.
6.6.1.5 Crosslinking of the the Acrylic/styrene Part of the Hybrid
Table 6.27 shows that the properties of hybrid dispersions prepared with additional
crosslinking of acrylic/styrene polymer do not differ from the properties of dispersions
of the same composition prepared without additional crosslinking. Also the properties
of films made from both dispersions were very similar (see Table 6.28). However, lack of
positive effects of additional crosslinking of the acrylic/styrene part of the hybrid may
result from improper selection of starting materials for hybrid synthesis. Therefore, we
intend to investigate this effect further in another study along with further studies on the
effect of introducing double bonds to the polyurethane-urea part of the hybrid.
6.6.2 Mechanism of Hybrid Particle Formation
Based on the results of supplementary investigations (see Section 6.5.4) that were carried
out to better understand the mechanism of hybrid particle formation and to determine
particle morphology, the following observations can be made:
326
(a) Investigations of the kinetics of the process of swelling the DPUR particles with
monomers (see Section 6.5.4.1) have shown that the number of ‘bigger’ particles
(particles swelled with monomer and monomer droplets) increases gradually while
the number of ‘smaller’ particles (DPUR particles not swelled with monomers)
decreases. After some time (about 5 hours), equilibrium is reached and then a
bimodal particle size distribution occurs. This direct observation of the process of
swelling DPUR particles with monomers is very interesting because it does not
correlate with the course of swelling the film with monomers (compare with Section
6.5.4.2). In the process of swelling the film with monomers, equilibrium is reached
after a much longer time (12 hours) regardless of the monomer used. This happens
at a much higher degree of swelling (approximately 90%) as compared to the process
of swelling DPUR particles (maximum 40% assuming that all monomer diffused
into the DPUR particles). In practice, a significant amount of the monomer remains
in the form of monomer droplets suspended in DPUR.
It is also interesting to note that during the feeding of the monomers, the zeta
potential becomes less negative which indicates that the uniformity and stability of
the whole system is diminishing.
Investigations of swelling of DPUR particles with monomers indicate that although

all monomer being fed into the system may theoretically enter DPUR particles,
since the maximum degree of swelling is more than twice that of the monomer/
DPUR solids w/w ratio used commercially in synthesis of hybrid dispersions, in
practice there will always be a natural tendency of the system to reach equilibrium
between monomer droplets, non-swollen DPUR particles and swollen DPUR
particles. Therefore, when hybrid dispersions are prepared according to method
1a, 1b or 2 (see Section 6.3.2) the result will always be a mixture of particles of
hybrid structure with DPUR and ASD particles, as has been explained in Section
6.3.2.1).
(b) The results of investigations of crosslink density of films made from hybrid
dispersions (see Section 6.5.4.2) show that when the values of the crosslink density
of the films determined by swelling in toluene are compared it can be concluded
that regardless of the method used for synthesis of hybrid dispersions the films are
all crosslinked, or at least they behave as if they were crosslinked. This may mean
either that the polymers in the films are actually crosslinked or very strongly branched
(by the grafting of monomers on polyurethane-urea) and/or that there is strong
domination of ‘core-shell’ structure with a ‘shell’ made of polyurethane-urea. The
latter possibility is supported by the properties of films made from hybrid dispersions
prepared according to method 3 (emulsifying of prepolymer-ionomer in ASD and
then crosslinking with polyamine). It may also be additionally supported by:
327
• the experimentally proven existence of an outer polyurethane-urea shell in the

particles of hybrid dispersions prepared not only according to method 3 (which
seems quite obvious), but also according to method 2 (see Figures 6.32
and 6.33).
• the values of the polar and non-polar (dispersed) components of surface free
energy determined for the films made from hybrid dispersions being very similar
to the values found for the films made from DPUR, not ASD (see Table 6.30).
This may be considered as evidence for ‘hiding’ of the acrylic/styrene part of the
hybrid under the film surface, which results presumably from the ‘core-shell’
structure of the coalesced dispersion particles that form the film, where
polyurethane-urea constitutes the shell and acrylic/styrene polymer the core.
(c) The morphology of hybrid dispersion particles shown in Figure 6.31 looks quite
interesting. It can be clearly seen that regardless of the method of synthesis, resulting
in particles of different morphologies, they all have ‘core-shell’-like structures and
differ substantially from the particles of ASD, which have a uniform structure.
Deeper analysis of these structures leads to the conclusion that for MDPUR-ASD
prepared according to Method 1b, the particle morphology resembles that described
as ‘engulfed’ [15] for other types of hybrid dispersions (see Figure 6.1). For our
hybrid dispersion, small round-shaped particles of acrylic/styrene polymer are
‘engulfed’ or ‘englued’ in the bulky core made of polyurethane-urea.
The most interesting result seems to be, however, the specific morphology of the
particles of hybrid dispersions prepared according to method 2 shown in Figures
6.32 and 6.33. It is shown schematically in Figure 6.34.
Here, the acrylic/styrene polymer constitutes an under-surface sphere ‘embedded’ in

a particle made of polyurethane-urea. This sphere is approximately 25-40 nm thick
and is situated approximately 15-20 nm from the particle surface. After coalescence
of the particles this specific structure is retained (see coalesced particles in Figure
6.32) so that the film made from a dispersion of this particular particle morphology
should have the structure presented schematically in Figure 6.35.
This kind of structure is undoubtedly very interesting since it is a ‘nanostructure’

where ‘nanospheres’ of acrylic/styrene polymer are embedded in a polyurethane-
urea matrix. Such a structure suggests that very specific properties of the film could
be obtained if the components of the hybrid were especially selected.
328
Figure 6.34 Schematically presented ‘embedded sphere’ morphology of the particles of

hybrid dispersions prepared according to method 2 (diluting the prepolymer-ionomer with
monomers, emulsifying it in water, crosslinking with polyamine and polymerisation)
Figure 6.35 Schematically presented structure of film made from a hybrid dispersion
of the particle morphology shown in Figure 6.34
329
6.7 Summary
In this study, aqueous hybrid polyurethane-urea-acrylic/styrene polymer dispersions were

obtained using four different methods. The dispersions are stable and their viscosity, and
pH as well as average particle size and particle size distribution are similar to those
observed for DPUR. Most of the hybrid dispersions formed transparent films of good
mechanical properties, water resistance and organic solvent resistance.
Detailed investigations of coating properties of hybrid dispersions proved that they could
form transparent coatings of reasonable hardness, adhesion and water resistance.
The effect of various factors on the properties of hybrid dispersions as well as of

films and coatings made from them was determined. The results are summarised in
Table 6.31.
Based on the data in Table 6.31 the following dependencies may be concluded:
• the properties of hybrid dispersions: dependent on method of hybrid synthesis and

chemical structure of the polyurethane-urea part of the hybrid
• the properties of films made from hybrid dispersions: dependent on method of hybrid
synthesis, chemical structure of the polyurethane-urea part of the hybrid, presence of
double bonds in the polyurethane-urea and the chemical structure of the acrylic/
styrene part of the hybrid
• the properties of coatings made from hybrid dispersions: dependent on chemical structure
of the polyurethane-urea part of the hybrid and presence of double bonds in the
polyurethane-urea
The morphology of dispersed particles revealed by TEM appeared to be very

interesting. It was found that the method of hybrid synthesis had a substantial influence
on the particle morphology and that usually ‘core-shell’ or ‘englued’ morphologies
described earlier in the literature were observed. However, in one case the unusual
‘embedded sphere’ morphology was seen. In these particles, the core made of
polyurethane-urea is surrounded by a 25-40 nm thick sphere made of acrylic/styrene
polymer and covered by a 15-20 nm thick outer layer of polyurethane-urea. The
structure of film made from such dispersions is very interesting since it is a two-
phase structure where ‘nanospheres’ of acrylic/styrene polymer are suspended in a
polyurethane-urea matrix.
The supplementary experiments, and especially investigations of the process of swelling

of dispersion particles with monomers and film surface free energy determinations, allowed
confirmation of the assumed mechanism of hybrid particle formation.
330
Table 6.31 Effect of various factors on the properties of hybrid polyurethane-urea-acrylic/styrene polymer
dispersions synthesised in this study
Properties of dispersions Properties of films Properties of coatings
Water
Stability Particle size
Mechanical and Water
Viscosity and size MFFT Tg Drying Hardness Adhesion
properties solvent resistance
pH distribution
resistance
Method of hybrid
synthesis
- ++ - + + - + + + +
Type of initiator - - - - - - - - - -
Coalescent content - + - - - - + - + -
Chemical structure
of polyurethane-urea - - ++ ++ ++ ++ + + ++ +
part of hybrid
Presence of double
bonds in
polyurethane-urea
- - - ++ ++ ++ ++ - ++ -
part of hybrid
Chemical structure
of acrylic/styrene - - - ++ + ++ - + + +
part of hybrid
Crosslinking of
acrylic/styrene - - - - - - - - - -
polymer
+: some effect was observed
-: no effect was observed
++: distinct effect was observed
331
Acknowledgements
The authors wish to thank Professor I. A. Grickova (Lomonosov University, Moscow)

and Professor A. E. Czalych (Institute of Chemical Physics, Russian Academy of Sciences,
Moscow) for valuable consultations. The assistance of our co-workers from the Industrial
Chemistry Research Institute in carrying out the experiments and testing is also gratefully
acknowledged. This study was carried out under project 3TO9811410 sponsored by the
Polish National Committee for Scientific Research.
References
1. R. R. Roester and R. W. Rimmer, Paint and Coatings Industry, 1991, 7, 3, 22.
2. J. Kozakiewicz in Adhesion 15, Ed., K. W. Allen, Elsevier Applied Science

Publishers, London, 1991, Chapter 6.
3. J. Kozakiewicz, Aqueous Polyurethane Dispersions as Coating Binders, presented

at Ekolak Symposium, Ustron, Poland, 1993.
4. J. W. Rosthauser and K. Nachtkamp, Journal of Coated Fabrics, 1986, 16,

July, 39.
5. J. Goldsmith, Journal of Coated Fabrics, 1988, 18, July, 12.
6. Waterborne PU Dispersions, ICI leaflet.
7. H. C. Goos and G. C. Overbeek, inventors; Polyvinyl Chemie Holland BV,

assignee; EP 0308115A2, 1989.
8. M. Hartung, M. Grabbe and P. Mayenfels, inventors; BASF Lacke + Farben,

German Patent DE 4 010 176 A1, 1991.
9. M. Guagliardo, inventor; Inmont Corporation, assignee; US 4318833, 1982.
10. J. T. Huybrechts, inventor; E.I. DuPont de Nemours and Company, assignee; US

4888383, 1989.
11. R. G. Coogan and R. Vartan-Boghossian, inventors; ICI Americas, Inc., assignee;

US 4927876, 1990.
12. P. Penczek in Polymer Blends, Eds., E. Maruscelli, R. Palumbo and M.

Kryszewski, Plenum Press, New York, 1986, p.333.
332
13. S. Muroi, H. Hashimoto and K. Hosoi, Journal of Polymer Science: Polymer

Chemistry, 1984, 22, 6, 1365.
14. J. Kozakiewicz, Presented at the 7th European Polymer Federation Symposium on

Polymeric Materials, Szczecin, 1998, p.94.
15 D. E. Mestach and F. Loos, Presented at the 23rd FATiPEC Congress, Brussels,

1996, Paper No.B-91.
16 N. Subramaniam, M. J. Monteiro, J. R. Taylor, A. Simpson-Gomes and R. G.

Gilbert, Presented at the 7th European Polymer Federation Symposium on
Polymeric Materials, Szczecin, 1998, p.53.
17 J. Kozakiewicz, Hybrid Dispersion Systems as Coating Binders, Presented at the

Seminar of Polifarb Cieszyn-Wroccaw, 9.05.1998, Ustron-Zawodzie.
18 U. Desor, B. Lean and R. Kuropka, Presented at the 25th FATiPEC Congress,

Torino Lingotto, 2000, Volume 2, p.117.
19 Z. Florianczyk and S. Penczek, Polymer Chemistry, Warsaw Technical University

Press, Warsaw, 1995.
20 M. Schwartz and H. Kossmann, European Coatings Journal, 1998, 3, 134.
21 J. W. Rosthauser and K. Nachthamp, Advances in Urethanes Science and

Technology, 1987, 10, 121.
22 J. Kozakiewicz, Presented at the 2nd Symposium on Aqueous Dispersions and

Solutions of Polymers, Ustron, Poland, 1993, p.27.
23 D. Dieterich, Angewandte Makromolekulare Chemie, 1981, 98, 133.
24 R. E. Tirpak and P. H. Markusch, Journal of Coatings Technology, 1986, 58,

738, 49.
25 I. Bechara, Journal of Coatings Technology, 1998, 70, 236.
26. P. Loewrigkeit and K. A. Van Dyk, inventors; Witco Corporation, assignee; EP

0189945B1, 1990.
27. B. Gruber, Presented at the ACS Meeting, San Francisco, CA, 1992, Paper
No.108.
333
28. C. R. Hegedus and K. A. Kloiber, Journal of Coatings Technology, 1996, 68,

860, 39.
29. R. Tennebroek, J. M. Geurts, A. Overbeek and A. Hermsen, European Coatings

Journal, 1997, 11, 1016.
30. J. M. Geurts, R. Tennenbroek, A. Overbeek and Y. W. Smak, Presented at the

23rd FATiPEC Congress, Brussels, Belgium, 1996, Paper No.D-259.
31. H. R. Lucas, W. E. Mealmaker and N. Giannopous, Progress in Organic

Coatings, 1996, 27, 1-4, 133.
32. M. Locatelli, V. Alonzo, S. Giordano, M. Piccinini and E. Sironi, Presented at the

25th FATiPEC Congress, Torino Lingotto, 2000, Volume 2, p.135.
33. G. C. Cornelius, Y. W. Smak and E. Martin, inventors; Zeneca Resins BV,

assignee; WO Patent 9916805A1, 1999.
34. A. E. Czalych, unpublished results
35. ISO 1522 Paints and Varnishes - Pendulum Damping Test, 1998.
36. ISO 2812-1 Paints and Varnishes - Determination of Resistance to Liquids - Part
1 - General Methods, 1993.
37. DIN 53150 Testing of Paints, Varnishes and Similar Coating Materials;
Determination of the Drying stage of Coatings (Modified Bandow Wolff
Method), 1995
38. ISO 527-1, Plastics – Determination of Tensile properties – General Principles,

1993.
39. ASTM D3418-99, Standard Test Method for Transition Temperatures of

Polymers by Differential Scanning Calorimetry.
40. G. C. Overbeek, Y. W. Smak and E. Martin, inventors; Avecia BV, assignee;

EP1015507A1, 1999.
41. I. Legocka, J. Kozakiewicz and A. Czalych, unpublished results.
334
7
Adhesion Behaviour of Urethanes
Ashok Sengupta and H.P. Schreiber
7.1 Introduction
Two-component polyurethanes (PU) are applied in many areas of advanced technology.

For example PU are used as architectural/maintenance coatings or as adhesives for a
variety of substrates including glass and polymers such as polyvinyl chloride (PVC),
acrylonitrile-butadiene-styrene (ABS) and polymer blends, e.g., XenoyTM. Two
component PUs are created by the reaction of a polyisocyanate and a polyol or co-
reactant. The strength and permanence of bonds forged by the adhesive is a vital part of
the system’s performance. A comprehensive understanding of factors influencing the
polymer/PU bond is therefore important.
The adhesion behaviour of urethanes depends not only on their composition but also on
the contribution of physico-chemical factors, in particular on the surface properties of
urethanes. Two specific aspects of surface behaviour are considered in this chapter, which
is arranged in three sections: the first concerns the ability of some polymers, including
PU to adopt a variety of surface structures or orientations, as dictated by preparation
conditions and the medium in contact with the urethane polymer. The ability to undergo
surface restructuring is a factor in the well documented difference between surface and
bulk properties of all polymers. A second aspect of surface behavior, exerting major
influence on the adhesion of urethanes to a variety of plastics or glass, is the acid-base
interaction between the adhesive polymer and the substrate. Acid-base interactions are a
subject of discussion in the second section of this chapter. Finally, the role of silane
modifiers in affecting the adhesion behavior of defined urethane adhesive formulations
is considered.
7.2 Surface Characteristics of PU Adhesive Formulations
This study involves surface analyses on formulations typical of PU adhesives. The objective
is to examine the surface properties of such polymers; to investigate the possibility of
surface changes occurring when the adhesive, cured to different degrees, is contacted
with orienting fluids notably water; and to indicate the degree to which surface
restructuring may influence the bonding characteristics of PU adhesives.
335
7.2.1 Experimental
7.2.1.1 Materials
The major portion of this work used as reference a two-part soft-segment PU formulation.
A prepolymer of methylene bis-4-cyclohexylisocyanate (MDI) with a large amount of
2,4-isomer constituted Part A. Part B was a mixture of two tri-functional polyols with
molecular weights of 900 and 500. These were used in weight ratios of 70/30. Part B also
contained about 0.08 wt% of a tin catalyst (UL-28, Witco Chemicals).
The formulations were cured to various degrees. In one cure procedure, the polymer was
first hardened at 100 oC for 1 hour and then exposed to ambient conditions for five
days. In a number of cases, this was followed by further curing at 50 °C/50% relative
humidity. In an alternative procedure, the initial 100 °C/1 hour exposure was followed
by conditioning for varying lengths of time at room temperature and 50% RH. These
alternative post-cure processes were followed to produce a range of crosslink levels and
to vary also the degree of enolisation occurring during cure.
7.2.1.2 Surface Analyses
In order to produce PU films, parts A and B were mixed to give ratios of NCO:OH of
1.03, and in some cases, 1.13. These mixtures were cast onto previously degreased
glass microscope slides and drawn down with doctor blades to give final polymer
coating thicknesses of 1.2 mm. Samples were cured by the regimes outlined previously.
Surface energies were obtained from experimental determinations of contact angles
for sessile drops, using a Rame-Hart goniometer. All experiments were conducted at
30 °C. Data were obtained for wetting by dispersion force fluids, represented by a
series of n-alkanes, and by formamide, glycerol, ethylene glycol, and water (liquids
with appreciable non-dispersive forces). In all cases, the dead space around the enclosed
sample was in equilibrium with the vapour of the contacting liquid, and contact angles
at zero contact time were obtained by extrapolation of data at finite times of contact.
This avoided the risk of changes due to any possible liquid-substrate interactions. The
procedures of Gent and Schultz [1] were used for determinations of dispersive and
non-dispersive contributions to the overall surface energies, γsd and γsnd. These were
obtained with experimental uncertainties of less than 6%.
Following initial surface energy evaluations, the PU films were immersed in water at
controlled temperatures and for controlled times. Following immersion, films were
dried under vacuum (room temperature, 24 hours) and surface energies were
redetermined.
336
Analyses of chemical structure in cured films, before and after immersion, were carried
out by IR spectroscopy, utilising a Bonem-Michelson-100 FTIR instrument.
Another aspect of surface analysis involved the use of inverse gas chromatographic (IGC)
techniques [2]. Specifically, IGC was used to evaluate the acid-base interaction potential
of PU surfaces and of substrates against which the adhesive was to be bonded. In the
IGC determination, the polymers are the non-volatile phase, while the volatile phase
included n-alkane vapours and vapours defined as acids and bases by contemporary
theories. Such as the theory of Gutmann [3], applied in the present case along with
developments reported separately by Saint Flour and Papirer [4] and by Deng and Schreiber
[5]. In this protocol [5], chloroform represents a pure acid vapour; tetrahydrofuran and
diethylether are strong bases; while acetone may be used as an amphoteric vapour. The
IGC procedure, described in detail elsewhere [2, 4, 5], yields interaction parameters for
the test solids. The parameter acceptor number (AN) is a measure of surface acidity; the
donor number (DN), evaluates the base interaction potential; and an averaged interaction
potential is given by
Ki = DN – AN. (1)
Positive values of Ki designate a surface which is predominantly basic. Predominant

surface acidity will produce a negative Ki. Generally, polymers show finite values of both
AN and DN, with different groups of the surface region acting as electron donors and
acceptors. A surface is considered to be amphoteric when AN and DN are finite and of
similar values, with Ki ~ 0. When both AN and DN are zero, the surface is considered to
be neutral.
For IGC work with PU, the polymer was cured against Teflon sheet, peeled off, and
powdered by pestle and mortar. About 1.0 g of powder was packed into previously
washed and dried steel columns, 15 cm long and 1.2 cm in diameter. Polymer substrates,
such as PVC and ABS, were deposited onto Chromosorb support (acid-washed, 60/40
mesh diatomaceous earth) following well-established procedures [6]. Small, nanoliter
amounts of the volatile phase were injected into the chromatograph, with helium as the
carrier gas at a flow rate of 10 cm3/min.
7.2.1.3 Adhesion
Bond strengths of PU adhesives were obtained from single lap-shear determinations.

Substrate/adhesive/substrate joints were made with ABS and PVC coupons, 8 x 2.5 cm,
as substrates; the overlap area was 4.5 cm2. The reference PU here was compounded
with glass beads to provide adhesive layers with uniform thicknesses of 1.27 mm. Lap
337
shear data were obtained with an Instron tester at 25 mm/min jaw separation speed. At
least three, and in most cases five to eight, separate determinations were carried out for
each of the systems, with averaged results presented here. The experimental uncertainty
in these determinations ranged from 8 to about 20%.
7.2.2 Results and Discussion
7.2.2.1.Surface Analyses
Throughout this section, reference will be made to PU specimens cured to varying

degrees. For convenience, cure processes will be coded as indicated by the entries in
Table 7.1.
Table 7.1 Summary of PU cure procedures

Cure Code Procedure
C0 0.5 h, 100 °C
C1 1 h, 100 °C
C2 1 h, 100 °C + 5 days, RT
C3 1 h, 100 °C + 5 days, RT + 1 day, 50 °C, 50% RH
C4 C2 + 2 days, 50 °C, 50% RH
C5 C2 + 5 days, 50 °C, 50% RH
C6 C2 + 10 days, 50 °C, 50% RH
C7 C2 + 14 days, 50 °C, 50% RH
C8 C1 + 1 day, RT, 50% RH
C9 C1 + 2 days, RT, 50% RH
C10 C1 + 5 days, RT, 50% RH
C11 C1 + 10 days, RT, 50% RH
C12 C1 + 14 days, RT, 50% RH
RT = Room temperature
RH = relative humidity
Reproduced with permission from A. Sengupta and H. P. Schreiber, Journal of
Adhesion Science and Technology, 1991, 5, 11, 947, Table 1. © 1991, VSP BV.
338
The capability of (partially) cured PU surfaces to restructure under the influence of

orienting fluids is illustrated in Figure 7.1. Here, the polymer cross-linked by procedure
C2 initially shows a non-dispersion force contribution of about 2mJ/m2 to a measured
total surface energy of about 38 mJ/m2. If the surface and bulk of the polymer are
identical in composition, γnd is lower than an expected value near 98.5 mJ/m2. The
reference polymer has a 41 wt% contribution from the polar hard segment, leading
to the conclusion that as initially prepared, the polymer surface has an excess
concentration of the soft-segment moiety. Essentially, this is a hydrocarbon with an
expected surface energy in the 35 mJ/m2 range. This finding confirms those of Chen
and Ruckenstein [7] and further substantiates results from earlier studies [5]. As
shown in [5], a marked increase in γnd takes place on contact with water. The non-
dispersive component rises toward a plateau value of about 8.5 mJ/m2, again in
Figure 7.1 Time-dependent increase of non-dispersive surface energy for polyurethane

immersed in water. Polymer cure code C2 (Table 7.1). Immersion at (▲ ) 38.5 °C,
(●) 60 °C, and (● ) 81 °C.
Adhesion Science and Technology, 1991, 5, 11, 947, Figure 1. ©1991 VSP BV
339
agreement with data in reference [5], and the rate of change is strongly temperature-
dependent. Activation energies for an assumed diffusion-dependent process may be
calculated from the results in Figure 7.1. The value obtained, 11.4 kcal/mol, is in
excellent agreement with expected values for diffusion processes of chain molecules
through polymer matrices, reported to be in the 10-12 kcal/mol interval [8]. By this
interpretation, contact with water (γnd = 52 mJ/m2) leads to the diffusion of hard
segments into the surface region of the PU, driven by the thermodynamic need to
minimise the interfacial tension. In the new equilibrium state, the polymer has a
considerably higher total surface energy, since as shown in Figure 7.2, the dispersion-
force component is not greatly affected by contact with water. When in the
conformation dictated by water, the total γs of the PU surface is 42.5 mJ/m2, more
than 10% greater than when this polymer is in its ‘air-conformation’ state.
Figure 7.2 Response of the polyurethane dispersion-force surface energy to water

immersion at (●) 38.5 °C, (● ) 60 °C, and (■) 81 °C.
340
While the emphasis above is on structural reconformation as the cause of changes in γsnd,
other mechanisms may be considered. They include:
(i) plasticisation of the polymer by water; and

(ii) enolisation, by water, of NCO linkages in the polymer.
The former of these may be rejected, since the data in Figure 7.1 were shown to be
independent of the drying time following removal of samples from water. Vacuum-drying
for 5 hours, for the standard 24 hours, and 48 hours produces samples in which γsnd was
unchanged within experimental error. The observed surface energy effects are therefore
unlikely to be caused by the physical incorporation of water in the polymer.
The second mechanism, that of enolisation, may be investigated using IR data, focusing on
the NCO absorption peak at 2300 cm–1 and on the OH signal at 3300 cm–1. Pertinent
results are given in Table 7.2 for specimens prepared under the full range of cure conditions.
Table 7.2 IR Spectra of PU adhesive: effect of cure variables

Peak Area (cm2)
Cure Code a -NCO (2300 cm-1) -OH (3300 cm-1)
C0 1.31 2.22
C1 1.06 2.17
C2 0.84 1.88
C3 0.77 1.37
C4 0.64 1.72
C5 0.70 1.58
C6 0.43 1.60
C7 0.52 1.44
C8 0.93 2.04
C9 0.74 2.15
C10 0.61 1.73
C11 0.68 1.87
C12 0.59 1.70
a
For definitions, see Table 7.1
Adhesion Science and Technology, 1991, 5, 11, 947, Table 2. © 1991, VSP BV.
341
Comparison of the NCO and OH absorption peak areas shows that chemical changes
continue to take place as the urethane polymer ages. Specimens made by routes C0 and C1
show that an additional 30 minutes at 100oC reduces both signals, and more particularly
that for NCO. Additional reductions are observed for samples cured via routes C2 and C3.
The series C3-C7 shows continued decreases in the OH peak and a slight downward
tendency for the NCO peak. The sequence C8-C12, referring to room temperature exposure
at controlled humidity, follows similar patterns, though the magnitude of the reductions in
peak areas is somewhat diminished. It is concluded that chemical changes do indeed take
place in the curing polymer, and that even after 14 days at 50 °C these changes have not
gone to completion. The speculation on enolisation effects therefore appears to be supported
analytically. The relative contribution of the supposed enolisation effects to observed changes
in surface energy must now be questioned.
One aspect of the question is considered by the results in Figure 7.3. This shows the response
of γnd of the reference polymer to immersion in a non-polar, dispersion-force fluid
Figure 7.3 Response of the non-dispersion force surface energy of reference

polyurethane to immersion in heptane, 60 °C. Polymer previously immersed in water.
342
(n-heptane). Prior to immersion in heptane at 60 °C, the polymer had been immersed in
water at the same temperature for 48 hours to bring the surface state into equilibrium with
the orienting fluid. Consequently, the ordinate in Figure 7. 3, namely the difference between
γnd of the polymer in the ‘water’ and the ‘air’ steady states, originates at about 6 mJ/m2. If
this increase, shown in Figure 7.1, were due entirely to surface restructuring, then immersion
in heptane would restore the ‘air’ steady-state and Δγnd = 0. Instead, however, the non-
dispersive surface energy levels out at about 1.8 mJ/m2. Conformational and reversible
restructuring accounts for the major portion of surface energy changes in the partially
cured PU. A smaller, yet significant irreversible portion, however, arises from changes in
the surface chemistry of the polymer when it is allowed to condition in aqueous media.
Another view of the relationship between surface mobility and the level of cure in the PU
is shown in Figure 7.4. This follows the γsnd on immersion in water at 60 °C of samples
cured under procedures C1, C5, and C10 (see Table 7.1). Clearly, in each case there is a
significant rise in γnd, but the magnitude of the increase varies with the cure procedure.
Figure 7.4 Effect of the degree of cure on the surface restructuring of polyurethane on
water immersion, 60 °C. Cure states coded according to Table 7.1.
(● ) C1, (■ ) C5; (●) C10.
343
The most drastic cure in this group was applied to sample C5, which produces the lowest
restructuring effect; C10 and C1 represent progressively milder cure strategies and the
restructuring tendency correspondingly increases. Thus, surface chain dynamics of PUs
are a function of the degree of cure, but under each of the procedures used in this work
the restructuring effect remains sufficiently important, potentially, to affect adhesion,
and related properties of the polymer surface.
7.2.2.2 Adhesion Performance
The lap-shear experiments described previously, clearly show that the adhesive bond
between PU and a polymer substrate is not uniquely defined by the composition of the
materials in the joint. This is shown by the results in Table 7.3 which gives the adhesive
bond strengths of ABS/PU joints, in which the adhesive was cured by the various routes
Table 7.3 Adhesive strength of ABS/PU joints

(all data are lap-shear tests at 30 °C)
Cure Code a Wa (MPa)
C1 3.6± 0.3
C2 2.1± 0.3
C3 1.7± 0.3
C4 1.5± 0.3
C5 1.2± 0.3
C6 1.2± 0.3
C7 1.2± 0.3
C8 3.6± 0.3
C9 3.1± 0.3
C10 2.3± 0.3
C11 2.4± 0.3
C12 2.2± 0.3
a
For definitions, see Table 7.1
Reproduced with permission from A. Sengupta and
H. P. Schreiber, Journal of Adhesion Science and
Technology, 1991, 5, 11, 947, Table 3. © 1991, VSP BV.
344
described in Table 7.1. A wide variation in bond strengths is noted; the major trend is
toward reduced adhesion with increasing duration of cure, and thus also with increasing
contact time between PU and ABS. In this case, of course, the orienting medium for the
adhesive is the ABS surface. The results, therefore, suggest that the steady-state
conformation of PU relative to ABS is less favourable to strong bonding than is an initial,
transient conformation of the adhesive surface. This somewhat surprising result may be
rationalised with a knowledge of the acid-base characteristics of the polymer.
IGC determinations of AN, DN, and Ki values for ABS, PVC, and PU are summarised in
Table 7.4, all data being at 30 °C.
Table 7.4 AN, DN and Ki values

AN DN Ki
ABS 5.1 8.5 3.4
PVC 9.4 2.1 -7.3
PU 2.4 4.4 2.0
These results show ABS to be a moderate base and PVC a strong acid. PU, measured here
in its surface conformation relative to air, is mildly basic. There is, therefore, no tendency
for specific non-dispersive forces to act across the ABS/PU interface, the basicity of the
materials being unfavourable to the establishment of strong, short-range forces of this
kind. On prolonged contact, the initial tendency for dispersion-force soft segments to
populate the PU surface preferentially should become more pronounced, accounting for
the data sequence in Table 7.3. Of course, the trends should be reversed with PVC, for in
this case acid-base attraction should promote adhesive bond strength. Only fragmentary
experimental results are available to test the hypothesis, but as shown in Figure 7.5,
these support it. They are also consistent with the recent work of Berger [9], showing the
influence of non-dispersion forces on the lap shear strength of polymer/metal joints.
A matter of much practical importance is the durability of bond strength when joints
are exposed to aggressive environments. A cursory examination of this point was carried
out as follows: joints of PVC/PU and ABS/PU were prepared by cure procedure C2.
Several of these were aged at 50 °C/50% relative humidity for up to 10 days and lap-
345
Figure 7.5 Effect of ageing at 50 °C, 50% RH on lap-shear adhesion of polyurethane/

