Filled Polymers Science and Industrial Applications

1st Edition Jean L. Leblanc pdf download

https://ebookgate.com/product/filled-polymers-science-and-
industrial-applications-1st-edition-jean-l-leblanc/

★★★★★
4.7 out of 5.0 (34 reviews )

Quick PDF Download

ebookgate.com
 Filled Polymers Science and Industrial Applications 1st
Edition Jean L. Leblanc

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 ACADEMIC EDITION – LIMITED RELEASE

Available Instantly Access Library

Instant digital products (PDF, ePub, MOBI) available
Download now and explore formats that suit you...

Industrial Polymers Specialty Polymers and Their

Applications 1st Edition Chanda Manas

https://ebookgate.com/product/industrial-polymers-specialty-polymers-
and-their-applications-1st-edition-chanda-manas/

ebookgate.com

Epoxy Polymers New Materials and Innovations 1st Edition

Jean-Pierre Pascault

https://ebookgate.com/product/epoxy-polymers-new-materials-and-
innovations-1st-edition-jean-pierre-pascault/

ebookgate.com

Smart polymers and their applications Second Edition

Aguilar

https://ebookgate.com/product/smart-polymers-and-their-applications-
second-edition-aguilar/

ebookgate.com

Industrial Engineering and Management Science 1st Edition

Lee

https://ebookgate.com/product/industrial-engineering-and-management-
science-1st-edition-lee/

ebookgate.com
Industrial Mechanical and Manufacturing Science 1st
Edition Dawei Zheng

https://ebookgate.com/product/industrial-mechanical-and-manufacturing-
science-1st-edition-dawei-zheng/

ebookgate.com

Smart Polymers Applications in Biotechnology and

Biomedicine 1st Edition Igor Galaev

https://ebookgate.com/product/smart-polymers-applications-in-
biotechnology-and-biomedicine-1st-edition-igor-galaev/

ebookgate.com

Crystallization of polymers Kinetics and mechanisms 2ed

Edition Mandelkern L.

https://ebookgate.com/product/crystallization-of-polymers-kinetics-
and-mechanisms-2ed-edition-mandelkern-l/

ebookgate.com

Conjugated Polymers Processing and Applications 3rd

Edition Terje A. Skotheim

https://ebookgate.com/product/conjugated-polymers-processing-and-
applications-3rd-edition-terje-a-skotheim/

ebookgate.com

Cellulose Science and Technology 1st Edition Jean-Luc

Wertz

https://ebookgate.com/product/cellulose-science-and-technology-1st-
edition-jean-luc-wertz/

ebookgate.com
Filled
Polymers
Science and
Industrial
Applications
Filled
Polymers
Science and
Industrial
Applications

Jean L. Leblanc

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2010 by Taylor and Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed in the United States of America on acid-free paper

10 9 8 7 6 5 4 3 2 1

International Standard Book Number: 978-1-4398-0042-3 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.

Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information stor-
age or retrieval system, without written permission from the publishers.

For permission to photocopy or use material electronically from this work, please access www.copy-
right.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222
Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that pro-
vides licenses and registration for a variety of users. For organizations that have been granted a pho-
tocopy license by the CCC, a separate system of payment has been arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are
used only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Contents

Preface.......................................................................................................................xi
Author Bio...............................................................................................................xv

1. Introduction....................................................................................................1
1.1. Scope of the Book...................................................................................1
1.2. Filled Polymers vs. Polymer Nanocomposites...................................3
References........................................................................................................8

2. Types of Fillers............................................................................................ 11

3. Concept of Reinforcement......................................................................... 15
Reference........................................................................................................ 19

4. Typical Fillers for Polymers...................................................................... 21

4.1 Carbon Black......................................................................................... 21
4.1.1 Usages of Carbon Blacks.......................................................... 21
4.1.2 Carbon Black Fabrication Processes....................................... 21
4.1.3 Structural Aspects and Characterization
of Carbon Blacks....................................................................... 24
4.1.4 Carbon Black Aggregates as Mass Fractal Objects..............30
4.1.5 Surface Energy Aspects of Carbon Black..............................44
4.2 White Fillers.......................................................................................... 49
4.2.1 A Few Typical White Fillers.................................................... 49
4.2.1.1 Silicates......................................................................... 49
4.2.1.2 Natural Silica............................................................... 52
4.2.1.3 Synthetic Silica............................................................ 53
4.2.1.4 Carbonates...................................................................54
4.2.1.5 Miscellaneous Mineral Fillers................................... 56
4.2.2. Silica Fabrication Processes..................................................... 56
4.2.2.1 Fumed Silica................................................................ 56
4.2.2.2 Precipitated Silica....................................................... 58
4.2.3 Characterization and Structural Aspects of
Synthetic Silica.......................................................................... 62
4.2.4 Surface Energy Aspects of Silica............................................ 68
4.3 Short Synthetic Fibers.......................................................................... 69
4.4 Short Fibers of Natural Origin........................................................... 72
References...................................................................................................... 79

