Reology of Filled Polymer Systems

Rheology of Filled
Polymer Systems
Aroon V. Shenoy
Advisory Consultant
Pune, India
KLUWER ACADEMIC PUBLISHERS

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ISBN 0-412-83100-7
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Preface
Polymeric materials have been replacing other conventional materials

like metals, glass and wood in a number of applications. The use of
various types of fillers incorporated into the polymer has become quite
common as a means of reducing cost and to impart certain desirable
mechanical, thermal, electrical and magnetic properties to the polymers.
Due to the energy crisis and high prices of petrochemicals, there
has been a greater demand to use more and more fillers to cheapen
the polymeric materials while maintaining and/or improving their
properties.
The advantages that filled polymer systems have to offer are
normally offset to some extent by the increased complexity in the
rheological behavior that is introduced by the inclusion of the fillers.
Usually when the use of fillers is considered, a compromise has to be
made between the improved mechanical properties in the solid state,
the increased difficulty in melt processing, the problem of achieving
uniform dispersion of the filler in the polymer matrix and the
economics of the process due to the added step of compounding. It has
been recognized that addition of filler to the polymer brings a change in
processing behavior. The presence of the filler increases the melt
viscosity leading to increases in the pressure drop across the die but
gives rise to less die swell due to decreased melt elasticity. The decrease
in melt elasticity can raise the critical shear rate at which melt fracture
during extrusion starts to occur and hence one could often consider
increasing throughput rate in the case of filled polymer melt
processing.
The purpose of the present book is to treat the rheology of filled
polymer systems in as much detail as possible. With the idea of
addressing readers of this book who may come from different
backgrounds, a concerted effort has been made to provide the initial
three chapters with material needed for familiarizing with the basics
about polymers, fillers, physico-chemical interactions between the two,
rheology and rheometry.
The first chapter introduces the subject and gives an overview. It
briefly discusses the various types of polymers and fillers that can
go into the formation of filled polymer systems. It also gives an
outline about the physico-chemical interactions between polymers
and fillers.
The second chapter deals with the fundamentals of rheology and
provides definitions of all the basic rheological parameters. It dwells on
the non-Newtonian character of filled polymeric systems and explains
the various anomalies that are encountered during the flow of
viscoelastic materials. Various viscoelastic phenomena are depicted and
these give an idea about the complexities involved in the flow of
polymeric materials, which gets further complicated in the presence of
fillers.
The third chapter presents some of the different methods of
rheological measurements. The entire range of rheometers has not been
explained here as the focus in this chapter has been to include only
those that find relevance to filled polymer characterization.
The fourth chapter presents some constitutive theories and equations
for suspensions. Suspension rheology normally deals with the flow
behavior of two-phase systems in which one phase is solid particles like
fillers but the other phase is water, organic liquids or polymer solutions.
Literature on suspension rheology does not include flow characteristics
of filled polymer systems. Nevertheless, this chapter needs to be
included as the foundations for understanding the basics of filled
polymer rheology stem from the flow behavior of suspensions. In fact,
most of the constitutive theories and equations that are used for filled
polymer systems are borrowed from those that were initially developed
for suspension rheology.
Chapter 5 goes into the details of how to prepare filled polymer
systems. It discusses the criteria for good mixing and the various
mixing mechanisms by which fillers get compounded with polymers.
The compounding techniques are discussed and compounding/mixing
variables are highlighted so that the sensitivity of these variables is
understood in order to obtain well-dispersed filled polymer systems
under optimum conditions.
Chapters 6 to 9 discuss the steady shear viscous properties, steady
shear elastic properties, unsteady shear viscoelastic properties and
extensional flow properties, respectively. The effect of filler type, size,
size distribution, concentration, agglomerates, surface treatment as well
as the effect of polymer type are elucidated. The tenth chapter has been
included to recapitulate the important aspects discussed in the
presented work.
It is hoped that this book will provide all the necessary background
needed to understand the various aspects relating to the rheology of
filled polymer systems so that even new entrants to this exciting field
may benefit from the information. For those who have already whetted
their appetite with a taste for this research area, it is hoped that this
book will provide complete details under one cover and entice them to
probe into vacant areas of research that may become obvious to them
on reading this book.
Aroon V. Shenoy
Contents
Preface ............................................................................ ix
1. Introduction ............................................................. 1
1.1 Polymers ...................................................................... 1
1.1.1 Thermoplastics, Thermosets and
Elastomers .................................................. 1
1.1.2 Linear, Branched or Network Polymers ....... 2
1.1.3 Crystalline, Semi-Crystalline or
Amorphous Polymers .................................. 5
1.1.4 Homopolymers ............................................ 6
1.1.5 Copolymers and Terpolymers ..................... 7
1.1.6 Liquid Crystalline Polymers ......................... 9
1.2 Fillers ............................................................................ 9
1.2.1 Rigid or Flexible Fillers ................................ 10
1.2.2 Spherical, Ellipsoidal, Platelike or
Fibrous Fillers ............................................. 10
1.2.3 Organic or Inorganic Fillers ......................... 11
1.3 Filled Polymers ............................................................ 11
1.4 Filler-Polymer Interactions ........................................... 16
1.4.1 Filler Geometry ........................................... 18
1.4.2 Volume Fraction .......................................... 19
1.4.3 Filler Surface ............................................... 19
1.4.4 Wettability ................................................... 19
1.4.5 Filler Surface Treatment .............................. 21
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vi Contents
1.5 Rheology ...................................................................... 39

References .......................................................................... 43
2. Basic Rheological Concepts .................................. 54

2.1 Flow Classification ....................................................... 55
2.1.1 Steady Simple Shear Flow .......................... 55
2.1.2 Unsteady Simple Shear Flow ...................... 59
2.1.3 Extensional Flow ......................................... 62
2.2 Non-Newtonian Flow Behavior .................................... 66
2.2.1 Newtonian Fluids ........................................ 66
2.2.2 Non-Newtonian Fluids ................................. 67
2.2.3 Viscoelastic Effects ..................................... 71
2.3 Rheological Models ..................................................... 79
2.3.1 Models for the Steady Shear Viscosity
Function ...................................................... 79
2.3.2 Model for the Normal Stress Difference
Function ...................................................... 84
2.3.3 Model for the Complex Viscosity
Function ...................................................... 86
2.3.4 Model for the Dynamic Modulus
Functions .................................................... 90
2.3.5 Models for the Extensional Viscosity
Function ...................................................... 93
2.4 Other Relationships for Shear Viscosity
Functions ..................................................................... 99
2.4.1 Viscosity-Temperature Relationships .......... 99
2.4.2 Viscosity-Pressure Relationship .................. 103
2.4.3 Viscosity-Molecular Weight
Relationship ................................................ 104
References .......................................................................... 104
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Contents vii
3. Rheometry ............................................................... 112

3.1 Rotational Viscometers ................................................ 113
3.1.1 Cone and Plate Viscometer ......................... 115
3.1.2 Parallel-Disc Viscometer ............................. 117
3.2 Capillary Rheometers .................................................. 118
3.2.1 Constant Plunger Speed Circular Orifice
Capillary Rheometer ................................... 119
3.2.2 Constant Plunger Speed Slit Orifice
Capillary Rheometer ................................... 124
3.2.3 Constant Speed Screw Extrusion Type
Capillary Rheometers .................................. 124
3.2.4 Constant Pressure Circular Orifice
Capillary Rheometer (Melt Flow
Indexer) ....................................................... 126
3.3 Extensional Viscometers ............................................. 128
3.3.1 Filament Stretching Method ........................ 128
3.3.2 Extrusion Method ........................................ 130
References .......................................................................... 131
4. Constitutive Theories and Equations for

Suspensions ........................................................... 136
4.1 Importance of Suspension Rheology .......................... 136
4.2 Shear Viscous Flow ..................................................... 137
4.2.1 Effect of Shape, Concentration and
Dimensions on the Particles ........................ 137
4.2.2 Effect of Size Distribution of the
Particles ...................................................... 147
4.2.3 Effect of the Nature of the Particle
Surface ....................................................... 150
4.2.4 Effect of the Velocity Gradient ..................... 150

viii Contents
4.2.5 Effect of Flocculation ................................... 151

4.2.6 Effect of the Suspending Medium ................ 153
4.2.7 Effect of Adsorbed Polymers ....................... 154
4.2.8 Effect of Chemical Additives ........................ 160
4.2.9 Effect of Physical and Chemical
Processes ................................................... 160
4.2.10 Effect of an Electrostatic Field ..................... 162
4.3 Extensional Flow .......................................................... 164
References .......................................................................... 167
5. Preparation of Filled Polymer Systems ................ 175

5.1 Goodness of Mixing ..................................................... 175
5.2 Mixing Mechanisms ..................................................... 183
5.3 Compounding Techniques .......................................... 186
5.3.1 Selection Criteria ......................................... 186
5.3.2 Batch Mixers ............................................... 189
5.3.3 Continuous Compounders ........................... 192
5.3.4 Dump Criteria .............................................. 218
5.4 Compounding/Mixing Variables .................................. 221
5.4.1 Mixer Type .................................................. 223
5.4.2 Rotor Geometry .......................................... 224
5.4.3 Mixing Time ................................................. 225
5.4.4 Rotor Speed ................................................ 229
5.4.5 Ram Pressure ............................................. 229
5.4.6 Chamber Loadings ...................................... 231
5.4.7 Mixing Temperature .................................... 232
5.4.8 Order of Ingredient Addition ........................ 236
References .......................................................................... 237

Contents ix
6. Steady Shear Viscous Properties .......................... 243

6.1 Effect of Filler Type ...................................................... 244
6.2 Effect of Filler Size ....................................................... 246
6.3 Effect of Filler Concentration ....................................... 248
6.4 Effect of Filler Size Distribution .................................... 262
6.5 Effect of Filler Agglomerates ....................................... 272
6.6 Effect of Filler Surface Treatment ................................ 273
6.7 Effect of Polymer Matrix .............................................. 279
6.8 Unification of Steady Shear Viscosity Data ................. 287
References .......................................................................... 303
7. Steady Shear Elastic Properties ............................ 312

References .......................................................................... 332
8. Unsteady Shear Viscoelastic Properties .............. 338


x Contents
8.8 Effect of Matrix Additives ............................................. 387

References .......................................................................... 390
9. Extensional Flow Properties .................................. 395

References .......................................................................... 409
10. Concluding Remarks .............................................. 416
Appendices .................................................................... 425

Appendix A Glossary .......................................................... 425
Appendix B ASTM Conditions and Specifications for
MFI ............................................................................... 430
Appendix C Data Details and Sources for Master
Rheograms .................................................................. 433
Appendix D Abbreviations .................................................. 439
Appendix E Nomenclature ................................................. 441
Appendix F Greek Symbols ............................................... 449
Author Index .................................................................. 455
Index ............................................................................... 469

Introduction I
1.1 POLYMERS
Polymers are high molecular weight organic substances that have
usually been synthesized from low molecular weight compounds
through the process of polymerization, using addition reaction or
condensation reaction.
In addition polymerization, the reaction is initiated by a free radical
which is usually formed due to the decomposition of a relatively
unstable component in the reacting species. In this reaction, repeating
units add one at a time to the radical chain, and reasonably high
molecular weight polymers can be formed in a short time by this
polymerization.
In condensation polymerization, the reaction takes place between
two polyfunctional molecules to produce one larger polyfunctional
molecule with the possible elimination of a small molecule such as
water. Long reaction times are essential for forming high molecular
weight polymers by this step reaction.
An elementary introduction to polymers is given here and those
wishing to gain more knowledge about the physics, chemistry and
engineering aspects of polymers should consult some of the standard
references [1-13] on the subject.
Polymers formed through the polymerization processes discussed
above can be classified in a number of different ways based on
certain chosen characteristics for comparison.
1.1.1 THERMOPLASTICS, THERMOSETS AND ELASTOMERS

Thermoplastics are those polymers that can be made to soften and take
on new shapes by application of heat and pressure. The changes that
occur during this process are physical rather than chemical and hence
products formed from such polymers can be remelted and reprocessed.
Table 1.1 Some candidate polymers used in the formation of filled
polymer systems
Thermosets Elastomers Thermoplastics
Epoxies Neoprenes Nylons
Phenolics Nitriles Polypropylene
Unsaturated polyesters Styrene butadienes Polystyrene
Thermosets are materials that have undergone a chemical reaction,

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

A polymer can be classified as linear or branched depending upon its
structure. The thermoplastic polyethylene serves as a good example
because it exists with linear as well as branched structure as can be
seen from Figure 1.1. Based on the pressure (low or high), the
reaction temperature and the choice of the catalyst during the
polymerization process, polyethylenes with different densities and
structures are formed. High-density polyethylene (HDPE) has a linear
molecular structure and a density ^0.94g/cm3, low-density poly-
LOW PRESSURE HDPE
HIGH PRESSURE LDPE
LOW PRESSURE LLDPE
Figure 1.1 Comparison of structures of HDPE1 LDPE, and LLDPE.
ethylene (LDPE) has a branched structure and a density ^0.92g/cm3,

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

network polymer of low crosslink density as
The last stage of the heating process results in the formation of

resites, which is a network polymer of high crosslink density as
It should be noted that the structure of phenolics is much more
random than that shown above. The pictorial representation is
basically a simplified version only for the sake of exemplifying the
formation of a three-dimensional network.
Other thermosets besides phenol-aldehyde which are formed into
network polymers by similar reactions are urea-aldehyde and
melamine-aldehyde polymers.
1.1.3 CRYSTALLINE, SEMI-CRYSTALLINE OR AMORPHOUS POLYMERS

Polymers can also be classified as crystalline, semi-crystalline or
amorphous polymers depending on their degree of crystallinity. A
crystal is basically an orderly arrangement of atoms in space.
Polymers that are able to crystallize under suitable temperature
conditions are called crystalline polymers. The primary transition
temperature, when a crystalline polymer transforms from a solid to a
liquid, is the melting temperature designated Tm.
On the other hand, an amorphous polymer does not crystallize
under any conditions. The phase transition for this type of polymer
occurs from the glassy state to rubbery state at a temperature termed
the glass transition temperature and often designated Tg.
Most thermoplastics have both Tg and Tm. This is because it is
relatively difficult to get to the extreme case of a completely
crystalline polymer with an ideal formation of single crystals having
the relative arrangement of atoms strictly the same throughout the
volume. In fact, deviations from the completely ordered arrangement
as well as completely disordered arrangement always exist. Thus, it
is the degree of crystallinity that truly determines whether a polymer
could be classified as a crystalline, amorphous or semi-crystalline
polymer.
1.1.4 HOMOPOLYMERS
When a single repeating unit such as A or B exists in a polymer, it is
termed a homopolymer. Thus, homopolymer is AAAAAAAA or
BBBBBBB. For example,
when R = H, then the result is the homopolymer polyethylene (PE);

when R = CH3, it is polypropylene (PP); when R = C6H5, it is
polystyrene (PS) and when R = Cl, it is polyvinyl chloride (PVC).
The materials mentioned above namely, PE, PP, PS and PVC are
among the largest volume thermoplastics utilized. They are used in a
maximum number of applications, mostly in those which do not
require high performance or special properties. In terms of cost they
are among the cheapest of the thermoplastics. Hence they are often
referred to as commodity plastics.
Another important class of polymers which are formed by addition
polymerization like the above are based on one of the following three
repeating units
1,4 addition 3,4 addition 1,2 addition
When X = H, the resulting polymer is polybutadiene; when X = CH3,

it is polyisoprene and when X = Cl, it is polychloroprene. The double
bond may be 'cis' or 'trans' and would thus give the cis or trans
forms of these polymers. It is the 1,4 addition form that
predominantly goes into the formation of commercial dienes which
are all elastomers.
Typical examples of homopolymers that are formed by
condensation polymerization are the polyamides and polyesters
When R E=(CH2)S, the resulting polymer is polyamide: nylon-6; when
R'=(CH 2 ) 6 and R"=(CH 2 ) 4 , it is nylon-66; when X = (CH2), and
X' = C6H5, it is polyester: polyethylene terephthalate (PET).
These thermoplastics have properties which are superior to those of
commodity plastics (namely, olefinics and styrenics). They go into a
number of engineering applications and are termed engineering
thermoplastics. Besides poly amides (nylons) and polyesters, some of
the other homopolymers which fall into this category of engineering
thermoplastics are the acrylics, acetals and polycarbonates.
High performance engineering thermoplastics have recently assumed
increasing importance due to their exceptional properties at elevated
temperatures. A number of such specialty polymers have been intro-
duced into the market for high temperature applications and examples
of some of the outstanding ones are polyphenylene oxide (PPO),
polyphenylene sulfide (PPS), polyether sulfone (PES), polyaryl sulfone
(PAS), polyether ketone (PEEK), polyether imide (PEI) and polyarylate
(PAr).
Each of the above mentioned specialty polymers exhibits enhanced
rigidity at high temperatures. This is a consequence of their high
glass-transition temperatures, presence of aromatic ring structures in
the backbone chain and relatively strong hydrogen bonds.
1.1.5 COPOLYMERS AND TERPOLYMERS

When two different monomers are used in the polymerization
process, the result is a copolymer. The repeating units A and B both
exist in the polymerized product and their varying configurations
give different types of copolymers
(i) Random copolymer: AA B AAA BB A BBB
(ii) Uniform copolymer: AB AB AB AB AB
(iii) Block copolymer: AAA BBB AAA BBB AAA
B
B
(iv) Graft copolymer: AAAAAAAAAAAAA.
B B
B B
B B
B
Block copolymers may be arranged in various star arrangements,
wherein polymer A radiates from a central point with a specified
number of arms and polymer B is attached to the end of each
arm.
Copolymerization is often used to alter the properties of homo-
polymers and to achieve specific performance. For example, the flow
behavior of PVC is considerably improved by incorporating vinyl
acetate as comonomer. Similarly, the thermal stability of polyoxy-
methylene is improved considerably by incorporation of -CH2-CH2-O
units in the chain yielding an oxymethyline or acetal copolymer.
If either of the comonomers on its own could yield a crystalline
homopolymer, then copolymerization can have a very marked effect
on properties by inhibiting crystallization. For example, PE crystal-
linity is decreased by increasing the amount of vinyl acetate content in
the copolymer leading to a softer, tougher product, namely, ethylene-
vinyl acetate (EVA).
The properties of block copolymers are dependent on the length of
the sequences of repeating units or domains. The domains in typical
commercial block copolymers of styrene and butadiene are suffi-
ciently long to produce flexible plastics called thermoplastic elastomers.
In fact, the copolymer butadiene-styrene is a good example of how the
thermoplastic characteristics can be changed by altering the portion of
two components of the copolymer. Polybutadiene is a synthetic rubber
with a high level of elasticity, while polystyrene is a clear brittle plastic
which is often used for making disposable containers. A copolymer
made with 75% butadiene and 25% polystyrene is styrene butadiene
rubber (SBR) with direct applications to carpeting, padding and seat
cushions. On the other hand, a copolymer of 25% butadiene and 75%
styrene gives an impact styrene which is often used for the manufacture
of equipment cabinets and appliances. Most commercial varieties of
high-impact polystyrene (HIPS) are graft copolymers in which the main
chain is that of butadiene while styrene forms the branches.
Copolymers of styrene, with acrylonitrile (SAN) and maleic anhydride
(SMA) are typical examples of uniform alternating copolymers.
Copolymers represent an industrially important class of polymeric
materials, due to their unique combination of properties such as
impact resistance, elasticity and processibility. Block copolymers, in
particular, have great technological importance because of the ability
of these materials to form thermoplastic elastomers which can be
processed by conventional thermoplastic processing techniques. Readers
wishing to know more about copolymers may refer to the excellent
monographs [14-20] that are available.
Polymerization of acrylonitrile and styrene in the presence of buta-
diene rubber results in a terpolymer called acrylonitrile-butadiene-
styrene (ABS). Besides grafting styrene and acrylonitrile into
polybutadiene in latex form, ABS may also be produced by blending
emulsion latexes of styrene-acrylonitrile (SAN) and nitrile rubber
(NBR). Since ABS is a three component system, many variations are
possible. Acrylonitrile imparts chemical resistance while butadiene
provides increased toughness and impact resistance. A variety of
grades are available - some for general purposes, some for various
levels of impact resistances and others for ease of plating. The major
applications include plumbing systems, telephone housings and auto-
mobile grills (either painted or electroplated).
1.1.6 LIQUID CRYSTALLINE POLYMERS

Polymers in which rigid, anisotropic moieties are present in the
backbone of the polymer chain are known to give rise to liquid
crystalline behavior and are therefore known as liquid crystalline
polymers (LCP) [21]. Such types of polymer have attained immense
importance due to the possibility of producing ultrahigh modulus
fibers and plastics. The main interest in the subject of LCP was
kindled by the commercialization of the aromatic polyamide fiber,
namely, Kevlar which was as stiff and strong as steel but at one-fifth
the density of steel, and with excellent chemical and heat resistance.
Kevlar is a lyotropic liquid crystal, that is, it attains liquid crystalline
order only when dissolved in an appropriate solvent. Since the
removal of the solvent is a necessary step during fabrication of the
product, such lyotropic LCPs are restricted to the formation of thin
fibers and films. For thicker products, however, polymers are needed
which become liquid crystalline upon heating i.e. 'thermotropic'
LCPs. There has been increasing interest in using LCPs as rein-
forcing additives in polymers to form blends and composites [22,23].
But moldable LCPs, regrettably, do not have immense commercial
importance.
The exceptional physical properties of these uniquely structured
systems are a direct consequence of the morphology and orientation
induced into the polymers due to the flow history during processing.
Thus understanding the rheological behavior associated with liquid
crystallinity is undoubtedly essential for processing the LCPs into the
appropriate structure to exhibit their desirable properties [24].
1.2 FILLERS
The term 'filler' in the present context is used for describing those
inert, solid materials which are physically dispersed in the polymer
matrix, without significantly affecting the molecular structure of the
polymer. Further, the term is restricted to those materials which are
in the form of discrete particles or of fibers not exceeding a few
inches in length. Continuous filaments or fabrics either woven or
nonwoven are not included in this category of fillers discussed
Table 1.2 Examples of rigid and flexible fillers
Filler type
Rigid Flexible
Aluminum oxide Asbestos fiber
Barium carbonate Cotton flock
Calcium carbonate Cotton !inters
Calcium hydroxide Jute fiber
Calcium silicate Kevlar fiber
Clay Nylon fiber
Glass fiber Polyester fiber
Magnesium hydroxide Sisal
Metal fiber
Mica
Talc
Wollastonite
herein. Readers wishing to know more about fillers may refer to the
excellent handbook on the subject [25].
Filler categorization can be done in a number of different ways as
shown in Tables 1.2-1.4. In the following, a brief discussion is given
under a variety of headings based on certain chosen characteristics
for comparison.
1.2.1 RIGID OR FLEXIBLE FILLERS

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

shown in Table 1.3. Among the classifications shown, only spherical
fillers are symmetric in physical form and hence provide symmetric
changes in properties in all three spatial directions. It is normally rare
to find exactly spherically well-formed fillers. There is always a slight
defect in shape, especially for finer size particles. For instance, even
when controlled conditions are used in the preparation of mono-
disperse silica spheres in the micron size range [26,27], all particles
Table 1.3 Filler classification by physical form
Filler form
3-dimensional 2-dimensional 1-dimensional
Spherical Ellipsoidal Flakes Platelets Fibers Whiskers
Glass beads Wood flour Mica Clay Glass fibers Wollastonite
produced are not exactly spherical when viewed under the scanning
electron microscope. Thus, the terms spherical or ellipsoidal can be
viewed as those referring to nearly spherical or nearly ellipsoidal
fillers.
When the physical form of the filler is two-dimensional, the fillers
may be available as flakes (larger size plates) or platelets (smaller size
plates). Thus, mica particles exist as flakes whereas clay particles exist
as platelets.
In the one-dimensional form, filler may be available in the thicker
variety as a fiber or thinner (acicular-needle-shaped) variety as a
whisker. Fillers available as fibers are glass, nylon, polyester, carbon
and so on. Wollastonite stands out as a good example of an acicular
filler.
1.2.3 ORGANIC OR INORGANIC FILLERS

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

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

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

1. To increase stiffness, strength and dimensional stability
2. To increase toughness or impact strength
3. To increase heat deflection temperature
4. To increase mechanical damping
5. To reduce permeability to gases and liquids
6. To modify electrical properties
7. To reduce the cost of the product
in the case of high-impact polystyrene or polypropylene, deformable
rubber particles are added; asymmetric fillers such as fibers and
flakes increase the modulus and heat distortion temperature; and
electrical and thermal properties are modified by the use of
metallized fibrous fillers. With fibrous fillers, the improvements can
be further magnified due to the influence of the fiber aspect ratio and
anisotropy as well as fiber orientation. The most effective reinforcing
fillers are fibers of high modulus and strength. Glass fibers, which are
non-crystalline in nature, or asbestos - a crystalline fiber - provide the
reinforcement in most commercial fiber-reinforced thermoplastics.
Carbon fibers or whiskers, single crystal fibers, are the other crystalline
fibers used as reinforcement.
The improvements in mechanical properties through the use of
fillers acting as reinforcing agents have been discussed in detail by
Nielsen and Landel [3O]. Such filled systems wherein the fillers
provide reinforcements are often referred to as reinforced polymer
systems or reinforced plastics. However, in the present book, the
term 'filled polymer systems' is used in the most general sense and
includes all systems wherein fillers are present as cost reducing
agents as well as reinforcing or property modifying agents.
One or more of the physical, mechanical and thermal properties of
polymers can be effectively modified by the use of different types of
fillers. For example, in the tyre industry, the presence of the filler
carbon black in vulcanized rubber enhances properties like elastic
modulus, tear strength and abrasion resistance [31-33] and also
influences extrusion characteristics like extrudate distortion, extensional
viscosity and die swell behavior [34-^4O]. Thus, carbon black functions
as a reinforcing agent and a processing aid in the rubber industry.
Different types of fillers serve different types of purposes. For example,
titanium dioxide acts as a delustering agent in the fiber industry and
aluminum trihydroxide as an economic flame retardant and smoke
suppressing agent. In most applications, the proper balance of properties
is no less important than an improvement of an individual property. It
must be accepted that an improvement in one property can in all
likelihood lead to deterioration of others and consequently, it is the overall
performance of the filler in a given formulation that determines its choice.
The predominant function of some typical fillers is given in Table 1.7.
Selection of a filler is not just an art but a science and various
factors would have to be considered in the choice such as,
1. Cost and availability

2. Wettability or compatibility with the polymer
3. Effect on polymer flow characteristics
4. Physical properties
Table 1.7 Predominant function of some typical fillers
Function Typical fillers
Cost savings Wood flour, saw dust, cotton flock
Reinforcement Glass fibers, cellulosic fibers, synthetic fibers, asbestos fibers
Hardness Metallic powders, mineral powders, silica, graphite
Thermal insulation Asbestos, ceramic oxides, silica
Chemical resistance Glass fibers, synthetic fibers, metallic oxides, graphites
5. Thermal stability
6. Chemical resistivity
7. Abrasiveness or wear
8. Toxicity
9. Recyclability
Undoubtedly the idea of adding the fillers is to achieve reduction
in cost. However, there are some special type of fillers which are
used purely on a functional basis with an accepted trade-off in the
cost reduction, for example, some fiber glass reinforcements for
polyesters, barium ferrite as a magnetizable filler, metallic powders
for electrical and thermal conductivity improvement. In fact all these
specialty fillers are more expensive than general purpose fillers and
in some cases even more expensive than the polymer which they fill.
In any case, the cost-effectiveness of the filler ought to be determined.
The objective should be to compare the full cost of the completed
product with and without the filler.
The first step involves obtaining the raw material costs which must
be converted from cost per pound to cost per volume. This is because
cost per pound of the filler is meaningless unless adjusted for specific
gravity differences. The volume of the polymer that is displaced by
the filler becomes the main consideration. A three-step calculation
method [41] can be used to get the polymer saved and thus to
determine the cost-effectiveness of filled systems. If the filled polymer
system is compounded in-house, then that cost has to be included.
Similarly, added labour cost or savings due to the use of filled polymer
systems must be considered. Often it is found that a minimum of 30
volume percent of low-cost filler is required to get a cost benefit
when switching from unfilled polymer to filled polymer system.
When selecting a filler, it is important to bear in mind that for
adequate stress transfer, wettability and good adhesion between the
filler and the polymer is essential. Physical properties like, for example,
the density should be low so that the filler stays in suspension or at
worst is able to be resuspended with minimum mixing. Thermal
stability and chemical resistivity are also very important so that the
filler does not change characteristics during the preparation of the filled
polymer system. Fibrous materials and non-symmetrical fillers are more
abrasive than others and could cause increased wear to the processing
equipment. Hence care has to be taken when selecting such fillers as
they may not turn out to be cost-effective due to excessive damage to
the equipment. Also the effect of fillers on polymer flow characteristics,
namely, the rheology must be carefully assessed as that determines its
processibility and hence is a very important parameter.
1.4 FILLER-POLYMER INTERACTIONS

When a filler is added to a polymer with the specific idea of
reinforcement, it is expected that the reinforcing filler component
which is strong and stiff should bear most of the load or stress
applied to the system while the polymer which is of low strength,
fairly tough and extensible should effectively transmit the load to the
filler. Maximum reinforcement benefits would be achieved from fillers
when conditions occur in accordance with this concept [42]. In order
that the load transfer takes place effectively, the matrix must have
sufficiently high cohesive and interfacial shear strength. Thus, apart
from the filler and the polymer, it is the inevitable region between
them, namely, the interphase which plays a vital role in the
fabrication and subsequent behavior of the filled polymer systems in
service. The interphase is that region separating the filler from the
polymer and comprises the area in the vicinity of the interface. It
would be synonymous with the words 'interfacial region' but different
from the term 'interface' which would be the contacting surface
where two materials under consideration meet. Thus, for some filled
polymer systems, there could exist more than one interface as in the
case of coated fiber-filled polymer. In such cases, the fiber-coating
interface and the coating-polymer interface would have characteristics
of their own. However, normally a less atomistic view is taken and
the characteristics of the 'interfacial region' as a whole are generally
investigated.
Good mechanical strength can be achieved only by uniform and
efficient stress transfer through a strong interfacial bond between the
filler and the polymer. It is important that the bond is uniform on a
fine scale rather than unevenly strong in local regions as areas of the
filler-polymer interface which are not in contact begin to act as
cracks under an applied stress. In the absence of a good interfacial
bond, fibrous fillers will pull out of the polymer and result in an
annulment of the reinforcing effect [43]. Controlled debonding at the
Next Page
Basic Theological r\
concepts 4—
Filled polymer theology is basically concerned with the description of

the deformation of filled polymer systems under the influence of
applied stresses. Softened or molten filled polymers are viscoelastic
materials in the sense that their response to deformation lies in varying
extent between that of viscous liquids and elastic solids. In purely
viscous liquids, the mechanical energy is dissipated into the systems in
the form of heat and cannot be recovered by releasing the stresses. Ideal
solids, on the other hand, deform elastically such that the deformation
is reversible and the energy of deformation is fully recoverable when
the stresses are released.
Softened or molten filled polymer may behave as a viscous liquid or
elastic solid during processing operations depending upon the relation-
ship between the time scale of deformation to which it is subjected and
the time required for the time-dependent mechanism to respond. The
ratio of characteristic time to the scale of deformation is defined as the
Deborah number by Reiner [1,2] as
De = /lc//ls
where Ac is the characteristic time, A8 is the time scale of deformation.
The characteristic time, Ac/ for any material can always be defined as
the time required for the material to reach 63.2% or [1 — (l/e)] of its
ultimate retarded elastic response to a step change. If De > 1.0, elastic
effects are dominant while if De < 0.5, viscous effects prevail. For any
values of Deborah numbers other than these two extremes given above,
the materials depict viscoelastic behavior.
Filled polymer systems display the ability to recoil by virtue of their
viscoelastic nature. However, they do not return completely to their
original state when stretched because of their fading memory.
Viscoelasticity allows the material to remember where it came from, but
the memory of its recent configurations is always much better than that
of its bygone past, thus lending it the characteristics of a fading memory.
Meissner [3] found that a filament of low density polyethylene (LDPE) at
423 K, which is stretched rapidly from 1 to 30cm length, and then
suddenly set free, recovers to a length of 3 cm, thereby giving a recovery
factor of 10. If the filament were made of filled LDPE, the recovery
factor would be much smaller because the presence of the filler greatly
reduces the stretchability as well as the recoil of the material.
2.1 FLOW CLASSIFICATION

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

Fluid deformation under steady simple shear flow can be aptly
described by considering the situation in Figure 2.1 wherein the fluid is
held between two large parallel plates separated by a small gap dx2 and
sheared as shown.
The lower plate is moving at a constant velocity V1 while the upper
plate is moving at a constant velocity of V1 H- Au1 under the action of a
force / applied to it. A thin layer of fluid adjacent to each plate moves
at the same velocity as the plate, assuming the no-slip condition at the
solid boundary. Molecules in the fluid layers between these two plates
move at velocities which are intermediate between V1 and V1 + Av1.
Under steady-state conditions, the force / required to produce the
motion becomes constant and is related to the velocity. The velocity
profile of the fluid within the gap is given by dt^ = y dx2 where y is a
constant.
Figure 2.1 Simple shear flow of a fluid trapped between two parallel plates.
A. Shear rate
The velocity gradient [Av1JdX2], which is termed the shear rate y can
also be written as
f
7 = ^ = Afel=lfel l(21)
;
dx2 dx2[dt\ dt[dx2\
The term [dxi/dx2] represents the deformation of the material and is
defined as the shear strain y. Thus, the shear rate is the rate of
deformation or the rate of shear strain and is expressed as reciprocal
seconds (sec"1).
6. Shear-stress and extra stress tensor

The force per unit area [f/A] required to shear the material between
two parallel plates is defined as the shear stress T2i, and it is basically a
function (/cn) of the velocity gradient. Thus,
The units of shear stress are dynes/cm2 or Newtons/m2 (i.e. Pascals).
It must be noted that i2i is just one component of the stress and, in
principle, there are a number of components of stress that must be
specified to completely define the state of stress. For example, a general
constitutive equation which describes the mechanics of materials in
classical fluid dynamics can be written as:
f =-pf + f + ijv[trl5]I (2.3)

where T(X, t) denotes the symmetric Cauchy stress tensor at positron x
and time t, p(x, t) is the pressure in the fluid [T being the unit tensor), f
is the extra stress tensor, T/V is the volume viscosity and D is the
symmetric part of the gradient tensor of the velocity field v(x, t):
^••^[1+5]
Note that Cartesian coordinates are used and vectors are denoted by
single bar [—] above the letter while tensors are denoted by double bars
[=] above the letter.
If the fluid does not undergo a volume change, i.e. it is density
preserving or incompressible, then the mass balance equation, better
known as the continuity equation, reduces to
tr 15 = Jp = O (2Ab)
In such cases, the last term on the right-hand side of equation (2.3)
drops out and the volume viscosity has no role to play. It should also be
noted that, for flow of an incompressible fluid, the absolute value of the
pressure p has no significance because it is only the pressure differences
that are truly relevant. Thus, in essence, the constitutive equation (2.3)
fpr an incompressible fluid connects only the 'extra stress tensor' f or
T -f pi uniquely with the local motion of the fluid but always leaves
the pressure p indeterminate.
A general form of the constitutive equation can be written as
f = ri(l H, IH)H (2.5a)

The apparent viscosity Y] in the above equation is a function of the first,
second and third invariants of the rate of deformation tensor. For
incompressible fluids, the first invariant I becomes identically equal to
zero. The third invariant III vanishes for simple shear flows and is
normally neglected in non-viscometric flows as well. The apparent
viscosity then is a function of the second invariant II alone. Hence
equation (2.5a) is written in the simplified form as
In steady shearing flow, only a limited number of stress components
of the extra stress tensor are necessary to completely define the fluid
motion and these are written as follows:
T11 T12 O I
f= T21 T22 O (2.6)

O O T 33 1
The subscript 1 denotes the direction of flow, the subscript 2 denotes
the direction perpendicular to the flow (i.e. the direction along the
velocity gradient) and the subscript 3 denotes the neutral direction. The
various stress components are shown on a representative cubic volume
of the fluid in Figure 2.2. All the components are not shown in the
figure in order to maintain clarity. Note that in steady shearing flow,
the stress components T13, T23, T 315 T 32 , are identically equal to zero.
T12 = T21 is called the shear stress and T11, T22, T33, are called normal
stresses.
Figure 2.2 Various stress components on a representative cubic volume of fluid

(stress components T12, T13, T31, T32, have not been shown in order to maintain clarity
of the figure).
C. Normal stress difference
The absolute value of any particular component of normal stress is of
no rheological relevance, whereas the values of the normal stress
differences T11 — T22 and T22 — T33 do have considerable rheological signifi-
cance. The first is termed the primary normal stress difference while the
latter is termed the secondary normal stress difference. Thus,
N1 - T11 - T22 (2.7)
N2 = T22 - T33 (2.8)
For most fluids, N1 ^> N2 and hence the latter is often excluded in
rheological discussions. Attempts to determine the value of secondary
normal stress difference experimentally have been made by several
rheologists but without success. It is still a challenge to quantitatively
determine this material function. Nevertheless, it is not very important
in most hydrodynamic calculations barring, of course, wire coating [5]
wherein the secondary normal stress difference helps in providing the
necessary restoring force for stabilizing the wire position whenever it
becomes off-centered.
D. Viscometric functions
The viscosity function r\ (referred to as the steady shear viscosity), the
primary and secondary normal stress coefficients ^1, and ^2, respec-
tively, are the three viscometric functions which completely determine
the state of stress in any Theologically steady shear flow. They are
defined as follows:
T12 = T21 = ri(y)y (2.9)
Tn-T 2 2 = iAi(7)y2 (2.10)
2
T 22 - % = *2(y)y (2.11)
Viscosity is the resistance of the material to any irreversible positional
change of its volume elements while the normal stress coefficients
exemplify the response of the material due to its elasticity or its ability
to recover from the deformation.
2.1.2 UNSTEADY SIMPLE SHEAR FLOW

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

Small-amplitude oscillatory flow is often referred to as dynamic shear
flow. Fluid deformation under dynamic simple shear flow can be
described by considering the fluid within a small gap dx2 between
two large parallel plates of which the upper one undergoes small
amplitude oscillations in its own plane with a frequency CD. The
velocity field within the gap can be given by Av1 — y dx2 but y is not a
constant as in steady simple shear. Instead it varies sinusoidally and is
given by
y(t) = J0COSCDt (2.12)
The shear stress in simple dynamic shear flow is expressed in terms
of the amplitude and phase shift functions of the frequency as,
^21 (O = Jo[G'(cD) sin CDt + G'(CQ) cos cot] (2.13)
= r°2l sm[cDt + 6] (2.14)
where d is the phase angle, y0 and T^ are the amplitudes of the strain
and stress, respectively, and G, G" are linear viscoelastic material
functions, respectively, referred to as the dynamic storage modulus and
dynamic loss modulus.
To
Dynamic storage modulus: G(CD) = -^- cos d (2.15)
Vo
To
Dynamic loss modulus: G"(CD) — -^- sin d (2.16)
7o
Another term of importance is the ratio of loss to storage modulus,
defined as
Loss tangent: —^- = tan 6 (2.17)

G(CD)
It is also possible to define a dynamic complex viscosity in terms of G

and G" as follows:
/•"•/// \
Dynamic viscosity: rj'(cD) = —— (2.18)
Imaginary part of the complex viscosity: Y\"(CD) = (2.19)
Complex viscosity function: jf(ico) = ^(CD) — irj"(cD) (2.20)

In the same manner as above, a complex modulus can be defined as
below:
Complex modulus: G*(ico) = G(CO) + iG"(co) (2.21)
The storage modulus G(CO) and the imaginary part of the complex
viscosity, i.e. rjf/(co), are to be considered as the elastic contributions to
the complex functions. They are both measures of energy storage.
Similarly, the loss modulus G"(CD) and the dynamic viscosity rj'(co) are
the viscous contributions or measures of energy dissipation.
B. Stress growth
The aim of a stress growth experiment is to observe how the stresses
change with time as they approach their steady shear flow values. This
is done by assuming that the fluid sample trapped in a small gap
between two parallel plates is at rest for all times previous to t = O
implying that there are no stresses in the fluid when steady shear flow
is initiated at t = O. For t > O when a constant velocity gradient is
imposed, the stress is monitored with respect to time till it reaches
steady state value.
C. Stress relaxation
The aim of a stress relaxation experiment is to observe how the stresses
decay with time (i) after cessation of steady shear flow or (ii) after a
sudden shearing displacement. In case (i) the fluid sample trapped in a
small gap between two parallel plates is allowed to maintain constant
shear rate that was started long before t = O so that all the transients
during the stress growth period have evened out. Then at t = O, the
flow is stopped suddenly and the decay of the stress is monitored with
respect to time till it becomes insignificant or dies out. The stress would
relax monotonically to zero and more rapidly as the shear rate in the
preceding steady shear flow is increased.
In case (ii), a constant shear rate lasting only for a brief time interval
is imposed. The decay of the stress that is generated by this sudden
small displacement is monitored. The stress would decrease
monotonically with time. For small shear displacements the relaxation
modulus is known to be independent of shear rate.
D. Creep
The aim of a creep experiment is to observe the changes in shear
displacement as a function of time expressed in terms of creep
compliance, after a constant shear stress has been applied and
maintained at that value on a sample trapped in a small gap between
two parallel plates. The steady-state compliance /e is defined as -y/T21.
If the driving shear stress T21 is small enough then the value of the
compliance is independent of the driving shear stress.
E. Constrained recoil
The aim of a constrained recoil experiment is to observe the shear
displacement in a fluid sample trapped in a small gap between two
parallel plates when driving shear stress is suddenly removed after
steady-state and then held at zero. The shear rate would then only be a
function of time in the recoiling fluid. The ultimate recoil of the fluid at
infinite time can be determined in this manner.
2.1.3 EXTENSIONALFLOW
Problems associated with fiber spinning, film blowing and foaming
process have indicated that the shear flow material functions discussed
earlier are not truly the crucial parameters. This realization led to the
study of another type of flow, namely, the extensional flow. Extensional
flow differs from both steady and unsteady simple shear flows in that it
is a shear-free flow. In such a flow, the volume of a fluid element must
remain constant. Extensional flow can be visualized as that occurring
when a material is longitudinally stretched as, for example, in fiber
spinning. In this case, the extension occurs in a single direction and
hence the related flow is termed uniaxial extensional flow. Extension or
stretching of polymer takes place in other processing operations as well,
such as film blowing and flat-film extrusion. In such cases, the
extension occurs in two directions simultaneously, and hence the flow
is referred to as biaxial extensional flow in one case and planar
extensional flow in the other. Extensional flows can orient polymer
chains as well as fillers which are of the !-dimensional or 2-dimensional
type and hence determine the performance and appearance of a
product.
A. Uniaxial extension
Uniaxial extensional flow may be best visualized as a deformation
caused by forces acting in a direction perpendicular to the opposite
faces of a cylindrical body as shown in Figure 2.3. The velocity field in
simple uniaxial extensional flow is given by
V1 = SX1; V2 = - \ £X2; V3 = - \ £X3 (2.22)
(a) BEFORE EXIENSIOKAL DEFORMATION
(b) AFTER EXTENSIONAL DEFORMAUON
Figure 2.3 Schematic diagram of a fluid element in uniaxial extensional flow.
where e is the uniaxial extensional rate. For such a flow field, the rate of
deformation tensor is given as
_ B O O
U = O -s/2 O (2.23)
O O -s/2
in which
'-£ <2->
The uniaxial extensional rate may be constant or vary in the X1
direction of flow. When s is constant, i.e. when the axial velocity is
proportional to X1, the resulting flow is steady uniaxial extensional flow.
In such a flow situation, a cylindrical rod of length / is stretched along
its axis according to the following equation:
ft = el (2.25)
Integrating this equation for a constant strain rate gives,
/ = /oexp(gt) (2.26)
From equation (2.26), it is evident that extensional flow involves severe
deformation since fluid parts are separated exponentially. The dimen-
sions of the fluid elements change drastically in contrast with shear
flows where particles in neighboring shearing surfaces separate linearly
in time.
6. Biaxial extension
In biaxial extensional flow, too, the dimensions of the fluid elements
change drastically but they change in two directions as against the one-
direction in uniaxial extensional flow. Thus, biaxial extensional flow can
be visualized as a deformation caused by forces acting in two directions
perpendicular to the opposite faces of a plate as shown in Figure 2.4.
The velocity field in simple biaxial extensional flow is given by,
V1 = E3X1; V2 = 63*2; ^3 = -2eB*3 (2.27)
where £B is the biaxial extensional rate. For such a flow field, the rate of
deformation tensor is given as,
(a) BEFORE EXTENSIONAL DEFORMATION
(b) AFTER EXTENSIONAL DEFORMATION
Figure 2.4 Schematic diagram of a fluid element in biaxial extensional flow.