PVC (▲ ) and polyurethane/ABS (● ) joints. Polyurethane adhesive cured according to
code C2 (Table 7.1)
shear evaluations were carried out as described previously. The results in Figure 7.5,
however, are limited for the most part to single specimen evaluations. A lower degree
of confidence therefore applies to them. The effects seen in the figure, however, are
entirely consistent with the preceding analyses. With ABS, as before, a slight
deterioration takes place in bond strength. The initial bond strength with PVC as
substrate is significantly higher than that with ABS, and, moreover, increases with
ageing, as called for by the acid-base concept. The orienting potential of polymers
including PU therefore may arise from the nature of acid-base interactions at the point
of contact between materials. These effects may have serious consequences on the
performance parameters of materials such as PU adhesives.
346
7.2.3 Conclusions
The results of this study lead to the following conclusions:
(1) The surface energy of a PU formulation has been shown to vary with the nature of
the medium in contact with the polymer. The variations are attributed to the non-
dispersive part of the overall surface energy. The observed trends follow closely
earlier observations on two-part, linear PU surfaces.
(2) Thermodynamic or acid-base interaction forces appear to be the dominant driving

force for surface restructuring in PU, leading to the surface energy effects.
(3) Chemical changes in the PU surface following prolonged exposure to high

temperatures and/or high humidity contribute to a lesser degree to variations in the
surface energy.
(4) The adhesive bond strength of PU varies with the degree of acid-base interaction
with the substrate and with the conformational state of the adhesive molecule at
the time of testing. Being basic, PU develops stronger bonds with acidic substrates
(PVC in this case) than with basic ones, this is exemplified by ABS.
7.3 Acid/Base Interactions and the Adhesion of PUs to Polymer

Substrates
As noted in the preceding section, IGC is an excellent tool for measurements of surface
properties and of acid base interaction potentials of macromolecular solids (2, 10, 16).
In this section the importance of acid-base interactions relative to the adhesion of PUs
is considered in greater detail. IGC has been applied to a series of PU adhesives and to
selected polymer substrates, allowing quantitative measurements to be made of the
acid/base (electron donor-acceptor) interaction parameters applicable to the surfaces
of these materials. Acid base pair-interaction parameters for substrate/PU combinations
have been calculated. The bond characteristics of polymer/PU combinations have been
measured, in part by conventional lap-shear procedures and in part, by the more recent
constrained blister detachment method [11, 12]. Possible relationships between bond
properties and acid base interactions have been considered, and a comparison of the
two adhesion tests has been made.
347
7.3.1 Experimental
7.3.1.1 Materials
Six PU adhesives, modelled on practical formulations, have been studied. They are coded
PU1 – PU6. All were two-part compounds, denoted as A and B in Table 7.5. In all cases,
part B contained a tin catalyst.
In each of these formulations A and B were thoroughly mixed, applied to the substrate
and bonded in less than 3 minutes following mixing.
The substrates were rigid PVC, ABS impact resin and the GE polyblend Xenoy. All were
commercial samples, and all were injection moulded to form 8.0 cm x 2.5 cm rectangles,
1.5 mm in thickness.
Table 7.5 Formulation of PU adhesives PU1-PU6

PU1 A Aromatic polyisocyanate (Mondur XP-744) with NCO:OH of 1.03.
B A mixture of castor oil and polycaprolactone-based triol.
PU2 A Aromatic polyisocyanate as in PU1.
B A mixture of polycaprolactone diol (MW 1250) and 1,4-butane diol
PU3 A Aromatic polyisocyanate (XP-744, obtained from Bayer Corporation)
with NCO:OH of 1.03.
B OH-terminated epichlorohydrin polyol (MW 1000) and 1,4-butane diol.
PU4 A Rubinate 9225 Polyamine, Mn = 1000;
B Polyamine Mn = 1000. The two mixed at a ratio of 20:5.2 by weight.
PU5 As PU1 but with addition to B of silane adhesion promoter at 1.4 g/100
parts of B.
PU6 As PU4 but with addition to B of silane adhesion promoter at 0.8
parts/100 parts of polyol in B.
Mn = number-average molar weight
7.3.1.2 Procedures
For IGC work, PU and substrate polymers were coated onto Chromosorb AW support
(60/80 mesh) from solution. From 6.0 – 11 wt% of polymer was supported on the
348
Chromosorb. The coated support was packed in stainless steel columns (0.5 cm id, about
0.8 m long) and served as the stationary phase in IGC. The stationary phases were
contacted with selected vapours at very high dilution and described procedures were
followed [6, 11] to measure the net retention volume, Vn, of the vapours probing the
deposited solids. A Perkin-Elmer Sigma-2 chromatograph with hot wire detector was
used. All determinations were in the range 30 – 60 °C, and values of Vn were measured
in at least triplicate, with a reproducibility better than 4%.
The use of IGC data to obtain acid and base interaction parameters for polymer solids has
been described in detail elsewhere [2,13,14]. The procedure calls for a reference relationship
between RTln Vn and the normal boiling point of mobile-phase materials able to interact
through dispersion forces only, represented in this work by n-alkanes (C6-C9) . Vapours
known to be acids and bases were then injected into the columns, again at extreme dilution.
Following the theories of Gutmann [3], diethyl ether (DEE) and chloroform (CHL) were
used as reference base and acid, respectively. As shown in Figure 7.6 for PVC as stationary
Figure 7.6 Retention volume of vapour probes interacting with PVC as function of
normal boiling point of probe liquids. Data are for 40 °C.
Reproduced with permission from PU Congress.
349
phase, the points for DEE and CHL both deviate from the straight line defined by the
alkanes. Thus, PVC interacts with both the acidic and basic probe, but with a pronounced
prevalence of interaction with DEE. The polymer is therefore a net acid. Following the
principles of reference [1], electron acceptor and donor indices, AN and DN for the polymers
are calculated from the behaviour of the DEE and CHL vapours.
The adhesion at substrate/PU interfaces was measured by lap-shear and by constrained

blister test methods [11, 12]. For lap-shear testing, adhesives were mixed with glass
beads, Class 4A from Ferro Microbeads, and deposited on PVC and Xenoy substrates to
yield dry films 0.35 mm thick. The adhesives were cured by exposure of 3 days at room
temperature and 50% relative humidity, followed by 4 days at 50 °C, 0% relative humidity.
The lap-shear specimen arrangement si shown in Figure 7.7a. All determinations were
Figure 7.7 Schematic of arrangements for adhesion tests. (a) Specimen construction for
lap-shear test. (b) Specimen construction and installation for blister detachment test.
350
made in triplicate with an Instron tester, at a separation speed of 50 mm/min. The blister
test arrangement, used with all substrates, is shown schematically in Figure 7.7b. The
support polymer here had a central hole, 6 mm in diameter, which connected to a pumping
system able to channel distilled water onto the polymer/adhesive assembly. During
application of the adhesive this opening was blocked by a Teflon plug, removed after the
urethane was cured. Adhesive films, again 0.35 mm thick, were deposited on the PVC,
ABS and Xenoy surfaces and cured as above. Bond energies, Ea, were obtained by following
protocols described in recent literature [4, 5]. These require measurement of the pressure
generated by the liquid pumped against the joint at which the adhesive debonds from the
substrate. Bond energy data were reproducible to better than 8%; lap-shear determinations
carried a similar uncertainty.
7.3.2.1 IGC Determinations
Acid-base interaction parameters for the materials of this research are given in Table 7.6.
As anticipated by the results in Figure 7.7, and in agreement with the results shown in
the preceding section, these show PVC to be predominantly acidic. ABS has a moderately
basic surface and Xenoy is an amphoteric solid with nearly equal AN and DN indices.
All of the PU systems function as both donors and acceptors, with PU5 and PU6 skewed
to acidity, PU1 and PU4 to basicity, while PU3 and (to a lesser degree) PU2 are amphoteric.
Table 7.6 Acid/base indexes of PU and polymer substrates (all at 30 °C).

Material AN DN
ABS 3.2 7.0
Xenoy 6. 6 6.8
PVC 8.5 2.1
PU1 2.7 4.3
PU2 3. 7 5.3
PU3 6.6 6.9
PU4 3.9 7.6
PU5 8. 2 5.3
PU6 7.2 3.9
351
The acidic adhesives would be expected to interact strongly with ABS, the basic ones
with PVC. The magnitude of acid-base forces is open to question when amphoteric surfaces
such as Xenoy are involved.
Any attempt to relate acid/base interactions between adhesives and substrates to the
bond properties of the relevant pair depend on a quantitative evaluation of a pair
interaction parameter. There are no broadly accepted theoretical guidelines to such an
evaluation, but a pair interaction parameter, Isp, can be defined by
Isp = ([AN]1 [DN]2)1/2 + ([AN]2 [DN]1)1/2
Here subscripts 1 and 2 designate adherent and adhesive, respectively. Values of Isp for
the polymer/adhesive pairs are given in Table 7.7.
Table 7.7 Pair interaction parameters at 30 °C

Isp PVC ABS Xenoy
PU1 8.4 8.0 9.6
PU2 9.5 9.2 10.9
PU3 11.4 11.5 10.4
PU4 10.9 10.1 13.8
PU5 12.6 11.7 14.4
PU6 9.7 10.6 12.1
7.3.2.2 Adhesive Bond Properties
A summary of lap-shear and blister detachment test data is presented in Table 7.8. The
six adhesives perform differently with each of the substrates, suggesting a link with specific
interactions at the adherent/adhesive interface. This is considered in the next section.
Although lap-shear evaluations are more familiar, they do not necessarily evaluate the
strength of adherent/adhesive interfaces. Cohesive failure of the weaker component of
an assembly can be a complicating factor, tearing of the PU layer being a possibility in
certain of the present measurements. In principle, the detachment of the adhesive in the
blister test is a pure interfacial event and one that can be quantified provided parameters
352
Table 7.8 Lap shear and blister detachment values at 30 °C

Substrate PVC ABS Xenoy
Adhesive LS Ea LS Ea LS Ea
PU1 20.5 37.5 - 40.8 27.0 42.5
PU2 26.0 42.5 - 40.5 28.5 44.0
PU3 27.2 47.5 - 48.2 29.7 46.5
PU4 25.8 47.0 - 44.7 31.5 49.7
PU5 28.0 49.0 - 47.8 31.2 50.3
PU6 25.5 42.5 - 47.2 30.0 48.0
LS: lap shear in J/m-2
Ea: bond energy in J/m-2
such as adhesive thickness and the geometry of the detaching blister are known [11, 12].
The two test methods may therefore complement each other and the existence of
quantitative correlations between the test data is a point of interest. The theory is tested
by means of Figure 7.8. Although the results for PVC and Xenoy substrates are separated
by a significant margin, in both cases the correlations are very satisfactory. The correlation
coefficient for the more strongly bonded Xenoy-PU system is 0.988, that for the weaker
PVC-PU bonds is 0.935.
Thus it is concluded that for assemblies of the type used here, lap-shear and blister
detachment test methods produce sets of internally consistent data which correlate in a
statistically acceptable manner. The choice of test procedure, therefore, may rest on
convenience and on the proven relevance of test results to field performance.
7.3.2.3 Adhesion and Acid/Base Interaction
As already noted, the adhesion test data suggests the existence of significant
contributions to bond strengths from non-dispersion forces acting at the adhesive/
substrate interface. Indeed, quantitative correlations have been confirmed between Isp
and either of the two sets of adhesion performance results. A demonstration is given in
Figure 7.9, using the more complete blister test data. The correlation coefficient for
this linear plot is 0.982.
353
Figure 7.8 Correlation between lap-shear and blister detachment evaluations of bond
strengths in Xenoy/PU and PVC/PU assemblies.
The value is in fact surprisingly large when it is noted that no account has been taken of
contributions made to bond strengths by dispersion (van der Waals) forces. Acid/base
forces appear to play a determinant role when bonding occurs at interfaces of materials
with pronounced electron donor and acceptor tendencies. This alone seems to justify
concern for expressing these tendencies quantitatively, and for favouring the IGC technique
as a convenient route to the objective.
Another noteworthy feature in Figure 7.9 is the inclusion of all polymer-substrate pairs is
the relationship. This encourages speculation that Isp is an objective measure of the
interactions generated by electron donor and acceptor sites in the surfaces of the present
polymers. It also suggests that IGC determinations of Isp may be useful for screening purposes
in designing PU adhesives for optimum performance with specified polymeric substrates.
These suggestions form the origin of further research which is being carried out.
354
Figure 7.9 The dependence of equilibrium bond energies for PU/polymer assemblies
on acid/base pair interaction. ● - PU1, ● - PU2, ▲ - PU3, ■ - PU4
7.4 The Effectiveness of Silane Adhesion Promoters in the

Performance of PU Adhesives
One of the most frequent procedures in the formulation of adhesives is the addition of
adhesion promoters. Of these, silanes are by far the most frequently used. The silanes form
a multi-membered family of chemicals. Numerous publications have described aspects of
silane chemistry and the applications of silanes [15-18]. Although many silanes are readily
available, in many industrial formulations of adhesives the most frequently used of these
are the primary amine and diamine versions because of their relatively low cost. However,
these do not necessarily produce optimum benefits in adhesion for all applications.
Guidelines for the selection of silanes best suited for specific applications would therefore
be useful. These should be based on a fundamental understanding of the manner in which
silane compounds affect the interface and interphase in adhesively bonded systems. The
355
last section relates to this objective by describing the effect of various silanes on the adhesion
performance of a model PU adhesive in joints involving selected polymers and glass. The
adhesion and its retention under aggressive ageing conditions is interpreted in terms of
acid-base interactions at the adhesive/substrate interface. The interpretative basis appears
suited for the selection of preferred silanes in the cases under study.
7.4.1 Experimental
7.4.1.1 Materials
The adhesive used was a model semi-structural PU, similar to one described in an earlier
work [7]. The two component formulation consisted of methylene bis-4-cyclohexyl
isocyanate prepolymer and trifunctional polyols with molecular masses in the range 500-
900. A small amount of tin catalyst (UL-28, Witco Chemicals) was also present. The PU
was used as control without additives and was modified by the following silanes:
APS - aminopropyl triethoxy silane

CS - chloropropyl trimethoxy silane
VS - vinyl trimethoxy silane
MS - mercaptobutyl trimethoxy silane
ES - epoxy trimethoxy silane
The silanes were obtained from Dow-Corning Corporation and were added at 0.5 wt%
levels. All formulations were cured by a standard procedure of 1 hour at 100 °C, followed
by 5 days at 50 °C and 50% relative humidity.
As in the preceding section, the polymers to be bonded were PVC, ABS, and the thermoplastic
polyester blend Xenoy. In addition microscope slide glass was also studied. Surfaces of
these materials have been shown to be capable of widely differing acid-base interactions.
The PVC was an unplasticised polymer (MW = 54,000 g/mol) from Synergistic Chemicals,
Inc. It contained 5 phr of Advastab TM-821SP thermal stabiliser. The ABS (Cycolac AR
3501), was a moulding grade, commercial product of GE Plastics, Inc. The same source
supplied the Xenoy blend; the exact composition of this material was not determined.
7.4.1.2 Procedures
The establishment of silane concentration in modified PU adhesives was based on the

tendency of PU to restructure in response to the orienting strength of media in contact
356
with the polymer [5, 19]. The process involves the diffusion-controlled accretion of polar
moieties from the bulk to the surface layer of the polymer. It has been shown earlier in
this chapter that surface restructuring can be followed by monitoring γnd, the non-
dispersive contribution to the polymer surface energy, when a film, initially dried in air,
is immersed in a polar medium. Static contact angles were measured for n-decane,
methylene iodide and water, on a freshly prepared film specimen of pure PU, and also on
films of PU containing up to 2 wt% APS and ES. The harmonic mean procedure [20]
was used to compute γnd. The measurements were repeated after each of the films had
been exposed for 7 days to water at 90 °C. Preliminary work showed that this was
adequate to allow the PU surface to equilibrate with respect to the aqueous environment.
Whilst the silane-free film restructured in water to increase γnd by about 5 mJ/m2, the
presence of silane sharply reduced the effect. The silane apparently anchors surface-
localised moieties and restricts their ability to adopt new conformations. Of the silanes,
ES appeared to be more successful in inhibiting the restructuring effect, but both ES and
APS, when added at a concentration of 0.5 wt%, were found to greatly reduce
restructuring. This was, therefore, chosen as the concentration level in subsequent work.
For testing bond properties, single lap-shear specimens were assembled from polymer
and glass coupons cut following the practice outlined in reference [19]. The polymers
were moulded to a thickness of 1.5 mm and cut to 8 x 2.5 cm size. No mould release
agents were used in moulding operations. For convenience, the selected overlap area of
4.5 cm2 was bonded with adhesives drawn to a thickness of 0.4 mm. Following
conditioning (24 hours, room temperature), initial bond strengths were measured in
triplicate with an Instron apparatus at a draw speed of 10 mm/min. To ascertain property
retention, certain of the systems were exposed in air ovens to 60 °C, 100% relative
humidity for up to 3 weeks under an applied stress. To generate stress, small holes
were drilled near the ends of the lap-shear coupons, one of the holes being used to
suspend the test pieces from a horizontal beam within the oven. Consistent with certain
industrial procedures, stress was generated by a 200 g weight, suspended from the free
end of the joint. Repeat evaluations of lap-shear bond strengths were carried out after
various ageing times.
Interfacial properties in assemblies were represented by acid-base interactions, as evaluated

by methods of IGC [2], as described earlier. PU and polymer stationary phases were
prepared as described in preceding sections. Since grinding microscope slides proved to
be ineffective for the production of a solid with sufficiently high surface area, powdered
glass beads were used as a representative glass substrate. Following well-established
procedures [2, 6], the solids were investigated at infinite dilution with vapours including
n-alkanes (C6 to C10), and with acidic and basic probes chosen on the basis of Gutmann’s
classification [3]: chloroform and benzene as acids, diethyl ether, tetrahydrofuran as bases
and acetone as an amphoteric substance. The temperature throughout IGC determinations
357
was in the range 35-65 °C. Net retention volumes, Vn, were obtained from at least triplicate
vapour injections, generally with a reproducibility better than 4%.
The protocols leading to the determination of acid-base interaction potentials in this

portion of the work were somewhat different from those documented earlier. Here the
interaction potential of solids is described by the acid and base interaction constants, Ka
and Kb. The derivation of these is given in detail in recent publications [4, 14, 21]. As
before, an initial requirement is the establishment of a linear plot of log Vn against the
normal boiling point, Tb, of the alkane vapours [9]; this represents the dispersion-force
interactions between solid and vapour. The slope of the linear plot may also be used to
evaluate the dispersion contribution to the solid’s surface energy, γsd. The position of Vn
for the acid and base probes, at their respective Tb, defines the contribution of acid-base
interactions to the free energy of adsorption, ΔGab. When measured over a specified
temperature range, the corresponding enthalpy, ΔHab, is also obtained. The enthalpy is
then used to estimate Ka and Kb from the expression [4, 14, 21]:
-ΔHab/AN = KaDN/AN + Kb
Here AN and DN are Gutmann’s values [3] for the acidity and basicity of the vapour
probes. When Ka and Kb values for substrates and adhesives are known, an acid-base
pair interaction value Isp is calculated:
Isp = (Ka)1(Kb)2 + (Ka)2(Kb)1
where subscripts 1 and 2 refer to adhesive and polymer (or glass) substrate, respectively.
In this work, Isp values were primary tools for the generation of correlations between
component interactions and the performance of the bonded systems. In so doing, the
relevance to adhesion of a parameter related to the acid-base contribution to the enthalpy
of component interaction is established.
The acid-base interaction potentials of polymer substrates and of the various adhesive
formulations are given in Table 7.9 as are the relevant values of Isp. The IGC experiments
show the model PU to interact as both mild acid and base, with these tendencies well
balanced. The presence of APS has no pronounced effect on the electron acceptor capacity
of the surface, but shifts the balance to basicity, presumably because of the surface
localisation of the silane’s primary amine groups. Each of the CS, VS and MS additives
produces the opposite trend, the adhesive surface now displaying stronger acidity, but
without significant change in the basic interaction potential. Addition of ES raises both
358
Table 7.9 Interaction constants and pair interaction parameters for polyurethane
adhesives and substrates
A: Acid-base interaction constants
Material Ka Kb Ka + Kb
PVC 8.5 2.1 10.6
ABS 3.2 7.0 10.2
Xenoy 6.6 6.8 13.4
Glass 2.6 1.9 4.5
PU 3.1 3.8 6.9
+ APS 3.7 6.0 9.7
+ CS 4.9 4.0 8.9
+ MS 5.0 4.2 9.2
+ VS 4.6 3.9 8.5
+ ES 5.0 6.2 11.2
B: Pair interaction, Isp
PVC ABS Xenoy Glass
PU 39 34 46 16
+ APS 59 45 65 23
+ CS 44 47 60 20
+ MS 46 48 62 20
+ VS 41 45 57 19
+ ES 64 55 74 26
See text for definition of Silane codes
Reproduced with permission from H. P. Schreiber, R. Qin and A. Sengupta, Journal of
Adhesion, 1998, 68, 1-2, 31, Table 1. © 1998, Gordon and Breach Science Publishers.
the acid and base interaction potential with a predominance of basicity. Furthermore,
the total interaction potential, given by the sum Ka + Kb, is most affected by the ES
adhesion modifier. As expected, the PVC surface is strongly acidic, that of ABS is basic,
and Xenoy is amphoteric with excellent balance between donor and acceptor capabilities.
The glass surface is a weak acid. As a result of choosing the Gutmann concept of acidity/
basicity, all of the surfaces retain both acidic and basic interaction potentials.
359
The resulting Isp data in Table 7.9, show ES and APS to be the most effective promoters
of interaction between adhesives and PVC. APS is not an effective interaction modifier
for ABS substrates; all the other surface modifiers exert a greater effect. Indeed, for each
of the four substrates in this work, ES produces the maximum increase of interaction,
although for glass the interaction level with these adhesives remains low when compared
with the polymeric substrates.
The effects of silane additives on the bond characteristics of assemblies is summarised in

Table 7.10. The initial bond strength, prior to accelerated ageing, is reported. The contribution
made by the silanes is variable, ranging from a few percentage points, e.g., PVC/PU + MS, to
a doubling of the bond strength (Glass/PU + ES). The largest increment in bond strength is
generated by ES. As seen in Table 7.9, this confers the largest increase to the total interaction
potential of the adhesive surface, while maintaining a balance between donor and acceptor
characteristics. For the systems selected for study in this work, ES is closest to a ‘universal’
adhesion modifier. In other cases, the effects of acid/base functionality are evident. Thus, the
acidic substrate (PVC) benefits from the presence of the basic APS modifier, but does not
respond well to silanes which accentuate the acidity of the adhesive surface. ABS demonstrates
the analogous effect of responding more strongly to the acidic modifiers than it does to APS.
In joints based on Xenoy, a strongly amphoteric substrate, the choice of silane is less critical,
although ES maintains a slight advantage over the remainder. The strong performance of the
epoxy silane notwithstanding, it seems doubtful whether a ‘universal’ silane promoter can be
identified for application to a wide range of substrates.
Table 7.10 Initial bond strength of assemblies joined by PU adhesive modified

by silane additives
Lap-shear bond (J/m2) for PVC ABS Xenoy Glass
substrate and adhesive
PU no additive 27 20 28 14
+ APS 34 24 35 21
+ CS 28 24 34 19
+ MS 30 287 34 19
+ VS 31 29 31 17
+ ES 39 34 39 27
All silanes at 0.5wt%; see text for definition of silane codes
360
The critical question of interdependence between initial lap-shear bond strengths and the
Isp parameters is addressed in Figure 7.10. Although each of the substrates tends to define
a specific envelope of behaviour (more particularly evident for glass), the first order regression
line drawn through all of the points has a correlation coefficient of 0.915, sufficient to
justify the claim of a true relationship. A more rigorous correlation is probably unrealistic,
since no account is taken here of varying chemical interactions between the silanes and the
substrates, or of variations in the contributions to bonding made by longer range dispersion
forces. Acid-base interactions at the adherent/adhesive interface thus make important
contributions to the initial lap-shear bond strength of these systems. The extrapolation to
Isp = 0 suggests that dispersion forces make a net contribution of about 12 J/m2 to the bond
property. Within experimental error (~10%) this is the initial bond strength for glass joined
by unmodified PU, even though an Isp value of 16 is reported for this pair in Table 7.7.
Figure 7.10 Initial bond strengths as a function of pair interaction parameter

Adhesion, 1998, 68, 1-2, 31, Figure 2. ©1998 Gordon and Breach Science Publishers.
361
Table 7.11 Effect of ageing (60 °C, 100% relative humidity) on lap-shear bond strength
Age time (h) 0 1.3 3.5 6.9 11 22.4 R
Bond strength (J/m2)
PVC/PU 27 22 17 14 14 9 0.33
+ APS 34 33 30 27 24 22 0.65
+ VS 31 28 23 21 17 14 0.45
+ ES 38 37 37 33 30 28 0.74
ABS/PU 20 18 16 12 8 7 0.35
+ APS 24 21 21 16 17 13 0.54
+ VS 28 25 24 22 20 19 0.68
+ ES 34 34 30 29 27 26 0.76
Xenoy/PU 28 23 19 16 16 12 0.43
+ APS 35 35 32 28 28 25 0.71
+ VS 31 29 27 24 19 17 0.55
+ ES 38 36 35 32 32 29 0.77
Glass/PU 14 12 7 0 0 0 0.00
+ APS 21 20 16 11 11 7 0.33
+ VS 18 17 12 9 7 4 0.22
+ ES 27 25 25 20 17 13 0.48
See text for definition of silane codes
R represents the ratio of final to initial bond strength
Evidently at this level of Isp, the strength of specific interactions is insufficient to influence
the lap-shear bond strength as measured by the chosen procedure.
Of equal interest to the initial bond strength is the ability of the assembly to withstand
aggressive ageing. Joints using as adhesives the unmodified PU and the PU with 0.5 wt%
APS, VS or ES adhesion promoters were subjected to the ageing protocol of this work.
362
Results of the procedure are presented in Table 7.11. Ageing periods are shown as the
square root of exposure hours, in the expectation that property loss would be a diffusion-
controlled process due to the intrusion to the interface of water. In Table 7.11, R is
defined as
R = (Bond Strength)f /(Bond Strength)i
where the subscripts f and i represent the bond strength after three weeks of ageing
and the initial value, respectively. Each of the systems is adversely affected, but R
varies significantly among the systems as well as within them. Qualitatively, a
relationship between R and the initial bond strength becomes apparent on inspection
of the data. The ES modified PU, which has the strongest acid-base interaction with
each of the substrates, produces the strongest initial bond, also produces the smallest
property loss.
A clearer view of the apparent correlation is presented in Figure 7.11. This indicates
that below initial bond strengths of about 13-14 J/m2, corresponding to Isp < 18-20,
the selected ageing regime will totally destroy the bonded assembly. The best fit of
the data is obtained from the second order regression curve shown, with a coefficient
of 0.932. However, a first order linear fit to the data (not shown) with a coefficient
of 0.917 is not much inferior and has the attraction of being extrapolatable to R =
1.0. If the linear fit is accepted as realistic, then the extrapolation predicts that an
assembly with an initial lap-shear bond strength > 45 J/m2 would withstand the chosen
ageing exposure indefinitely, without loss of bond strength. As the correlation in
Figure 7.11 makes evident, the degree of acid/base interaction at the bonded interface
also should correlate with the residual bond property. The matter is put to the test
with results shown in Figure 7.12. The resulting linear fit to experimental data has a
correlation coefficient of 0.938, with much of the scatter contributed by the glass
joints, where acid-base interactions are feeble and most subject to uncertain
determination. An extrapolation to R = 1.0, identifies Isp to be greater than or equal
to 85, as the strength of acid-base interactions required to ensure long-term resistance
to the selected ageing procedure. The forecasts should be useful in optimising the
choice of silane (and other) adhesion promoters in the formulation of adhesives such
as the present PU. However, the physico-chemical analyses on which these are based
cannot specify the chemical approaches to be followed. Moreover, the general
applicability of the physico-chemical analyses followed here calls for the study of a
broader range of adhesive/additive/substrate systems.
363
Figure 7.11 Bond strength ratio versus initial bond strengths

7.4.3 Conclusions
1. A strong correlation has been shown to exist between initial bond strengths displayed
by polymer and glass surfaces bonded by PU adhesives containing a variety of silane
adhesion promoters and the acid-base interaction at substrate/adhesive interfaces.
2. Silane additives change the surface interaction potential of PU in distinct ways; APS
accentuates surface basicity, while CS, MS and VS accentuate surface acidity. The
addition of ES results in significant increases in both surface acidity and basicity.
3. Within the scope of the present work, ES was found to be the most effective adhesion
promoter for each of the substrates. APS was particularly useful with the acidic PVC
substrate, but the CS, MS and VS were preferred additives for the basic ABS substrate.
364
Figure 7.12 Dependence of pair interaction parameter on bond strength ratio

4. A correlation has been developed between the residual adhesion of bonded assemblies
following accelerated ageing and the magnitude of acid-base interfacial interactions.
The strength of interactions needed to avoid property loss under the chosen ageing
conditions can be estimated. This capability represents a guideline to the selection of
preferred silane additives for the adhesion of PU adhesives to substrates with known
acid-base interaction potentials.
5. IGC was shown to be a convenient and effective tool for evaluation of acid-base
interactions at substrate and adhesive surfaces.
365
References
1. A. Gent and J. Schultz, Journal of Adhesion, 1972, 3, 4, 281.
2. Inverse Gas Chromatography, Eds., D. R. Lloyd, T. C. Ward and H. P. Schreiber

ACS Symposium Series No. 391, American Chemical Society, Washington, DC
1989.
3. V. Gutmann, The Donor-Acceptor Approach to Molecular Interactions, Plenum

Press, New York, 1978.
4. C. Saint Flour and E. Papirer, Industrial and Engineering Chemistry Product

Research and Development, 1982, 21, 4, 666.
5. Z. Deng and H. P. Schreiber in Contemporary Topics in Polymer Science, Vol. 6,

Ed., W. M. Culbertson, Plenum Press, New York, 1989, p.385.
6. D. G. Gray, Progress in Polymer Science, 1977, 5, 1.
7. J. H. Chen and E. Ruckenstein, Journal of Colloid and Interface Science, 1990,

135, 496.
8. V. Stannett in Diffusion in Polymers, Ed., J. Crank Butterworths, London, 1968,

Chapter 2.
9. E. J. Berger, Journal of Adhesion Science and Technology, 1990, 4, 5, 373.
10. J. M. Braun and J. E. Guillet, Advances in Polymer Science, Volume 21, Springer
Verlag, Berlin, 1976, p.108.
11. A. N. Gent, and L. H. Lewandowski, Journal of Applied Polymer Science, 1987,

33, 5, 1567.
12. Y-S. Chang, Y-H. Lai and D. A. Dillard, Journal of Adhesion, 1989, 27, 4, 197.
13. C. Saint Flour and E. Papirer, Journal of Colloid and Interface Science, 1983,
91, 63.
14. U. Panzer and H. P. Schreiber, Macromolecules, 1992, 25, 14, 3633.
15. E. P. Plueddemann, Interfaces in Polymer Matrix Composites, Academic Press,

New York, 1974, p.173.
16. E. P. Plueddemann, Silane Coupling Agents, Plenum Press, New York, 1982.
366
17. D. E. Leyden, Silanes, Surfaces and Interfaces, Gordon and Breach Science, New
York, 1986.
18. H. Ishida in The Interfacial Interactions in Polymeric Composites, Ed., G.