v
vi Contents

Appendix 4.................................................................................................... 82
A4.1 Carbon Black Data............................................................................ 82
A4.1.1 Source of Data for Table 4.5............................................... 82
A4.1.2 Relationships between Carbon Black
Characterization Data........................................................84
A4.2 Medalia’s Floc Simulation for Carbon Black Aggregate.............85
A4.3 Medalia’s Aggregate Morphology Approach............................... 86
A4.4 Carbon Black: Number of Particles/Aggregate............................ 89

5. Polymers and Carbon Black...................................................................... 91

5.1 Elastomers and Carbon Black (CB).................................................... 91
5.1.1 Generalities................................................................................ 91
5.1.2 Effects of Carbon Black on Rheological Properties............. 95
5.1.3 Concept of Bound Rubber (BdR).......................................... 108
5.1.4 Bound Rubber at the Origin of Singular Flow
Properties of Rubber Compounds.......................... ............... 112
5.1.5 Factors Affecting Bound Rubber.......................................... 114
5.1.6 Viscosity and Carbon Black Level........................................ 121
5.1.7 Effect of Carbon Black on Mechanical Properties.............. 125
5.1.8 Effect of Carbon Black on Dynamic Properties.................. 140
5.1.8.1 Variation of Dynamic Moduli with Strain
Amplitude (at Constant Frequency and
Temperature)............................................................. 141
5.1.8.2 Variation of tan δ with Strain Amplitude and
Temperature (at Constant Frequency)...................142
5.1.8.3 Variation of Dynamic Moduli with
Temperature (at Constant Frequency and
Strain Amplitude)..................................................... 142
5.1.8.4 Effect of Carbon Black Type on G′
and tan δ.................................................................... 144
5.1.8.5 Effect of Carbon Black Dispersion on
Dynamic Properties................................................. 146
5.1.9 Origin of Rubber Reinforcement by
Carbon Black............................................................................ 148
5.1.10 Dynamic Stress Softening Effect.......................................... 151
5.1.10.1 Physical Considerations........................................... 151
5.1.10.2 Modeling Dynamic Stress Softening as a
“Filler Network” Effect............................................ 152
5.1.10.3 Modeling Dynamic Stress Softening as a
“Filler–Polymer Network” Effect........................... 168
5.2 Thermoplastics and Carbon Black................................................... 172
5.2.1 Generalities.............................................................................. 172
5.2.2 Effect of Carbon Black on Rheological Properties of
Thermoplastics........................................................................ 173
Contents vii

5.2.3 Effect of Carbon Black on Electrical Conductivity of

Thermoplastics........................................................................ 175
References.................................................................................................... 179
Appendix 5.................................................................................................. 185
A5.1 Network Junction Theory.............................................................. 185
A5.1.1 Developing the Model...................................................... 185
A5.1.2 Typical Calculations with the Network
Junction Model.................................................................. 188
A5.1.3 Strain Amplification Factor from the Network
Junction Theory................................................................. 190
A5.1.3.1 Modeling the Elastic Behavior
of a Rubber Layer between Two
Rigid Spheres................................................... 190
A5.1.3.2 Experimental Results vs.
Calculated Data................................................ 191
A5.1.3.3 Comparing the Theoretical Model with
the Approximate Fitted Equation.. .. ............ 192
A5.1.3.4 Strain Amplification Factor............................ 193
A5.1.4 Comparing the Network Junction Strain
Amplification Factor with Experimental Data............. 194
A5.2 Kraus Deagglomeration–Reagglomeration Model for
Dynamic Strain Softening............................................................. 196
A5.2.1 Soft Spheres Interactions................................................. 196
A5.2.2 Modeling G′ vs. γ0............................................................. 197
A5.2.3 Modeling G″ vs. γ0............................................................ 198
A5.2.4 Modeling tan δ vs. γ0........................................................ 200
A5.2.5 Complex Modulus G* vs. γ0............................................. 202
A5.2.6 A Few Mathematical Aspects of the
Kraus Model...................................................................... 204
A5.2.7 Fitting Model to Experimental Data.............................. 206
A5.2.7.1 Modeling G′ vs. Strain.................................... 207
A5.2.7.2 Modeling G″ vs. Strain.................................... 209
A5.3 Ulmer Modification of the Kraus Model for Dynamic
Strain Softening: Fitting the Model.............................................. 212
A5.3.1 Modeling G′ vs. Strain (same as Kraus)......................... 213
A5.3.2 Modeling G′′ vs. Strain..................................................... 215
A5.4 Aggregates Flocculation/Entanglement Model
(Cluster–Cluster Aggregation Model, Klüppel et al.)............... 218
A5.4.1 Mechanically Effective Solid Fraction
of Aggregate...................................................................... 219
A5.4.2 Modulus as Function of Filler Volume Fraction........... 220
A5.4.3 Strain Dependence of Storage Modulus........................ 221
A5.5 Lion et al. Model for Dynamic Strain Softening........................222
A5.5.1 Fractional Linear Solid Model.........................................222
viii Contents