C. Planar extension
Planar extensional flow is the kind of flow where there is no deforma-
tion in one direction and the velocity field is represented as follows:
V1 = SpX1-, V2 = -SpX2; V3=O (2.29)
where sp is the planar extensional rate. In this case, the rate of
deformation tensor is given as,
8P O O
5= O -fip O (2.30)
0 0 0
Extensive reviews [6-10] and a monograph [11] summarize the litera-
ture covering significant aspects of extensional flows in various
commercial processes, theoretical treatment for the hydrodynamics of
such flows and different methods of determining material functions such
as uniaxial, biaxial and planar extensional viscosities.
D. Material functions in extensional flow

The material function of prime importance in extensional flow is the
extensional viscosity which is basically a measure of the resistance of
the material to flow when stress is applied to extend it.
In extensional flow, the diagonal components of TZ; are non-zero (i.e.
i{j = O for i ^j). In the case of uniaxial extension, T11 is the primary
stress that can be measured, while T22 and T33 are generally equal to the
pressure of the environment. Thus, the uniaxial extensional viscosity rjE
is defined by,
T11 - T22 = T11 - T33 = rjE(s)s (2.31)
By the same token, the biaxial extensional viscosity t]EB can be defined
as,
^33 - T11 = T33 - T22 = -*?EB(£B)£B (2.32)
and further, the planar extensional viscosity rjEP can be written as,
T11 - T22 = J?Ep(eP)£p (2.33)

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

Isaac Newton was the first to propose the basic law of viscosity
describing the flow behavior of an ideal liquid as,
? = i?0D (2.34)
where the constant rj0 is termed the Newtonian viscosity.
Fluids, whose flow behavior follows the above constitutive equation,
are known as Newtonian fluids. Some of the common Newtonian
fluids with which most people are familiar are water Oy0 ^ 1 mPa.sec),
coffee cream (rjQ % lOmPa.sec), olive oil (rjQ ^ 102mPa.sec) and honey
Of0 % 104 mPa.sec).
For a Newtonian fluid, equation (2.34) yields the following stress
components in simple shear flow:
T n = T22 = T33 = -p (2.35)
T = T12 = T21 = rj0y (2.36)

All other stress components vanish. According to equation (2.35), it can
be seen that the three normal stress components are equal. The non-
vanishing shear stress T varies linearly with shear rate and has a pro-
portionality constant f/ 0 which is the shear viscosity of the Newtonian fluid.
In general, incompressible Newtonian fluids at constant temperature
can be characterized by just two material constants: the shear viscosity
rj0 and the density p. Once these quantities are measured, the velocity
distribution and the stresses in the fluid can, in principle, be found for
any flow situation. In other words, different isothermal experiments on
a Newtonian fluid would yield a single constant material property,
namely, its viscosity. On the other hand, a variety of flow experiments
performed on a softened or molten filled polymer system, which is a
non-Newtonian fluid, would yield a host of material functions that
depend on shear rate, frequency and time.
When the viscosity is a function of shear rate, then the relationship
between shear stress and shear rate is given by equation (2.9). Since its
form is similar to equation (2.36) except for the shear rate dependent
viscosity, the equation is said to represent a Generalized Newtonian
fluid. In such a fluid, the presence of normal stresses defined by
equations (2.10) and (2.11) is considered to be negligible for a specific
flow situation. In effect, equation (2.5b) represents the constitutive
equation for a Generalized Newtonian fluid. The hypothesis of a
Generalized Newtonian fluid differs from the simple Newtonian case
by the assumption that the functional relationship between the stress
tensor and the kinematic variable need not be only linear. It holds,
however, the suggestion that only the kinematic variable of the first
order can influence the state of stress in the fluid and no attempt is to
be made to describe the normal stresses in it.
2.2.2 NON-NEWTONIAN FLUIDS

Non-Newtonian fluids are Theologically complex fluids that exhibit one
of the following features:
(a) Shear rate dependent viscosities in certain shear rate ranges with
or without the presence of an accompanying elastic solid-like
behavior.
(b) Yield stress with or without the presence of shear rate dependent
viscosities.
(c) Time-dependent viscosities at fixed shear rates.
The definitions of various types of non-Newtonian fluids along with
examples of common real systems falling into each category are given
in Table 2.1. Detailed discussions relating to non-Newtonian fluids are
available in a number of books [18-27] as well as other review articles
[28-33]. From Table 2.1, it can be seen that filled polymer systems fall
within the non-Newtonian category of pseudoplastic fluids, pseudo-
plastic fluids with a yield stress, thixotropic fluids and viscoelastic
fluids.
For pseudoplastic fluids, the shear rate at any given point is solely
dependent upon the instantaneous shear stress, and the duration of
shear does not play any role so far as the viscosity is concerned. The
shear stress vs. shear rate pattern for a pseudoplastic fluid with and
without yield stress is shown in Figure 2.5.
In the case of thixotropic fluids, the shear rate is a function of the
magnitude and duration of shear as well as a function possibly of the
time lapse between consecutive applications of shear stress. The shear
Table 2.1 Various types of non-Newtonian fluids
Fluid type Definition Typical Examples
• Pseudoplastic • These fluids depict a • Filled polymer systems
decrease in viscosity with • Polymer melts
increasing shear rate and • Polymer solutions
hence are often referred to • Printing inks
as shear-thinning fluids. • Pharmaceutical
• Preparations
• Blood
• Dilatant • These fluids depict an • Wet sand
increase in viscosity with • Starch suspensions
increasing shear rate and • Gum solutions
hence are often referred to • Aqueous suspension of
as shear-thickening fluids. titanium dioxide
• Bingham Plastics • These fluids do not flow • Thickened hydrocarbon
unless the stress applied greases
exceeds a certain • Certain asphalts and
minimum value referred to bitumen
as the yield stress and • Water suspensions of clay/
then show a linear shear fly ash/metallic oxides
stress vs. shear rate • Sewage sludges
relationship. • Jellies
• Tomato ketchup
• Toothpaste
• Pseudoplastic with a yield • These fluids have a non- • Filled polymer systems
stress linear shear stress vs. • Heavy crude oils with high
shear rate relationship in wax content
addition to the presence of
a yield stress.
• Thixotropic • These fluids exhibit a Filled polymer systems
reversible decrease in Water suspensions of
shear stress with time at a bentonite clays
constant rate of shear and Drilling muds
fixed temperature. The Crude oils
shear stress, of course, Coal-water slurries
approaches some limiting Yoghurt
value. Salad dressing
Mayonnaise
• Rheopectic • These fluids exhibit a • Some clay suspensions
reversible increase in
shear stress with time at a
constant rate of shear and
fixed temperature. At any
given shear rate, the shear
stress increases to
approach an asymptotic
maximum value.
• Viscoelastic • These fluids possess the • Filled polymer systems
added feature of elasticity • Polymer melts
apart from viscosity. These • Polymer solutions
fluids exhibit process
properties which lie in-
between those of viscous
liquids and elastic solids.
FSEDDOPLASTIC
FLlTD WnU
YIELDSTlESS
PSEUDOPLASHC
FLUID
NEWTONIAN
FLUID
Figure 2.5 Variation of shear stress vs. shear rate for pseudoplastic fluids with and
without yield stress.
stress pattern with time for such fluids is shown in Figure 2.6. If the
shear stress is measured against shear rate which is steadily increasing
from zero to a maximum value and then immediately decreasing
steadily to zero, a hysteresis loop is obtained as shown in Figure 2.7.
Viscoelastic fluids have a certain amount of energy stored in the
fluids as strain energy thereby showing a partial elastic recovery
upon the removal of a deforming stress. At every instant during the
deformation process, a viscoelastic fluid tries unsuccessfully to
recover completely from the deformed state but lags behind. This lag
is a measure of the elasticity or so-called memory of the fluid. Due to
the presence of elasticity, viscoelastic fluids show some markedly
peculiar steady state and transient flow behavior patterns. Viscoelastic
effects become important when there are sudden changes in the flow
rate (e.g. during start-up and stopping operations of the polymer
processing), in high shear rate flows (e.g. in processes like extrusion
and injection molding) and in flows where changes in cross-section
are encountered (e.g. entry into the mold cavity during injection
molding). Some of the common encountered effects due to visco-
elasticity are discussed below.
mxoiROPic
FLHID
Figure 2.6 Variation of shear stress with time for a thixotropic fluid.
THIXOTROPIC JLUID
HYSTERESIS LOOP
Figure 2.7 Variation of shear stress with shear rate (which is steadily increased from
zero to maximum and brought down) for a thixotropic fluid.
Figure 2.8 Weissenberg effect showing how the viscoelastic fluid climbs up the
stirrer-rod when stirred at moderate speeds. (Reprinted from Ref. 34 with kind
permission from Chapman & Hall, Andover, UK.)
2.2.3 VISCOELASTIC EFFECTS
A. Weissenberg effect
When a viscoelastic fluid is stirred with a rod at moderate speeds, the
fluid begins to climb up the rod instead of forming a vortex as shown
pictorially in Figure 2.8. The first normal stress difference is much
larger than the shear stress and hence gives rise to this startling effect.
This type of phenomenon is commonly termed the Weissenberg effect,
as Weissenberg was the first to explain such an effect in terms of the
stresses in fluids undergoing a steady shear flow [34-36]. In actuality,
this effect was observed earlier by Garner and Nissan [37].
B. Extrudate swell
When a viscoelastic fluid flows through an orifice or a capillary, the
diameter of the fluid at the die exit is considerably higher than the
diameter of the orifice. This happens because, at the die exit, the
viscoelastic fluid partially recovers the deformation it underwent when
it was squeezed through the capillary. This type of phenomenon is
known variously as extrudate swell, die swell, jet swell, Barus effect or
Merrington effect. Metzner [38] discusses the history of extrudate swell
Figure 2.9 Extrudate swell effect showing how the viscoelastic fluid swells in diameter
when it exits from a die or orifice. (Reprinted from Ref. 34 with kind permission from
Chapman & Hall, Andover, UK.)
and argues against using the last two names. A review on extrudate
swell has been given by Bagley and Schrieber [39]. Extrudate diameter
(DE) of up to three or four times the orifice diameter (D0) is possible
with some polymers. The swell ratio Sw (i.e. D E /D 0 ) decreases with the
increase of tube length because of the fading memory of the viscoelastic
fluid to deformation. This implies that if longer and longer tubes are
used, Sw should ultimately approach unity. But it is known [40] that the
limiting value of the swell ratio is greater than unity even as the length
to diameter ratio of the orifice approaches infinity. The phenomenon of
die swell is shown pictorially in Figure 2.9.
Theoretical analyses of this phenomenon, for flow in round capil-
laries, are available [41-45] in which the most basic [44] of them is built
upon the free recovery calculations set down by Lodge [13] using the
theory of Berstein, Kearsley and Zapas [46]. The developed expression
for die swell Sw in which the elastic strain recovery SR is balanced by
the shear stresses arising in the die, is given by,
Sw = (l + iS2R)1/6 + 0.1 (2.37)
where,
SR=^ (2.38)
The above analysis does not include the rearrangement of the stress
and velocity fields at the die exit, and consequently, it was found
necessary [44] to empirically modify the die swell expression by
including a factor of 0.1 in the above expression. The 0.1 term has been
added to improve the fit with data for small values of (T11 — T22)w/T2i,w
and the ratio (TU - T22)/^ has been taken to be constant. Later work
[47] has shown that die swell depends not only on the recoverable
shear strain, but also on the ratio of the second to first normal stress
difference coefficients ^2/1Ai as well.
The influence of this phenomenon in the filled polymer industry can
hardly be overlooked. The industrial problems involving extrudate
swell are particularly complex and challenging because the diameter
increase depends not only on the particular type of polymer but also on
the type and amount of filler as well as on the operating conditions
such as temperature and flow rate.
C. Draw resonance
Draw resonance or surging is defined as the non-uniformity in the
diameter of the extrudate when a polymer is stretched at different
take-up speeds as it comes out of an orifice. This phenomenon is shown
schematically in Figure 2.10. When take-up speed is small or when
there is no stretching, only die swell is observed as can be seen from
Figure 2.10(a). When take-up speed is higher and the stretched
extrudate is solidified by quenching, then the contour appears as shown
in Figure 2.10(b). Now draw ratio is defined as the ratio of the linear
velocity v of the extrudate settled in the quenching bath to the smallest
linear velocity VQ at the die swell region. When the draw ratio DR goes
beyond a critical value DRC, then the resulting phenomenon is draw
resonance as shown in Figure 2.10(c). The theory of draw resonance has
been developed and a method for calculating the critical draw ratio is
also available [48]. Once draw resonance occurs its severity enhances
with increasing take-up speed.
D. Melt fracture
When softened or molten polymer flows out of a capillary, a striking
phenomenon of the distortion of the emerging stream is observed at
shear stresses beyond a critical higher value and this is termed melt
fracture [49,5O]. The extrudate distortion is a result of polymer
molecules reaching their elastic limit of storing energy, thus causing
Figure 2.10 Draw resonance effect occurring when polymer melt is extruded from
an orifice at various take-up speeds, (a) Extrudate without stretching, (b) extrudate
with stretching DR<DR C and no draw resonances, (c) extrudate with stretching
DR > DRC showing draw resonance.
melt fracture as a means of stress relief either at the capillary wall or at

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

A characteristic flow pattern at the capillary entrance develops when a
polymer flows at high shear rates from a cylindrical reservoir through a
capillary or die as shown in Figure 2.12. The qualitative difference
between the capillary entry flows of linear and branched polyethylenes
has been convincingly presented by Tordella [50] and discussed by
others [67-7O]. For linear polymers, the converging flow at the die entry
fills the available space, while for branched polymers there is a large
Figure 2.12 Capillary entry flow pattern for a branched polymer showing the flow
cone and the recirculating vortex.
dead space filled by recirculating vortices. Vortices are induced by the

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

During the process of calendering, very stable abnormal fringe patterns
may appear on the roll surface at regular intervals. Though the exact
mechanism for abnormal fringe patterns in calendering is as yet
unclear, it is certainly related to the viscoelasticity of the material.
Depending on the frequency of roll rotation and clearance of roll nip,
its intensity would increase or decrease on account of the effect of such
changes on the viscoelastic response of the calendered material.
PRESSURE TRANSDUCER
NEWTONIAN FLUID VISCOELASTEC FLDTO

Figure 2.13 Pressure hole error occurs in a viscoelastic fluid while it is absent in a
Newtonian fluid. (Reprinted from Ref. 23 with kind permission from John Wiley & Sons,
Inc., New York, USA.)
G. Pressure hole error

For Newtonian fluids, the pressure measured at the bottom of the
pressure hole pM is the same as the true pressure p at the wall. For a
viscoelastic fluid, on the other hand, the pressure (p + T22)M measured
at the bottom of the pressure hole is always lower than the true
pressure (p + T22) at the wall, no matter how small the hole is. This
pressure difference arises because the elastic forces tend to pull the
fluid away from the hole and results in the pressure hole error
pH = (p + T22)M -(p + T22). This effect is illustrated in Figure 2.13. The
possible sources of error in the measurement have been considered by
Higashitani and Lodge [73] along with a review of published data. The
effect of pH has been well substantiated for polymer solutions but the
same is not the case for polymer melts with or without fillers.
H. Parallel plate separation

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

illustrated in Figure 2.14.
I. Tubeless siphon
During the siphoning process, when the siphon tube is lifted out of the
fluid, a Newtonian fluid will stop flowing whereas a viscoelastic fluid
will continue unabated. At times, even 75% of the viscoelastic fluid in
the container may get siphoned out in this manner. This effect is
illustrated in Figure 2.15.
NEWTONIAN FLUID VISCOELASIIC FLUID
Figure 2.15 Tubeless siphoning can be done for a viscoelastic fluid but not for a
Newtonian fluid. (Reprinted from Ref. 23 with kind permission from John Wiley & Sons,
This viscoelastic effect indicates the stability of a stretching filament
of fluid with respect to small perturbations in its cross-sectional area. It
has definite implications in the fiber spinnability of polymers.
J. Uebler effect
It has been observed [74,75] that when a polymeric fluid flows in a tube
with a sudden contraction, large bubbles of the order of 1/6 to 1/8 of
the small tube diameter, come to a sudden stop right at the entrance of
the contraction along the centerline before finally passing through after
a hold-time of about one minute. This particular behavior has been
termed the Uebler effect [74,75].
This phenomenon has implications in the production of foamed
plastics wherein a gas, normally nitrogen, is added to polymers such as
PE, PP and PS during two-phase processing.
2.3 RHEOLOGICAL MODELS

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

From the typical viscosity vs. shear rate curve for unfilled polymer
shown in Figure 1.2, it can be seen that in the low shear rate range, the
material is essentially Newtonian in flow behavior with a constant
apparent viscosity, which at zero shear rate, is termed the zero-shear
viscosity rj0. In the medium shear rate range, the apparent viscosity r\
begins to decrease, depicting the shear-thinning characteristic until it
stabilizes to a constant value ^00 at a considerably high shear rate in the
upper Newtonian region. It is quite obvious from this figure, that a
constitutive equation with about three to four parameters would be
necessary to describe the rheological behavior of an unfilled polymer
over the entire shear rate range. However, when dealing with
processing problems, only certain shear rate ranges attain significance
and hence only portions of the flow curve need to be described by the
constitutive equations thereby requiring less parameters. As a matter of
fact, the very high shear rate range is invariably never reached and
Next Page
Rheometry O
Rheometry is the measuring arm of rheology and its basic function is to

quantify the rheological material parameters of practical importance.
A rheometer is an instrument for measuring the rheological
properties and can do one of the following two things:
1. It can apply a deformation mode to the material and measure the
subsequent force generated, or
2. It can apply a force mode to a material and measure the subsequent
deformation.
The best designs of rheometers use geometries so that the forces/
deformation can be reduced by subsequent calculation to stresses and
strains, and so produce material parameters. It is very important that
the principle of material independence is observed when parameters
are measured on the rheometers. The flow within the rheometers
should be such that the kinematic variables and the constitutive
equations describing the flow must be unaffected by any rigid rotation
of both body and coordinate system - in other words, the response of
the material must not be dependent upon the position of the observer.
When designing rheometers, care is taken to see that the rate of
deformation satisfies this principle for simple shear flow or viscometric
flow. The flow analyzed can be considered as viscometric (simple
shear) flow if sets of plane surfaces (known as shear planes) are seen
to exist and each is moving past the other as a solid plane, i.e. the
distance between every two material points in the plane remains
constant.
The importance of viscometric flows becomes apparent when one
appreciates that the equation of motion for most viscometric flows can
be solved analytically. This is the reason why viscometric flows have
been used for evaluating the viscosity function from viscometric data
and this fact has brought about the alternative name for simple shear
flows. All flows that do not conform to the viscometric behavior as
described above are termed non-viscometric flows. All rheometers
have viscometric flows or at least 'near-viscometric' flows in them and
hence are amenable to produce reliable material functions.
Rheometers used for determining the material functions of filled
polymer systems can be divided into two broad categories - (a) rotational
type and (b) capillary type. Further subdivisions are possible and
these are shown in Table 3.1. In what follows only those
rheometers which are popularly used for rheological characterization
of filled polymer systems are described and discussed in detail. For
example, though the bob and cup rotational viscometer has been used
[1] in the fifties for polyethylene melts, it has not been included in
further detail. This is because this geometry is not at all popular even
for unfilled thermoplastic melt studies, though Cogswell [2] did
suggest it in the seventies for measuring shear viscosities under
conditions of controlled pressure. Similarly, other rheometers which
were developed for rheological measurements of filled systems,
particularly suspensions such as cement [3], red mud [4] or other
slurries [5,6], sealants [7], paints, foodstuffs or greases [8], dental
composites [9-11], propellants [12], etc. are also not described here, as
they are considered to be beyond the scope of this book. For a general
discussion on rheometry, as applicable to various types of fluids, it is
advisable to refer to some of the excellent monographs on this subject
[13-18].
3.1 ROTATIONAL VISCOMETERS

For filled polymer studies, rotational viscometers with either the cone-
plate or parallel-disc configuration are used.
The major advantages of cone and plate viscometers are:
(i) a constant shear rate is maintained throughout the melt sample,
(ii) a small quantity of sample is required for measurement.
On the other hand, the chief advantage of the parallel disc
configuration is that it can be used for filled polymer systems of
extremely high viscosity and elasticity.
The basic limitation in rotational viscometers is that they are
restricted in their use only to low shear rates for unidirectional shear
and low frequency oscillations during oscillatory shear.
At higher shear rates as well as at higher frequencies, a flow
instability normally sets in the polymer sample which then begins to
emerge out of the gap between the cone and plate or parallel-disc
[19,20], thereby giving erroneous results. As a consequence of the
above, the measured material functions do not actually conform to the
Table 3.1 Rheometers for filled polymer systems
Rotational Capillary
Unidirectional Oscillatory Constant Constant

shear shear speed pressure
Plunger Screw Plunger

type extrusion type
type
Cone-n-plate Parallel Circular
disc orifice
Circular Slit
orifice orifice
Circular Slit
orifice orifice
(a) Rheometrics mechanical (a) Monsanto Han's (a) Haake rheocord* Melt flow
spectrometer* automatic slit (b) Brabender plasticorder* indexer
(b) Sangamo Weissenberg rheometer* rheometer (a) Kayeness*
rheogoniometer* (b) lnstron (b) Ceast*
capillary (c) Davenport*
rheometer*
* Commercial instrument.
higher deformation rates which are normally prevalent in processing
operations.
Commercially available rotational instruments, such as the
Mechanical Spectrometer (Rheometrics Inc., Piscataway, NJ, USA) and
Weissenberg Rheogoniometer (Carri-Med Ltd, Dorking, England)
can be used for unidirectional rotational shear as well as oscillatory
shear and come with interchangeable cone and plate/parallel-disc
configurations.
3.1.1 CONE AND PLATE VISCOMETER

The cone and plate viscometer is a widely used instrument for shear
flow rheological properties of polymer systems [21-32]. The principal
features of this viscometer are shown schematically in Figure 3.1. The
sample whose rheological properties are to be measured is trapped
between the circular conical disc at the bottom and the circular
horizontal plate at the top. The cone is connected to the drive motor
which rotates the disc at various constant speeds while the plate is
AXIAL IHKUST
MEASDHWGDEVICE
TORQUE
MEASDWNG
DEVICE STATIONARY
FLAT DISK POLYMER
MELT
RQTA3TNG
CONICAL
DISK
Figure 3.1 Schematic diagram showing the principal features of a cone and plate
rotational viscometer.
connected to the torque-measuring device in order to evaluate the
resistance of the sample to the motion. The cone is truncated at the top.
The gap between the cone and plate is adjusted in such a way as to
represent the distance that would have been available if the
untruncated cone had just touched the plate. The angle of the cone
surface is normally very small (O0 < 4° or 0.0696 radius) so as to
maintain [14] cosec2 O0 = 1. The cone angles are chosen such that for
any point on the cone surface, the ratio of angular speed and distance
to the plate is constant. This ensures that the shear rate is constant from
the cone tip to the outer radius of the conical disc. Similarly, the shear
rate can be assumed to be constant for any point within the gap because
of the predesigned method of gap adjustment as described earlier.
The flow curve for a sample held between the cone and plate is
generated from measurements of the torque experienced by the plate
when the cone is rotated unidirectionally at different speeds. The
various parameters of relevance are determined as follows.
A. Shear rate
For a constant speed of rotation of N rpm, the linear velocity (v = cor) is
27rrN/60m/sec where co is the angular velocity (rad/sec) and r is the
radial position in meters. The gap height at r is rtan90 where 90 is the
cone angle. Hence shear rate in reciprocal seconds at r can be written
as, _ __ __
. _ 2nrN _ nN ^ nN
y
~ 60rtan0 0 ~ 30tan00 ^ 306^ '
Since the cone angle is always maintained to be very small, the
approximation of tan O0 = O0 does hold good.
B. Shear stress
The following expression defines the relationship between the
measured torque and the shear stress:
- f* -*
T = 2TiT21 / r2 dr = f nRi2l (3.2)
Jo
Thus,
Tf
T 2 I=-Z 5 (3-3)
2nR
The shear stress is then obtained in pascals when T is expressed in
newtons.m and R in meters. The ratio of equation (3.3) to equation
(3.1) results in the apparent viscosity expressed in Pa.sec.
C. Normal stress difference
The cone and plate configuration can be used for estimating the
primary normal stress difference of the sample. If p is the pressure at a
point on the plate in excess of that due to the atmospheric pressure,
then it can be shown [14] that the total normal force NF on the plate is
given by,
Np = f 2nrpdr (3.4)
JO
which on integration gives

nR2
NF=-J-Ni (3,5)
Thus
N,=^ (3.6)
nR
Using equations (3.1) and (3.6), a plot of primary normal stress vs. shear
rate can be generated.
The shear stress and primary normal stress measurements can be
done simultaneously on the sample when it is subjected to
unidirectional rotational shear in the gap of a cone and plate
viscometer.
D. Oscillatory shear
The cone and plate viscometer can be used for oscillatory shear
measurements as well. In this case, the sample is deformed by an
oscillatory driver which may be mechanical or electromagnetic. The
amplitude of the sinusoidal deformation is measured by a strain
transducer. The force deforming the sample is measured by the small
deformation of a relatively rigid spring or tension bar to which is
attached a stress transducer. On account of the energy dissipated by the
viscoelastic polymer system, a phase difference develops between the
stress and the strain. The complex viscosity behavior is determined
from the amplitudes of stress and strain and the phase angle between
them. The results are usually interpreted in terms of the material
functions, */', G', G" and others [33-4O].
3.1.2 PARALLEL-DISC VISCOMETER
The parallel-disc viscometer used for measuring the shear stress and
normal stress difference of filled polymer systems is similar in principle
to the cone and plate viscometer except that the lower cone is replaced
by a smooth circular disc. This type of viscometer was initially
developed for measuring the rheological properties of rubber [41-45]
and hence made use of serrated discs placed in a pressurized cavity to
prevent rubber slippage. When it was adapted for other polymeric
systems [27,46,47], measurements were performed using smooth discs
and without pressure.
The rheological properties in the parallel-disc viscometer are based
on the shear rate at the outer radius of the disc. Thus,
ya = coR/H (3.7)
where co is the angular velocity (rad/sec), R is the radius of the disc (m)
and H is the gap between the two parallel discs (m).
Shear stress and normal stress differences are given by the following
relationships:
,R=jr/1+Î) (3.8)
2nR\ 3dln yJ
(,,-„) -(*- *>=SH^g) M
Oscillatory shear measurements can be done with the parallel-disc

arrangement in a similar manner as in the case of the cone and plate
viscometer and similarly the material functions, r\ ,G, G" and others
can be generated. However, a slightly different technique [48] is at
times used wherein the polymer sample is deformed between two
oscillating parallel eccentric discs as shown in Figure 3.2. In this case,
too, it has been shown that the fluid elements undergo a periodic
sinusoidal deformation and the forces exerted on the disc are thus
interpreted in terms of G and G" [14].
3.2 CAPILLARY RHEOMETERS

Capillary rheometers of various types are used for determining the
rheological properties of polymer melts as can be seen from Table 3.1.
The principal feature is that these rheometers are capable of extruding
polymer samples at different speeds through the capillary of
appropriate size. They are broadly categorized as
(i) those operating at constant speed and
(ii) those operating at constant pressure.
A further categorization is possible based on the melt transport
mechanism being of the plunger or the screw type and on the orifice
AXIALIHRUST
MEASDMNGDEVICE
TORQUE
MEASURING
DEVICE STAUQNARY
FLATDISK
POLYMER
MELT
ROTAUNG
FLATDISK
Figure 3.2 Schematic diagram showing the principal features of a parallel eccentric
discs rotational viscometer.
shape, through which the melt is extruded, being of the circular or slit
type. Each type of capillary rheometer is discussed in detail in the
following subsections.
3.2.1 CONSTANT PLUNGER SPEED CIRCULAR ORIFICE CAPILLARY

RHEOMETER
Commercially available instruments such as the Monsanto Automatic

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

extrudate distortion or melt fracture at die wall shear stress levels
greater than 1O5Pa [49-53]. The die wall shear stress TW can be easily
calculated by taking a force balance across the capillary die as,
7ÂPdie = 27TRN/NTW (3.10)
or
TW = ^^ (3.11)
^N
where RN and /N are the radius and length of the capillary die, while
APdie is the pressure drop required to extrude the polymer melt. Since
the polymer flows from a wide reservoir into a capillary die in a
converging stream and then exits into open air or another wide
reservoir in a divergent stream, it is necessary to correct the shear stress
value for these entrance and end effects. The use of long capillaries in
the vain hope that the end effects might be negligible is not
recommended and in fact, should be discouraged. In capillaries longer
than D0, pressure dependence effects become significant. Hence, end
effects can never be assumed to be negligible. The customary method of
incorporating end effects correction is through the use of an effective
capillary length (/N + £RN) as suggested by Bagley [54]. It must be
emphasized here that basically there is no alternative but to carry out
the Bagley procedure to make end corrections. The wall shear stress for
fully developed flow over the length (/N + £#N) is then written as,
_ ^NAPdie
w
~~ A'N
in +_i_rj?
C^N)^t ^ >
The shear rate at the die wall is expressed by the Rabinowitsch-
Weissenberg [55] equation for steady laminar flow of a time-
independent fluid as,
,4QT3 ldln(4Q/^N)1
w
" ^3N [4 4 dlnr w J (6 L6)
'
The term d In (^Q/nR^)/d In TW is basically equal to l/n where n is
the power-law index depicting the non-Newtonian character of the
polymer system. Thus, from equations (3.12) and (3.13), the following
relationship is written
RNAPdie /4Q\
= (3 14a)
2(/^Ki^ H^J '
or,
'N r . &Pdie /oi/iu\
= c ( }
^ ~ 57M
/cn
Uy
The above equation is a straight line when a plot of / N /K N vs. APdie
is constructed at different constant values of (4Q/nR^) as shown in
Figure 3.4(a). This is done using dies of various / N /# N ratios and the
intercept on the / N /^N ordinate at APdie = O determines the value of
—(. There are possibilities of observing slight non-linearity in the plots
as can be seen for data at 3.6 and 10.8 s'1 in Figure 3.4(a). These are
probably due to the breakdown of the assumptions made during the
derivation of equation (3.14) of time-independence and no wall slip.
True mechanical wall slip can occur during polymer flow when the
shear stresses are large enough to overcome the static friction between
the wall and the flowing material [56-62]. Mechanical slip can occur as
either a steady-state phenomenon or as an unsteady phenomenon
known as 'stick-slip' [62-64]. This wall slip may induce the slight non-
linearity in the plots shown in Figure 3.4(a). It must be shown that the
Bagley plot is linear before any capillary viscometry data are regarded
PRESSUREDROP
(1O6PASCAIS)
INTERCEPT
Figure 3.4(a) Plot for determination of the Bagley correction term during polymer
melt flow through a capillary rheometer.
as meaningful. Hence, only those plots which are basically linear in

Figure 3.4(a) are to be used. Once the plots have been shown to be
linear for a particular capillary length and class of material, it is only
then the capillary can be selected for viscometric measurements. From
a linear regression of these plots, the correction term is determined.
Using equation (3.12), the corrected shear stress value at the wall is
estimated. It should be noted that, since polymers are viscoelastic, the
entrance effect needs an elastic-energy correction too. This is because
when the melt converges into the capillary, elastic stresses develop
and begin to relax inside the capillary. This effect is taken into account
[65] by modifying equation (3.12) to include the recoverable shear term
as follows:
APdie ,gjgx
^ 2(/ N /R N + C + SR/2) ^1DJ
Thus, the elastic energy stored at the capillary entrance is related to the
correction term by the following expression [65].
ec = C + y (3.16a)
Assuming Hooke's law in shear, TW = G x SR where G is the apparent
melt shear modulus, the correction term is rewritten as
GLASS BEAD FILLED
POLYPROPYLENE
UNITS
Figure 3.4(b) Variation of capillary correction term with true wall shear stress for
glass bead filled polypropylene. (Reprinted from Ref. 66 with kind permission from
Society of Plastics Engineers Inc., Connecticut, USA.)
ec = C + ^ (3.16b)
This suggests that when ec is plotted against TW, a straight line

should emerge with a slope of ^G. When such a plot is prepared in the
case of filled polymer systems, an interesting behavior is observed [66]
as can be seen from Figure 3.4(b). The corrections for various
concentrations of glass beads in polypropylene have been plotted. It
can be seen that the correction term decreases with increasing filler
volume concentration at constant shear, with the exception of the filled
polypropylene system containing 26 vol.% of glass beads. The
decreasing trend of the correction term with increasing glass beads is
consistent with studies such as the one using glass bead filled styrene
acrylonitrile (SAN) systems [67]. The decreasing trend indicates that
the amount of stored energy must be decreasing and hence the
recovered energy or die swell would also decrease with increasing
glass bead volume fraction. This was indeed found to be the case [66]
when a few measurements of die swell were qualitatively compared.
The slope ec vs. TW lines are seen to be constant, except for </> = 0.21
and hence can be assumed to be independent of glass bead
concentration [66]. In the case of glass bead filled SAN systems,
however, the ec vs. TW lines are highly non-linear [67].
The capillary rheometer can be used for estimating the normal stress
difference using the total ends pressure loss [65,68] and the exit
pressure loss [69-71], wherein the latter has a more rigorous
theoretical basis. However, the assumption of fully developed flow
existing up to the tube exit may not hold true, especially in slow flows
[72] and the errors introduced by the velocity field distortions at the
exit may prove significant.
3.2.2 CONSTANT PLUNGER SPEED SLIT ORIFICE CAPILLARY

RHEOMETER
This rheometer is similar in all respects to that discussed in section 3.2.1
except for the fact that it has a slit orifice cross-section rather than a
circular one. The major credit for the development of the concept and
use of this rheometer goes to Han [69,71,72] though others [73] have
also used it for polymer melt studies. The instrument makes use of a
series of flush mounted transducers located along the flow channel wall
which measure the pressure gradients along the flow direction. These
are then converted into wall shear stress values [69] as follows:
TW =fro^ (3.17)
dX
where b0 = half thickness of the channel.
The wall shear rate is determined from the following expression
given in Refs 14 and 69:
y 3Q T2 lln(3Q/4^)1
7w
~4fl 0 *d3 + 3 lnr w J (3 18)
'
where U0 is the half width of the channel.
In general, this instrument is capable of providing data in the higher
shear rate ranges comparable to those obtainable from the circular
orifice capillary rheometer described in section 3.2.1. Using exit
pressure losses, this instrument can also be used for determination of
normal stresses. However, the probable velocity-profile distortions at
the exit may introduce errors that may not be negligible though
experimental evidence based on limited data [26,71] suggests otherwise.
3.2.3 CONSTANT SPEED SCREW EXTRUSION TYPE CAPILLARY

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

RHEOMETER (MELT FLOW INDEXER)
This rheometer is also similar to the one described in section 3.2.1
except for two differences. Firstly, the capillary used is of very short
length and secondly, the polymer is extruded by the use of dead
weights (i.e. constant pressure) rather than constant plunger speed. This
instrument, popularly known as the Melt Flow Indexer, is very popular
in the thermoplastics industry due to its ease of operation and low cost,
which more than compensates for its lack of sophistication. The
parameter measured through the melt flow indexer contains mixed
information of the elastic and viscous effects of the polymer. Further,
no end loss corrections have been developed for this capillary
equipment nor can the melt flow index be easily related to the
Weissenberg-Rabinowitsch shear rate expression.
In most monographs and texts on polymer rheology, the Melt Flow
Indexer has been treated in a very brief manner because it has
generally been considered as an instrument meant only for quality
control. It was specified as a standard rheological quality control test
in the ASTM, BS, DIN, ISO and JIS (see Appendix D, Abbreviations
list for complete forms of these standards). However, it has been
shown in the recent past [80] that the Melt Flow Indexer provides
more than just a quality control rheological parameter. In fact the book
on Thermoplastic Melt Rheology and Processing [81] shows the multiple
uses of the data from the Melt Flow Indexer, and treats this particular
instrument in the utmost detail. Hence, in the present book the Melt
Flow Indexer and the Melt Flow Index are discussed rather briefly;
and readers are encouraged to refer to the other book [81] for more
comprehensive discussion on the subject.
The basic principle employed in the MFI test by any of the
standards is that of determining the rate of flow of molten polymer
through a closely defined extrusion plastometer whose important parts
are shown in Figure 3.6. The cylinder is of hardened steel and is fitted
with heaters, lagged, and controlled for operation at the required
temperature with an accuracy of ±0.5°C. The piston is made of steel
and the diameter of its head is 0.075 ± 0.015 mm less than that of the
internal diameter of the cylinder, which is 9.5mm. The die (or 'jet')
has an internal diameter of 2.095 ± 0.005 mm or 1.180 ±0.005 mm
(depending on the procedure used) and is made of hardened steel. All
LOAD
PISTON
BARBEL
HEATER A 3NSUIATEQN
REMOVABLE DIE
POLYMER
Figure 3.6 Schematic diagram of the melt flow index apparatus showing a cross-
sectional view of the important parts.
surfaces of the apparatus which come into contact with the molten
polymer are highly polished.
MFI is basically defined as the weight of the polymer (g) extruded
in lOmin through a capillary of specific diameter and length by
pressure applied through dead weight under prescribed temperature
conditions. ASTM D1238 specifies the details of the test conditions as
summarized in Appendix B for commonly used polymers. The test
conditions include temperatures between 125 and 30O0C and different
applied dead loads from 0.325 to 21.6kg giving pressures from 0.46 to
30.4kgf/cm2. The specifications have been selected in such a way as to
give MFI values between 0.15 and 25 for reliable results. ASTM D1238
gives the accuracy of the MFI value obtainable from a single measure-
ment as carried out by different operators at different locations to be
in the range of ±9 to ±15% depending upon the magnitude of the
MFI.
3.3 EXTENSIONAL VISCOMETERS

The rotational viscometers and the capillary rheometers described in
sections 3.1 and 3.2 are those applicable for shear flows. However, there
are processing operations that involve extensional flows. These flows
have to be treated differently for making measurements of extensional
viscosity. The extensional viscosity of a material is a measure of its
resistance to flow when stress is applied to extend it. In general,
measurement of steady-state extensional viscosity has proven to be
extremely difficult. Steady extensional rate would be achieved by
pulling the ends of the sample apart such that / = I0 exp(ef) or in other
words, at a rate that increases exponentially with time. Steady-state is
reached when the force is constant. However, often the sample breaks
before steady-state is achieved or the limits of the equipment are
exceeded or at the other extreme, the forces become too small for the
transducer to differentiate between noise and response signal.
Nevertheless, there have been various methods attempted for the
measurement of extensional viscosity.
3.3.1 HLAMENT STRETCHING METHOD

The most common method for measurement of extensional viscosity is
to stretch the filament of material shown in Figure 3.7 vertically as done
by Ballman [82] or horizontally as done by Meissner [83]. The polymer
must have a high enough melt viscosity of 104 Pa.sec or greater in order
to be amenable for such extensional experiments.
Hence such data are restricted to high viscosity polyolefins such as
polyethylene and polypropylene rather than low viscosity nylon and
polyester. Further, the deformation rates are to be maintained at low
values to prevent breakage of filament and hence the deformation
rates are limited to 5 sec"1 or less.
In the method of Ballman [82], which has been used by others
[84,85], a vertical thermostated filament is clamped at both ends and
stretched at the rate dl/dt such as to maintain a constant deformation
rate. Thus,
,-i*
(a) VERTICAL FILAMENT STKBTCHING
CB) HORIZONTAL FILAMENT STKCTCHINO
Figure 3.7 Schematic diagram showing the principal features of the filament
stretching method for extensional viscosity measurements: (a) vertical filament
stretching; (b) horizontal filament stretching.
In the method of Meissner [83], a horizontal filament immersed in
thermostated immiscible oil is held at both ends between pairs of
toothed wheels rotating with a linear velocity of V/2. Thus,
deformation rate is written as,
i= V/2= V
(3 20)
ik J -
There are other variations of the filament stretching technique. For
example, filaments are clamped at one end and taken up on a rotating
roll [86,87]. This reduces the amount of filament stretching to a more
uniform level and produces a more constant extensional rate. In fact,
when the following filament is taken up on a cold roll [87] a better
constancy in the extensional rate is obtained.
Extensional viscosity based on constant stress measurements [88]
has also been reported [89,9O]. In one case [89], the filament is
extended vertically on top of a bath whereas in the other case [90], the
vertical sample is immersed in the bath. The commercial equipment
available for the measurement of extensional viscosity from
rheometrics is based on the latter [9O].
A new universal extensional rheometer for polymer melts has been
described by Munstedt [91]. It was specifically designed with the idea
of making measurements on small samples possible in research
laboratories under a variety of physical conditions, e.g. at constant
stress or constant stretching rate, as well as relaxation and recoil
experiments.
The rotary clamp consisting of a pair of gears is a basic construction
element for the design of various types of extensional rheometer
described earlier. The fact that the design is amenable for use in
uniaxial and biaxial extensional rheometry has been shown by
Meissner et al. [92]. Other biaxial extensiometers have also been
described [93,94] by other researchers.
A method for measurement of viscoelastic properties of polymers in
the prestationary extensional flow has been investigated by Leitlands
[95]. A special experimental device using a vibrorheometer with
automatic control has been suggested. Some other methods of experi-
mental studies with regard to the extension of polymer melts have
been discussed by Prokunin [96]. In terms of uniform extensional flow
of polymers, a rather comprehensive review is that of Petrie and Dealy
[97] which may be referred to for further information on the subject.
3.3.2 EXTRUSIONMETHOD
A typical example of extensional flow is the flow at the entrance of a
capillary die. Besides the converging flow analysis of Cogswell [98,99],
there have been other analyses [100,101] in more recent times which are
improved versions of the same ideas, and these can be used as better
alternatives especially when dealing with filled polymer systems.
Cogswell [102] has shown that the pressure losses through such dies
can be used as a measure for the extensional viscosity. This method has
not gained popularity because of the skepticism in accepting the
complex converging flow patterns at the die entrance as representative
of true extensional flow with constant extensional rate. Cogswell [103]
did suggest later that the die ought to be lubricated to reduce the shear
flow and the profile of the die wall should vary at all cross-sections in
such a way as to ensure constant extensional rate along the die axis.
Such a rheometer has been known to be developed and used for
extensional viscosity data of polystyrene melt [104].
The extrusion method using a lubricated die [104,105] allows the
measurements of systems with viscosity levels as low as 102Pa.sec.
Thus, it can be used for extensional viscosity determinations in the
case of nylon and polyester which are often spun to make synthetic
fibers. Higher extensional rates, even 200 sec"1 are also achievable in
this apparatus [104,105], thus making the information relevant for the
polymer processing industries involved in fiber spinning.
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Constitutive theories
and equations for A
suspensions H"
4.1 IMPORTANCE OF SUSPENSION RHEOLOGY

A suspension is a system in which denser particles, that are at least
microscopically visible, are distributed throughout a less dense fluid
and settling is hindered either by the viscosity of the fluid or the
impacts of its molecules on the particles. In the present terminology of
filled polymer systems, the fillers form a disperse phase and the
softened or molten polymers form the continuous phase and together
they could represent a suspension. However, suspension rheology does
not normally refer to filled polymer rheology. In fact, it commonly
discusses the rheological behavior of two-phase systems in which one
phase is solid particles like fillers but the other phase is water, organic
liquids (e.g. benzene, fuel oil) or polymer solutions. These systems are
much easier to study than filled polymer systems as the preparation
and rheological characterization of the systems can be done at room
temperature. Further such systems are encountered in a number of
areas other than polymer technology, namely, biotechnology [1-17],
cement and concrete technology [18], ceramic processing [19], coal
transportation [20-28], coating and pigment technology [29-32], dental
research [33-38], propellants and explosive science [39], poultry waste
handling [40,41], mineral processing [42-46], soil science [47] and
various slurry flow technology [48]. Hence, the rheology of suspensions
has received a lot of attention.
There are a number of reviews [49-61] which discuss various aspects
of the rheology of suspensions and may be referred to for detailed
study. In the present chapter, the topic is touched upon rather briefly
and only certain aspects are discussed in a limited manner just enough
to lay the foundations for understanding the basics of filled polymer
rheology.
Suspensions basically show strong departures from simple
Newtonian laws of fluid flow and hence form complex rheological
systems. When the dispersing medium is a Newtonian fluid or behaves
like one under a given range of shear rates, then the suspension exhibits
Newtonian behavior at low concentration of solids and non-Newtonian
behavior with increasing concentration. When the suspending medium
is a polymer solution which itself is non-Newtonian in character, the
presence of solid particles magnifies the complexities of its rheological
behavior.
The important rheological properties which need to be studied and
measured in order to be able to characterize suspensions are the same as
those which have already been indicated in Chapter 2. However, only
the viscous flow behavior in shear and extensional flow will be discussed
in this chapter. In particular, shear viscosity will be dealt with in
sufficient detail because of the wealth of information that exists on it.
4.2 SHEAR VISCOUS FLOW

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

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

Einstein [63-65] was the pioneer in the study of the viscosity of dilute
suspensions of neutrally buoyant rigid spheres without Brownian
motion in a Newtonian liquid. He proposed the following relationship
between the relative viscosity of the suspension rjr and the volume
fraction of the suspended particles 0
>7r = l + aE0 (4.1)
where rjr is the ratio of the viscosity of the suspension rjs to the viscosity
of the suspending medium q0 and aE is Einstein's constant. aE equals 2.5
when the suspended particles are neutrally buoyant, hard and spherical
in shape, the mean interparticle distance is large compared to the mean
particle size, the particle movement is so slow that its kinetic energy
can be neglected and there is no slip relative to the particle surface.
Experimental determinations of Reiner [66] and Kurgaev [67]
revealed that for filler concentrations of </> = 0.003-0.05, aE was indeed
equal to 2.5. Rutgers [68] concluded through experimental evidence that
equation (4.1) with aE = 2.5 was valid for values up to 0 < 0.1.
However, a slight disagreement in the value of aE = 2.5 was established
from the works of Hatschek [69], who theoretically found that aE — 4.5
for (j) = 0-0.4 and Andres [70] who found that for dilute magnetic
suspensions aE = 4.5 for (/> = 0-0.09. In fact Kurgaev [67] showed that
when (j) = 0.15-0.18, aE = 4.5-4.75 depending upon the nature of the
solid particles. The disagreement was accentuated when Happel [71]
suggested a value of aE — 5.5 and Pokrovskii [72] a value of 1.5. It was
revealed by Kambe [73] that the lack of agreement among the
experimental results was due, among other things, to differences
between the dimensions of the particles under study and the velocity
gradients used for the experiments. It appears that for solid spheres
with diameters large enough compared to the molecular dimensions
but small enough compared to the characteristic length of the
measuring instrument and for no slip at the sphere surface, the value of
aE = 2.5 is generally accepted though values ranging from 1.5 to 5.5
have been suggested.
Based on the theoretical analysis of Simha [74] for concentrated
suspensions. Thomas [75] proposed the following expression for dilute
suspensions ($ < 0.1)
n, = l + 2.5<t>(l +^JjJ (4.2)
where U1 is an empirical coefficient whose value lies between 1 and 2.