Akovali, NATO ASI Series E, Volume 230, Kluwer Academic Publishers, The
Netherlands, 1993, p.169.
19. A. Sengupta and H. P. Schreiber, Journal of Adhesion Science and Technology,

1991, 5, 11, 947.
20. D. T. Sawyer and D. J. Brookman, Journal of Analytical Chemistry, 1968, 40,

1847.
21. J. Schultz, L. Lavielle and C. Martin, Journal of Adhesion, 1987, 23, 1, 45.
367
368
8
HER Materials for Polyurethane Applications
Raj B. Durairaj
8.1 Introduction
Polyurethane elastomers have a wide range of industrial applications due to their unique
combination of valuable physical and mechanical properties. These elastomers, in
general, are composed of phase separated flexible soft segments and crystalline hard
segments. The soft segment is based on polyether or polyester type aliphatic diols and
the hard segment is the result of reaction between aromatic diisocyanate and low
molecular weight diol chain extenders [1]. The soft segments have low polarity and are
longer than the hard segments and provide a soft and flexible matrix. On the other
hand, the hard segments are shorter, highly polar and have a strong tendency to
aggregate. The thermodynamic incompatibility of these two segments leads to phase
separation, which ultimately influences the physical and mechanical properties of
urethane elastomers.
In the development of cast polyurethane elastomers, various chain extenders are used
with toluene diisocyanate (TDI) and 4,4´-diphenylmethane diisocyanate (MDI)
terminated prepolymers based on polyether or polyester polyols. With MDI-terminated
prepolymers, 1,4-butanediol is the most commonly used chain extender. In order to
maintain desired mechanical properties at elevated temperature and to improve hardness
and tear resistance, aromatic diols such as bis-(β-hydroxyethyl) ether of resorcinol
(HER) or hydroquinone (HQEE) are often used. One of the difficulties with HQEE is
its processing problem associated with a high melting point (~102 °C). On the other
hand, the structurally similar isomer HER offers a lower melting point (89 °C), thus
facilitating more forgiving chemistry and processing ease. Previous studies [2-5] have
shown that HER chain extender offers significant processing advantages over HQEE
and the properties of HER extended elastomers are comparable to those of HQEE
cured elastomers.
With the development of technical grade HER (HER TG), the processing temperature
of the HER was further lowered without sacrificing the physical and mechanical
properties of the final cured cast elastomers. The major difference between HER HP
and HER TG chain extenders is the presence of some higher molecular weight (MW)
reactive aromatic diol monomer in the technical grade material. With this unique
369
product, HER TG, there is no need to add plasticisers, diluents or aliphatic diols to
lower the melting points of aromatic diol chain extenders. It is also important to note
that the presence of about 10 weight percent of this higher MW aromatic diol monomer
does not appear to affect the performance of the cast elastomers. With this discovery,
it was decided to investigate different grades of HER materials with varying levels of
higher MW monomer and to study their performance in cast elastomers based on MDI
terminated polyether prepolymer.
The following are some of the objectives of this chapter:
1. To develop low melting and highly processable aromatic diol extenders from resorcinol
and ethylene carbonate (HER materials).
2. To determine the nature of products or by-products formed by the resorcinol-ethylene

carbonate reaction.
3. To investigate how the high MW aromatic diol monomer affects the phase separation
behavior of polyurethane elastomers.
4. To examine the effect of various HER chain extenders on the physical, mechanical
and dynamic mechanical properties of cast polyurethanes made with MDI-terminated
prepolymers.
5. To study both polyether- and polyester-based polyurethane systems.
8.2 Experimental Conditions
8.2.1 Chain Extenders
HER materials used as chain extenders in this work were prepared based on INDSPEC
Chemical Corporation’s patented technology and the product details are given in
Table 8.1.
Hydroquinone (di-β-hydroxyethyl) ether (HQEE) and 1,4-butanediol (BD) were obtained

from commercial sources.
8.2.2 Prepolymers
Polyether and polyester-based MDI prepolymers obtained from commercial sources were
used. The details are given in Table 8.2
370
Table 8.1 Development of HER materials for polyurethane applications
Extender Type HER-HP HER- HER- HER- HER- HER-LIQ
TG210 TG225 TG250 TG275
(TG-210) (TG-225) (TG-250) (TG-275)
Physical form Crystalline Molten Molten Waxy solid Pasty solid Liquid
solid solid solid
Viscosity (Pa-s, 25 °C) nd nd nd nd nd 20
Capillary melting point (°C) 88-92 78-90 76-85 65-78 63-65 nd
DSC analysis (endotherm)
Onset temperature (°C) 86.7 81.6 71 65.6 3 PEAKS nd
Peak temperature (°C) 89.1 85 80.6 71.7 35-65
HER content (wt. %, by GC) > 99 93 82 68 54 13
HER/H(OCH2CH2)nO-R-O(CH2CH2O)nH 100/0 93/7 83/17 68/32 54/46 0/100
(n = 2 and 3; Theoretical; wt. ratio)
HER/H(OCH2CH2)nO-R-O(CH2CH2O)nH >99 96/4 85/15 69/31 60/40 nd
( n = 2; by NMR; wt. ratio)
Hydroxyl number : Determined 555-560 545-550 525-535 500-520 470-480 379
: Theoretical, calculated 566 554 535 506 469 382
Status COM COM DEV DEV DEV DEV
COM: Commercial
DEV: Developmental
nd: Not determined
HP: High purity
TG: Technical grade
GC: Gas chromatography
371
Table 8.2
MDI-Prepolymer Supplier % NCO
Polyester
1. Baytec MS-242 Bayer 6.6
2. Baytec MS-090 Bayer 9.0
Polyether
1. VIBRATHANE B 625 Uniroyal Chemical 6.4
2. Baytec ME-050 Bayer 5.8
8.2.3 Preparation of Cast Elastomers
All elastomers used in this project were prepared by the following standard procedure.
A known quantity of prepolymer was weighed in a glass jar. Separately, in another glass
jar, the chain extender was weighed to achieve 95 or 90% stoichiometry. Both jars were
then placed in a vacuum oven at the desired temperatures and held under vacuum until
the bubbles disappeared indicating that all the dissolved gases and any moisture, if present,
was removed. This process required about 1 mm Hg vacuum and 2.5 to 3.0 hours at
about 80-110 °C depending on the chain extenders (HER materials or HQEE) used for
casting. After degassing, both the prepolymer and extender were mixed thoroughly for
one minute using a stirrer to avoid bubbles. The mix was poured into a heated stainless
steel plate mould pretreated with Teflon or silicone mould release agent. After pouring,
the mould was placed in a programmable oven and cured for 16 hours. The samples,
after curing, were allowed to cool slowly to room temperature. Test specimens were cut
from the cured sheet for determination of tensile, tear strength and dynamic mechanical
analysis (DMA) and then stored for at least 7 days at 22 °C, 50% relative humidity
conditions before testing. Compression set samples were prepared separately, following
the degassing procedure similar to that for plate casting, and aged similarly before testing.
8.2.4 Physical and Mechanical Properties Determination
The following test methods were used to determine the properties of cast polyurethane elastomers:
• Pot life determinations were done using a Brookfield viscometer at controlled temperatures.
• Shore Hardness, Durometer A/D (ASTM D2240) [6].
• Tensile Modulus, strength and % elongation (ASTM D412) [7].
372
• Tear Resistance, Die C (ASTM D624) [8].
• Bashore Rebound (ASTM D2632) [9].
• Compression Set % (ASTM D395) [10], Method B.
• DMA was determined using a Rheometrics RMS-800 instrument at 1 Hz frequency

with a heating rate of 2-10 °C/minute.
• Differential scanning calorimetry (DSC) analysis of the cast elastomers was performed
on a Perkin Elmer (DSC-7) instrument at a heating rate of 10 °C/minute under a
nitrogen atmosphere.
• Fourier transform-infra-red (FT-IR) analysis was performed on a Perkin Elmer System-

2000 instrument.
8.3 HER Materials Synthesis and Characterisation
High purity (HP) and technical grade HER materials were synthesised by the reaction of
various ratios of resorcinol and ethylene carbonate. Previous studies had demonstrated
that the HER TG has a performance equal to that of the HER HP material [5]. It was
also observed that, in the cast polyurethanes, HER TG could be processed at a lower
temperature than the HER-HP. These interesting experimental facts prompted the
development of various HER-TG materials and an investigation into their effectiveness
as chain extenders to enhance the processing of cast and other polyurethanes. By varying
the molar ratios of resorcinol and ethylene carbonate, the technical grade materials such
as HER TG-210, HER TG-225, HER TG-250, HER TG-275 and HER LIQ were
developed. HER TG-210 is the same as HER-TG reported in prior work and in this
chapter. The major difference between the HP and TG materials is the presence of higher
MW reactive diol monomers present in the TG materials. From the resorcinol and ethylene
carbonate reaction, depending upon the excess of ethylene carbonate, two types of higher
MW diols can be expected:
HOH2CH2CO-R-OCH2CH2OCH2CH2OH
and
HOH2CH2C(OH2CH2C)n-O-R-O(CH2CH2O)nCH2CH2OH
where R = meta phenylene, n = 1 and 2
373
On the basis of theoretical calculations and also from the gas chromatography (GC)
analysis, hydroxyl number and nuclear magnetic resonance (NMR) analysis results, it
has been confirmed that the reactive high MW diol present in the technical grade materials
has the structure:
HOH2CH2C(OH2CH2C)nO-R-O(CH2CH2O)nCH2CH2OH
where n = 1 and 2
For HER TG-210, TG-225 and TG-250 materials, the reactive high MW diol has
predominantly n = 1 and is present at approximately 7, 17 and 32 weight percent,
respectively. With higher molar ratios of ethylene carbonate:resorcinol, high MW
diol with n = 1 and 2, having MW of 286 and 374, respectively, are observed to be
present. In HER LIQ, the HMW diol monomers were estimated to be as high as 87
weight percent.
It was suspected that the presence of these reactive diol monomers in the HER
could have several advantages. Since they have primary hydroxyl groups, their
reactivity towards isocyanate groups is similar to that of other reactive diol chain
extenders. The molecular weight of these high MW diols is still low enough that
they act as chain extenders and not as polyols. In addition, they can act as reactive
plasticisers in various polyurethanes and other polymers. Due to the presence of
this high MW material, the melting point of HER is lowered, thereby increasing its
processability in polyurethane applications. Laboratory observations indicated that
HER and other technical grade HER materials have supercooling tendencies. In
fact, HER TG-275 stays liquid at room temperature for a period of 2-3 months.
The TG-250 remains liquid at room temperature indicating that processing could
be easier with this material alone and it would be a good candidate for mixing with
other small chain extenders, such as butane diol, and polyols (polyether and
polyester) at lower temperatures.
The melting points determined by the capillary method and DSC analysis are given
in Table 8.1. The varied melting point determined by the capillary is associated with
the high MW diol impurity. To determine the melting point by DSC, measurements
were done at a heating rate of 5 °C/minute under a nitrogen atmosphere. HER-HP
showed one sharp endothermic peak. With HER TG-210, TG-225 and TG-250
materials, the major endothermic peak shifted to lower temperatures and also showed
one minor peak, indicating one impurity. For HER TG- 275, three endothermic peaks
were observed between 35-65 °C indicating three components. For this material, GC
analysis showed two major peaks in addition to the HER peak.
374
8.4 Cast Poly(Ether Urethanes)
8.4.1 Pot Life Determination
Before making the castings, pot life determinations were performed to determine the
processing window of the prepolymer and chain extender materials. As a standard practice,
both the prepolymer and chain extender were preheated to the desired temperatures,
degassed thoroughly, mixed at the desired stoichiometry (90 or 95%) and poured into a
thermostatted vial. The viscosity was measured, using a Brookfield viscometer, as a
function of time. The measurements were terminated when either the time of measurement
reached 20 minutes or the viscosity of the mix reached 0.1 Pa-s.
Figure 8.1 shows the viscosity-time plots of VIBRATHANE B 625 extended with HQEE
and various HER materials. As can be seen, the pot life temperatures for HER materials
are considerably lower than HQEE. The shorter pot life for HQEE is due to the higher
processing temperature. If the processing temperature were lower than 110 °C, then
HQEE would crystallise out from the solution. Premature crystallisation is a major
problem encountered by most users of HQEE. But these problems are eliminated with
HER-HP and other HER-TG materials due to their supercooling behaviour.
Figure 8.1 Pot-life curves for Vibrathane B-625-HER materials
375
8.4.2 Polyurethane Castings
The prepolymer % NCO content and the equivalent weight of the chain extender materials
were determined to calculate the amount of each material to achieve 95% stoichiometry.
After careful degassing and mixing, the material was poured into the stainless steel mould
and cured for 16 hours continuously at 110 °C. Table 8.3 summarises the experimental
details relating to cast elastomer preparation.
In order to compare the properties of cast polyurethanes, conditions relating to castings,

ageing and testing were kept constant throughout this work.
8.4.3 Calculation of Hard and Soft Segment Contents
HER-HP has a purity of >99%. The other HER-TG materials contained at least one or
two high MW reactive diol monomers. The presence of these reactive diol monomers
can play a major role in the formation of hard segments, hard segment content and
phase separation behavior of the polyurethanes, which will ultimately dictate the final
cured physical and mechanical properties of the cast elastomer materials. A previous
study on HER-LIQ showed that the cast elastomers based on this extender produced
softer material compared to HER-HP [5]. The elastomeric materials developed using
HER-LIQ appeared to be more transparent indicating that the high MW diols present in
this chain extender were responsible for this change. The MW of these high MW diols
are still low enough to produce a hard segment in the polyurethanes, but the nature of
the hard segment can be different from that formed between the isocyanate and HER
due to a longer and more flexible chain.
Based on the extensive study made on HER and HQEE chain extenders, it is well known
that HER can produce hard segments with MDI and other isocyanate monomers, which
are crystalline in character [4]. Due to their high flexibility, the high MW reactive diol
monomers can produce hard segments which may be more amorphous than crystalline
in character. The amorphous hard segment formed can mix with the soft segment of the
polyurethane elastomers and ultimately change the physical and mechanical properties
of the elastomeric materials. Therefore, it was decided to calculate the amount of hard
and soft segment contents of the polyurethanes resulting from the VIBRATHANE B 625
prepolymer and HER materials containing various levels of the high MW reactive diols.
VIBRATHANE B 625 is a polyether prepolymer based on polytetramethylene glycol

(PTMEG) and MDI raw materials. Based on the 6.5% NCO content, it can be assumed
that this was prepared using 1 mole of PTMEG-1000 polyol and 2.2 moles of MDI. It
can also be assumed that the HER chain extender produces crystalline hard segments
376
Table 8.3 Cast elastomers based on Uniroyal B-625 (polyether) prepolymer elastomers performance
with various HER-TG materials
HER Materials HQEE HER-HP HER- HER- HER- HER- HER-
TG210 TG225 TG250 TG275 LIQ
Prepolymer temperature, (°C) 110 10 0 90 90 90 90 80
Extender temperature, (°C) 110 100 90 90 90 90 80
Mix ratio (Prepolymer/extender) 100/14.6 100/14.5 100/14.9 100/15.5 100/16.1 100/17.2 100/20.7
Stoichiometry, (% theoretical) 95 95 95 95 95 95 90
Cure, (h/110 °C) 16 16 16 16 16 16 16
Tensile Properties (MPa)
100% Modulus 11.35 10.56 10.71 8.84 7.98 9.94 3.99
200% Modulus 13.04 13.71 14.57 11.77 11.35 10.44 6.63
300% Modulus 14.64 17.33 19.08 15.6 16.35 16.79 11.55
Tensile strength 3419 3816 3937 3712 4037 3682 2301
% Elongation 538 559 47 6 462 413 372 321
Energy to break, (kN/m) 67 79 70 53 49 40 20
Tear strength, DIE C, (kN/m) 127 11 5 102 97 86 72 44
Compression set, % 21 15.4 17.4 17 17.5 29.4 9.1
Bashore rebound, % 55 58 60 60 54 46 49
Hardness, Shore-A (D) 96 95 95 (48) 92 (44) 90 (43) 89 (40) 78 (30)
377
and the high MW diols produce amorphous hard segments. Taking into account the
amount of HER and high MW diols present in the chain extender, for the 95%
stoichiometry, the crystalline hard segment, amorphous hard segment and polyether soft
segment contents were calculated for different cast polyurethanes made using the
VIBRATHANE B 625 prepolymer.
These calculations were based on the reaction scheme (8.1) shown opposite and an
idealised polyurethane structure from this scheme and the details are given in Table 8.4.
As can be seen from Table 8.4, the crystalline hard segment content is decreased from
48.7% to 35.4% when the high MW diol content increases from 0% to 87%.
Concurrently, the amorphous hard segment content increases from 0% to 16.6%. At the
same time, the soft segment content resulting from the polyol was affected only slightly
(changed from 51.3% to 48%). Since the high MW diol changed the concentrations of
the hard and soft segments, it is interesting to see how this will affect the physical and
mechanical properties of the cast elastomers.
In general, the contributions of both the soft and hard segments in the polyurethanes can
be correlated with the properties observed. The soft rubbery block primarily affects
resiliency, wear, tear, compression set and low temperature properties, while the hard
block affects hardness, modulus and tensile properties [11].
8.4.4 Hard Segment Versus Hardness
The Durometer hardness was measured after the cast elastomers were aged for at least 7
days at 23 °C and 50% relative humidity. The details are given in Table 8.3. From the
results, it is evident that as the crystalline hard segment content of the elastomer is
decreased, the elastomer hardness also decreases. By analysing the soft and hard segments
and their relation to hardness, it appears that the amorphous hard segment behaves like
the polyether soft segment.
8.4.5 Tensile Properties
The tensile data obtained from the cast elastomers are summarised in Table 8.3, plotted
and shown in Figure 8.2. From this figure, it can be seen that the 100% modulus and %
elongation decreased for the HER-TG materials compared to HQEE and HER-HP chain
extenders. On the other hand, the 200% and 300% modulus values were higher for
HER-HP and HER TG-210 extenders compared to HQEE and the values were lower for
the other technical grade materials. Except for HER-LIQ extender, all HER based
378
Table 8.4 Distribution of hard and soft segments in cast polyurethanes
Polymer-chain Extender Theoretical Calculation
HER Materials Analysis Hard Segment (%) Soft
HER Content H(OCH2CH2)nORO(CH2CH2O)nH Crystalline Amorphous Segment
(%) (%) (%)
1. Prepolymer (MDI/PTMEG-1000) No extender 0 41.3 0 58.7

(NCO=6.5%; Mole ratio = 2.2/1)
2. Vibrathane B-625 + HER-HP 100 0 48.7 0 51.3
3. Vibrathane B-625 + TG210 93 7 48 0.9 51.1
4. Vibrathane B-625 + TG225 82 18 46.9 2.2 50.9
5. Vibrathane B-625 + TG250 68 32 44.4 5.1 50.5
6. Vibrathane B-625 + TG275 54 46 43.1 6.7 50.2
7. Vibrathane B-625 + HER-LIQ 13 87 35.4 16.6 48
OCN-R-NHCOO(Polyether)OOCHN-R-NCO + HO(H2CH2CO)n-R′-(OCH2CH2)n-OH
(Prepolymer) (n = 1-3, chain extender)
O-H2CH2CO-R′-OH2CH2C-OOCHN-R-NHCOO-(Polyether)-OOCHN-R-NHCOO(CH2CH2O)2-3-R′-(OCH2CH2)2-3-O
| Soft | | |
|— Crystalline Hard Segment —| Segment | |— Amorphous (Hard) Segment —|
where R - diphenyl methane and R´-1,3-phenylene groups.

379
Reaction scheme 8.1
Figure 8.2 Tensile properties of cast polyurethanes
extenders showed either equal or better tensile strength values than the HQEE extender.
In general, the HER-TG materials showed good tensile properties.
8.4.6 Tear, Compression Set and Rebound Properties
These properties are summarised in Table 8.3.
Tear strength is generally a very important property in many applications. By comparing

the tear strength values of the technical grade materials against HQEE and HER-HP,
they can be seen to decrease continuously as the hardness of the elastomers is decreased.
HER-HP had a lower compression set than the HQEE extended elastomer. This value
increases when the concentration of high MW aromatic diols content is increased in the
HER-TG extenders. In fact, HER TG-275 extender with about 46% high MW aromatic
diol showed a high compression set of 29.4%. On the other hand, when this high MW
aromatic diol concentration reached 87% in HER-LIQ, the elastomer based on this chain
extender produced a very low compression set material.
380
The most important property to look for in choosing materials for applications such as
skate wheels is resilience or rebound [12]. The ether-based elastomers, in general, give
higher rebound resilience. The measured Bashore technique rebound values, show that
HER-HP, HER TG-210 and HER TG-225 extenders have slightly better resilience than
HQEE. The rebound values appeared to be lower for HER TG-250- and HER TG-275-
based elastomers. This value was higher for HER-LIQ (49%) when compared to TG-
275 (46%) extender. Since the rebound is generally measured at room temperature, its
value would relate to tan δ data given in Table 8.5. A comparison of the two indicates a
correlation between tan δ and the rebound values. Obviously, HER-LIQ extender showed
lower tan δ (0.044) compared to HER TG-275 (0.076) material.
8.4.7 Differential Scanning Calorimetry
The influence of the high MW diols present in the HER chain extenders on the transition
behavior of cast elastomers was studied by DSC analysis. Figure 8.3 compares the DSC
curves of HQEE, HER-HP and different HER-TG extended polyurethanes. The transitions,
which are observed to occur above room temperature, are associated with the melting of
Figure 8.3 DSC curves of cast polyurethanes from Vibrathane B-625-HER materials
381
Table 8.5 Cast elastomers based on Uniroyal B 625 (polyether) prepolymer elastomers performance
382
with various HER-TG materials
Dynamic Mechanical Analysis Results
HER Materials HQEE HER-HP TG210 TG225 TG250 TG275 HER-LIQ
Crystalline HS content (%) 48.7 48 46.9 44.4 43.1 35. 4
Amorphous HS content (%) 0 0.9 2.2 5.1 6.7 16.6
Storage Modulus, G′ (MPa)
at 25 °C 47 30 28 21 14 14 39
at 150 °C 43 22 19 14 9.8 8.4 3 .1
Thermal Stability (Temperature maximum for constant G′)
Temperature (°C) 170 160 160 160 160 155 160
G′, MPa x 108 39.5 19.9 17.4 12.6 8. 8 7.7 2 .9
Loss Modulus, G′′ (MPa)
Peak temperature, Tg (°C) -70.9 -70.8 -68.8 -67 -65.3 -63.5 -59.2
Peak modulus 90.2 95.8 90.9 89.6 83.3 76.9 6 5 .4

at 25 °C 1.9 1.1 1.1 0.88 0.69 1.0 0 .1 7
at 150 °C 0.89 0.35 0.31 0.25 0.18 0.16 0 .0 5
Tan Delta
Peak temperature, Tg (°C) -63.3 -61.4 -59.2 -51.4 -43.4 -45.3 -35.4
Peak tan delta 0.198 0.255 0.251 0.307 0.295 0.246 0 .4 7 1
at 25 °C 0.039 0.038 0.038 0.043 0.047 0.076 0.044
at 150 °C 0.02 0.016 0.016 0.016 0.018 0.02 0.018
at 10 Hz /23 °C (frequency) 0.055 0.044 0.042 0.05 0.057 0.092 0 .0 7 2
Loss Compliance, J′′ (MPa)
Peak temperature (°C) -53.3 -53.3 -49.4 -39.3 -24.9 5.4 -14.8
Peak compliance 1100; 700 1700; 1300 1800; 1600 3900 6400 5600 32600
at 25 °C 800 1300 1400 2100 3300 5600 11100
at 150 °C 500 700 800 1100 1900 2300 5600
Table 8.6 DSC results on cast polyurethanes from Vibrathane

B 625 - HER materials
Endothermic Peak Temperature
First Heating Second Heating
Chain Extender Temperature (°C) ΔH (J/g) Temperature (°C)
1. HQEE 20 5 17 205, 234
2. HER-HP 186, 199 22 184, 224
3. HER-TG210 195 19 155, 192
4. HER-TG225 183 13 162, 192
5. HER-TG250 181 9 150
6. HER-TG275 173 13 143
7. HER-LIQ nd nd nd
hard segment domains. The melting behaviour of the hard segments can be seen as an
endothermic peak in the DSC curve. The hard segment melting temperatures and heats of
transitions observed from the DSC analysis are given in Table 8.6. From the heats of
transition data (ΔH), it is clear that when the hard segment content is decreased, the energy
associated with the melting of the hard segments is also decreased. In addition to this, the
presence of amorphous hard segments appeared to decrease the melting temperatures of
the crystalline hard segment. Since the temperature at which the first transition takes place
above room temperature in the DSC curve is considered to indicate the limit of the thermal
stability of the polyurethane elastomer, the thermal stability of these elastomers was found
to be decreased when the high MW diol contents were increased. This might be due to the
reduction of hard segment content. Higher hard segment transition in the DSC indicates
higher thermal stability of the resulting polyurethane.
8.4.8 Dynamic Mechanical Analysis
DMA is an analysis technique used to determine the dynamic properties of the

elastomers [13, 14]. Dynamic properties of the elastomeric materials are important
because they influence the performance of certain parts such as wheels and tyres.
This method determines the storage modulus G´ (elastic behaviour), loss modulus
G´´ (energy dissipation), tan δ, loss compliance J´´ and glass transition temperature
(Tg) values. The Tg of the soft segment can determine the low temperature behaviour
of polyurethane elastomers. This is not only influenced by the nature of the soft
383
segment (polyether) but also the degree of phase separation between the hard and
soft segments. In this work, the DMA method was utilised to understand the effect
of HQEE, HER-HP and various HER-TG materials on the cast elastomers made
using VIBRATHANE B 625 (PTMEG-Polyether) prepolymer. The results are
summarised in Table 8.5.
8.4.8.1 Storage Modulus G´ Property
The storage modulus, G´, values determined by the DMA for the elastomers extended
with HER chain extenders are given in Table 8.5, and the storage modulus curves are
shown in Figure 8.4. Storage modulus quantitatively measures the material’s elastic
properties and also qualitatively determines the elastomer’s stiffness and hardness.
Since the hardness of the elastomer is related to its hard segment content, the DMA
storage modulus was found to decrease as the hardness of the elastomers was decreased
due to the increasing amounts of high MW diols present in the HER-TG materials.
From the DMA curve, it was observed that the G´ was considerably decreased for
HER-LIQ extended elastomer which contained about 87% of the high MW diol
Figure 8.4 Storage modulus (G′) curves of cast polyurethanes
384
monomers. It has been observed and reported in the literature [13, 15] that elastomers
based on PTMEG polyol exhibit a secondary transition (additional dispersity) which
appears as a step in the temperature—shear modulus function curves. The same kind
of behaviour is observed for elastomers based on HQEE, HER-HP and HER TG-210
chain extenders at temperatures below 0 °C. A sharp transition in the G´ curve may
be associated with good phase separation of the elastomer. In this respect, a gradual
transition occurs with HER TG-225, TG-275 and HER-LIQ compared to HQEE,
HER-HP and HER-TG-210 extended elastomers indicating that poor phase separation
occurrs in these elastomers.
8.4.8.2 Thermal stability of Elastomers
The thermal stability of urethane elastomers can be determined by the DMA method.
The temperature at which the storage modulus (G´) decreases significantly in the
rubbery region is considered to be the limit of thermal stability of the elastomers
[16]. From the G´ values of the elastomers, it was determined that HER extended
materials were stable up to 160 °C whereas HQEE extended elastomer showed a
10 °C higher stability.
8.4.8.3 Loss Modulus Property (G´´)
The loss modulus, G´´, is a quantitative measure of energy dissipation in the

elastomers. Low values of G´´ are indicative of low energy dissipation, low hysteresis
and, consequently, low heat build up, an important requirement for applications
such as in-line skate wheels [17]. Figure 8.5 shows the plots of loss modulus as a
function of temperature. The loss modulus values are high at low temperature and
found to decrease as the temperature is increased. The curves show maxima
corresponding to the T g of the soft segments of the elastomers which gradually
shift to higher temperatures indicating the effect of high MW diol monomer of the
HER materials.
In the temperature range between 0 and 160 °C, the loss modulus decreases into a long
plateau and then starts to increase when the temperature reaches beyond 170 °C and
180 °C. This might be due to the melting of the hard segments.
Figure 8.6 shows the plots of storage modulus (G´) and loss modulus (G´´) as a function
of various technical grade HER materials along with HQEE and HER HP measured at
25 and 150 °C. The curves clearly demonstrate that G´ and G´´ decrease as the hard
segment content is decreased in these elastomers.
385
Figure 8.5 Loss modulus (G′′) curves of cast polyurethanes
Figure 8.6 Effect of HER materials on shear modulus properties
386
8.4.8.4 Tan Delta Property (tan δ)
The measure of tan δ is a qualitative tool to determine the hysteresis or heat build up in
an elastomer during dynamic flex conditions. Figure 8.7 shows the plot of tan δ as a
function of temperature and the values obtained from this determination are shown in
Table 8.5. As the hard segment content is decreased, the tan δ peak height is increased
indicating higher hysteresis of the elastomers associated with the higher amounts of high
MW diols. The peak widths are also observed to increase, corresponding to the decrease
in the hard segment content of the elastomers. By comparing the tan δ peak (Tg) to that
of loss modulus peak (Tg) temperatures, the tan δ temperatures appeared to be higher.
The Tg associated with the soft segment were found to shift higher as the amorphous
hard segment content of the elastomers increased. This temperature shift might be
associated with the restriction of mobility of the soft segments due to phase mixing.
Also, the greater the amount of hard segment dissolved in the soft segment phase, the
higher the expected Tg of the soft segment.
Figure 8.7 Tan delta curves of cast polyurethanes
387
The Tg of the elastomers increased gradually when the hard amorphous content of
these materials was increased. Since this hard amorphous segment is the result of
reaction between the isocyanate and high MW aromatic diol monomers containing
ether linkages, there is a possibility that this amorphous hard segment can mix
effectively with the soft polyether polyol segments of the elastomers. As the amorphous
hard segment content is increased, it is possible that the effect of phase mixing between
this phase and the soft polyol segment is enhanced, thereby increasing the Tg of the
soft segment of the resulting polyurethane elastomers. The Tg of the HER-LIQ
extended elastomer is increased by as much as 26 °C with 16.6% amorphous hard
segment content. These results indicate that the high MW aromatic diol monomers
present in the HER-TG materials, influence the low temperature properties of the
cast polyether elastomer materials.
8.4.8.5 Loss Compliance Property (J´´)
Loss compliance quantifies the heat generated during dynamic loading in applications
like tyres, wheels and rollers. Polyurethane elastomers with lower loss compliance
values will experience less heat build up and, consequently, may suffer fewer field
failures [14]. Figure 8.8 shows the graph of loss compliance as a function of
temperature for the cast elastomers made with HER extended materials. The results
are summarised in Table 8.5.
Loss compliance curves show peak maxima at the soft segment Tg. The values appear
to be lower for elastomers containing higher hard segment contents. In the case of
HQEE, HER-HP and HER-TG 210 extended elastomers, loss compliance curves showed
two peaks at the Tg. The two peaks appear to merge into a single peak as the amorphous
hard segment of the elastomers is increased. Based on the loss compliance values, it
appears that HQEE based elastomers show less heat generation than the HER materials
containing higher levels of high MW diols. However, HER-HP and HER TG-210 based
elastomers behave similarly and, therefore, comparable performance can be expected
in their applications.
In order to compare the Tg observed from the peak temperatures of loss modulus (G´´),
tan δ and loss compliance (J´´) curves, the peak temperatures are plotted as a function
of the amorphous hard segment and shown in Figure 8.9. As can be seen in the figure,
the amorphous hard segment produced by the high MW aromatic diol extenders has a
pronounced effect on the soft segment Tg which, in turn, ultimately dictate the low
temperature properties of the elastomers made from them.
388
Figure 8.8 Loss compliance (J′′) curves of cast polyurethanes
Figure 8.9 Amorphous hard segment versus peak temperatures
389
8.5 Cast Poly(Ester Urethanes)
Polyurethane elastomers containing polyester soft segments are used in applications such
as wheels, rollers, gaskets, seals, sheet goods, belting, cyclone liners and forklift tyres
due to their high tensile strength, tear strength, abrasion resistance, oil resistance and
heat-aging properties.
In this work, MDI-terminated polyester prepolymer based on ethylene adipate polyol