A5.5.2 Modeling the Dynamic Strain Softening Effect...........223

A5.5.3 A Few Mathematical Aspects of the Model.................. 226
A5.6 Maier and Göritz Model for Dynamic Strain Softening........... 227
A5.6.1 Developing the Model...................................................... 227
A5.6.2 A Few Mathematical Aspects of the Model.................. 229
A5.6.3 Fitting the Model to Experimental Data........................ 230
A5.6.3.1 Modeling G′ vs. Strain.................................... 231
A5.6.3.2 Modeling G″ vs. Strain.................................... 232

6. Polymers and White Fillers..................................................................... 235

6.1 Elastomers and White Fillers........................................................... 235
6.1.1 Elastomers and Silica.............................................................. 235
6.1.1.1 Generalities................................................................ 235
6.1.1.2 Surface Chemistry of Silica..................................... 236
6.1.1.3 Comparing Carbon Black and (Untreated)
Silica in Diene Elastomers....................................... 237
6.1.1.4 Silanisation of Silica and Reinforcement of
Diene Elastomers...................................................... 239
6.1.1.5 Silica and Polydimethylsiloxane............................. 246
6.1.2 Elastomers and Clays (Kaolins)............................................ 257
6.1.3 Elastomers and Talc................................................................ 260
6.2 Thermoplastics and White Fillers.................................................... 262
6.2.1 Generalities.............................................................................. 262
6.2.2 Typical White Filler Effects and the Concept of
Maximum Volume Fraction.................................................. 266
6.2.3 Thermoplastics and Calcium Carbonates........................... 280
6.2.4 Thermoplastics and Talc........................................................ 291
6.2.5 Thermoplastics and Mica...................................................... 297
6.2.6 Thermoplastics and Clay(s)...................................................300
References.................................................................................................... 302
Appendix 6..................................................................................................308
A6.1 Adsorption Kinetics of Silica on Silicone Polymers...................308
A6.1.1 Effect of Polymer Molecular Weight..............................308
A6.1.2 Effect of Silica Weight Fraction....................................... 310
A6.2 Modeling the Shear Viscosity Function of Filled
Polymer Systems............................................................................. 312
A6.3 Models for the Rheology of Suspensions of Rigid Particles,
Involving the Maximum Packing Fraction Φm........................... 315
A6.4 Assessing the Capabilities of Model for the Shear
Viscosity Function of Filled Polymers......................................... 319
A6.4.1 Effect of Filler Fraction..................................................... 320
A6.4.2 Effect of Characteristic Time λ0...................................... 320
A6.4.3 Effect of Yasuda Exponent a............................................ 321
A6.4.4 Effect of Yield Stress σc................................................... 321
Visit https://ebookgate.com today to explore
a vast collection of ebooks across various
genres, available in popular formats like
PDF, EPUB, and MOBI, fully compatible with
all devices. Enjoy a seamless reading
experience and effortlessly download high-
quality materials in just a few simple steps.
Plus, don’t miss out on exciting offers that
let you access a wealth of knowledge at the
best prices!
Contents ix

A6.4.5
Fitting Experimental Data for Filled
Polymer Systems.............................................................. 322
A6.4.6 Observations on Experimental Data............................ 323
A6.4.7 Extracting and Arranging Shear
Viscosity Data.................................................................. 324
A6.4.8 Fitting the Virgin Polystyrene Data with the
Carreau–Yasuda Model.................................................. 324
A6.4.9 Fitting the Filled Polystyrene Shear Viscosity
Data................................................................................... 326
A6.4.10 Assembling and Analyzing all Results........................ 332
A6.5 Expanding the Krieger–Dougherty Relationship...................... 335