Thomas [75] suggested that U1 = 1.111 for </> < 0.15. Simha and
Somcynsky [76] suggested that the expression (4.2) proposed by
Thomas [75] could be written as follows:
i/r = 1+2.5^1(0) (4.3)
where
*<>-(>^>
when higher terms in 0 in the expression suggested [76] are dropped.
When (j) = 0.10, however, higher terms in (/> are not negligible and to
compensate for this, Thomas [75] had to use the value of ^1 — 1.111
when actually U1 = 1.85 in the unapproximated expression of A((/>) gave
excellent results.
Ford [77] modified Einstein's equation (4.1) using a binomial
expression and wrote
-=l-aE0 (4.4)
'Ir
where l/rjr is defined as the fluidity and is equal to zero when

4> = l/a E . Equation (4.4) has been shown to be valid for 4> < 0.15 by the
experimental data of Cengel et al. [78].
Though there is varied opinion about the relationship between the
relative viscosity of a suspension and the volume concentration of the
spheres for dilute suspension, one could get a reasonable estimate on
using the simplest equation (4.1) of Einstein for 0 < 0.1. When
0.1 < (f> < 0.15, Thomas's [75] equation (4.2) or Ford's [77] equation (4.4)
could be used for a reliable estimate. Of course for 0 < 0.1 too, these
equations could be used and the result averaged out with the prediction
from equation (4.1) to obtain a good conservative estimation.
(b) Concentrated suspension

Generally, when 0.1 < 0 < 4>m the suspensions are considered to be
concentrated and the above discussed equations do not apply. Here 0m
is defined as the maximum attainable concentration and has the
following form: 0m = 1 — e, where e is the void fraction or porosity, and
is defined as the ratio of the void volume to that total volume.
Theoretically, the value of </>m is 0.74 for equal spheres in compact
hexagonal packing, but in practice it is more like 0.637 for random
hexagonal packing or 0.524 for cubic packing ([79]).
When the filler concentration is increased, various phenomena take
place, for example (i) the number of particles per unit volume which
come in contact during the flow increases, (ii) the interparticle attraction
and repulsion effects become stronger due to electrostatic charges,
which depend upon the polarity of the medium, (iii) the rotation of the
particles during flow, as well as the formation of doublets and their
rotation during flow, produces additional dissipative effects which lead
to an increase in the viscosity.
Unlike the dilute suspensions, the size of the filler drastically changes
the viscosity behavior of concentrated suspensions. De Brujin [80]
showed that when the filler diameter is less than 10 (am, a concentrated
suspension exhibits non-Newtonian behavior and the viscosity
increases with a decrease in the filler diameter. Clarke [81] found that
for a filler diameter greater than 10 jam, the viscosity increases linearly
with the diameter. For spheres, with increasing diameter the lateral
displacement of the particles towards the centre of the tube (central
tube effect) increases, thereby increasing the energy dissipated resulting
in a tendency for the viscosity of the suspension to increase with
increasing diameter.
As there are many-fold effects of increasing the concentration of the
fillers, a variety of physical models have been proposed but most of
them (theoretical or experimental) can be expressed by the nonlinear
relationship between rjr and c/> in the following power series form as
given in Thomas [75]
*/r = 1 + a a 0 + a2(/>2 ± a3(/>3 ± ... (4.5)
where (X1 is generally assumed to have a value of 2.5 as given by
Einstein [63], while the coefficients a2, a 3 ,... have been assigned
different values by different authors. For example, the value of a2 was
14.1 as determined by Guth and Simha [82], 7.349 by Vand [83], 12.6 by
Saito [84]. 10.05 by Manley and Mason [85] and 6.25 by Harbard [86].
These varied values of a2 are the result of taking into account one or
several effects appearing due to the increase in solid concentrations.
Similarly, a3 values of 16.2 and 15.7 have been proposed by Vand [83]
and Harbard [86], respectively. Alfrey [87] has also developed
relationships of the power series form (4.5) and enlisted values of a,-
based on the works of Arrhenius [88], Fikentsher and Mark [89],
Bungenberg de Jong et al [90], Papkov [91], Hauwink [92] as well as
Brede and De Boojs [93].
As an example of the use of equation (4.5) to determine the viscosity
of suspensions, one can refer to the works of Mullins [94] and Feldman
and Boiesan [95] on rubbers containing fillers which are chemically
inactive like wood flour or chemically active like carbon black. When
the filler introduced is chemically inactive (with any (/>) or chemically
active (with 0 < 0.10), the quadratic form of equation (4.5) with Oc1 = 2.5
and oc2 = 14.1 could be used to give a good estimate of the viscosity of
the suspension. For higher concentrations of the chemically active filler
(carbon black), particle interaction begins and the viscosity of the
suspension increases markedly and equation (4.5) as such cannot then
be used for an estimate. However, if particle interaction leads to
agglomeration, then Mullins [94] and Feldman and Boiesan [95]
recommend the use of Oi1 = 0.670, and a2 = 1.620? in equation (4.5),
where a{ is the index of asymmetry of the elastomer macromolecules.
The main drawback of equation (4.5) is that the termination of the
series after 02 term means an error of 10% or more in the relative
viscosity for </> > 0.15-0.20. The validity of the series increases to
(j) cz 0.40 on the inclusion of <£3 term. However, the values of the
coefficients of higher order terms are less accurate since they must include
more complicated interactions than it is theoretically possible to treat.
Based on the work of Eyring et al. [96] who suggested that the term
OC3^3 in equation (4.5) should be of the exponential form, Thomas [75]
arrived at the following expression
r\r = I + 2.5(1) +10.05</>2 + 0.00273 exp(16.6<£) (4.6)
Thus a closed form expression is obtained which fits experimental data
as well as the power series form with three or four adjustable
coefficients. The validity of expression (4.6) is for a filler concentration
varying between 0.15 and 0.60.
Another power series type of expression is given by Ford [77], who
added higher order terms to his expression (4.4) for dilute suspensions,
making use of the data of Vand [83], to give
- = 1 - 2.50 + 11<£5 - 11.5</>7 (4.7)

*ir
He suggested that the inclusion of the term </>5 takes into account the
onset of the inhibition of particle rotation, and the term ^7 takes into
account the onset of particle interlocking.
Mooney [97] proposed that at very high concentrations an Arrhenius
type equation (with the addition of crowding factor (1 — ac</>)) of the
following form could be used:
*-«*&]
where ac has a value between 1.35 and 1.91. Mooney's relationship
has been known to be in good agreement with experimental data
([66], [98]).
The empirical expression (4.3) as suggested by Simha [74] can also be
used for concentrated suspensions if the relationship for A(</>) given by
him is not approximated and all the higher order terms in <f> are
retained. Simha's analysis was based on the idea that the neighbors of
each sphere in the suspension can be replaced by a rigid spherical
enclosure, and that the finite size of the particles effectively shields the
central particle from interaction with any other particle than the nearest
neighbors as the concentration is increased.
For concentrations up to </>m, experimental data are seen to validate
the following empirical expression obtained by Eilers [99]
* r = [ l + n 1^ J (4-9)
L (1 - 0/0m)J
Note that for </> -> 0m, r\r ->> oo and rightly so.
Frankel and Acrivos [100] did away with all empiricisms and
artificial boundaries and provided an expression for highly
concentrated suspensions of uniform solid spheres intending to
complement the classical Einstein's equation (4.1) valid only for very
dilute suspensions.
Their final result is written as follows:
9 0Mn)178 (410)
(4 10)
"'-81-OMA n T '
With so many theoretical expressions (4.5) to (4.10), it is increasingly
difficult to make a choice between them and decide which one would
give the most reliable estimate for the relative viscosity of a
concentrated suspension. For concentrated suspensions, it is necessary
to account for the hydrodynamic interaction of particles, particle
rotation, particle collisions, doublet and higher order agglomerate
formation and mechanical interference between particles as packed bed
concentrations are approached. Different authors have taken into
account one or several aspects mentioned above during the derivation
of their theoretical expressions. For concentrated suspensions of
uniform solid spheres, the use of expression (4.6) of Thomas [75] is
recommended for 0.15 < </> < 0.60 and the expression (4.10) of Frankel
and Acrivos [100] for 0 -> <£m to obtain reliable estimates.
Though equation (4.10) predicts the correct experimental trends at
large values of $ -> </>m, it does not reduce to equation (4.1) when
0 ^ 0 . Further, the averaging process used for deriving equation (4.10)
has been shown to be incorrect [101] and it has been argued that the
dissipation in pair interactions is too small to explain the observed
trends. But since equation (4.10) does fit experimental data rather well
for high solids concentrations, it can be simply considered as yet
another empirical equation.
Attempts [102-104] to fit the entire range of volume fraction from
(j) -* O to 0 -> 0m have resulted in equations which give a unique curve
through the use of a plot of relative viscosity versus the ratio of 4>/4>m.
The work of Chong et al. [102] has shown a good fit between
experimental results and an equation of the following type:
'"Mi^fc)]'
0m is normally determined from the experimental data. It is to be noted
that equation (4.11) reduces to equation (4.1) at low values of (/) when
(J)n takes a value of 0.6.
One of the best available empirical expressions which fits the entire
range of volume fraction, is the Maron-Pierce type equation that was
carefully evaluated by Kitano, Kataoka and co-workers [103,104], and
extensively tested by Poslinski et al [105,106].
rjr = [1 - 4>/(t>m}-2 (4.12a)
For suspensions of smooth spheres, a value of 0m = 0.68 has been
suggested [107] and a value of 0m = 0.60-0.62 has been determined
through liquid displacement experiments [105,106]. In reality, of course,
using ^1n as 0.6 or 0.62 or 0.68 does not improve the data fit appreciably.
But at times it may be best to view </>m as an adjustable parameter and
then equation (4.12a) is rewritten as follows:
iyr = (1 - <£/Apr2 (4.12b)
The adjustable parameter Ap is now considered to give some measure
of the thickness of the immobilized polymer adsorbed on the filler
surface and thereby indicates the affinity of the polymer for the filler
[108].
B. Ellipsoidal particles
The theory of the viscosity of dilute ellipsoidal suspensions without
Brownian motion was developed by Jeffrey [109]. He observed that
Einstein's equation (4.1) could be used to estimate the viscosity by
appropriately defining the Einstein constant aE. Jeffrey [109] has
tabulated the values of aE for prolate and oblate spheroids. He found
that aE depended on the ratio of the semi-axes of the ellipsoid of
rotation.
For a prolate spheroid, Guth [110,111] developed the following
relationship based on Jeffrey's theory [109] when the axis ratio re ^> 1.
Thus,
>7r = l + a rl 0 + ar2</>2 (4.13)
where
«"=<2tafe>) + 2 <4
"a)
-01&
Pokrovskii [112] demonstrated theoretically that concentrated
suspensions of solid ellipsoidal bodies in a Newtonian fluid give rise to
a viscoelastic behavior. He showed that for such suspensions it is
possible to use the concept of transverse viscosity which expresses the
effect of normal stresses and found that the transverse viscosity
increases with velocity gradient.
C. Rod-shaped particles
Suspensions of rod-shaped particles have received greater attention
than ellipsoidal particles due to the obvious increasing demand for
fiber-reinforced plastics. Exact theories exist for the viscosity of very
dilute suspensions of rod-shaped particles. However, this is not the case
for higher concentrations. The reason is evident from the fact that
differences in viscosities of suspensions of different shaped particles are
small at low concentrations. With an increase in the concentration,
particle rotation causes the frequency of contacts between adjacent
particles to increase, resulting in an increase in the viscosity (Figure
4.1). For rod-shaped particles, the above effect is accentuated with an
increase in the aspect ratio as can be seen from the work of
GLASS RODS
GLASS PLATES
QUARTZ GRAINS
GLASS SPHERES
EINSTEIN'S EQUATION
Figure 4.1 Effect of concentration on the relative viscosity of different shaped

particles in water at a shear rate of 327.7 sec~1. (Reprinted from Ref. 81 with kind
permission from The Institution of Chemical Engineers, Rugby, UK.)
Maschmeyer and Hill [113] who showed that the presence of only a few
percent of relative long fibers in the particle distribution doubled or
tripled the suspension viscosity. From the work of Clarke [81] shown in
Figure. 4.1, it can be conclusively seen that the viscosity of a suspension
is higher for the same concentration of the particles for larger
departures in shapes from spheres.
In the case of dilute suspensions of rod-shaped particles, too,
Einstein's equation (4.1) can be used with the appropriately defined
constant <XE. Burgers [114] has established the following relationship for
straight rigid rod-shaped suspensions under shear
(415)
^^l-1.8)] ^^
where ra is the aspect ratio (/P/D) and 6 and \l/ are the spherical
coordinates giving the orientation of the rod (see Figure 4.2). Burgers
[114] found that rod-shaped particles (and also elongated ellipsoidal
particles) cause an increase in the Einstein's coefficient with increasing
aspect ratio (ra) as shown in Figure 4.3, for randomly oriented particles
such as would occur at very low rates of shear. At high shear rates, of
course, orientation of the rods would result in a decrease in the effective
value of the Einstein coefficient.
Figure 4.2 Coordinate system for a rigid rod in a field of simple shear.
Figure 4.3 Einstein's coefficient as a function of the aspect ratio of randomly
oriented rod-shaped particles,
For dilute suspensions in rotational motion, Mason [115] gave the

following expression for critical concentration $cr below which the
interaction between the rods can be neglected. Thus,
0 c r -¥ (4.16)
â
Blankeney [116] observed that below this critical concentration the
relative viscosity of a rod-shaped particle suspension increases slowly
and linearly with $. A slight non-linear region then follows after which
the relative viscosity increases rapidly. Experimentally, it was found
that the value of (/>cr depended .upon the nature of the solid phase. For
example, Clarke [81] found that for glass rods </>cr = 0.15 and for PMMA
spheres 0cr = 0.40.
For concentrated suspensions of rod-like particles (i.e. for <j> > 0cr),
the following relationship was suggested by Simha [117] and later
verified by Blankeney [116]
>7r = l + aE</> + a(aE(/>)2 (4.17)
For randomly oriented rods with purely hydrodynamic interactions
between them, Simha [117] determined the value of a to be equal to
0.73.
For concentrated fiber suspensions in tube flow, Brodnyan [118]
suggested the following equation:
,, =expp+ o^.-i)"Vj (418)
but the experimental data of Brodnyan [118] themselves were not found
to fit for high concentration of suspension.
Taking into account the particle interaction and the degree of
flocculation, Ziegel [119] proposed the following equation:
3
-( f^>--)SI-
where Ji is an interaction parameter, /J0 is a rate constant for the
equilibrium between free particles and floccules and Z0 is the degree of
flocculation.
Hashin [120] used the flow-elasticity analogy to give the following
equation which was valid only for parallel, randomly placed infinitely
long fibers
^r = l +1-0
A (4-20)
Nielsen [121] used the same analogy, but his equation has not been
tested for concentrated fiber suspensions.
The shape of the rod (whether straight or curved) does affect the
relative viscosity of the suspension. The viscosity for curved fiber
suspension is known to be higher than that for a straight fiber
suspension and the difference increases with increasing concentration
(Figure 4.4).
4.2.2 EFFECT OF SIZE DISTRIBUTION OF THE PARTICLES

Clarke [81] observed that mixed suspensions of mainly coarse particles
and relatively few fine particles showed a marked decrease in the
viscosity compared to an all coarse suspension. Contrarily, suspensions
with mainly fine particles and few coarse particles showed very little
change from an all fine suspension. It could thus be concluded that
STRAIGHT FIBERS
CURVED FIBERS
Figure 4.4 Variation of the relative viscosity of suspensions with concentration for
(a) curved fibers and (b) straight fibers.
smaller particles are interposed between larger particles, causing a

reduction in the interparticle impact resulting in a decrease in viscosity.
Ward and Whitmore [122], Ting and Luebbers [123] and Moreland
[124] also noticed similar results using different techniques of
measurement.
Shaheen [125] suggested that the addition of a little amount of small
particles acts as a lubricant to facilitate the rotation of larger particles,
leading to a reduction in the relative viscosity. Experimentally, it was
shown that the viscosity of a mixture of two different-sized particles
goes through a minimum at about a volume fraction of small particles
equal to 0.25. Shaheen [125] wrote the modified form of Mooney's
equation (i.e. equation (4.8)) for a mixture of spherical particles of two
different sizes as follows:
= / 2/5</>a \ / 2.502 \ (421)

'~ Mr^Mi^^J
where
<-«fi?T®r
« _ Js1^nS
U
f (4.23,
\ Io / \ r/
Parkinson et al [126] arrived at a Mooney type equation for the

relative viscosity of a dispersion of polydisperse spheres containing /
size fractions as
/ \ / 2.5^1 \ / 2.502 \ / 2.50f \ ,,^,
<4 24)
"4E) -Mi^Mi=Iy-"(T=W '
where 015 0 2 ... 0f are the volume concentrations of each size fraction,
and the values of /C1, fc2... fcz are derived from an empirical equation of
the following general form
Ic1 = 1.079 + exp(0.01008/Dp/) + exp(0.0029/D*,) (4.25)
The above equation (4.24) is not suitable for a continuous distribution
of particle diameters and the equation given by Mooney [97] has to be
then resorted to:
rjr = exp (2.50 T Af"'' ) (4.26)

V Ja1 1-0T 1 ^d(T7./
where 0 is the total volume concentration of spheres, a;l the crowding
factor, Pf the particle size frequency function and alf O2 the upper and
lower limits of the dimensionless radius, respectively.
The two main difficulties in the use of equation (4.26) are that the
nature of oc;j is known only in special cases and hence the distribution
function to accurately describe the particle size distributions of different
grades of the same filler is almost impossible to find.
Hsieh [127] suggested a quadratic model of the following canonical
form for an M-component system of particle size distribution.
/M M \
Vr = exp ( Y, Bixt + £ V<*;) (4-27>

V i=l Ki^j '
where x{ is the weight proportion of the zth component in the blend of

the total number of M components. The coefficients B1 and B^ were
determined experimentally and for a tetramodal size distribution, Hsieh
[127] has given the derived expression from equation (4.27) which was
seen to agree well with the experiments for four basic aluminum
trihydroxides with distinctively different particle sizes in an
unsaturated polyester resin.
4.2.3 EFFECT OF THE NATURE OF THE PARTICLE SURFACE
Moreland [124] obtained viscosity data of suspensions of coal in mineral
oil during which he concluded that slurry viscosities for irregular
particles were greater than for spherical particles. A similar result was
obtained by Clarke [81], who showed that suspensions of sharp-edged
particles have a much larger viscosity than those of round-edged ones.
Roughened particles are likely to increase the viscosity of suspensions
in two ways: (a) primarily by harsh frictional contact and (b) secon-
darily, by trapping layers of inert liquid on its surface thereby causing
an effective increase in the concentration as suggested by Ward and
Whitmore [128].
4.2.4 EFFECT OF THE VELOCITY GRADIENT

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

In pipe flow of a suspension, the presence of a wall and a velocity
gradient causes the particles to migrate towards the tube axis and
correspondingly decrease the concentration of the solid phase near the
wall. This effect known as the wall effect has been observed by
Goldsmith and Mason [129] for suspensions of different shaped
particles in Poiseuille flow.
A consequence of the wall effect is the central tube effect wherein the
migration of the particles towards the tube axis causes an increase in
the solid phase concentration within a narrow region of about 0.6.R1
(where R( is the internal radius of the tube). The wall effect and the
central tube effect appear simultaneously and after a certain time from
the start of the flow due to the velocity gradient being set up. Segre and
Silberberg [130,131] have shown that these effects manifest themselves
only at small concentrations of the solid phase. These effects have been
taken into account during the estimation of the suspension viscosity of
PMMA spheres in a ternary mixture of water, glycerol and 1.3-
butanediol by Segre and Silberberg [132]. A detrimental effect in the
measurement of properties of a suspension, other than the viscosity,
could result due to the presence of the wall and the central tube effect.
Care should be taken during property measurements with probes
through tube walls as the measured quantities could easily be the
properties of the suspending medium rather than of the suspension.
The migration of the particles towards the tube axis due to the
velocity gradient also leads to a characteristic slippage at the wall
surface (Morrison and Harper [133]). A direct consequence of the slip is
the increased flow rate through the tube compared to that which would
occur if slip were absent. The value of shear rate calculated from the
famous Mooney-Rabinowitsch equation will, therefore, be erroneous
and a correction ought to be made as given by Jastrzebski [134].
B. Particle rotation
At high concentrations of the solid phase, the existence of a velocity
gradient results in rotation of the particles, followed by an increase in
the viscosity of the suspension. Concentrated suspensions are known to
exhibit non-Newtonian behavior and hence viscosity would change as
the shear rate (velocity gradient) changes.
It is generally assumed that the viscosity dependence on shear rate is
due to some structural changes in the suspensions such as the breaking
up of agglomerates during shear. For example, Chapman and Lee [135]
as well as Goel [136] found that, at low shear rates (y < lsec"1) talc-
filled polypropylene was more viscous than the base propropylene, but
such was not the case at higher shear rates (7 > lsec"1) wherein break
up of the network-like structure took place, resulting in the viscosity of
the talc-filled systems equivalent to that of propropylene alone. Similar
behavior was observed by Ferraro [137] for other systems.
Concentrated suspensions often exhibit a yield stress below which no
shear deformation takes place and after which the suspension could
behave as a Newtonian, pseudoplastic or dilatant fluid. Shear
dependent theories for such flows have been considered by Krieger and
Dougherty [138] as well as Gillespie [139].
4.2.5 EFFECT OF FLOCCULATION

The degree of flocculation of dispersed particles strongly influences the
rheology of suspensions ([14O]). The viscosity of the suspension is
known to increase sharply with flocculation, probably due to the
relative immobilization of a fraction of the suspended particles trapped
in the agglomerates. In shearing flow, both shear-thinning and shear-
thickening behavior have been observed. Govier and Winning [141]
found concentrated clay suspensions to be shear-thinning. Heywood
and Richardson [45] found that flocculated kaolin suspensions were
shear-thinning and could be characterized by the power-law model at
shear rates below 200OSeC"1. With increasing solid concentration, the
flow behavior index n was seen to fall progressively while the
consistency index K was seen to increase exponentially. At shear rates
above 2000 sec l, the behavior would be characterized by the Bingham
plastic model with the yield stress and the plastic viscosity increasing
monotonously with increasing solid concentration.
Dilatant behavior is observed in certain flocculated systems with
extremely high concentration of suspensions. Umeya and Kanno [142]
found that concentrated suspensions of titanium dioxide in water
stabilized with sodium pyrophosphate showed dilatancy. The effect of
shear history on the dilatant behavior is shown in Figure 4.5, and is
seen to be pronounced at high shear rates. A suspension deflocculated
by shear does not recover its structure immediately after the removal of
shear since the thermal energy of the particles is insufficient to
overcome the energy barrier for the flocculation. As the degree of
flocculation is decreased by applying high shear rates, the onset of
dilatant flow occurs, the dependence of apparent viscosity on shear rate
and the increase in the apparent viscosity decreases. Umeya and Kanno
[142] also found that dilatant behavior of flocculated systems did
UNTTS Water Shear Siren

Ctaatase, 4 »0.4 *) prrooudy appSed
Figure 4.5 The effect of shear histories on the flow properties of titanium dioxide
(TiO2) water 27.7% suspensions stabilized with 5mg/g TiO2 of Na4P2O7-IOH2O.
(Reprinted from Ref. 142 with kind permission from Society of Rheology, USA.)
depend upon the size of the particles as the degree of dispersion of
larger particles was better than that of smaller ones.
Hudson et al. [31] studied the time dependent effect of suspensions of
pigment particles. Experimental work was undertaken to relate steady,
transient and time dependent oscillatory flow in a unified manner.
Hudson et al. [31] also developed a theory to explain the suspension
behavior in terms of the structure formed as a result of flocculation. The
viscosity rjf of a homogeneous suspension of floccules containing NJ
floccules was given by
In^ = f(0 f ) + vIn(N{) (4.28)
>7o
where r]0 was the viscosity of the suspending medium, f was a function
of the volume fraction ($f) of the floccules in the suspension and v as a
constant. A comparison of the experimental data with the theory
enabled values of the model constants to be calculated.
4.2.6 EFFECT OF THE SUSPENDING MEDIUM

The nature of the suspending medium, whether Newtonian, viscous
non-Newtonian, viscoelastic or viscoplastic affects the viscosity of the
suspension. This has been the subject of research of a number of
workers.
Nicodemo et al. [143] studied the shear rate dependence of the
viscosity of suspensions in non-Newtonian liquids and compared it
with that of suspensions in Newtonian liquids. The relative viscosity,
when the suspending medium was Newtonian, decreased with
increasing shear rate toward an asymptotic value which was a function
of the filler content. The concentration dependence could be correlated
by equations given in section 4.2.1.
When the suspending medium was non-Newtonian, Nicodemo et al.
[143] found that the dependence of relative viscosity on shear rate was
similar and could be correlated by a modified form of the equation of
Krieger and Dougherty [138]. However, as the relative viscosity at high
shear rates did not fit the existing equation, Nicodemo and Nicolais
[144] searched for a mechanistic explanation. It was found that two
different mechanisms in the range of low and high shear rates,
respectively, existed for suspensions in polymeric solutions.
When the suspending medium could be described by the power-law
model, Kremesec and Slattery [145] derived the following expression
for the viscosity of a dilute suspension of spheres
If8 = (U-O0^)Ky"-1 (4.29)
The coefficient a0 was defined by the rate of energy dissipation within
the neighborhood of a typical sphere in the suspension. For n = \,
a0 = 2.5 could be easily derived as in Einstein's equation (4.1).
However, for n^\, the equations of motion, being nonlinear, are
difficult to solve and hence only the upper and lower bounds for a0 as a
function of n were obtained and compared with the available
experimental data of Highgate and Warlow [146] to find reasonable
agreement.
4.2.7 EFFECT OF ADSORBED POLYMERS
Polymers are often added as processing additives to suspensions used

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

behavior over the entire shear rate range. In contrast, at pH = 3.7 when
the zeta potential is approximately OmV, the silica suspension with no
PVA is flocculated, adjudging from the high viscosity and highly shear-
thinning behavior.
In Figure 4.7(a), it can be seen that initial additions of PVA result in
higher viscosity and greater shear-thinning characteristics, thus
indicating the occurrence of bridging flocculation at the low PVA
adsorption densities. With additional PVA adsorption, the trend
observed in Figure 4.7(a) is reversed as can be seen from Figure 4.7(b).
Beyond the adsorbed amount of 1.1 mg adsorbed PVA/g silica, the
bridging flocculation gives way to steric stabilization. Low suspension
viscosity, approximately Newtonian behavior over the entire range of
shear rate and absence of any yield stress are observed when the
adsorption of PVA is such as to ensure monolayer coverage of particles.
It is known that maximum flocculation occurs at approximately half
coverage of the particles [44,149]. In the adsorbed PVA/silica
suspension case, too, the maximum flocculation did occur at
approximately half coverage of the particles as evidenced from the
maximum value of the yield stress at that adsorption level as shown in
RELATIVE VISCOSITY
Amount Atf»0ib«d
SHEAR RATf (•"')

RELATIVE VISCOSITY
Amount Adaorfe**
SHEAU RATE (•'')
Figure 4.7 Variation of relative viscosity with shear rate for 20 vol% silica suspensions
prepared at pH = 3.7 with varying concentrations of poly(vinyl alcohol). The relative
viscosity vs. shear rate plot for an electrostatically stabilized suspension (pH = 7.0) with
no poly(vinyl alcohol) is also shown. (Reprinted from Ref. 19 with kind permission from
The American Ceramic Society Inc., Westerville, Ohio, USA.)
Figure 4.8. It should be noted that the amount of adsorbed polymer

depends not only on the overall suspension polymer-particle, polymer-
liquid and particle-liquid interactions. The adsorption densities are
known to depend on the amount of isolated or free surface hydroxyl
groups on the particles [150,151].
The effect of the adsorbed polymer in achieving different levels of
dispersion also depends on the 'goodness' of the solvent for that
polymer. For example, when the solvent is good, it is known [147,148]
that steric stabilization is promoted because the loops and tails of the
YIELD STRESS (Pa)
ABSORBEb AMOUNT (mg PVA/g Silica)

Figure 4.8 Variation of yield stress with adsorption density of poly(vinyl alcohol) on
silica for suspensions prepared at pH = 3.7 with 20 vol% silica and varying
concentration of poly(vinyl alcohol). Yield stress values were determined from shear
stress vs. shear rate curves. (Reprinted from Ref. 19 with kind permission from The
American Ceramic Society Inc., Westerville, Ohio, USA.)
polymer which extend out from the particle surface are well solvated.
When the solvent is not good for the polymer, then bridging
flocculation is likely to occur.
The effect of solvent quality on particulate dispersion was
investigated [19] using alumina (Al2O3)/poly(vinyl butyral) (PVB)
suspensions prepared in methanol (MEOH), which is a poor solvent,
and in a 3:1 volume ratio mixture of methyl isobutyl ketone (MIBK)
with MEOH, which is a better solvent.
Figure 4.9(a) and (b) shows the relative viscosity versus shear rate
behavior in these two solvents for varying PVB concentration from O to
2.0vol%. In either of the solvents, highly shear-thinning behavior is
observed when no PVB is added. These suspensions show poor stability
against flocculation due to relatively low zeta potentials (< 25 mV) and
therefore, low electrostatic repulsive forces [152].
The effect of PVB additions on the dispersion behavior can be seen
from Figure 4.9 to be dependent on the suspension liquid composition.
In MEOH suspension, though addition of PVB reduces the viscosity of
the suspension, the system is shear-thinning indicating that the
suspensions remain flocculated in poorer solvents for the added
CCMAMIC: 3O *«(% Al/>,
RELATIVE VISCOSITY LtQOIO : MCOH
SHCAP RATE (»-')
CCRAMtC: 3O v*l% *>}Oj

UOUID: 3:1. HMK'MCOM
RELATIVE VISCOSITY
SMEAA RATE U•')

Figure 4.9 Variation of relative viscosity with shear rate for 30 vol% alumina
suspensions prepared with (a) methanol and (b) 3:1 methyl isobutyl ketone/methanol
with indicated poly(vinyl butyral) concentrations. (Reprinted from Ref. 19 with kind
permission from The American Ceramic Society Inc., Westerville, Ohio, USA.)
polymer. In 3:1 MIBK/MEOH suspensions, PVB additions (0.5 to

2.0vol%) give much lower relative viscosity and almost Newtonian
behavior. A slight dilatancy has been observed which is not unusual
in highly loaded suspensions in which repulsive forces are large
[153,154].
The level of loading makes a lot of difference in the adsorption of the
polymer. It can be seen from Figure 4.10(a) that for 30 vol% AÔs, there
is only a small difference in the shear stress versus shear rate flow
curve for the two polymer concentrations of 0.25 vol% and 0.5vol%
CERAMIC : 30 V<*X AJjO3
UOlHD : 3:1, MAK MEOH
SMC ARSTfIESS(Pa)
SHEAR RATE U'1)
CtRAMtC : 45 «* % AI2O3
LIOiMD: 3:1, MBK/MCOH
SHEAR STRESS (Pat
SHCAM RATl U-1I

Figure 4.10 Variation of shear stress vs. shear rate for 3:1 methyl isobutyl ketone/
methanol suspensions prepared using (a) 30 vol% alumina and (b) 45 vol% alumina
with indicated poly(vinyl butyral) concentrations. (Reprinted from Ref. 19 with kind
permission from The American Ceramic Society Inc., Westerville, Ohio, USA.)
PVB. In both cases, approximately Newtonian behavior is observed and

the viscosities are relatively low, indicating that the suspensions are
well dispersed. However, when the filler loading is 45 vol% Al2O3, the
0.25 vol% PVB suspension shows a yield stress and an initial region of
highly shear-thinning behavior, indicating that the suspension is highly
flocculated at low shear rates (Figure 4.10(a)). This happens because
complete monolayer coverage of the Al2O3 particle does not occur at
this concentration of polymer. In contrast, the system is far better
dispersed when the 0.5 vol% PVB suspension is used, due to the higher
adsorption density.
4.2.8 EFFECT OF CHEMICAL ADDITIVES

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

Physical processes (e.g. crystallization) and chemical processes (e.g.
polymerization) are known to modify the viscosity of a suspension with
time.
For a crystallization process, for example, Mistry and Warburton
[156] have shown that if the solid phase concentration is small such that
in Water
SHEAR STRESS (Pa)
SHEAR STRESS (Pa)

Silane
Silane
in Water
SHEAR STRESS (Pa)
SHEAR STRESS (Pa)
Titanate UCA 12
Zircoaluminaie CAVCO UOD APG
SHEAR RATE (1/s)
Figure 4.11 Variation of shear stress vs. shear rate for suspension prepared with
20 vol% alumina in distilled water along with (1 wt% of filler) various surface modifiers
as indicated. (Reprinted from Ref. 155.)
Einstein's equation (4.1) holds and the crystals in the disperse phase
increase with time, the relative viscosity can be estimated from the
following expression.
i?r(0 = l+a E (0o+*oO (4.30)

where ^0 is the initial volume of the crystals, X0 the rate constant for
volume increase of the crystals and t the time. Similarly, for
concentrated suspensions, expressions like (4.6), (4.7) or (4.8) could be
in Water
SHEAR STRESS (Pa)
Zircoaluminate
CAVCO MOD APG
DI Water
SHEAR RATE (1/s)

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

(/>0 H- K^t.
4.2.10 EFFECT OF AN ELECTROSTATIC FIELD

When suspension particles are charged, the electroviscous effects that
arise strongly influence the viscosity of the suspension as was shown
by the experiments of Fryling [157] as well as Krieger and Eguiluz
[158]. Pseudoplastic as well as dilatant behavior was observed in the
data of Fryling [157] and when the electroviscous effects were at their
maximum, the suspensions of Krieger and Eguiluz [158] were seen to
have a yield stress. Electroviscous effects are essentially of three types -
first, second and third, and are discussed in detail by Conway and
Dobry-Duclaux [159].
The combined effect of the three electroviscous effects on the
viscosity of a suspension can be written as follows:
fr = l + (*vl +**+**)* (431)
where evl,ev2 and ev3 correspond to each of the three electroviscous

effects. Separation of the constituent effects is difficult but was attempted
by Dobry [16O]. The three effects are discussed below separately in
order to appreciate the influence of each one of them on viscosity.
A. First electroviscous effect
The first electroviscous effect is due to the electrostatic contribution of
charged colloidal particles and its effect on the viscosity of a dilute
suspension can be expressed in an extension of Einstein's equation (4.1)
as follows:
>/r = l + a E <Kl+O (4.32)
Smoluchowsky [161] and Booth [162] both accounted for the increase in
viscosity as due to the electrical double layer round a charged particle
in an electrolyte and gave expressions for ev which included the specific
conductivity of the electrolyte, the dielectric constant of the suspending
medium, the electrokinetic potential of the particles with respect to the
electrolyte and the radius of the particle (which was to be large in
comparison with the thickness of the double layer for the validity of the
expression). Experimental verification by Chan and Goring [163] of the
expressions for ev provided by Smoluchowsky [161] and Booth [162]
gives confidence for their use.
B. Second electroviscous effect

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

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

Addition of fillers during the spinning of synthetic textile fibers and the
phenomenon of drag reduction with fibers inculcated an interest in the
study of the rheological properties of suspensions in extensional flows.
The first of such studies was that of Bachelor [166,167], who provided
expressions for extensional viscosity of suspensions with long slender
particles subjected to extension. The analysis of Batchelor [166] resulted
in the following expression for suspensions which are so dilute that the
velocity field surrounding one particle remains unaffected by
neighboring particles. Thus,
. L 2 ^ |"0.64 + ln2ra 1.659 / 1 YIl ^ 00 .
=3 1+ + + (433)
^ ^| 9i^LT5Ti^ ^^ Hai^)jl
YIQ denotes the viscosity of the suspending medium, $ the volume
fraction of the particles having an aspect ratio ra. It is obvious from
equation (4.33) that particles with large aspect ratios would give large
values of the extensional viscosity even at small concentrations of the
particles.
Batchelor [167] considered the effect of hydrodynamic interaction of
parallel elongated particles in pure extension on the bulk stress. The
governing equations were solved under the assumption that the effect
on one particle by all the others could be replaced by a cylindrical
boundary condition (cell model) and the geometry and concentration of
the particles satisfied the following inequality.
ra > d > I (4.34)
where d = Hf/Df (Hf being the average distance between the fibers and
Df the diameter of the fiber). The resulting expression for extensional
viscosity was as follows:
i+ (435)
*•=^ [ yy
Equation (4.35) predicts the extensional viscosity only for high
concentrations and does not give results akin to equation (4.33) at lower
concentrations. However, at an intermediate concentration of the
suspended particles, both theories are known to predict nearly identical
results and hence in this region the extensional viscosity can be
estimated by interpolation.
An expression similar to the above was obtained by Insarova [168]
for the extensional viscosity of uniformly distributed rigid rods
subjected to axially symmetric extension as follows:
(436)
*-^°H(*-£*-i)]
Insarova [168] showed by calculation that for a particle with an
aspect ratio ra = 50, the viscosity is increased by a factor of 4 for
0 = 0.01 and by 80 for (/> = 0.1. Equation (4.36) has not been tested with
experimental data but the equations of Batchelor [166,167] have been
the subject of experimental verification.
With the then available data of Weinberger [169], Batchelor [166,167]
compared the bulk stress in a suspension of glass-fiber rods (with
(/> = 0.013) in each of the liquids, 'Indopol' and 'Silicone' but found that
the extensional viscosity was much higher than that predicted by the
close-particle theory. Later, Weinberger and Goddard [170] noted that
suspensions used in Weinberger's work neither satisfied the dilute-
suspension nor the close-particle description, but fell somewhere
between the two. Proper interpolation was shown to predict that the
tensile stress was 8.4 times that of the suspending medium from
Batchelor's theory and was found to be in good agreement with the
values of 9 to 10 found by Weinberger and Goddard [170] through
experiment.
Mewis and Metzner [171] studied the extensional flow of fiber
suspensions (with 0.001 < </> < 0.01) and large aspect ratios
(280 < ra < 1260). Experimental data showed that the extensional
viscosities were independent of strain rate and up to 260 times larger
than that of the suspending medium. The effect of particle con-
centration was as predicted by equation (4.35) proposed by Batchelor
[167]. On the other hand, the effect of particle geometry was in close
agreement with the theory only for lower values of ra like 282 and 586,
but for ra = 1259 the experimental data were found to be about 30%
lower than that predicted by Batchelor [167].
Kizior and Seyer [172] experimentally determined stress levels in
extensional flow of suspensions with fibers having an aspect ratio of
340 and volume fraction of 0.001. It was found that the experimental
value of the stress was higher than that predicted by Batchelor's theory.
However, the dependence of stress on concentration and aspect ratio
was well predicted by the theoretical expressions of Batchelor [167].
From the above experimental efforts, it can be concluded that
sufficient evidence has been generated to verify the propriety of
equations (4.33) and (4.35) given by Batchelor [166,167]. Equation (4.33)
for dilute suspensions, equation (4.35) for close-particle distribution and
an interpolation between the two could predict the extensional flow
behavior of suspensions of slender particles over a large range of
particle concentration. However, the results of Batchelor [166,167] are
valid only when the suspending medium is Newtonian. The entire
body of literature which analyses the extensional flow of slender
particles in non-Newtonian fluids goes to the credit of Goddard
[173-175].
Goddard [173] derived a formula to describe the stress field for dilute
suspensions of oriented slender fibers in a non-Newtonian fluid. The
treatment was quite rudimentary but brought out an important result
that particle-stress effect was considerably smaller in a shear-thinning
non-Newtonian fluid compared to the Newtonian case, possibly due to
tensile stiffening in the fluid itself. Qualitative agreement with the
experimental data of Charrier and Rieger [176] was observed. A more
sophisticated analysis of the same problem was presented by Goddard
[174] using a general quasi-steady state rheological model for the
suspending medium, with the assumption that in the near-field of the
suspended particles the flow is shear-dominated and extends
asymptotically to the extension-dominated flow in the far field. The
conclusions of this analysis were the same as those arrived at earlier
in Goddard [173]. The complex theoretical treatment of Goddard
[173,174] are not included here. Results are available for the simplified
case of the suspending medium being a power-law fluid in Goddard
[175].
Goddard [175] carried out a qualitative comparison with the
rheological data of Chan et al. [164] for simple shear and simple
extension of polymer melts containing chopped glass fibers. It was seen
that the agreement with the power-law theory was not satisfactory and
even worse for the Newtonian case. Goddard concluded that the
disagreement was not due to failure of the theory, but possibly because
of lack of fiber alignment during experiments.
Nicodemo et al. [177] were the first to show, experimentally, the
spectacular reductions (at times by an order of magnitude) in the
extensional viscosities of polymer solutions containing spherical
particles (namely, glass microbeads) in contrast to solutions containing
rod-shaped particles (namely, fibers), which are known to increase the
extensional viscosities.
The extensional viscosity of fiber suspension depends to a large
extent on the orientation of the fiber and this has been the subject of
study of a number of investigators (e.g. Taksermann-Krozer and
Ziabicki [178], Bell [179], Goettler [180,181], Nicodemo et al. [182],
Takano [183], Lee and George [184]). In polymer processing, as most of
the flow takes place through converging dies, the study of the
rheological properties in extensional flow and the orientation of the
polymer molecules and fiber are extremely important in order to
control the quality of the end products.
Despite the importance of extensional viscosity studies in filled-
polymer processing it is unfortunate that the effects of various factors
like size distribution of the fillers, nature of the surface, flocculation,
etc. as in the case of shear viscosity (section 4.2), has not been studied
at all. Only the effect of the shape of the filler on the extensional
viscosity has been brought out by Nicodemo et al. [177]. A lot more
research in this area is thus warranted. The main reason for the dearth
of information in this area is probably due to the absence of a cheap
and simple apparatus for the measurement of extensional viscosity.
Most of the workers have had to design their own apparatus for
determining extensional viscosities depending on the system to be
measured and the facilities available.
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Preparation of. filled jr-
polymer systems O
In context with the preparation of filled polymer systems, there are

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

The important aspect in mixing is to evaluate the quality of mixtures [2]
or the goodness of mixing [3]. The most straightforward method of
characterizing the quality of the mixtures is to measure to what extent
the desired properties have been attained. Industrial quality control
follows that route whenever feasible. However, this requires a detailed
description of the structure of the mixture and to theoretically establish
this, the spatial position of each ultimate minor particle in the matrix
must be determined. It is often not possible to predict the exact path of
individual ultimate particles during the mixing process because most
compounding equipments achieve the mixed state randomly, though,
of course, there are some in which mixing progresses at least in a partly
ordered fashion.
In the random mixed state there are more possible arrangements of
the minor component than in the completely unmixed state. In the
latter state the probability is unity and in the former case it is very large
equal to
0 _ (N; + Nj)!
mixed (5 1)
~ N;!Ni! '
N; and N'2 are the number of ultimate particles of the major and minor
component respectively. A very great number of possible random
distributions have to be considered [4] to be the most uniform
distribution which can be achieved with common random type
compounding equipments as shown in Figure 5.1. From the inspection
of Figures 5.1(d) and 5.1(e), it can be seen that in the case of filled
polymer systems, this type of regular random state would undoubtedly
be preferable to any other random state. In the case of small ultimate
particles which cluster together to form large agglomerates (blobs), the
clusters have to be broken up into ultimate particles (aggregates) and
uniformly distributed by the dispersive mixing action. The random
distribution of a component 'A' in a component 'B' is achieved if the
probability of finding an ultimate particle of 'A' is the same at all points
in the mixture and is equal to the volume fraction a of the component
'A' in the mixture. In the completely unmixed state as shown in Figure
5.1 (a), a sample of volume Vs will have a concentration of component A
of either 1 or O.
The probability to find XA = 1 is 'a' and to find XA = O is b, as shown
in Figure 5.2 on the left-hand side. The mean is given by
M=* (5.2a)
and the variance as
°2 = d> (5.2b)
The probability distribution for finding a particular level of

concentration in a sample after drawing a great number of samples can
be calculated [4] from the following expression
(a) THE COMPLETELY <b) THE PERFECTLY
UNMIXED STATE. MIXED STATE
O «1 _ (N1 + N2)!
QMI
«° ' N1IN2!
COMPONENT: A,B
VOLUME FRACTION: a,b
ULTIMATE PARTICLE SIZE: a,0
Figure 5.1 Number of possible random distributions of fillers in a polymer matrix which can be achieved with common random type
compounding equipments. (Reprinted from Ref. 4 with kind permission from John Wiley & Sons, Inc., New York, USA.)
STAUSTtCAL DEFINITION OF
THE STATE OF MIXTURE.
THE COMPLETELY SAMPLE StZE V5 THE COMPLETELY

UNMIXED STATE. MIXED STATE.
P(X*) P(X*)
VOLUME OF CONCENTRATION VOLUME OF'CONCENTRATION

OF COMPONENT A MEAN:^ = a OFCOMPONENTA
MEAN: M = a VARIANCE:**= a.b^
VARIANCE: 0*= a.b
Figure 5.2 Variation of the probability of filler distribution with its concentration in the polymer matrix. (Reprinted from Ref. 4 with kind
permission from John Wiley & Sons, Inc., New York, USA.)
/ 1(XA-û) 2 N
eXp
(~2 V
P(XA)=
7(2^) ^ <W
where the mean is given by
/* = a (5.3b)
and the variance as
*2 = ^ (5.3c)
Again it can be seen that for a sample of the size of an ultimate

particle, the variance and the probability are the same as for the
completely unmixed state. On the other end of the spectrum is a sample
of very large size, possibly a whole batch, in which case the measured
concentration will always indicate that the sample is well mixed.
Obviously, in order to make a statement about the quality of mix, series
of varying sample sizes have to be analyzed. During each series N"
samples of the same size are collected. Using equation (5.3c), the
variance for the completely mixed state for each series can be calculated
introducing the sample size for that serve. The actual mean concen-
tration XA and the actual variance S2 can be calculated [4] from the
measured values XA. as follows (Table 5.1)
N
— 1 "
X X
A = xpE
v A« (5.4)
I=I
S2 2
= IM^XX-XA)
V X
(5.5)
f=l
If the mixture has been properly sampled then XA should not be

significantly different from a. The normal proportion test can be used to
determine if any observed difference is significant. The test is applied
by calculating the quantity
Z-^-M* ,5.6)
Numerous indices to quantify the extent of mixing have been
proposed and these are reviewed by Fan and co-workers [5,6]. In
general these are based on standard deviation S or the variance S2 of
the composition of spot samples taken from the mixture. The simplest
such index [7] is given by
S _ (j
Tn1=- or Tn1=- (5.7)
O o
where a is the standard deviation of composition for a random
Table 5.1
Mean: XA = ^7]T X A/ ;
Variance: S2 == ^L-JT(X*, = XA)2
A/". . . number of samples

Significance of XA Significance of S2
_ (XA - a)-v/A/" chi-square test
Z
~ S
Mixing index
Mixing index Perfectly mixed Completely unmixed
E
2
; K
c «
4^4
<7 0 -t7
In^-InS 2 1 Q
In al - In <r2
^ o o-a>H)
or2, = a. b = a(1 - a) the variance of the completely unmixed state
Source: Ref. 4 (reprinted with kind permission from John Wiley & Sons, Inc., New York, USA).
homogeneous mixture defined as a mixture in which the probability of

finding a particle of a given component is the same at all the locations
in the mixture and a is equal to ^/[a(l — a)/N'] for a binary number of
mixture where a is the proportion of one component and N' is the
number of particles in the sample [7]. The number of particles in the
sample are often difficult to estimate and in that case, the value of N'
may be taken as VJOL. The sampling of mixtures and treatment of results
has been extensively reviewed by Weidenbaum [8] as well as by Hold
[4] and may be referred to for better understanding. Different ways of
characterizing the degree of mix by a mixing index based upon a2 and
S2 have also been proposed [9]. They are summarized in Table 5.1. The
chi-square test is the statistical test of significance used in comparing S2
with a2. The chi-square test can be used to determine whether the
difference between S2 and a2 is significant indicating a deviation from a
random mix or a deviation by chance [1O]. If the mixing index is plotted
vs. the size of the sample, the size of the domains with nonuniform
composition and the degree of nonuniformity can be established from
the graph. Two properties which are useful in adjudging the goodness
of mixing are the scale and intensity of segregation.
Scale of segregation is a measure of the average separation between
regimes comprising the same component and may be correlated to the
average striation thickness, which is the average distance between like
interfaces in a mixture [U]. On other hand, intensity of segregation is a
measure of concentration [U].
Danckwerts [3] defines the scale of segregation SL as the integral of
the coefficient of correlation between concentrations at two points
separated by a distance
SL= f RQjdr (5.8)

Jo
The definition of the coefficient of correlation is given by the following
equation
N
" _ _
£(XAj. -X A )(X;-X A )
^ =- ATS2 (5 9)
'
where X A/ , XA. are the concentrations at two points at a distance r. The
variance S2 is calculated from the concentrations at all points using
equation (5.5). The coefficient of correlation R(r) ranges from 1 to —1. A
value of 1 indicates that both points in each couple have the same
concentration. The value —1 indicates that the concentration in one
point is pure minor and in the other is pure major.
The intensity of segregation is defined as follows:
I = -0 2 (5.10)
O
It expresses the ratio of the measured variance to the variance of a
completely segregated system. The intensity of segregation as defined
in equation (5.10) reflects to some extent 'gross uniformity' on a scale of
examination reduced to the scale at which texture or local structure is
being examined.
Danckwerts [3] thus introduced a different method of characterizing
texture and local structure. In Figure 5.3, the sample on the left-hand
side has a large scale of segregation and unless the intensity of
segregation, i.e. the difference in concentration between these areas is
very low, the sample is poorly mixed. The specimen on the right-hand
side shows a small scale of segregation: in this case a higher intensity of
segregation can still be tolerated without classifying the state of mix as
poor. This provides a good insight into the importance of the scale of
SCALE OF SEGREGATION:
INTENSITY OF SEGREGATION:
GROSS
UNIFORMITY
SCALE OF EXAMINATION
TEXTURE
LOCAL
STRUCTURE
Figure 5.3 Definition of the scale and intensity of segregation along with the scale
of examination. (Reprinted from Ref. 4 with kind permission from John Wiley & Sons,
examination in relation to the interpretation of the results of the

examination. Large scale examination renders information about the
gross uniformity of a mixture. With decreasing scale, information is
gained about the texture and finally the local structure of a
mixture.
Gross uniformity is important in most mixtures. However, the degree
of fineness in the texture that is needed is, of course, dependent upon
the individual application requirements of the mixed material. In order
to evaluate the texture, the size of the analyzed samples has to be
reduced to the level which permits characterization of the texture
significant to a specific application. On the other hand, the local
structure has to be examined at the scale of the ultimate particles.
Naturally, the local structure would depend upon the efficiency of the
mixing action and also upon the compatibility of the materials.
In summary, the process of mixing involves the breaking down of the
individual components into smaller elements and then dispersion of the
elements of one component in the space occupied by the other [12],
thereby reducing compositional non-uniformity. In the case of the filled
systems, the process includes the breaking down of agglomerates, their
separation and segregation, until a final random distribution is achieved
of each component in the system. The purpose of mixing is to attain an
acceptable degree of homogeneity or uniformity of composition,
assessed through the appropriate scale of scrutiny, which is defined
[11,13,14] as the minimum size of the segregation region that would
cause the mixture to be imperfect for the intended purpose. It is thus
reasonable to define the perfect admixture as the state in which no
variations in composition or morphology are observed at the relevant
closeness of examination.
5.2 MIXING MECHANISMS

Having discussed the various methods of characterizing the quality
(uniformity) of a mixture, the next step is to find functional
relationships between these quantitative measures of the quality of the
mixture and the mixing process, the mixer geometry, operating
conditions, properties and initial conditions of the components.
Theoretically each ultimate minor particle has to be followed
throughout the mixing process to establish the final spatial distribution
and evaluate it by applying these measures of quality. During the
movement of the particles in the mixing action, three basic types of
motion can be encountered as shown in Figure 5.4: molecular diffusion;
eddy diffusion (turbulent flow); convection.
In a viscous polymer system, the influence of molecular and eddy
diffusion is generally negligible, leaving forced convective flow as the
main mixing process [9]. If convection causes (a) the movement of the
melt elements and the solid fillers from one spatial location to another
such that the interfacial area between them increases or (b) that solid
filler particles are distributed throughout the polymer matrix without
necessarily increasing interfacial area, then distributive mixing is said
to have occurred.
Distributive or simple mixing is induced by plug or bulk convection.
Bulk convection can be random or ordered. Ordered bulk convection
rearranges constant volumina in a well defined way, and the progress
of mixing action can be predicted mathematically. In random bulk
convection, chunks of material are randomly redistributed, and model-
ing the mixing action is for most cases not possible.
Distributive mixing is basically defined as an operation which is
employed to increase the randomness of the spatial distribution of the
minor constituent within the major base with no further change in size
of that minor constituent. Distributive mixing is influenced by the strain
EDDY MOLECULAR
DiFFUStON DIFFUSION CONVECTION
NONEXISTENT
PLUG (BULK) LAMINAR
CONVECTION CONVECTION
SIMPLE MIXING
DISTRIBUTIVE
MIXtNG(STRAIN) LAMINAR,
MIXING
DISPERSIVE MIXING
ORDERED RANDOM
BULK BULK
INTENSIVE,
EXTENSIVE
CONVECTION CONVECTION
(STRESS)
IMPROVES:
GROSS
UNIFORMITY
TEXTURE
LOCAL
STRUCTURE
Figure 5.4 Various types of mixing mechanisms. (Reprinted from Ref. 4 with kind
imposed on the mixture. However, in the case of a viscoelastic

polymer system containing agglomerated fine filler particles which
show yield stress characteristics, the application of strain is necessary,
but insufficient, to achieve mixing. The strain rate and hence shear
stress imposed on the material determine the extent of mixing and
this is known as dispersive mixing [9]. This type of mixing is
accomplished by laminar convection through various types of flow:
shear, extensional and squeezing. However, shear plays the major
role during the mixing process and the main action occurs along
streamlines.
Dispersive mixing is basically defined as an operation which reduces
the agglomerate size of the minor constituent to its ultimate particle
size. During compounding of polymer melts with filler, it is the effect
of the mixing action on the solid filler particle that achieves importance.
Available research results for predicting the effect of a specific flow
field on agglomerates indicates that there are a number of possible
motions corresponding to the initial conditions of the velocity field and
the shape of the particles. The motions are periodic and the resultant of
all the forces acting on the surface and their moments equal to zero.
The periodic motion of the particles is necessary to maintain the forces
and their moments in equilibrium. The forces create a stress distribution
throughout the agglomerate which will result in the rupture of the
agglomerate along a surface or surfaces where the stress exceeds the
local cohesive forces between the ultimate particles. The breakdown of
agglomerates in shear flow is described quantitatively by Tadmor and
Gogos [9]. It has been shown that the maximum forces tending to
divide a dumbbell shaped agglomerate in a fluid of viscosity rj is given
by
F max = ^yT1T2 (5.11)
where T1 and r2 are the radii of the two particles and y is the rate of
change of shear experienced by the fluid, and occurs when the
dumbbell axis is at an angle of 45° to the direction of shear. Thus
improved mixing is achieved at higher shear stresses and, clearly, small
filler particles are more difficult to separate than large filler particles,
because the magnitude of the attracting forces increases with decreasing
particle diameter. High shear stresses may be applied to non-
reinforcing filler particles to achieve better dispersion. However, mixing
of a polymer with a reinforcing fiber presents a different problem. In
this case it is of importance not to break the fiber because only if the
bond strength of the fiber with the matrix on both sides of a point of
high stress is equal or greater than the strength of the fiber, is it possible
to utilize the fiber optimally. Hence, stress levels will have to be
maintained reasonably low to prevent drastic fiber breakage. Another
point of importance that must be borne in mind is that dispersive
mixing is laminar or streamline mixing. The streamlines never cross
during the laminar flow of the mixing action. Hence initial
nonuniformities of the distribution of the minor component across the
streamlines of the mixing flow can only be eliminated if laminar mixing
is combined with plug convection.
Viewing mixing as distributive or dispersive is clearly an oversimpli-
fication when applied to practical mixing problems since both actions
will occur simultaneously. Homogeneity will have been achieved when
both the dispersive elements and the distributive elements of the
mixing have achieved a fluctuation in average composition below a
certain fixed and acceptable level.
However, before either distributive mixing or dispersive mixing can
effectively take place, there is an initial step in which the originally
separate ingredients form a coherent mass. This process is known as
incorporation or wetting.
Filler particles, especially those of submicron size, are available in an
aggregated form. At times, this is done on purpose by the suppliers
because agglomerates are easier to handle, are dustless, and are therefore
less hazardous to health. However, due to a variety of forces such as
van der Waals, electrostatic, liquid bridges, etc. [15] it is often the strong
filler bonds that tend to hold finely divided particles together. In the
preparation of filled polymer system, difficulties arise in dispersing the
fillers in the polymer matrix due to the basic incompatibility between
filler and polymer. Polymers, being organic in nature, have surface
tensions that are quite different from those of most inorganic fillers.
They have, thus, a natural tendency to resist wetting of the filler during
compounding. Hence, during preparation of filled systems, there is
certainly a possibility for increased agglomeration in this non-wetting
environment, as well as an enhanced probability of forming microvoids
around particle clusters.
In summary, compounding of fillers with polymers basically involves
four steps - the initial incorporation, then wetting, followed by de-
agglomeration and finally distribution of the fillers within the polymer
matrix. This is achieved through the use of a variety of compounding
techniques that are discussed below.
5.3 COMPOUNDING TECHNIQUES