(Baytec MS-242) was used to prepare cast poly(ester urethane) materials. The HER-
TG materials, HER-HP and HQEE were used as chain extenders. As discussed in
section 8.4, technical grade HER materials contain various levels of high MW diols
as reactive impurities. Therefore, as with poly(ether urethanes), the high MW diols
are expected to play a major role in the performance of poly(ester urethanes) made
with these materials.
8.5.1 Pot Life Determination
The experimental details on the pot life determination and elastomer casting conditions
are given in Table 8.7.
Pot lives exceeding 20 minutes can be easily achieved with HER materials due to
their low melting and processing temperatures. Because of their supercooling
behaviour and tendency to stay liquid after cooling to room temperature, further
enhancement in the pot life can be achieved by lowering the mixing temperature of
TG-250 and TG-275 materials.
8.5.2 Tensile Properties
The data obtained from the tensile measurements are summarised in Table 8.7 and the
graphs are shown in Figure 8.10. From the results, it can be seen that 100% modulus
and %elongation are decreased and the tensile strength increased as the high MW diols
content of the chain extender is increased.
8.5.3 Tear, Fracture Energy, Compression Set and Rebound Properties
These properties are summarised in Table 8.7 and the values are plotted against elastomer
hardness and shown in Figure 8.11.
390
Table 8.7 Cast elastomers based on Bayer MS-242 (polyester) prepolymer
Effect of HER - HQEE Composition on Elastomer Properties
HER/HQEE Materials HQEE HER-HP HER-TG210 HER-TG225 HER-TG250 HER-TG275
Pot-life Determination
Temperature (°C) 110 100 85 85 85 85
Pot-life (minutes) 7.5 20 >20 >2 0 >20 >2 0
Pot-life viscosity (Pa-s) 10.1 10.8 4.7 6.15 5. 5 5. 3
Casting Conditions
Prepolymer temperature (°C) 110 100 85 85 85 85
Extended temperature (°C) 110 100 85 85 85 85
Mix ratio (prepolymer/extender) 100/14.7 100/15 100/15.1 100/16 100/17 100/17.6
Stoichiometry, % theoretical 95 95 95 95 95 95
Cure, (h/110 °C) 16 16 16 16 16 16
Cast Polyurethane (Calculated)
Hard segment (%) ND 37.3 36.6 35.4 33. 7 31. 8
Soft segment (%) ND 62.7 62.5 62.3 61. 8 61. 4
Amorphous hard segment (%) ND 0 0.9 2.3 4. 5 6.8
Tensile Property (MPa)
100% Modulus 11.53 11.13 10.55 8.9 7.09 5.19
200% Modulus 14.1 14.93 14.49 12.59 10.14 7.48
300% Modulus 16.39 18.8 19.13 17.3 15.62 10.73
Tensile strength 28.42 29.6 34.93 34.49 39.85 34.17
% elongation 726 699 579 499 45 8 43 0
Energy to Break (kN/m)
107 122 100 75 80 40
(area under stress-strain curve)
Tear Strength, Die C (kN/m) 148 144 137 110 10 4 77
Compression set (%) 26.2 30.4 32.4 51.9 55.5 51
Bashore rebound (%) 41 39 34 33 28 15
Hardness, Shore-A (D) 50 D 46 D 44 D 94 ( 40 ) 89 ( 39 ) 84( 34 )
391
Figure 8.10 Tensile property of Baytec MS-242 prepolymer extended with

HER chain extenders
Figure 8.11 Variation of cast polyurethanes properties as a function of hardness
392
The hardness of cast polyurethanes is decreased as the high MW diols content of the
chain extender is increased. This eventually affects some of the most important elastomer
properties such as the tear strength, 100% tensile modulus and fracture energy. The
presence of high MW diols in the TG materials also increases the amount of amorphous
hard segment which, in turn, interferes with the phase separation of hard and soft
segments of the polyurethane elastomers. The continuous reduction in the rebound
property is associated with the formation of higher amorphous hard segments from
these TG materials.
8.5.4 Differential Scanning Calorimetry Analysis
During the DSC analysis, the elastomer sample is first heated to 225 °C (first heating),
cooled back to room temperature (cool down) and then heated again to 250 °C (second
heating) at 10 °C/minute heating and cooling rates. The endothermic transitions observed
above room temperature during the heating are associated with the melting of hard
segments and exothermic peaks are due to the crystallisation of the hard segment upon
subsequent cooling. DSC studies made on the segmented polyurethanes revealed three
hard segment-associated endotherms at temperatures of 60-80 °C, 120-190 °C and above
200 °C [18-21]. These endothermic transitions are due to short-range, long-range and
microcrystalline ordering of hard segment domains.
The endothermic peak temperature determined from the second heating is taken to be
the thermal stability limit of the elastomer. The hard segment melting and crystallisation
temperatures and their heats of transitions determined from the DSC analysis are given
in Table 8.8. Figure 8.12 shows the DSC curves obtained during the heating and cooling
of cast elastomers based on HER-HP and HER TG-250 chain extenders.
From the second heating endothermic peak temperatures, HER-HP extension resulted
in a thermal stability at 177 °C and the stability decreased to 135 °C for an elastomer
made from TG-275 extender. An interesting observation was also made in the DSC
analysis during cooling. An exothermic peak associated with the crystallisation of hard
segment was seen for the elastomers made from HER-HP, TG-210 and TG-225
extenders. Although this exothermic peak is not seen for TG-250 and TG-275 extenders
during the DSC cooling curve, this exothermic behaviour is seen during the second
heating. This strongly suggests that the higher amorphous hard segments formed from
the isocyanate and high MW diols interfere with the crystallisation of the crystalline
hard segment.
From the endothermic transition energy, HER-HP extension produced a higher hard
segment content compared to the other TG materials.
393
394
Table 8.8 DSC results on cast polyurethanes from MS-242-HER materials
First Heating Cooling Down Second Heating
Endotherm Exotherm Endotherm Exotherm
Peak Energy Peak Energy Peak Energy Peak Energy
HER/HQEE Material Peaks °C J/g °C J/g °C J/g °C J/g
1. HQEE Major 190 28 102 10 188 10 ND ND
Minor 201 218 9
2. HER-HP Major 188 33 83 14 177 13 ND ND
Minor 203, 211
3. HER-TG210 Major 189 23 73 10 173 7 ND ND
Minor ND 140
4. HER-TG225 Major 185 15 66 6 168 6 ND ND
Minor 204 140
5. HER-TG250 Major 170 14 ND ND 143 4 71 6
Minor 215
6. HER-TG275 Major ND ND ND 135 3 74 5
Minor 217 2
ND = Not detected
Figure 8.12 DSC curves of cast polyurethanes from Baytec MS-242
The storage modulus (G´), thermal stability, Tg and loss compliance (J´´) properties
obtained from the DMA are given in Table 8.9.
Poly(ester urethanes) based on HER chain extenders behaved in the same way as poly(ether
urethanes). When the high MW diol content of the extender is increased, the storage
modulus is decreased due to the reduction of the hard segment content. As was seen
from thermal analysis, the thermal stability of the HER-HP extended elastomer is slightly
higher than the technical grade materials.
In addition to storage modulus reduction, a continuous reduction in the Tg, an increase

in tan δ and increase in the loss compliance values are also noticed when the amorphous
hard segment content of the elastomers is increased.
395
Table 8.9 DMA results of cast elastomers from Baytec MS-242

HER Materials HQEE HER-HP TG210 TG225 TG250 TG275
at 25 °C 51.5 30.3 28.7 23.8 12.4 6.5
at 100 °C 36.7 18.2 16.4 12.1 6.3 3
at 150 °C 33.5 15.7 10.6 7.4 4.1 2.2
Thermal Stability (Temperature
maximum for constant G′)
Temperature (°C) 170 170 160 160 150 15 0
G′, MPa 20.6 7.8 8.7 4. 7 4.1 2.2
Loss modulus, G′′ (MPa)
Peak temperature, Tg (°C) -29.6 -27.7 -26 -27.6 -19.8 -13.9
Peak modulus 152 166 173 15 9 104 14 6
at 25 °C 3.29 1.64 1.79 2.18 1.27 0.54
at 100 °C 1.48 4.62 0.37 0.5 0.16 0.05
at 150 °C 1.59 4.19 0.37 0.51 0.24 0.1
Tan Delta
Peak temperature, Tg (°C) -21.5 -20.1 -19.8 -19.4 -7.6 0.5
Peak tan delta 0.27 0.467 0.452 0.409 0. 5 0.749
at 25 °C 0.064 0.054 0.062 0.091 0.102 0.085
at 100 °C 0.04 0.025 0.022 0.04 0.026 0.019
at 150 °C 0.047 0.027 0.035 0.07 0.058 0.043
at 10 Hz /23 °C (frequency) 0.085 0.077 0.083 0.124 0.154 0.22
Loss compliance, J′′ (MPa)
Peak temperature (°C) 0.9 -11.9 -9.9 10.5 5.7 10.1
Peak compliance 1660 4060 3960 4100 1200 350 0
at 25 °C 1230 1780 2160 3820 8150 128 0
at 100 °C 1090 1400 1380 3460 4070 630 0
at 150 °C 1410 1690 3320 9400 1420 193 0
396
8.6 Cast Polyurethanes from HER/HQEE Blends
Although the cast polyurethanes made using HQEE chain extender produce high
performance materials, processing problems are always encountered with this
material. In order to use HQEE, the processing temperatures must be as high as
120-130 °C. If the temperatures are lower than this, then ‘starring’ (after curing a
‘snowflake’ type material embedded in the continuous matrix, (cast elastomer) can
be seen) occurs due to the crystallisation of HQEE out of the elastomer system. To
overcome this processing problem, HQEE is often blended with various aliphatic
diols such as ethylene glycol, butanediol, and so on [22-24]. The addition of aliphatic
diols into HQEE, therefore, is expected to affect the high temperature physical and
mechanical properties of the resulting elastomers. These problems can be easily
overcome if an aromatic diol chain extender like HER is used in the place of aliphatic
diols. Due to the supercooling behaviour of HER, this extender offers a unique
opportunity to lower the melting point of HQEE without the customary degradation
of properties.
8.6.1 Freezing Point Determination of HER/HQEE Blends
To study the eutectic nature of the HER/HQEE blends, freezing point determinations
were made. HER/HQEE blends were prepared at different weight ratios and melted
at elevated temperatures. Then the melt was allowed to cool slowly under controlled
conditions. The temperature at which the first crystallisation was observed was
considered to be the freezing point of the melt corresponding to that particular HER/
HQEE composition.
The plot of freezing point versus HER/HQEE blend is shown in Figure 8.13. As can
be seen from the plot, HQEE melting can be considerably reduced with the help of
an HER extender.
397
Figure 8.13 Apparent freezing points of HER/HQEE blends
8.6.2 Cast elastomers and Their Properties
The experimental details on the cast elastomers prepared using Baytec MS-242 and Baytec
ME-050 prepolymers and their physical, mechanical and dynamic mechanical properties
are given in Tables 8.10 and 8.11.
In the case of poly(ester urethanes), HER and HQEE extended elastomers showed
comparable tensile, tear, glass transition temperature (Tg) and hysteresis (tan δ) properties.
Compared to HER, HQEE extension produced elastomer with about 2 Shore-D units
higher hardness. An improvement in the tensile strength value was observed for the
HER/HQEE blend at 25:75 weight ratio. In general, all the physical and mechanical
properties were slightly affected or lowered with HER/HQEE blends compared to either
HER or HQEE extended material.
In the case of poly(ether urethanes), HQEE extended elastomer had slightly higher hardness,
tensile strength and tear strength values than the HER extended material. HER extension
produced elastomer with a lower compression set compared to HQEE extension.
DMA properties of HER and HQEE extended elastomers are similar. All the other physical
and mechanical properties of the elastomers from the HER/HQEE blends were lower
than the HER or HQEE extenders.
398
Table 8.10 Cast elastomers based on Baytec MS-242 (polyester) prepolymer.

Effect of HER-HQEE composition on elastomer properties
HER/HQEE (wt. ratio) 100/0 75/25 50/50 25/75 0/100
Prepolymer temperature, (°C) 110 103 110 105 110
Extender temperature, (°C) 110 110 110 110 110
Mix ratio 100/15.0 100/15.0 100/15.1 100/15.3 100/14.7
(prepolymer/chain extender)
Stoichiometry, (% theoretical) 95 95 95 95 95
Cure, (h/110 °C) 16 16 16 16 16
100% Modulus 11.13 8.65 8.91 10.47 11.53
200% Modulus 14.93 11.6 11.86 13.08 14.1
300% Modulus 18.8 15.6 15.35 17.2 16.4
Tensile strength 4293 4421 3393 4718 4122
% Elongation 699 648 507 634 726
Tear strength , Die C (kN/m) 144 126 120 135 148
Compression set, (%) 30.4 29.2 28.5 27.1 26.2
Hardness, Shore-D 52 50 50 52 54
Dynamic Mechanical Analysis
Tan delta at 10 Hz / 23 °C 0.073 0.106 0.097 0.092 0.076
(frequency)
Tan delta at 25 °C 0.054 0.072 0.069 0.063 0.056
(temperature sweep)
Tg (tan delta peak), °C -21.9 -16.2 -15.5 -18.1 -24.1
Tg (G′′ peak), °C -29.4 -23.8 -25.8 -25.9 -29.7
399
Table 8.11 Cast elastomers based on Baytec ME-050 (polyether) prepolymer.

Effect of HER-HQEE composition on elastomer properties
HER/HQEE (wt. ratio) 100/0 75:25 50:50 25:75 0:100
Mix ratio 100/12.5 100/12.1 100/12.9 100/12.6 100/12.7
Stoichiometry, (% theory) 90 90 90 90 90
Cure, (h/110 °C) 16 16 16 16 16
100% Modulus 9. 3 8.3 8.8 9 10.2
200% Modulus 12.1 11.9 11.3 11.3 12
300% Modulus 15.3 15.6 14.8 13.5 13.6
Tensile strength 3412 3434 3931 3787 3732
% Elongation 605 509 528 561 632
Tear strength, Die C (kN/m) 110 98 101 109 118
Compression set, (%) 14.6 16.4 15.9 18.3 16.4
Harness, Shore-D 47 48 50 50 50
Dynamic Mechanical Analysis
Tan delta at 10 Hz / 23 °C 0.038 0.039 0.038 0.037 0.033
(frequency)
Tan delta at 25 °C 0.032 0.03 0.05 0.034 0.029
(temperature sweep)
Tg (tan delta peak), °C -62.9 -59.8 -57.1 -57.5 -61.4
Tg (G′′ peak), °C -70.4 -69.5 -67 -69.3 -69.3
400
8.7 High Hardness Cast Polyurethanes
High hardness polyurethanes are used in applications such as rolls and rollers. When
the hardness of the elastomer is increased, certain other physical and mechanical
properties such as the tensile strength, tear strength, compressive strength and tensile
modulus are also increased. To develop materials with the best possible properties
such as high hardness, solvent, oil and abrasion resistance, MDI-terminated prepolymers
with NCO contents of greater than 9% are often used.
Hard polyurethane elastomers, produced from the higher NCO containing prepolymers,
are generally more hydrolytically stable than the soft ones, since the hard segment is
hydrophobic and is less rapidly attacked [16]. With the high NCO containing
prepolymers, HER chain extended materials are expected to produce harder
polyurethane elastomers due to longer chain length than the conventional 1,4-butanediol
chain extender. On the other hand, the presence of a high MW diol chain extender
impurity in the HER-TG materials would affect the physical and mechanical properties
of the resulting polyurethanes.
The main objective of this work was to investigate and study the properties and
performances of hard cast polyurethane elastomers obtained from the HER chain
extenders.
8.7.1 Cast Elastomers and Their Hard and Soft Segment Contents
Cast elastomers were prepared using Baytec MS-090 prepolymer and HER chain
extenders with 95% stoichiometry. The experimental details of the elastomer castings
and the mix ratios of the prepolymer and chain extender are given in Table 8.12.
Since the cast urethane elastomer properties are greatly influenced by the soft and
hard segment contents and their phase separation behaviour, they are theoretically
calculated from the molar ratios of the prepolymer and chain extenders and are
reported in Table 8.12. Table 8.12 shows the hard segment content of the elastomer
is 45.5% for HER-HP and is reduced to 38.2% for TG-275. This reduction in the
hard segment content is due to the formation of 8.8% amorphous hard segment
from TG-275 chain extender.
8.7.2 Hardness, Tensile, Tear, Compression Set and Rebound Properties
These properties are summarised in Table 8.12.
401
Table 8.12 Properties of cast elastomers

HER Materials HER-HP TG-210 TG-225 TG-250 TG-275
Casting Conditions
Mix ratio 100/20.4 100/20.2 100/21.1 100/21.8 100/24
Stoichiometry, (% theoretical) 95 95 95 95 95
Cure, (h/110 °C) 16/110 16/110 16/110 16/110 16/110
Cast polyurethanes (calculated)
Hard segment (%) 45.5 44.5 43 40.6 38.2
Soft segment (%) 54.5 54.3 54 53.5 53
Amorphous hard segment (%) 0 1.2 3 5.9 8.8
100% Modulus 20.44 20.24 17.97 15.42 10.98
200% Modulus 23.32 23.66 22.3 21.26 17.02
300% Modulus 25.82 26.59 27.5 29.44 27.01
Tensile strength 26.42 26.79 29.14 32.04 33.96
% Elongation 45 4 389 403 345 355
Fracture energy (kN/m) 105 81 82 73 55
Tear strength, Die C, (kN/m) 149 142 135 166 91
Compression set, (%) 28 36.4 37.9 45.4 47.8
Bashore rebound, (%) 31 31 28 26 24
Hardness, Shore-A (D) 62 D 62D 98 (56D) 97(56D) 95(48D)
402
HER-HP and TG-210 chain extenders produced elastomer hardnesses in excess of 60

Shore D, but the hardness decreased to 48 Shore D for the elastomer extended with TG-
275 material.
By correlating the elastomer hardness with that of other physical and mechanical
properties, a clear trend can be seen showing that as the hardness is decreased, the 100%
tensile modulus, fracture energy and tear strength values are also decreased.
On the other hand, a gradual increase in tensile strength and compression set values is
observed for cast elastomers containing more amorphous hard segment contents.
Polyurethane elastomers with higher hard segment content result in more hard segments
mixed into the soft phase [25-27]. Also, polyester soft segments are more compatible
with urethane hard segments. The decrease in Bashore rebound values of TG-225, TG-
250 and TG-275 extended materials is associated with the lower degrees of phase
separation in the polyurethanes.
8.7.3 FT-IR Analysis of Cast Polyurethanes
In order to understand the effect of high MW diols on the formation of amorphous hard
segments and their interaction with the crystalline hard segments, FT-IR analysis of the
cast polyurethanes was performed. Samples were cast as films on a NaCl plate from a
hot dimethyl sulphoxide (DMSO) solution.
The crystalline structure of polyurethanes is controlled by the formation of hydrogen

bonds between NH and C=O groups of the urethane linkages [28, 29]. From the IR
analysis, the hydrogen bonded C=O present in the crystalline domain can be identified
by the peak absorbance at 1699-1706 cm-1 and the non-bonded or free C=O group
shows peaks at 1735 cm-1 and 1748 cm-1.
Figure 8.14 shows the C=O stretching vibration bands of FT-IR spectra of cast
polyurethanes obtained from the HER materials. The appearance of peaks at 1695 cm-1
and 1705 cm-1 strongly suggests hydrogen bonded C=O groups exist with all the HER
extended materials. The intensities of these two peaks are gradually reduced when the
hard segment content of the elastomer is decreased. The complete disappearance of the
1695 cm-1 peak might be associated with the strong interaction or interference of the
amorphous hard segment in the phase separation of elastomers.
IR analysis also showed a peak at 1736 cm-1 associated with the free C=O groups of the
elastomers. From the IR absorbances of bonded and free C=O groups, the hydrogen-
bonding index, ‘R,’ which is the ratio of Abonded C=O/A nonbonded C=O, can be calculated [30].
403
Figure 8.14 FT-IR stretching vibration bands of HER materials extended

cast polyurethanes
The greater the value of R indicates an increase in participation of the C=O group in the
hydrogen bonding. The values of R calculated from the absorbance of hydrogen bonded
C=O (1705 cm-1) and free C=O (1736 cm-1) peak values are given in Table 8.13.
The values clearly suggest an increased hydrogen bonding with HER HP extended material
due to high hard segment content. The reason for the higher R value for TG-225 extender
is not known at the present time.
Table 8.13 Value of nydrogen bonding index for cast polyurethanes

Chain Extender Hydrogen Bonding Index
R = A1705/A1736
HER HP 0.80
HER TG-210 0.67
HER TG-225 0.83
HER TG-250 0.60
HER TG-275 0.50
404
8.7.4 Differential Scanning Calorimetric Analysis

The crystalline hard segment melting, crystallisation and heats of transition observed
during the DSC analysis are given in Table 8.14.
From the endothermic melting temperatures, HER-HP and TG-210 extended elastomers
show a thermal stability of 180 °C. Increase in hard segment content in the elastomer
results in an increase in hydrogen bonding between adjacent hard segments which may
result in higher transition energy. By comparing the energies of endothermic peaks observed
during the first and second heating DSC experiments, HER-HP extended elastomer has
the highest hard segment content. The presence of amorphous hard segment appeared to
affect the crystallisation behaviour, during cooling, and also the thermal stability of the
urethane elastomers.

The DMA analysis results are summarised in Table 8.15
Due to higher hard segment content, HER-HP and TG-210 extended elastomers had
high storage modulus (G´) compared to the other HER chain extenders. By comparing
the tan δ, Tg and loss compliance properties, it is seen that HER-HP and TG-210 extended
elastomers behaved similarly.
8.8 High Thermal Stability Polyurethane with Low Heat Generation

It is well known that conventional polyester-based urethane elastomers extended with
butanediol can withstand continuous use temperatures of about 80 °C. At higher
temperatures, a reduction in the physical and mechanical properties is seen due to
degradation of the material. The thermal stability of the polyurethanes is related to the
nature of the starting materials such as the aromatic diisocyanate and diol chain extender.
The hard segment of the urethane elastomer is primarily responsible for temperature
resistance, and the soft segment determines the material’s performance at low temperature.
Butanediol chain extender has four aliphatic carbon atoms in the chain. On the other
hand, HER is an aromatic diol chain extender with the following structure:
HOH2CH2CO OCH2CH2OH
405
406
Table 8.14 DSC results on cast polyurethanes from MS-090-HER materials
Endotherm Exotherm Endotherm Exotherm
Peak Energy Peak Energy Peak Energy Peak Energy
HER/HQEE Material Peaks °C J/ g °C J/ g °C J/ g °C J/g
HER-HP Major 186 31 84 18 180 15 nd nd
Minor nd 144 1
HER-TG210 Major 193,180 25 72 15 181 20 nd nd
Minor 16 4 152
HER-TG225 Major 188 19 58 9 175 8 57 1. 5
Minor 173,163 152
HER-TG250 Major 171 20 nd nd 148 6 71 10
Minor nd
HER-TG275 Major 166 10 nd nd 142 5 81 11
Minor 216 1
nd = Non-detected
Table 8.15 DMA results of cast elastomers based on MS-090 prepolymer

HER Materials HER-HP TG210 TG225 TG250 TG275
at 25 °C 98.6 93.6 75.4 48.7 29.5
at 150 °C 33.7 25.8 22.2 12.9 8.5
Thermal Stability(Temperature
Maximum for Constant G′)
Temperature (°C) 165 150 150 150 150
G′, (MPa) 33 26 22 13 9
Loss modulus, G′′ (MPa)
Peak temperature, Tg (°C) -12.7 -14.4 -8.53 -2.5 5.4
Peak modulus 138 143 147 147 146
at 25 °C 10.5 10.3 10 8.9 11.9
at 150 °C 0.79 0.67 0.47 0.22 0.14
Tan Delta
Peak temperature, Tg (°C) -6.4 -6.2 -0.4 7.1 14.4
Peak tan delta 0.259 0.246 0.3 0.4 0.57
at 25 °C 0.106 0.11 0.133 0.183 0.396
at 150 °C 0.023 0.026 0.021 0.017 0.016
at 10 Hz /23 °C (frequency) 0.14 0.14 0.18 0.3 0.61
Peak temperature, (°C) 29.5 29.9 29.5 19.8 24.7
Peak compliance 1070 1190 1750 3730 11700
at 25 °C 1060 1160 1730 3630 11700
at 150 °C 700 1000 960 1340 1900
Based on the structures of butanediol and HER, it can be expected that the HER-based
hard segment would have a longer chain length than the butanediol-containing hard
segment. The domains containing these longer hard segments are also expected to show
a higher melting temperature than the shorter ones. Therefore, HER based elastomers
are expected to be more thermally stable than the butanediol extended material.
407
In order to demonstrate that HER compared to butanediol-based elastomer has better

physical and mechanical properties at elevated temperatures, cast elastomers with 95%
stoichiometry have been made from an MDI terminated polyester prepolymer (Baytec
MS-242) extended with butanediol and HER-HP (from INDSPEC Chemical Corporation).
Test specimens were cut from a sheet post cured at 110 °C for 16 hours, for the tensile,
tear, DSC and DMA determinations. In the preparation of material for the dry heat
aging evaluation, tensile, DSC and DMA samples were placed in an air oven with the
temperature controlled within ± 2 °C of the set point and aged for 28 days at 100 °C, 21
days at 120 °C and 14 days at 135 °C. Then, all the samples were stored for at least
seven days at room temperature and 50% relative humidity before testing.
8.8.1 Hardness Measurements
The Durometer hardness measured on the elastomers before and after the heat aging is
given in Table 8.16. Since hardness is the measure of hard segment content of the elastomer,
the unaged HER elastomer showed a 96A (Shore) hardness compared to 88A for the
butanediol elastomer clearly suggesting a higher hard segment content with HER
extension. On heat ageing, the HER elastomer maintained its hardness even after 21 and
14 days of aging at 120 °C and 135 °C, respectively. The butanediol extended elastomer’s
hardness was reduced by 4 Shore A units at all heat-ageing temperatures suggesting
material deterioration during the heat treatment.
8.8.2 Tensile Measurements
Polyurethane elastomers are known for their high elongation, tensile strength and modulus
properties. The combination of these properties provides toughness and durability in
fabricated parts. Cast elastomers extended with butanediol can maintain these tensile
properties when the use temperature is about 80 °C. When these elastomers are subjected
to higher temperatures, reduction in the tensile properties are observed due to the
weakening of physical bonds in the elastomer.
The tensile properties measured on the unaged and heat-aged elastomer materials made
from HER and butanediol are given in Table 8.16.
The 100, 200 and 300% tensile modulus values of unaged elastomers are higher for
HER than for the butanediol elastomer. Analysing the 100, 200 and 300% modulus
values of 100 °C heat-aged samples showed that HER elastomer retained about 95-97%
of its original unaged values compared to 75-76% for butanediol. At 120 °C, there was
93-94% modulus retention for HER whilst 85-88% was observed for butanediol. When
408
Table 8.16 Heat ageing and mechanical properties of cast elastomers from Baytec MS-242
HER-HP 1,4-Butanediol
Heat Ageing Conditions
Temperature (°C) RT 100 120 135 RT 100 120 135
Days at ageing None 28 21 14 None 28 21 14
Hardness, Shore-A 96 94 96 96 88 84 84 84
Tensile property (MPa)
100% Modulus 10.96 10.38 10.35 9.86 6.58 4.93 5.34 5.0
(100) (95) (94) (90) (100) (75) (81) (76)
200% Modulus 14.53 13.75 13.66 12.84 9.51 7.35 8.04 7.37
(100) (95) (94) (88) (100) (77) (85) (77)
300% Modulus 18.46 17.35 17.17 15.97 15.04 11.40 13.24 11.38
(100) (94) (93) (88) (100) (76) (88) (76)
Tensile strength 28.19 27.28 26.15 21.95 46.72 38.80 42.33 35.61
(100) (97) (93) (78) (100) (83) (90) (76)
% Elongation 619 691 635 646 534 642 600 619
Energy to break (kN/m) 110 124 111 104 92 100 98 91
Tear strength, Die C (kN/m) 142 nd nd nd 105 nd nd nd
Note: The values in the parenthesis are the percentages of properties retained after the heat ageing.
nd: Not determined
409
the aging temperature is increased to 135 °C, HER elastomer showed better modulus
retention property than the butanediol (87% versus 77%).
Although the butadiene elastomer has an unaged tensile strength of 46.72 MPa, this
value drops to 38.80 MPa (83% retention) when this material is heated for 28 days at
100 °C. On the other hand, the HER extended elastomer retains 97% of its original
(unaged) tensile strength under the same temperature heat-aging conditions, indicating
its excellent high temperature stability.
In spite of the severe aging conditions, HER extended elastomer maintained its excellent
(greater than 600%), tensile elongation property. The combination of higher modulus
and good elongation of the HER-based elastomer clearly demonstrates its ability to
withstand higher tensile loads without the risk of failure.
Tensile measurements can also be used to determine the fracture energy of the material.
The area under the stress-strain curve is the measure of fracture energy which is recognised
as a measure of toughness. As can be seen in Table 8.16, HER extended elastomer showed
higher fracture energy before and after heat aging suggesting that it has a higher toughness
than the butanediol elastomer.
Tear strength is a property commonly used to determine the cut growth propagation in
an elastomeric material. The unaged tear strength is much higher for HER than the
butanediol elastomer. The combination of fracture energy and tear strength properties
clearly predicts that the HER elastomer will have better wear resistance than the butanediol
extended elastomer.
8.8.3 Differential Scanning Calorimetric Analysis
From the DSC analysis, the thermal stability of polyurethanes can be determined by the
endothermic transition temperatures associated with the melting of hard segment domains.
The results are summarised in Table 8.17 and also shown in Figure 8.15. The first heating
DSC endothermic peaks for HER extended elastomer are broader and appeared at higher
temperatures than the butanediol elastomer. Higher endothermic peak energy suggests
that larger size crystalline hard segment domains exist within the HER elastomer.
Considering the molecular structures of HER and butanediol chain extenders, there is
no doubt that the higher thermal stability of the HER elastomer is associated with the
formation of large size hard segments from the aromatic isocyanate and extender reaction.
On cooling the heated samples, exothermic peaks, due to the crystallisation of hard
segment domains, were seen in the DSC curves. Again, the higher exothermic peak
temperature suggested the existence of larger size hard segments for HER elastomer.
410
Table 8.17 DSC results of heat aged cast elastomers from

Baytec MS-242 prepolymer
Endotherm Exotherm Endotherm
Peak Energy Peak Energy Peak Energy
°C J/g °C J/g °C J/g
Chain Extender: 1,4 Butanediol
Ageing Temperature (°C)
RT 173 10 70 5 160 4
220 1
100 176 11 70 5 16 8 2
120 175 9 72 2 16 6 3
135 180 7 ND ND
217 <0.5 17 0 2
Chain Extender: HER-HP
Ageing Temperature (°C)
RT 176 17 76 12 179 11
204 <0.5
100 179, 196 24 82 12 187 11
215 <0.5 21 5 <0.5
120 178, 193 20 81 11 187 11
219 <0.5
135 179, 195 21 80 8 186 11
DSC Experiment:
1. Heat the sample from 25 to 225 °C at 10 °C/min (first heating)
2. Cool from 225 to 25 °C at 10 °C/min (cooling down)
3. Heat the sample from 25 to 225 °C at 10 °C/min (second heating)
During the second heating, DSC curves showed that a well-defined endothermic melting
peak appeared at higher temperature confirming the higher HER elastomer thermal
stability. Based on the DSC results, HER extension produced about 20 °C higher hard
segment melting temperature indicating the superior high temperature properties of HER
compared to butanediol elastomer.
411
Figure 8.15 DSC curves of 135 °C heat aged urethane elastomers from Baytec MS-242
DMA measures the ability of the material to store and dissipate mechanical energy. DMA
properties of the elastomeric materials are important because they often correlate to
actual field performance. This method determines the storage modulus (G´, elastic
behaviour), loss modulus (G´´, energy dissipation), tan δ, loss compliance (J´´) and Tg
values. In this work, the DMA method was effectively utilised to understand the
advantages of HER over the butanediol extended elastomer. The results are summarised
in Table 8.18.
8.8.4.1 Storage Modulus Property (G´)
Storage modulus quantitatively measures the material’s elastic properties and also
qualitatively determines the elastomer’s stiffness and hardness. The unaged elastomer
storage modulus values are higher for HER at 25, 100 and 150 °C temperatures compared
to butanediol. On heat ageing at 100 °C, the HER elastomer retained about 85-86% of
its original G´ value compared to 60-85% for butanediol. After ageing for 28 days at
412
Table 8.18 DMA of heat aged cast polyurethane from Baytec MS-242 prepolymer
HER-HP 1,4-Butanediol
Ageing Temperature (°C) RT 100 120 135 RT 100 120 135
at 25 °C 33.1 28.9 30 29.4 10.9 9.3 9.7 9.1
at 100 °C 21.2 18 18 12.8 7.2 5.1 5.3 3.9
at 150 °C 14.4 12.4 12.7 8.9 6.1 3.7 3.9 2.8
Loss Modulus, G′′ (MPa)
Peak temperature, Tg (°C) -29.8 -29.6 -30 -29.6 -27.4 -25.6 -28 -26
Peak modulus 171 168 167 165 167 117 164 159
Tan Delta
Peak temperature, Tg (°C ) -23.9 -23.7 -21.8 -23.6 -19.3 -16 -17.8 -17.7
Peak tan delta 0.392 0.404 0.401 0.386 0.657 0.628 0.65 0.623
at 25 °C 0.072 0.08 0.083 0.091 0.051 0.087 0.08 0.103
at 100 °C 0.019 0.032 0.033 0.064 0.024 0.081 0.064 0.097
at 150 °C 0.029 0.052 0.051 0.08 0.027 0.075 0.066 0.091
Peak temperature, (°C) -11.6 -12.1 -9.4 -13 -9.3 -6 -7.7 -3.6
Peak compliance 2580 3000 2810 2600 1460 1640 1530 15100
at 25 °C 2160 2770 2750 3090 4720 9220 8210 11200
at 100 °C 900 1780 1850 5000 3350 1580 1190 25100
at 150 °C 2030 4210 4040 8940 4450 20000 1690 32000
Peak area: 0 —> 150 °C 22 34 35 67 57 190 160 292
Peak area: -50 —> 150 °C 28 41 41 73 82 216 185 316
413
100 °C temperature, a very sharp decline in G´ values (60%) for butanediol and a high
retention for HER were observed at 150 °C.
For 120 °C heat-aged samples, 85-90% retention of G´ values for HER compared to 63-
89% for butanediol were seen. The same kind of trend is seen with 135 °C heat-aged
elastomer storage modulus values. Thus the HER extended elastomer has better retention
of storage modulus at higher temperatures than the butanediol elastomer.
8.8.4.2 Loss Modulus Property (G´´)
Loss modulus measures the energy dissipation in the elastomer. The Tg measured from
the loss modulus curves (Table 8.18) showed lower values for the HER than butanediol
elastomer suggesting good phase separation.
8.8.4.3 Tan Delta Property (tan δ)
The soft segment Tg is often defined as the maximum in the tan δ versus temperature
curve which determines the low temperature behavior of urethane elastomers. The results
obtained are summarised in Table 8.18. The Tg obtained from the tan δ curves confirms
again that a good phase separation existed with HER elastomer. As a consequence, the
HER-based polyurethane has a higher flexibility at low temperature.
Although the unaged 25 °C tan δ value appeared to be higher for HER, the effect of heat
ageing showed an increase of 26% compared to 101% for BD. Similarly, the 100 °C and 135
°C heat-aged samples showed very high percentages of elevated temperature (100 °C and
150 °C) tan δ value increases in butanediol-based elastomer as compared to the HER material.
These experimentally determined tan δ values from the DMA analysis strongly suggest
that more heat generation problems can be anticipated with butanediol-based elastomer
when they are exposed to temperatures above 80 °C than with HER elastomer.
8.8.4.4 Loss Compliance Property (J´´)
Figures 8.16 and 8.17 show the plots of loss compliance for butanediol and HER
elastomers, respectively and the results are summarised in Table 8.18.
The loss compliance values of unaged and heat-aged butanediol extended elastomer are
about 3-5 times greater than the HER elastomer.
414
Figure 8.16 Heat ageing study - loss compliance of MS-242-butanediol elastomer
Figure 8.17 Heat ageing study - loss compliance of MS-242-HER elastomer
415
In addition to the loss compliance data at various temperatures, the area under the loss
compliance curve can also be used to predict the tendency of the elastomeric materials to
convert mechanical energy to heat. A smaller area means less mechanical energy is
converted to heat, indicating better dynamic performance of the elastomer over the
temperature range of interest.
By comparing the loss compliance peak areas of heat-aged samples, there is no doubt the
HER extended elastomer is far superior in performance to butadiene elastomer.
Based on the current study, HER extended elastomers has the following room temperature
and high temperature physical and mechanical properties advantages over butanediol-
based elastomers:
• Excellent retention of hardness.