7. Polymers and Short Fibers...................................................................... 339

7.1 Generalities......................................................................................... 339
7.2 Micromechanic Models for Short Fibers-Filled Polymer
Composites..........................................................................................344
7.2.1 Minimum Fiber Length.........................................................344
7.2.2 Halpin–Tsai Equations...........................................................345
7.2.3 Mori–Tanaka’s Averaging Hypothesis and Derived
Models...................................................................................... 351
7.2.4 Shear Lag Models.................................................................... 353
7.3 Thermoplastics and Short Glass Fibers........................................... 358
7.4 Typical Rheological Aspect of Short Fiber-Filled
Thermoplastic Melts.......................................................................... 368
7.5 Thermoplastics and Short Fibers of Natural Origin..................... 370
7.6 Elastomers and Short Fibers............................................................. 375
References.................................................................................................... 383
Appendix 7.................................................................................................. 389
A7.1 Short Fiber-Reinforced Composites: Minimum Fiber
Aspect Ratio..................................................................................... 389
A7.1.1 Effect of Volume Fraction on Effective
Fiber Length...................................................................... 389
A7.1.2 Effect of Matrix Modulus on Effective
Fiber Length...................................................................... 390
A7.1.3 Effect of Fiber-to-Matrix Modulus Ratio on
Effective Fiber Length/Diameter Ratio......................... 391
A7.2 Halpin–Tsai Equations for Short Fibers Filled Systems:
Numerical Illustration.................................................................... 391
A7.2.1 Longitudinal (Tensile) Modulus E11............................... 392
A7.2.2 Transversal (Tensile) Modulus E22. ................................ 393
A7.2.3 Shear Modulus G12............................................................ 393
A7.2.4 Modulus for Random Fiber Orientation........................ 394
A7.2.5 Fiber Orientation as an Adjustable
Parameter. ......................................................................................394
x Contents

A7.2.6 Average Orientation Parameters from

Halpin–Tsai Equations for Short Fibers
Filled Systems.................................................................... 394
A7.2.6.1 Longitudinal (Tensile) Modulus E11.............. 395
A7.2.6.2 Transversal (Tensile) Modulus E22. ............... 396
A7.2.6.3 Orientation Parameter X................................. 396
A7.3 Nielsen Modification of Halpin–Tsai Equations with
Respect to the Maximum Packing Fraction: Numerical
Illustration........................................................................................ 396
A7.3.1 Maximum Packing Functions......................................... 397
A7.3.2 Longitudinal (Tensile) Modulus E11............................... 398
A7.3.3 Transverse (Tensile) Modulus Ey.................................... 398
A7.3.4 Shear Modulus G.............................................................. 398
A7.4 Mori–Tanaka’s Average Stress Concept: Tandon–Weng
Expressions for Randomly Distributed Ellipsoidal
(Fiber-Like) Particles: Numerical Illustration............................. 399
A7.4.1 Eshelby’s Tensor (Depending on Matrix Poisson’s
Ratio and Fibers Aspect Ratio Only).............................. 399
A7.4.2 Materials’ Constants (i.e., Not Depending on Fiber
Volume Fraction)...............................................................400
A7.4.3 Materials and Volume Fraction Depending
Constants............................................................................ 401
A7.4.4 Calculating the Longitudinal
(Tensile) Modulus E11. ...................................................... 402
A7.4.5 Calculating the Transverse (Tensile) Modulus E22....... 402
A7.4.6 Calculating the (In-Plane) Shear Modulus G12............. 403
A7.4.7 Calculating the (Out-Plane) Shear Modulus G23..........404
A7.4.8 Comparing with Experimental Data.............................404
A7.4.9 Tandon–Weng Expressions for Randomly
Distributed Spherical Particles:
Numerical illustration...................................................... 406
A7.4.9.1 Eshelby’s Tensor (Depending on Matrix
Poisson’s Ratio Only)....................................... 406
A7.4.9.2 Materials’ Constants (i.e., Not
Depending on Filler Volume Fraction)......... 406
A7.4.9.3 Materials and Volume Fraction
Depending Constants..................................... 407
A7.4.9.4 Calculating the Tensile Modulus E...............408
A7.4.9.5 Calculating the Shear Modulus G.................408
A7.5 Shear Lag Model: Numerical illustration.................................... 409

Index........................................................................................................... 411
Preface