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

When selecting a compounding equipment, careful consideration should
be given to the size of the unit required. The full cost at the maximum
daily or hourly production rate must be established. It should be borne
in mind that use of several small equipment units rather than one large
unit will usually increase labor costs and initial investment.
Bearing in mind process economics, equipment availability and
preference, the decision as to what compounding technique and what
Table 5.2 Effect of compounding on mechanical properties of fiber glass-filled
polypropylene
Compounding technique3
Single- Continuous Twin-screw Twin-screw Twin-screw Twin-screw
screw mixer compounder compounder compounder compounder
extruder 1 2 3 4
wt % glass fiber 25 25 25 23 25 25
Type of fibers 1/8 in 1/4 in Roving Roving Roving 1/8 in

chopped chopped chopped
glass glass glass
Tensile strength 6100 4700 4900 5800 8000 8000
(psi)
Flex, modulus 580 460 600 550 550 550
(m psi)
Izod impact 1.45 0.7 0.9 1.1 1.2 1.3
ft Ib/in notched
Heat defl. temp. 264 153 203 184 268 266
C 264 psi (0F)
% of fibers 29
smaller than
0.5mm
Remarks Glass was Screw with Moderate Mild screw
fed into very strong screw after after
the feed sections addition of addition of
section after glass glass
addition of (No. 14)
glass
Source: Ref. 16 (reprinted with kind permission from American Chemical Society,' Washington
DC, USA).
compounding equipment to utilize often centers around the question of

how much shear is required. Compounding of non-reinforcing fillers
usually requires the highest degree of dispersion. Therefore, equipment
should be able to generate high shear stresses to separate the
agglomerates, particularly since these fillers usually have very small
particle sizes. In compounding reinforcing fillers, the opposite approach
is taken as low shear compounding must be used to prevent damage to
the fillers. The main consideration is to wet the filler uniformly,
devolatilize and discharge.
Each material formulation presents a distinct problem. It is important
to know how sensitive the compound and/or compounding ingredients
are to temperature. The need to control or change the temperature and
pressure during compounding should be considered. Purchase of light-
duty equipment should not be overlooked if the material will be
dispersed at a high temperature.
Also, thought should be given to the materials which will come in
contact with the final product. When dealing with glass fibers, abrasion
or corrosion of the compounding equipment plays a substantial role in
economics. Although a product may not be contaminated by plain steel,
a polished stainless steel unit is easier to clean. Labour that is saved
may more than justify the additional cost of a stainless steel unit. Other
constructions such as the use of high manganese steel may also be
considered. The flexibility of the unit is also worth a good look. Can the
compounding equipment be readily cleaned to change from one
product to another and adapt to future production demands? Thus, the
simplicity, accuracy and adaptability of the compounding process are
important.
The equipment for compounding fillers and polymers must fulfil the
following requirements: (a) provide steady-state running conditions, (b)
give reproducibility of processing conditions, (c) have ease of cleaning
and (d) show versatility to adapt to new formulations. The equipment
has to be chosen with care to ensure that correct product properties are
achieved while no undesirable effects are introduced. Proper selection
of compounding equipment and optimizing equipment parameters can
substantially increase the mechanical properties of the final product.
To achieve optimum material quality, the equipment for compounding
fillers into a polymer must be capable of performing some of the
following process tasks:
1. Incorporation and homogenization of fillers without exceeding
degradation temperatures;
2. Generation of sufficiently high internal shear stresses to facilitate
good dispersion of non-reinforcing fillers;
3. Provision of uniform shear stress to each filler particle at any heat
history;
4. Provision of short and uniform residence time distribution to
minimize heat history;
5. Provision of precise temperature control over the process to ensure
narrow temperature distribution throughout the process and at
discharge, again to regulate and minimize heat history.
Using the above discussed factors as the criteria for analysis, the
processor can select either a separate or in-line system, whichever is
most efficient for his needs. Each has its merits and each its limitations.
A batch system may be considered more flexible since it need not be
tied in with other in-line equipment, but, on the other hand, batch to
batch variations, for whatever reason, may not be acceptable in the final
product. A continuous system should give a consistent product, but to
be fully effective it must have the back-up of reliable feeding and take-
off equipment.
Some of the factors which need to be considered in the choice of
machinery have been dealt with; the various categories of machine
available and the important features of each category [20-32] are
discussed next.
5.3.2 BATCH MIXERS
A. Open mills
The mixing mill predates all the other mixing devices [21]. Originally
many mixing operations were carried out on two- or three-roll open
mills [2O]. As shown in Figure 5.5, it consists of two counter-rotating
differential speed rolls with an adjustable nip and imposes intense
shear stresses on the material as it passes the nip.
The major component, i.e. the polymer, is first melted by the
introduction of heat to the rolls and from the shearing action between
the rolls. Once the polymer is melted, fillers and other additives are
introduced.
Extensive mixing takes place at the entrance of the nip due to
extensional flow. Intensive (dispersive) mixing is accomplished in the
nip. To achieve homogenization some means of lateral mixing of the
banding action must be included. There is little transverse mixing and
thus constant operator attention is needed to displace the strip trans-
versely. Folding of the sheet by the operator prior to reintroduction to
the milling action takes care of a random plug flow distributive mixing.
This method allows very good temperature control of the product
since the rolls can be cooled or heated and they present a very large
surface area to the polymer system. The region of high shear is very
NIP
"BANDING'
ACTION
Figure 5.5 Schematic diagrams of a two-roll open mill showing the banding action
and nip. (Reprinted from Ref. 20.)
small avoiding large temperature build-up. The degree of dispersion
obtained with such a system can be very high.
The two-roll mill is a mixer ideally suited to the processing of high
viscosity materials and was used by Birchall et al. [33] to produce very
high solids content moldable cement pastes. Although still available for
use, this type of system would not be considered for anything but very
specialist operations.
Obvious disadvantages arise from the open nature of the operation,
difficulty in obtaining an initial melt and initial incorporation of
pigments and fillers, giving long cycles. The system is inevitably dirty
and it is difficult to achieve a uniform product.
B. Internal mixers
The internal mixer too is among the oldest members of the mixer family.
The cross section of such a mixer is shown in Figure 5.6. It has adopted
the open mill mixing principle but has a completely enclosed mixing
chamber in which two rotors are mounted. The rotors are sealed at each
end to avoid leakage of material from the chamber. The internal mixer
is generally a very high powered machine with drives up to 300OkW
for a machine with 600 litre mixing chamber [2O]. Maximum capacity is
about lOOOlb/batch, and depending upon the material to be mixed,
production rates can be as high as 40 batches/hr.
Three different mixing actions take place in the internal mixer [21]:
intensive or dispersive mixing around the tips of the rotor blade;
extensive mixing due to simple shear flow and extensional flow
between the chamber walls and the cylindrical portions of the rotors
and in the entrance region to the narrow gaps between rotor tip; and
distributive mixing due to random plug convection, as a result of the
interaction between the two rotor tips.
The rotors can be fully intermeshing in which case they must
obviously rotate at identical speeds, or non-intermeshing when, as on a
two-roll mill, friction ratios (generally 1.3 to 1) can be applied. The
speed of the rotors can be changed and even varied during the mixing
cycle. It can be lowered for a certain period of time to cool the material
down and then increased again to restart the mixing. The residence
time of the material in the mixer, for instance, can be changed by
changing the cycle time. Cycle times as low as 2-3 minutes are claimed
and with use of refrigerated cooling still shorter times may be made
possible. The amount of material put into the chamber can be varied to
change the intensity of mixing and the cycle can be interrupted to add
material at times which are most favorable to obtain optimum results.
An internal mixer is never operated completely full of material, though
pressure is maintained in the mixing chamber by means of a piston or
Figure 5.6 Cross-sectional view of an internal mixer. (Reprinted from Ref. 21 with kind
ram. It is found that by increasing ram pressures certain polymers can

be completely massed even without heating to rotors or chamber.
One of the earlier shortcomings of the internal mixer system when
used for polymers was that of the single mass form of discharge, which
was difficult to handle. Nowadays effective dump extruders are
employed which can accommodate up to three batches from the mixer
to give a continuous product through some form of pelletizing system.
These dump extruders can be fitted with screens for elimination of
agglomerates or foreign matter, and venting ports for removal of
volatiles.
One of the problems inherent in an internal mixer is that of batch to
batch variation in the product. However, accurate automatic weighing
Table 5.3 Advantages and disadvantages of the internal mixer
Advantages
Versatility of operations
Generally good temperature control
Robust machines
Relatively simple to operate
Short mixing times
Disadvantages
High capital cost
High and uneven power load
Batch to batch variations dependent on accurate feeding and process control
Rapid temperature rise needs good control
Source: Ref. 20.
and dosing devices minimize changes in formulation, while automatic

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

To meet the present demands for higher product quality and
uniformity, combined with higher volume requirements, continuous
compounding equipments are required [17]. In continuous com-
pounding systems, variation between batches is eliminated and the
possibilities of human error are minimized. Because of economics and
the large volume requirements of filled polymers, continuous systems
are usually preferred. Any efficient processing system will allow the
compounder to operate economically at high volume, and continuous
compounding systems, being more efficient than batch systems, have
capacities of 3000kg/hr and higher [16]. The two essential elements in a
successful continuous system are absolute control over residence time
and residence time distribution
Continuous compounding and mixing [23,24] is accomplished by a
variety of machines ranging from single-screw to twin screw extruders
with variations in design and additional equipment units to achieve a
range of end products. The type of compounder or mixer chosen
depends upon the specifications and properties required of the end
product, volume requirements, overall economics, and whether the
compounding is done in-house or by a custom compounder.
The basic functions of any compounding extruder are to melt the
polymer and to introduce a closely controlled amount of shear energy
into the melt to properly disperse and distribute additives or fillers.
A. Conventional single screw extruders

The simplest form of continuous compounding equipment is the single
screw extruder [20,25]. The single screw extruder has been used for
many years in polymer forming operations. The advantages and
disadvantages of the single screw extruder are given in Table 5.4. There
is much to be said for the mechanical simplicity of such machines,
where motor drive can be transmitted through a straightforward gear
box designed to accept the high thrust forces generated.
Table 5.4 Advantages and disadvantages of the single screw extruder

Advantages
Mechanically fairly simple
Relatively easy to operate
Capable of high pressure generation
Disadvantages
Lack of positive conveying characteristics
Limited compounding and homogenizing capabilities
Large machines with long L/D
Source: Ref. 20.
In the single screw extruder, a series of unit operations combine to
transform the solid polymer in pellet or granular form at room
temperature to a molten mass at elevated temperatures and further
drive the mass at sufficiently high pressures into downstream shaping
devices. The sequence of events is accomplished by different sections
of the screw, namely, the feed, melting and metering zones. The
polymer pellets or granules (virgin or sometimes in combination with
regrind of scrap) are normally fed to the extruder throat through a
conical hopper. The hopper geometry, the height of the fill and the
physical properties of the particulate solids dictate the rate of delivery
of solids to the feed zones of the extruders as well as the pressure under
the hopper. The feeding through the hopper relies on the influence of
gravity as well as the interparticle and particle/wall friction forces for
the rate at which the material is picked up at the extruder feed throat.
At times there are aberrations such as arching, piping and funneling
flow in the hopper because of which the feed is improper and
uncontrolled. Feeding by hopper is at times referred to as 'flood
feeding7 as against 'starve feeding' which occurs when material is
metered into the extruder feed throat by special feeding devices at
controlled rates.
Single screw extruders [9,10,34] are pumps that convey the material
by a combination of pressure and drag flows. The operation of a single
screw extruder relies on the frictional forces between the polymer and
the barrel to push the polymer forward. When the ratio of polymer/
barrel friction vs. polymer/screw friction is low, then the polymer will
adhere to the screw and simply rotate with it, resulting in no forward
motion. If the ratio is high enough, then forward motion will occur. The
lack of positive displacement characteristics means that the machines
are far from self wiping.
The section which is downstream of the feed zone is the melting
zone. When frictional forces are present, their energy becomes apparent
as heat, resulting in increased product temperatures. This effect assists
the melting process, which is enhanced by pressure generation in the
screw. At times, very large temperature differentials are generated
between melt and unmelt. In an extreme, the region of unmelt may be
surrounded by low viscosity melt and effectively insulated from the
thermal or shear energy of the screw.
The actual melting process in a single screw extruder is fairly well
understood [34-47], and a good understanding of the extruder action
too has been developed due to theoretical and computer modeling
[48-51]. It is now widely accepted that, in a cold feed extruder, melting
occurs at the barrel and screw surfaces and a melt pool accumulates on
the leading edge of the extruder screw fight (see Figure 5.7). Melting of
the solid bed takes place slowly over a length equivalent to several
FUMOP SOIJD
BAKEtEL MOLTEN MELT
SDlPACE POLYMER INTERFACE SOLED
KLIOHT
CIRCULATORY
FLOWOF
PREVIOUSLY
MELTED
SCREW
POLYMER
Figure 5.7 Melting process in the conventional single screw extruder. (Reprinted from
Ref. 29 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA.)
screw diameters and the rate of melting is dependent on heat transfer

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

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

CROSS FLOW CROSS FLOW
Figure 5.8 Velocity and stress distributions in single screw extruders. (Reprinted from
USA.)
the material which passes over the flights as it alone is exposed to the
shear action.
The velocity distribution in the extruder channel in the down channel
and the cross channel direction result in the spiral path of the material.
The material does not back flow even at higher back pressures, but
rather moves back and forth in a spiral fashion over a relatively short
distance. Due to the spiral motion, the residence time in the extruder is
reasonably uniform but the mixing action is very limited.
By observing the velocity and stress profile of down channel and
cross flow, it can be seen that the zero shear point exists inside the
channel. In this area, very little or no mixing will occur. This has been
confirmed by actual experiments.
Further, the lack of effective reorientation of the material elements at
the flights causes the bulk of the interfacial area to be oriented parallel
to the channel bottom in a relatively short downstream distance,
regardless of the initial orientation. Consequently, the mixing achieved
in single screw extruders is generally poor [58]. Efforts to improve the
mixing efficiency of the single screw extruder have, therefore, never
ceased.
B. Modified single screw extruders

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

barrier type
Undercut spiral barrier type
Figure 5.9 Mixing section designs in single screw extruders. (Reprinted from Ref. 25
with kind permission from The Institution of Chemical Engineers, Rugby, UK.)
screw are the hold-up of the material and dead spots [59,6O]. These can
be minimized by proper selection of the helix angle, tapering the inlet
channel to zero depth and by reversing the depth profile in the outlet
channel.
In the Maillefer type screw design, there is a spiral barrier or
secondary screw flight extending over the entire length of the modified
section of the screw. The mass and force balances across the Maillefer
type screw are available [61] and can be used to estimate the increase in
power requirements due to this modification. Additional barriers or
flights may be introduced to split the flow into two or more streams,
which in the limit arrives at a series of longitudinal grooves or flutes
spread around the circumference of a cylinder.
Static mixers, i.e. those which are motionless and do not contain any
moving parts, may be incorporated into single screw extruders between
the screw and the die in order to introduce distributive mixing. A
review of the various types of static mixers, their mixing characteristics
and performance is available [62]. They consist of a string of alternating
right and left handed helical elements fixed in a tubular housing which
helps in splitting and recombination of streams, resulting in a predicted
increase in the number of striations. The energy for mixing is derived
from the pressure loss incurred as the melt flows through the static
mixer. On account of the substantial pressure drop introduced by a
battery of these mixing elements, they have restricted use in filled
polymer melt systems especially those with higher loading and high
viscosities.
Many different modifications of the geometry of the single screw
extruder have been contrived (all of which are not described herein)
but even then, the achievable level of dispersion of fillers is limited.
Improvement in filler dispersion can be achieved only by powerful
shear forces. If the speed is increased to intensify mixing, the output
increases at the same time, whereby back pressure control is lost but,
more importantly, the energy input to the polymer due to the viscous
shear forces rises even more rapidly and can lead to excessive melt
temperatures. It is this heat build-up which eventually limits screw
speeds to even as low as 100-150 rpm.
In summary, the limited compounding and homogenizing ability of
single screw extruders usually restricts their application to straight-
forward melting and extrusion operations but use of mixing devices
can extend their range. Their favorable economics makes them
attractive for low volume compounding jobs especially for filled
systems of mainly commodity plastics [63]. For tougher applications,
such as compounding fillers with engineering polymers at low as well
as high loadings, single screw kneaders and twin screw extruders are
more ideally suited.
C. Single screw kneaders
This form of continuous compounding equipment may appear as a
variation of a single screw extruder. But truly it is not and hence not
included in the category of modified single screw extruders, because of
the radically different mixing action in it [27,64].
In this single screw compounding equipment, various types of
protrusion, grooves or profiles are built into the barrel with correspond-
ing elements along the flights of the screw in the particular section
known as the 'kneading section' as shown in Figure 5.10. This induces
dispersive mixing as the material passes repeatedly through the high
shear stress zones in the narrow gaps formed by the interrupted screw
flights and the kneading teeth on the barrel (Figure 5.11). The mixing
action is unique in that the rotational motion gets superimposed by
reciprocating motion, thereby giving a kneading effect to the melt. This
results in a good dispersion of fillers in the polymer system even at
relatively low shear rates, thus allowing good processing control for
temperature sensitive materials.
The kneading action is illustrated in Figure 5.12. It can be seen that
the kneading teeth wipe off all the corresponding flanks of a flight
during one full turn, and the material thus gets subjected to high shear
stresses in the small gap between the flight flank and the barrel teeth,
thereby giving good dispersive mixing. As a consequence of the good
mixing action such extruders are generally only one half or even one-
third of the length of conventional single screw units. Further, since the
unit does not generate high pressures, when pelletized product is
required, the kneader is generally coupled to a single screw extruder to
pump the polymer up to die pressures.
COOLED SOLIDS CONVEYIbTG SECTION
ENEADINGTEEIH
FEED SCBEW
ENEAD]NQ SCREW SCREW FLIGHTS
ZONES
Figure 5.10 Schematic diagram of a single screw kneader. (Reprinted from Ref. 23
with kind permission from Gulf Publishing Co., Houston, Texas, USA.)
ISPLTT BARREL
2HEATJNGJACKET
3ENEADttJGTOOTH
4 SCBEW FLIOET
SNAKROWQAP
6 CLAMPING BAR
Figure 5.11 Cross-sectional view of a single screw kneader. (Reprinted from

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

Twin screw extruders evolved as a result of the desire to overcome
some of the limitations of single screw extruders [65]. They are the most
expensive mixers per kilogram of output. The advantages of twin screw
extruders are listed in Table 5.5. The term 'twin screw extruder' is
basically a generic term but to treat all twin screw machines in one
general category is truly not correct. Various types of twin screw
extruders are commercially available and these differ widely in their
operating principles and function [18] as can be seen from Figure 5.13.
They differ in their abilities for distributive and dispersive mixing and
hence in their application areas. A possible classification of twin screw
extruders [30] is shown in Table 5.6 along with commercial examples
for each category. However, it should be borne in mind that this listing
is by no means exhaustive. The main distinction is made between
intermeshing and nonintermeshing twin screw extruders (Figure
STARTING POSITION FIRST QUARTER TDlN (90°) FULL TURN
COMPLETED
Figure 5.12 Kneading action in a single screw kneader. (Reprinted from Ref. 23 with
kind permission from Gulf Publishing Co., Houston, Texas, USA.)
Table 5.5 Advantages and disadvantages of the twin screw extruder

Advantages
Positive displacement characteristic gives throughputs independent of the nature of
the product being processed
Earlier and more complete melting allows machines to be shorter and gives better
mixing
Self-wiping characteristic avoids any product hang-up in the machines
Disadvantages
High capital cost
Mechanically more complex with difficulties of fitting adequate thrust bearings to
two closely positioned shafts
Source: Ref. 20.
SCREW SYSTEM COUNTER-ROTATING CO-ROTATING
ENGAGEMENT
LENOTHWISEAND THEORETICALLY
CROSSWISECLOSED NOT POSSIBLE
INTERMESHING LENGTHWISE OPEN
DISKS SCREWS
FULLY
AND THEORETICALLY
CROSSWiSE CLOSED NOT POSSIBLE
THEORETICALLY POSSIBLE
INTERMESHtNG
"SB"
LENGTHWISE AND
CROSSWISE OPEN 5_ BUTPRACTICALLY
NOT REALIZED
LENGTHWISE OPEN THEORETICALLY
AND NOTPOSSIBLE
INTERMESHING
CROSSWISE CLOSED
PARTIALLY
LENGTHWISE AND
CROSSWISE OPEN
INTERMESHING
INTERMESHING
LENGTHWISEAND
NOT
NOT
CROSSWISEOPEN
Figure 5.13 Types of twin screw extruders. (Reprinted from Ref. 18 with kind
permission from Society of Plastics Engineers Inc., Connecticut, USA.)
5.14(a)), each of which may be divided on the basis of the direction of

the rotation of the screw into co-rotating or contra-rotating (Figure
5.14(b)), also termed counter-rotating.
The benefits and the drawbacks of each system have been discussed
in many publications. However, arguments in favor of one system more
often seem to be based on a personal preference or bias than on an
objective engineering analysis. The plain fact that the systems have
coexisted for a number of years must be sufficient evidence that these
systems fulfil a practical need. In some applications, the co-rotating
extruders may be better suited; in other cases, counter-rotating
extruders may be preferred. For many filling operations, however, twin
screw co-rotating systems have the widest application because of their
high degree of flexibility. Instead of arguing against or in favor of a
particular system, it is more useful to determine both the advantages
and the disadvantages of the systems and to identify the applications
for which each system would be best suited.
The first known twin screw device was an intermeshing co-rotating
extruder invented in 1939, and patented in 1949 [66]. Developments in
twin screw extruders have come a long way since then. The mech-
anisms of different types of twin screw extruders shown in Figure 5.13
make a distinction between axially open machines, where there is a
Table 5.6 Classification of twin screw extruders
Low speed extruders
-LMP Colombo
—Windsor
—Bamberger
Corotating extruders
High speed extruders
-Werner and Pfleiderer
—Baker Perkins
-Berstorff
lntermeshing extruders Conical extruders
—Kraus Maffei
—Cincinnati Milacron
-AGM
—Cylindrical extruders
Counterrotating extruders —Leistritz
—Kraus Maffei
—Maillefer
Twin screw extruders —Reifenhauser
-Mapre
—Kesterman
—Troester, etc.
Equal screw length
-Bausano
-Japan Steel Works
Counterrotating extruders
Unequal screw length
Nonintermeshing extruders —Welding Engineers
Corotating extruders No commercial examples known
Source: Ref. 30 (reprinted with kind permission from Society of Plastics Engineers Inc., Connecticut, USA).
intermeshing non-intermeshing
co-rotating co-rotating
contra-rotating contra-rotating
Figure 5.14 Diagram showing the difference between (a) intermeshing and non-
intermeshing as well as (b) co-rotating and contra-rotating or counter-rotating types
of twin screw extruders. (Reprinted from Ref. 20.)
continuous passage between the inlet and outlet, and the axially closed
machines, where the passage is interrupted at regular intervals.
Considerable variations of screw design are possible to balance
pumping and mixing characteristics [67]. The right-handed, forward,
regular flighted elements shown in Figure 5.13 are only one of many
types of elements employed in twin screw extruders. The other types
may include left-handed, reverse, regular flighted elements, forward
and reverse kneading discs, shearing discs, etc.
Most twin screw extruders can be assembled using the building block
principle, which involves the use of screw elements of different
lengths/pitches and special kneading elements of various widths
available as blocks that are interchangeable. This makes it possible to
design the processing section exactly as required for obtaining optimum
processing conditions because the screw elements and kneading
elements blocks can be varied to tailor-make the screw configuration for
the shear intensity required by a specific material. If properly designed,
twin screw extruders provide maximum process control, especially
with respect to shear and stock temperature. Also, twin screw com-
pounders allow the removal of large quantities of volatiles.
The diversity among twin screw extruders is so large that a compre-
hensive discussion of all the various types would be an enormous
undertaking. A description of some of the important characteristics of
three basic types of twin screw extruders is given below. Non-
intermeshing co-rotating twin screw extruders are not produced
commercially and hence are not treated in this section.
(i) Intermeshing co-rotating screw extruders

These have the flights of one screw protruding into the channel of the
other screw, thereby providing positive displacement pumping [68]
when both screws rotate in the same direction. The degree of
intermeshing can range from almost fully intermeshing to almost non-
intermeshing with a corresponding range in the degree of positive
conveying characteristics. The design of intermeshing screws includes
variations in lengthwise and crosswise open and closed positions,
which directly affect the conveying conditions, the mixing action, and
the pressure buildup capacity of the screw system.
Co-rotating twin screw extruders are commonly produced only as
fully intermeshing and operate on the building block principle. De-
pending on the requirements of the compounding task at hand, proper
screw elements are selected and assembled along with the right choice
of kneading elements blocks. Commonly employed elements include
right-handed and left-handed (forward and reverse) regular flighted
elements, forward and reverse kneading discs, as well as mixing and
shearing pins. For regular flighted elements, fully intermeshing co-
rotating screws are open lengthwise, but are closed crosswise, except
for leakage over the flights.
When the twin screws are intermeshing, the extruder can be
considered to be self-wiping, that is, all the surfaces within the
processing chamber are wiped of polymer. This characteristic is
important when heat sensitive materials are being processed. Self-
wiping is advantageous to the operational economics as the screws
require much less downtime for cleaning. Efficient self-wiping ensures
no material hang-up in the machine and can be demonstrated by a
short residence time distribution for the material being processed
(Figure 5.15).
In intermeshing co-rotating twin screw extruders, self-wiping
characteristics can be improved through the use of kneading elements
within the screw configuration which can allow varying degrees of
mixing energy to be developed in the machine. Such elements are
INDICATOR GOOD SELP WIPING
CONCEN-
TRATION
POORSELF WIPING
TIME
Figure 5.15 Residence time distribution for self-wiping twin screw extruders.
(Reprinted from Ref. 25 with kind permission from The Institution of Chemical
Engineers, Rugby, UK.)
particularly useful in achieving good dispersion of fillers in the

polymers. The co-rotation of the screw helps in the homogenization and
dispersion because material is transferred back and forth between the
screws.
Co-rotating twin screw extruders allow for the possibility of adjusting
the amount of axial mixing. Mathematical modeling can be found in the
works of Erdmenger [69], Armstroff [70], Kim et al [71] and Booy
[72,73]. Mixing studies were done by Todd [74], Wyman [75], Maheshri
and Wyman [76,77]. Experimental data have been obtained by Werner
[78], Jewmenow and Kim [79], and Kim et al [71,80,81].
In co-rotating machines, the flow pattern of polymer system is such
that the material is actually conveyed in a figure 8-shaped pattern.
Observing the velocity profile and the shear stress distribution for co-
rotating machines as shown in Figure 5.16, it is seen that zero shear
stress point can be influenced by operating variables, such as by
changing the throughput and/or screw speed as well as by changing
geometry. It is imperative that uniform stress distribution is
maintained even with increased throughput. This is possible in co-
rotating machines, because the degree of uniform dispersion is directly
related to stress/strain distributions, and the most uneven stress
distribution occurs at closed discharge which is meaningless in actual
operation. In co-rotating machines, the proper selection and arrangement
of individual screw sections and kneading elements [82] is customary in
Figure 5.16 Shear stress distribution in a co-rotating twin screw extruder. (Reprinted from Ref. 18 with kind permission from Society of
Plastics Engineers Inc., Connecticut, USA.)
Figure 5.17 Screw design for (a) co-rotating (b) counter-rotating twin screw
extruders. (Reprinted from Ref. 18 with kind permission from Society of Plastics
Engineers Inc., Connecticut, USA.)
order to further improve the uniformity of stress distribution (Figures

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

This acts as a positive displacement pump due to the intermeshing
of the screws as discussed earlier. The conveying capacity of the
machine is virtually independent of the nature of the material being
processed, especially when the screws are counter-rotating. However,
it should be noted that full intermeshing is necessary but not
sufficient condition for positive conveying. In some geometries, there
is very little sealing of the screw channels, even when the screws are
fully intermeshing. Positive conveying requires that the screw
channels are closed off so that the material contained in the various
channel sections is fully occluded. Any amount of back leakage into
upstream channel sections will adversely affect the positive conveying
behavior. The output in volume per unit time is given by the
difference between the theoretical flow rate and the sum of the
leakage flows described in Figure 5.19
Q = QIH - QL = 2mNVc/60 - (Qr + Qc + Q4 + Q8) (5.13)
where m is the number of thread starts per screw, Vc is the volume^ of
the C-shaped channel between the flanks of successive flights and N is
the rotation rate. Qr is the leakage between screw flight and barrel wall,
Qc is the leakage between the screw flight and the other screw, Qt is the
leakage between the flanks of screw flights and Q8 is the leakage
between flanks perpendicular to the plane through the screw axis. The
leakage paths have a strong influence on residence time in the extruder.
The intermeshing point for counter-rotating screws acts as a 'calender
nip7 forcing material through it. Only a small proportion of the material
passes through the nip between the screws, while the remainder is
carried along axially in closed chambers. Since the relative speeds of
TRANSPORT DIRECTION
Figure 5.19 Leakage flow paths in an intermeshing counter-rotating twin screw
extruder. (Reprinted from Ref. 65.)
the two screws must be identical, high 'calender nip' shear forces are
not generated. Material is forced through the nip but then out against
the sides of the barrel. This effect can aggravate sticking to the barrel
walls. The passage of material between the 'calender nip' generates
normal stresses which tend to force the screws apart leading to
potentially higher barrel wear and limitations on screw speeds for
counter-rotating screw extruders. This is one of the reasons why
counter-rotating extruders generally operate at lower screw speeds than
co-rotating units, typically at less than 200 rpm [83].
Due to the lower relative velocities of the screws at the meshing
point, the shear stresses in the counter-rotating extruders would be
lower. In an analysis of the velocity and stress distribution in counter-
rotating twin screw machines, it is seen that there is actually no
improvement regarding velocity profile and zero shear stress point
location, in comparison to single screw machines. When superposition
of the shear stress distribution of down channel and cross flow (for a
given coordinate system) is done for counter-rotating machines, a
characteristic minimum inside the screw channel is observed in the area
of y/h = 0.38 (Figures 5.20 and 5.21). Shearing takes place in each
individual spiral chamber between two contacts of the faces of flights
with the surface of the root of the screw. The residence time distribution
is therefore very narrow which is important for processing of heat
COUNTER-ROTATING MACHINES:
SUM OF STRESSES OF DOWN CHANNEL
AND CROSS FLOW COMPONENTS
Figure 5.20 Sum of stresses of down channel and cross flow components for
counter-rotating twin screw extruders. (Reprinted from Ref. 18 with kind permission
from Society of Plastics Engineers Inc., Connecticut, USA.)
DOWN CHANNEL FLOW CROSS FLOW
Figure 5.21 Schematic flow orientation in counter-rotating twin screw extruders.
(Reprinted from Ref. 18 with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA.)
sensitive materials. The mixing efficiency can be increased by the

introduction of special mixing sections.
Since closely intermeshing counter-rotating twin screw units convey
material by positive displacement in a series of closed C-shaped segments,
compression is generally achieved, as in single screw extruders, by
continuously decreasing the pitch or the flight depth. Thus the melting
process can be an extended one and takes place gradually over a length
equivalent to several diameters. Intermeshing counter-rotating twin
extruders are available with conical as well as cylindrical screws.
Conical twin screw extruders provide more space for the installation of
thrust bearings while the cylindrical ones have the advantage of being
amenable to be built by the building block method [3O].
The intermeshing counter-rotating twin screw extruders are normally
used when narrow residence times for compounding are required, for
example, PVC profile extrusion and color-concentrate preparations [84].
(iii) Non-intermeshing counter-rotating twin screw extruders

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

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

The co-rotating disk extruder introduces the concept of two moving
drag inducing surfaces [89,9O]. This is in contrast to all the earlier
discussed continuous compounders wherein there was one moving
boundary (the screw) along with one stationary surface in the channel
(the barrel). This particular equipment known as the Disk pack
processor manufactured by Parrel Corporation, consists of a single rotor
with toroidal processing chambers fitted in a circular housing. The
processing chambers may be connected in parallel, in series or in
combination, and are assembled on the building block principle.
In the co-rotating disk extruder, the material is transported by the
action of two moving walls, the sides of the disks, which can form a
parallel-faced or a wedge-shaped chamber as shown in Figure 5.23. An
analysis of the velocity distribution in the parallel-faced chamber with a
restriction to flow at the outlet shows two flow patterns [21]. A circular
flow in planes perpendicular to the axis of rotation and another circular
flow in cylindrical surfaces around the axis of rotation. The super-
position of both flows is conducive to extensive mixing.
To achieve intensive mixing, mixing blocks with narrow clearances
between the surfaces of the blocks and rotating walls are introduced as
CHANNEL BLOCK
PARALLEL-FACED WEDGE-SHAPED
RADIAL-THICKNESS RADIAL-THICKNESS
PROFILE
INLET PROFILE
OUTLET
SHAFT SHAFT
DISK DISK
BARREL BARREL.
PROCESSCHAMBER
Figure 5.23 Sectional view of co-rotating disk extruder without mixing blocks.
(Reprinted from Ref. 21 with kind permission from John Wiley & Sons, Inc., New York,
USA.)
shown in Figure 5.24. The extensive mixing action described above

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

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

normally adjudged by the observed constancy of the torque level in the
mixer's motor drive unit after a certain length of time. A constant
torque implies internal homogeneity of the mixture that is achieved
within the system's capability limits. A typical torque-time curve
generated during a mixing operation [91] of filler and polymer is shown
in Figure 5.25. The major peak represents the moment when the
addition of all the filler and polymer to the mixing bowl is complete
and when the shearing action begins to disperse the filler into the
polymer matrix. As the filler becomes better dispersed, the viscosity of
the composite begins to decrease, as exemplified by the recorded
torque, till it reaches its equilibrium value beyond which the mixedness
would not improve or would improve only marginally due to the
system constraints. In fact, it is not advisable to continue mixing once
the equilibrium torque level is reached because it could only lead to
thermomechanical degradation of the polymer, especially in highly
(M-KG)
(*C)
TEMPERATURE
TORQUE
TIME (mfn.)
Figure 5.25 A typical torque-time curve generated in an internal mixer during

compounding of fillers into polymers. (Reprinted from Ref. 91 with kind permission
from Marcel Dekker, Inc., New York, USA.)
filled systems, where local shear rates between filler particles could be
extremely high.
Time and temperature have been the most commonly used criteria to
determine when to terminate the mixing process. The aims are to
guarantee the quality of the end product, avoid overmixing, and reduce
variation between batches. There is an increasing body of evidence that
a more precise and reproducible control of the mixing cycle can be
obtained by following the energy inputs at various stages in the cycle.
This is because the changes in power consumption are indicative of the
wetting, deagglomeration and dispersion stages in the process.
Mixing to a preset time does not allow for variations in metal
temperature at the start of the mix, for cooling rate or for ingredient
addition times. This can result in significant batch to batch variation.
When mixing to a predetermined temperature the major limitation is
the accuracy with which the batch temperature can be measured. The
large heat-sink provided by the machine often makes temperature
measurement inaccurate, though there are now available infrared probe
thermocouples that are more accurate.
Mixing to a predetermined power input into the batch overcomes
these limitations and gives improved batch to batch consistency for
mixes requiring longer mixing times. However, following the work or
energy input alone is not sufficient. In addition, one has to establish the
effect of process variables on the shape of the power curve. In other
words, a recording chart, which indicates both the instantaneous power
and the integrated power or work done is required. Furthermore, these
data should be additional to the established control criteria of time and
temperature and not a completely separate alternative set of criteria.
5.4 COMPOUNDING/MIXING VARIABLES

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

Compounding variables
Machine variables Operating variables
Mixer Rotor Mixing Rotor Ram Chamber Mixing Order of

type geometry time speed pressure* loading* temperature ingredient
addition
* Applicable particularly to internal mixers. Next Page
Steady shear viscous r*
properties D
There is extensive literature on the rheology of filled polymer systems

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

Fillers Source Specific Size, (im Aspect ratio
gravity (particle or
fiber
diameter)
Carbon black Continental Carbon 1.8 0.045
Titanium dioxide du Pont 4.1 0.18
Calcium carbonate Pfizer 2.7 0.5
Mica Hayden Mica Company 2.9 Flake, 25-50
Glass beads Potters Industries, Inc. 2.48 10
Franklin fibers Certain Teed Corp. 2.96 0.5-2 -100
Aramid fibers du Pont 1.44 12.2 -60
Cellulose fibers Westvaco 1.5 12 -100
Glass fibers Fiberfil 2.5 12.7 -10
Source: Ref. 29 (reprinted with kind permission from American Chemical Society, Washington
DC, USA).
The rheology of filled polymer systems will be discussed in this and
subsequent chapters under various headings, namely steady shear
viscous properties, steady shear elastic properties, unsteady shear
viscoelastic properties and extensional flow properties. The effects of
filler type, size, size distribution, concentration, agglomerates, surface
treatment as well as the effect of the polymer type will be elucidated
wherever information is available.
The material parameters that are involved in steady shear measure-
ments are the steady shear viscosity and the normal stress difference.
These will be treated in separate chapters as the information available
on these two parameters is not balanced equally.
The information on steady shear viscosity of filled polymer systems
far outweighs that which is available on other parameters. Hence, the
effect of a number of variables on the steady shear viscosity is discussed
in utmost detail.
6.1 EFFECT OF FILLER TYPE

The effect of filler type on the steady shear viscosity of a filled polymer
system has been brought out in the work of White et al. [29]. The
polymer used was polystyrene of one specific grade, namely, Dow
Styron 678U. The filler loading was fixed at 20vol%. Nine different
types of filler were used as summarized in Table 6.1. The filler types
included rigid fillers (such as glass fibers, mica, glass beads, calcium
carbonate, carbon black, titanium dioxide and Franklin fibers) and
flexible fillers (such as aramid fibers and cellulose fibers). They covered
different types of shapes such as spherical (glass beads), particulate
(calcium carbonate, carbon black, titanium dioxide) and fibrous (glass
fibers, aramid fibers, cellulose fibers, Franklin fibers).
Steady shear measurements were carried out using the Rheometrics
Mechanical Spectrometer at a fixed temperature of 18O0C using a cone-
plate mode.
Plots of steady shear viscosity rj as a function of shear rate y for
various filled systems at a fixed loading of 20vol% are shown in
Figures 6.1 and 6.2. The curves exhibit qualitative as well as quanti-
tative differences. The filled systems containing glass fibers, aramid
fibers, cellulose fibers, mica and glass beads exhibit qualitatively similar
behavior with low shear rate Newtonian viscosities and a decreasing
viscosity function at higher shear rates. On the other hand, the filled
systems containing calcium carbonate, carbon black, titanium dioxide
and Franklin fibers exhibit unbounded viscosity buildup at low shear
rates. Generally, the viscosity levels in these systems are higher than
those found in the former group of fillers.
The extent of the steady shear viscosity increase is the lowest for 3-
FILLED POLYSTYSENE
DOTTS
FRANKLINFIBERS
Figure 6.1 Variation of steady shear viscosity with shear rate for filled-polystyrene
melts at 20vol% of various types of fillers as indicated. (Reprinted from Ref. 29 with
kind permission from American Chemical Society, Washington DC, USA.)
FILLED POLYSTYMNE
GLASS BEADS UNITS

ARAKOD FIBERS
CELLULOSE FIBERS
MICA
GLASS FIBERS
PS
Figure 6.2 Variation of steady shear viscosity with shear rate for filled-polystyrene
melts at 20voi% of various types of fillers as indicated. (Reprinted from Ref. 29 with
kind permission from American Chemical Society, Washington DC, USA.)
dimensional spherical fillers such as glass beads, higher for 2-
dimensional platelet fillers such as mica and highest for !-dimensional
fibrous fillers such as glass fibers. When considering rigid and flexible
fillers, the increase in the level of steady shear viscosity would be more
for rigid fillers than for flexible fillers because they resist deformation to
a greater extent. This is evident when the effect of glass fibers is
compared with aramid and cellulose fibers filled PS systems in Figure
6.2. All three fibers have nearly the same fiber diameter (Table 6.1), yet
the filled system with glass fiber shows the highest viscosity even when
the aspect ratio of the glass fiber is the lowest.
The existence of unbounded viscosity buildup at low shear rates as
shown in Figure 6.1 is not an effect of the filler rigidity or shape, but of
the filler size and will be discussed in the next sub-section.
6.2 EFFECT OF FILLER SIZE

Systems in Figure 6.1 exhibit the yield stress which is a manifestation of
strong particle-particle interaction and has direct relation to the particle
size. From Table 6.1, it can be seen that carbon black, titanium dioxide
and calcium carbonate have a much smaller particle size than mica and
glass beads. Similarly, from among the fibers, it is the Franklin fiber
that has a much smaller diameter than the other three fiber types. It is
only the smaller size fillers, specifically those having diameters below
0.5 jam, that have shown the yield stress. The smaller the particles, the
higher is the yield value [27]. In fact, with decreasing particle size, the
entire steady shear viscosity curve is pushed to a significantly higher
level [19,27]. The existence of yield stress in the steady shear viscosity
curve for filled polymer systems containing small size fillers has been
noted by other researchers [2,3,7,11,12,52] as well. Yield stress is
observed when the filler particles are extremely small as with carbon
black [19] or finely divided mineral particles [2,3,11,12,52]. Apparently,
the particles link temporarily into a network of finite strength. It must
be borne in mind that there may be a difference between yield stress
values obtained by extrapolating a flow curve to zero shear rate [7,11]
and those obtained by stressing a sample at rest until it yields [12].
For filled systems with larger particles, the response to deformation is
determined by hydrodynamic interaction and not by particle-particle
interaction. These non-interacting particle systems would not show the
yield stress as can be seen from Figure 6.2 wherein the smallest particle
dimension exceeds 10 jim (Table 6.1).
Tanaka and White [86] have developed a cell theory of the steady
shear viscosity of a suspension of interacting spheres to account for the
viscous behavior of filled polymer systems. Essentially, they compute
the enhanced energy dissipation through the existence of interaction
energy between the particles, E1n^ and hydrodynamic viscous dissi-
pation Evis. Specifically the ratio of the viscosity r\ of the suspension to
that of the matrix rj° is
i//f/° = (4it + Evis)/^ (6.1)
This energy-based method of calculation of viscosity Y\ is due to
Einstein [87], who considered hydrodynamic dissipation in a very
dilute suspension of non-interacting spheres. Tanaka and White [86]
base their calculations on the Frankel and Acrivos [88] cell model of a
concentrated suspension, but use a non-Newtonian (power law) matrix.
The interaction energy is considered to consist of both van der Waals-
London attractive forces and Coulombic interaction, i.e.
Efat = EV + EC (6.2)
which are computed from the calculations of Hamaker [89] and
Derjaguin [90] for interacting spheres. It is shown that
Eint/Evis = B1 (0, n)/y, Evis/îs = B2(0, n) (6.3)
so that
n(4>* y) = TY/V + q*(<l>, y) (6.4)
where
TY=CA Hf 1 I2Ce0^ (6 5a)
^ L/^-ir-ir- -
^'^W(^MVl (63b)
In equations (6.5a) and (6.5b), TY is the yield stress, n is the power
law index, K is the consistency index, C is a positive constant
representing the total number of nearest neighbours of each sphere, AH
is Hamaker's constant, $m the maximum volume fraction, e0 the
dielectric constant of the matrix, ke the thickness of the electrostatic
interaction layer, ^0 the surface potential of the particulates, D the
particle diameter and y the shear rate. Basically, equation (6.4) along
with (6.5b) is identical to the empirical Herschel-Bulkley [91] model
given by equation (2.45), and has been suggested also by Jarebski [92].
There are other theories which relate yield stress to volume fraction and
particle size, and these are available in Rajaiah [93].
From equation (6.5a), it can be seen that the yield stress increases
when volume fraction or surface potential or Hamaker's constant
increases and when particle size decreases. The usefulness of equation
(6.5a) is limited by the fact that most filler particles are neither
monodisperse particles nor are values of Hamaker's constant, the
surface potential and thickness of the interaction layer readily available.
If the electrostatic interaction is assumed to be negligible compared to
van der Waals interaction, then TY may be expressed as follows
-^bîT
If a value of (j) of 0.2 is taken, this predicts TY to be 101 ~ 102 pascal for a
diameter of 1 jam, 103 ~ 104 pascal for 0.1 |im and 104 ~ 105 pascal for
0.01 ^m if Hamaker's constant is 10"12 - 10~13 erg.
Tanaka and White [86] were able to show semi-quantitative agree-
ment between calculated and experimental values of yield stress for
typical fillers such as carbon black, titanium dioxide and calcium
carbonate.
Yield stresses are generally observed in dispersions with fine particle
size having a high specific surface area and when the filler loading is
high. Increasing filler concentration has a pronounced effect on the
rheology of the filled systems.
6.3 EFFECT OF FILLER CONCENTRATION

With increasing concentration of the filler, the interparticle interactions
increase weakly at first and then rather strongly as the concentration
becomes higher and higher. The concentration at which particle-particle
interactions begin depends on the geometry and surface activity of the
filler particles. For example, high aspect ratio fillers would begin to
interact at much lower concentrations, while non-agglomerated large
size spherical particles would not interact until about 20vol% [94]. The
final concentration-dependent regime is that when a complete network
formation occurs due to particle-to-particle contact, which would occur
at concentrations of less than 1% for fibers and 40vol% for non-
agglomerated, randomly dispersed spherical particles. This is exempli-
fied by the sharp rise in the relative viscosity rjT at the concentration
beyond which particle-to-particle contact occurs as can be seen from
Figure 6.3(a).
Various fillers were dispersed in different polymer matrices [21,22]
and their relative viscosity vs. volume fraction was plotted as shown in
Figure 6.3(a). It is seen that the relative viscosity of the filled polymer
system adjudged at the same volume fraction varies with the properties
of the filler such as shape, size, size-distribution, surface appearance,
etc. It is quite obvious what the effect of the physical nature of the filler
surface would be on the steady shear viscous properties of the filled
polymer systems. The higher the surface roughness the greater the
resistance to flow deformation and hence the viscosity of filled system
FITJJRD POLYEIHYLENE AND POLYPItOFYLENE
Figure 6.3(a) Variation of relative viscosity at constant shear stress with filler volume
fraction 0 for various filled polymer systems. The capital letters indicate the filler and
the numbers designate the average aspect ratio of the fiber. The dashed lines
represent the curve through the experimental points. (Reprinted from Ref. 22 with kind
permission from Steinkopff Verlag Darmstadt, Germany.)
would be higher. This can be deduced intuitively. Experiments to

verify this are not easy because it is very difficult to find two fillers
with the same size and size distribution but different surface
roughness. Some indication of the effect of roughness can be got from
the data available in the works of Kataoka et al. [21] and Kitano et al.
[22]. This is shown in Figure 6.3(b) which gives the relative viscosity
of systems filled with precipitated calcium carbonate (CC) and natural
calcium carbonate (NC). The surface of the precipitated calcium
carbonate is much rougher than that of the natural calcium carbonate,
and as a consequence, the viscosity of systems filled with CC is seen to
be higher than those filled with NC Of course, this is not the isolated
effect of roughness alone. The CC particles had a much smaller size
and a much narrower size distribution than the NC particles and hence
these factors would also contribute to the viscosity increase.
In Figure 6.3(a), the values of r\r of materials filled with natural
calcium carbonate powder NC are the lowest because they are basically
CAI£IOM CAKBONATS FELED POLYEIEYIENE;
Figure 6.3(b) Variation of relative viscosity as a function of the volume fraction for
polyethylene melts filled with precipitated calcium carbonate (CC) and natural
calcium carbonate (NC). (Reprinted using data from Refs 21 and 22 with kind
permission from Steinkopff Verlag Darmstadt, Germany.)
particulate systems with an average of about lOjim particle size. The

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

the shear stress for a suspension of 15 jam diameter glass spheres in a thermoplastic
polymer. (Reprinted from Ref. 95 with kind permission from Elsevier Science-NL, Sara
Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)
M <67)
>=1 k/*M"
Agreement between data and theory can be seen to be excellent. 0m is
taken as 0.62 and the values of power law index n are chosen to be
different during the calculation depending on the chosen shear rate. At
shear rates below 1 s~l the polymer matrix and the filled system at most
concentrations is near Newtonian while the value of n reduces to 0.75 at
10s""1 and finally to 0.5 at shear rates in excess of 1Os"1. Of course, the
point of onset of shear thinning moves to lower shear rates with
increasing filler concentrations.
It is also seen in Figure 6.5 that the data at three different
temperatures superimpose on a single curve for each shear rate
considered. This is in contrast to the findings of Saini et al [63] who
also prepared plots of relative viscosity with filler volume fraction for
four different polymer matrices at three levels of loading as shown in
GLASS SPHERE FILLED THERMOFLASUC POLYMER
JARZEBSZI'S EQUAHOK
AS AFUNCTIQN QFn
Figure 6.5 Variation of relative viscosity at constant shear rate with filler volume
fraction. (Reprinted from Ref. 95 with kind permission from Elsevier Science-NL, Sara
Burgerhartstraat 25,1055 KV Amsterdam, The Netherlands.)
Figures 6.6-6.9. The curves are distinctly different at the various

temperatures in all cases and the change in viscosity with filler
concentration is exponential, in particular, with a major rise occurring
beyond a filler volume concentration of 0.25 to 0.30. Note that the plot
in Figure 6.5 is on a semi-logarithmic scale while Figures 6.6-6.9 are
not. Hence, it is possible that the differences in values are masked in
Figure 6.5, thereby leading to a conclusion that the plot is unique and
independent of temperature. A closer look at the plot does indicate this.
The temperature sensitivity of the relative viscosity can be easily
estimated [63] as follows.
The viscosity of a polymer melt decreases with increasing
temperature due to the greater free volume available for molecular
motion at the higher temperature. In the case of filled systems, the free
volume change is limited only to the polymer fraction of the composite.
BARIOM FERRJTE FILLED
LOW DENSIIY POLYEIHYLlHE
Figure 6.6 Variation of the relative viscosity with volume fraction of ferrites for low
density polyethylene at three different temperatures. (Reprinted from Ref. 63 with kind
BARIUM FERRTTE FILLED

POLYURETHANE TEERMOPLASIIC
ELASTOMER
Figure 6.7 Variation of the relative viscosity with volume fraction of ferrites for
polyurethane thermoplastic elastomer at three different temperatures. (Reprinted from
USA.)
BARIDM FERRIIE FILLED
STYRENE • ISOPlENE - STYRENE
BLOCK COPOLYMER
styrene-isoprene-styrene block copolymer at three different temperatures. (Reprinted
from Ref. 63 with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA.)
BAHIUM FERSITE FILLED

POLYESIER ELASTOMER
polyester elastomer at three different temperatures. (Reprinted from Ref. 63 with kind
It is therefore expected that the filled polymer melt viscosity would be
less temperature sensitive than the unfilled melt viscosity. Referring to
Figures 6.6 through 6.9 at a given filler loading, the relative viscosity
increases with increasing temperature. This is because the drop in the
unfilled melt viscosity with increasing temperature is more than the
drop in the filled melt viscosity.
The Arrhenius type equation, (2.6a), proposed by Eyring [96], is most
commonly used to analyze the temperature dependence of melt viscosity.
For unfilled polymer systems, the viscosity ^0 T at a temperature T can
be related to the viscosity rjojR at a reference temperature by the
following expression:
%T = ^rRexp(^J (6.8)
where E0 is the activation energy of the flow process for the unfilled
system and R is the universal gas constant.
For a filled system, with volume fraction (j> of the filler equation (6.8)
can be written as
^.T = ^.rRexp^J (6.9)
where ^ r and ^TR are the viscosities for a filler concentration of 0.