• Retention of high tensile modulus and elongation.
• Higher fracture energy.
• High tear strength.
• Higher thermal stability due to high crystalline hard segment melting.
• High flexibility due to low Tg.
• High storage modulus.
• Lower hysteresis and compliance values.
• Broader service temperature.
8.9 Conclusions
The HER materials developed for polyurethane and other applications have a wide
range of melting characteristics. Lower melting temperatures of these materials can
provide improved processability in the development of cast and thermoplastic
polyurethane elastomers. The high MW diols present in the HER materials not only
reduce the melting point of the HER extender, but also exhibit a profound influence on
the concentration of crystalline hard segments and, as a result, ultimately affect the
physical and mechanical properties of the elastomers. Polyurethanes with varying
properties can be obtained by using HER materials containing different concentrations
of high MW diols. Since the high MW diols can act as plasticisers, the addition of
external plasticisers can be avoided by use of these materials. Cast polyurethanes show
good tensile, tear, compression set and hysteresis properties with HER-based chain
extenders. This results in a wide choice in the selection of a suitable aromatic diol
chain extender from the HER materials family.
416
Acknowledgements
The author would like to thank Jason Burchianti and Stephen J. Ondrey for preparing
elastomer samples and for conducting pot life measurements, Richard F. George for the
DMA, physical properties and DSC work and Vaughn J. Romell for the FT-IR analysis
work. My special thanks to Fred M. Covelli, V.P. Technology, and Joseph de Almeida,
Marketing Manager of Specialty Products, for their continuous encouragement in this
work.
References
1. K. C. Frisch and S. L. Reegen in Advances in Urethane Science and Technology,

Volume 2, Eds., K. C. Frisch and D. Klempner, Technomic Publishing Co., Inc.,
Lancaster, PA, 1973, 29.
2. D. Klempner and K. C. Frisch in Advances in Urethane Science and Technology,

Volume 8, Eds., K. C. Frisch and D. Klempner, Technomic Publishing Co., Inc.,
Lancaster, PA, 1981, 93.
3. J. E. Tiedemann, Presented at the Fall PMA Meeting, Miami, FL, USA, 1993.
4. M. A. Mendelsohn, F. W. Navish and D. Kim, Rubber Chemistry and

Technology, 1986, 58, 5, 997.
5. R. B. Durairaj, J. Burchianti, S. J. Ondrey, R. F. George and J. de Almeida, Paper

Presented at the Fall PMA Meeting, Baltimore, MD, USA, 1998.
6. ASTM D2240-00
Standard Test Method for Rubber Property-Durometer Hardness.
7. ASTM D412-98a
Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbers and
Thermoplastic Elastomers-Tension.
8. ASTM D624-00e1
Standard Test Method for Tear Strength of Conventional Vulcanized Rubber and
Thermoplastic Elastomers.
9. ASTM D2632-96
Standard Test Method for Rubber Property-Resilience by Vertical Rebound.
417
10. ASTM D395-98

Standard Test Methods for Rubber Property-Compression Set.
11. Polyurethane Handbook, 2nd Edition, Ed., G. Oertel, Hanser Publications,

Munich, 1994.
12. R. Palinkas, Paper Presented at the Fall PMA Meeting, Cincinnati, OH, USA, 1990.
13. J. E. Doyle, Paper Presented at the PMA Meeting, Milwaukee, WI, USA, 1994.
14. S. M. Clift, Paper Presented at the Fall PMA Meeting, Charlotte, NC, USA, 1991.
15. J. R. Lin and L. W. Chen, Journal of Applied Science, 1998, 69, 8, 1575.
16. C. Hepburn, Polyurethane Elastomers, 2nd Edition, Elsevier Applied Science,

London, 1992.
17. S. Madan, S. Franyutti, K. Recker and R. S. Pantone, Presented at the

Polyurethanes World Congress ‘97, Amsterdam, The Netherlands, 1997, 381.
18. R. W. Seymour and S. L. Cooper, Journal of Polymer Science, Part B, Polymer

Letters, 1971, 9, 7, 689.
19. T. R. Hesketh, J. W. C. van Bogart and S. L. Cooper, Polymer Engineering and

Science, 1980, 20, 3, 190.
20. L. M. Leung and J. T. Koberstein, Macromolecules, 1986, 19, 3, 706.
21. G. Pompe, A. Pohlers, P. Potschke and J. Pionteck, Polymer, 1998, 39, 21, 5147.
22. Eastman HQEE-80, As a Chain Extender for Liquid Castable Urethane

Elastomers, Industrial Chemical Division, Eastman Chemical Products, Inc.,
Kingsport, TN-37662, USA, Publication No. D-161, December 1982.
23. M. Palmer, Paper Presented at the Spring PMA Meeting, Kansas City, KY, 1983.
24. M. Palmer, J. H. Davis, T. L. Douglas and M. R. Wilhelm, Paper Presented at the

Fall PMA Meeting, Chicago, IL, USA, 1977.
25. J. W. C. van Bogart, A. Lilaonitkul, L. E. Lerner and S. L. Cooper, Journal of

Macromolecular Science B, 1980, 17, 2, 267.
26. J. W. C. van Bogart, P. E. Gibson and S. L. Cooper, Journal of Polymer Science:

Polymer Physics, 1983, 21, 1, 65.
418
27. C. B. Hu, R. S. Ward, Jr., and N. S. Schneider, Journal of Applied Polymer

Science, 1982, 27, 6, 2167.
28. R. Bonart, L. Morbitzer and E. H. Muller, Journal of Macromolecular Science,

1974, B9, 3, 447.
29. J. Blackwell, J. R. Quay, M. R. Nagarajan, L. Born and H. Hespe, Journal of

Polymer Science: Polymer Physics, 1984, 22, 7, 1247.
30. R. W. Seymour, G. M. Estes and S. L. Cooper, Macromolecules, 1970, 3, 5, 579.
419
420
9
Ultra-Low Monol PPG: High-Performance
Polyether Polyols for Polyurethanes
Stephen D. Seneker, Nigel Barksby and Bruce D. Lawrey
9.1 Introduction
Polyoxypropylene glycols (PPG) have been available since the early 1960s.
Polyurethanes based on these polyols are used in a diverse range of applications
including flexible foams (moulded and slabstock), sealants and adhesives. Until
recently, their use in high-performance applications such as cast and thermoplastic
urethane elastomers has been limited due to their inferior physical properties and
processing characteristics. These problems can be largely attributed to the considerable
amount of monol (monofunctional hydroxyl-containing species) present in these
polyols. Monol acts as a chain terminator, which severely reduces both the molecular
weight (MW) build during polymer formation (processability) and the ultimate
polymer MW (physical properties).
Conventional polyoxypropylene diols are produced commercially through the base-

catalysed (KOH) propoxylation of glycol starters such as propylene glycol. However,
the base catalyses not only the addition of propylene oxide to the growing polyol
molecule, but also a side reaction in which propylene oxide isomerises to allyl alcohol
[1, 2, 3]. Allyl alcohol acts as a monofunctional starter resulting in propoxylated
allyl alcohol (‘monol’) as shown in Figure 9.1. Since each monol chain contains a
terminal double bond, the amount can be quantified by measuring the unsaturation
level. The level of unsaturation is typically reported in milliequivalents of unsaturation
per gram of polyol (meq/g).
Table 9.1 shows the relationship between conventional polyoxypropylene diol MW

and unsaturation level, functionality, and monol content (mole%). As the MW of
conventional PPG increases, there is a dramatic increase in the monol content. For
example, a PPG with a MW of 2000 typically has an unsaturation or monol level of
about 0.03 meq/g, corresponding to a functionality of 1.94, while a diol with a MW
of 4000 has a monol content of 0.09 meq/g and a functionality of only 1.69. A
conventional diol with a MW of 4000 is considered to be a mixture of about 70%
diol and 30% monol (molar basis). This is why the practical upper limit for commercial
PPG is a 2000 equivalent weight (4000-MW diol or 6000-MW triol).
421
Figure 9.1 Reaction of propylene oxide to form polyoxypropylene diol and monol
Table 9.1 Monol (unsaturation), functionality and mole % monol of

conventional PPG polyols
PPG Diol OH# Unsat. (meq/g) Functionality Mole % Monol
1000 MW 111 0.01 1.99 1
2000 MW 56 0.03 1.94 6
3000 MW 37 0.05 1.86 14
4000 MW 28 0.09 1.69 31
8000 MW* 14 —* —* —*
*Cannot produce an 8000-MW PPG with conventional KOH catalyst using commercially
feasible reaction conditions. OH# is the hydroxyl number, which is a measure of the
concentration of hydroxyl groups. It is related to the polyol equivalent weight by the
equation: 56,100/OH# = equivalent weight.
422
Ultra-Low Monol PPG: High-Performance Polyether Polyols for Polyurethanes
Advances in catalyst technology demonstrated that PPG could be prepared with

significantly lower monol contents using double metal cyanide (DMC) catalysts such as
zinc hexacyanocobaltate [4, 5, 6, 7, 8]. This technology was originally developed by
General Tire Inc., [9, 10, 11]. These DMC catalysts produce PPG with monol contents
typically in the range of 0.015 to 0.020 meq/g, which corresponds to a diol with a MW
of 4000 with a functionality of 1.94. The synthesis and utility of these low monol PPG
polyols in polyurethanes have been reported extensively [6, 7, 8, 12, 13, 14]. Although
the physical properties and processability of polyurethanes improved significantly with
low monol PPG polyols, the cost to performance ratio was still considered unacceptable;
therefore, these polyols achieved limited commercial success.
Further improvements in catalyst technology resulted in Lyondell (formerly ARCO

Chemical Company) commercialising a new family of PPG with ultra-low monol contents
designated Acclaim Polyols. Table 9.2 summarises the unsaturation, functionality, and
monol contents of these polyols. Comparing Tables 9.1 and 9.2, one can clearly see the
dramatic improvements in functionality. For example, a 4000-MW, ultra-low monol
PPG (Acclaim Polyol 4200) has a functionality of 1.98 versus 1.69 for a conventional
4000-MW PPG diol.
In this chapter, the dramatic effect that monol content or polyol functionality has on
processability and properties of polyurethane cast elastomers is discussed. This effect is
shown for elastomers prepared by both the prepolymer and one-shot processes. Further
improvements in elastomer processability and formulating latitude can be achieved by
incorporating oxyethylene moieties into the polyol backbone. For one-shot elastomer
processes, ultra-low monol PPG polyols capped with ethylene oxide have been
commercialised.
Table 9.2 Monol (unsaturation), functionality and mole % monol of Acclaim

polyols (ultra-low monol PPG polyols)
Polyol (MW) OH# Unsat. (meq/g) Functionality Mole % Monol
1000-MW PPG* 112 0.005 1.995 0.5
2000 56 0.005 1.99 1
3000** 35 0.004 1.99 1
4000 28 0.005 1.98 2
8000 14 0.005 1.96 4
* Experimental sample
** Polyoxypropylene-oxyethylene diol containing 20 weight percent oxyethylene moieties.
OH#: hydroxyl number
423
This chapter also focuses on the effect of the polyol molecular weight distribution (MWD)
or polydispersity on mechanical and dynamic properties of polyurethanes and
polyurethane/ureas. Ultra-low monol PPG polyols are unique in that they have a very
narrow MWD in comparison to other high-performance polyols such as
polytetramethylene ether glycol (PTMEG) or polyester polyols. Narrow polydispersity
results in lower viscosity polyols as well as lower viscosity isocyanate-terminated
prepolymers based on those polyols. However, a not so obvious effect is that polyols
with a narrow MWD result in polyurethanes with significantly different mechanical and
dynamic property profiles. These differences will be highlighted in various polyurethane
and polyurethane/urea systems and explained using dynamic mechanical thermal analysis
(DMTA). By understanding the effect of polyol MWD, we will illustrate how the
polydispersity can be adjusted in order to maximise the mechanical and dynamic properties
obtained from ultra-low monol PPG polyols.
The experimental procedures utilised to prepare the various polyurethane and

polyurethane/urea polymers described in this chapter are discussed in the Appendix.
9.2 MDI/BDO Cured Elastomers Based on Ultra-Low Monol PPG Polyols
9.2.1 Effect of Monol Content on 4,4´-Methylene Diphenylmethane

Diisocyanate (MDI)/1,4-Butanediol (BDO) Cured Elastomers
The importance of monol content in 4,4´-MDI/BDO cured elastomer systems was determined
by comparing 4000-MW PPG diols prepared via ultra-low monol technology, DMC and
potassium hydroxide. They are designated as ultra-low monol, low monol and conventional
and have monol contents of 0.005, 0.016 and 0.085 meq/g, respectively. This corresponds
to functionalities of 1.98, 1.94 and 1.71. We prepared 6% NCO 4,4´-MDI prepolymers
and chain extended with BDO at an isocyanate to hydroxyl ratio (NCO:OH) of 1.03 [15].
Table 9.3 summarises the monol effect on elastomer processing characteristics (pot life
and demould time), and physical properties.
The monol content has a major effect on elastomer processability. Lower monol content
results in a faster molecular weight build, which reduces demould time. Elastomers based
on the 4000-MW, ultra-low monol PPG had demould times as short as 20 minutes,
whereas, the low monol PPG gave demould times of over one hour. The elastomer based
on conventional polyol had a demould time greater than three hours.
Lower monol content clearly has a positive effect on all elastomer physical properties.
Dramatic property improvements are even seen when comparing elastomers based on
ultra-low monol and low monol polyol. This is particularly surprising considering the
424
Table 9.3 Comparison of polyurethane elastomers based on ultra-low monol,

low monol and conventional 4000-MW diols
(6% NCO MDI prepolymers; BDO cured)
Monol Content (meq/g) 0.005 0.016 0.085
Polyol Functionality 1.98 1.94 1.71
Prepolymer Viscosity, Pa-s
20 °C 8.5 7.5 8.1
40 °C 2.2 1.9 2.0
60 °C 0.78 0.69 0.73
80 °C 0.38 0.32 0.38
PROCESSING CHARACTERISTICS
Pot life (minutes) 1-3 1-3 1-3
Demould Time (minutes) 20-45 60-120 >180
ELASTOMER PROPERTIES
Hardness, Shore A 72A 68A (66A)* 51A (38A)*
Pendulum Rebound, % 70 62 48
Ultimate Elongation, % 910 1020 130
Tensile Strength, MPa 20.6 12.4 1.4
100% Modulus, MPa 3.4 3.0 1.6
200% Modulus, MPa 4.9 4.3 —
300% Modulus, MPa 6.3 5.5 —
400% Modulus, MPa 7.8 6.7 —
Die C Tear, kN/m 67 49 10
Compression Set, % (22 h @ 70 °C) 25 40 53
Compression Deflection, MPa
5% 0.8 0.4 0.1
10% 1.2 0.8 0.2
15% 1.7 1.2 0.3
25% 2.8 1.9 0.8
*
Shore Hardness needle slowly penetrated into the sample to the value indicated in parenthesis
425
small difference in functionality (1.98 versus 1.94). For example, Shore A hardness
increased from 68 to 72; rebound from 62 to 70%; tensile strength from 12 to 21
MPa; Die C tear strength from 49 to 67 kN/m; and compression set decreased from 40
to 25%. The load bearing capabilities improved significantly as shown by the
compression deflection results. The stress/strain curves in Figure 9.2 clearly show that
the elastomer based on ultra-low monol PPG exhibits much greater modulus build
with increasing elongation.
Figure 9.2 Elastomer stress/strain curves

(6% NCO MDI/4000-MW diol prepolymers; BDO cured)
426
Reducing the monol content also improves the dynamic properties of cast elastomers.
Figure 9.3 shows the DMTA response for the two polymers described above. The polymer
derived from the ultra-low monol polyol has a flatter rubbery plateau region. The higher
modulus in the rubbery plateau is consistent with the polymer’s higher tensile modulus.
The substantial reduction in tan delta (δ) across the entire temperature range should also
be noted. Lower tan delta translates into improved performance in dynamic applications
due to lower heat buildup and improved rebound as noted above.
Figure 9.3 Elastomer DMTA curves

(6% NCO MDI/4000-MW diol prepolymers; BDO cured)
427
All these improvements indicate that significant changes are occurring in the elastomer
as the monol content is reduced and the polyol functionality increased from 1.94 to
1.98. We believe the benefits are directly attributable to an increase in the polymer
molecular weight. Figure 9.4 shows the relationship between functionality and theoretical
elastomer molecular weight (calculated from the Carothers equation). Raising the
functionality from 1.94 to 1.98 increases the ultimate polymer molecular weight by a
factor of three from 82,000 to 270,000. This increase in MW could easily account for
the observed improvements in processability and properties.
Figure 9.4 Effect of polyol functionality on theoretical elastomer molecular weight
428
9.2.2 Processability and Property Latitude of Elastomers Based on Ultra-Low

Monol PPG Polyols
Ultra-low monol PPG diols are commercially available in molecular weights from 2000
to 12,000. A product summary is given in Table 9.4. To determine the formulating range
of the various diols in MDI/BDO cured elastomers, we prepared MDI prepolymers based
on the 2000, 4000 and 8000 MW diols at a wide range of isocyanate contents. These
prepolymers were chain extended with BDO to produce elastomers with a broad range
of properties. Tables 9.5 to 9.7 summarise the prepolymer compositions and viscosities,
processing characteristics and physical properties of these elastomers.
Table 9.4 Acclaim polyol product line

Acclaim Molecular Composition Functionality Hydroxyl Type
Polyol Weight
2200 2000 PO Diol 1.99 Secondary
3205 3200 EO/PO Diol 1.99 Secondary
6300 6000 PO Triol 2.97 Secondary
2220 2250 EO-Capped Diol 1.99 Primary (>85%)
4220 4000 EO-Capped Diol 1.97 Primary (>85%)
6320 6000 EO-Capped Triol 2.94 Primary (>85%)
429
Table 9.5 Polyurethane elastomers based on 2000-MW ultra-low monol PPG

(MDI prepolymers; BDO cured)
PREPOLYMER COMPOSITION
% NCO Prepolymer 4.0 6.0 8. 0 10.0 12.0
NCO/OH 2.2 3.0 3.8 4.8 6.0
4,4´-MDI (pbw) 27.7 36.9 47.7 60.2 75.0
2000-MW PPG (pbw) 100 100 10 0 100 10 0
20 °C 25 15 7.5 4. 0 3.3
40 °C 4.6 2.7 1.45 0.93 0.58
60 °C 1.45 0.85 0.49 0.33 0.22
80 °C 0.74 0.40 0.25 0.15 0.1
PROCESSING Prepolymer @ 65 °C; BDO @ RT; NCO/OH = 1.03; dibutyltin
CHARACTERISTICS dilaurate catalyst; Moulds @ 100 °C; cured 16 hours @ 100 °C
Prepolymer (pbw) 100 100 10 0 100 10 0
1,4-butanediol, BDO (pbw) 4.2 6. 2 8.3 10.4 12.5
Pot life (minutes) 1-3 1-3 1-3 1- 3 1- 3
Demould Time (minutes) 20-45 20-45 20-45 30-60 60-12 0
ELASTOMER PROPERTIES Samples conditioned 4 weeks @ 23 °C/50% relative humidity
Hardness, Shore A 57A 68A 80 A 89A 97A (45D)
Pendulum Rebound, % 60 61 61 56 54
Ultimate Elongation, % 810 710 70 0 640 58 0
Tensile Strength, MPa 15.9 22.1 26.2 25.5 23.4
100% Modulus, MPa 1.4 3.5 5. 7 8.5 11.7
200% Modulus, MPa 1.8 5.3 8.1 10.9 13.7
300% Modulus, MPa 2.5 7.4 10.3 13.0 15.4
400% Modulus, MPa 3.5 9.9 12.8 15.4 17.5
Die C Tear, kN/m 26 58 74 91 10 7
Compression Set, % 29 22 18 16 20
(22 h @ 70 °C)
5% 0.3 0.5 0. 9 1.4 2.1
10% 0.6 1.0 1.9 2. 8 4.1
15% 0.8 1.6 2. 6 4.1 6.1
25% 1.5 2.8 4.7 6. 8 10.4
pbw: parts by weight; RT: room temperature
430
Table 9.6 Polyurethane elastomers based on 4000-MW, ultra-low monol PPG

% NCO Prepolymer 4.0 6. 0 8.0 10.0
NCO/OH 3.3 4. 7 6.3 8.2
4,4´-MDI (pbw) 20.6 29.4 39.5 51.3
4000-MW PPG (pbw) 100 100 10 0 100
20 °C 16 8.5 4.5 3.1
40 °C 3.8 2. 2 1.25 0.89
60 °C 1.32 0.78 0. 5 0.36
80 °C 0.63 0.38 0.25 0.18
CHARACTERISTICS dilaurate catalyst; Moulds @ 100 °C; Cured 16 hours @ 100 °C
Prepolymer (pbw) 100 100 100 100
1,4-butanediol, BDO (pbw) 4.2 6.3 8. 3 10.4
Pot life (minutes) 1-3 1- 3 1-3 1-3
Demould Time (minutes) 20-45 20-45 30-60 60-120
ELASTOMER PROPERTIES Samples conditioned for 4 weeks @ 23 °C/50% humidity
Hardness, Shore A 60A 72A 82 A 91A
Pendulum Rebound, % 70 70 65 60
Ultimate Elongation, % 890 910 970 690
Tensile Strength, MPa 15.9 20.7 17.2 15.2
100% Modulus, MPa 1.9 3.4 4. 5 6.6
200% Modulus, MPa 2.9 4.9 6. 2 8.7
300% Modulus, MPa 4.0 6.3 7. 6 10.1
400% Modulus, MPa 5.3 7. 8 8.9 11.3
Die C Tear, kN/m 47 67 75 88
Split Tear, kN/m 4.7 8.8 9.6 14.2
Compression Set, % 19 25 19 21
(22 h @ 70 °C)
5% 0.3 0.8 1.0 1.5
10% 0.6 1.2 1. 8 3.0
15% 0.9 1.7 2.5 4.3
25% 1.7 2.8 4. 0 7.3
pbw: parts by weight; RT: room temperature
431
Table 9.7 Elastomers based on 8000-MW ultra-low monol PPG: Effect of 6000-
MW ultra-low monol triol addition (MDI prepolymers; BDO cured)
% NCO Prepolymer 2. 0 3.0 4.0
NCO/OH 2.9 3.1 4.0 4.2 5. 1 5.5
4,4´-MDI (pbw) 9.9 9.6 13.5 13.2 17.4 17.1
6000-MW PPG triol (pbw) 2.6 — 2.6 — 2.6 —
8000-MW PPG diol (pbw) 97.4 100 97.4 100 97.4 100
20 °C 72 50 40 35 24 22
40 °C 18 12 10 9 6.4 5. 9
60 °C 6.7 4.5 3.7 3. 3 2.4 2.3
80 °C 3.2 1.7 1.6 1. 5 1.1 0.83
CHARACTERISTICS dilaurate catalyst; Moulds @ 100 °C; Cured 16 hours @ 100 °C
Prepolymer (pbw) 100 100 10 0 100 100 100
1,4-butanediol, BDO (pbw) 2.1 2.1 3.1 3.1 4.2 4.2
Pot life (minutes) 1-3 1-3 1- 3 1-3 1-3 1-3
Demould Time (minutes) 30-60 >180 20-45 20-45 20-45 20-45
ELASTOMER PROPERTIES Samples conditioned for 4 weeks @ 23 °C/50% humidity
Hardness, Shore A 34A 27A 49A 45A 58A 56A
(32A)* (16A)* (41A)* (53A)*
Pendulum Rebound, % 59 55 68 65 71 69
Ultimate Elongation, % 1030 >1300** 1130 1190 920 960
Tensile Strength, MPa 4.0 2.9 12.7 10.1 13.2 11.8
100% Modulus, MPa 0.5 0.5 1. 2 1.2 1.7 1.6
200% Modulus, MPa 0.7 0.5 1.8 1.7 2.5 2.3
300% Modulus, MPa 0.8 0.6 2.4 2.2 3.4 3.1
400% Modulus, MPa 1.0 0.7 3. 1 2.9 4.4 4.0
Die C Tear, kN/m 16 13 42 42 49 47
Compression Set, %
34 53 22 40 19 21
(22 h @ 70 °C)
5% 0.1 0.1 0. 2 0.2 0.3 0.3
10% 0.3 0.3 0.4 0. 4 0 .6 0.6
15% 0.4 0.4 0.6 0. 6 1.0 0.8
25% 0.7 0.7 1.0 1. 0 1.7 1.5
*
Shore Hardness needle slowly penetrated into the sample to the value indicated in parenthesis
**
Samples did not break during testing
432
A review of the elastomer processability and physical property data indicates that there
is an optimum hardness range for each polyol MW. Based on the demould time and the
percent compression set, the following elastomer Shore hardness ranges are recommended.
The lower hardness limits of these ranges can be extended by addition of low levels (less
than 10%) of 6000-MW, ultra-low monol triol (Acclaim Polyol 6300).
Acclaim Polyol 2200 (2000-MW diol) 70 to 90 Shore A

The rebound of the elastomers based on 2000-MW, ultra-low monol PPG ranges from
55 to 60%. For high-performance dynamic applications, use of higher MW diols are
recommended, which give rebound values up to 10 units higher, ranging from 65 to
70%. Figure 9.5 shows the DMTA response for the 70 Shore A elastomers based on the
2000, 4000 and 8000 MW diols. The glass transition temperature (Tg) for the elastomers
based on the higher MW diols is about 15 °C lower, which probably accounts for the
higher rebound of these materials.
Figure 9.5 DMTA curves of 70 Shore A elastomers: Effect of polyol molecular weight
(6% NCO MDI prepolymers; BDO cured)
433
The 8000-MW, ultra-low monol PPG is used particularly in the development of soft,
plasticiser-free elastomers [16, 17]. The use of this high MW, low polydispersity polyol
allows for the preparation of low viscosity prepolymers with low isocyanate contents.
Initial evaluations of these very soft elastomers showed lower than expected physical
properties. The lower properties can be attributed to the very low hard-segment content
of these polymers. The lack of hard segment (physical crosslinks) can be compensated
for by the incorporation of low levels of chemical crosslinks (triol) [18]. This is
accomplished by the addition of a 6000-MW, ultra-low monol triol (Acclaim Polyol
6300) into the polymer matrix. Table 9.7 shows the triol effect on prepolymer viscosities,
elastomer processability and physical properties. It should be noted that very low levels
of crosslinking are needed to improve the elastomer properties.
9.2.3 Processing Latitude Improves by Incorporating Oxyethylene Moieties
The ultimate goal for MDI/BDO cured elastomers was to design a polyol that would
have a combination of good processability and high rebound in the mainline hardness
range of 80 to 95 Shore A. This was an elusive goal as one can see from the elastomer
data in Tables 9.5 and 9.6. A 90 Shore A elastomer based on the 4000-MW diol had
poor processability but a high rebound, whereas, the 90 Shore A elastomer based on the
2000-MW diol was processable but had a lower rebound.
We attributed the poor processability of the 90 Shore A elastomer based on the 4000-
MW diol to the excessive phase-separation of the MDI/BDO hard segment [19]. To
alleviate the hard segment phase-separation problem, the compatibility of the MDI/BDO
hard segment in the soft-segment phase was increased by incorporating oxyethylene
moieties into the polyol backbone. This technique dramatically enhanced the elastomer
processability. The polyol MW and oxyethylene content were varied to obtain the best
possible combination of processability, high hardness and high rebound. This optimisation
process led to the development of Acclaim Polyol 3205, a 3200-MW diol containing
approximately 20 weight percent oxyethylene moieties. Table 9.8 shows the enhanced
processing latitude of elastomers based on this polyol. In addition to enhanced
processability, elastomer physical properties were improved. Acclaim Polyol 3205 is a
unique material in that it allows the formulation of MDI/BDO cured elastomers from 75
to 95 Shore A with excellent processability and high rebound.
434
Table 9.8 Polyurethane elastomers based on Acclaim polyol 3205

% NCO Prepolymer 4.0 6.0 8. 0 10.0 12.0
NCO/OH 2.9 4.0 5.3 6.9 8.7
MDI (pbw) 22.4 31.2 41.5 53.5 67.7
Acclaim Polyol 3205 (pbw) 100 100 100 100 100
20 °C 14 8.5 4. 6 3.0 1.4
40 °C 3.2 1.9 1.0 0.8 0.65
60 °C 1.0 0. 7 0.41 0.32 0.26
80 °C 0.5 0. 3 0.19 0.16 0.14
CHARACTERISTICS dilaurate catalyst; Moulds @ 100 °C; cured for 16 hours @ 100 °C
Prepolymer (pbw) 100 100 100 100 100
1,4-butanediol, BDO (pbw) 4.2 6.2 8. 3 10.4 12.5
Pot life (minutes) 1-3 1-3 1- 3 1-3 1-3
Demould Time (minutes) 15-40 15-40 15-40 20-50 30-60
Green Strength @ 30 minutes excellent excellent excellent good average
ELASTOMER PROPERTIES Samples conditioned for 2 weeks @ 23 °C/50% relative humidity
Hardness, Shore A 43A (36A) 68A 82A 90 A 95A
Ultimate Elongation, % 650 720 960 850 810
100% Modulus, MPa 1.5 3.0 4. 9 7.1 9.8
200% Modulus, MPa 2.1 4.7 6.7 8.9 11.4
300% Modulus, MPa 3.2 6.6 8.4 10.8 12.7
400% Modulus, MPa 4.7 8.9 10.3 12.6 14.1
Die C Tear, kN/m 30 54 70 89 93
Compression Set, %
(22 h @ 70 °C) 60 42 19 21 24
5% 0.2 0. 5 1.0 1.6 3.2
10% 0.4 1.0 2. 1 3.3 5.8
15% 0.6 1.4 3.0 4.7 7.8
25% 1.1 2.5 5.0 7. 3 11.5
435
9.3 One-Shot Elastomer System Based on EO-Capped, Ultra-Low