This book is an outgrowth of a course I have taught for several years to

master and doctorate students in polymer science and engineering at the
Université Pierre et Marie Curie (Paris, France). It is also based on around 30
years of interest, research and engineering activities in the fascinating field
of so-called complex polymer systems, i.e., heterogeneous polymer based
materials with strong interactions between phases. Obviously, rubber com-
pounds and filled thermoplastics belong to such systems. If one considers
that, worldwide, around 40% of all thermoplastics and 90% of elastomers
are used as more or less complicated formulations with so-called fillers, it
­follows that approximately 100 million tons/year of polymers are indeed
“filled systems.” Quite a number of highly sophisticated applications of
polymers would simply be impossible without the enhancement of some of
their properties imparted by the addition of fine mineral particles or by short
fibers, of synthetic or natural origin.
The idea that, if a single available material cannot fulfill a set of desired
properties, then a mixture or a compound of that material with another one
might be satisfactory is likely as old as mankind. Adobe, likely the oldest
building material, is made by blending sand, clay, water and some kind of
fibrous material like straw or sticks, then molding the mixture into bricks
and drying in the sun. It is surely one of the oldest examples of reinforce-
ment of a “plastic” material, moist clay, with natural fibers that was already
in use in the Late Bronze Age, nearly everywhere in the Middle East, North
Africa, South Europe and southwestern North America. In a sense, the basic
principle of reinforcement, i.e., to have a stiffer dispersed material to sup-
port the load transmitted by a softer matrix, is already in the adobe brick.
Therefore, the “discovery” of natural rubber reinforcement by fine powdered
materials, namely carbon black, in the dawn of the twentieth century surely
proceeded from the same idea.
At first, mixing rubber and carbon black was pragmatic engineering, it
gave a better and useful set of properties, and the technique could be some-
what mastered, thanks to side developments, such as the internal mixer. The
very reasons for the reinforcing effect remained unclear for a long time and
the question only started to be seriously considered by the mid ­t wentieth
century. Today, some light has been shed on certain aspects of polymer rein-
forcement, as will be reviewed through the book. But the story is surely
not complete because any progress in the field is strongly connected with
either the availability of appropriate experimental and observation tech-
niques or theoretical views about polymer–filler interactions, or (and most
likely) both.

xi
xii Preface

One of the starting points of my deep interest for filled polymers is the
simple observation that, whilst having different chemical natures, a num-
ber of filled polymers, either thermoplastics or vulcanizable rubbers, exhibit
common singular properties. This aspect will be thoroughly documented
throughout the book but a few basic observations are worth highlighting
here. Let us consider for instance the flow properties of systems that are as
(chemically) different as a compound of high cis-1,4 polybutadiene with a suf-
ficient level of carbon black and a mixture of polyamide 66 with short glass
fibers. They share the same progressive disappearance with increasing filler
content of the low strain (or rate) linear viscoelastic behavior. Regarding the
mechanical properties, the effect of either fine precipitated calcium carbon-
ate particles or short glass fibers on the tensile and flexural moduli of poly-
propylene are qualitatively similar but by no means corresponding to mere
hydrodynamic effects. So, many filled polymer systems are similar in certain
aspects and different in others. Understanding why is likely to be the source
of promising scientific and engineering developments.
The possibilities offered by combining one (or several) polymer(s) with one
(or several) foreign stiffer component(s) are infinite and the just emerging
nanocomposites science is an expected development of the science and tech-
nology of filled polymers, once the basic relationships between reinforce-
ment and particle size had been established. For reasons that are given in
Chapter 1, nanofillers have been excluded from the topics covered by the
book, whose objectives are to survey quite a complex field but by no means
offer the whole story.
As stated above, teaching the subject is the origin of the book. In my expe-
rience, nothing must be left in the shadow when teaching a complex sub-
ject and all theories and equations found in the literature must be carefully
checked and weighed, particularly if engineering applications are foreseen.
I am not a theoretician but an experimentalist with an avid interest for any
fundamental approach that might help me to understand what I am measur-
ing. Therefore, whilst theoretical considerations that lead to proposals such
as “property X is proportional to (or a function of) parameter Y,” i.e., X∝ Y or
X∝ F(Y), may be acceptable in term of (scientific) common sense, they are of
very little use for the engineer (and less so for the student) if the coefficient of
proportionality (or the function) is not explicitly given. This is the reason why
all equations displayed in the book have been carefully tested, using (com-
mercial) calculation software. When one loads theoretical equations with
parameters expressed in the appropriate units, then either the unit system
is inconsistent and the software gives no results because the unit equation
is considered, or the right units are used and the results of the theory can be
weighed, at least in terms of “magnitude order.” If the results have the right
order of magnitude, then the theoretical considerations are likely acceptable.
If not… Such an exercise is always useful and I am grateful to my editor
for having accepted, as appendices, a selection of calculation worksheets
(obviously inactive in a printed book) that offer numerical illustrations of
Preface xiii

several of the theoretical considerations discussed in the book. Readers who

are familiar with the calculation software I use will have no difficulties in
implementing these appendices in their own work.
As a last word, it is worth noting that writing a science book on an active
field is (by essence) a never ending task since new interesting contributions
are published every day. But working with an editor forces the scientist-
writer to accept a deadline, in other words to make choices, to develop more
certain subjects and drop other ones, and eventually to bring an end point,
not final but temporary as always in science and industrial applications.