Thus combining equations (6.8) and (6.9) gives
ln^ = ln!VlR + ^- £ o) (6>10)
>?0,T >?0,TR ^T
It is obvious that a plot of ^^,T/Ô,T vs- V^ on a semi-logarithmic scale

would result in a straight line from whose slope AE which is the
difference in the activation energy of viscous flow due to presence of
the filler can be calculated.
The values of E0 (i.e. the activation energy for viscous flow of unfilled
systems) and values of E0 (i.e. activation energy for viscous flow for
filled systems) are shown in Table 6.2. It is seen that the E0 values are
lower than E0 values in all cases, indicating that rj^T is less temperature
sensitive as compared to r]QT which is obviously true because the fillers
provide very little free volume change with temperature in relation to
the matrix.
In Figures 6.3, 6.5-6.9, the *-axis is not normalized though this is a
common practice to be followed if a theoretical equation fit of the
Maron-Pierce [97] type is sought as shown in Figure 6.10. The simplest
one parameter equation which has been evaluated [21,22], and tested
extensively [71,72] is given as
i/r = (i - 4>/</>m)~2 (6.ii)
Table 6.2 Values of activation energies calculated from equation (6.10)
Filler amount 0% 40% v/v 47% v/v 57% v/v
E (kJ/mole) @ y = 100 sec'1 E0 E40 E47 E57
SIS block copolymer 23.5 18.3 15.8 12.0
Polyurethane thermoplastic elastomer 71.9 50.2 42.9 39.7
Polyester elastomer 53.8 36.9 34.7 28.7
Low density polyethylene 15.9 5.7 5.1 4.9
Source: Ref. 63 (reprinted with kind permission from Society of Plastics Engineers Inc., Connecticut,
USA).
GLASS SPHERE FILED POLYMERS

CHEVRON GRADE
CHEVRON GRADE
CHEVRON GRADE
CHEVRON GRADE
THERMOPLASTIC
THERMOPLASTIC
THERMOPLASTIC
EQUATION (6.11)
Figure 6.10 Variation of average relative shear viscosity as a function of the reduced
volume fraction of filler. (Reprinted from Ref. 71 with kind permission from Society of
Rheology, USA.)
In Figure 6.10, the maximum packing parameter 0m was determined
[71] experimentally by liquid displacement technique as 0.62. Several
different values have been reported in the literature. From geometrical
considerations, </>m ranges from 0.52 for simple cubic packing to 0.74 for
rhombohedral packing. However, Kitano et al. [22] have suggested an
average value of 0.68 for spherical particulates whose aspect ratio is
close to one. Nielsen [78], on the other hand, noted that maximum
packing usually ranges from 0.601 to 0.637 for random packing of
spheres, and it is generally smaller for agglomerated and non-spherical
fillers. Chong et al. [98] used a value of 0.605 for uniformly sized glass
beads which is in agreement with the observation of Nielsen [78].
Another method of interpreting flow data of filled polymer systems
is by following the route suggested by Shenoy and Saini [51]. Since the
relative viscosity r\r at constant shear stress gives a uniqueness to the
plot (Figure 6.3 vs. Figure 6.5), it is logical to choose a rheological
parameter which is determined under constant shear stress conditions,
and also one which is far from the zero shear rate region wherein filled
systems generally show the yield stress. The melt flow index (MFI)
becomes an ideal choice because it is determined at constant shear
stress in the medium shear rate range.
Using the inverse relationship between steady shear viscosity and
MFI [99], Shenoy and Saini [51] write the modified form of Doolittle's
equation [100] in the following form:
In MFI(T, 0) = In A" - —1— (6.12)

J(T9 0)
where MFI(T, 0) is the melt flow index of the filled polymer system at
temperature T and containing 0 volume fraction of filler, A' is a
constant. It is now assumed that the addition of filler alters the free
volume state of the unfilled polymer. The free volume of the polymer is
specified by /(T, O). Its melt flow index is written as MFI(T, O) and the
following relationship derived from equation (6.12) would then hold:
InMFI(T, O) = InA" - -L^ (6.13)
The altered free volume state of the filled polymer system is given, of
course, by equation (6.12).
As a first approximation, the free volume in the altered free volume
state resulting from the addition of a filler can be considered to reduce
the free volume of the reference medium and to be a linear function of
the volume fraction (/> of the added entity similar to that given by Fujita
and Kishimoto [101]:
/(T, 0)=/(T, O)-/J(T^ (6.14)
where /J(T) represents the difference between the free volumes of the
polymer and the filled system.
Combining equation (6.12) to (6.14) and rearranging the terms gives
^=-2.303/(T,Q) +2'3°^0)l (6.15)

log *MFI ^ P(T) </>
where
aMFl = MFI(T, 0)/MFI(T, 0)
Based on the assumptions made during the derivation of equation
(6.15), it is imperative to choose MFI(T, O) > MFI(T, </>). In the case of
filled systems, this condition is naturally satisfied when the polymeric
matrix is taken as the reference medium. Equation (6.15) predicts that a
plot of I/log 0MFI vs. 1 /(J) should be linear, and the propriety of this
model has been examined quantitatively in the light of the reported
experimental data. Existing viscosity data in the literature available for
all filled systems are in the form of viscosity vs. shear rate or shear stress
vs. shear rate curve. In each case the data are transformed into specific
MFI values using the method discussed in Shenoy and Saini [99].
Figures 6.11-6.16 show plots of l/log0MFI vs. 1/0 for different filled
QTJARTZ FILLED LOW DENSTTY POLYEIHYLENE
Figure 6.11 Melt Flow Index variation with filler composition for low density
polyethylene/quartz powder composite at 22O0C and 2.16kg test load condition for
MFI using data from Ref. 16. (Reprinted from Ref. 51 with kind permission from
Steinkopff Verlag Darmstadt, Germany.)
CALCIUM CARBONAU FILLED POLYPROPYLENE
Figure 6.12 Melt Flow Index variation with filler composition for polypropylene/
calcium carbonate composite at 20O0C and 2.16kg test load condition for MFI using
data from Ref. 5. (Reprinted from Ref. 51 with kind permission from Steinkopff Verlag
Darmstadt, Germany.)
polymer systems. The systems are so chosen as to include different

generic types of polymers as the matrix, and to include fillers with
different shapes and types. In all cases, despite the apparent diversity,
there is a uniqueness in the altered free volume state model, adjudging
from the straight line fits obtained in all plots.
Though it is recommended that the relative viscosity rjT or the
relative MFI value aum be used for estimating the rheological changes
due to filler concentration, at times a simple plot of MFI vs. the weight
fraction of the filler can certainly provide the same information as
done by Arina et al [17]. The effect of fillers on the melt flow
properties of polyethylene were investigated [17] by determining the
melt flow indices of the compounded filled systems. It was found that
finely divided fillers reduced the melt flow index of polyethylene more
than coarsely divided fillers, a result similar to that discussed in
section 6.2. As regards the effect of concentration, the melt flow index
was not affected much at small concentrations but there was a sharp
CARBON BLACZ FILLED POLYSTYlENE
Figure 6.13 Melt Flow Index variation with filler composition for polystyrene/carbon
black composite at 18O0C and 5.0kg test load condition for MFI using data from
Ref. 27. (Reprinted from Ref. 51 with kind permission from Steinkopff Verlag Darmstadt,
Germany.)
TTTANIDM DIOXIDE FILLED POLYSTYBENE
Figure 6.14 Melt Flow Index variation with filler composition for polystyrene/titanium
dioxide composite at 18O0C and 5.0kg test load condition for MFI using data from
Germany.)
GLASS FIBER FILLED POLYCARBONATE
Figure 6.15 Melt Flow Index variation with filler composition for polycarbonate/glass
fibers composite at 29O0C and 1.2kg test load condition for MFI using data from
Germany.)
GLASS FIBER FELED POLYEmYlEOT TBREPHIHMAEB
Figure 6.16 Melt Flow Index variation with filler composition for poly(ethylene
terephthalate)/glass fibers composite at 2750C and 2.16kg test load condition for MFI
using data from Ref. 20. (Reprinted from Ref. 51 with kind permission from Steinkopff
Verlag Darmstadt, Germany.)
drop with increasing concentration as can be seen in Figures 6.17(a)
and (b).
6.4 EFFECT OF FILLER SIZE DISTRIBUTION

In order to study the effect of filler size distribution, it is necessary to
work with uniform monodisperse particles. These would have to be
available in different sizes so that controlled mixtures of two or three
different sizes can be studied. There are various methods of getting
uniform-sized particles and these have been discussed in a number of
articles [102-106].
The simplest technique of getting uniform mono-sized particles is by
precipitation from solution due to the controlled generation of solutes
by a single burst of nuclei [102]. This method is commonly used to form
hydrated metal oxides by hydrolyzing the appropriate metal salt. Thus,
spherical aluminum hydroxide can be obtained [102] from alum and
spherical colloidal rutile can be prepared from TiCl4. Similarly, mono-
TALC/DOLOMTTE FHTFD
LOW DENSITY POLYHHYLENE
UWTTS
TALCA
TALCB
DOLOIgCTE
TALCA
Figure 6.17(a) The influence of some fillers on the melt flow indices of B3024 and
B8015 polyethylene grades. (Reprinted from Ref. 17 with kind permission from Society
of Plastics Engineers Inc., Connecticut, USA.)
MICA FILLED LOW DENSITY POLYElHYLENE
UNITS
Figure 6.17(b) The influence of mica A on the melt flow index of B 8015 polyethylene
at various temperatures. (Reprinted from Ref. 17 with kind permission from Society of
Plastics Engineers Inc., Connecticut, USA.)
sized silica particles can be prepared by precipitation of solutes

[103,104].
The other method of developing fine, spherical particles is through
the use of plasma techniques which may involve a physical
phenomenon or a chemical reaction [105]. In the former case, a simple
spherodizing process takes place when irregular shaped powder is
introduced into the plasma which melts it and then vaporizes it to form
uniform spheres. When a chemical reaction is involved, the reactants in
the solid or gaseous form in contact with the plasma are allowed to
react in the vapor phase and the products are allowed to condense as
deposits of fine powder on the cooler regions of the chamber after
leaving the plasma. Colloidal spheres of aluminum, copper, aluminum
nitride and silicon carbide are made in this way.
Uniform-submicron size polymer spheres can be made through
emulsion polymerization [106]. When a sparingly water-soluble vinyl
monomer like styrene that polymerizes by a free radical mechanism is
dispersed in water in the presence of a surfactant and a water-soluble
initiator, uniform-sized polystyrene beads can be obtained by
controlling the number of micelles and ensuring that each micelle traps
an initiator at about the same time.
The various methods employed to get uniform-sized particles have a
set goal to get model filler particles so that filled system experiments
can be controlled effectively to isolate the effects of various parameters.
This is especially important when studying filler size distribution effect
on the rheology. Despite all efforts to get uniform-sized particles, there
is often a distribution involved, however narrow it may be. Hence, to
study the effect of a bimodal size distribution on the rheological
behavior of filled polymer systems, glass spheres obtained from Potters
Industries Incorporated were fractionated by Poslinski et al. [72] into
narrow size ranges. Two size ranges of spheres were picked in the
preparation of the bimodal mixtures, and Table 6.3 lists their particle
size distribution, with the number of fractions of the zth component /j
vs. the diameter of the zth component D1 being tabulated.
Polydispersity tends to reduce the viscosity of filled systems at a
fixed loading level [107-112]. For dilute suspensions having a volume
fraction of solids less than 0.2, the effect of variation of particle size on
filled system viscosity is minimal [108,111]. However, at high loading
levels the viscosity can be reduced dramatically when the particle size
Table 6.3 Average particle size and particle

size distribution using digital image analyzer
Small spheres Large spheres
D
f\ \ (^m) f\ D\ (Hm)
0.04 2 0.01 45
0.11 5 0.04 50
0.15 9 0.04 56
0.24 12 0.15 62
0.10 16 0.10 70
0.13 19 0.20 78
0.08 21 0.21 83
0.06 25 0.15 90
0.04 29 0.06 99
0.03 32 0.03 105
0.02 35 0.01 110
Source: Ret. 72 (reprinted with kind permission from
Society of Rheology, USA).
modality is increased [98,113-115]. Henderson et al [114] reported a
reduction in filled system viscosity as high as 96% when the modality
was changed from a unimodal to a bimodal size distribution of spheres
at a fixed volume fraction of 0.66.
Theories on the viscosity of polydisperse systems have been developed
[109,113] and a method to predict the viscosity of multimodal filled
systems from the data for monomodal filled systems is also available
[113].
Farris [113] has shown that the relative viscosity of the filled polymer
system can be described by
^ = (1 - (t>Tk (6.16)
where k is a constant which varies according to the particle size
distribution and depends on the number of components making up the
distributions. In practice, k varies from 21 for monomodal to 3 for
infinite-modal distributions. Figure 6.18(a) graphically shows the
relationships. For uniform spherical particles viscosity increases steeply
after 0 = 0.5, approaching infinity at 0 = 0.74.
However, if the total volume of particulate filler is split into 25% fines
and 75% coarse, very high loading can be obtained without increase in
viscosity; this is shown in Figure 6.18(b).
MQNOMODALk -21
BlMODALk -5.8
TRIMODALk. -3.6
MFINTTE MODAL k - 3
Figure 6.18(a) Comparison of calculated relative viscosity for the best multimodal
system. (Reprinted from Ref. 113 with kind permission from Society of Rheology, USA.)
MONOMODAL
Figure 6.18(b) Variation of relative viscosity as a function of vol% solid spheres in

monomodal and bimodal suspensions, with volume fraction of small spheres being
25%. (Reprinted from Ref. 113 with kind permission from Society of Rheology, USA.)
If the ratio of the coarse to fine particle diameters is 7:1 the volume of
filler can be increased to </> = 0.73 from the monomodal loading of
(j) = 0.59 without increase in viscosity. Figure 6.18(c) shows the pro-
portion of coarse and fine particles to give minimum viscosity for a
range of total filler loading, indicating minima in the region of 30% fines.
Further reductions may be possible with increasing modality; but for
modalities greater than trimodal, the effects are not dramatic.
A natural consequence of the above findings is that for a given level
of filled system viscosity, it is always possible to increase the loading
level of the fillers through a careful choice of particle size distribution.
This particular point has a direct significance when dealing with
ceramic and metal processing [48,66-69,73-75,116-127] as well as during
the preparation of functional filler composites [60-63] where the prime
intention is to have as high a filler loading as possible and yet maintain
good processibility.
Mangels [116,117] has made use of the reduced viscosity of wide size
distribution powders to produce injection molding blends of high
powder loading (73.5 vol%). Working with silicon powder, particle size
distributions were obtained [116] by dry ball milling and air classifying,
and it was subsequently shown that a 140 h dry ball-milled powder
with the broadest particle size distribution yielded the best viscosity in
Figure 6.18(c) Comparison of calculated relative viscosity for bimodal suspension
of various blend ratios and concentrations. (Reprinted from Ref. 113 with kind
permission from Society of Rheology, USA.)
a spiral flow mold test [117]. In general, by altering the particle size
distribution from a sharp, monomodal type [118] distribution to a very
broad distribution, the solids content can be increased without
increasing the viscosity of the system [119]. Similar requirements have
been noted by Adams [120] for slip cast ceramics and there is a
similarity with the requirements for achieving high compaction density
in a pressed powder [121-123].
Chong et al. [98] were able to achieve volume concentrations close to
Eiler's value of 0.74 for rhombohedral packing by using a bimodal
mixture of spheres. They identified the diameter ratio of small to large
spheres, 6, and volume percent of smaller particulates in the total solids
mixtures, 0S, as two important parameters characterizing a bimodal
solids mixture. By fixing 0S at 25%, Chong et al. [98] showed that the
filled system viscosity was reduced as 6 decreased from 1.0 to 0.138;
however, they surmised that no significant reductions would occur
below a limiting particle size ratio of approximately 0.1 as the small
spheres could easily migrate through the interstices of the large spheres.
Calculations with varying </>s [98] suggested that there also exists an
optimum volume percent of smaller spheres where the filled system
viscosity is minimized.
Higher packing densities can be achieved if the particle sizes are not
uniform. This enables the finer particles to fill the holes between the
larger particles. The particles size range can be broadened in two ways.
Mixtures of two particles sizes can be blended, for example, coarse and
fine particles, or a continuous wide distribution of particle sizes can be
selected.
Increasing the number of particles sizes in the mixture can increase
the calculated packing density [123]. Table 6.4 shows the maximum
packing density attainable for random packing mixed spheres (with
from one to four sizes) [124]. An extension of the idea of bimodal
packing of spheres, is the packing of combined fibers and spheres.
These have been well described and discussed in detail by Milewski
[128]. It is pointed out that packing parameters change with respect to
fiber length to diameter ratio and choosing proper size combinations of
the mixed fillers optimizes the benefits from packing.
Gupta and Seshadri [129] used Ouchiyama and Tanaka's results [130]
to calculate the maximum packing parameter of polydisperse systems
of spheres given the value for the monodisperse samples and taking
into account particle size, size distribution and modality as follows
</>m = T^^ (6.17)

£(DZ - D3)3/;. + -[(D1- + D3)3 - (D1- - D3)3]/.
where
2
V(D
LJ\î + â/) Tl
' D
1 x
/pv ——1
, x \Ji f
n
'-'+*<*-'*>• EP--k~D.m <"8>

and
D11 = J]D1./. (6.19)
Table 6.4 Effect of particle size distribution on maximum packing density

of randomly dispersed spheres
Ratio of Ratio of fractions Maximum packing
particle diameter(s) of (wt%) density
the size fractions (vol%)
Cy1 100 64
Qf 11 VTCy 1 84/15 86
Cy11VTCy1JMQCy1 75/14/11 95
Cy1, 1 /7Cy1, 1 /49Cy1, 1 /343Cy1 72/14/10/3 98
Source: Ref. 124 (reprinted with kind permission from American Chemical Society
Inc., Westerville, Ohio, USA).
Here ^n denotes the maximum packing of spheres of uniform size
which may be taken to be the average value of 0.619 as suggested by
Nielsen [78]. D3 is the average diameter of the different sizes of the
particulates, D1 is the diameter of the fth component, and the abbrevi-
ation (D1 ~ D3) is defined as:
(D1 - D3) = O for D1 < D3 (6.2Oa)
and
(D, - D3) = D1 - D3 for D1 > D3 (6.2Ob)
In addition,/ is the number fraction of the zth component defined by:
*-%/£% <«»
where v{ is the volume fraction of the zth component in the mixture.
The number fraction may also be directly obtained if a size distribution
of the solids, / vs. D1, is available as in Table 6.3. The maximum
packing parameter can be calculated with equations (6.17)-(6.21) for
any solids mixtures of spherical particulates, and equation (6.11) may
then be used to estimate the value of the filled system viscosity at a
fixed shear stress level.
Poslinski et al. [72] undertook the study of the influence of a bimodal
size distribution of glass spheres on the rheology of filled polymer
systems. They used small and large glass spheres of sizes as given in
Table 6.3. The average diameter of the two size ranges calculated by
equation (6.19) was 15 and 78 (im, respectively, and therefore the
particle size ratio was 0.192 based on these average values. Bimodal
size distributions were prepared by mixing together various volume
percents of the smaller 15 ^m spheres with the larger 78 jam spheres;
specifically, <£s = 0,10,30,50,75 and 100%. Figure 6.19 shows the maxi-
mum packing data obtained for a bimodal solids mixture of 15 and
78 ^m glass spheres with </>s, the volume percent of smaller spheres,
ranging from O to 100% of the total solids mixture. The experimental
values of the maximum packing fraction were obtained by the
sedimentation technique, and these indicated that </>m increased for a
bimodal system depending on the amount of the smaller spheres. Also
shown in Figure 6.19 is the value of the maximum packing calculated
from the data of Chong et al. [98] for a bimodal distribution of spheres
at (/> = 0.60 and Ss = 0.138 as well as Sweeny's data [115] at 4> = 0.55
and <5S = 0.048. The highest value of the maximum packing parameter,
0.752, was obtained by mixing approximately 15% of the 15jnm and
85% of the 78 jam glass spheres in the total solids volume. The error
bars shown in Figure 6.19 represent the random error in the experi-
mental measurements of the maximum packing.
GLASS SPHERE FILLED POLYBUTENE
Eq.(6.17) USING DISTRIBUTION VALUES
Eq.(6.17) USING AVERAGE VALUES
DATAOF POSDNSiQ ET AL. [72 ]
DATA OF CHONG ET AL. [ 98 ]
DATAOF SWEENY [115]
Figure 6.19 Variation of maximum packing as a function of the bimodal size

distribution of the 15 and 78 jam glass spheres. (Reprinted from Ref. 72 with kind
permission from Society of Rheology, USA.)
Various bimodal mixtures were compounded into a polybutene grade

24 polymer obtained from the Petrochemical Division of the Chevron
Company, at total solids concentrations up to 60% by volume. The
polybutene polymer was a Newtonian liquid at room temperature
whose viscosity and density at 220C were 25 Pa sec and 898kg/m3,
respectively. Due to the relatively high viscosity of the polybutene, it
was found that the glass spheres suspended in the polymer remained
dispersed for at least 24 h before complete settling occurred.
Upon addition of glass spheres to the polybutene grade 24 matrix,
the magnitude of the shear viscosity at 220C was observed to increase
and it remained approximately constant for shear rates ranging from
0.1 to 100 sec'1. As a result, the relative viscosity data determined at the
same shear stress were obtained by averaging data over the entire shear
rate range of measurement.
To see the effect of particle size and size distribution, the average
relative viscosities of the various glass sphere suspensions are plotted
against $s, the volume percent of the 15 j^m spheres, ranging from O to
100% of the total solids mixtures as shown in Figure 6.20. When the
GLASS SPHERE FILLED POLYBUIEHE
TOTAL SPHERES
EQUATION (6JlJ)
DATA OF OHONO ET AL. [98]
DATAOF SWEENY 1115]
Figure 6.20 Variation of average relative shear viscosity as a function of 0S, the
vol% of the 15 jam glass spheres in the total solids mixture suspended in a polybutene
grade 24 matrix at 220C. (Reprinted from Ref. 72 with kind permission from Society
of Rheology, USA.)
two sizes were mixed together, the relative viscosities were actually
reduced, especially for volume fractions of total solids greater than 0.3.
The lowest values of i\r were obtained for 0S = 10 to 30% of the smaller
spheres, the same range in which the maximum packing parameter was
observed to be highest. The 60% by volume loading level could not be
achieved for a unimodal size distribution due to difficulty in obtaining
a fully homogeneous compound; however, it was possible to reach this
high concentration for 0S = 10, 30 and 50%.
The solid lines in Figure 6.20 represent the predictions of equation
(6.11) with the maximum packing fraction determined by equation
(6.17) using the particle size distribution values of the bimodal
components listed in Table 6.3. The agreement between theory and
experiment is excellent. The optimum reduction in the relative
viscosity is correctly predicted by equations (6.11) and (6.17) to be
(j)s — 15%, which corresponds to the highest value of the maximum
packing.
6.5 EFFECT OF FILLER AGGLOMERATES
The presence of agglomerates has a considerable effect on the maximum
possible loading of the filler, as can be seen from Table 6.5. If the
agglomerates are all broken down into individual particles, then
63.7 vol% of the filler can be incorporated into the polymer. However, if
a dozen particles are clustered together in each agglomerate, then the
maximum loading possible would be only 43vol%. At maximum filler
loading, the viscosity of the filled system is close to a hundred to a
thousand times greater than that of the polymer itself, as can be seen
from Figure 6.10. Agglomerates occlude liquid in their interparticle
voids, thereby increasing the relative viscosity value at any given solids
loadings. Thus, the viscosity would be the same for 43vol% of
agglomerated filler with a dozen particles in each agglomerate as it is
for 63.7 vol% of non-agglomerated particles.
For highly filled polymer systems, it is therefore important to reduce
the degree of agglomeration to a minimum level, in order to decrease
the system viscosity for easier processing and to increase the extent of
filler loading.
The adhesion forces between particles have been discussed by Rumpf
and Schubert [131]. In addition to electrostatic and van der Waals
forces, the presence of liquid and solid bridges contributes to high
agglomerate strength. The dispersion of powders in liquids is
influenced in part by the wetting characteristics of the liquid on the
solid surface, and is related to the hydrogen-bonding capability of the
liquid which can be expressed as its cohesive energy density [132]. The
initial drying of powders and the heating associated with processing of
a high molecular weight organic vehicle help to reduce the effect of
Table 6.5 Effect of aggregration on maximum filler concentration 0m

Number of particles in Maximum filler concentration
aggregated spheres 0m, (vol%)
1 63.7
3 60
5 53
8 47
12 43
18 39
32 37
57 35
122 34
250 32
Source: Ref. 76 (reprinted with kind permission from Marcel Dekker Inc., New
York, USA).
liquid bridges. The presence of solid bridges when a small amount of
additive has been incorporated in the powder via a salt by spray
drying, such as magnesia in alumina or yttria in zirconia, gives rise to
more serious problems. Such agglomerates can only be broken down by
milling of the powder or by using mixing devices which impose high
shear stresses.
High shear mixing generates velocity gradients which are normally
strong enough to break agglomerates in fillers of micron size or larger.
In the case of submicron fillers, the forces holding the particles together
are stronger than the shear force created by the velocity gradient. In such
circumstances, even high shear mixing does not break the agglomerates
or eliminate the microvoids within the filled system, and one has to
take recourse to filler surface treatment [9,15,34,36,37,43-45,52,54,60]
which is capable of altering the interparticle forces, resulting in
deagglomeration, better dispersion, and hence lower viscosity with
maximum possible loading.
6.6 EFFECT OF FILLER SURFACE TREATMENT

An approach to improving filler-polymer compatibility is the use of
surface-modifiers on the filler through a pretreatment process. Surface
treatment is meant to help the polymer wet the filler and disperse it.
However, the extent of wetting and degree of adhesion are different
for each polymer, filler, and surface modifier combination. Some
modifiers that will effectively coat the filler surface may not interact
with the polymer, whereas others that are compatible with the
polymer may not adhere to the filler, and hence, will not effectively
modify its surface. It is thus very difficult to predict the performance
of the surface modifier a priori for any filler-polymer combination. It
is, therefore, a common practice to select the appropriate surface
modifier for a filler-polymer combination rather empirically. One
could, of course, refer to the extensive information available in the
form of books, reports and papers [133-135] on various types of
surface modifiers listed in Table 1.5.
Surface modifiers are generally bifunctional molecules with one end
capable of adhering to the filler and the other end compatible with the
polymer, and at times even capable of reacting with it. There have been
extensive studies on the effect of surface treatment on the steady shear
viscous properties of filled polymer systems [9,13,15,18,32,34,36,38,
39,52,53,6O].
There is enough evidence that the increased melt viscosity introduced
by filler addition can be significantly reduced by the application of
surface modifiers to the fillers. Some typical examples of viscosity
reductions achieved through the addition of surface modifiers to
selected filled polymer systems are given in Table 6.6. The maximum
reduction in viscosity is seen to be 73% in the 40phr high aspect ratio
mica in unsaturated polyester.
Reductions in viscosity can also be achieved through the use of
wetting agents such as W-900 manufactured by Bye-Mallinckrodt as
shown by Cope and Linnert [32]. With low-profile fillers like clay, silica
and mica, viscosity reductions of 70, 80 and 90% respectively have been
observed. Presence of low-profile filler in a 50% blend of wollastonite
and polyester have been seen to give 35 to 41% lower viscosity. Cope
and Linnert [32] observed an interesting synergistic effect when wetting
agents and silanes were used in combination. A 60% quartz/epoxy
Table 6.6 Effect of surface modifiers on some selected filled polymer systems
Polymer Filler, loading (phr) Surface Viscosity Melt flow Source
modifier, (Pa sec) index Ref.
amount (g/10min)
(phf)
Unsaturated polyester Wollastonite, 150 90 [13]
Unsaturated polyester Wollastonite, 150 A-174,0.5 54 [13]
Unsaturated polyester Calcined kaolin clay, 100 56 [13]
Unsaturated polyester Calcined kaolin clay, 100 A-174, 0.5 37 [13]
Unsaturated polyester Hydrous kaolin clay, 88 95 [13]
Unsaturated polyester Hydrous kaolin clay, 88 A-174,0.5 36 [13]
Unsaturated polyester Talc, 100 58 [13]
Unsaturated polyester Talc, 100 A-174,0.5 30 [13]
Unsaturated polyester Mica (high aspect ratio), 104 [13]
40
Unsaturated polyester Mica (high aspect ratio), A-174,0.5 28 [13]
40
Unsaturated polyester Silica 10/*, 120 52 [13]
Unsaturated polyester Silica 10/1, 120 A-174,0.5 14 [13]
Unsaturated polyester Alumina trihydrate 65 [13]
Unsaturated polyester Alumina trihydrate A-174,0.5 48 [13]
HOPE Wollastonite, 43 16.5 [13]
HOPE Wollastonite, 43 TTS, 3 16.5 [13]
HOPE Calcium carbonate, 150 16.3 [13]
HOPE Calcium carbonate, 150 TTS, 3 17.8 [13]
HOPE Barium sulfate, 150 16.3 [13]
HOPE Barium sulfate, 150 TTS, 3 22.0 [13]
PP Calcium carbonate, 50 4.4 [30]
PP Calcium carbonate, 50 Stearic 5.2 [30]
acid, 1.0
PP Calcium carbonate, 100 3.6 [30]
acid, 0.2
acid, 1.0
acid, 1.5
system produced a 60% viscosity reduction with a hydrophobic wetting
agent and an 80% reduction with a silane/BYK additive combination.
The general conclusions of Cope and Linnert [32] are that greater effects
occur with increasing filler concentration and with those fillers that are
most difficult to wet and disperse. Similarly, thermoplastic filled systems
produce greater effects than those seen in thermosets because these
resins do not wet fillers well. Cope and Linnert [32] have shown how
wetting agents can be effectively used in low density sheet molding
compound (SMC) for lowering viscosities.
Observing the published data, it is seen that, in some cases, the effect
on the steady shear viscosity is only marginal. There are a few select
cases [9,18] wherein the viscosity is seen to reduce even below that of
the virgin polymer (Figures 6.21(a) and (b)). Figure 6.21(b) taken from
Monte and Sugerman [18] shows how the concentration of the titanate
changes the flow behavior of 70% calcium carbonate filled
polypropylene. The work of Han et al [15] also indicates that the melt
viscosity decreases with the addition of TTS to CaCO3-PP and fiber
glass-PP system. The extent of decrease depends on the type of the
surface modifier and the type of the filler-polymer combination. It was
found that the effect of TTS in decreasing the viscosity was more than
in the case of ETDS-201; so also there was a profound effect on the
viscosity of CaCO3-PP system than fiberglass-PP system. A possible
MICA FILLED POLYPROPYLENE UNITS
40 % FILLER UNTKEAIED
40%FILLERTEtEATED
WTTH Z-6032 SHANE
UNFILLED
Figure 6.21 (a) Variation of steady shear viscosity with shear rate. (Reprinted from
Ref. 9 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
CALCIDM CARBONATE FILLED POLYPROPYLENE
UNITS
70% FILLER TREATED

WTIH 0.5 w % KR TTS
70% FILLER TREATED
WTIH 1.0 w % KR ITS
UNFILLED
Figure 6.21 (b) Variation of steady shear viscosity with shear rate. (Reprinted from
Ref. 18 with kind permission from Marcel Dekker Inc., New York, USA.)
explanation for this viscosity decrease has been suggested by Han et al.
[15,34] to be due to the plasticizing effect of the organic groups in
titanate coupling agents. It is more likely that the titanium oxide
monomolecular layer formed by monoalkyl titanates and the silanol
monomolecular layers formed by silanes on the filler surface, modify
the surface energy so that the viscosity of the filled polymer system is
reduced. The effect of viscosity reductions in these systems [15,34] was
not as drastic as observed [9,18] in Figures 6.21(a) and (b).
The normal expected behavior from the use of surface modifiers is
one in which the viscosity reduction occurs to a different extent
depending on the type of surface modifier, its amount and method of
treatment. The maximum achievable reduction would most likely be
very close to the flow behavior of the unfilled polymer at least at higher
shear rates. This is well illustrated in the work of Saini et al. [60] for
highly filled polymer systems.
Saini et al. [60] used pretreated fillers in their study of the effect of
surface modifier on the melt rheology of styrene-isoprene-styrene block
copolymer. The platelet-shaped barium ferrite that was used as filler
was not monosized, and had an average particle size of about 3|im.
Two silanes: Z6075 and Z6076; and three titanates: KR38S, KR138S,
and KRTTS (Table 1.5 for chemical description) were used as surface
modifiers. The treatment method consisted of using a solution of 95
parts methanol and 5 parts of water by volume for the silanes and 100
parts of xylene for the titanates. Surface modifiers of an amount equal
to 1% by weight of barium ferrite were dispersed in the solvent. The
slurry was formed by wetting the required quantity of barium ferrite
with the prepared solution and stirring for about 30 minutes. It was
then allowed to stand overnight and the solvent was removed in the
oven at 1050C for silanes and 13O0C for titanates.
The viscosity vs. shear rate data obtained by Saini et al. [60] for
57vol% of barium ferrite pretreated with different surface modifiers is
shown in Figure 6.22(a). It can be seen that all titanates aid in reducing
the viscosity of the filled polymer system while the silanes show a very
marginal effect. Though there have been a number of articles in the
literature [7,9,15,34,36,44,133-135] on the mechanism by which surface
modifiers act, not all seem to show coherent agreement. Some have
BAMDM FERBITE FILLED STYIUENE-ISOPSENE-STYaENE

UNITS
FERSITE UNTREATED (57 v% FILLER)

FESSTTE TREATED WTTH SHANE - Z6076
FEESITE TREATED UTCTH SILANE - Z6075
FERBITE TREATED WITH TJTANATE - KR38S
FERBITE TREATED WITH TTTANATE - KR138S
FERBITE HEATED WTTH TTTANAIE' KR TTS
UNFILLED
Figure 6.22(a) Variation of apparent viscosity with shear rate at 22O0C for unfilled,
57 vol% untreated ferrite filled, and 57vol% treated ferrite-filled SIS block copolymer
systems. (Reprinted from Ref. 60 with kind permission from Society of Plastics
postulated [15,43] that there is a tendency to produce a plasticizing
effect, due to the modification of the interfacial characteristics of the
filled system. The titanates in the case of Saini et al. [60] could have
acted as good dispersing agents, but not as coupling agents, and
provided no chemical bridge between the polymer and the filler
particles. The scanning electron micrographs shown by Saini et al. [60]
give evidence of the fact that the dispersion level is better with the
titanates than with the silanes. However, since no low steady shear data
were presented, this conclusion cannot be ascertained with confidence.
It is quite plausible that the titanates act as good dispersing agents and
provide a plasticizing effect as well, thereby resulting in drastic reduc-
tions in viscosity of the filled polymer systems [6O].
The effect of surface modifier concentration was also studied by Saini
et al. [60] as shown in Figure 6.22(b). It is seen that the optimum
concentration is in the range of 0.6-0.8% by weight of filler. Their
results confirm the range suggested by Monte and Sugerman [18] and
Sharma et al. [36]. The exact optimum concentration would, of course,
vary for each filler, polymer, and surface modifier combination, and
may need to be determined each time.
It must be emphasized here that the method of pretreatment also
plays an important role in the final performance of the filled polymer
system. This point has not been addressed by earlier investigators. The
silanes, for example, are known to undergo hydrolysis/condensation
VISCOSTlT
RAUO
%TTS
Figure 6.22(b) Variation of viscosity ratio at a shear rate = 100 sec"1 of treated to
untreated 57vol% ferrite-filled SIS with different percentages of KR TTS for
determining the optimum treatment level. (Reprinted from Ref. 60 with kind permission
reactions, and the extent of these reactions is a function of the nature of
the solvent phase, silane concentration in solution, pH of the solution,
and filler treatment time [133]. Prehydrolysis of the silane is known to
be beneficial because the silanols formed in the reaction can then react
with the filler surface. However, two silanols can undergo a parallel
self-condensation reaction reducing the systems activity towards the
filler. By adjusting the pretreatment variables in a favorable manner, it
would thus be possible to make either of the possible reactions dominate.
This would naturally result in differences in the efficacy of the filler
surface modification. Further, it is known that the preferred orientation
of a silane molecule at the inorganic filler surface is with silanol function
attached to it and the organofunctional group extending away from it.
Deposition of the silane from water or alcohol would naturally assist
this favorable orientation, provided the pH is equal to or less than the
isoelectric point of the inorganic surface. By altering the pH, it might be
possible to deposit the silane in an inverted fashion as suggested by
Plueddeman [133]. This would alter the rheological characteristics of
the filled polymer system. It is not known to what extent the rheology
of the filled system could be altered by manipulations in the treating
method, and this may need systematic investigation.
6.7 EFFECT OF POLYMER MATRIX

The effect of the polymer matrix on the steady shear viscosity of filled
systems would depend on the chemical nature of the polymer as
well as its unfilled viscous characteristics. The polymer melt itself
could be Newtonian, moderately shear-thinning or predominantly
shear-thinning.
In the case of polymers like nylon, polyethylene terephthalate (PET)
and polycarbonate (PC), the steady shear viscosity is near Newtonian
up to even a shear rate of a little over 10Os"1 as can be seen from
Figures 6.23-6.25. As an example of a moderately shear-thinning
polymer, polyetherimide (PEI) could be considered [136] as shown in
Figure 6.26; while, for a predominantly shear-thinning polymer, poly-
propylene (PP) is a reasonable example as shown in Figure 6.27. Note
that in Figures 6.24 and 6.27, the plots are shown as shear stress vs.
shear rate which is, of course, another method of representation of the
same information.
In all cases, it can be seen that the addition of fillers whether they are
particulates like calcium carbonate (CaCO3) or glass fibers (GF), sys-
tematically moves the entire curves to a higher level. The viscosity
increase is greater at lower shear rates whereas lower at higher shear
rates. The extent of the effect would, of course, depend on the nature of
the polymer and the filler type, size, size distribution, etc.
Next Page
Steady shear elastic -7
properties /
Despite the fact that the literature on the rheology of filled systems is
extensive [1-85], the work related to the steady shear elastic properties of
such systems is quite limited [5,19,27,29,31,34]. This is, of course, due to
the experimental difficulties in these measurements. The usual signs of
elastic behavior in filled systems are recognized by the presence of larger
normal stress differences during relatively low shear measurements on a
cone and plate rheogoniometer and by higher exit pressure as well as
larger die swell values during high shear capillary or slit rheometry. As
normal stress difference is mathematically connected with exit pressure
and recoverable shear strain and, conceptually, with die swell ratio,
knowledge of these would also provide the same information. The exit
pressure is the small finite value pexit which is obtained when the
pressure in the capillary or slit is plotted against downstream distance
and the extrapolated pressure at the exit is non-zero. With appropriate
assumptions, it has been shown that pexit can be related to primary
normal-stress difference [77]. However, since the theory has been
questioned [86] and a controversy arisen [87], it has not gained
popularity as a useful measure of elasticity. The use of the recoverable
shear strain to determine the effect of fillers on the elastic properties of
polymer melts has been uncommon, whereas study of die swell ratio has
been extensive, especially in the determination of the effect of carbon
black on the extrudate swell of elastomers.
Some special problems exist in normal stress measurement of filled
polymer systems. Abnormal effects at low rates are observed due to the
interactions between the measuring equipment and the yield stress
property associated with the filled systems. As a result, a proper zero
point for measurement cannot be obtained. Furthermore, the
uncertainty is proportional to the level of the yield stress [19]. It is thus
difficult to measure normal stresses accurately especially at low shear
rates [27].
In low shear measurements, the difficulty lies in the gap setting of
the cone and plate, firstly, due to the high residual stresses which do
not relax easily and secondly, due to the filler particles which interfere
on account of their individual particle size or the agglomerate size. In
high shear measurements, the particle or agglomerate size again may
interfere with the extrusion process on account of the obstruction that
they may create at the die exit. Nevertheless, with a great deal of
careful experimentation, useful elastic property data on filled polymer
systems can be generated as has been shown by some researchers
[5,19,27,29,31,34].
The generated data may appear confusing at the outset if looked at
cursorily. The presence of fillers in the polymers seems to show
decreases as well as increases in elasticity and the reports may appear
contradictory at times. However, a careful look at the elastic properties
data of filled polymer systems shows that it is the method of
representation and certain categories of fillers which show unexpected
trends. The effects of various parameters on the steady shear elastic
properties are discussed in various subsections as was done for the
steady shear viscous properties in the preceding chapter. However, all
subcategories may not be covered and the extent of discussion is at
times concise due to limited information.

The experimental studies of the influence of fillers on the rheological
properties of polymer melts by White et al. [29] best illustrate the effect
of filler type. The steady shear elastic data were generated in terms of
the first normal stress difference using the cone and plate arrangement
of the Rheometrics Mechanical Spectrometer at a fixed temperature of
18O0C.
The filled systems were prepared with a fixed grade of polystyrene
Dow Styron 678U and involved the use of nine different types of filler
as summarized in Table 6.1. Various filler types were thus covered from
rigid to flexible, as well as spherical, particulate to fibrous. The filler
loading was fixed at 20vol% and hence the generated data bring out
the exclusive effect of the filler type on the elastic properties.
Figures 7.1 and 7.2 show the variation of primary normal stress
difference with shear stress for the various filled systems studied [29]. It
is seen that glass beads hardly affect the values of N1 while the presence
of Franklin fibers, titanium dioxide (TiO2), calcium carbonate (CaCO3),
carbon black (CB) and mica, respectively, show greater and greater
reductions in N1. However, on the other hand, the addition of certain
fibers like cellulose fiber, glass fiber and aramid fiber, respectively,
increases N1 values to a larger and larger extent.
FILLED POLYSTYRENE
UNTTS
PASCALS
PS
GLASS BEADS
FRANZLINFIBER
TiO2
CaCO3
CB
MICA
Figure 7.1 Variation of primary normal stress difference with shear stress for filled
polystyrene melts containing 20 volume fraction of various types of fillers as indicated.
(Reprinted from Ref. 29 with kind permission from American Chemical Society,
Washington DC1 USA.)
FILLED POLYSTYRENE
UNITS
PASCALS
ARAMID FIBER
GLASS FIBER
CELLULOSE FIBER
PS
Figure 7.2 Variation of primary normal stress difference with shear stress for filled
polystyrene melts containing 20 volume fraction of various types of fillers as indicated.
(Reprinted from Ref. 29 with kind permission from American Chemical Society,
Washington DC, USA.)
From Table 6.1 it can be concluded that fibrous fillers (aramid, glass
and cellulose fiber) tend to increase the normal stress difference value
at a fixed shear stress, particulate fillers (titanium dioxide, calcium
carbonate and carbon black) tend to depress it while spherical fillers
(glass beads) leave it nearly unchanged. The large increase in normal
stresses in fiber-filled polymer systems is probably due to a hydro-
dynamic particle effect, associated with orientation in the direction of
flow [29]. There is an indication that the increase in N1 is a function of
the fiber modulus and aspect ratio. The higher the modulus and the
longer the fibers, the larger the value of N1 as depicted in Figure 7.2. It
has been noted elsewhere by Czarnecki and White [28] that mastication
of fiber-filled systems breaks up the fibers into smaller lengths and also
reduces the value of N1. Among the fibers studied in Table 6.1, the lone
fiber which depresses the value of N1 is the Franklin fiber. Though the
aspect ratio of the fiber is comparable to the other fibers, its diameter is
much smaller. Thus, the observed lowering of the normal stress in this
case is more of an effect due to size than its shape and hence is
discussed in the next subsection.