Monol PPG Polyols
The lower reactivity of secondary hydroxyl groups on the initial ultra-low monol PPG
polyol products limited their use to mainly prepolymer systems. PTMEG and polyester
polyols have primary hydroxyl groups, allowing them to be easily formulated with
curatives such as 1,4-butanediol and reacted with polyisocyanates using a ‘one-shot’ or
‘quasi-prepolymer’ approach. For this reason, high-reactivity versions of ultra-low monol
PPG were developed. These polyols give the performance enhancements expected from
ultra-low monol PPG with the added benefit of being one-shot processable [20, 21]. The
higher reactivity is achieved by capping the propylene-oxide based polyols with ethylene
oxide (EO) resulting in products with a high percentage of primary-hydroxyl groups. A
significant amount of work has been reported on polyurethanes based on EO-capped
low monol PPG [20, 21, 22, 23, 24, 25].
9.3.1 Effect of Primary Hydroxyl Concentration on One-Shot Elastomer

Processability
A key factor in determining whether or not a polyol can be used in a one-shot process is
reactivity. As a general rule, the polyol reactivity needs to be nearly equal to or greater
than the reactivity of the curative. For example, most one-shot elastomers based on MDI
use BDO as a curative which contains primary hydroxyl groups. A typical PPG polyol
contains about 95% secondary hydroxyl groups. If one attempts to process a blend of
MDI, BDO and PPG, the MDI will react preferentially with the BDO to form an MDI-
BDO hard segment. The MDI-BDO hard segment is incompatible in the system and
phase separates before the PPG polyol has a chance to react. The end result is a low MW,
two-phase system in which the MDI-BDO hard segment is dispersed in partially reacted
polyol, which results in very poor physical properties. Therefore, successful one-shot
processing requires that the polyol and curative have similar reactivities.
The reactivity of PPG polyols can be increased by reacting with EO, which ring opens to
form a primary hydroxyl group. A 100% primary hydroxyl content cannot be achieved
using this approach since EO has a tendency to form chains instead of distributing evenly
to each secondary hydroxyl group; however, it is well known that a 100% primary
content is not required to achieve one-shot processability. The effect of the primary
hydroxyl content on the processability of a one-shot elastomer system is discussed next.
To determine the effect of the polyol primary content on the processability of a one-shot
system, two 4000-MW, ultra-low monol PPG diols, which were EO-capped to obtain
primary contents of 80 and 87 percent were prepared. These were compared with a
436
2000-MW PTMEG-2000, which has 100 percent primary hydroxyl content. These polyols
were evaluated in a one-shot elastomer system consisting of carbodiimide-modified MDI
(29.3% NCO), polyol and BDO formulated to an 80 Shore A hardness. Processability
was assessed by measuring the hardness build up with time. The reaction rate was held
constant by adjusting the dibutyltin dilaurate catalyst concentration to achieve a constant
pot life of 90 seconds. Pot life is defined as the work life of the solution, which is the time
period until the solution becomes too viscous to be poured into a mould. The elastomer
solution was poured into moulds preheated to 100 °C and then placed into a 100 °C
vented oven until the elastomer had developed enough integrity to be demoulded. After
demoulding, the elastomer hardness was measured at regular intervals and placed back
in the oven. The final hardness measurement was made after 16 hours cure at 100 °C.
All the data were normalised to 100% using the final hardness measurement. The
normalised hardness versus time were then plotted.
The hardness build of 80 Shore A, one-shot elastomers based on polyols with primary
contents of 80, 87 and 100 percent are shown in Figure 9.6. As expected, the elastomer
Figure 9.6 Hardness buildup of 80 Shore A one-shot elastomers

(carbodiimide-modified MDI/polyol/BDO)
437
based on PTMEG-2000 has the fastest hardness build, achieving 90% of its final
hardness after only 30 minutes. The 87% primary content, 4000-MW, EO-capped diol
gave the next fastest hardness build as it took 60 minutes to achieve 90% of its final
hardness. Surprisingly, there was a large difference between the 80 and 87% primary
content 4000-MW, EO-capped diols as the time to achieve 90% of its final hardness
went from 60 minutes to over 4 hours. Based on this information, it was decided that
the primary-hydroxyl content needs to be at least 85%.
The previous studies led to the development of three products, a 2250-MW diol (Acclaim
Polyol 2220), 4000-MW diol (Acclaim Polyol 4220) and a 6000-MW triol (Acclaim
Polyol 6320). Table 9.4 shows the typical properties of these new higher-reactivity,
ultra-low monol PPG polyols. The behaviour of these products in one-shot systems is
discussed below.
9.3.2 Effect of Monol Content on One-Shot Elastomer Processability

and Properties
The effect of monol content on the processability and properties of one-shot elastomers
is shown in Table 9.9. We prepared 80 Shore A elastomers based on carbodiimide-
modified MDI and BDO using a 4000-MW, EO-capped, ultra-low monol diol
containing 3% monol content and a conventional EO-capped diol containing 15%
monol. These polyols had comparable primary hydroxyl concentrations of 87 and
89%, respectively.
As expected, the monol content of the EO-capped PPG diols has a significant effect
on the elastomer processability. The Shore hardness of the conventional elastomer
was only 57A after 16 hours cure at 100 °C, whereas the elastomer based on ultra-
low monol PPG had a hardness of 78A. It took three weeks for the conventional
elastomer to achieve its final hardness of 82A.
Virtually all elastomer properties improved with lower monol contents (see Table 9.9). Of
particular note, the rebound increased from 59 to 68 percent, the elongation from 470 to
550%, tensile strength from 10 to 19 MPa, tear strength from 49 to 68 kN/m, compression
set decreased from 64 to 23%, and the Taber abrasion loss (ASTM D4060-95 [26]) decreased
from 220 to 80 mg loss/1000 cycles. The improvement in the stress/strain curves is shown
in Figure 9.7. Lower monol content results in significantly higher ultimate polymer MW,
which results in improved mechanical properties.
438
Table 9.9 One-shot elastomer comparison: Ultra-low monol versus conventional

EO-capped PPG (cardodiimide-modified MDI/polyol/BDO)
POLYOL COMPOSITION
Polyol Conventional Ultra-Low Monol
Monol Content, molar % 15 3
Primary Hydroxyl Content, % 89 87
ELASTOMER COMPOSITION
CD-MDI (pbw) 42.9 43.0
Polyol (pbw) 100 100
1,4-Butanediol, BDO (pbw) 10.9 10.9
Pot life (minutes) 1.5 1.5
Demould Time (minutes) 20 20
Green Strength @ 30 minutes Good Excellent
Initial Shore Hardness (16 h cure, 100 °C) 57 A 78A
Hardness Shore A 82A 82A
Pendulum Rebound, % 59 68
Ultimate Elongation, % 470 550
Tensile Strength, MPa 10.4 19.4
100% Modulus, MPa 4.3 5.3
200% Modulus, MPa 6. 0 7.8
300% Modulus, MPa 7.6 10.0
400% Modulus, MPa 9.4 12.5
Die C Tear, kN/m 49 68
Compression Set, % (22 h @ 70 °C) 64 23
Taber Abrasion*, (mg loss/1000 rev) 220 80
5% 1.2 1.3
10% 2.1 2.3
15% 3.0 3.3
25% 4.4 5.2
*
Elastomer contained 1 wt% Irganox 1076 (Ciba-Geigy)
439
Figure 9.7 Stress/strain curves of 80 Shore A one-shot elastomers based on 4000-MW,

EO-capped PPG: Ultra-low monol versus conventional
9.3.3 Processability and Property Latitude of Elastomers Based on

EO-Capped, Ultra-Low Monol Polyols
The processability and property latitude of elastomers based on EO-capped, ultra-low

monol polyols were determined by preparing a series of elastomers at varying hard-
segment contents. The percent hard-segment content is defined as:
(weight MDI + weight BDO)/total elastomer weight x 100.
The elastomers were prepared using the one-shot process by the hand-casting technique
at a pot life of 1.5 minutes.
The compositions, processability and properties of elastomers prepared using the one-
shot process are given in Tables 9.10 to 9.12. For the 4000-MW, EO-capped diol, the
upper hardness processability limit via hand casting is about 85 Shore A as indicated by
the green strength in Table 9.10. Machine casting using a shorter pot life (30 to 45
440
Tables 9.10 One-shot elastomers based on 4000 MW, EO-capped, ultra-low

monol PPG (carbodiimide-modified MDI/polyol/BDO)
Hard-Segment Content 15 20 25 35 40 45
CD-MDI (pbw) 15.2 20.8 27.2 43.0 53.2 64.4
Acclaim 4220 Polyol 100 100 100 10 0 100 100
1,4-Butanediol, BDO (pbw) 2.5 4.2 6.1 10.9 13.9 17.5
Pot life (minutes) 1.5 1.5 1.5 1. 5 1.5 1.5
Demould Time (minutes) 20 20 20 20 20 20
Green Strength Excellent Excellent Excellent Excellent Good Poor
Hardness, Shore A 50A 60A 70 A 80A 90A 95A
(45D)
Pendulum Rebound, % 68 69 70 68 60 56
Ultimate Elongation, % 640 610 58 0 550 500 450
Tensile Strength, MPa 4.9 7.6 10.7 19.4 20.4 21.4
100% Modulus, MPa 1.1 1.8 2.4 5.3 7.6 10.0
200% Modulus, MPa 1.5 2.5 3.6 7.8 10.7 13.1
300% Modulus, MPa 1.9 3.4 5.0 10.0 13.1 15.9
400% Modulus, MPa 2. 4 4.6 6.6 12.5 15.9 18.7
Die C Tear, kN/m 21 35 47 69 70 85
Compression Set, %
(22 h @ 70 °C) 40 33 30 25 20 22
5% 0.2 0.4 0.6 1.3 1.2 3.0
10% 0.4 0.7 1. 0 2. 3 2.8 5.3
15% 0. 6 1.0 1.5 3.3 4.2 6.9
25% 1.0 1.8 2.6 5.2 7.3 10.4
seconds) could extend the hardness limit to the low to mid-90s. The lower hardness limit
as indicated by the increase in compression set is about 60 Shore A. The lower hardness
limit can be extended down to at least 40 Shore A by replacing some of the 4000-MW
441
Table 9.11 One-shot elastomers based on ultra-low monol, EO-capped,

4000-MW diol/6000-MW triol blends (CD-MDI/polyol/BDO)
Hard-Segment Content 10 10 10 10 10
CD-MDI (pbw) 10.2 10.2 10.2 10.2 10.2
1,4-Butanediol, BDO (pbw) 0.9 0.9 0. 9 0.9 0.9
Pot life (minutes) 1.5 1. 5 1.5 1.5 1.5
Demould Time (minutes) 20 20 20 20 20
Green Strength Excellent Excellent Excellent Excellent Excellent
Hardness, Shore A 40 A 42A 43A 45A 45A
Tensile Strength, MPa 2.5 2. 3 1.9 1.7 1.5
100% Modulus, MPa 0.8 0. 9 0.9 0.9 1.0
200% Modulus, MPa 0.9 1.2 1.2 1.2 1.3
300% Modulus, MPa 1.1 1.4 1.5 1.6 —
400% Modulus, MPa 1.1 1.6 1.7 — —
Die C Tear, kN/m 15 14 12 11 9
Compression Set, % (22 h @ 70 °C) 45 38 20 15 12
5% 0.1 0.1 0.1 0.1 0.1
10% 0.3 0. 3 0.3 0.3 0.3
15% 0.4 0.4 0. 5 0.5 0.5
25% 0.8 0.8 0.9 0. 9 0.9
diol with the 6000-MW, EO-capped, ultra-low monol triol as shown by the reduction in
compression set in Table 9.11. Thus, using combinations of 4000-MW diol and 6000-
MW triol, a broad hardness range from about 40 to 85 Shore A can be achieved.
442
The 2250-MW (50 OH#) EO-capped, ultra-low monol diol was designed to enhance
processability at higher Shore hardnesses. The processability and properties of one-shot
elastomers based on this polyol are shown in Table 9.12. One-shot elastomers with
excellent processability and properties can be formulated from an 80 Shore A up to
about a 55 Shore D. Thus, a broad range of Shore hardnesses (40A to 55D) can be
achieved using EO-capped, ultra-low monol polyols.
Table 9.12 One-shot elastomers based on 2250 MW, EO-capped, ultra-low

monol PPG (CD-MDI/polyol/BDO)
Hard-Segment Content 25 35 45 55 65
CD-MDI (pbw) 28.5 44.2 65.6 96.6 145.2
1,4-Butanediol, BDO (pbw) 4.8 9.6 16.2 25.6 40.5
Potlife (minutes) 1.5 1.5 1. 5 1.5 1.5
Demould Time (minutes) 20 20 20 20 20
Green Strength Excellent Excellent Excellent Excellent Average
Hardness, Shore A 67A 82A 94A 52D 60D
(44D)
100% Modulus, MPa 2.6 5. 1 9.7 15.9 19.4
200% Modulus, MPa 3.7 7.6 13.1 19.4 25.6
300% Modulus, MPa 5.4 10.4 16.6 21.4 —
400% Modulus, MPa 8.3 14.5 20.0 — —
Die C Tear, kN/m 44 67 88 97 127
Compression Set, % (22 h @ 70 °C) 38 28 24 nd nd
nd: not determined
443
9.4 Comparison of Ultra-Low Monol PPG Polyols with PTMEG
When comparing ultra-low monol PPG polyols with PTMEG it is essential to keep in
mind the fundamental differences between these two high-performance polyether polyols
in order to obtain the maximum benefit in urethane applications. Table 9.13 summarises
these differences in terms of their chemical structure, hydroxyl type (reactivity), MWD
and crystallisability.
Table 9.13 Comparison of fundamental characteristics of ultra-low monol PPG

polyols and PTMEG
Ultra-Low Monol PPG PTMEG
Chemical Structure -O(-CH2-CH-O)x-CH3 -O(-CH2CH2CH2CH2-O)x-
Tg ≈ -75 °C Tg ≈ -84 °C
Hydroxyl Type Secondary Hydroxyl Primary Hydroxyl
(Lower Reactivity) (Higher Reactivity)
Molecular Weight Narrow: Mw/Mn = 1.02-1.15 Broad: Mw/Mn = 1.7-2.4
Distribution (Acclaim 2200: 0.165 Pa-s @ 40 °C) (PTMEG-2000: 12 Pa-s @ 40 °C)
Crystallisability Non-crystallisable Crystallisable
(Liquid; Pour Point: -33 °C) (Waxy Solid; mp: 28-40 °C)
mp: melting point
Both PPG and PTMEG have polyether backbones, which inherently impart excellent
hydrolytic stability and microbial resistance to polyurethanes. The Tg of PPG
approaches that of PTMEG resulting in polyurethanes that can be used in cold, harsh
environments. PTMEG has primary hydroxyl groups, whereas, ultra-low monol PPG
are available with secondary hydroxyl groups or EO-capped versions for primary
hydroxyl contents in excess of 85%. Ultra-low monol PPG polyols have narrow MWD,
which gives polyols that are an order of magnitude lower in viscosity than PTMEG.
The storage and handling requirements for PPG polyols are minimal since they are
non-crystallising liquids with pour points of about –30 °C. Additionally, polyurethanes
based on non-crystallising polyols will not ‘cold harden’ like some of those based on
crystallisable polyols. A comparison of ultra-low monol PPG versus PTMEG in MDI/
BDO cured elastomers is given below.
444
9.4.1 MDI/BDO Cured Elastomers: Acclaim Polyol 3205 Versus PTMEG-2000
For a comparison of PTMEG in MDI/BDO cured elastomers the 3200-MW ultra-low

monol PPG diol was chosen which contains about 20 wt% EO (Acclaim Polyol 3205)
since it gives the best overall properties in this type of system. A 2000-MW PTMEG was
used since it gives the best performance at an 80 Shore A hardness. Elastomers of 80
Shore A hardness were prepared using the prepolymer process. Table 9.14 summarises
their prepolymer viscosities, elastomer processing characteristics and physical properties.
The initial surprise was to find that it takes an 8% NCO MDI/Acclaim 3205 prepolymer to
make a 80 Shore A elastomer, whereas, PTMEG-2000 requires a 6% NCO prepolymer. This
finding will be explained in the section on the effect of polyol MWD (see section 9.5.4).
Note the dramatic difference in prepolymer viscosities in Table 9.14. The prepolymer
based on ultra-low monol polyol has a viscosity almost ten times lower than that of
PTMEG-2000. This is due to a combination of the narrower MWD and the higher %
NCO of the Acclaim 3205 prepolymer.
Lower viscosity prepolymers offer significant advantages in processability. This gives the
polyurethane manufacturer much more latitude in terms of processing conditions such
as temperature and catalyst combinations. Elastomers based on Acclaim Polyol 3205
have demould times and green strengths comparable to those based on PTMEG-2000.
When hand casting elastomers using a 1 to 3 minute pot life, this can give demould times
of significantly less than 30 minutes.
As expected, the fundamental differences in the polyols also have a significant impact on
the elastomer physical properties. Although elastomers based on ultra-low monol PPG
have pendulum rebounds significantly higher than conventional or low monol polyols,
they are about 10 units lower that PTMEG at an equal Shore hardness. It is believed this
is due to fundamental differences in the polyol backbone structure. PPG polyols have a
pendant methyl group which may inherently absorb more energy than the linear methylene
chain of PTMEG.
Elastomers based on Acclaim Polyol 3205 have ultimate elongations that are twice that
of PTMEG. It is believed that this is due to the fact that PTMEG stress crystallises as it is
stretched. Crystallites behave like crosslinks and lower the elongation. To test this theory,
a series of MDI/BDO cured elastomers were prepared using 2000-MW crystallisable
polyesters (polybutylene adipate and polycaprolactone) and non-crystallisable polyesters
(polyethylenebutylene adipate and poly-2-methyl-1,3-propylene adipate). Figures 9.8 and
9.9 compare the stress/strain curves of the crystallisable versus non-crystallisable
polyethers and polyesters, respectively. From these figures the importance of the polyol
stress crystallisability in determining the elastomer stress/strain profile can be seen.
445
Table 9.14 Acclaim 3205 elastomers compared with PTMEG-2000 at 80 Shore

hardness (MDI prepolymers: BDO cured)
Polyol Type Acclaim 3205 PTMEG-2000
% NCO Prepolymer 8.0 6.0
NCO/OH 5.3 3.0
20 °C 4.6 42
40 °C 1.0 11
60 °C 0.41 3.7
80 °C 0.19 1.6
PROCESSING CHARACTERISTICS Acclaim Prepolymers @ 65 °C; PTMEG Prepolymers @
80 °C; BDO @ RT; NCO/OH = 1.03; dibutyltin dilaurate
catalyst; Moulds @ 100 °C; cured for 16 hours @ 100 °C
Pot life (minutes) 1-3 1-3
Demould Time (minutes) 15-40 15-40
Hardness, Shore A 82A 83A
Pendulum Rebound, % 65 75
Ultimate Elongation, % 960 510
Tensile Strength, MPa 24 31
400% Modulus, MPa 10.3 14.7
Die C Tear, kN/m 70 70
Compression Set, % (22 h @ 70 °C) 19 15
5% 1.0 0.8
10% 2.1 1.7
15% 3.0 2.6
25% 5.0 4.6
446
Figure 9.8 Stress/strain curves of 80 Shore A elastomers: Crystallisable versus

non-crystallisable polyethers
The tensile strengths of ultra-low monol based elastomers are lower than that of PTMEG.
However, if one considers the total energy to break as measured by the area under the
stress/strain curve, the elastomers based on Acclaim Polyol 3205 are significantly tougher
than those based on PTMEG. The tear strengths of the elastomers are comparable.
9.4.2 Enhanced Elastomer Properties Utilising Ultra-Low Monol

PPG/PTMEG Blends
Previously, it was shown that elastomers based on non-crystallising polyols such as ultra-
low monol PPG have twice the ultimate elongation of crystallising polyols such as PTMEG.
The next experiments were aimed at determining how much ultra-low monol PPG it would
take to eliminate the stress crystallisability of PTMEG [19]. A series of 80 Shore A elastomers
447
Figure 9.9 Stress/strain curves of 80 Shore A elastomers: Crystallisable versus

non-crystallisable polyesters
were prepared using MDI prepolymers based on 4000-MW, ultra-low monol PPG/
PTMEG-2000 blends chain extended with BDO. The results of the addition of 0, 10, 40
and 100 weight percent 4000-MW PPG based on the total polyol weight are given in
Table 9.15.
It was found that only about 10 weight percent of 4000-MW PPG is required to break
up the stress crystallisability of PTMEG-2000 as shown in Table 9.16 with the elongation
increasing from 510 to over 1000%. Surprisingly, it was found that 4000-MW PPG
addition gave a synergistic response in terms of elongation, tensile and tear strength.
Even more surprising was that the synergy doesn’t reach a maximum until up to 40
weight percent of 4000-MW PPG. This elastomer has a 1270% elongation, 35 MPa
tensile strength and a 77 kN/m tear strength. Additionally, the rebound was only three
units lower than the PTMEG elastomer system and the prepolymer viscosity was
significantly lower which enhances processability.
448
Table 9.15 Effect of 4000-MW PPG addition to 80 Shore A elastomers based

on PTMEG-2000 (MDI prepolymers: BDO cured)
PREPOLYMER CHARACTERISTICS
Wt% 4000-MW PPG 0 10 40 100
% NCO Prepolymer 6 6 6 8
Prepolymer Viscosity, Pa-s @
20 °C 42 30 22 4.5
40 °C 11 7.7 5.9 1.3
60 °C 3.7 2.7 2.1 0.5
80 °C 1.6 1.2 0.9 0.3
Hardness, Shore A 83A 82A 82A 82A
Tensile Strength, MPa 31 33 35 17
100% Modulus, MPa 5. 3 5.0 4.5 4.5
300% Modulus, MPa 9.9 8.4 7.9 7.6
Die C Tear, kN/m 70 81 77 75
So one can maximise the benefit from ultra-low monol PPG polyols in urethane
systems such as MDI/BDO cured elastomers by understanding their fundamental
differences in comparison to other high-performance polyols like PTMEG. A detailed
look at the effect of the polyol MWD on the mechanical and dynamic properties of
polyurethanes follows.
9.5 Polyol Molecular Weight Distribution Effect on Mechanical and

Dynamic Properties of Polyurethanes
A less well-understood factor, which affects the properties of polyurethanes, is the

polyol MWD. Ultra-low monol PPG polyols have very narrow MWD (polydispersity
< 1.1) compared to other high-performance polyols such as PTMEG or polyester polyols
(polydispersity: 1.7 to 2.4) as illustrated by the gel permeation chromatography (GPC)
curve in Figure 9.10. As expected, a narrower MWD results in an order-of-magnitude
449
Figure 9.10 GPC comparison of 4000-MW ultra-low monol PPG to 2000-MW PTMEG
reduction in polyol and prepolymer viscosities [7]. Additionally, it was found that
polyol MWD has a dramatic effect on the polymer mechanical and dynamic properties,
particularly in polyurethane/urea systems [19, 27].
9.5.1 TDI Prepolymers Cured with Methylene Bis-(2-Chloroaniline) [MBOCA]
In formulating polyurethane/urea systems using ultra-low monol PPG polyols, it was

found that polyol MWD has a major effect on polymer properties. A broadened MWD
is required to achieve a property profile similar to a PTMEG-based system. The MW-
distribution effect is illustrated using TDI prepolymers cured with MBOCA, TDI moisture-
cured prepolymers and aqueous polyurethane/urea dispersion coatings.
Traditionally, high-performance TDI/MBOCA-cured elastomers are based on PTMEG. They

are prepared by reacting TDI with PTMEG at a 1.7:1 to 2:1 NCO to OH ratio to form a
prepolymer and then extend the polymer chain with MBOCA. For these studies, prepolymers
were prepared using pure 2,4-TDI reacted with polyol at a 2:1 NCO to OH ratio.
The properties of a MBOCA-extended prepolymer based on a 1000-MW PPG compared

to a 1000-MW PTMEG are shown in columns 1 and 2 of Table 9.16. Surprisingly, the
450
elastomer properties were much lower than expected as shown by the hardness (83A
versus 96A); rebound (15 versus 45%); tensile strength (9.2 versus 45 MPa) and tear
strength (39 versus 110 kN/m). After several attempts to improve the properties via
processing conditions, catalyst, etc., it was decided to artificially broaden the MWD of
an ultra-low monol PPG polyol to approximate that of PTMEG-1000. This was achieved
by blending a 4000-MW PPG with a low-MW glycol diethylene glycol (DEG), to an
average MW of 1000. The property profile of this elastomer is shown in the last column
of Table 9.16. Interestingly, the property profile is now closer to the elastomer based on
PTMEG-1000 and is very similar to a commercial PTMEG-based 93A product, Airthane
PET-93A, which is a product of Air Products and Chemicals, Inc.
Table 9.16 Mechanical properties of MBOCA-cured TDI prepolymes

Polyol Type PPG-1000 PTMEG-1000 Airthane 4000-MW
PET-93A* PPG/DEG
Blend
Hardness, Shore A 83A 96 A 93A 92A
Tensile Strength, MPa 9.3 44.8 37.9 21.7
100% Modulus, MPa 2.8 14.2 11.0 11.0
Die C Tear, kN/m 39 110 72 88
*
Data taken from Engineering Properties of Castable Polyurethane Elastomers,
Air Products and Chemicals, Inc., 1994.
Airthane is a registered trademark of Air Products and Chemicals, Inc.
It is thought that PTMEG gives a higher hardness/modulus polymer because a significant

amount of the low-MW tail (see Figure 9.10) ends up in the hard-segment phase. Also,
the PTMEG-based elastomer gives a higher rebound because the soft-segment phase
consists of PTMEG with MW significantly higher than 1000.
The above conclusions are supported by the DMTA curves shown in Figure 9.11. The storage
modulus in the rubbery plateau region is significantly higher for the elastomer based on the
PPG/DEG blend, supporting the theory that DEG is contributing to the hard segment. Also,
note the transition at 130-150 °C, which is likely to be the softening point of the DEG/TDI/
MBOCA hard segment. The dramatic lowering of the soft-segment Tg from 0 °C to -42 °C
also supports the view that the PPG polyol and DEG are going into separate phases.
451
Figure 9.11 DMTA curves of TDI prepolymers cured with MBOCA-PPG-1000 versus
4000-MW PPG/DEG blended to 1000 MW
In Figure 9.12, the effect of varying the glycol chain length on the DMTA profiles is
shown by using propylene glycol (PG), dipropylene glycol (DPG), tripropylene glycol
(TPG) and a 400-MW PPG. The short-chain glycols (PG, DPG, TPG) all gave similar
storage-modulus profiles, while the 400-MW PPG gave a dramatically different profile.
This indicates that if the MW of the glycol is too high it becomes miscible in the soft-
segment phase and increases the Tg, thus reducing the elastomer rebound and dynamic
performance.
In some cases it may not be practical or cost effective to perform DMTA analysis on all
samples. It was found that materials can be screened by measuring hardness and rebound
at a series of temperatures (-10 °C, 23 °C and 105 °C) and these results are shown in
Table 9.17. Small changes in properties imply a broad temperature use range for the
polymer. These results are consistent with the DMTA findings.
In Table 9.18 the effect of a higher average MW polyol is shown by comparing 2000-
MW ultra-low monol PPG with a blended product (4000-MW PPG/DEG). Again, the
differences in hardness, rebound and modulus are dramatic and are consistent with the
above trends.
452
Figure 9.12 Effect of glycol chain length on DMTA curves of TDI prepolymers
cured with MBOCA
Table 9.17 Mechanical properties of MBOCA-cured TDI prepolymers (effect of

glycol chain strength)
Polyol Type – Shore Hardness Bashore Elongation Tensile 100% Die C
1000 MW @ Rebound @ % Strength Modulus Tear
-10/23/105 -10/23/105 MPa MPa Strength
°C °C kN/m
PPG-1000 74D/83A/69A 51/14/42 340 9.3 2. 8 39
4000/PG 94A/92A/88A 27/42/62 410 29.0 10.9 93
4000/DPG 95A/94A/91A 28/48/62 350 24.8 12.0 93
4000/TPG 95A/92A/89A 28/42/58 36 0 29.0 13.0 97
4000/PPG400 69D/58D/86A 46/38/35 360 28.3 12.3 86
453
Table 9.18 Mechanical properties of MBOCA-cured TDI prepolymers

Polyol Type 2000-MW PPG Airthane PET-80A 4000-MW PPG
DEG Blend
Hardness, Shore A 68A 80A 80 A
100% Modulus, MPa 2.1 4. 1 4.3
*
Data taken from Engineering Properties of Castable Polyurethane Elastomers, Air Products
and Chemicals, Inc., 1994.
Airthane is a registered trademark of Air Products and Chemicals, Inc.
9.5.2 Moisture-Cured TDI Prepolymers
To determine if the polyol MWD effect can be seen in other polyurethane/urea systems,
a moisture-cured film was prepared using a 2:1 prepolymer based on 2,4-TDI and PPG-
1000 and this was compared with one based on 4000-MW PPG blended with DEG to a
MW of 1000. Table 9.19 shows the mechanical properties of the films in bold type. The
dramatic increases in 100% modulus (1.3 to 3.6 MPa), tensile strength (14 to 35 MPa)
and tear strength (18 to 58 kN/m) obtained by broadening the MWD of the polyol can
Table 9.19 Effect of 4000-MW PPG/DEG blend MW on mechanical properties

of moisture-cured TDI prepolymers
PPG-1000 4000-MW PPG/Diethylene Glycol Blends
Polyol Blend MW 1000 3000 1600 1000 770
Prepolymer % NCO (theory) 6.23 2.54 4.24 6.23 7.53
Elongation, % 730 1280 850 720 540
100% Modulus, MPa 1.3 0. 4 2.0 3.6 8.3
300% Modulus, MPa 2.1 0. 6 4.0 5.6 14.6
Die C Tear, kN/m 18 12 40 58 93
454
clearly be seen. The DMTA curves of these materials show the same trends as with the
MBOCA-cured TDI prepolymers as seen in Figure 9.13. A formulation with 4000-MW
PPG decreases the soft-segment Tg from –16 °C to –58 °C greatly enhancing the low
temperature performance of this system.
The versatility of using this approach can be clearly seen by blending 4000-MW PPG
and DEG to a wide range of MW (770 to 3000) as shown in Table 9.19. By simply
blending these two components, one can vary the 100% modulus from 0.4 to 8.2 MPa.
Traditionally, hardness would be adjusted by using various polyol MWs; however, when
using this approach there is a reduction in the low-temperature flexibility as shown by
the DMTA curves in Figure 9.13.
Figure 9.13 DMTA curves of TDI moisture-cured prepolymer films - PPG-1000 versus
4000-MW PPG/DEG blended to 1000 MW
Using the blend approach, the hardness can be varied over a wide range while retaining
the low-temperature flexibility as shown by the DMTA curves in Figure 9.14. Note
that with increasing amounts of DEG, there is a transition beginning at about 100 °C
that becomes more pronounced and shifts to about 80 °C. This transition is likely
455
Figure 9.14 Effect of 4000-MW PPG/DEG blend MW on DMTA curves of TDI

moisture-cured prepolymer films
associated with the Tg of the TDI/DEG/urea hard segment. Similar property profiles
are observed in isophorone diisocyanate-based (IPDI), moisture-cured systems utilised
in deck-coating materials.
9.5.3 Aqueous Polyurethane/Urea Dispersion Coatings
We also determined the effect of polyol MWD in aqueous polyurethane/urea

dispersion coatings by first comparing a 2000-MW, ultra-low monol PPG with
PTMEG-2000. The dispersions were prepared by the prepolymer-mixing process
using the formulations given in Table 9.20 [15]. The prepolymer was based on
IPDI, polyol and dimethylol propionic acid (DMPA). It also contained 10 weight
percent N-methyl pyrrolidone (NMP) as a coalescing aid. Triethylamine was used
as a neutraliser and ethylene diamine as chain extender. All aqueous dispersions
were prepared to 40% solids content. A detailed experimental procedure is given
in a previous article [28].
456
Table 9.20 Aqueous polyurethane/urea dispersion formulations