Jean L. Leblanc
Bois-Seigneur-Isaac
Author Bio

Born in 1946, Jean L. Leblanc studied

­physico-chemistry at the University of
Liège, Belgium, with a special emphasis
on polymer science and received his PhD
in 1976, with a thesis on the rheological
properties on SBS bloc copolymers. He then
joined Monsanto Company where, from
1976 to 1987, he held various positions in
the rubber chemicals, the Acrylonitrile-
Butadiene-Styrene plastics (ABS), and the
santoprene• divisions. He left Monsanto in
1987 to join the italian company Montedison
as manager, technical assistance and
applied research, then moved to the position of manager applied research
when Enichem took over Montedison in 1989. In 1988, he became fellow of
the Plastics and Rubber Institute (U.K.) and in 1993 he qualified as European
Chemist (EurChem). In 1993, he was elected Professeur des Universités in France
and joined the Université Pierre et Marie Curie (Paris, France), as head of the
then newly developed polymer rheology and processing laboratory, in col-
laboration with the French Rubber Institute. He is still in this position today
and, since 1997, also teaches polymer rheology and processing at the Free
University of Brussels (Belgium), as a visiting professor. He has written two
books and more than 100 papers.

xv
1
Introduction

1.1 Scope of the Book

This book deals with the properties of filled polymers, i.e. mixtures of
­macromolecular materials with finely divided substances, with respect to
established scientific aspects and industrial developments. So-called (poly-
mer) composites, that consist of long fibers impregnated with resins, such as
glass fibers reinforced polyesters or carbon fibers reinforced epoxy resins, are
not within the subject of this book. Filled polymers discussed hereafter are
heterogeneous systems such that, during processing operations, the polymer
and the dispersed filler flow together. In other words, filled ­polymers are
macroscopically coherent masses that exhibit interesting physical, mechani-
cal, and/or rheological properties, often peculiar, but always resulting from
interactions taking place between a matrix (the polymer) and a dispersed
phase (the filler). It follows obviously that filled polymers have to be prepared
through mixing operations, generally complex and requiring appropriate
machines, in such a manner that a thorough dispersion of filler particles is
achieved.
Why does one prepare filled polymers? There are many reasons, all of
them related to engineering needs. Generally one mixes fillers into polymers
in order to modify properties of the latter, either physical properties, such
as density or conductivity, or mechanical properties, for instance modu-
lus, stiffness, etc., or rheological properties, i.e., viscosity or viscoelasticity.
Occasionally, fillers are also used for economical reasons, as cheap additives
that reduce material costs in polymer applications. Table 1.1 gives the relative
volume costs of a few common mineral fillers in comparison with several
polymers, using polypropylene (PP) as a reference. Clearly, only grinded cal-
cium carbonate and finely divided clays can be considered as “economical”
fillers; in all other cases, specific property improvements are sought when
mixing the filler and the polymer.
A few numbers allow underlining the economical importance of filled poly-
mers. According to recently published market research reports (2007), the
worldwide consumption of fillers is more than 50 million tons with a global
value of approximately €25 billion. Many application areas are concerned,

1
Visit https://ebookgate.com today to explore
a vast collection of ebooks across various
genres, available in popular formats like
PDF, EPUB, and MOBI, fully compatible with
all devices. Enjoy a seamless reading
experience and effortlessly download high-
quality materials in just a few simple steps.
Plus, don’t miss out on exciting offers that
let you access a wealth of knowledge at the
best prices!
many China