Normal stress measurements for polymer melts filled with large
particles [14,28,29,31] and those filled with small particles [7,15,27,29]
are available. When plotted in terms of N1 vs. T12, the primary normal
stress differences are consistently found to be reduced by the presence
of smaller particles (for example, Figure 7.1). From Table 6.1, it can be
seen that titanium dioxide, calcium carbonate and carbon black are
small in size compared with the other fillers and show lower normal
stress differences. From among the fibers, it is the Franklin fiber which
has the smallest dimension, almost in the range of the three particulate
fillers, and thus behaves in the manner similar to that of TiO2, CaCO3
and CB. However, the extent of normal stress difference reduction is
less due to the effect of the high aspect ratio which tends to raise the
value as explained in section 7.1.
It should be noted that Figures 7.1 and 7.2 are plotted as N1 vs. T12
rather than N1 vs. y. Where the latter representation was used then the
data would appear as shown in Figure 7.3(a). Only curves for
particulate fillers - titanium dioxide and carbon black - are shown for
illustration purposes. It can be seen that both these fillers appear to
increase normal stress differences of the polymer melt at the same shear
rate. Thus from Figure 7.3(a) it can be concluded that small particulate
fillers like carbon black and titanium dioxide increase the elasticity of
polymer melts. This is contrary to the trend in Figure 7.1 for the same
filled systems using the same data but different representation wherein
FILLED POLYSTYRENE
UNITS
PASCALS
Figure 7.3(a) Variation of primary normal stress difference with shear rate for filled
polystyrene melts containing 20 volume fraction of carbon black and titanium dioxide
fillers. (Reprinted from Ref. 27 with kind permission from Society of Plastics Engineers
Inc., Connecticut, USA.)
it was concluded that small participate fillers decrease the elasticity of

polymer melts. It is important to establish, therefore, which of the
representations is truly correct.
In order to do this, it is best to deal with another useful parameter of
elasticity, namely, the steady-state shear compliance /e which gives a
measure of the stored energy or the elastic recovery of the system.
When represented mathematically as /e = (T11 - T22)/2T12, the plot of
J6 vs. y would give the correct trend based on a molecular interpretation.
The usefulness of plotting normal stress N1 vs. shear stress T12 for
unfilled polymer melts is known [77,88,89]. Such plots are independent
of temperature and molecular weight (though not its distribution), and
rheological behavior for such viscoelastic fluids is interpretable in terms
of the steady state shear compliance Je. Addition of the carbon black
reduces the N1 values at fixed T12 as already discussed with reference to
Figure 7.1. The same effect would be observed in case /e values are
plotted against shear rate. Another method of representation of
elasticity is through the use of the characteristic time of the system.
Figure 7.3(b) gives the plot of relaxation time vs. shear rate for high
density polyethylene melts containing glass fibers. It is seen that the
presence of glass fibers increases the relaxation time and gives the same
interpretation as Figure 7.2. Thus, it can be concluded that the method
GLASS FIBEJl FTlLED POLYSTYRENE UNITS
GLASS FmER
GLASS FIBER
Figure 7.3(b) Variation of relaxation time with shear rate for polystyrene melt filled
with glass fiber. (Reprinted from Ref. 14 with kind permission from John Wiley & Sons,
of representation of N1 vs. T12 as given in Figures 7.1 and 7.2 is the

correct one and should be followed. Particularly in the case of filled
systems, the shear rate or velocity gradient may not be continuous at
the interface between the filler and polymer, whereas shear stress is
likely to be continuous at the interface assuming no slippage occurs
between filler and polymer [81]. Hence, interpretation of normal stress
difference through shear stress becomes more meaningful. In systems
showing a yield stress, as the shear stress is decreased towards it, the
normal stress difference approaches zero [27,90] as suggested by the
developed phenomenological constitutive equations [19]. However, this
response is not observable in Figures 7.1 and 7.2 because of lack of
normal stress data at very low shear rates. The view that N1 is small
relative to T12 because of the existence of a yield value is, of course, a
reasonable one.

In order to obtain data representation in the form of N1 (or ^1 = N1/^2)
vs. volume fraction </>, attempts [7,71] have been made to obtain
graphical similarity with the viscous counterpart as shown in Figure
6.10. Minagawa and White [7] showed that the ratio of N1 or ^1 of the
filled systems to that of the unfilled polymer matrix at the same shear
rate was independent of the shear rate and an increasing function of </>.
The function was not found to be unique and depended on the chosen
filler-polymer combination. An empirical Taylor series expansion for
\l/ltT at low volume fraction was shown to successfully describe the
increase with volume fraction in the range of O < 0 < 0.25.
Poslinski et al [71], on the other hand, found that all their glass
sphere data could be correlated by the following form analogous to
equation (6.11) for relative viscosity
*-£tf=" -*/«* ™
The ^1 r experimental values were obtained by averaging the relative
data over the entire range of shear rate measurement from 1 to 10Os"1.
It can be seen from Figure 7.4 that the experimental data are fitted rather
well by the above equation (7.1) over the entire volume fraction range
up to as high as 0.6. In Figure 7.4, the value of 0m was taken as 0.62 as
GLASS SPHERE FILLED POLYMERS

CHEVRON GRADE-18
CHEVRON GRADE-24
CHEVRON GRADE -32
CHEVRON GRADE -122
THERMOPLASTIC @ 130 0 C
THERMOPLASTIC (§150° C
THERMOPLASTIC @ 170 0C
EQUATION a-1)
Figure 7.4 Variation of average relative primary normal stress coefficient as a

function of the reduced volume fraction of filler. (Reprinted from Ref. 71 with kind
determined experimentally [71] by the liquid displacement technique.
Despite the fact that theoretical interpretation of experimental data
[7,71] works out well as represented, intuitively the predicted trend is
reversed. The presence of the particulate fillers has been shown to
decrease the elasticity of the polymer melt as demonstrated in
Figure 7.1. This fact is also supported by exit pressure measurements
[5,34]. With increasing filler concentration, it is thus logical to expect
that normal stress difference would decrease. This has, in fact, been
shown by Han [77,81] as given in Figure 7.5(a). It has also been shown
[7] that extrudate swell decreases with increasing filler concentration as
can be seen from the plot given in Figure 7.5(b) of extrudate swell ratio
vs. filler concentration for high density polyethylene melts filled with
titanium dioxide determined at a constant shear rate (10 sec"1) with a
capillary having an L/D ratio of 28. Hopper [91], Gotten [92], Medalia
[93], Vinogradov et al [94] and White and Crowder [6] all studied the
effect on die swell ratio of carbon black-filled polymer systems. The
unanimous observation was that, as the filler concentration was
increased, the die swell ratio decreased showing a decrease in the
elasticity. The effect of this was an improved extrusion characteristic
and an increased value of the critical shear stress before melt fracture
could occur. Plots of relaxation time vs. filler concentration as given in
Figure 7.5(c) for various polymers filled with TiO2 particulate filler,
support the fact that elasticity decreases with increasing concentration.
CALCIUM CARBONATE FILLED POLYPROPYLENE

UNITS
Figure 7.5(a) Variation of primary normal stress difference with shear stress for
polypropylene at 20O0C filled with calcium carbonate. (Reprinted from Refs 77, 81 with
kind permission from Academic Press Inc., New York, USA.)
TUAKIDM DIOXIDE FILLKD HIGH DENSITY POLYETHYLENE
Figure 7.5(b) Variation of extrudate swell ratio with volume fraction for high density
polyethylene at 18O0C filled with titanium dioxide. (Reprinted from Ref. 7 with kind
XUAITDM DIOXEDB FILLED POLYMERS

UNITS
Figure 7.5(c) Variation of relaxation time with volume fraction for polymer melts filled
with titanium dioxide. Data at shear rate of 0.5sec~1. (Reprinted from Ref. 7 with kind
It is obvious that the mobility of the polymer chains under the influence
of an applied stress is reduced by the presence of the filler, thereby
decreasing the elastic response of particulate filled polymer systems
with increasing concentration. Note that Figure 7.5(a) is a plot of N1 vs.
T12 rather that y and correctly so. The trend of increasing elasticity with
increasing filler concentration will be noticed only in fiber-filled systems
as evidenced from Figure 7.3(b).
Thus, it should be borne in mind that equation (7.1) may be used for
data representation but not for data interpretation, as the predicted
trend does not describe the actual situation. In fact, it might be better to
define ^1 r as equal to N1(^, T12VN1(O, T12) and then seek a relationship
with (j).

Poslinski et al. [72] undertook the study of the influence of a bimodal
size distribution of glass spheres on the rheology of filled polymer
systems as already discussed in section 6.4. The bimodal size
distribution was prepared by mixing together various vol% of the
smaller 15 |im spheres with the larger 78 jim spheres given in Table 6.3.
Various bimodal mixtures were compounded into a polybutene grade
24 polymer obtained from Petrochemical Division of the Chevron
Company, at total solids concentrations up to 60% by volume.
To see the effect of particle size and size distribution on elasticity of
the system, the average relative normal stress difference coefficients are
plotted against (/>s, the volume percent of the 15|im spheres, ranging
from O to 100% of the total solids mixture as shown in Figure 7.6.
Similar to the relative viscosity case in Figure 6.20, the relative primary
normal stress coefficient is also reduced when the two sizes of spheres
are mixed together, and again the lowest values are obtained for
0S = 10 to 30% of the smaller spheres, which happens to be the same
range when the maximum packing parameter is the highest.
The solid lines in Figure 7.6 represent the predictions of equation
(7.1) with maximum packing fraction determined by equation (6.17)
using the particle size distribution values of the bimodal components
listed in Table 6.3. The agreement between theory and experiment is
quite adequate. However, as discussed in section 7.3, there is a problem
with data interpretation because the curve of 60% by volume of total
spheres shows the highest elasticity which is incorrect.

Agglomerates occlude liquid in their interparticle voids and thereby
leave a less volume fraction of the liquid around it. This would create
GLASS SPHERE FILLED POLYBDTENE
TQTALSPHERES
EQUATION CT. D
Figure 7.6 Variation of average relative primary normal stress coefficient as a

function of 0S, the volume percent of the 15^m glass spheres in the total mixture
suspended in a polybutene grade 24 matrix at 220C. (Reprinted from Ref. 72 with kind
an apparent situation of higher filler loading than is actually present.

Hence, the effect of filler agglomerates would be similar to that of filler
concentrations; or, in other words, with larger number of filler
agglomerates, the system would behave Theologically in a manner
similar to a system with a higher filler concentration than what actually
exists.
It can be thus expected that with increasing number of filler
agglomerates when dealing with particulate fillers, the normal stress
difference would be lower. The extent of lowering of the normal stress
difference depends on the amount of occluded liquid by the agglomer-
ates, the average number of particles in each agglomerate and hence the
size of the agglomerates. In an unagglomerated filled system, the extent
of normal stress difference lowering would be less if the particle size is
larger. When an agglomerate is formed or present, it is as though the
particle size of the filler has increased throughout the system. Thus,
with increasing number of particles in the agglomerates, the extent of
normal stress difference lowering decreases. On the other hand, because
of the occluded liquid in the interparticle voids of the agglomerates, the
extent of normal stress difference lowering increases. It is basically the
net effect of these two opposing factors that determines exactly how
much the normal stress difference would be lowered.
In the case of fiber-filled systems, too, the effect of agglomerates
would be to lower the normal stress difference. It has already been
shown in section 7.1 that fiber-filled systems show increases in
elasticity. The extent of the increase would be thus reduced if
agglomerates are formed because the fibers that gather to make up the
agglomerates are restrained and cannot orient during flow.
There are no experimental data specifically to support the intuitive
thoughts put forth in this section. The reason is that determination of
normal stress difference in the presence of agglomerates is extremely
difficult. The agglomerates interfere with the gap setting during cone
and plate rheological measurements due to their increased size. Despite
lack of actual data, the conclusions on the effect of agglomerates can be
drawn by carefully understanding the effect in analogous situations as
done here.

One of the effective methods of reducing the number of filler
agglomerates in a filled polymer system is through the use of surface-
modifiers such as those listed in Table 1.5. Surface modifiers are
generally bifunctional molecules with one end capable of adhering to
the filler and the other end compatible with the polymer, and at times
even capable of reacting with it. Surface treatment basically helps the
polymer to wet the filler better and disperse it, thereby reducing and
preventing agglomeration because of promotion of filler-polymer
contact as against filler-filler contact. Research work on the effect of
surface treatment on the steady shear elastic properties of filled
polymer systems is limited [27,34] but good enough to draw adequate
conclusions.
Figure 7.7 shows the effect of surface treatment on 30% calcium
carbonate filled polystyrene [27]. It can be seen that the data are
presented in both forms of representations. N1 vs. y (Figure 7.7(a)) and
N1 vs. T12 (Figure 7.7(b)). In Figure 7.7(a), it appears that surface
treatment reduces elasticity to a level even below that of the pure
polymer. However, conclusions drawn from this type of representation
CALCIUM CARBONATE FILLED POLYSTYRENE
UNITS
PASCALS
UNTREATED
TELEATED
Figure 7.7(a) Variation of primary normal stress difference with shear rate for
calcium carbonate filled polystyrene containing 30% untreated and treated filler.
Connecticut, USA.)
CALCIDH CARBONATE FILLED POLYSTYUENE

UNITS
PASCALS
TKEKTED
UNTREATED
Figure 7.7(b) Variation of primary normal stress difference with shear stress for
Connecticut, USA.)
would not be correct because the untreated 30% CaCO3 shows an
increase in elasticity, which is against intuition and logic as discussed
in section 7.2. Thus, the representation given in Figure 7.7(b) is the true
one and shows that surface treatment increases the values of N1 as
against that of the untreated system of a fixed filler loading at the same
level of shear stress.
Figure 7.8 gives the plot of first normal stress difference vs. shear
stress for CaCO3 filled polypropylene. Similar to the effect observed in
Figure 7.7(b), the use of the surface modifiers, namely, silanes Y9187
and AIlOO, shows an increase in the normal stress difference over that
of the untreated system irrespective of the temperature of measurement.
Note that Y9187 is an N-octyltriethoxysilane while AIlOO is a y-
aminopropyltriethoxysilane. The same effect is, however, not found to
be the case when considering a different filler such as glass beads in the
polypropylene.
CALCIUM CAEBONATE FILLED POLYPROPYLENE

UNITS
PASCALS
Figure 7.8(a) Variation of primary normal stress difference with shear stress at
20O0C for calcium carbonate filled polypropylene treated with silane surface modifiers.
Connecticut, USA.)
CALCIUM CABBONATE FILLED POLYPROPYLENE
UOTTS
PASCALS
Figure 7.8(b) Variation of primary normal stress difference with shear stress at
24O0C for calcium carbonate filled polypropylene treated with silane surface modifiers.
Connecticut, USA.)
Figure 7.9 shows that neither the silane Y9187 nor AIlOO is effective
in influencing the normal stress difference of the untreated glass beads-
PP systems at 20O0C. However, at 24O0C, the surface modifier Y9187
decreases the melt elasticity while AIlOO increases it. Note that the data
in Figures 7.8 and 7.9 are all in the high shear rate range and obtained
using the Han slit/capillary rheometer.
When the surface modifier is changed from the silane to a titanate in
the case of the CaCO3-PP system, as in Figure 7.10, the effects are
qualitatively not different from those observed in Figure 7.7(a) or (b). It
is seen that the normal stress difference of the titanate KR-TTS treated
CaCO3-PP system is higher than that of the untreated CaCO3-PP
system. In Figure 7.10, the low-shear data were obtained on the
Weissenberg rheogoniometer and the high-shear data were got using
the Han slit/capillary rheometer.
When the filler is changed to glass fiber and the same titanate KR-
TTS is used as a surface modifier, it is seen that the untreated and
GLASS BEADS FILLED POLYPROPYLENE
UNITS
PASCALS
PP
PP/GLASS BEADS
PP/GLASS BEADS/Y9187
PP/GLASS BEADS/AIlOO
Figure 7.9(a) Variation of primary normal stress difference with shear stress at
20O0C for glass bead filled polypropylene treated with silane surface modifiers.
Connecticut, USA.)
GLASS BEADS FILLED POLYPROPYLENE
UNITS
PASCALS
P?
PP/GLASS BEADS
PP/GLASS BEADS/Y9187
PP/GLASS BEADS/Al 100
Figure 7.9(b) Variation of primary normal stress difference with shear stress at
24O0C for glass bead filled polypropylene treated with silane surface modifiers.
Connecticut, USA.)
CALCIUM CARBONATE FILLED
POLYPROPYLENE
UNTTS
PASCALS
Figure 7.10 Variation of primary normal stress difference with shear stress for
calcium carbonate filled polypropylene treated with titanate surface modifier TTS.
Open symbols represent Weissenberg rheogoniometer data and closed symbols
represents Han slit/capillary rheometer data. (Reprinted from Ref. 34 with kind
treated filled polypropylene systems do not show any difference in the

normal stress characteristics as shown in Figure 7.11.
The normal stress difference data in Figures 7.7-7.11 all go to show
that the effect of surface modifier is quite system specific. Hence,
GLASS FIBER FILLED
POLYPROPYLENE
UNITS
PASCALS
PP
PP/GLASS FIBER/ITS
PP/GLASS FIBER
Figure 7.11 Variation of primary normal stress difference with shear stress for fiber
filled polypropylene with 50% untreated and treated filler using titanate surface
modifier TTS. Open symbols represent Weissenberg rheogoniometer data and closed
symbols represent Han slit/capillary rheometer data. (Reprinted from Ref. 81 with kind
permission from Academic Press Inc., New York, USA.)
extrapolation of information with regard to this effect can at times be

dangerous. The efficiency of the surface modifiers will depend on the
type of filler, type of polymer, amount of modifier and method of
treatment as already discussed in section 6.6.
7.7 EFFECT OF POLYMER MATRIX
As already mentioned in section 6.7, the effect of polymer matrix on the
rheological properties of filled polymer systems would depend on the
chemical nature of the polymer as well as its unfilled rheological
properties. In order to understand this effect, it would be essential to
observe normal stress difference response using different polymer
systems but with the same filler of a fixed size/size distribution and at
a fixed level of loading. This information is not available from one
source as in the steady shear viscous case [63]. Hence, this effect is
exemplified by presenting data from different sources for different
polymer systems but with the same fillers. Of course, the physical
characteristics of the chosen filler are unlikely to be the same and so
also, it is unlikely to find a particular filler loading as a common
denominator in all cases. Nevertheless, the data would give some
general idea of the effect of the polymer matrix.
GLASS FIBER FILLED UNITS

NYLON PASCALS
NYLON 6,6/33% GLASS FIBER

NYLON 6,6
Figure 7.12 Variation of primary normal stress difference with shear stress for glass
fiber filled nylon 6,6 with 33 vol% of fiber. (Reprinted from Ref. 95 with kind permission
Figures 7.12-7.14 show the effect of glass fibers at different loading
levels on the normal stress difference behavior of nylon, polycarbonate
(PC), and polystyrene (PS). Since the plots have been made as N1 vs. T12,
they are independent of temperature. This is specifically clear from
Figure 7.12 which shows a uniqueness of data at the three temperatures
of 2750C, 2850C and 2950C [95].
In Figure 7.13 for polycarbonate [31], it is seen that N1 does not rise
systematically with filler concentration at a fixed shear stress. The 30%
loaded system coincides with the 10% loaded glass fiber filled
polycarbonate instead of lying between the 20% and the 40%. No
apparent explanation can be presented for such anomalous behavior.
In the case of glass fiber filled polystyrene [28], the loading level is
limited to 10% and 22% and hence whether a reversal of the type that
was observed in Figure 7.13 for PC takes place cannot be established.
Figure 7.11, which also gives the normal stress difference information
GLASS FIBER FTTIED POLYCARBONATE
MAKROLON FILLER
GRADE
UOTTS
PASCALS
fiber filled polycarbonate of different grades of Makrolon. (Reprinted from Ref. 31 with
kind permission from John Wiley & Sons, Inc., New York, USA.)
GLASS FIBER FILLED POLYSTYlEKE
UOTTS
PASCALS
PS/22% GLASS FIBER

PS/10% GLASS FIBER
PS
fiber filled polystyrene with different volume fraction. (Reprinted from Ref. 28 with kind
permission from John Wiley & Sons, Inc., New York, USA.).
on glass fiber filled systems [81] but using a different polymer, namely
polypropylene (PP), presents an unusual behavior. It is seen that this is
the lone case where a fiber filled system shows a decrease in elasticity
of the polymer melt. The behavior is inexplicable considering the fact
that even a Newtonian fluid containing fibers is known to show an
increase in elasticity [96].
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52. Suetsugu, Y. and White, J.L. (1983) The influence of particle size and surface
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Unsteady shear Q
viscoelastic properties O
In the preceding two chapters, various effects on steady shear viscous

and elastic properties of filled polymer systems were discussed. The
present chapter focuses on the unsteady shear viscoelastic properties of
these systems. The unsteady shear characteristics are mainly discussed
with respect to small-amplitude oscillations, namely, dynamic
rheological data. In some cases, the thixotropic sweep responses and
the stress relaxation behavior are also included because they bring out
the rheological characteristics in some situations in a much better
manner. The extensive literature [1-85] on the rheology of filled
polymer systems, however, contains quite limited information on the
unsteady shear data [1,8,43-45,54,61,62,64,68,71,72,74,91,92].
The reason for this is because unsteady shear data were normally not
used when dealing with low loading levels of fillers where the bulk of
information is available. For highly filled systems, this is the only mode
of obtaining reliable rheological data, but since the work on highly
filled polymer systems is not extensive, the information on unsteady
shear data is naturally limited.
With higher filler loading, it becomes increasingly difficult to gap set
in a cone and plate arrangement of the rheogoniometer; whereas through
the use of the parallel-plate arrangements, it is possible to obtain
rheological data at any level of loading. The use of steady shear in the
case of highly filled systems is not recommended because the material
trapped between the plates of the rheometer during data generation
normally tends to hang outside the plate dimensions, thereby giving
erroneous results. On the other hand, when dealing with unsteady
shear data generation, small-amplitude dynamic oscillation keeps the
material between the plates of the rheometer intact and hence gives
much more reliable and reproducible data. Thus, dynamic data are often
the preferred mode for viscoelastic information of highly filled polymer
systems. Of course, it need not be restricted only to high filler loadings
as it would certainly provide reliable information even in low filler
loadings as well.
As a matter of fact, the most reliable rheological data on filled
polymer systems can be obtained through the use of dynamic
oscillatory measurements. The dynamic rate sweep and the dynamic
strain sweep would be most suitable for assessing the internal structure
of the system. During a strain sweep, a plot of storage modulus vs.
percentage strain at low frequency would be the best indicator of the
level of homogeneity in the system. A decrease in storage modulus with
percentage strain would be an indicator of the occurrence of the
structural breakdown in the system. During a frequency sweep, it is
best to maintain the strain as low as possible within the system
constraints, in order to be in the linear viscoelastic region of the
material. The response of complex viscosity, storage modulus, loss
modulus and tangent delta that is then obtained would give a measure
of the dispersion of the filler in the matrix. A highly agglomerated
system would show the existence of a yield at low frequency, the
storage modulus would be high and vary minimally with frequency
giving a more solid like response and the tangent delta would be lower.
However, generation of reliable and consistent data in case of filled
systems depends to a large extent on the preparation of the sample for
the rheological test. Premolding samples under high pressure to a shape
and size as would be used for the parallel-plate rheometer test, would
ensure that the variation in the observed rheological response is related
to the filled system characteristics and is not an experimental artifact.
During generation of dynamic data, it is important to use a fixed low
amplitude when collecting data for comparison on various systems.
The effect of the amount of strain during dynamic data measurement
on filled polymer systems has been brought out by Bigg [44]. Figure 8.1
shows the strong effect of strain on the complex viscosity and storage
modulus for low density polyethylene filled with 50vol% of spherical
stainless steel particles at 16O0C. It can be seen that the difference
between the complex viscosity at 1(T1 rad/s with a 1% strain (rf =
106 Pa.sec) to that with a 25% strain (rf = 2 x 104 Pa.sec) is almost two
orders of magnitude. Much greater differences are observed in the
storage modulus response with increasing strain. When the unfilled low
density polyethylene is tested using different levels of strains, it is seen
from Figure 8.2 that the complex viscosity remains unaffected by strain
and remains so at all temperatures. Thus, for unfilled polymers, it may
be all right to determine dynamic data at any level of strain. However,
for filled systems, because of the sensitivity of the dynamic response to
the level of strain, it is always important to determine the dynamic
viscoelastic properties at a strain that is low enough not to affect the
material response. As the filler loading increases, the level of strain
STEEL SPHERE FILLED LOW DENSITY POLYETHYLENE
UNITS
STRAIN
Figure 8.1(a) Effect of strain on the complex viscosity vs. frequency curves for
NA-250 low density polyethylene with 50vol% of spherical stainless steel particles at
16O0C. (Reprinted from Ref. 44 with kind permission from Society of Plastics Engineers
below which the response is unaffected is reduced [44]. For loadings

close to the maximum packing fraction, this strain level may be even
below the minimum obtainable within the experimental constraints. In
such cases, one could use a higher strain level, but keep this value fixed
in all systems studied so that meaningful comparison of information
can be done. This would not induce any errors if the systems studied
have same filler loadings, but in systems containing different loadings
levels, this point ought to be borne in mind when drawing conclusions
from the generated data.
In Figure 8.1, it is worth noting that at all levels of strains, a yield
stress (indicated by a slope of -1 on the In 77* - lnco plot) is observed at
frequencies below 1 rad/sec. This is because the filler loading level was
high (50vol%) and the interparticle network dominated the rheological
behavior of such highly filled polymer systems at all levels of strain
[44]. A similar behavior was observed by Saini and Shenoy [61] when
STEEL SPHRRF. FILLED LOW DENSITY POLYETHYLENE
UNITS
PASCALS
RAD/SEC
STRAIN
Figure 8.1(b) Effect of strain on the storage modulus vs. frequency curves for
NA-250 low density polyethylene with 50vol% of spherical stainless steel particles at
16O0C. (Reprinted from Ref. 44 with kind permission from Society of Plastics Engineers
dealing with high filler loading using a different type of filler, namely,
barium ferrite. The theoretical equations for modeling this type of
dynamic response would also be different from the conventional ones.
Theoretical equations for modeling dynamic response of filled
systems have been suggested for low [64] as well as high [61] levels of
loading and have been discussed at length in sections 2.3.3 and 2.3.4.
However, some important equations are recalled and presented here for
convenience. Shenoy and Saini [64] suggested a form similar to that of
Carreau [86] but modified it appropriately for describing the dynamic
rheological behavior of low filled systems as:
11,I = IiJSI(I+ AV)^ (8.1)

where r\l = zero-frequency viscosity function, q* = complex viscosity,
co = frequency, /I = time constant, N = power-law parameter.
STEEL SPHERE RLLED LOW DENSTY POLYETHYLENE
UNITS
STRAIN
Figure 8.2 Complex viscosity vs. frequency curves for unfilled NA-250 low density
polyethylene at various temperatures and different levels of strain. (Reprinted from
USA.)
This equation is ideal for use when the complex viscosity curves
show a plateau region in the low frequency range along with a
decreasing trend in the higher frequency range (like Curve 1 in
Figure 1.3). The model given by equation (8.1) thus naturally presumes
no yield stress. On the other hand, when the filler loading increases, the
particle network formed leads to the existence of yield stress in the low
frequency region. In such cases of highly filled systems, Saini and
Shenoy [61] proposed a modified form of the above equation as:
m <8 2)
=^F^ '
where K — complex viscosity at frequency of 1 rad/s and at ri = n"
ri = slope of the \q*\ vs. co curve in the region of 0.1 < CD < I
n" = slope of the \rj*\ vs. co curve in the region of 1 < co < 102
Equation (8.2) was suitable for the systems studied by Saini and Shenoy
[61] because the complex viscosity in all cases showed the existence of
two distinct straight lines one in the low frequency region below CD
equal to 1, and the other in the high frequency region above co equal to
1 (like Curve 3 in Figure 1.4). However, in cases where the complex
viscosity vs. frequency curves show an initial yield stress followed by
a plateau and then a frequency-thinning region, (like Curve 2 in
Figure 1.4), neither of the two equations suggested above can be used.
In such circumstances, it might be necessary to break up the curves into
two or three regions and fit separate equations in each region.
A correlation between complex viscosity rf and the storage modulus
G7 was derived [61,64] by analogously following the method of Wagner
[87,88] for relating the elastic response to the viscous response of the
material (equation (2.61) in section 2.3.4). The expression obtained
[61,64] was as follows:
G' 1 dto'lfro) (8 3)
^-~^~d^~ -
where m' is an adjustable parameter. Equations (8.1) and (8.3) can be
combined to give:
G_ 2Nr^Co 2 (N+1)
co m
for low filler loadings.
Equations (8.2) and (8.3) can be combined to give:
% = Ad - n'K'-d + «r-Ml + n (n' 7Jfy J (8.5)

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

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

The smaller the size of the filler, the greater the particle-particle
interaction and this reflects greatly on the unsteady shear viscoelastic
properties. In the case of complex viscosity vs. frequency curves, it
would be natural to expect yield stress with decreasing particle size as
was discussed in section 6.2. With larger particles, since the response to
deformation is determined by hydrodynamic interaction and not by
particle-particle interaction, such filled systems do not show yield
stress.
In the case of storage modulus, the plot of G vs. co is comparable
with the plot of N1 vs. y shown in the earlier chapter. All conclusions
that could be drawn through the plot of N1 vs. y would hold good
when G vs. a> are viewed. But then it must be borne in mind that the
type of data representation (N1 vs. y or N1 vs. T12) does make a
difference to the derived conclusions. In the case of storage modulus,
the data representation is always in the form of the G vs. co curves and
hence the conclusions should be the same as those derived from the N1
vs. y curves. Actual unsteady shear data on filled polymer systems
using a single polymer matrix but different sized fillers at a fixed level
of loading from one source are unfortunately not available for validation.

Dynamic data in the form of complex/dynamic viscosity and storage/
loss moduli vs. volume fraction (j> are available [8,71]. Faulkner and
Schmidt [8] obtained dynamic modulus data on glass bead filled
polypropylene composites using about 10% strain over the frequency
range of 0.01-10 rad/sec. The data for frequencies between 0.01-
O.lrad/sec were found to have larger scatter and great deviations from
the higher frequency trends. Hence, the data range was restricted to
0.1-10 rad/sec and the relative storage and loss moduli data were
determined in this range. One representative curve at 11 rad/sec is
shown in Figure 8.3. It is seen that the glass beads enable the polymer
to store more energy elastically and to dissipate more mechanical
energy when compared at equal strains, with trends similar to those
obtained by Mills [3] for glass bead polystyrene systems. Within the
limited range of volume fraction of up to 0.26, it has been shown [8]
that the loss moduli (or, in other words, the dynamic viscosity)
increases at a greater rate than the storage moduli with increasing filler
volume fraction.
1
Faulkner and Schmidt [8] correlated their data as follows:
87
and
m-'+ * < - °>
G"Qft» co) = I + 2 0 + 3.30 2
___ (8.Tb)
The above equations clearly show how the viscous response dominates
GLASS BEAD FILLED POLYPROFYUNE
LOSS MODULUS
STORAGE MODULUS
RADÊC
RELATIVE
MODCfLUS
Figure 8.3 Variation of relative storage and loss moduli with volume fraction of filler
in glass bead filled polypropylene system at frequency co = 1 rad/sec and strain
y = 10%. (Reprinted from Ref. 8 with kind permission from Society of Plastics
the elastic response with increasing filler concentration in the case of

glass bead filled polypropylene.
Poslinski et al. [71] showed that when average relative dynamic
viscosities in higher frequency ranges are plotted as a function of the
reduced volume fraction, </>/</>m, the data approximately fall on a single
curve which is independent of the polymer matrix and temperature as
shown in Figure 8.4. The value of <j>m was taken as 0.62 based on an
experimental evaluation. The experimental data in Figure 8.4 are fitted
by two curves using the following theoretical expressions analogous to
those of Kitano et al [22] and Chong at al. [89] for the steady shear case
by substituting r(r for rjr. Thus,
IJi = (I-^n)-2 (8.8a)

CHEVRON GRADE - 18
CEEVUON GRADE - 24
CHEVRON GRADE - 32
CHEVRON GRADE - 122
THERMOPLASTIC @ 1300 C
THERMOPLASTIC @ 150 0 C
THERMOPLASTIC @ 1700C
EQUATION (8.8a1
EQUAUON (8.8b)
Figure 8.4 Average relative dynamic viscosity at high frequencies as a function of

the reduced volume fraction of filler. (Reprinted from Ref. 71 with kind permission from
John Wiley & Sons, Inc., New York, USA.)
and
*-('*£&)'
It is seen from Figure 8.4 that equation (8.8a) consistently gives high
values in comparison to (8.8b) but the fit provided by both equations is
reasonably good. It is to be noted that equation (8.8a) is used for
theoretical fit in Figure 8.4 instead of the expression of Kitano et al. [56]
used by Poslinski et al [71].
Poslinski et al. [71] found that the storage modulus was far too low to
be measurable for polybutene grades 18, 24 and 32 over the entire range
of investigated frequencies. Hence, the relative storage modulus data
were available only for polybutene grade 122 and the thermoplastic
polymer at three different temperatures. The average relative storage
modulus at high frequencies was plotted vs. the reduced volume
fraction </>/</>m as shown in Figure 8.5. The average values were obtained
for each volume fraction from experimental data between 10 and
lOOrad/sec. It is seen that experimental data fall on a reasonably
unique curve fitted by the following theoretical expression [71]
analogous to the equations (6.11) and (7.1) by simply substituting G'r for
the material parameter as
G; = (l-0/0 m )- 2 (8.9)
The effect of filler concentration on the complex viscosity and storage

CHEVRON GRADE -122
THERMOPLASTIC @130°C
EQUAHON (8.9)
Figure 8.5 Average relative storage modulus at high frequencies as a function of

the reduced volume fraction of filler. (Reprinted from Ref. 71 with kind permission from
modulus vs. frequency has been brought out by the data of Bigg [44] on
alumina filled low density polyethylene systems as shown in Figure 8.6.
For the same system but using a very low viscosity polyethylene, the
effect of filler concentration on dynamic viscosity and loss modulus vs.
frequency has been presented by Dow et al. [68] as shown in Figures
8.7(a) and (b). Independent of the base viscosities of the polyethylene
(20Pa.sec and 0.2Pa.sec respectively), it is seen that the complex/
dynamic viscosity as well as storage/loss modulus increase by orders
of magnitudes with increasing filler concentration, the effect being more
prominent at lower frequencies. The storage and loss moduli begin to
depict more solid like behavior at higher concentrations, as exemplified
by its independence with respect to increasing frequency.
ALUMINA FILLKP
LOW DENSITY POLYETHYLENE
UNITS
PASCALS
RAD/SEC
Figure 8.6 Effect of filler concentration on the complex viscosity and storage
modulus variation with frequency for alumina-filled low density polyethylene.
Connecticut, USA.)
ALUMINA FILLED LOW DENSITY POLYETHYLENE
UNITS
Figure 8.7(a) Plots of dynamic viscosity vs. frequency for alumina filled low density
polyethylene prepared at the indicated concentrations of AI2O3. Mixing was carried
out at 15O0C and the rheological measurements were made at 1250C. (Reprinted from
Ref. 68 with kind permission from The American Ceramic Society Inc., Westerville,
Ohio, USA.)

The effect of filler size distribution is normally the most difficult to
isolate due to added complexities in performing reliable controlled
experiments. Hence, it often remains a neglected area. However, in the
case of highly filled systems, Bigg [54] has used a very systematic
procedure to investigate the effect of different particle size distributions
on the packing behavior and the dynamic rheological properties of the
filled systems. Filler particles were chosen very discretely to include
both agglomerating and non-agglomerating types, as well as bimodal,
narrow, and broad particle size distribution. Table 8.1 gives the
characteristics of the particles investigated by Bigg [54] while Table 8.2
ALTJMINA FILLED LOW DENSITY POLYETHYLENE
UNITS
PASCALS
Figure 8.7(b) Plots of loss modulus vs. frequency for alumina filled low density
polyethylene prepared at the indicated concentrations of AI2O3. Mixing was carried
out at 15O0C and the rheological measurements were made at 1250C. (Reprinted from
Ref. 68 with kind permission from The American Ceramic Society Inc., Westerville,
Ohio, USA.)
Table 8.1 Characteristics of filler particles investigated to study the effect of filler
particle size distribution (PSD)
Type Supplier Grade Gf1GIm) G(2Qim) QU-cfie ^84/^16 PSD
Stainless Amdry 136F 15 30-9.3 3.2 Narrow
steel (SS)
Stainless 6(36%) 54(64%) Bimodal
steel (SS)
Alumina (AI2O3) Alcoa A16-SG 0.6 1 .2-0.35 3.4 Narrow
Alumina (AI2O3) 2(30%) 15(70%) 3.4 Narrow
Zirconia (ZrO2) Zircoa Type C 3 8.0-1 .5 5.3 Broad
Silicon nitride GTE Sylvania SN 5 <1
(Si3N4)
Source: Ref. 54.
Table 8.2 Maximum packaging fraction of various filled systems used in the study
of the effect of filler particle size distribution (PSD)
Type PSD 0m Surface treatment
Stainless steel (SS) Narrow 0.63 None
Stainless steel (SS) Bimodal 0.69 None
Alumina (AI2O3) Narrow 0.57 None
Alumina (AI2O3) Narrow 0.63 W-910, Kemamide E
Alumina (AI2O3) Bimodal 0.70 W-910, Kemamide E
Zirconia (ZrO2) Broad 0.60 None
Zirconia (ZrO2) Broad 0.70 W-910, Kemamide E
Silicon nitride (Si3N4) Unspecified 0.62 Kemamide E, W-900, none
Source: Ref. 54.
gives the maximum packing fraction of the filler that could be loaded in
the polyethylene matrix under the same mixing conditions.
As expected, it was found [54] that using a broad distribution or a
bimodal dispersion improved the level of maximum packing fraction
as compared to that using a narrow size distribution. In the case of
random shaped alumina and zirconia, which normally exist in agglo-
merated form, matrix additives were needed to achieve the maximum
packing fraction. In the case of unagglomerated spherical steel particles,
a bimodal distribution alone could produce the desired effect, as the
smaller particles could easily be segregated into the interstices of the
larger particles. Of course, its non-random packing is not completely
achievable in a random mixing process. Broadly distributed powders do
have random packing arrangement at their maximum packing fraction.
Bigg [54] has shown how the difference between the two packing
arrangements can be detected by changes in the storage modulus-
frequency response of the filled polymer melt during dynamic
measurements in the low strain region. Figure 8.8 shows that, though the
complex viscosity for bimodal distribution of stainless steel spheres and
alumina particles is the same, their storage modulus responses are
different. Bigg [54] attributed the initial drop in the modulus value at
low frequency to the movement of the smaller particles during their flow
into the interstitial spaces between the larger particles. The low level of
oscillatory motion provides sufficient energy to initiate the movement
and create a more efficient packing. This occurs favorably for bimodal
distribution but fails for broad distribution of zirconia particles, as
shown in Figure 8.9. Even the use of matrix additive does not show the
effect observed for the bimodal distribution. Bigg [54] concluded that
bimodally distributed powders had the potential of higher loadings than
broadly distributed powder, and one cannot achieve the theoretical
maximum fraction by the usual random mixing procedures.
FILUED LOW DENSITY POLYETHYLENE UNITS
PASCALS
STAINLESS STEEL
ALUMINA
Figure 8.8 Variation of complex viscosity and storage modulus with frequency,
showing the effect of bimodal distribution of stainless steel and alumina in low density
polyethylene at 20O0C. (Reprinted from Ref. 54.)
The study of the influence of bimodal size distribution of fillers on

the rheology of glass sphere filled polymer systems has also been done
by Poslinski et al [72]. The bimodal size distributions were prepared by
mixing together various volume percentages of the smaller 15 pm
spheres with the larger 78 ^m spheres given in Table 6.3. Various
bimodal mixtures were compounded into a polybutene grade 24
polymer obtained from Petrochemical Division of the Chevron
Company, at total solids concentrations of up to 60% by volume.
The effect of the particle size and size distribution on dynamic
viscosity is shown in Figure 8.10 through a plot of average relative
dynamic viscosity vs. </>s, the vol% of the 15 jim spheres, ranging from O
to 100% of the total solids mixture. It was found that in the limit of low
frequencies, the dynamic viscosities of the filled polymer systems [72]
were equal to the shear viscosities at the same shear rate. However, the
relative dynamic viscosity was found to be a decreasing function of the
frequency approaching a constant value at the higher frequencies.
Consequently, relative values were obtained by averaging the data in
ZIRCONIA. FILLED UNITS
LOW DENSITY POLYEIHYLENE
PASCALS
WIHOTJT ADDITIVE
WTTH KEMAMIDE ADDITIVE
Figure 8.9 Variation of complex viscosity and storage modulus with frequency for
zirconia-filled polyethylene at 20O0C with an additive. (Reprinted from Ref. 54.)
Table 8.3 Summary of important torque values for mixing polyethylene with alumina
powders treated with different surface modifying agents
Sample description Peak torque Final torque
(g.m) (g.m)
No additive 370 70
Silane Z-6020 305 60
Silane Z-6076 200 60
Zircoaluminate CAVCO MOD APG 425 15
Titanate LICA-12 170 50
Source: Ref. 92.
the 10 to 100 rad/sec frequency range. As shown in Figure 8.10, the

experimental data at higher !frequencies indicate that the relative
dynamic viscosities are also lowered when the two sizes of spheres are
mixed together, however, the reduction is not as significant as observed
for both rjr and ^1 r discussed in sections 6.4 and 7.4, respectively. The
lowest values of relative dynamic viscosity are seen to be obtained for
(/>s = 10 to 50% of the smaller spheres. The solid lines in Figure 8.10
represent the predictions of equation (8.8b) with the maximum packing
fraction determined by equation (6.17) using the particle size distri-
GLASS SPHERE FILLED POLYBUIEHE
TOIALSPHERES
EQUAHON
Figure 8.10 Average relative dynamic viscosity as a function of 0S, the volume
fraction of the 15 urn glass spheres in the total solids mixture suspended in a
polybutene grade 24 matrix at 220C. (Reprinted from Ref. 72 with kind permission from
bution values of the bimodal components listed in Table 6.3. The

agreement between theory and experiment can be seen to be quite
adequate.
In the case of the storage modulus, it was found that G values of
the polybutene grade 24 matrix measured out as zero. Only at 40, 50
and 60% total glass spheres by volume were the filled polybutene G
values measurable. Since a relative storage modulus could not be
defined, the investigation [72] of the storage modulus was restricted to
a bimodal size distribution at high concentrations. Figure 8.11 shows
the storage modulus for 40, 50 and 60% volume fraction of total
spheres for various volume percentages of the 15 jam spheres at a
frequency of 1.0 rad/sec. It is seen that the storage modulus is also
GLASS SPHERE FILLED POLYBUTENE
UNITS
PASCALS
RAD/SEC
TOTAL SPHERES
EXPERIMENTAL CURVES
Figure 8.11 Dynamic storage modulus as a function of ^8, the volume fraction of
the 15^m glass spheres in a polybutene grade 24 matrix at 220C and a frequency of
1 rad/sec. The solid lines represent the best fit of the experimental data. (Reprinted
from Ref. 72 with kind permission from John Wiley & Sons, Inc., New York, USA.)
reduced when two sizes of spheres are mixed together, and the lowest
values are obtained for ^8 = 10 to 30% of the smaller spheres, which
of course happens to be the same range when the maximum packing
parameter is the highest.

As already discussed in sections 6.5 and 7.5, the presence of
agglomerates creates an apparent situation of higher filler loading than
is actually present. This is because the agglomerates trap part of the
surrounding liquid in their interparticle voids thereby decreasing the
volume fraction of the liquid around it.
It is known that high shear mixing helps in reducing the
agglomerates whereas low shear mixing may at times increase the
number of agglomerates. This happens because during mixing the
probability of particle-particle contact as well as particle-liquid contact
is increased. If the mixing is done under low shear, then the
agglomerates that are formed during particle-particle contact do not get
an opportunity to break down. On the other hand, the high shear
provides the energy to break the particle-particle bonds and once the
polymer wets the particle, the bonds fail to reform, thereby giving a
better dispersion. The effect of filler agglomerates is thus best illustrated
by observing the unsteady shear response of the filled polymer system
prepared under conditions of low shear and high shear mixing.
Dow et al. [74] prepared alumina filled low density polyethylene
under two different rotor speeds of lOrpm and 200 rpm. The mixing
temperature was held at 15O0C which was found by them to be the
optimum for the system under investigation as discussed in section
5.4.7. Figure 8.12 shows the torque curves in the mixing bowl during
the mixing operation. It is seen that the maximum torque generated
during mixing at 10 rpm was only 0.33 of the peak value obtained when
mixing at a rotor speed of 200 rpm.
Figure 8.13 shows the plots of dynamic viscosity vs. frequency for
samples mixed at the two rotor speeds. As expected, the low torque
generated during mixing at 10 rpm results in higher viscosities,
indicating poorer dispersion and larger number of agglomerates.
Quantitative microscopy measurements confirmed this [74]. These
measurements were done on plasma etched samples. Experiments
showed that polymer was preferentially removed from larger inter-
particle regions during etching. Thus, etched samples tended to have
polymer remaining in the fine pores of agglomerated particles. These
agglomerated regions appear as single particles in micrographs. Thus,
measured particle sizes would be larger in poor-dispersed systems
containing more agglomerates. The particle size measure used was the
projection circumscribing diameter Dpc [9O]. The sample mixed at
10 rpm had an average Dpc value of 0.50 jam while the average Dpc was
0.43 jim for the sample mixed at 200 rpm.
Besides using the small-amplitude oscillation response to understand
the effect of agglomerates on rheology of filled systems, one could also
use the shear stress growth and first normal stress difference growth
function as was done by KaIyon [91]. Figures 8.14 and 8.15 show the
comparison of the rheological behavior of a surface-treated calcium
carbonate filler with an untreated silica-based filler having similar
particle size distribution. The filler loading was 30% in both cases and
they were incorporated under identical compounding conditions into
low density polyethylene. The plots show T*2,r and i/^r which are the
50 vol% Al2 O3 Uncalcined
Mixing Conditions: 15O0C, 200 rpm
TORQUE (g*m)
TIME (min)
50 vol% Al2O3
TORQUE (g-m)
Mixing Conditions: 15O0C, 10 rpm
TIME (min)
Figure 8.12 Plot of torque vs. mixing time for 50vol% of alumina in low density
polyethylene mixed at rotor speed of 200 rpm (A) and 10rpm (B)1 respectively.
(Reprinted from Ref. 74 with kind permission from The American Ceramic Society Inc.,
Westerville, Ohio, USA.)
normalized values obtained by division of the respective parameters

with the values for pure polymer at 0.1 sec"1.
It is seen that the surface treated calcium carbonate filled system
behaves similarly to the pure polymer and reaches the steady torque
and normal force values quite instantly. On the other hand, steady-state
shear stress and first normal stress difference values are not reached
with the silica-based filler, particularly the first normal stress difference
which exhibits a spectacular rise with the time of deformation. This
suggests that agglomeration and strong interaction occur between
agglomerates of the silica-based filler. These interactions convert the
structure during simple shear into a network that approaches more
solid-like behavior. The effect of agglomerates is no different from that
SOVOKAI 2 Q 3
Mixing Temperature = 15O0C
DYNAMIC VISCOSITY (Pa-s)
FREQUENCY (rad/s)
Figure 8.13 Plot of dynamic viscosity vs. frequency at 1250C for 50vol% in low
density polyethylene mixed at rotor speeds of 10rpm and 200 rpm using a fixed mixing
temperature of 15O0C. (Reprinted from Ref. 74 with kind permission from The
American Ceramic Society Inc., Westerville, Ohio, USA.)
FUJJED LOW DENSTTY POLYEIHYUENE

UNTTS
DYNES
SEJCA
Figure 8.14 Shear stress growth function of a low density polyethylene filled with
two different fillers. (Reprinted from Ref. 91 with kind permission from Gulf Publishing
Co., Houston, Texas, USA.)
FELLED LOW DEHSTTY
POLYETHYLENE
UNITS
DYNES.S[EC2;CM2
SILICA
Figure 8.15 First normal stress difference coefficient growth function of a low density
polyethylene filled with two different fillers. (Reprinted from Ref. 91 with kind
permission from Gulf Publishing Co., Houston, Texas, USA.)
of filler concentration. With larger number of filler agglomerates, the

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

Surface modifiers such as those listed in Table 1.5 are often used in
order to achieve better filler dispersion and reduced agglomeration due
to improvement in the wettability of the filler and on account of
promotion of filler-polymer contact rather than filler-filler contact. The
effect of surface treatment on unsteady shear viscoelastic properties has
been studied in highly filled systems [43^5,54,92] and the available
data do provide some basis for understanding the use of surface
modifiers.
The major thrust of the efforts of Bigg [43,44,54] and Althouse et al
Next Page
Extensional flow Q
properties vy
The bulk of the extensive literature on the rheology of filled polymer

systems [1-85] is focused on the flow behavior in shear. The exten-
sional flow properties have been treated in a rather limited manner
[1,4,14,27,29,86,87], despite the fact that knowledge of the rheology in
shear mode generally does not allow prediction of the behavior in
extension [88]. The reason for this is because steady extensional
viscosity is in general difficult to measure, and also because filled
polymers go less into applications involving the film blowing, fiber
spinning and flat-film extrusion processes wherein the extensional flow
is of importance.
Extensional flow occurs when the material is not in contact with solid
boundaries, as is the case during drawing of filaments, films, sheets or
inflating bubbles. Converging flows at the inlets of dies are also
extensional in nature. In extension, the material is stretched continually
in a particular direction as already explained in section 2.1.3. The
principal axis of strain keeps doubling in length at equal intervals of
time during a steady extensional flow. For example, a circular filament
having a length I0 initially and / at time t undergoes steady extensional
flow when / = I0 exp(ef) where s is the extensional rate. There are a few
different ways in which extensional flow can be measured as discussed
in section 3.3. However, it is often difficult to keep the apparatus
running for long enough time to achieve steady state extensional flow
conditions for sure. Where such steady flows are achievable then the
ratio of the tensile stress along the filament, to the extensional rate e
gives the extensional viscosity rjE; or else, the ratio that results from
such measurements basically depends in a rather complicated manner
on the transient viscoelastic properties.
The limited information on the extensional flow properties of filled
polymer systems does not leave much room for extensive discussion on
this subject. Thus, this chapter is rather restricted and though the
intention was to discuss the effects of various factors on the extensional
flow properties as was done earlier for the shear flow properties in the
preceding three chapters, the same could not be done due to lack of
available information. Certain subcategories are absent and even in the
subcategories that are covered in this chapter, the discussion is quite
concise.