4000 MW
Polyol 2000 MW PPG PTMEG-2000
PPG/PPG
Polyol Blend, MW 2000 2000 2000
PREPOLYMER COMPOSITION g (equiv.)
Isophorone Diisocyanate 65.2 (0.587) 65.2 (0.587) 65.1 (0.586)
Polyol 195.6 (0.196) 195.6 (0.196) 188.9 (0.095)
Dipropylene Glycol — — 6.8 (0.101)
Dimethylolpropionic acid 9.2 (0.137) 9.2 (0.137) 9.2 (0.137)
N-Methylpyrrolidone 30 30 30
Total Weight 300 300 300
PREPOLYMER CHARACTERISTICS
NCO/OH 1.76 1.76 1.76
% NCO (theoretical) 3.6 3.5 3.6
% NCO (actual) 3.25 3.22 3.30
% Carboxylate 1.12 1.10 1.11
Viscosity @ 80 °C, Pa-s nd 3.7 0.7
DISPERSION AND CHAIN EXTENSION
Neutraliser Triethylamine Triethylamine Triethylamine
Chain Extender Ethylene diamine Ethylene diamine Ethylene diamine
DISPERSION CHARACTERISTICS
Solids Content, wt % 40 40 40
Cosolvent Content, wt % 4.0 4.0 4.0
The stress/strain curves in Figure 9.15 show that the film based on the 2000-MW PPG
has a significantly lower hardness than that based on PTMEG-2000. To take into account
the differences in polyol MWD, we then prepared an aqueous dispersion using 4000-
MW PPG and DPG blended to a 2000 MW. Figure 9.15 shows that these stress/strain
curves are now very similar up to 200% elongation. At higher elongations, the film
based on PTMEG-2000 begins to stress crystallise resulting in increased modulus and
reduced ultimate elongation. The DMTA curves in Figure 9.16 show that the film based
on the blend of 4000-MW PPG and DPG has a profile more similar to PTMEG-2000
than to that based on 2000-MW PPG.
457
Figure 9.15 Stress/strain curves of aqueous polyurethane/urea dispersion films
Figure 9.16 DMTA curves of aqueous polyurethane/urea dispersion films
458
9.5.4 MDI Prepolymers Cured with BDO
Table 9.21 demonstrates the polyol MWD effect by comparing BDO cured 6% NCO
4,4´-MDI prepolymers based on 2000-MW PPG and PTMEG-2000. The elastomer based
on the narrow-MWD polyol has a significantly lower hardness (68A versus 83A) and
rebound (60 versus 75%). This is consistent with PTMEG-2000 containing some short-
chain diol, which phase separates into the hard segment promoting higher hardness.
Also, the soft-segment Tg of the PTMEG-2000 elastomer would be lower since the soft
segment actually consists of PTMEG with MW significantly higher than 2000. Based on
our previous discussion, to best approximate the property profile of a broad-MWD polyol
such as PTMEG, one needs to use a higher MW ultra-low monol PPG polyol with some
additional chain extender (BDO).
Table 9.21 illustrates this effect by increasing the PPG MW from 2000 to 4000 and the
prepolymer % NCO from 6 to 8. This increases the hardness to the same level as the
PTMEG-based elastomer and increases the rebound to 65%. As an aside, increasing the
prepolymer % NCO from 6 to 8 represents a polyol/BDO blend of 2160 MW.
We conclude with some remarks regarding recommendations as to which short chain

diols to use with polyurethanes versus polyurethane/ureas. In elastomeric materials,
optimal dynamic performance is obtained in a well phase-separated system (a low soft-
segment Tg and a high softening or melting-temperature hard-segment). For polyurethane
systems, optimal dynamic performance is achieved by maintaining symmetry in the hard
segment. This is accomplished by using a symmetrical diisocyanate (such as pure 4,4´-
MDI) with a symmetrical chain extender (such as ethylene glycol, BDO, DEG or 1,6-
hexanediol). This symmetry results in a high-melting-temperature crystalline hard-segment
phase, enhancing phase separation in the polymer. Complete phase separation results in
a low soft-segment Tg and excellent rebound or dynamic performance. Disrupting the
symmetry of the hard segment potentially reduces the rebound or dynamic performance.
In formulating with ultra-low monol PPG in polyurethane systems, optimal properties
are attained using a high MW polyol with additional symmetrical chain extender. Use of
mixed chain extenders will disrupt the hard-segment symmetry and lead to a reduction
in dynamic properties.
In polyurethane/urea systems, phase separation and optimal dynamic performance is

driven by the hydrogen bonding of the urea linkage and not by the hard-segment symmetry.
So when formulating ultra-low monol PPG polyols in polyurethane/urea systems, there
is more latitude in the choice of short-chain glycols. However, it is undesirable to choose
an extender that is so short or symmetrical that the isocyanate adduct is incompatible in
the isocyanate-terminated prepolymer. Additionally, the glycol MW must be limited to
prevent it from phase mixing with the soft segment.
459
Table 9.21 Elastomer properties of MDI prepolymers cured with BDO

Polyol Type 2000-MW PPG PTMEG-2000 4000-MW PPG
% NCO Prepolymer 6.0 6.0 8.0
NCO/OH 3.0 3.0 6.3
4,4´-MDI (pbw) 36.9 36.9 39.5
Polyol (pbw) 100 100 100
20 °C 15 42 4.5
40 °C 2.7 11 1.25
60 °C 0.85 3.7 0.5
80 °C 0.4 1.6 0.25
Prepolymer (pbw) 100 100 100
1,4-butanediol, BDO (pbw) 6.2 6.2 8.3
Pot life (minutes) 1-3 1-3 1-3
Demould Time (minutes 20-45 20-45 30-60
ELASTOMER PROPERTIES Samples conditioned for 4 weeks @ 23 °C/50%
relative humidity
Hardness, Shore A 68A 83A 82A
Ultimate Elongation, % 710 510 970
100% Modulus, MPa 3.5 5.3 4.5
200% Modulus, MPa 5.3 7.1 6.2
300% Modulus, MPa 7.4 9.9 7.6
400% Modulus, MPa 9.9 14.7 8.9
Compression Set, % (22 h @ 70 °C) 22 15 19
5% 0.5 0.8 1.0
10% 1.0 1.7 1.8
15% 1.6 2.6 2.5
25% 2.8 4.6 4.0
460
The benefits from using ultra-low monol PPG polyols in polyurethane or polyurethane/
urea systems can be realised by understanding the fundamental differences between them
and other high-performance polyols such as PTMEG. In particular, when considering
the polyol MWD, PTMEG should be regarded as a high MW polyol blended with a low
MW chain extender (or pseudo chain extender). In contrast, ultra-low monol PPG contain
no low-MW fraction, therefore, to mimic the behavior of PTMEG it is necessary to add
additional low MW glycol into the prepolymer or resin components. Because of this
feature, ultra-low monol PPG have a broader formulating latitude, since chain extender
can be added to tailor the property profile to the specific application.
9.6 Conclusions
Ultra-low monol PPG polyols have excellent properties and ease of processing. The
elimination of monol enables polymers to be produced having much higher final MW,
i.e., improved properties, as well as significantly faster MW buildup during polymer
formation, i.e., shorter demould times and excellent green strength.
Another important feature of these polyols is their narrow MWD. Low polydispersity
results in lower viscosities in both the polyol and isocyanate-terminated prepolymers.
Polyol MWD has a significant effect on the mechanical and dynamic properties of
polyurethane and polyurethane/urea systems. Broad-MWD polyols such as PTMEG or
polyester polyols contain significant amounts of hard-segment diol, which limits their
softness. Acclaim polyols contain no hard-segment diol and thus have inherent superior
properties in soft systems. They can be made to approximate broad-MWD polyols such
as PTMEG by incorporation of a low MW glycol.
Acknowledgements
We would like to thank Steve Bailey, Daphne Hale, Beth Lambert, Tony Loveday and
Mike Robinson, who carefully and conscientiously prepared the samples and carried out
the physical property testing.
References
1. D. M. Simons and J. J. Verbanc, Journal of Polymer Science, 1960, 44, 144, 303.
2. G. Gee, W. C. E. Higginson, K. J. Tailor and H. W. Trenholme, Journal of the

Chemical Society, 1961, 4298.
461
3. W. H. Snyder, K. J. Tailor, N. S. Chu and C. C. Price, Transactions of the New

York Academy of Science, Series II, 1962, 24, 341.
4. R. J. Herold in Macromolecular Syntheses, Volume 5, Ed., E. L. Wittbecker, John

Wiley and Sons, Inc., New York, 1974, 9.
5. H. van der Hulst, G. A. Pogany and J. Kuyper, inventors; Shell Oil Company,
assignee; US Patent 4,477,589, 1984.
6. J. L. Schuchardt and S. D. Harper, Presented at the 32nd Annual Polyurethane

Technical/Marketing Conference, San Francisco, CA, USA, 1989, p.360.
7. R. L. Mascioli, Presented at the 32nd Annual Polyurethane Technical/Marketing

Conference, 1989, San Francisco, CA, USA, p.139.
8. J. W. Reisch and D. M. Capone, Presented at the 33rd Annual Polyurethane

Technical/Marketing Conference, Orlando, FL, USA, 1990.
9. J. Milgram, inventor; General Tire Corporation, assignee; US Patent 3,278,457,

1966.
10. R. J. Belner, inventor; General Tire Corporation, assignee, US Patent 3,278,458,

1966.
11. R. J. Herold, inventor; General Tire Corporation, assignee, US Patent 3,278,459,

1966.
12. R. J. Herold and R. A. Livigini, Polymerization Kinetics and Technology, Ed., N.

A. J. Platzer, Advances in Chemistry Series No.128, American Chemical Society,
Washington, DC, 1973, 208.
13. C. P. Smith, J. W. Reisch and J. M. O’Connor, Presented at the Polyurethane

World Congress, 1991, Nice, France, p.313.
14. N. Barksby, G. L. Allen, Presented at the Polyurethane World Congress, 1993,

Vancouver, BC, Canada, p.445.
15. N. Barksby, S. D. Seneker and G. L. Allen, Presented at the Polyurethane

Manufacturing Association Conference, Pittsburgh, PA, November 1995.
16. S. D. Seneker and N. Barksby, Presented at the Utech 96 Conference, The Hague,
The Netherlands, March 1996, Paper No.46.
17. N. Barksby, S. D. Seneker and G. L. Allen, Urethanes Technology, 1996, 13, 1, 36.
462
18. R. J. Tuinman, T. L. Fishback and C. J. Reichel, Presented at the Polyurethanes

Expo ’98 Conference, Dallas, TX, 1998, p.535.
19. S. D. Seneker, N. Barksby and B. D. Lawrey, Presented at the Polyurethanes Expo

’96 Conference, Las Vegas, NV, 1996, p.305.
20. S. D. Seneker, C. C. Shen and N. Barksby, Presented at the Polyurethanes World

Congress ‘97, Amsterdam, The Netherlands, 1997, p.568.
21. S. D. Seneker, C. C. Shen and N. Barksby, Presented at the Polyurethane

Manufacturing Association Conference, San Diego, CA, March 1998.
22. R. J. Tuinman, R. L. Fishback and C. J. Reichel, Presented at the Polyurethanes

World Congress ‘97, Amsterdam, The Netherlands, 1997, p.560.
23. T. L. Fishback and C. J. Reichel, Presented at the Polyurethanes Expo ‘96

International Conference, Las Vegas, NV, 1996, p.282.
24. A. T. Chen, R. R. Wells, C. P. Smith, J. W. Reisch, M. M. Emmet and J. M.

O’Connor, Presented at the Polyurethanes World Congress 1993, Vancouver, BC,
Canada, 1993, p.388.
25. C. P. Smith, J. W. Reisch and J. M. O’Connor, Journal of Elastomers and Plastics,

1992, 24, 4, 306.
26. ASTM D4060-95, Standard Test Method for Abrasion Resistance of Organic
Coatings by the Taber Abraser.
27. S. D. Seneker, N. Barksby and B. D. Lawrey, Presented at the Polyurethanes Expo

’98 Conference, Dallas, TX, 1998, p.195.
28. S. D. Seneker, N. Barksby and G. B. Ellerbe, Presented at the Utech Asia ‘97
Conference, Suntec City, Singapore, 1997, Paper No.41.
463
464
APPENDIX
Laboratory Preparation of 2,4-TDI and 4,4´-MDI Prepolymers
Isocyanate prepolymers were prepared in glass reaction vessels in a laboratory fume

hood. The reaction vessel was equipped with a stirrer, temperature controller and nitrogen
inlet. The reaction was carried out under a dry-nitrogen atmosphere to minimise exposure
to atmospheric moisture and polyol oxidation.
Isocyanate is added first to the reaction vessel and heated to approximately 50 to 60 °C.
Polyol is then added to the isocyanate, carefully controlling the addition rate to ensure
the reaction temperature does not exceed 85 °C. Higher temperatures can cause harmful
side reactions that can affect prepolymer performance. After reacting at 80 °C for
approximately 4 hours, the extent of reaction was determined by measuring the percent
isocyanate content (% NCO) of the prepolymer. Heating was continued until the
prepolymer was slightly below the theoretical % NCO value.
Laboratory Casting of 4,4´-MDI Prepolymers Cured with BDO
MDI/BDO cast-elastomer systems were made by mixing and reacting two components,
the MDI-terminated prepolymers (described previously) and BDO. The elastomers in
this chapter were prepared using the hand-mixing procedure. The MDI prepolymer was
preheated to ~65 °C and degassed under vacuum (130 to 665 Pa) until foaming stopped.
Catalyst (25-50 ppm dibutyltin dilaurate) was added to the prepolymer and mixed
thoroughly to give the desired pot life of 1 to 3 minutes.
The BDO was added (isocyanate to hydroxyl ratio (NCO:OH) of 1.03) and mixed thoroughly
using a Jiffy mixer until the blend was homogeneous. This solution was immediately poured
into preheated moulds at 100 °C treated with mould release. After demoulding, the samples
were post-cured at 100 °C for 16 hours. The polymer samples were conditioned at 23 °C and
50% relative humidity for at least four weeks prior to testing.
Laboratory Casting of One-Shot Elastomers Based on Carbodiimide-

Modified MDI, Polyol, and BDO
One-shot elastomers were prepared by mixing and reacting three components:

carbodiimide-modified MDI (CD-MDI), high primary-hydroxyl-content polyol and BDO.
The polyol was preheated to 60 °C and degassed under vacuum (130 to 665 Pa). The
465
CD-MDI, polyol and BDO were charged to a 250 ml glass jar. Dibutyltin dilaurate catalyst
(25-50 ppm) was added to adjust the pot life to approximately 90 seconds. These
components were mixed thoroughly and poured into preheated moulds at 100 °C, treated
with mould release. After demoulding, the samples were post-cured at 100 °C for 16
hours. The polymer samples were conditioned at 23 °C and 50% relative humidity for at
least four weeks prior to testing.
Laboratory Casting of 2,4-TDI Prepolymers Cured with MBOCA
The TDI/MBOCA cured elastomers were prepared by mixing and reacting two
components: 2,4-TDI prepolymers (described previously) and MBOCA. The elastomers
in this chapter were prepared using the hand-mixing procedure. The 2,4-TDI prepolymer
was preheated to 90 °C and degassed under vacuum (130 to 665 Pa) until foaming
stopped. The MBOCA was melted at 120 °C. The 2,4-TDI prepolymer and MBOCA
were stirred thoroughly using a Jiffy mixer at an NCO:NH ratio of 1.05 without catalyst.
The solution was immediately poured into preheated moulds at 100 °C treated with
mould release. After demoulding, the samples were post-cured at 100 °C for 16 hours.
The polymer samples were conditioned at 23 °C and 50% relative humidity for at least
four weeks prior to testing.
Laboratory Moisture-Curing of 2,4-TDI Prepolymers
The 2,4-TDI prepolymers were cast as films on glass plates using a 0.762 mm draw-
down bar (a draw-down bar is a metal bar with a gap, which is pulled down a glass plate
leaving a thin film of prepolymer. The prepolymer is then moisture-cured to form the
polymer film). The films were cured/conditioned at 23 °C and 50% relative humidity for
at least four weeks prior to testing.
Laboratory Preparation of Aqueous Polyurethane/Urea Dispersions

using the Prepolymer Mixing Process
Isocyanate prepolymers were prepared in glass reaction vessels in a laboratory fume

hood. The reaction vessel was equipped with a stirrer, temperature controller, and nitrogen
inlet. The reaction was carried out under a dry-nitrogen atmosphere to minimise exposure
to atmospheric moisture and polyol oxidation. The stepwise procedure is:
Charge polyol, DMPA, (stabiliser), NMP, (coalescing aid) in a reaction vessel equipped
with a thermocouple (thermometer) and agitator. Care should be taken to keep
466
moisture away from the reaction mixture by using a drying tube or a positive pressure
of dry nitrogen.
Heat the mixture to 95 °C and apply vacuum to remove any residual water (DMPA and
polyol stored in the laboratory may contain high water levels).
Cool the mixture to 50-60 °C, then weigh in isocyanate (IPDI, etc.)
Heat the mixture to 80 to 100 °C for aliphatic diisocyanates or 60 to 80 °C for aromatic

diisocyanates. If necessary, a small amount of a tin catalyst, (e.g., 25 to 100 ppm of
stannous octoate) can be added.
React this mixture until the % NCO content is 0.2-0.5 units lower than the theoretical
% NCO. Reaction time is usually 6 to 12 hours depending on the % NCO of the
prepolymer.
Cool the mixture to 50-60 °C, and then add neutraliser, i.e., triethylamine, to the
prepolymer. Mixing is critical during this step. The neutralisation forms the water-
dispersible carboxylate ammonium salt.
Heat the prepolymer amine salt to 60 to 80 °C and slowly pour into a resin kettle charged
with a known amount deionised water at 25 to 50 °C with strong agitation. Add the
prepolymer to give the desired solids content.
Immediately add the chain extender (ethylene diamine), which has been diluted in water
slowly to the aqueous polyurethane/urea dispersion. Typically chain extend only 80-
90% of the actual free NCO groups because some will be lost due to reaction with water.
As an alternative, the amine extender may be added to the water prior to dispersing the
neutralised prepolymer.
Cook out the residual excess isocyanate by heating the aqueous dispersion at 60-80 °C
for two hours. Excess unreacted isocyanate in an aqueous polyurethae/urea dispersion
will lead to carbon dioxide gas and pressure buildup in the container.
467
468
Abbreviations and Acronyms
ABA Alternative blowing agents

ABS Acrylonitrile butadiene styrene
AN Acceptor number
APCI Air Products and Chemicals, Inc.
APS Aminopropyl triethoxy silane
ASD Acrylic-styrene dispersion
ASTM American Society for Testing and Materials
AVG Average
BA Butyl acrylate
BD 1,4-butadiene
BDO 1,4-butanediol
CD-MDI Carbodiimide-modified MDI
CFC Chloroflurorocarbons
CHL Chloroform
CHP Cumene hydroperoxide
COM Commercial
CP Cyclopentane
CS Chloropropyl triethoxy silane
DAPS Data acquisition and plotting system
DC Dabco
DEE Diethyl ether
DEG Diethylene glycol
DEOA Diethanolamine
DEOA-LF Diethanolamine liquid form
DMA Dynamic mechanical analysis
DMC Double metal cyanide
DMPA Dimethyl propionic acid
DMSO Dimethyl sulphoxide
DMTA Dynamic mechanical analysis
DN Donor number
DPG Dipropylene glycol
DPUR Polyurethane dispersions
469
DSC Differential scanning calorimetry

ECR Energy consumption reduction
EO Ethylene oxide
ES Epoxybutyl trimethoxy silane
FEA Finite element analysis
FR Fire retardant
FTC Force-to crush
FT-IR Fourier transform infra-red spectroscopy
GC Gas chromatography
GPC Gel permeation chromatography
GWP Global warming potential
HACS Humid aged compression sets
HCFC Hydrochloroflurocarbon
HDPE High density PE
HER Bis-(beta-hydroxyethyl) ether of resorcinol
HER-TG HER Technical grade
HFC Hydrofluorocarbons
HP High purity
HQEE Hydroquinone (di-beta-hydroxyethyl) ether
id Internal diameter
IFD Indentation force deflection
IGC Inverse gas chromatography
ILD Indentation load deflection
IPDI Isophorone diisocyanate
IPN Interpenetrating polymer network
IR Infrared
KOH Potassium hydroxide
LD-SRIM Low density structural RIM
LFI-PU Long fibre injection PU
MBOCA Methylene bis- (2-chloroaniline)
MDI Methylene diphenyl isocyanate
MDPE Medium density PE
MDPUR Modified polyurethane
MEK Methyl ether ketone
MFFT Minimum film formation temperature
MHW Modified hot wire
MM Methyl methacrylate
Mn Number average molecular weight
470
Abbreviations and Acronyms
MOCA Methylene bis – (2-chloroaniline)

mp Melting point
MS Mass spectrometer
MS Mercaptobutyl trimethoxy silane
MW Molecular weight
MWD Molecular weight distribution
NCO Isocyanate
ND Not detected
nd Not determined
NEG Non-evaporable getter
NM Not measured
NMP N-methyl pyrrolidone
NMR Nuclear magnetic resonance
OCF Owens Corning fibre glass
ODP Ozone depletion potential
OEM Original equipment manufacturer
OH# Hydroxyl number
OTR Oxygen permeation rate
PAN Polyacrylonitrile
Pbw Parts by weight
PDMS Polydimethylsiloxane
PE Polyethylene
PEG Polyethylene glycol
PET Polyethylene terephthalate
PG Propylene glycol
PLC Programme logic controller
PO Propylene oxide
PPG Polyoxypropylene glycol
PPH Parts per hundred
pphp Parts per hundred polyol
ppm Parts per million
PPUR Polyurethane prepolymer
PS Polystyrene
PTMEG Polytetramethylene ether glycol
PTMG Polytetramethylene glycol
PU, PUR Polyurethane
PVC Polyvinyl chloride
PVDC Polyvinylidene chloride
471
QA Quality assurance
QC Quality control
R&D Research and Development
RGA Residual gas analysis
RH Relative humidity
RIM Reaction Injection Moulding
RRIM Reinforced reaction injection moulding
RT Room temperature
RUF Recycled urethane fluff
S Styrene
SAE Society of Automotive Engineers
SD Standard deviation
SEM Scanning electron microscope
SLM Standard litres per minute
SRG Spinning rotor guage
SRIM Structural RIM
SSF Silica surfactant
STP Standard temperature and pressure
TCP Trimethylsilyl-capped polysilicate
TDI Toluene diisocyanate
TEDA Triethylene diamine
TEM Transmission electron microscopy
Tg Glass transition temperature
TG Technical grade
THF Tetrahydrofuran
TOC Top-of-the-cup
TP Thermoplastic
TPG Tri propylene glycol
TPR Time pressure release
TPU Thermoplastic PU
VIP Vacuum insulated plate
VOC Volatile organic compounds
VPF Variable pressure foaming
VS Vinyl trimethyl silane
WTR Water permeation rate
472
Contributors
Gary D. Andrew Daniel Klempner

Air Products and Chemicals, Inc. Polymer Institute
7201 Hamilton Blvd. University of Detroit Mercy
Allentown, PA 18195 4001 W. McNichols Road
USA Detroit
MI 48219-0900
Nigel Barksby USA
Bayer Corporation
South Charleston Technical Center Jane G. Kniss
3200 Kanawha Turnpike Air Products and Chemicals, Inc.
Building 727 7201 Hamilton Blvd.
South Charleston Allentown, PA 18195
WV 25303 USA
USA
Anita Koncka-Foland
Richard J. Braun Industrial Chemistry Research Institute
Department of Mathematical Science 8, Rydygiera Street
University of Delaware 01-315 Warsaw
Newark Poland
DE 19716
USA Janusz Kozakiewicz
Industrial Chemistry Research Institute
Georg Burkhart 8, Rydygiera Street
Goldschmidt AG 01-315 Warsaw
Goldschmidtstrasse 100 Poland
D-45127 Essen
Germany Bruce D. Lawrey
Bayer Corporation
Raj B. Durairaj South Charleston Technical Center
Director of Research 3200 Kanawha Turnpike
Indspec Chemical Corporation Building 727
Pittsburgh South Charleston
PA 15238 WV 25303
USA USA
473
Izabella Legocka Dow Corning Corporation

Industrial Chemistry Research Institute Midland
8, Rydygiera Street MI 48686-0994
01-315 Warsaw USA
Poland
Arturo Plana
Mark L. Listemann Air Products and Chemicals, Inc.
Air Products and Chemicals, Inc. 7201 Hamilton Blvd.
7201 Hamilton Blvd. Allentown
Allentown, PA 18195 PA 18195
USA USA
Paolo Manini H.P. Schreiber

SAES Getters SpA Chemical Engineering Department
Viale Italia 77 Ecole Polytechnique
20020 Lainate (MI) P.O. Box 6079
Italy Stn. Centre-Ville
Montreal
Lisa A. Mercando Quebec
Air Products and Chemicals, Inc. Canada
7201 Hamilton Blvd. H3C 3A7
Allentown, PA 18195
USA Stephen D. Seneker
Anderson Development Company
Shailesh Naire 1415 E Michigan street
Department of Mathematical Science Adrian
University of Delaware MI 49221
Newark USA
DE 19716
USA Ashok Sengupta
Corporate Research & Development
Benjamin M. Nugent 3M Canada Company
Central Research and Development London
Mail # CO43C1 Ontario
Dow Corning Corporation Canada
Midland N6A 4T1
MI 48686-0994
USA Jan Skarzynski
Industrial Chemistry Research Institute
Udo C. Pernisz 8, Rydygiera Street
Central Research and Development 01-315 Warsaw
Mail # CO43C1 Poland
474
Contributors
Steven A. Snow James D. Tobias

Central Research and Development Air Products and Chemicals, Inc.
Mail # CO43C1 7201 Hamilton Blvd.
Dow Corning Corporation Allentown, PA 18195
Midland USA
MI 48686-0994
USA Andreas Weier
Degussa AG
Robert E. Stevens Karl-Arnold Plazt 1a
Air Products and Chemicals, Inc. D-40474 Dusseldorf
7201 Hamilton Blvd. Germany
Allentown
PA 18195-1501 Stephan Wendel
USA Air Products and Chemicals, Inc.
Robert Koch Strasse 27
Max Taverna 22851 Norderstedt
Cannon Group Germany
Via C Colombo 49
20090 Trezzano s/Naviglio
Milano
Italy
475
476
Author Index
Adam, S.J. 210 Born, L. 419

Akabori, K. 215, 257 Boudreau, R.J. 111, 256
Akita, J. 211 Bovenkerk, H.P. 208
Akkurt, A.S. 211 Brandrup, J. 210
Allen, G.L. 462 Braun, J.M. 366
Allen, K.W. 332 Braun, R.J. 259, 260
Alonzo, V. 334 Breck, D.W. 210
Andrew, G.D. 82 Brenner, H. 259
Arkles, B. 91, 110 Brochhagen, F.K. 109
Armistead, J.P. 111 Brookman, D.J. 367
Artavia, L.D. 215, 257 Bundy, F.P. 208
Ashby, M.F. 82 Burchianti, J. 417
Bachelor, G.K. 259 Burkhart, G. 82, 102, 109, 111
Baines, F.L. 258 Cairncross, R.A. 260
Bankoff, G.B. 259 Caloi, R.M. 211
Barksby, N. 462, 463 Capone, D.M. 462
Barosi, A. 210 Carley, J. 210
Battice, D.G. 83 Carson, S. 110
Bayer, O. 85 Cavenaugh, G.C. 110
Bechara, I. 333 Cavender, K.D. 82
Belner, R.J. 462 Chang, Y-S. 366
Benson, D.K. 212 Charles, A. 110
Berger, E.J. 366 Chaya, J.E. 109
Beu, T.A. 209 Chen, A.T. 463
Biesmans, G. 208, 210 Chen, J.H. 339, 366
Biondich, B. 154 Chen, L.W. 418
Blackwell, J. 419 Childs, K.W. 212
Boffito, B. 210 Christfreund, A. 209
Boffito, C. 210, 211 Chu, N.S. 462
Bohman, R.H. 212 Clift, S.M. 418
Bonansea, A. 155 Clunie, J.S. 257
Bonart, R. 419 Coogan, R.G. 332
Bonekamp, J. 176, 210 Cooper, S.L. 418, 419
Borghi, M. 210 Cornelius, G.C. 334
Borgogelli, R. 111 Corradi, P. 154
477
Covington, J. 210 Figini, A. 210

Creswick, M.W. 111 Fine, H.A. 208, 212
Cunningham, A. 209 Fiorentini, C. 110, 154
Czalych, A.E. 319, 334 Fishback, T.L. 463
Dahm, M. 256 Florianczyk, Z. 333
Dai, D.G. 109 Francais, E. 208
David, C.E. 210 Frankel, S.P. 214, 257
Davis, H.T. 110, 111 Franyutti, S. 418
Davis, J.H. 418 Fremerey, J.K. 211
Davis, S.H. 259 Fricke, J. 208
de Almeida, J. 417 Frisch, K.C. 417
De Vos, R. 209, 210, 211 Fujimoto, K. 215, 257
De Vries, A.J. 258 Gabbard, W.A. 210
Decker, T.G. 91, 92, 110, 256 Gasparini, G. 209
della Porta, P. 210 Gee, G. 461
Deng, Z. 337, 366 Gent, A. 336, 366
Deschaght, J. 211 Gentle, T.E. 259
Desor, U. 333 George, R.F. 417
Dieterich, D. 333 Geurts, J.M. 334
Dietrich, K.W. 209 Giannopous, N. 334
Dillard, D.A. 366 Gibson, L.J. 82
Dixon, C. 192, 211 Gibson, P.E. 418
Doni, F. 210 Gilbert, R.G. 333
Douglas, T.L. 418 Giordano, S. 334
Doyle, E.N. 110 Glicksman, L.R. 160, 208, 209
Doyle, J.E. 418 Goddard, E.D. 256
Droste, W. 109 Goldsmith, J. 332
Drye, J.L. 110 Goodman, J.F. 257
Dubjaga, J.E. 256 Goos, H.C. 332
Dubyaga, E.G. 256 Grabbe, M. 332
Durairaj, R.B. 417 Graff, G. 155
Edwards, D.A. 259 Graves, R.S. 208
Eiben, R.G. 110 Gray, D.G. 366
Ellerbe, G.B. 463 Grickova, I.A. 283, 287, 306, 311
Emmet, M.M. 463 Griffith, M. 110
Eschbach, C.S. 258 Griffiths, T. 110
Estes, G.M. 419 Grizwold, A.A. 109
Evans, D.F. 257 Gruber, B. 266, 333
Feinerman, A.E. 256 Guagliardo, M. 332
Fenton, W.N. 257 Güclü, H. 211
Ferrario, B. 209, 210 Guillet, J.E. 366
478
Author Index
Gutmann, V. 337, 349, 357, 359, 366 Kheshgi, H.S. 242, 259
Hamann, H. 256 Kim, D. 417
Hamilton, A.J. 199, 212 Kingston, B.M. 110, 256
Harper, S.D. 462 Kistler, S.F. 259
Hartung, M. 332 Klempner, D. 417
Hashimoto, H. 333 Klincke, M. 82, 111
Haworth, G.J. 212 Kloiber, K.A. 266, 334
Hegedus, C.R. 266, 334 Koberstein, J.T. 418
Heimenz, P.C. 259 Koczo, K. 258
Hepburn, C. 418 Koczone, J.K. 258
Hermsen, A. 334 Kodama, K. 160, 209
Herold, R.J. 462 Kollmeier, H.J. 109, 257
Herrington, R.M. 258 Komarova, A.B. 256
Hesketh, T.R. 418 Kopusov, L.I. 256
Hespe, H. 419 Kossmann, H. 333
Higginson, W.C.E. 461 Kovac, J. 211
Hildebrand, J.H. 111 Kozakiewicz, J. 332, 333, 334
Hilker, B.L. 111 Kryszewski, M. 332
Hill, R.M. 255 Kücükpinar, E. 202, 211
Hilyard, N.C. 209 Kulkarni, R.D. 256
Höchtlen, A. 109 Kuropka, R. 333
Hock, K. 258 Kushner, S.A. 82
Hoogendoorn, P. 208 Kuyper, J. 462
Hoppe, P. 109 Lai, Y-H. 366
Hosoi, K. 333 Lamb, W. 175, 210
Hu, C.B. 419 Langenhagen, R. 111
Huber, L.M. 111 Lassila, K.R. 83
Hudales, J.B.M. 258 Lavielle, L. 367
Hutzinger, O. 109 Lawler, L.F. 111
Huybrechts, J.T. 332 Lawrey, B.D. 463
Immergut, E.H. 210 Lean, B. 333
Ingram, B.T. 257 Lee, K.D. 111
Ishida, H. 367 Legocka, I. 334
Ivanov, I.B. 257, 258 Lerner, L.E. 418
Jensen, O.E. 260 Leung, L.M. 418
Juran, R. 210 Lewandowski, L.H. 366
Kanner, B. 91, 92, 231, 256, 258 Leyden, D.E. 367
Kanner, T.G. 110 Lidy, W. 109, 257
Keane, N.W. 209 Lilaonitkul, A. 418
Kendrick, T.C. 110, 256 Lin, J.R. 418
Khemani, K.C. 111 Lin, J.Y. 209
479
Lindenau, B.E. 211 Miller, C.A. 257