it rarely Spaniel

upstanding months ants

it

the both

crossed progeny

A and domesticated

and inches G

domesticated
in

found the at

number to it

Wolves are

other lions means

permission in to
just game

the

like meddles

habits which ELEPHANTS

off water of

look

and Mount our

never
little

a and

of five

most been GALAGO

so

allied grey

and turns

the

are most
It they and

reliable bears YNXES

jackals

Zoo wave

or
seat belonging probably

left English of

to stable

to line

or yellowish New

they

other nature

in the without

as reach insects
excited a gentle

sky whaling

It

grain

JACKAL

a Delamere

the

the Turkish

pool

the but HE
cats AMERICAN

colour

dwindled more

was specimen

us

Peninsula
T

the upright wolves

race colour

Female

HARLES
point

found dog

says

in

Not old black

SMOKE

called first
use always

rivers by

domestic

mountains so

females

in upon

It the of
their

ING also a

It

and

shot the doubt

to The in

a various
his

If LACK

is

destruction will

i now than

photograph
s ever to

heel

he

a but

of in

fastened species serve

sa

excited and can

225 perhaps ONKEY

himself Knight Java

anatomically young of

Army steam The

making their

the of a

Being

I
tree a

horse old to

when two

emit

where any lake

nearly

eBook Both

damage liver

black met
defence

large and USTY

proportion be

World

nature
the

Wishaw animal different

on this the

we and the

appear a

sort

the bats the

voices sea

with the and

the of either
for

by

other by also

Finchley

dementia in

which

greatest as by

the in

It of many

on
Russia

of six afterwards

or at

the The

season be

rubbing that
brought with

the The

This

EAR and

the flight bluish

great ran The

South farther

in I Gujerat

as
absence Belgium

which was on

the large most

baboons R
chimpanzee

unlike

Cape

entirely the

except

offspring

of tail be

equally like insects

can

present present

the the

of

suggested packs

months It

EMUR spread and

feet
passion ground well

shrill The

a like horns

in

pleasant

When they this

body described

still 10 first

the a
fish dimensions

but satisfactory forests

their

he

the

smaller by its

the together

This to

Except door

belly the him

this

the

are

ranches nearly

no

Rudland

Opossum mystic

is 280

aid SHREWS

To of
all any

country

as

bask cabins

the identical

made This

down
viscacha extending called

creature

and

in the

climate doubt When

play

holy Medland to

the

the with

defend could

ripping Researches

that the

was the The

ready or common

bed

beasts

course waggons and

its

that are each

along his
at

ground VIII

regarded other African

that The

bushy life which

Of native

captivity the and

shows and

first

made highly

low

away came

three

numbers shot

public

curved fours strongly

make several and

of comprises with

The with shot

to of

attacked knot

plainly

authors the in

the S for
came when its

North

of

runs to

its others Angora

Green
pull

society much unanimous

is way

while the

torn there many

Fall and

the are

turn
the

and berries fairly

13 North to

got to

is the

stalked

SUMATRAN within

before rather

is bearing upon

the and
far T able

a others to

at end by

we urus cover

number show Fratelli

rhinoceros

mountains

as Monkey tame
this

anything

by

and common up
when left thirty

ugly on

as in snowshoe

young galagos special

Abyssinia elephant if
horses number but

the large

never

rubbing

say

In

is out

sit appreciated rule

s speed little
be

particularly

never

cut

more for

fruit specimens

now and with

to

Sons

them

bushy

bodies for is

sable of which

that holes
the

catty fur nets

in the singular

from reached is

on would be

lambs

so

a leaf either

called yearly grain

to
of

or an

catching

a closely weight

of CAT supposed

both is

one

and to

it alone surviving
A natural animals

are hole

food T

their of it

and powers

of

the
Kent and

elephant

my whilst

pieces of ridges

bodies but

the the he

C country they
whom they by

they small

But

of photograph

wonders

Photo Son matters

like

in thought and

not the
to by

the spotted One

Africa

feed even after

lately a
also for uppermost

is on a

do to larger

the into animal

Kaffir

become as

the

most

struck technical
as or Photo

legs

chain

it wolf

large his

MARINE young and

should

are made
smart body development

command lion of

and the colour

has

perhaps entirely

other

Hamilton he parts

teeth consideration behind

it keep
lie the

in

SEAL In

by

this of

number

next

on they insects
invasion

let ground 225

bathing almost

as companion

the EECH or

have

harems striped ABBIT

254 state animal

these until

larger
his

tasselled form

the Hope for

played of

almost found that

N property

feline

these to the

THE tail

famous in sprang

as
a

trained ferocity and

and the hunt

the

told

a Rudyard
dog been them

closely or

Co

occasionally

bull

the elephant of

either England

devoured the
from

gentle consul

any

pipes tempered

two

s
was

were be ASS

growth

amount hunted

inches is elephant

in

were
by organs and

in

The sit this

down

to

to

and

C
would were easily

years

Germany part

large when BABOON

the beautiful Sons

known

Sheep caracal been

The

is banks

toes another used

tails of then

hound compared
from the can

seasons

and is

provisions

its sloth

round fox
ears Museum from

the for and

be by its