The experimental studies of White et al [29] illustrate the effect of the
filler type on the extensional flow properties of filled systems. Though
nine fillers were covered as given in Table 6.1 when studying shear
flow properties, the extensional flow studies were restricted only to
three of them, namely, titanium dioxide (TiO2), carbon black (CB) and
calcium carbonate (CaCO3). The filled systems were prepared using a
fixed grade of polystyrene Dow Styron 678U and the loading level was
fixed at 30vol%. The extensional viscosity measurements were done
using an extensional rheometer developed in house by Ide [89].
Figure 9.1 shows the variation of extensional viscosity with exten-
sional rate for the three filled polystyrene systems containing TiO2, CB
and CaCO3. A comparison between Figure 9.1 and Figure 6.1 indicates
the fillers appear in the same sequence when their levels of increases
are considered. The highest viscosity increase occurs in CaCO3 filled
system, the lowest in TiO2 filled system and the medium in CB filled
system both in extensional as well as shear flow. This naturally leads to
the conclusion that the effect of filler type on the extensional viscous
properties would be qualitatively akin to the effect on the shear viscous
properties.
Even though the available information on the effect of filler type on
the extensional flow properties is not as extensive as in shear, it
provides a sufficient premise to draw reasonable conclusions due to the
qualitative behavioral similarity. Thus, the extent of extensional
viscosity increase would always be lowest for three-dimensional
spherical fillers, higher for two-dimensional platelet fillers and highest
for one-dimensional fibrous fillers. Also when considering rigid and
flexible fillers, the increase in the level of steady extensional viscosity
would be more for rigid fillers than for flexible fillers because the rigid
fillers would resist deformation to a greater extent.
Where extensional flow occurs due to converging flow fields through
dies, then orientation of the filler, particularly the one-dimensional
fiber, and, to some extent, the two-dimensional platelet types, affects
the extensional flow behavior. Theory for the flow of concentrated
dispersions of chopped fibers in polymer melts in different extensional
flow situations is available [90,91] and the equilibrium fiber orientation
FILLED POLYSTYRENE UNTTS
Figure 9.1 Variation of steady state extensional viscosity with extensional rate for
filled polystyrene melts at 30vol% of various types of fillers as indicated. (Reprinted
from Ref. 29 with kind permission from American Chemical Society, Washington DC,
USA.)
can be calculated. The limitation of the approach [90,91] is that the

polymer matrix is considered as a second order fluid and only two-
dimensional flow has been considered. It has been shown elsewhere
[92] that extensional strain is more effective than shear strain for
aligning fibers.
In capillary rheometers, when short fiber filled polymer melt enters
the die [93-96], the fibers get aligned due to the extensional strain and a
partial plug flow is at times observed [94,96,97]. Alternatively, the
migration effect [98,99] is observed because the flow front is found to
be deficient in polymer for the glass bead filled low density poly-
ethylene in a spiral mold test [98] and for glass filled epoxy systems
flowing in a rectangular section end-gated mold [99]. Observations of
fiber orientation under conditions of converging, diverging and
shearing flows are available [24].
Convergent flow results in higher fiber alignment along the flow
direction, whereas diverging flow causes the fibers to align at 90° to the
major flow direction. It was also observed [24] that shear flow, on the
other hand, produces a decrease in alignment parallel to the flow
direction and the effect is pronounced at low flow rates.
Contact microradiography was used [24] to study extrudates pro-
duced using a Davenport constant volume flow rate capillary rheometer.
A variety of dies of different diameters was used, and in each case the
entry angle was 180°. Contact microradiographs were made at various
flow rates and the fiber orientation was found to depend strongly on
flow rate. Figure 9.2 shows contact microradiographs of sections cut
parallel to the cylinder axis in extrudates obtained from 2mm diameter
dies for a commercially available glass fiber-filled polypropylene pro-
duced by ICI (Propathene HW60GR/20). This material was in the form
of roughly spherical granules, containing 20% by weight of well-
dispersed glass fibers having a diameter of 10 jim and modal length of
500 jim.
Figure 9.2(a) shows an extrudate collected at a shear rate of 1.5 sec"1
from a die of 100mm length. The fibers show little sign of alignment
and appear to form a fairly random tangled mesh. In Figure 9.2(b) the
shear rate is 24 sec"1 from the same die. The fibers are more highly
aligned along the flow direction at this flow rate. Figure 9.2(c) shows an
extrudate collected at a shear rate of 24 sec"1 from a 2 mm diameter die
of length 0.3mm, and the alignment in the flow direction is more
pronounced than for the 100 mm die. Figure 9.2(d) shows a section cut
from the extrudate at a shear rate of 1430 sec"1 from a die of length
0.3 mm, and in this case the fibers are aligned almost completely in the
flow direction. From these contact microradiographs it appears that fiber
alignment increases with flow rate, but decreases with die length.
In order to improve the tensile properties of low-density polyethylene,
Mead and Porter [100] added high density polyethylene fibers and film
strips. This resulted in an increase in the extensional viscosity and
consequently, the tensile modulus of the composite was increased by a
factor of 10. The effect of different mineral fillers (e.g. talc, mica, clay,
dolomite) on the rheological properties of low density polyethylene
films was studied by Arina et al. [17]. It was found that the fillers
increased the extensional viscosity of a polymer matrix in concurrence
with the earlier observations of Han and Kim [86] as well as Mead and
Porter [10O].
Nakajima et al. [101] studied the viscoelastic behavior of butadiene-
acrylonitrile copolymer filled with carbon black. Capillary extrusion
measurements with an Instron and dynamic oscillatory measurements
with a Rheovibron suggested the occurrence of 'strain hardening7 in
filled elastomer due to tensile extension causing structural changes in
the carbon black filled elastomer. It is possible that the structure built
by the carbon black in the elastomer increasingly jams against
Figure 9.2 Contact microradiography of extrudate from a capillary rheometer of commercially available glass fiber filled polypropylene
produced by ICI (Propathene HW60GR/20). Extrudate was obtained at 21O0C dies of 2mm diameter: (a) 100mm long die, shear
rate = 1.5sec"1; (b) 100mm long die, shear rate = 24sec"1; (c) 0.3mm long die, shear rate = 24sec~1; (d) 0.3mm long die, shear
rate = 1430sec"1. (Reprinted from Ref. 24 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
extension until finally the structure yields and, thereafter, the sample
breaks.
The effect of adding carbon black in styrene-butadiene rubber (SBR)
compounds has received the attention of Gotten and Thiele [102]. It was
shown that, in extensional flow, the stress in carbon black filled SBR
compounds continues to grow with increasing strain up to the point of
rupture. Gotten and Thiele [102] evaluated their data using the Denn-
Marrucci equation (2.66b) given in section 2.3.5. It was concluded that
whenever stiffening of SBR compounds during extension was desired,
low structure carbon black with high surface area ought to be used.
Fedors and Landel [103] pointed out that stress-strain behavior of
swollen elastomers can be determined experimentally more conveniently
by measurements in uniaxial compression than uniaxial extension. In
extension, strains of the order of a few hundred percent are required
whereas, in compression, strains of the order of only a few percent
provide sufficient data for analysis. SBR-glass bead composites cured
by means of dicumyl peroxide were used for stress-strain measure-
ments to estimate the concentration of the effective network chains per
unit volume of the whole rubber. It was found that with decreasing
volume fraction of the composite, the effective network density
decreased linearly at first and then rather rapidly in an unexpected and
inexplicable manner.

When the extensional viscosity is plotted as a function of the applied
tensile stress [27] as shown in Figure 9.3, the effect of filler size becomes
obvious. It is seen that filled polystyrene systems containing the two
fillers TiO2 and CB at the same loading level of 30vol% show the
existence of the yield stress during extensional flow. This behavior is
identical to that observed for steady shear viscosity in Figure 6.1 for the
same two systems. In fact, it is seen that the higher yield stress value is
observed for CB filled system and the lower for TiO2 filled system for
both shear and extensional flow.
A look at the particle size of these fillers in Table 6.1 indicates that
though both have small particle sizes, CB is the smaller of the two by a
factor of 4. The smaller the particle size, the higher the yield stress, as
was concluded in section 6.2, happens to hold for extensional viscosity
as well. The smaller size fillers, especially those below a diameter of
0.5 |xm would have strong particle-particle interactions which would
aid in forming a network of finite strength and manifest this by a
display of yield stress.
The yield stress values in shear and extensional flows have been given
[29] in Table 9.1 for filled polystyrene systems containing three different
FILLED POLYSTYMNE
UHTTS
PASCALS
Figure 9.3 Variation of steady state extensional viscosity with tensile stress for filled
polystyrene melts at 30vol% of two types of fillers as indicated. (Reprinted from Ref.
27 with kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
Table 9.1 Elongational and shear flow yield values for some filled polystyrene
systems at 18O0C
Filler Loading Y6 x 10~3 Y5 x 10~3 YJ Y5
(vol%) (Pa) (Pa)
Carbon black 20 -4.5 25 ~1.8
Carbon black 30 17 9 M.9
Titanium dioxide 20 ~1.6 ~1.0 ~1.6
Titanium dioxide 30 4 2.2 —1.9
Calcium carbonate 20 ~5.0 3.0 —1.7
Calcium carbonate 30 22 12 —1.8
(untreated)
Calcium carbonate 30 -0.7 -0.4 -1.75
(treated)
Source: Refs 27 and 29 (reprinted with kind permission from Society of Plastics Engineers Inc.,
Connecticut, USA and American Chemical Society, Washington DC, USA).
types of filler - CB, TiO2 and CaCO3 at a loading level of 20vol%. The
yield value in extension is seen to be 1.6 to 1.9 times greater than that
measured in shear [27]. This is very close to the von Mises criterion [104]
of 1.73 or approximately equal to the J3 suggested [105] for plastic
yielding, which is referred to as a critical distortion strain energy in the
interpretation by Hencky [106,107]. The existence of a von Mises criterion
equivalent to a critical distortional strain energy seems reasonable to
explain the breakup of particle network structures formed due to
interparticle forces. The yield stress in extension and shear can thus be
understood to relate to the particle-particle interaction energy per unit
volume, especially in the case of small size particles.
Filled systems with larger particles would be non-interacting and
hence would show no yield stress. In fact, their response to deformation
is determined by hydrodynamic interaction and not by particle-particle
interaction. Extensional viscosity measurements on styrene acrylonitrile
(SAN) melts with large glass beads have been reported by Nazem and
Hill [4]. They found that extensional viscosity is equal to three times the
zero shear viscosity, thereby endorsing the fact that there is no particle-
particle interaction when dealing with larger particles, especially at
volume fractions of less than 20%. However, at higher volume fractions
of 36%, it was found that the ratio of extensional viscosity to shear
viscosity dropped to 1.7.

One of the effects of increasing filler concentration is that constant
extensional viscosities, namely, steady-state conditions are reached
more easily and earlier in the filled systems than in unfilled systems
and the values decrease with increasing extensional rate. This point has
been brought out in the work of Lobe and White [19] who studied the
influence of carbon black on the rheological properties of a polystyrene
melt.
Figure 9.4 shows the extensional viscosity vs. time curves for unfilled
polystyrene melt at different extensional rates. It was found [19] that
the extensional viscosity may tend to become constant at very low
deformation rates, but become unbounded at higher and higher
deformation rates. With filler concentration at low loading levels of 5
and 10% of carbon black filler, it was found [19] that the plots
resembled those in Figure 9.4. However, at higher filler concentrations,
constant extensional viscosities were achieved with time and these
values were found to decrease with increasing extensional rate as
shown in Figures 9.5 and 9.6 for 20 and 25 vol% carbon black loading.
The extensional behavior of a polymer system containing particulate
filler was studied experimentally by Han and Kim [86]. It was found
that, at a fixed extension rate, the extensional viscosity increased with
increasing filler concentrations because the solid particles of calcium
carbonate did not deform under stretching and hence exerted more
resistance to the flow of the molten threadline with an increase in
concentration.
It is natural that the effect of filler concentration on steady-state
TTKnRTTJJm POLYSTYRENE
UNITS
Figure 9.4 Variation of extensional viscosity with time at different extensional rates
for unfilled polystyrene melt at 17O0C. (Reprinted from Ref. 19 with kind permission
extensional viscosity is qualitatively not any different from that on

steady shear viscosity [27,86]. From Figures 9.7-9.9, it can be seen that,
as expected, extensional viscosity increases with increases in loading
level and decreases rapidly with increasing extensional rate.
In Figures 9.7 and 9.8, the data were generated using an in-house
developed rheometer [89], while in Figure 9.9, the data were obtained
using a melt spinning apparatus [86]. It should be noted that the melt
spinning apparatus does not provide steady extensional flow conditions
and hence the extensional viscosities determined from such an instru-
CARBON BLACK HTTED POLYSTYRENE
UNITS
for 20vol% carbon black filled polystyrene melt at 17O0C. (Reprinted from Ref. 19 with
kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
ment are at times referred to as spinning viscosities indicating the

unsteady state conditions.
In general, the relative influence of different kinds of particulate
fillers on the extensional viscosity at the same loading level is the same
as that of the shear viscosity [27]. In the case of fiber-filled polymer
systems, the same comment cannot be made as can be seen from Figure
9.10. For unfilled high density polyethylene (HDPE), rjE/rj0 is 3 at low
extensional rates, while it is much higher for glass fiber filled HDPE
[14]. This result can be explained qualitatively through the theoretical
25% CARBONBLACK
FILLED POLYSTYRENE
UNITS
for 25vol% carbon black filled polystyrene melt at 17O0C. (Reprinted from Ref. 19 with
kind permission from Society of Plastics Engineers Inc., Connecticut, USA.)
arguments put forth by Batchelor [108]. However, what is unusual in

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

There is enough evidence, at least in the case of shear viscosity, that
any increase due to filler addition can be significantly reduced through
filler surface treatment. The same effect can be expected for extensional
viscosity as well. In the case of shear viscosity, there have been a
number of studies to support conclusions drawn on the effect of various
CARBON BLACK FILLED POLYSTYItENE
UNITS
carbon black filled polystyrene melt at 18O0C with different levels of filler loading as
indicated. (Reprinted from Ref. 27 with kind permission from Society of Plastics
TTTANIDM DIOXIDE FILLED POLYSTYRENE

UNITS
titanium dioxide filled polystyrene melt at 18O0C with different levels of filler loading as
indicated. (Reprinted from Ref. 27 with kind permission from Society of Plastics
CALCIDM CAKBONATC FILLED POLYPROPYLENE
UNITS
Figure 9.9 Variation of apparent extensional viscosity with extensional rate for
calcium carbonate filled polypropylene at 20O0C with different levels of filler loading
as indicated. (Reprinted from Ref. 86 with kind permission from John Wiley & Sons,
surface treating agents. However, in the case of extensional viscosity,

the available information is limited [27].
Figure 9.11 shows the effect of surface treatment on extensional
viscosity for 30% calcium carbonate filled polystyrene [27]. The data are
presented in two forms, namely steady state extensional viscosity vs.
extensional rate in Figure 9.11 (a) and steady state extensional viscosity
vs. tensile stress in Figure 9.11(b). Irrespective of the type of data
representation, it is seen that surface treated calcium carbonate reduces
the level of extensional viscosity and brings it closer to that of the
unfilled polymer. The yield stress value is reduced considerably though
the values of the ratio of yield stress in extension to that of shear is still
maintained nearer to the von Mises value of 1.73 as can be seen from
Table 9.1. Surface treatment tends to modify the forces of particle-
particle interaction and hence show reduced yield stress values due to
lowering of the interaction forces [2,27].
The effects of titanate coupling agents on the rheological properties of
particulate filled polyolefin melts were studied by Han et al. [15]. Experi-
GLASS FIBER FILLED HIGH DENSITY POLYEIHYLENE
UNITS
Figure 9.10 Variation of relative extensional viscosity with extensional rate for glass
fiber filled high density polyethylene at 18O0C with different levels of filler loading as
indicated. (Reprinted from Ref. 14 with kind permission from John Wiley & Sons, Inc.,
New York, USA.)
CALCIDM CABBONAU FILLED

POLYSTYRENE
UNITS
UNTREATED (30% CaCO3)

TREATED (30% CaCO3)
UNFTTJ-KD
Figure 9.11 (a) Variation of steady state extensional viscosity with extensional rate
for calcium carbonate filled polystyrene containing 30% untreated and treated filler.
Connecticut, USA.)
CALCIUM CARBONATE FILLED
POLYSTYRENE
UNITS
PASCALS
UNTBEA1IED (30% CaCO3)

TREATED (30% CaCO3)
Figure 9.11(b) Variation of steady state extensional viscosity with tensile stress for
Connecticut, USA.)
ments were carried out with systems like calcium carbonate-filled

polypropylene and fiber glass-filled polypropylene with the addition of
titanate coupling agents, and an increased extension of the filled
systems was observed in the presence of these additives. In fact
addition of titanate coupling agents to calcium carbonate-filled
polypropylene decreased the extensional viscosity to such an extent that
it almost equalled the extensional viscosity of pure polypropylene.
Effect of the additives on fiber glass-filled polypropylene was the
same but the decrease in extensional viscosity was to a much lesser
extent.
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Concluding remarks I U
This final chapter of the book is meant to provide a forum for

recapitulation of some of the matters of importance discussed in all the
preceding chapters.
Chapter 1 introduced the various materials which go into the making
of filled polymer systems. The polymer could be a thermoplastic,
thermoset or elastomer. Further, it could be linear, branched, amor-
phous, crystalline or semi-crystalline. At the same time, it may fall into
the category of a homoploymer, copolymer, or liquid crystalline
polymer. Any type of such a polymer could be compounded with fillers
to form filled polymer systems.
The fillers, on the other hand, include those solid materials that are
added as reinforcing agents to provide strength or mere extenders to
reduce cost. There are various reasons for the use of fillers besides
increasing stiffness, strength, toughness, impact strength or reduction in
cost. They may be included to get better dimensional stability, increased
heat deflection temperature, reduced permeability to gases or liquid,
and to modify electrical/magnetic properties of the polymer matrix into
which they are incorporated.
Available fillers are of various types and forms, namely, rigid,
flexible, spherical, ellipsoidal, flakes, platelets, fibers or whiskers. They
may be organic or inorganic in nature. All varieties of fillers have been
tried in polymers in order to impart various advantageous benefits. The
presence of the fillers in the polymer matrix alters the rheological
properties of the polymer.
Rheological measurements are often used as an effective tool for
quality control of raw materials, manufacturing process/final product
and predicting material performance. The rheological properties of the
filled polymers are dictated, not only by the type of the filler, but also
by its size, size distribution and amount. A key factor in the use of
fillers without adversely affecting material properties is the stress
transfer at the filler-matrix interface. The physico-chemical interactions
between the filler and matrix then achieve a great deal of importance.
The interfacial adhesion can be substantially enhanced through use of
a surface modifying agent which is capable of adhering well to both the
matrix and filler particles. Not all surface modifying agents can couple
at both ends of their chemical moieties. In fact, some surface modifiers
attach only to the filler, others react only with the polymers and some
others do not react at all. In all these cases, they may be treated as
lubricants. Only those surface modifiers which react with filler and
polymer can be termed coupling agents, though in most available
literature this term has been loosely used to describe any surface
modifying agent.
Chapter 2 discusses the fundamentals of rheology and classifies flow
as shear and extensional. Definitions of various rheological parameters
under the three subheadings of steady simple shear flow, unsteady
simple shear flow and extensional flow are given. The important
material parameters that burgeon out of the discussion are the steady
shear viscosity, the normal stress difference, complex viscosity, dynamic
viscosity, storage modulus, loss modulus and extensional viscosity. This
chapter sets the platform for rheological discussions that are under-
taken in Chapters 6, 7, 8, and 9 to study the effect of different
parameters related to filler and polymer on the rheology of the filled
polymer systems.
Basic description of non-Newtonian fluids is provided so that
concepts of shear rate dependent viscosities with or without elastic
behavior, yield stress with or without shear rate dependent viscosities
and time dependent viscosities at fixed shear rates get classified. The
filled polymer systems fall into the category of pseudoplastic fluids
with or without yield stress and also often depict the behavior of
thixotropic fluids. Their viscoelasticity may give rise to various
anamolous effects that are discussed in Chapter 2, such as the
Weissenberg effect, extrudate swell, drawn resonance, melt fracture and
so on.
Rheological models have been described for steady shear viscosity
function, normal stress difference function, complex viscosity function,
dynamic modulus function and the extensional viscosity function. The
variation of viscosity with temperature and pressure is also discussed.
Chapter 3 deals with rheometry which is the method of measurement
of the various rheological parameters described in Chapter 2. The
rheometers may be of the rotational type or the capillary type for shear
flows and the shear free type for extensional flows.
Chapter 4 deals with constitutive theories and equations for
suspensions and lays down the foundations for understanding the
basics of filled polymer rheology. Starting from the simplest dilute
suspensions for spherical particles to the complex concentrated
suspensions of fibrous fillers, the various relationships between relative
viscosity with volume fraction are highlighted. The effect of filler shape,
concentration, size, size distribution on the viscous behavior is
discussed. The migration of particles towards the tube axis and the
consequences of the wall effect on the rheological properties are
described. Particle rotation is also shown to affect the rheology and
result in an apparent display of increased viscosity. The effect of
flocculation is seen to increase the viscosity of suspension rather
sharply. The effect of the suspending medium and its interaction with
the suspended particles results in an increase in effective particle size
and decrease in molecular mobility. Similarly, the effect of physical
processes such as crystallization and chemical processes such as
polymerization modify the viscosity of suspensions with time. There is
considerable effect of the electrostatic field and displays of increased
viscosity due to the combined effect of the first, second and third
electroviscous effects.
Extensional viscosity is modified by the presence of suspended
particles. Particularly long slender particles have a drastic effect on the
extensional viscosity of suspensions as seen from the constitutive
equations provided for these systems.
Chapter 5 describes methods for the preparation of filled polymer
systems. The quality of the mixture resulting from any compounding
action of filler with polymer must be evaluated as there are various
mixing mechanisms involved. The efficiency of the dispersive and
distributive mixing determines the goodness of mixing. The com-
pounding techniques that are used are the traditional two-roll mills or
internal mixers and the modern-age single or twin-screw extruders. The
techniques vary considerably in their method of operation and results.
When setting up a compounding operation, it is important to use
proper selection criteria to decide whether batch or continuous mixers
are appropriate and pay attention to the dump criteria. It is known that
the physical properties of the compounded filler system vary con-
siderably with the selected compounding techniques. The goodness of
mixing is best adjudged by the determination of the rheological
properties of the filled polymer systems.
There are a number of compounding/mixing variables that affect the
final quality of the mix. Variables affecting the compounding operations
could be machine variables or operating variables. The mixer type,
rotor geometry, mixing time, rotor speed, ram pressure and chamber
loadings (in the case of internal mixers), as well as the mixing
temperature all have a considerable effect on the goodness of the final
mix. It is important to understand the sensitivity to these variables so
that the mixing can be carried out under optimum conditions.
The rheological properties of the filled polymer systems are discussed
under various headings, namely, steady shear viscous properties,
steady shear elastic properties, unsteady shear viscoelastic properties
and extensional flow properties, in Chapters 6, 7, 8 and 9, respectively.
The effect of filler type, size, concentration, size distribution,
agglomerates, surface treatment and polymer matrix on the rheology of
the filled systems is discussed in detail in most cases. Only where
information is lacking, such as in the case of extensional flow properties
in Chapter 9, are some of the effects missing, and the discussion is
concise on the treated effects.
In general, steady shear viscosity and extensional viscosity bear very
similar results when the effects of the various parameters are
considered. Addition of fillers increases the viscosity of the base
polymer. The extent of viscosity increase is the lowest for 3-dimensional
spherical fillers, higher for 2-dimensional platelet fillers and the highest
for !-dimensional fibrous fillers. Rigid fillers show greater increases in
the level of viscosity than flexible fillers.
The size of the filler determines whether the filled systems would
show unbounded viscosity buildup at low shear/extensional rates
during shear and extensional flows, respectively. The smaller the
particle size, the greater the yield stress. The ratio of the yield stress in
extension to that in shear, is approximately quite close to the value of
the von Mises criterion for plastic yielding of 1.732 or ^/3.
Polydispersity reduces the viscosity of filled systems at a fixed
loading level. For dilute suspensions having a volume fraction of solids
less than 0.2, the effect of the variation of particle size on filled system
viscosity is normally minimal. However, at high loading levels, the
viscosity can be reduced drastically when the particle size modality is
increased.
Agglomerates occlude liquid in their interparticle voids, thereby
increasing the relative viscosity value at any given solids loading.
With increasing number of agglomerates, the maximum possible filler
loading is decreased. Thus, for highly filled polymer systems, it is
important to reduce the degree of agglomeration to a minimum level,
in order to decrease the system viscosity for easier processing and also
to increase the extent of filler loading if desired.
With increasing concentration of filler, the interparticle interactions
increase weakly at first and then rather strongly as the concentration
becomes higher and higher. The concentration at which particle-particle
interactions begin depends mainly on the geometry and surface activity
of the filler. High aspect ratio fillers would begin to interact at much
lower concentrations, while non-agglomerated large size spherical
particles do not interact even up to 20vol%. Use of surface modifiers
helps to decrease particle-particle interaction as the surface treatment
helps the polymer to wet the filler better. However, the action of the
surface modifiers is system-specific and hence, it is very difficult to
predict the performance of the surface modifiers a priori for any filler-
polymer combination. Thus, most often a surface modifier is selected
rather empirically for the particular filler-polymer combination of
interest. The amount of surface modifier should be small but adequate
because too little of it does not give the desired effects and too much of
it does not improve rheological or product properties to more than a
certain extent besides adding extra cost to the product. The optimum
surface modifiers to be used are most often in the range of 0.6-0.8% by
weight of the filler. The method of surface treatment also affects the
performance. Pretreatment is more efficient in imparting favorable
improvements in rheological properties but adds to the cost due to the
extra step of pretreatment. Direct addition of surface modifier during
the filler-polymer compounding process saves on the cost of pre-
treatment but requires a greater amount of surface modifiers which
offsets this cost benefit. Proper evaluation of which is more apposite for
a particular situation must be done before opting for the preferred
method of surface treatment.
The chemical nature and the viscoelastic characteristics of the
polymer matrix do have an effect on the final rheological properties of
the filled polymer system. This is because the original characteristics of
the polymer determine the level of the shear imparted during the shear
mixing when the filled polymer systems are being prepared. Higher
viscosity polymer would develop higher shear stress and may be able
to break agglomerates better during mixing. Depending on the chemical
nature of the polymer, the matrix-filler affinity would also control the
level of the force to break filler-filler bonds during high shear mixing.
Polymers with greater filler affinity would provide greater force. Such
polymers, if they also have reasonably high viscosity which is not
highly shear-thinning, would probably help the most in getting the best
filler dispersion.
It has been shown that the steady shear viscosity vs. shear rate flow
curves of filled polymer melts at various temperature and filler
loadings can be unified when plotted on a log-log scale in terms of a
reduced viscosity parameter (77 x MFI) vs. a reduced shear rate
parameter (y/MFI). The unified curves are independent of the filler
type and shape, but depend on the polymer matrix. Thus, separate
unification is achieved for each generic type of polymer. They do
depend on the filler size and loading level. In cases wherein particle-
particle interaction gives rise to yield stress, the master curve would
not be unique in the low shear region. However, in the higher shear
rate region beyond 10"1S"1, the master curve would be unique
irrespective of the filler type, size, and amount as well as surface
modifier and amount. In fact, in this region, the master curve for the
filled polymer system is not different from the unfilled polymer
system. The master curves can be used to estimate the flow curves in
the higher shear rate region at the temperature of interest, merely from
the knowledge of MFI and the glass transition temperature of the
specific system.
There are certain precautions which should be borne in mind when
determining the MFI of filled polymer systems. The filler particle size
and shape may warrant modification of the MFI apparatus, and
possible yield stress characteristics of the filled polymer system may
demand a change from the standard ASTM temperature and load
conditions given in Appendix A. Whatever changes are done in order
to obtain reliable MFI data for the filled polymer systems, it is
important that these values are converted to those at standard
temperature and load conditions using equations from section 6.8
before using them in the master rheograms.
During normal stress measurement of filled polymer systems, there
are certain difficulties due to the abnormal effects of interactions
between the measuring equipment and the yield stress of the filled
systems. Further, there is always a problem of gap setting of the cone-
n-plate viscometer due to the high residual stresses which do not relax
for a long time and also due to the filler particle size or agglomerates
which may interface with the gap. Hence generating normal stress data
is often quite difficult. Nevertheless, reliable steady shear elastic data
are available in the literature which has obviously been generated with
great care.
It is seen that spherical fillers like glass beads do not affect the
normal stress difference. Particulate fillers like titanium dioxide,
calcium carbonate and carbon black, reduce the normal stress difference
whereas fibrous fillers like aramid, glass and cellulose fibers, increase it.
The large increase in normal stresses of fiber filled polymer systems is
explained on the basis of the hydrodynamic particle effect, associated
with orientation in the flow direction. Of course, if the fiber diameter is
very small then the increase in normal stresses is small and at times
may even show a decrease.
It is important to make plots of normal stress difference N1 vs. shear
stress T12 rather than vs. shear rate y if correct data interpretation is
intended. The former plots are independent of temperature and
molecular weight of the polymer matrix (though not its distribution)
and the rheological behavior is correctly interpretable by analogous
comparison with the steady state compliance /e.
It is obvious that the mobility of polymer chains under the influence
of an applied stress is reduced by the presence of the filler, thereby
decreasing the elastic response of particulate filled polymer systems
with increasing concentration. However, it was shown that a plot of
\l/ltt = N1(C/), 7VN1(O, y) vs. </>/</>m was unique and independent of shear
rate but an increasing function of filler concentration. This approach of
presenting the normal stress difference vs. filler concentration may be
acceptable for data representation but not for data interpretation.
Using a filler size distribution, the normal stress difference of the
filled polymer system can be altered. The relative primary normal stress
coefficient is reduced when a bimodal distribution is used and gives the
lowest values at about 10-30% volume fraction of the small particles.
With increasing number of filler agglomerates for particulate fillers,
the normal stress difference is lowered. The extent of lowering of the
normal stress difference depends on the amount of occluded liquid
by the agglomerates, the average number of particles in each
agglomerate and hence the size of the agglomerates. When an
agglomerate is formed or is present, it is as though the particle size
of the filler has increased throughout the system. Larger particles in
an unagglomerated system would lower the normal stress difference
less. By analogy then, with increasing number of particles in the
agglomerates, the extent of normal stress difference lowering decreases.
Contrary to this, if more liquid is occluded in the interparticle voids of
the agglomerates, then the extent of normal stress difference lowering
increases. These two opposing factors determine the eventual extent of
normal stress difference lowering due to agglomerates formed by
particulate fillers.
Agglomerates of fiber also would tend to decrease the normal stress
difference. But, since unagglomerated fibers are known to increase
normal stress difference, the extent of this increase would be reduced
due to presence of agglomerates as the fibers which form the
agglomerates are restrained and cannot orient during flow.
Use of surface modifiers often helps to reduce the number of
agglomerates, thus increasing the values of N1 as against that of the
untreated system of a fixed filler loading at the same level of shear
stress. The behavior is system-specific, and changing the filler or the
polymer or the type of surface modifier can accentuate or reduce the
effect that the surface treatment has on the normal stress difference.
Viscoelastic properties of filled polymer systems under shear can also
be studied through unsteady state data. Small amplitude oscillations for
getting dynamic rheological data are truly appropriate when handling
highly filled systems because they keep the samples in the gap of the
measuring instrument intact. During dynamic data generation, it is
important to use a low amplitude because the effect of strain on the
rheological response is quite strong. Unsteady shear data in terms of
thixotropic sweep responses and stress relaxation behavior also provide
a good insight into the dispersion level of the filler in the polymer.
The complex viscosity vs. frequency behavior on different types of
filler is qualitatively the same as that of shear viscosity vs. shear rate.
Only the extent of the viscosity increases due to the filler addition
would be different for the unsteady and steady state because the Cox-
Mertz rule is known to fail for filled polymer systems.
When storage modulus vs. frequency plots for different types of filler
are considered, it is revealed that all fillers increase storage modulus at
any frequency. On the other hand, the storage modulus for spherical
fillers is known to decrease with increasing frequency.
With increasing filler concentration, the complex/dynamic viscosity
as well as storage/loss moduli show a continually increasing trend.
However, the viscous response dominates the elastic response with
increasing filler concentration. The storage and loss moduli begin to
depict more solid like behavior at higher concentrations and show
independence with respect to frequency.
Using a filler size distribution, the filler loading can be increased. In
fact, if changes in filler size distribution are made, a good method of
tracking the packing arrangements is by observing the differences in
the storage modulus-frequency response of the filled polymer systems
during dynamic measurements in the low strain region. Bimodal
distributions are more effective than broadly distributed powders in
achieving higher filler loadings.
Presence of filler agglomerates can be detected by using the torque
vs. mixing time curves and the dynamic data in conjunction with each
other. By tracking the maximum torque, it can be deduced whether the
mixing was done under high shear stress conditions. When the peak
torque is high, the shear force is strong enough to break agglomerates
and this gets reflected in the dynamic viscosity and storage modulus
being lower.
Effect of filler surface treatment is quite dramatic, whether it is
through the use of surface modifiers or by heat treatment of the
filler. It is good to back up the dynamic data with other unsteady
measurements like the thixotropic sweep and stress relaxation
measurements and the torque curve when handling surface treated
fillers. This is because the effect of surface treatment is quite
complex and system-specific. Where the torque peak is high, while
the complex viscosity and storage modulus are low and the stress
relaxation time is short for a treated filler system when compared
with the untreated one, then it is definite that the surface treatment
has helped in dispersing the filler. This is because the high peak
torque shows that high shear forces broke down the agglomerates
and the surface treatment prevented any chance of their reformation
because the dynamic data and stress relaxation measurements
indicated so.
Effect of filler-matrix affinity can be quantitatively estimated through
dynamic viscoelastic data. An interaction parameter has been defined
which gives a measure of the postulated matrix immobilization at the
interphase of the filler. It has been shown that there is a correlation
between the interaction parameter in the melt state and the solid state
at comparable frequency of deformation. Thus, it is possible to generate
dynamic data in the melt state for quantitatively estimating the matrix-
filler interaction and then extrapolating the affinity behavior to the solid
state.
Rheology is a powerful tool for studying the dispersion level of the
filler and the matrix-filler affinity. The various methods that can be
used to understand the rheological behavior of filled polymer systems
have been elucidated in this book and it is hoped that it will serve as a
useful guide when indulging in further research areas related to filled
polymer systems in future.
Appendix A Glossary
Addition polymerization is a chemical reaction in which simple

molecules (monomers) are added to each other to form long chain
molecules (polymers) without the formation of byproducts.
Amorphous polymer is one that has no crystalline component and
there is no order or pattern to the distribution of the molecules.
Apparent viscosity is the ratio of shear stress by shear rate which has
not been corrected for entrance length effects in a capillary rheometer.
Barus effect or die swell or extrudate swell is the increase in diameter
of the polymeric melt extrudate upon emergence from the die.
Branched polymer is one in which the main chain in the molecular
structure is attached with side chains, that is in contrast to a linear
polymer.
Complex modulus consists of the real and imaginary part of the
modulus. The real part is called the storage modulus and the imaginary
part is called the loss modulus.
Compounding involves the process in which polymers are softened,
melted and intermingled with solid fillers and other liquid additives to
form filled polymer systems.
Condensation polymerization is a chemical reaction that takes place
between the polyfunctional molecules with the possible elimination of a
small molecule such as water.
Consistency is a rheological property representing the viscous behavior
of a non-Newtonian material.
Constitutive equation is an equation relating stress, strain, time and
sometimes other variables, such as temperature or pressure.
Couette flow is the shear flow in an annular gap between two coaxial
cylinders in relative rotation.
Crystalline polymer is one that has an ordered structural arrangement
of molecules.
Deborah number is defined as the ratio of characteristic time (or in
other words, the relaxation time) of the material to the scale of
deformation to which it is subjected (i.e. the duration of observation).
Die swell or extrudate swell or Barus effect is the increase in diameter
Dielectric constant is a dimensionless factor derived by dividing the
parallel capacitance of the material by that of an equivalent volume of
vacuum.
Dispersive mixing is defined as an operation which reduces the
agglomerate size of the minor constituent to its ultimate particle size.
Distributive mixing is defined as an operation which is employed to
increase the randomness of the spatial distribution of the minor
constituent within the major base with no further change in size of that
minor constituent.
Dump criteria is the standard taken in judging the moment when the
mixing is deemed as complete.
Dynamic viscosity is the ratio of the stress in-phase to the rate of strain
under sinusoidal conditions.
Elasticity represents a reversible stress-strain behavior.
Elastomer is a rubbery polymer that deforms upon the application of
stress and reverts back to the original shape upon release of the applied
stress.
Equation of state or constitutive equation is an equation relating
stress, strain, time and sometimes other variables, such as temperature
or pressure.
Extensional strain is the relative deformation in strain due to
stretching.
Extensional viscosity is the ratio of tensile stress to the extensional rate.
Extra stress tensor is the difference between the stress tensor and the
isotropic pressure contribution.
Extrudate swell or die swell or Barus effect is the increase in diameter
Filled polymer system is the softened or melted polymeric mass in
which one or more fillers have been dispersed.
Filler is the inert solid material added as cost reducing or reinforcing or
property modifying agent to a polymer without significantly affecting
the molecular structure of the polymer.
Flexural modulus is the term relating to stiffness of the material and
basically represents the force required to break a sample by bending or
flexing.
Flexural strength is the ability of a material to resist forces that tend to
bend it.
Flow activation energy is the energy required to activate the viscous flow.
Flow curve or rheogram is a curve relating shear stress or viscosity to
shear rate.
Glass transition temperature is the temperature at which increased
molecular mobility results in significant change in properties.
Heat distortion temperature is the temperature at which a material
bends by a predetermined amount under a given load.
Hysteresis is a material characteristic which results in different values
of the responses for the same values of corresponding stress or rate of
strain when applied in increasing and decreasing order.
Impact strength is the ability of a material to resist forces that tend to
break it when dropped or struck by a sharp blow.
Incompressible fluid is one that does not undergo a volume change,
i.e. it is density preserving.
Interface is the contacting surface where two materials meet.
Interphase is the region separating the filler from the polymer and
comprises of the area in the vicinity of the interface.
Loss modulus is the imaginary part of the complex modulus.
Melt Flow Index (MFI) is the weight of the polymer in grams extruded
in ten minutes through a capillary of specific diameter and length by
pressure applied through dead weight under prescribed temperature
conditions as per set international standards.
Melt flow indexer is the apparatus used for measuring MFI.
Melt fracture is the irregular distortion of a polymeric melt extrudate
upon passing through a die due to improper melt or process
characteristics.
Mixing describes the process of intimate intermingling of polymers
with filler s/additives or two polymers without any specific
restrictions.
Model is an idealized relationship of behavior expressible in mathe-
matical terms.
Molecular weight is a measure of the chain length of the molecules that
make up the polymer.
No-slip condition at a solid boundary implies that the molecules in the
thin fluid layer adjacent to the solid surface move at the same velocity
as that of the surface.
Normal stress coefficient is the ratio of the normal stress by the square
of the shear rate.
Normal stress difference is the difference between the normal stress
components.
Paraffin wax is a chemical substance obtained as a residue from the
distillation of petroleum and is made up of higher homologues of
alkanes with a melting range of 50 to 9O0C.
Plasticizer is a material generally of low molecular weight that is
incorporated into a thermoplastic melt to improve its workability
during processing and flexibility in the finished product.
Power-law model is behavior characterized by a power (n) relationship
between shear stress and shear rate.
Relaxation time is the time taken for the stress to decrease to an
exponentially inverse of its initial value under constant strain.
Rheology is concerned with the description of the deformation of the
material under the influence of stresses.
Rheogram or flow curve is a curve relating shear stress or viscosity to
shear rate.
Rheometry is an instrumental technique for measuring rheological
properties.
Steady flow is the flow in which the velocity at every point is the same.
Storage modulus is the real part of the complex modulus.
Suspension is a system in which denser particles, that are at least
microscopically visible, are distributed throughout a less dense fluid
and settling is hindered either by the viscosity of the fluid or by the
impact of its molecules on the particles.
Tensile strength is the ability of a material to withstand forces tending
to pull it apart.
Thermoplastic is a polymer that can be made to soften and take on
new shapes by the application of heat and pressure.
Thermoset is a polymeric material that has undergone a chemical
reaction, known as curing in A, B and C stages depending on the
degree of cure by the application of heat and catalyst.
Vortices are intense spiral motions in a limited region of a flowing
fluid.
Weissenberg effect is an effect exhibited by certain non-Newtonian
fluids and involves the climbing of the fluid up a rod rotating in it.
Yield stress is the stress corresponding to the transition from elastic to
viscous deformation of the flow curve.
Appendix B ASTM conditions
and specifications for MFI
Table B1a Standard testing conditions of temperature and load as per *ASTM
D1238andtASTMD3364
Condition Temp. Load Approximate pressure Shear stress
(0C) piston+ (x105 dynes/cm2)
weight (kg) (kg/cm2) (psi)
*A 125 0.325 0.46 6.50 0.3
*B 125 2.160 3.04 43.25 1.97
*C 150 2.160 3.04 43.25 1.97
*D 190 0.325 0.46 6.50 0.3
*E 190 2.160 3.04 43.25 1.97
*F 190 21.600 30.40 432.50 19.7
*G 200 5.000 7.03 100.00 4.6
*H 230 1.200 1.69 24.00 1.1
*l 230 3.800 5.34 76.00 3.5
*J 265 12.500 17.58 250.00 11.4
*K 275 0.325 0.46 6.50 0.3
*L 230 2.160 3.04 43.25 1.97
*M 190 1.050 1.48 21.00 0.96
*N 190 10.000 14.06 200.00 9.13
*0 300 1.200 1.69 24.00 1.1
*P 190 5.000 7.03 100.00 4.6
*Q 235 1.000 1.41 20.05 0.91
*R 235 2.160 3.04 43.25 1.97
*S 235 5.000 7.03 100.00 4.6
*T 250 2.160 3.04 43.25 1.97
t 175 20.000 28.12 400.00 18.4
Note: An asterisk (*) denotes ASTM D1238 and a dagger (t) denotes ASTM D3364.
Table B1b Testing conditions for commonly used polymers
Polymer Condition
*Acetals E1M
*Acrylics H11
*Acrylonitrile-butadiene-styrene G
'Cellulose esters D1 E 1 F
*Nylon K1 Q, R1 S
*Polychlorotrifluoroethylene J
*Polyethylene A1 B1 D1 E1 F1 N
*Polyterephthalate T
*Polycarbonate O
*Polypropylene L
*Polystyrene G, H 1 1 1 P
tPoly(vinyl chloride)
*Vinyl acetal C
Note: An asterisk (*) denotes ASTM D1238 and a dagger (t) denotes ASTM
D3364.
Table B1c Test temperature summary

Test temperature (0C) Condition
*125 A1B
*150 C
|175
*190 D1 E1 F1 M1 N1 P
*200 G
*230 H1 I1 L
*235 Q1 R 1 S
*250 T
*265 J
*275 K
*300 O
Note: An asterisk (*) denotes ASTM D1238 and a dagger
(t) denotes ASTM D3364.
Table Bid Test load summary
Load (kg) Condition
*0.325 A1 D, K
*1.000 Q
*1.050 M
*1.200 H1O
*2.160 B1C1E1L1R1T
*3.800 I
*5.000 G1 P1 E
*10.000 N
*12.500 I
t20.000
*21.600 F
Note: An asterisk (*) denotes ASTM D1238 and a dagger
(t) denotes ASTM D3364.
Table B1e ASTM specifications for piston and die dimensions

Piston Die
Diameter *, f (0.3730 ± 0.0003 in *, f (0.0825 ± 0.0002 in
= 9.474 ± 0.007 mm) = 2.095 ± 0.005 mm)
Length *, f (0.250 ± 0.005 in * (0.315 ± 0.0008 in
= 6.35 ± 0.13 mm) = 8.00 ± 0.02 mm)
t (0.916 ±0.0008 in
= 23.26 ± 0.02 mm)
Note: An asterisk (*) denotes ASTM D1238 and a dagger (t) denotes ASTM D3364.
Appendix C Data details and
sources for master rheograms