Lipatova, T.E. 256 Minnich, K.E. 83
Listemann, M.L. 82, 83 Monteiro, M.J. 333
Livigini, R.A. 462 Moraja, M. 211
Lloyd, D.R. 366 Morbitzer, L. 419
Lloyd, N.C. 110, 256 Moriarty, J.A. 245, 259
Locatelli, M. 334 Moser, K. 109
Loewrigkeit, P. 333 Muller, E.H. 419
Loos, F. 333 Muresan, L. 209
Lopes, W.I. 83 Muroi, S. 333
Luca, J. 154 Murphy, G.J. 258
Lucas, H.R. 334 Mysels, K.J. 214, 245, 246, 257
Lupinacci, J. 212 Nachtkamp, K. 332, 333
Macosko, C.W. 110, 111, 215, 257 Nagarajan, M.R. 419
Madan, S. 418 Naire, S. 259, 260
Magnano, E. 211 Narducci, E. 211
Maldarelli, C. 230, 258, 259 Navish, F.W. 417
Malone, B. 209 Neff, R.A. 110, 257
Manini, P. 209, 210, 211 Neogi, P. 257
Mansfield, K.F. 82 Nikolov, A.D. 110
Mapleston, P. 154, 155 Nugent, B.M. 258, 260
Mark, H.B. 210 O’Connor, J.M. 462, 463
Markusch, P.H. 333 Oertel, G. 418
Martin, C. 367 Ondrey, S.J. 417
Martin, E. 334 Oron, A. 259
Maruscelli, E. 332 Overbeek, A. 334
Mascioli, R.L. 462 Overbeek, G.C. 332
Masuda, Y. 209 Owen, M.J. 93, 110, 214, 256, 257, 258
Mathis, N.E. 192, 211 Özkadi, F. 211
Mattson, J.S. 210 Palinkas, R. 418
Mayenfels, P. 332 Palmer, M. 418
McCullogh, D.W. 209 Palumbo, R. 332
McElroy, D.L. 208 Pantone, R.S. 418
McVey, S.B. 111 Panzer, U. 366
Mealmaker, W.E. 334 Papirer, E. 337, 366
Mecea, V. 209 Pastore, G. 211
Mendelsohn, M.A. 417 Pcolinsky, M. 109
Mercea, P.V. 209 Penczek, P. 332
Merriman, P. 110 Penczek, S. 333
Mestach, D.E. 333 Pendergast, P. 209
Milgram, J. 462 Pernisz, U.C. 259, 260
480
Author Index
Perrut, M. 208 Ruschak, K.J. 242, 259

Peters, F. 155 Saint Flour, C. 337, 366
Petersen, I.H. 110, 256 Sancrotti, M. 211
Petrella, R.G. 82 Sand, J.R. 212
Piccinini, M. 334 Sanger, G. 256
Pile, B. 154 Savoca, A.C.L. 82
Pionteck, J. 418 Sawyer, D.T. 367
Platzer, N.A.J. 462 Schator, H. 109, 257
Plueddemann, E.P. 366 Schiabel, A. 211
Pogany, G.A. 462 Schlöns, H-H. 109
Pohlers, A. 418 Schneider, N.S. 419
Pompe, G. 418 Schreiber, H.P. 337, 338, 341, 342, 344,
Potschke, P. 418 347, 359, 360, 361, 362, 366, 367
Potter, T.F. 212 Schuchardt, J.L. 462
Prausnitz, J.M. 111 Schultz, J. 336, 366, 367
Price, C.C. 462 Schwartz, L.W. 259, 260
Prokai, B. 258 Schwartz, M. 333
Pugh, R.J. 257 Schwarz, E.G. 256
Qin, R. 360, 361, 362, 365 Sciuccati, F. 209
Quay, J.R. 419 Scott, R.L. 111
Randall, D. 208, 209 Scriven, L.E. 93, 110, 259
Recker, K. 418 Seneker, S.D. 462, 463
Redhead, P.A. 209 Sengupta, A. 338, 341, 342, 344, 347,
Reed, D. 255 359, 360, 361, 362, 365, 367
Reegen, S.L. 417 Seyffert, H. 256
Reichel, C.J. 463 Seymour, R.W. 418, 419
Reid, W.G. 110, 256 Sheinina, L.S. 256
Reisch, J.W. 462, 463 Shen, C.C. 463
Ricciardi, R. 109 Shinoda, K. 214, 257
Rimmer, R.W. 332 Simons, D.M. 461
Ritter, J. 256 Simpson-Gomes, A. 333
Rizzi, E. 210 Sironi, E. 334
Roester, R.R. 332 Slattery, J.C. 259
Rosai, L. 210 Smak, Y.W. 334
Rosbotham, I.D. 209, 210, 211 Smith, C.P. 462, 463
Rossmy, G. 94, 109, 256, 257 Smith, L.K. 212
Rosthauser, J.W. 332, 333 Smith, S. 211
Roth, A. 209 Smock, D. 154, 155
Roy, R.V. 260 Smudin, D.J. 109
Ruckenstein, E. 339, 366 Snow, S.A. 251, 255, 257, 258, 259, 260
Rumschitzki, D. 259 Snyder, W.H. 462
481
Solomou, N. 208 van Bogart, J.W.C. 418

Soyal, A. 211 van der Hulst, H. 462
Srikanth, R. 212 Van Dyk, K.A. 333
Stannett, V. 366 Vartan-Boghossian, R. 332
Stark, J. 155 Veltkamp, B. 208
Stebe, K.J. 230, 258 Vengerovskaya, S.H.G. 256
Stein, H.N. 225, 258 Verbanc, J.J. 461
Sternling, C.V. 93, 110 Vineyard, E.A. 212
Stevens, R.E. 255, 260 Vratsanos, M.S. 82
Stone, H. 109 Wacker, W. 209
Stone, H.A. 259 Wagner, R.D. 109
Stovall, T. 212 Ward Jr., R.S. 419
Strong, H.M. 208 Ward, T.C. 366
Subramaniam, N. 333 Wasan, D.T. 110, 258, 259
Sugiyama, A. 190, 209 Weaver, F.J. 208, 210
Sung, W.F. 209 Weidner, D.E. 260
Tabor, R.L. 208 Weier, A. 111
Tada, H. 209 Wells, R.R. 463
Tailor, K.J. 461, 462 Wennertröm, H. 257
Tanimoto, Y. 209 White, L. 154
Tao, W.H. 209 Wiemann, M. 109, 257
Tarakanov, O.G. 256 Wilhelm, M.R. 418
Taverna, M. 110, 154, 155 Wilkes, G.L. 111
Taylor, J.R. 333 Wilkes, K.E. 210, 212
Tennebroek, R. 334 Wittbecker, E.L. 462
Thomas, G. 110 Wong, H. 259
Tiedemann, J.E. 417 Wressell, A.L. 82
Tirpak, R.E. 333 Yarbrough, D.W. 208
Tobias, J.D. 82 Yasunaga, K. 110, 257
Trenholme, H.W. 461 Yoshimoto, M. 209
Tuck, E.O. 259 Yuge, K. 209
Tuinman, R.J. 463 Zeiler, R. 175, 210
Turner, R.B. 111, 258 Zellmer, V. 109, 111
Urso, C. 211 Zhang, X.D. 93, 110, 111, 257
Valdrè, S. 211 Zharkov, V.V. 256
482
Main Index
Main Index
A Analysis 174, 189, 195, 336, 373, 395,

403, 405, 410, 412
Acclaim elastomers 446 Differential scanning calorimetric
Acclaim polyol 423, 429, 435, 438, 445, 373, 381, 383, 393-395, 405, 406,
Acclaim polyols 410
Acetone process 265 Dynamic mechanical 373, 383, 395,
Acid copolymers 178 396, 405, 407, 412
Acid/base interactions 347 Finite element 174, 196
Acrylic dispersions 261 Fourier transform-infra red 373, 403
Acrylic polymer 262 Gel permeation chromatography 450
Activated charcoal 181 Head space 14, 62
Additives 3, 15, 16, 42, 63, 64, 67, 73 Inverse gas chromatography 345,
Dimensional stability 3, 16, 64 347-349, 354, 357-358, 365
Flexible slabstock low emission 73 Residual gas 189, 195
For TDI 16 Surface 336, 338
Low emission dimensional stability 42 Anisotropy 160
in MDI 64, 67 Cellular 160
MDI flexible moulded foam 63 Appliance 198
TDI flexible moulded 15 Household 198
Adhesion 218, 325, 337, 344, 353 Applications 135, 187
Acid/base interaction 353 Industrial 135
Bond properties 352 Shipping containers 187
Determination 277 Arcol 7
Performance 344 ASTM 15
Polyurethane 355 D3574, Indentation force deflection
Strength 344 test 15
Tests 350 Test methods 4
Adhesion promoter 355, 364
Silane 355
Adhesive Ageing 362 B
Air flow values 12
Alloy 182 Bag 158
Barium-lithium 182 Gas barrier 158
Aluminium 168 Barrier 168, 174, 198, 206
Sputtered 168 Aluminium foil-based 198
483
Gas 168 Preparation 372

Metallised 174, 206 Properties 398, 402
Multilayered plastic 206 Soft segment content 401
Film 167 Cast poly(ester urethanes) 390
Vacuum properties 167 Cast poly(ether urethanes) 375
Properties 168 Cast polyurethanes 379, 380, 392, 393,
Bashore rebound 373 397, 401, 404, 413
Beamech CO-2 90 Analysis 403
Blister detachment 350, 352, 353, 354 Hard segments 379
Block foaming 161 Hardness 392, 393
Blowing agents 4, 87, 88, 136, 178 Heat aged 413
Alternative 87 High hardness 401
Carbon dioxide 87, 88 HER/HQEE blends 397
CFC-11 87 Properties 392
Chloroflurorcarbon 187 Soft segments 379
Physical 87 Tensile properties 380
Bond strength 337, 360, 361, 364 Catalyst 16, 43, 52, 75, 81
Boundary 240 Activity 75
Conditions 240, 245 Cell opening 16, 52
Film-air 240 Cell opening blowing 43
Bubble coalescence 214 Non-fugitive 43, 52, 81
Bubble formation. See Nucleation Selectivity 75
Bulk stability 13 Cell opening 4, 93-94, 214, 217
Bulk viscosity 217 Blow off 94
Butyl acrylate 269 Cell structure 101, 107
Cell wall drainage 4
Chain extenders 370
C
Chamber 118
Calcium oxide 182 Mixing 118
CannOxide 129 Chem-Trend 7
Capillary number 241 Chem-Trend PRC-798 9
Carbon dioxide 88, 128, 166 Chemical foam model 75
Liquid 88 Flexible cellular polyurethane 4
Carbon monoxide 166 Chicken buckets 9
CarDio 88, 89, 90, 92 Chromatography 276, 337
Carrier 122 Gel permeation 276
Mould 122, 123 Inverse gas 337, 345. See also IGC
Cast elastomers 372, 377, 382, 391, 398- Closed cells 162
402, 409, 411 Coalescing agent 297-300
Hard segment content 401 NMP 297-300
Heat ageing 409, 411 Coating 277
Mechanical properties 409 Binder 264
484
Main Index
DPUR 284 Deforming surface 236

Drying time 277 Dehydrohalogenation 42
Properties 292-293, 300, 303, 305, Thermally induced 42
320, 322-326 Density 17
Coating Coatings 456 Differential scanning calorimetry 373,
Aqueous polyurethane/urea dispersion 381, 393
456 Diffusion 214, 215, 219, 220, 240
Coefficient 232 Diffusion coefficient 232, 234
Diffusion 232 Dimensional stability 11-12
Surface partition 232 Dispersion 264, 266, 267, 276, 279
Cohesion 218, 220 Acrylic 264, 267
Intermolecular 218 Characterisation 279
Failure 352 Hybrid 267
Collapse 23 Hybrid acrylic-urethane 266
Collapsing wedge model 226 Polyurethane 264
COMBOGETTER 181-187, 202, 203, Properties 323, 324, 325
207 Systems 263
for VIP 182 Hybrid 263
Comfort properties 3 DMA see Analysis
Compression set 373, 380, 390, 401 DMTA 427, 433, 452, 453, 454, 458
Tests 3 DPUR particle 312, 315
Container 206 Swelling of 312, 315
Shipping 206 Drainage rate 218, 219, 220, 229, 236
Contamination 165 DSC see Analysis
System 165 Dynamic creep testing 3
Control 119 Dynamic fatigue 14, 49
Pour pressure 119 Dynamic mechanical analysis see Analysis
Conveyor 126
Oval 126
E
Cooling 87
Lateral 87 EasyFroth 129
Creep 161 Edge effect 174
Crosslinking 278 Effect 226
Degree of 278 Bulk 226
Density 279 Surface 226
Crusher 9 Elastomer processability 424, 438
Black Brothers Roller 9 One-shot 438
Cumene hydroperoxide 269 Elastomers 385, 424, 433
MDI/BDO cured 424
D rebound 433
Thermal stability 385
Dabco 6, 80 Electron microscopy 277
485
Transmission 277 Film rupture 215, 216, 218, 221

Embedded sphere 329 Film stability 235
Emissions 4 Surface free energy 317
Emulsion polymerisation 265 Tangentially-immobile 242
Energy 218 Thin liquid 213
Cohesive 218 Thin liquid polyurethane 219
Efficiency 157 Wedge 236
Envirocure 87 Collapsing 236
Environmental concernS 86 Film drainage 219, 255
Equipment 114 Rate 227-229, 232, 235
Metering 114, 115 Surface variables 228
Vertical liquid 255
Fingering pattern 223, 254
F
FipurTec 139
FEA See Analysis Fire-retardants 96, 97, 98, 108
Filler 158 Flexible moulded foam 14, 46, 63, 73
Aerogels 158 MDI 14, 68, 73
Compressed powder 158 TDI 63
Fibre 158 Flexible slabstock 73-74, 88, 90, 95, 99
Fibre glass 158 Polyether 88
Perlite 158, 189 Polyurethane 229
Precipitated silica 189 FlexiDrum 126
Silica 158 Flux 219, 227, 230
Film 134, 178, 213, 215-217, 219, 221, Foam 74, 76, 78-80, 85, 88, 107, 128, 157-
226, 228, 231, 278, 317 159, 161, 163, 177, 179, 201, 213, 254
Adhesive 134 CFC-free 157
Bulk viscosity 215 Cooling 87
Crosslink density 327 Density 86
Drainage rate 216, 217, 226, 227, Hardness 86
228 Minimum 86
Formation 223 Encapsulating 177
Formulation 221 Evacuated 161
Free surface 239 Flexible slabstock 75
Mechanical properties 278 Formation 86
Mobile surface 217 Hardness 87
Models 239 Soft 87
Deforming 239 MDI flexible 79
Outgassing 178 Moulded 76
Properties 291, 293, 299, 302, 304, Mechanical properties 161
308-309, 311, 320-321, 323-325 Multi-density 128
Releasing 134 Multi-hardness 128
Rigid surface 216, 228, 231 Open cell 163, 179, 201
486
Main Index
Open cell PU 158, 163 Device 179

Physical properties 163 Material 181
Polyether 88 Non-evaporable 170
Polystyrene 159 SpiroTorr 193, 194, 201
Polyurethane 85, 96, 213 Technology 206
Porosity 161 Gibbs-Marangoni 93
Rise 93 Global warming 157
Stabilisation 93 Goniometer 336
Slabstock 80 Rame-Hart 336
TDI flexible 79 GPC See Analysis
Moulded 76 Gradient 230
Slabstock 74, 78 Gravitational energy 214
Foam & film 133 Gravity convection 225
Foam One 87 Greenhouse effect 157
Foaming 87, 90, 128 Guarded hot-plate 191
Carousel 128
In situ 128
H
Liquid carbon dioxide 90
Variable pressure 87 Handmix procedure 8
Fogging 14, 62 Mass-loss 18
Force to crush 3, 23, 66, 71, 72 Flexible moulded foam 8
Formulations 72 Flexible slabstock foam 8
MDI 72 Hard segment 378
Fracture energy 390 Content 376, 378
Freezer 177, 204 Hardness 86-87, 378, 401, 408
Ultra-low temperature 204 Determination 277
Froth 101, 213 Heat flow meter 191
Density 101 Heat reflectance 192
Gelatinous 213 Modified hot wire 192
FTC see Force to crush HER materials 369, 370, 371, 373
Full rise time 15 Characterisation 373
Polyurethane applications 369, 371
Synthesis 373
G
HER/HQEE blends 397, 398
Gas permeation 168, 176, 177 Freezing point determination 397
Flanges 176, 177 High vacuum benches 163
Gas transmission 168 Hot box 191
Gate Bar 88 Guarded-calibrated 191
Gauge 192 Hybrid 301, 306
Spinning rotor 192 Chemical structure 306, 325
Gel time 15 Crosslinking 306, 326
Getter 158, 170, 181, 183, 185, 193 Polyurethane-urea 301
487
Hybrid acrylic-urethane dispersions 261 K

Hybrid dispersion 269, 320
Chemical structure 324 Krauss-Maffei 14
Coalescent 323 Kyoto conference 157
Crosslinking 312, 317
Film 328 L
Initiator 320
Laboratory moisture-curing 466
Particle size 320, 321
2,4-TDI prepolymers 466
Properties 290, 291, 292, 298, 302,
303, 307, 311, 320, 330 Lamella 214, 215
Surface free energy 319 Laminate 201
Synthesis 269, 290, 320, 322 Aluminium foil 201
Hybrid dispersion particles Lamination 161, 162
Morphology 317, 328 Lap-shear 337, 344, 347, 352, 353, 354,
362
Hybrid dispersion system 262
Liquid carbon dioxide blowing 85
Preparation 262
Long fibre injection 139
Hybrid polymer dispersion 262
Long-term vibration 3
Hydrogen 166
Loss compliance 388, 414, 415, 416
Loss modulus 385, 386, 414
I Lubrication theory 240, 242, 245, 249
IGC See Analysis
INSOTEC 135 M
Instabilities 215, 218, 235
Machine 9
Fluid 215
Benard 215 Hi Tech SureShot MHR-50 9
Marangoni 215, 235 Machine evaluation 9, 25, 29, 33
Rayleigh-Taylor 215 Back formulation utilising TPR 29
Marangoni 218 Back formulation without TPR 33
Insulation 196 Cushion formulation utilising TPR 25
Interference fringe 222, 223, 224, 225, Cushion formulation without TPR 33
226, 231, 236 TDI flexible moulded foam 9
Interferometer 221 Marangoni
Interpenetrating polymer network 262 Effect 249, 250, 251, 252, 254
InterWet 138, 143, 144, 145, 146, 147, Flows 215, 225
150, 153 Marginal regeneration 225
Advantages 150 Mass spectrometer 163, 164, 189
Applications 152 Quadrupole 163
Improvements 148 Mass-loss/rate-of-rise 4
Ionomers 178 Maze flow mould 10, 56
Isopach 226 MDI Prepolymers 459-460, 465
Isophorone diisocyanate 268 Cured with BDO 459, 460
488
Main Index
Laboratory casting 465 Polyurethane 130

Laboratory preparation 465 Multi-component operation 117
Mechanical crushing 3
Mechanical properties 372 N
Melting points 374
Metal foil 168 N-methylpyrrolidone 269
Methyl methacrylate 269 Navier-Stokes equation 220, 238, 239
Micelles 273 NEG alloy 181
Micro-leaks 191 Zirconium-based 181
Microscopy 4, 40 Newtonian fluid 239
Scanning electron 4, 40 Nitrogen 166
Mill NovaFlex 90
Premier Mill Corporation dispersator Nucleation 91, 101, 105, 215
8 Nylon 168
Mixing head 116, 120, 142
Variable geometry 120 O
Molecular sieves 181
Mondur TD-80 8 OEM
Monolayer 218, 226 Specifications 3
Monomer 272, 275 One-shot elastomer 436-437, 439-443,
as active diluents 275 465
Polymerisation 272 Hardness buildup 437
Montreal Protocol 157 Laboratory casting 465
Morphology 262, 264, 267, 272 Processability 436
Dispersion particle 262, 272 Properties 438
Engulfed 264 Open cell 158, 159
Fruit-cake 264 PU 159
Gradient 264 PU foam 158
Particle 267 Ostwald ripening 214
Mould 56, 60, 124 Outgassing 163, 165, 202
Carrier 129 Load 166
Carrier exchange 125 Oxyethylene moieties 434
Carrying system 126 Oxygen transmission 176
FlexiDrum 126
Maze flow 56, 57, 58, 59, 60 P
Temperature control system 124
Moulded foam 3, 68 Pail test 13, 56
Low emission 68 Panel 158, 177, 207
Moulded formulation 69, 70 Encapsulated 177
MDI 69, 70, 71 Lifetime of 158
Moulding 127, 130 Open cell foam 207
Flexible foam 127 Partial pressure 164
489
Particle 327 Polytetramethylene glycol 268

Morphology 330 Polyurea 215
Swelling 327 Polyurethanes 85, 92, 113, 138, 139,
Particle formation 326 157, 262, 335, 347, 405, 449
Particle size 277, 313, 314
Distribution 277, 313
PDMS 218 Adhesion 347
Péclet number 241, 251 Adhesive 335, 360
Permeation 170, 171, 172 Formulations 335
Helium 170, 171, 172 IR spectra 341
Physical properties 3, 23, 33, 35, 37-39, Silane 356
47, 66, 68-70, 74, 372 Silane additives 360
Flexible slabstock foam 75 Co-injection 138
Foam 23 Cure 338
MDI 69, 70 Dynamic properties 449
Machine data 33 Filled 196
Review 39 Open cell 196
TPR 35, 37 Film 216, 236
Plateau borders 93, 214, 225, 226 Draining thin liquid 236
Gibb’s 93 Rate of drainage 216
Polarity 5 Vertical 236
Polyacrylonitrile 178 Foam 166, 200
Polycat 6 Closed cell 200
Polyester 168, 178 Open cell 166
Polyether chains 218 Insulation 157
Polyethylene 176 Glass-reinforced 139
Polyethylene terephthalate 168 High thermal stability 405
Polyisocyanate 85 History 85
Polymer dispersions 261 Markets 92, 113
Polymerisation 270 Mechanical properties 449
Radical 270 Multi-component formulations 113
Polyol 75, 77, 78, 449 Two-component 335
EO-tipped propylene oxide 77 Polyurethane castings 376
Ethylene oxide tipped 75 Polyurethane catalysts 42
Molecular weight distribution 449 Blowing 42
Polyolefin tipped 78 Non-fugitive gelling 42
Polyol functionality 428 Polyurethane elastomer 430, 431
Polyoxyethylene 215 Polyurethane Foams 3, 5, 93
Polyoxypropylene glycol 421 Catalysts 5
Ultra-low monol 421 Flexible 3, 93
Polysilicate 217 Non-fugitive catalysts 5
Trimethylsilyl-capped 217 Tertiary amine catalysts 5
490
Main Index
Polyurethane-urea 324 Rate-of-rise 18

Double bonds 324 Raw materials 92
Polyurethane-urea-acrylic dispersions Emulsification 92
261 Reactive amine catalysts 5
Polyurethane/urea dispersions 466 Reactivity 18, 23, 45, 65, 74
Formulations 457 Handmix rate of rise 65
Laboratory preparation 466 Machine free rise 23
Polyvinylidene chloride 178 Rebound properties 380, 390, 401
Pot life 372, 375 Recycling 162
Determination 375, 390 Refrigerators 162
PPG polyols 424, 429, 436 Reeves Brothers 87
One-shot elastomer system 436 Refrigerator 177, 203
Processability 429 Biomedical 203
Processing latitude 434 Laboratory 203
Property latitude 429 Reinforcement 141
Ultra-low monol 424, 444 Handling 141
PPG/PTMEG blends 447 Reynold’s
Elastomer properties 447 Equation 220, 227
Prepolymer-ionomer 265, 275, 276 Model 216
Processing 113, 167, 179 Number 241
Desorption 166 Rigid foam 158
Exhaust 179 Open cell 158
Latitude 3 Robots 121, 145
Polyurethane 113 Cartesian 122
Seal-off 179 Foaming 121
Thermally activated 167 Robotics 145
Yield 187
Propionic acid, dimethylol 269
S
PU see Polyurethane
PVC 136 Scalloping 23, 25
Seating 17
Q Automotive 113, 122, 130
Back formulation 19-22, 30-34, 36,
Quality assurance 191 38, 40, 44-46, 48, 60, 113
Quality control 172, 191 Cushion formulation 19-22, 26-29,
34-35, 37, 39, 43-44, 46, 49, 57, 59
Polyurethane 17
R
PU back formulation 18
Rapid Cure 87 PU cushion formulation 17
Rate 169 Service station 125
Helium transmission 169 Shear modulus 386
Water transmission 169 Shore hardness 372
491
Shrinkage 12, 61 Molecular structure 232

Foam 61 Non-ionic fluorocarbon 229
Template 12 Silicone 91, 92, 100, 213
Silanes 356 Synthesis 288
Additive 364 MDPUR 288
Silica 98 MDPUR-ASD 288
Silicone surfactant 4, 95, 99, 213, 215-
217, 219-220, 228-229, 254
T
Burning 95
Characterisation data 233 Tan delta 387, 414
Chemistry 99, 103 TDI 80, 465
Dabco 4 Laboratory preparation 465
Stabilisation 93 MBOCA 450, 453
Soft segment content 376 Mechanical properties 454
Solvated volume 232, 234 Moisture-cured 454
Sound deadening 130 Prepolymers 450, 453, 454, 466
Sponge 214 Laboratory casting 466
Stoke’s law 219 Tear 380, 390, 401
Storage modulus 384, 385, 412 Resistance 373
Stress conditions 239, 246 Strength 410
Normal 239, 246 Technology 130
Tangential 239, 246 Foam & film 130-132, 134-138
Stress/strain curves 426, 440, 447, 458 Tegostab 102
Structure 174 Tensile 401, 408
Laminate 174 Tensile
Styrene 269 Measurements 410
Polymer dispersions 261 Modulus 372
Surface characteristics 335 Properties 378, 390, 392
Surface energy 213, 214 Thermal conductivity 159, 174, 175, 180
Surface free energy 278, 317 Thermoregulation 124
Surface partition coefficient 219, 220 Time pressure release test 13
Surface tension 91, 230, 276 Toluene diisocyanate 85
Gradient 218-220, 225-226, TPR 23
229, 232, 234-235, 250, 252-253 TPR times 33
Surface viscosity 217 Transmission rate 169
Surfactants 64, 91-92, 101, 108, 213, Helium 173
229, 232 Water 169, 173
Activity 92 Transport 126
Concentration 229 Systems 126
Development 101 Treatment 165
Emulsification 92 Heat 165
Flexible moulded 64
492
Main Index
U Flange 168
Viscosity 217-218, 220, 227-228, 245,
Urethane elastomers 413 276
Heat aged 413 Bulk 220
Urethanes 335 Bulk dynamic 227
Adhesion behaviour 335 Finite surface 245
Surface 217-218, 220, 225, 227-232,
V 235-237, 242, 255
Surface dilatational 240
Vacuum panel 158, 161, 188, 191 Surface shear 240
Characterisation 188 Volatile organic compounds 4
Insulating performance 191 Voranol 7, 80
Manufacturing process 188
Vacuum panel technology 158
Van der Waals bonding 218 W
Vending machines 177, 204 Water resistance 277
Vibrathane 375-376, 378, 383 Water transmission 176
Video imaging 106 Window fogging 42
Video microscopy 103, 105
Vinyl staining 42, 62
VIP 190, 193, 197, 202, 203
Z
Longevity 203 Zeolite 181
Performance 202 Zeta potential 314
Reliability 202
493
494
ISBN: 1-85957-275-8

Rapra Technology is the leading independent
international organisation with over 80 years of
experience providing technology, information and
consultancy on all aspects of rubbers and plastics.
The company has extensive processing, analytical

and testing laboratory facilities and expertise,
and produces a range of engineering and
data management software products, and
computerised knowledge-based systems.
Rapra also publishes books, technical journals,

reports, technological and business surveys,
conference proceedings and trade directories.
These publishing activities are supported by
an Information Centre which maintains and
develops the world’s most comprehensive
database of commercial and technical
information on rubbers and plastics.
Shawbury, Shrewsbury, Shropshire SY4 4NR, UK

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net

Advances in Urethane Science and Technology

Încărcat de

Informații document

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Advances in Urethane Science and Technology

Încărcat de

Drepturi de autor:

Formate disponibile

Advances

Rapra Technology Limited

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

Rapra Technology Limited

©2001, Rapra Technology Limited

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

Typeset by Rapra Technology Limited

In memory of Kurt C Frisch

January 15th 1919 to October 21st 2000

1 Dimensional Stabilising Additives for Flexible Polyurethane Foams ................ 3

2 Demands on Surfactants in Polyurethane Foam Production with

3 Polyurethane Processing: Recent Developments ........................................... 113

4 Recent Developments in Open Cell Polyurethane-Filled Vacuum Insulated

Insulated Panels .................................................................................... 158

5 Modelling the Stabilising Behaviour of Silicone Surfactants During the

5.3.3 Quantitative Measurement of Film Drainage Rates:

6 Synthesis and Characterisation of Aqueous Hybrid Polyurethane-Urea-

6.5.4 Additional Experiments ............................................................. 312

7 Adhesion Behaviour of Urethanes ................................................................ 335

8 HER Materials for Polyurethane Applications ............................................. 369

8.4 Cast Poly(Ether Urethanes) ................................................................... 375

8.8.4 Dynamic Mechanical Analysis ................................................... 412

9 Ultra-Low Monol PPG: High-Performance Polyether Polyols

Abbreviations .................................................................................................... 469

Contributors ...................................................................................................... 473

Author Index ..................................................................................................... 477

Main Index ........................................................................................................ 483

This is a landmark issue of ‘Advances in Urethane Science and Technology’. Not

Polyurethanes continue to be one of the most versatile of all polymers, finding

Daniel Klempner, Ph. D.

Polymer Institute,University of Detroit Mercy

Another rapidly increasing environmental concern is over the emission of volatile

1.2 Experimental Procedures

The materials used are shown in Table 1.1.

Table 1 Materials used in experimental work

1.2.2 Handmix Evaluations

1.2.2.1 Flexible Moulded Foam Handmix Procedure

1.2.2.2 Flexible Slabstock Foam Handmix Procedure

1.2.3 Machine Evaluation

1.2.3.1 TDI Flexible Moulded Foam Procedure

1.2.3.2a Maze Flow Mould Test Description

Figure 1.1 Diagram of Maze Flow Mould (Top View)

1.2.3.2b Dimensional Stability Test

Dimensional stability can be measured on a freshly demoulded part by determining the

1.2.3.2c Shrinkage Test

An additional dimensional stability evaluation was done with a shrinkage template

Figure 1.2 Diagram of Shrinkage Template Apparatus

1.2.3.2d Time Pressure Release Test

1.2.3.2e Pail Test

1.2.3.2f Dynamic Fatigue Test

1.2.3.2g Fogging Test

1.2.3.2h Headspace Analysis Test

1.2.3.3 MDI Flexible Moulded Foam Procedure

1.3 TDI - Flexible Moulded Additives

MDI-based systems. Furthermore, changes in polyol technologies designed to improve

1.3.1 Dimensional Stability Additives for TDI

As polyurethane seating design changed from the relatively simple configurations of

Table 1.2 ~45 kg/m3 cushion formulation

Table 1.3 ~35 kg/m3 back formulation

1.3.1.1a Handmix Mass-Loss/Rate-of-Rise

Figure 1.3 Foam Height versus Time - Cushion Formulation

Figure 1.4 Foam Height versus Time - Back Formulation

Temperature profiles for control formulations I and V indicate reaction temperatures

Figure 1.5 Temperature versus Time - Cushion Formulation