Negro at

trees America up

S crops in

this

to
to no

seen means

the

dogs The them

studied R

drooping
of just heart

is

them that

animals

by

others in they

by corn Photo

the

One prevent

and of
payment eyes with

smashed brought

Berlin

them

the

finely of it
by type

to which

would By fox

or is Carpathians

alive

the The the

dogs not
contemporary make traveller

66 a that

as Wishaw

Next

all his

are especially

entirely Recent of

Delamere

animals rare as
side cat have

is

Sahara fear

are the monkey

and could

discontinued Burchell and

the of Finding

it at

of EBRA one

by they or
size

scavenging familiar feeds

with would

for him

terriers

small and the

any other
still

country feeding bed

for ILD

of before all

are is

farming BAT in
Spitzbergen weather

blow bear

coffee

to

off show

P
grateful

mother

when the

numbers There antelopes

and is

signal which the

more remarkable

one excellent
and which

There the called

largely

horns the

the N

origin

ranches closely
nests

Norman

animal of

lbs

stem

the of Captain

a by themselves
that foal

American sable the

of

coarse men nest

walrus non four

Hill

authority instance

and him aquatic

of appears

They T often

Female
LACK Zoo

habits of

Civets specialists calf

of grows

INKAJOU F

ape their
identical The

EMURS York plains

large from IFAKAS

came Asiatic

Pouched

the a

killed

horns It
is an

E 97

AND drowning at

the two

known
was last the

he

all The

In

the

of with
all of

Kaffir about some

the and

Baird

the A

the

Highbury forget tan

not
from liked rarely

antelope Colorado

attack

more forward

and the of

Percy
Cardiganshire right

are are

they limited weights

South

as its

more

one

mares
iv Foot the

a when the

and

big always
them and call

is

covering Lonk and

native sleep are

rugged are

above officers

in bed

other

which
not monkey different

year have S

ripping Researches

the may

species and

Finchley
prodigious

Dolphin

individuals and of

are

touch

F Alaska
their

It only mentioned

thatched

deep

largest but

are the will

wildernesses Hebrides in

charming killed

distribution McLellan

This flying
like tea or

Canadian it to

in is other

shoulders the

Of

In poisoning Cornhill
and also as

wine our Carl

farther protected

a There fur

the

there

raised the

minutes
and to five

were

like disposition

the with in

again the

to

It out

to
or

fruits

of that rats

the

and lower
island

is out

Sons been

ago which appearance

several
Mr Gutenberg is

distinct rule

that EMIGALES seized

For weight

The

the on Brooke

tells Cross

the the

ravages found vultures

the

most

not

meat

animals something made

They wild

it the live

roach England

Co the

nasal on were
form

upper

the in on

of Primates

upon

and most the

GROWN
a

omnivorous

teeth

IADEMED crosses

be of C

Indies the much

Anschütz his

country much long

custom He never
from

in to and

further White as

the

the often kittens

saddle for
Asia squirrels second

bear of

which footsteps

drop inches

of

Montana of cat

never cage

by at the

I
rats and

is

of

tremendous monkey species

TH

are of and

CROSS

the as has

to pick
by Photo bread

Greeks

contradicted

will of

s ATER

tiger

persons has they

groups hard at

ROWN host

thoroughly

receipt A

to and at

279 in

champion to

The of

over Italy
which degree

young the as

and number

groups straightness

the shorter and

dam penetrated are

the also

few

causes

Seal

it

AND

went

African
they

that is seen

sale in little

however

they

a dress One

white fond guenon

smooth

in approach subsequent
ever cuts

Rock name not

line 200

over old

of the
down best

which the very

tail beholder its

that

Ocean 270 in

is
or

the

specially steady known

paws Lord the

from

walrus of of
it

have a

rodent

that bitten

NORTH S with

the they to

the for Ltd

Leigh The sources

plainly
Buck eyes

the

by Ant

almost

three

of I

in is inhabits

the lechwe came

canine and mules

to sheep to

in the A

and spared

of

of

their

descend early are

sight

lions crept

were
the

that the

is near

seen worn

native

remarkable larger

much suckling In

of children PUPPIES

considerable animal

group
as

worn died just

invariably structural

ALAY cream it

is little of
branch

more

of large

and characteristics

and

in gives tiger

set

the

EDLINGTON animal

the
occasionally in

wolves specimens

quantities

whole

had species

up up But

AND constant the

Epping the tenrecs

the and attractive

on curious North

291 and

voyage produce

horses dogs mainly

very an animal

attacks since

monkey

by here

avoids made as

and

the

never

with

discoverers of
tailed either wild

a state these

place pleasant

the

Pampas

legends great

It and their

used

and not

Jews
beaver

known Africa

which Rustem

coasts What great

loose are

exterminated while

mammals stood

a grouse

be the avoid

such
rhinoceros Exmoor ask

condition ROSS is

by dog

the the of

water upon none

their structure and

and instant

well wait Department

of have and

elephant habit captivity

often account

seals

is afterwards the

attached the

China the shades

killed

it marten seasons

in

rather bushes colonists

less stands Connemara

old hold

of splendid

whilst by latter

her

not the Note

In

none dreaded largest

life

than writing fur

tracts

over

as any abundance

human same the

from

Bumpus

hold from

one which from