Table C1 Details of data used for master rheograms of filled polymers in Figures 6.32-6.39 (Source: Ch. 6 Refs [50] and [149])
Polymer Grade Filler type, amount Coupling MFI (temp.°C/ Data No. of data Data
agent, load condition, temp. points (shear source
0
amount kg) C rate Ch. 6
range, sec"1 Ref.
LDPE P1 4.9C (220/2. 16) 220 5(630-12000) [16]
P1 Quartz powder, 33 phr 16.7C (220/2.16) 220 4(630-12000) [16]
P1 Quartz powder, 100 phr 3.0C (220/2.1 6) 220 4(630-12000) [16]
P1 Quartz powder, 200 phr 1.7C (220/2. 16) 220 4(630-12000) [16]
P1 Calcium carbonate I1 33 phr 2.1 c (220/2.1 6) 220 4(630-12000) [16]
P1 Calcium carbonate I1 66 phr 0.4C (220/2.1 6) 220 4(630-12000) [16]
P1 Calcium carbonate II, 33 phr 5.4C (220/2.1 6) 220 4(630-12000) [16]
P1 Calcium carbonate II, 66 phr 2.0C (220/2.1 6) 220 4(630-12000) [16]
PP 10-2626 Talc, 66 phr 3.3a (200/2. 16) 200 6(10-500) [157]
10-2626 Talc, 66 phr 5.5b (230/2. 16) 230 6(10-500) [157]
10-2626 Talc, 66 phr 8.7a (250/2. 16) 250 6(10-500) [157]
E115 5.4C (200/2.1 6) 200 4(5-40) [5]
E115 CaCO3, 11 phr 3.0C (200/2.1 6) 200 5(5^0) [5]
E115 CaCO3, 25 phr 2.3C (200/2. 16) 200 5(4-40) [5]
E115 CaCO3, 66 phr 0.85C (200/2. 16) 200 5(1-40) [5]
E115 CaCO3, 230 phr 0.18C(200/2.16) 200 5(0.3^0) [5]
Profax 6523 15.7C (240/2. 16) 240 3(1-100) [18]
Profax 6523 CaCO3, 230 phr KR-TTS, 0.5 phf 7.6C (240/2.1 6) 240 4(0.1-100) [18]
Profax 6523 CaCO3, 230 phr KR-TTS, 1.5 phf 44C (240/2. 16) 240 3(1-100) [18]
Profax 6301 Mica, 66 phr 30C (220/2. 16) 220 3(3-60) [9]
Profax 6301 Mica, 66 phr Z-6032, 0.5 phf 108C (220/2.1 6) 220 4(2-10) [9]
Tabled (continued)
Polymer Grade Filler type, amount Coupling MFI (temp.°C/ Data No. of data Data
agent, load condition, temp. points (shear source
0
amount kg) C rate Ch. 6
range, sec"1 Ret.
PS STYRON 678 U 1.5C( 180/5) 180 6(0.01-100) [27]
STYRON 678 U Carbon black, 11 phr 0.93C( 180/5) 180 6(0.01-50) [27]
STYRON 678 U Carbon black, 25 phr 0.55C (180/5) 180 7(0.01-0.5) [27]
STYRON 678 U Carbon black, 43 phr 0.16c(180/5) 180 6(0.01-0.5) [27]
STYRON 678 U TiO2, 11 phr 0.83C( 180/5) 180 4(0.01-0.4) [27]
STYRON 678 U TiO2, 25 phr 0.53C( 180/5) 180 4(0.01-0.4) [27]
STYRON 678 U TiO2, 43 phr 0.44C (180/5) 180 3(0.01-0.4) [27]
STYRON 678 U Glass fiber, 25 phr 0.73C( 180/5) 180 4(0.01-100) [14]
STYRON 678 U Glass fiber, 66 phr 0.36C( 180/5) 180 4(0.01-100) [14]
STYRON 678 U CaCO3, 50 phr 0.27C (180/5) 180 4(0.01-0.4) [18]
STYRON 678 U CaCO3, 50 phr Treated 2.0C (180/5) 180 4(0.01-0.4) [18]
PET PET1 49C (275/2. 16) 275 4(10-5000) [20]
PET1 Glass fiber, 33 phr 11. 3C (275/2. 16) 275 5(6-5000) [20]
PET1 Glass fiber, 66 phr 4.9C (275/2. 16) 275 5(6-5000) [20]
PC Makrolon 2805 6.1 c (290/1 .2) 290 3(10-1000) [31]
Makrolon 9410 Glass fiber, 10 phr 3.3C(290/1.2) 290 4(1-1000) [31]
Makrolon 8344 Glass fiber, 40 phr 1.1° (290/1 .2) 290 4(1-1000) [31]
Nylon Zytel 40C (288/2. 16) 288 3(50-6700) [158]
Zytel 49C(291/2.16) 291 4(10-10000) [158]
Zytel Glass fiber, 15phr 29.4C(291/2.16) 291 4(10-1000) [158]
Zytel Glass fiber, SOphr 12.8C (288/2.1 6) 288 3(10-4400) [158]
Zytel Glass fiber, 50phr 15.7C(291/2.16) 291 4(10-10000) [158]
Maranyl A100 113C (280/2. 16) 280 5(100-10000) [25]
Maranyl A190 Glass fiber, 50phr 22C (280/2. 16) 280 5(100-1000) [25]
PEI ULTEM 1000 1 9.81 c (360/5) 360 5(5-5000) [136]
ULTEM 1000 Glass fiber, 11 phr or 10w% 5.9C (360/5) 360 5(5-5000) [136]
ULTEM 1000 Glass fiber, 25 phr or 20 w% 3.96C (360/5) 360 5(5-5000) [136]
ULTEM 1000 Glass fiber, 43 phr or 30 w% 2.45C (360/5) 360 5(5-5000) [136]
PEEK PEEK 45G 1.9C (380/5) 380 5(0.1-1000) [159]
PEEK 453OA Carbon fiber, 43 phr or 30 w% 16.7C (380/5) 380 5(0.01-1000) [159]
PEEK 453OG L Glass fiber, 43 phr or 30 w% 2.96C (360/5) 360 7(15^1000) [159]
PEEK 453OA Glass fiber, 43 phr or 30 w% 4.2C (395/5) 395 7(15-1000) [159]
a
b
MFI value calculated from equation (6.30) knowing the MFI value as per footnote b.
c
MFI value given by manufacturer or measured under ASTM test conditions.
MFI value read out from t vs. y curve using equations (6.26) and (6.27) by the method discussed in section 6.8.
Table C2 Parameters of the filled polymer systems covered in the data analyzed for
master rheograms of filled polymers in Figures 6.32-6.39 (Source: Ch. 6 Refs [50] and
[149])
Matrix Filler type Amount (phr) Coupling agent Shape
LDPE Quartz powder I 33 100 200 Particulate
Quartz powder Il 11 33 Particulate
Calcium carbonate I 33 66 Prismatic
Calcium carbonate Il 33 66 Prismatic
PP Talc 66 Platelet
Calcium carbonate 11 25 66 230 Prismatic
Calcium carbonate 230 0.5 to 1.0 phf Prismatic
titanate
Mica 66 Platelet
Mica 66 0.5 phf silane Platelet
PS Carbon black 11 25 43 Particulate
Titanium dioxide 11 25 43 Particulate
Glass fiber 25 66 Fibrous
Calcium carbonate 50 Treated Prismatic
Calcium carbonate 50 Untreated Prismatic
Nylon Glass fiber 15 50 Fibrous
PC Glass fiber 10 20 30 40 Fibrous
PET Glass fiber 33 66 Fibrous
PEI Glass fiber 11 25 43 Fibrous
PEEK Carbon fiber 43 Fibrous
Glass fiber 43 Fibrous
Table C3 Details of unfilled polymer data used for master rheograms in Figures 6.32-
6.39 (Source: Ch. 6 Refs [50] and [149])
Polymer Grade MFI (temp.°C/ Temperature No.of data points Data
load condition, at which data (shear rate source
kg) generated (0C) range, sec"1) Ch.6
Ref.
LDPE lndothene 22FA002 0.2ab (190/2.16) 190 9(0.01-1000) [144]
lndothene 24FS040 3.0 (175/2.16) 175 10(0.01-1000) [144]
lndothene 24FS040 4.0aa (190/2.16) 190 10(0.01-1000) [144]
lndothene 24FS040 5.0b (205/2.16) 205 10(0.01-1000) [144]
lndothene 26MA200 20 (190/2.16) 190 10(0.01-1000) [144]
PP 10-6016 3.9ba(210/2.16) 210 6(10-500) [157]
10-6016 6.5 a(230/2.16) 230 6(10-500) [157]
10-6016 10.3 (250/2.16) 250 6(10-500) [157]
PS Styrene666U 7.5b a(200/5) 200 10(5-5000) [160]
Styrene666U 37.Oa (220/5) 220 10(5-5000) [160]
Styrene666U 130 (240/5) 240 10(5-5000) [160]
H5M 15.4aa (210/5) 210 6(10-500) [157]
H5M 47.7a (230/5) 230 5(20-500) [157]
H5M 121 (250/5) 250 6(10-500) [157]
Nylon Plaskon8201 5.0C C(231/2.16) 231 4(10-4000) [161]
Plaskon8201 13.7 (260/2.16) 260 4(10-1000) [161]
Plaskon8201 29.5CC (288/2.16) 288 4(10-10000) [161]
Nylon 610 235C (280/2.16) 280 4(10-10000) [162]
PET Fiber grade IV = 0.57 54 (275/2.16) 275 9(1-5000) [163]
Fiber grade IV = 0.57 64°C (285/2.16) 285 9(1-5000) [163]
Fiber grade IV = 0.57 86 C(295/2.16) 295 9(1-5000) [163]
Fiber grade IV = 0.57 103 (305/2.16) 305 9(1-5000) [163]
Bottle grade IV =1.044 1.5CC (275/2.16) 275 8(1-1000) [163]
Bottle grade IV =1.044 1.6 C(285/2.16) 285 8(1-1000) [163]
Bottle grade IV =1.044 1.77C (295/2.16) 295 8(1-1000) [163]
Bottle grade IV =1.044 1.96 (305/2.16) 305 8(1-1000) [163]
PC Lexan141 1.3° (250/1.2) 250 4(20-300) [164]
Lexan 141 3.5Cc (270/1.2) 270 4(20-300) [164]
Lexan 141 6.1 (290/1.2) 290 4(20-300) [164]
PEI ULTEM 8.34C (355/5) 355 3(200-7000) [165]
ULTEM 22.08°C (375/5) 375 3(200-10000) [165]
ULTEM 39.25C (395/5) 395 3(200-10000) [165]
PEEK PEEK 951GV 10.8 (360/5) 360 4(15-1000) [159]
PEEK 951GV 22.6C (395/5) 395 4(^1000) [159]
a
b
MFI value calculated from equation (6.30) knowing the MFI value as per footnote b.
c
MFI value given by manufacturer or measured under ASTM test conditions.
MFI value read out from T versus y curve using equations (6.26) and (6.27) by the method
discussed in section 6.8.
Appendix D Abbreviations
STANDARDS
ASTM American Society for Testing and Materials
BS British Standards
DIN Deutsches Institut fiir Normung
ISO International Standards Organisation
JIS Japanese Industrial Standards
POLYMERS
ABS Acrylonitrile-butadiene-styrene
C-ester Cellulose ester
C-ether Cellulose ether
EVA Ethylene-vinyl acetate
HDPE High density polyethylene
HIPS High impact polystyrene
LDPE Low density polyethylene
LLDPE Linear low density polyethylene
PA Polyamide
POM Polyacetal
PAr Polyarylate
PAS Polyaryl sulfone
PBT Poly(butylene terephthalate)
PC Polycarbonate
PE Polyethylene
PEEK Polyether ether ketone
PEI Polyetherimide
PES Polyether sulfone
PET Polyethylene terephthalate)
PIB Poly(isobutylene)
PMMA Poly methyl methacrylate
PP Polypropylene
PPO Poly phenylene oxide
PPS Poly phenylene sulfide
PS Polystyrene
PVA Poly(vinyl alcohol)
PVB Poly( vinyl butyral)
PVC Poly(vinyl chloride)
PVDF Poly(vinylidene fluoride)
SAN Styrene acrylonitrile
SBR Styrene butadiene rubber
SBS Styrene-butadiene-styrene
SIS Styrene-isoprene-styrene
SMA Styrene-maleic anhydride
TPE Olefinic-type thermoplastic elastomer
UHMWPE Ultra high molecular weight polyethylene
VCVA Vinyl chloride-vinyl acetate
Appendix E Nomenclature
Table E1
Symbol Description Units Equation
1 2 3 4
a Volume fraction of component 1A' in (5.2a), (5.3b)
a mixture
a0 Half width of channel (3.18)
ai Empirical coefficient whose value lies (4.2)
between 1 and 2
^MFl MFI ratio (6.15)
a Model parameter (2.53)-(2.56)
A Surface area of plate in Figure 2.1 m2
A0 Frequency term depending on the Pa sec (2.69)
entropy of activation for flow
A'0 Constant (2.74)
A0 Constant (2.73)
A* Hamaker's constant (6.5a), (6.6)
\ Adjustable parameter (4.12b)
A" Constant dependent on the nature (6.12), (6.13)
of the continuous phase
b Volume fraction of component 1B' in (5.2b), (5.3c)
a mixture
bQ Half thickness of channel (3.17)
b Overall width of the residence time m (5.14)
distribution curve in Figure 5.28
B Filler-polymer interaction parameter (8.10)-(8.14)
Bo Constant (2.74)
B1, B11 Coefficients (4.27)
B1(^n) Function dependent on volume (6.3)
fraction and power-law index
82(0, n) Function dependent on volume (6.3)
fraction and power-law index
Table E1 (continued)
1 2 3 4
c Arbitrary adjustable parameter (2.57)
C 1 5 C 2 , C3 Constants (2.63)
C Positive constant representing the (6.5a), (6.6)
total number of nearest
neighbors of each sphere
C^ Constant (2.68)
C2 Constant (2.68)
ofp Particle diameter in Figure 4.4 m
c/ Particle diameter in Figure 4.5 m
D Diameter of sphere, rod or platelet- m (6.5a), (6.6),
shaped particle (8.11H8.13)
D3 Average diameter of different sizes of m (6.17)-(6.20)
particulates
D1 Diameter of the /th component m (6.17H6.21)
D0 Orifice diameter m
DE Extrudate diameter m
Dp1 , Dp2, Dp, Average diameter of suspending m (4.22), (4.23),
particles 1, 2 and /th fraction, (4.25)
respectively
Dpc Projection circumscribing diameter in jim
Table 8.4 from section 8.6
D1 Diameter of tube or pipe m (4.22), (4.23)
DR Draw ratio
DRC Critical value of draw ratio
D Symmetric part of the gradient or sec~1 (2.3), (2.4),
deformation tensor (2.23), (2.28),
(2.30)
e Exponential (where e' = 2.71828)
e Independent parameter (2.57)
ev Parameter contributing the (4.32)
electroviscous effects
evi . ev2> ev3 Coefficients corresponding to each (4.31)
of the three electroviscous effects
E Activation energy for viscous flow kJ/mole (2.69), (2.70)
Ec Coulombic interaction energy J (6.2)
Ev van der Waals interaction energy J (6.2)
Eint Interaction energy J (6.1)
E°s Viscous dissipation energy for matrix J (6.1), (6.3)
Evis Viscous dissipation energy for filled J (6.1), (6.3)
system
E0 Activation energy of the flow process kJ/mole (6.8), (6.10)
for unfilled polymer system
E00 Activation energy of the flow process kJ/mole (6.9), (6.10)
for filled polymer system containing
$ volume fraction of filler
1 2 3 4
ET Value of E determined under kJ/mole (2.71)
constant shear stress conditions
E) Value of E determined under kJ/mole (2.72)
constant shear rate conditions
Eg Dynamic loss modulus for filled Pa (8.14)
polymer in solid state
Ep Dynamic loss modulus for unfilled Pa (8.14)
polymer in solid state
AE Difference between the activation kJ/mole
energy for viscous flow of filled
and unfilled polymer system
f Force in Figures 2.1, 2.3, 2.4 Newtons (2.2)
f(4>r) Function of the volume fraction of (4.28)
the floccules in a suspension
/(7, O) Free volume of the continuous m3 (6.13), (6.14),
phase at temperature T but (6.15)
without the presence of any other
dispersed phase
f(T, 4>) Free volume of the multi-component m3 (6.12), (6.14)
system at temperature 7
containing <j> weight fraction of the
dispersed phase
^1 Number fraction of the /th (6.17)-(6.19)
component defined by eq. (6.21)
F Force exerted by the test load L on Newtons (6.24)
the polymer in the melt flow indexer
Fmax Maximum force tending to divide a Newtons (5.11)
dumbbell shaped agglomerate in
a fluid
G Apparent melt shear modulus Pa (3.16b)
Gc, Gmo Storage moduli for the filled and (6.23)
unfilled polymer, respectively
G' Dynamic storage modulus Pa (2.15)
G' (O, o>) Dynamic storage modulus at Pa (8.7a)
frequency of a> for unfilled
polymer system
G'((/>, CD) Dynamic storage modulus at Pa (8Ja)
frequency of co for filled polymer
system containing $ volume
fraction of filler
G'r Relative dynamic storage modulus Pa (8.9)
defined as the ratio of the
dynamic storage modulus for the
filled to unfilled polymer system
G" Dynamic loss modulus Pa (2.16)
1 2 3 4
G" (O, co) Dynamic loss modulus at frequency Pa (8.7b)
of co for unfilled polymer system
G"($, co) Dynamic loss modulus at frequency Pa (8.7b)
of co for filled polymer system
containing 0 volume fraction of
filler
GC Dynamic loss modulus for filled Pa (8.10)
polymer melt
Gp Dynamic loss modulus for unfilled Pa (8.10)
polymer melt
G* Complex modulus Pa (2.21)
77 Gap between two parallel discs of m (3.7)
viscometer
/ Intensity of segregation (5.10)
J6 Steady state compliance Pa"1 (2.50)
k Constant power index (6.16)
ke Thickness of the electrostatic (6.5a)
interaction layer
kj Hydrodynamic interaction coefficient (4.25)
kQ Constant (2.75)
K Consistency index whose values are g/cmsec2"" (6.35), (6.36)
tabulated in Tables 6.8 and 6.9 (g/10 min)n
K0 Rate constant for volume increase of (4.30)
the crystals
KJe Coefficient (2.49), (2.50)
K Consistency index kg/m sec2'" (2.39), (2.40),
(2Ma), (4.29),
(6.31)
/ Variable length of cylindrical rod in m
Figure 2.3
/o Initial length of cylindrical rod m (2.26)
/N Length of nozzle m (6.24)
/P Length of rod-shaped particle m (8.12)
L Test load, i.e. dead weight+ piston kg (6.26)
weight
L1 Test load 1 kg (6.32)
L2 Test load 2 kg (6.32)
m Damping constant (2.47), (2.48)
Tf? Number of thread starts per screw (5.13)
m' Adjustable parameter (2.60)
m" Adjustable parameter (2.61)-(2.63)
M Total number of components in a (4.27)
blend of suspended particles
MFI Melt flow index g/10min
1 2 3 4
MFI(T, O) Melt flow index of the continuous g/10min (6.13)
phase at temperature T but
without the presence of any other
dispersed phase
MFI(T, 0) Melt flow index of the multi- g/10min (6.12)
component system at temperature
T and containing (/> volume
fraction of the dispersed phase
MFI1 Melt flow index determined under g/10min (6.32)
test load 1
MFI2 Melt flow index determined under g/10min (6.32)
test load 2
MFI11 Melt flow index at ASTM g/10min (6.30)
recommended test temperature
MFI12 Melt flow index at required g/10min (6.30)
temperature
/7?i,7r?| Mixing index (5.7)
Mw Weight average molecular weight (2.49), (2.50),
(2-75)
MWc Critical weight average molecular (2.75)
weight
~M2 z average molecular weight (2.49), (2.50)
n Power-law index whose values are
given in Tables 6.8 and 6.9
n' Power-law index (2.52b), (2.62b)
n" Power-law index (2.52b), 2.62b)
7? Power index (8.10), (8.14)
N Power index in the Carreau model (2.42), (2.43),
(2.48), (2.52a),
(2.62a), (6.33)
/V1 Primary normal stress difference Pa (2.7)
/V2 Secondary normal stress difference Pa (2.8)
A/F Normal force Newtons (3.4H3.6)
N' Number of particles in sample
/V1 Number of ultimate particles of the (5.1)
major component
A/2 Number of ultimate particles of the (5.1)
minor component
A/'r Number of floccules (4.28)
N" Number of samples of same size (5.4H5.6)
/V Speed of rotation rpm (3.1), (5.12),
(5.13)
p Pressure Pa (2.3)
PH Pressure hole error Pa
pm Measured pressure Pa
1 2 3 4
P Power-index in the General (2.44), (6.36)
Rheological model whose values
are given in Table 6.9
PI, Pj Particle size frequency function of (4.26)
the /th and /th particle
P(XA) Probability distribution for finding XA (5.3a)
concentration in a sample
APdie Pressure drop in extrusion die Pa (3.10H3.12),
(3.14), (3.15)
O Volumetric flow rate nrrVsec (5.12), (5.13),
(5.15), (6.25)
Oc Leakage flow rate between screw m3/sec (5.13)
flight and other screw
Of Leakage flow rate between screw m3/sec (5.13)
flight and barrel wall
O1 Leakage flow rate rrvVsec (5.13)
O3 Leakage flow rate between flanks m3/sec (5.13)
perpendicular to the plane
through screw axis
Ot Leakage flow rate between flanks of m3/sec (5.13)
screw flights
Qth Theoretical flow rate rrvVsec (5.13)
r Radial position m (3.1)
T1 Radius of particle 1 in an m (5.11)
agglomerate
r2 Radius of particle 2 in an m (5.11)
agglomerate
ra Ratio of length of diameter of a rod- (4.15), (4.16),
shaped particle (4.18), (4.19),
(4.33)-(4.36)
re Ratio of the semi-axis of the ellipsoid (4.14a), (4.14b)
of rotation
R Gas constant = 8.314 J/molK (2.69)-(2.72)
R(r) Coefficient of correlation (5.9)
RN Radius of nozzle m (6.24), (6.25)
RP Radius of piston m (6.24)
fl Radius of disc or cone of viscometer m (3.2)-(3.9)
s Self-cleaning time sec (5.14)
S Standard deviation of composition of (5.6), (5.7)
spot samples
S2 Variance of composition of spot (5.5)
samples
SL Scale of segregation (5.8)
SR Elastic strain recovery (2.38), (3.15),
(3.16a)
1 2 3 4
Sw Die swell ratio of extrudate diameter (2.37)
to die diameter
t Time sec
~t Average residence time sec (5.14), (5.15)
tan 6 Loss tangent = G" /G' (2.17)
tr D Trace of the deformation tensor (2.5)
0
T Polymer melt temperature C
T1 ASTM recommended test K (6.30)
temperature
T2 Temperature at which MFI is K (6.30)
required
T9 Glass transition temperature of K
polymers
7
Qc' 7Q0 Characteristics glass transition K (6.23)
temperature for filled composite
and unfilled polymer
T3 Standard reference temperature K (2.68), (2.70),
equal to T9 +50 (6.30)
T Measured torque Newtons (3.2), (3.3)
T Symmetric Cauchy stress tensor Pa (2.3)
Vj Volume fraction of the /th (6.21)
component
V1, V2, V3 Velocity components along X1, X2, X3 m/sec
axis
Vc Volume of C-shaped channel m3 (5.13)
between flanks of successive
flights
Vf Free volume m3 (5.15)
V5 Volume of sample m3 (5.3c)
w Distance between the points of m (5.14)
inflection on the residence time
distribution curve in Figure 5.28
X1 , X2, X3 Distances along the X1 , X2, X3 axis m
xh X1 Weight proportion of the /th and /th (4.27)
component in a blend of
suspended particles
x Positional vector m (2.4)
X Thickness of platelet-shaped particle m (8.13)
XA Concentration of component 1A' in a (5.3a)
sample
XA. Measured value of XA for the /th (5.4), (5.5)
sample
X A/ Concentration of component 'A' at (5.9)
point 1 in the /th sample
1 2 3 4
X^. Concentration of component 'A' at (5.9)
point 2 in the /th sample
XA Actual mean concentration of (5.4H5.6)
component 'A' in a sample
Z Quantity calculated for checking (5.6)
mixing quality
Z0 Degree of flocculation (4.19)
Z(a) Model parameter (2.53)-(2.56)
Appendix F Greek symbols
Table F1 Greek symbols

1 2 3 4
a Ultimate particle size of component A (5.3c)
a0 Rate of energy dissipation within the (4.29)
neighbourhood of a typical sphere
in a suspension
0^,Of 2 Ja 3 Coefficients (4.5)
ac Coefficient in the crowding factor (4.8), (4.18)
expression
a/v Crowding factor coefficient (4.26)
Ocn Function of the axis ratio re (4.13), (4.14b)
OLf2 Function of the axis ratio re (4.13), (4.14b)
aE Einstein's constant (4.1), (4.4), (4.15),
(4.17)
a' Ellis model parameter (2.41), (6.34)
a'c Adjustable factor (4.21) ,(4.22)
«c Adjustable factor (4.21), (4.23)
a Constant (5.12)
a Coefficient (4.17)
/? Term defined by equation (6.18) (6.17)
P(T) Difference between free volumes of m3 (6.14), (6.15)
the polymer and the filled polymer
system
j50 Rate constant for the equilibrium (4.19)
between free filler particles and
floccules
/? Constant (5-12)
y Shear rate see'1 (2.1), (6.23), (6.27),
(6.29)
Table F1 Continued
1 2 3 4
y0 Amplitude of the sinusoidal variation (2.12), (2.13),
of shear rate (2.15), (2.16)
ya Shear rate at outer radius of disc sec"1 (3.7)
ym Amplitude of oscillation in the
maximum (or effective) shear rate
(yj
yw Wall shear rate sec"1 (3.13)
y'LS lnterfacial energy between liquid- J (1.1)
solid phase
y'LV lnterfacial energy between liquid- J (1.1)
vapour phase
7sv lnterfacial energy between solid- J (1.1)
vapor phase
6 Phase angle (2.14H2.17)
<5S Diameter ratio of small particle to
large particle in Figure 6.1 8(b)
£ Void fraction or porosity
e Dielectric constant (6.5)
£f Degree of fill m2/sec (5.15)
s Uniaxial extensional rate sec'1 (2.22)-(2.26),
(2.66a), (2.66b),
(3.19), (3.20)
£B Biaxial extensional rate sec"1 (2.27), (2.28)
£c Critical extensional rate sec"1
£P Planar extensional rate sec~1 (2.29), (2.30)
C Capillary entrance end effect (3.12), (3.14)-(3.16)
correction for viscous effect
r\ Steady shear viscosity Pa.sec
r\(y) Steady shear viscosity function Pa.sec (2-9)
rja Apparent viscosity of a fluid in Pa.sec
Figure 4.5
Â Viscosity value read from intersecting Pa.sec (2.44b)
asymptotes
rjc Viscosity of the filled composite Pa.sec (6.22)
material
Ê Uniaxial extensional viscosity Pa.sec (2.31), (2.66a),
f/E(0 Extensional viscosity as a function of Pa.sec (2.66b)
time
T/EB Biaxial extensional viscosity Pa.sec (2.32)
f7EP Planar extensional viscosity Pa.sec (2.33)
^f Viscosity of a homogeneous Pa.sec (4.28)
suspension of floccules
/ymc Viscosity of the polymer matrix Pa.sec (6.22)
v\mo Viscosity of the unaffected polymer Pa.sec (6.22)
Table F1 Continued
1 2 3 4
rjN Viscosity of filled polymer system in Pa.sec (2.45b)
the Newtonian plateau region
rjr Relative steady shear viscosity which Pa.sec (6.11)
is the ratio of viscosity of filled to
unfilled polymer system
0/r)f Relative viscosity at fixed shear rate (6.7)
>yrmjx Relative viscosity of a mixture of two (4.21)
suspended particles
rjs Viscosity of a dilute suspension of Pa.sec (4.29)
spheres
rj-f Trouton's viscosity in uniaxial Pa.sec (2.65)
stretching
T/V Volume viscosity Pa.sec (2.3)
rjQ Zero shear viscosity; also viscosity of Pa.sec (2.34), (2.36),
the suspending medium (4.22), (4.23),
(4.28), (4.33)-
(4.36)
riQJ Steady shear viscosity of unfilled Pa.sec (6.8), (6.10)
polymer system at a temperature T
rjOJn Steady shear viscosity of unfilled Pa.sec (6.8), (6.10)
polymer system at a reference
temperature 7R
rjjj Steady shear viscosity of filled Pa.sec (6.9), (6.10)
polymer system containing </>
volume fraction of filler at a
temperature T
Tj^jn Steady shear viscosity of filled Pa.sec (6.9), (6.10)
polymer system containing <j>
volume fraction of filler at a
temperature 7"R
r\ Dynamic viscosity Pa.sec (2.18)
rj'r Relative dynamic viscosity defined as (8.8)
the ratio of dynamic viscosity of
filled to unfilled polymer system
Y]' Imaginary part of complex viscosity Pa.sec (2.19)
r\* Complex viscosity Pa.sec (2.20), (2.51),
(2.52a), (2.52b)
Y]I Zero-frequency viscosity function Pa.sec (2.52a)
rj*((f), y) Viscosity function dependent on Pa.sec (6.5b)
volume fraction and shear rate
^00 Shear viscosity value at very high Pa.sec
shear rate
9 Spherical coordinate giving the
orientation of the rod as shown in
Figure 4.2
Table F1 Continued
1 2 3 4
9Q Cone angle in Figure 3.1 radians (3.1)
& Contact angle radians (1.1)
9 Half angle of convergence of stream radians (2.67)
line at the entrance of die
A Relaxation time; also time constant sec (2.42), (2.43),
and model parameter (2.48), (2.56),
(2.62a), (6.33)
A1 , A 2 Parameters of the Oldroyd model sec (2.66a)
Ac Characteristic time sec
A3 Time scale of deformation sec
A(0) Function of 0 (4.3)
IJL Mean of composition of a random (5.2a), (5.3b)
homogeneous mixture
/Z Interaction parameter (4.19)
v Kinematic viscosity m2/sec (5.15)
v Constant (4.28)
p Polymer melt density kg/m3
P0 Density of the suspending medium kg/m3 (4.22), (4.23)
a Standard deviation of composition of (5.7)
a random homogeneous mixture
a2 Variance of composition of a random (5.2b), (5.3c)
homogeneous mixture
(T1 , C2 Upper and lower limits of the (4.26)
dimensionless radius, respectively
<TE Average extensional stress Pa (2.67a)
T Shear stress Pa (2.36), (2.39)
TW Wall shear stress Pa (3.11), (3.12)
Ty Yield stress Pa (2.45), (6.5a), (6.6)
i1/2 Special value of shear stress when Pa (2.41) ,(6.32)
steady shear viscosity is half the
zero shear viscosity
T21 Amplitude of the sinusoidal variation Pa (2.14)-(2.16)
of shear stress
T12, T21 Shear stress components of the Pa (2.2), (2.6), (2.9)
stress tensor
*n » T22» T33 Normal stress components of the Pa (2.6)-(2.8)
stress tensor
T11 - T22 Primary normal stress difference Pa (2.10)
T
22 ~ T33 Secondary normal stress difference Pa (2.11)
f Extra stress tensor Pa (2.3), (2.6), (2.34)
0 Volume fraction of the suspended
particles or fillers
(j)' Weight fraction of filler in Figures
6.17(a),6.17(b) and 6.31
Table F1 Continued
1 2 3 4
00 Initial volume of the crystals m3 (4.30)
01 ' 02> 03 Volume concentration of suspended (4.21), (4.24)
particles for 1, 2 and /th size
fraction, respectively
0cr Critical concentration below which (4.16)
the interaction between the rods
can be neglected
c/>f Volume fraction of floccules in the (4.28)
suspension
0L Volume fraction of larger particles
0m Maximum attainable concentration of
fillers defined as 1 - s or maximum
packing fraction
0° Maximum packing of spheres of (6.18)
uniform size r
</>s Volume fraction of smaller particles
\l/ Spherical coordinate giving the
orientation of the rod as shown in
Figure 4.2
\I/Q Surface potential of particulates J (6.5a)
^1, \l/2 Primary and secondary normal stress kg/m
coefficients
^1(JO Primary normal stress coefficient kg/m (2.10), (2.46),
function (2.47)
^2Cx) Secondary normal stress coefficient kg/m (2.11)
function
^1 y Relative normal stress difference (7.1)
coefficient defined as the ratio of
normal stress of filled to unfilled
polymer system at the same shear
rate
1
F1 Enclosed angle for a curved fiber in
Figure 4.4
co Frequency of oscillations or angular rad/sec (2.12H2.21)
frequency
Qmixed Probability (5.1)
Author Index
Abbas, K.A. 41, 49, 243, 292, 305, 312, Arina, M. 41, 48, 243, 259, 304, 312,
313, 315, 331, 334, 338, 391, 395, 333, 338, 390, 395, 398, 410, 414
411 Armstroff, O. 208, 240
Abdel-Khalik, S.I. 83-5, 107, 108 Armstrong, R.C. 55, 59, 60, 67, 79, 104,
Abe, D.A. 41, 49, 243, 273, 305, 312, 105
334, 338, 391, 395, 411 Arrhenius, S. 140, 171
Acierno, D. 9, 44, 166, 174, 397, 414 Ashare, E. 85, 108
Acrivos, A. 136, 142, 170, 171, 247, Astarita, G. 67, 79, 81, 84, 105, 107,
308 108, 395, 414
Adams, E. F. 266, 309 Ayer, J.E. 266-8, 309
Adarns, J.W.C 117, 133,267
Adams- Viola, M. 136, 168 Bachmann, J.H. 18, 45
Adler, P.M. 136, 170 Baer, A.D. 142, 171, 257, 265, 267, 269,
Advani, S.G. 41, 51, 243, 308, 312, 337, 308, 346, 394
338, 394, 395, 414 Bagley, E.B. 72, 74, 105, 106, 121, 133
Agarwal, P.K. 98, 109 Baily, E.D. 117, 133
Aggarwal, S.L. 8, 44 Baird, D.G. 9, 44, 331, 337
Agur, E.E. 194, 239 Baker, F.S. 113, 132, 136, 169
Ahu, C.W. 262, 263, 309 Ballenger, T.F. 85, 108
Akay, G. 74, 106 Ballman, R.L. 100, 110, 128, 131, 134,
Alfrey, T., Jr. 140, 171 135
Allen, P.W. 1, 44 Balmer, J. 74, 106
Allen, T. 357, 394 Bamane, S.V. 81, 82, 86, 87, 107, 301,
Allport, D.C. 8, 44 302, 311
Alter, H. 18, 45 Bandyopadhyay, G. 41, 52
Althouse, L.M. 41, 49, 243, 273, 306, Bares, J. 1, 44
312, 335, 338, 360, 361, 387, 388, Barnes, H.A. 41, 47, 67, 79, 84, 105,
392, 394, 395, 412 107, 136, 170
Anderson, P.C. 136, 168 Barringer, E.A. 266, 267, 309
Andres, U.T. 138, 170 Bartenev, G.M. 14, 41, 45, 285, 310
Andrews, R.D. 117, 133 Batchelor, G.K. 136, 164-6, 170, 174,
Angerer, G. 121, 133 405, 414
Aoki, Y. 117, 133 Bauer, L.G. 136, 168
Aral, E. 41, 51, 243, 307, 312, 336, 338, Baumann, O.K. 189, 238
393, 395, 413 Baumann, G.F. 104, 111
Aral, B.K. 338, 390 Bayliss, M.D. 136, 153, 169
Becker, E. 67, 79, 105 Bowen, H.K. 262, 263, 266, 267, 272,
Beek, W.I. 194, 239 309, 310
Belcher, H.V. 100, 109 Bowerman, H. H. 398, 414
Bell, J.P. 166, 174, 397, 414 Bradley, H.B. 35, 46
Benbow, JJ. 74, 75, 106 Brandrup, J. 1, 44
Bennett, K.E. 131, 135 Brauer, G.M. 136, 169
Berger, S.E. 35, 46 Braun, D.B. 136, 169
Beris A.M. 88, 90, 108 Brede, H.L. 140, 171
Berlamont, J. 136, 168 Brenner, H. 136, 170
Bernier, R. 136, 169 Bretas, R.E.S. 41, 50, 243, 306, 312, 335,
Bersted, B.H. 74, 106 338, 393, 395, 412
Berstein, B. 72, 85, 106 Bright, P.P. 41, 48, 243, 305, 312, 334,
Bestul, A.B. 100, 109 338, 391, 395, 397, 398, 410, 414
Bhardwaj, LS. 41, 49, 243, 273, 277, Brodnyan, J. 147, 172
278, 305, 312, 334, 338, 391, 395, Broutman, LJ. 17, 45
411 Browned, W.E. 136, 169
Bhattacharya, S.K. 41, 52, 266, 268, 310 Bruch, M. 312, 332
Bhavaraju, S.M. 136, 168 Brydson, J.A. 41, 47
Bierwagon, G.P. 19, 45 Bulkley, R. 83, 107, 247, 308
Bigg, D.M. 41, 47, 49, 50, 196, 219, 225, Bungenberg de Jong, H.G. 140, 171
236, 237, 239, 241, 243, 273, 277, Burgers, J.M. 145, 172
278, 290, 304, 306, 312, 333, 335, Burke, JJ. 8, 44
338-40, 349, 350, 354, 360, 361,
387, 388, 390, 392, 394, 395, 410-12 Cameron, G.M. 36, 46
Billmeyer, Jr. F.W. 1, 43, 44 Carley, J.F. 103, 110, 196, 239
Binding, D.M. 98, 109, 131, 135 Carr, R. 136, 167
Birchall, J.D. 190, 238 Carreau, PJ. 41, 51, 74, 81, 85, 106-8,
Bird, R.B. 55, 59, 60, 65, 67, 79-81, 243, 284, 287, 308, 312, 337, 338,
83-5, 97, 104, 105, 107-9 341, 394, 395, 414
Birks, A.M. 74, 106 Carruthers, J.M. 113, 132, 222, 241
Blake, W.T. 125, 134 Carter, R.E. 113, 132, 136, 169
Blanch, H.W. 136, 168 Caso, G.B. 136, 169
Blankeney, W.R. 146, 147, 172 Castillo, C. 136, 168
Bludell, DJ. 103, 110 Cengel, J.A. 139, 171
Blyler, L.L. 118, 126, 133, 134 Cessna, L.C. 16, 45
Boger, D.V. 113, 131, 136, 170, 312, Chaffey, C.E. 41, 47, 49, 50, 243, 273,
337 275-7, 292, 304-6, 312, 333-5, 338,
Bogue, D.C. 85, 91, 108, 117, 133 390, 392, 395, 410-2
Bohn, E. 10, 44, 262, 263, 309 Chan, C.F. 79, 107
Boiesan, V. 102, 110, 140, 171 Chan, F.S. 163, 173
Boira, M.S. 41, 47, 243, 273, 275-7, 292, Chan, Y. 41, 48, 163, 166, 173, 243, 292,
304, 312, 333, 338, 390, 395, 410 304, 312, 315, 333, 338, 390, 395,
Boonstra, B. B. 226, 241 405, 410
Booth, F. 163, 173 Channis, C.C. 18, 45
Booy, M.L. 208, 240 Chapman, P.M. 41, 47, 115, 132, 151,
Borghesani, A.F. 136, 168 172, 243, 246, 303, 312, 332, 338,
Botsaris, G.D. 136, 168 390, 395, 407, 409
Boudreaux, Jr. E. 75, 106 Charles, M. 124, 134, 136, 168
Bourne, R. 299, 311 Charley, R. V. 74, 106
Bowen, B.D. 10, 44 Charrier, J.M. 166, 174
Chartoff, R.P. 118, 133 Crackel, P.R. 136, 168
Chattopadhyay, S. 290, 299, 310 Craig, R.G. 136, 169
Chen, IJ. 85, 108, 117, 133 Crawley, R.L. 72, 105
Chen, SJ. 179, 237 Cross, M.M. 81, 107, US, 132
Chen, Y.R. 136, 169 Crowder, J.W. 14, 41, 45, 85, 108, 243,
Cheng, D.C-H. 136, 170 304, 312, 319, 333, 338, 390, 395,
Cheremisinoff, N.P. 67, 79, 105, 136, 410
169, 189, 194, 238, 239 Crowson, RJ. 41, 48, 243, 292, 305,
Chhabra, R.P. 81, 107 312, 334, 338, 391, 395, 397, 398,
Chipalkatti, M.H. 41, 49, 243, 273, 305, 410, 411, 414
312, 334, 338, 391, 395, 411 Cuculo, J.A. 75, 106
Chong, J.S. 142, 171, 257, 265, 267, 269, Czarnecki, I. 41, 48, 49, 243, 244, 305,
308, 346, 394 312, 313, 315, 334, 338, 344, 391,
Christiansen, E.B. 142, 171, 257, 265, 395, 396, 400, 411, 414
267, 269, 308, 346, 398
Chung, C.I. 194, 239 Daane, J.H. 126, 134
Chung, J.T. 67, 105, 125, 126, 134 Daley, L.R. 41, 50, 243, 306, 312, 335,
Chung, K.H. 194, 239 338, 392, 395, 412
Churchill, R. W. 81, 82, 107 Danckwerts, P.V. 175, 181, 183, 237,
Churchill, S. W. 81, 82, 107 238
Clark, E.S. 86, 108, 316, 337 Danforth, S.C. 88, 90, 108
Clarke, B. 140, 145-7, 150, 171 Darby, R. 43, 52, 67, 79, 105, 136, 168,
Clegg, D.W. 43, 52 170
Clegg, P.L. 72, 75, 105 Daroux, M. 81, 107
Code, R. K. 136, 168 Davis, J.H. 19, 45
Cogswell, F.N. 41, 47, 65, 76, 98, 103, Davis, P.K. 136, 168
104, 107, 109, 110, 113, 130, 131, De Boojs, J. 140, 171
135 De Brujin, H. 139, 171
Cohen, L.B. 273, 277, 310 De Cindio, B. 166, 167, 174
Cohen, M. 103, 110 De Kee, D. 81, 107, 136, 168
Cokelet, G.R. 136, 167 De Simon, L.B. 113, 132, 136, 169
Coleman, B.D. 43, 52, 66, 104 De Waele, A. 80, 107
Coleman, G.N. 92, 109, 136, 168 Dealy, J.M. 41, 43, 47, 53, 65, 104, 113,
Collins, E. A. 1, 44, 103, 110, 398, 414 130, 132, 135
Collyer, A.A. 9, 43, 44, 52 Den Otter, J.L. 117, 124, 133, 134
Colwell, R.E. 43, 53, 113, 132 Denn, M.M. 73, 97, 106, 109, 142, 171,
Connelly, R. W. 113, 132, 222, 241 312, 337
Conway, B.E. 162, 173 Denson, C.D. 130, 135
Cook, J. 17, 45 Derjaguin, B. 247, 308
Cooper, E.R. 8, 37, 44, 47 Deryagin, B.V. 186, 238
Cooper, S.L. 8 Dhimmar, LH. 41, 49, 243, 273, 277,
Cope, D.E. 41, 49, 243, 273-5, 305, 312, 278, 305, 312, 334, 338, 391, 395,
334, 338, 391, 395, 411 411
Copeland, J.R. 30-33, 46, 243, 273, 304, Dibenedetto, A. T. 285, 286, 310
312, 333, 338, 390, 395, 410 Dillon, R.E. 74, 106, 120, 133
Cotten, G.R. 14, 45, 226, 241, 319, 337, Dintenfass, L. 136, 167
400, 414 Dobry, A. 162, 173
Cox, W.P. 86, 108 Dobry-Duclaux, A. 162, 173
Crabbe, P.G. 113, 131 Donovan, R.C. 194, 239
Crabtree, J.D. 36, 46 Doolittle, A.K. 257, 308
Doraiswamy, D. 88, 90, 108 Fiekhrnan, V.D. 97, 109
Dougherty, TJ. 151, 153, 173 Fielding, J.H. 118, 133
Dow, J.H. 41, 51, 136, 154, 157, 160, Fikentscher, H. 140, 171
168, 173, 229, 232, 236, 237, 241, Fikham, V.D. 128, 135
243, 266, 307, 312, 336, 338, 349, Filymer, Jr., W.G. 136, 168
357, 360, 367, 369-71, 393-5, 413 Fink, A. 10, 44, 262, 263, 309
Driol, E. 36, 46 Finnigan, J.W. 139, 171
Droste, D. H. 285, 286, 310 Fisa, B. 41, 49, 243, 305, 312, 334, 338,
Duffey, HJ. 72, 105 392, 395, 411
Dufresne, A. 286, 287, 310 Fischer, E.K. 151, 173
Dulik, D. 136, 169 Fiske, TJ. 395, 409
Flory, PJ. 1, 43
Edirisinghe, MJ. 41, 51, 52, 189, 238, Folkes, MJ. 9, 41, 44, 48, 243, 292, 305,
243, 266, 268, 307, 310, 312, 336, 312, 334, 338, 391, 395, 397, 398,
338, 393, 395, 413 410, 411, 414
Eguiluz, M. 162, 173 Ford, R.G. 41, 52
Eilers, H. 141, 171 Ford, T.F. 139, 141, 171
Einstein, A. 137, 140, 170, 247, 308 Forger, G. 15, 45
Eise, K. 186, 238 Fox, T.G. 104, 111
Eisenlauer, J. 155, 173 Frados, J. 1, 44
Eisenschitz, R. 121, 133 Franked N.A. 142, 171, 247, 308
Epstein, N. 10, 44, 262, 263, 309 Frechette, FJ. 41, 51, 83, 107, 143, 171,
Erdmenger, R. 208, 240 243, 250, 255, 257, 264, 269, 307,
Erenrich, E.H. 136, 168 308, 312, 316, 319, 321, 336-8,
Erickson, P. W. 35, 37, 38, 46, 47 345-8, 353, 355, 393, 395, 413
Erwin, L. 196, 215, 240 Fredrickson, A.G. 66, 104
Espesito, R. 200, 240 Freestone, A.R.I. 113, 131
Ester, G.M. 8, 44 French, K.W. 41, 52
Evans, J.R.G. 41, 51, 52, 189, 238, 243, Friedrich, C. 312, 332
266, 268, 307, 310, 312, 336, 338, Fryling, C.F. 162, 173
393, 395, 413 Fujita, H. 257, 308
Evans, R.L. 136, 167, 223, 224, 241 Fu-lung, L. 136, 167
Everage, A.E. 131, 135 Fukase, H. 194, 239
Eveson, G.F. 264, 309 Fukusawa, Y. 118, 133
Eyring, E.M. 141, 171
Eyring, H. 99, 109, 141, 171, 255, 308 Galgoci, E.G. 41, 52
Garcia, R.R. 272, 310
Fan, L.T. 179, 237 Gatner, F.H. 71, 105
Farooqui, S.I. 136, 169 Gaskins, F.H. 100, 109, 113, 122, 124,
Farris, RJ. 265, 309 131, 134
Faruqui, A.A. 139, 171 Geisbusch, P. 41, 48, 243, 292, 304, 312,
Faulkner, D.L. 41, 47, 123, 124, 134, 333, 338, 390, 395, 410
243, 304, 312, 333, 338, 345, 390, George, H.H. 166, 174, 397, 414
395, 410 German, R.M. 41, 52, 266, 268, 310
Fedors, R. F. 400, 414 Gerson, Ph.M. 194, 239
Feldman, D. 102, 110, 140, 171 Gibson, A.G. 98, 109, 131, 135
Fenner, R.T. 196, 239 Gillespie, T. 151, 173, 264, 309
Ferguson, J. 100, 109, 136, 153, 169 Glasscock, S.D. 72, 105
Ferraro, C.F. 151, 173 Glazman, Yu. M. 136, 168
Ferry, J.D. 41, 47, 99, 109 Goddard, J.D. 165, 166, 174
Godfrey, J. 200, 240 Hatshek, E. 138, 170
Goel, D.C. 41, 48, 151, 172, 243, 305, Hauwink, R. 140, 171
312, 334, 338, 391, 395, 411 Haw, J.R. 41, 49, 243, 273, 276, 277,
Goettler, L.A. 166, 174, 397, 414 305, 312, 313, 319, 323, 334, 338,
Gogos, C.G. 180, 183-5, 194, 237 391, 395, 411
Goldman, A. 266, 267, 309 Haward, R.N. 100, 109
Goldsmith, H.L. 150, 172 Hayashi, K. 41, 51, 243, 266, 307, 312,
Goodrich, J.E. 126, 134 336, 338, 393, 395, 413
Gordon, J. 17, 45 Heath, D. 136, 155, 169
Goring, D.A. 163, 173 Heertjes, P.M. 136, 169
Govier, G.W. 151, 173 Hencky, H. 401, 414
Graessley, W. W. 72, 105 Henderson, C.B. 265, 309
Grateh, S. 104, 111 Henderson, D. 141, 171
Greener, J. 113, 132, 222, 241 Herrick, J. 22, 46
Groto, H. 264, 309 Herschel, W.H. 83, 107, 247, 308
Gruver, J.L. 104, 111 Heywood, N.I. 136, 151, 169
Gunberg, P. F. 226, 241 Higashitani, K. 77, 107
Gupta, R.K. 41, 51, 83, 107, 143, 171, Highgate, DJ. 154, 173
243, 250, 255, 257, 264, 268, 269, Hildebrand, J. H. 103, 110
307, 308, 310, 312, 317, 319, 321, Hill, C.T. 41, 47, 145, 172, 243, 304,
336-8, 345-8, 353, 355, 393, 395, 312, 333, 338, 390, 395, 402, 409
413 Hill, J. W. 65, 104
Gurland, J. 248, 308 Hinkelmann, B. 41, 49, 50, 243, 305,
Guth, E. 140, 143, 171, 172 306, 312, 334, 335, 338, 392, 395,
411, 412
Hagler, G.E. 85, 108 Hlavacek, B. 74, 106
Hallouche, M. 201, 240 Hlavacek, V. 262, 263, 309
Harnaker, C. 247, 308 Hodgetts, G.B. 113, 131
Han, C.D. 41, 47-51, 91, 108, 115, 124, Hoffman, DJ. 103, 110
132, 134, 243, 273, 276-8, 292, Hofman-Bang, N. 117, 133
304-7, 312, 313, 315, 316, 319, 323, Hold, P. 175, 179, 180, 189, 190, 195,
332-8, 361, 390-2, 394, 395, 398, 215, 217, 237, 238, 240
402, 403, 407, 410-4 Holderle, M. 312, 332
Hancock, M. 41, 48, 243, 305, 312, 334, Holdsworth, PJ. 103, 110
338, 391, 395, 411 Holmes, L. A. 85, 108
Hanks, R.W. 136, 168 Honkanen, A. 41, 48, 243, 259, 304,
Hanna, R.D. 16, 45 312, 333, 338, 390, 395, 398, 410,
Happel, J. 138, 170 414
Harbard, E.H. 140, 171 Hooper, R.C. 37, 46
Harmsen, GJ. 163, 173 Hope, P.S. 9, 44
Harper, J.C. 151, 172 Hopper, J.R. 14, 45, 319, 337
Harris, J. 43, 52 Hori, Y. 74, 106
Harris, S.L. 194, 239 Horie, M. 113, 131
Hartlein, R.C. 29, 36, 38, 46, 47 Hornsby, P.R. 224, 241
Hartnett, J.P. 84, 107 Howards, AJ. 190, 238
Harwood, J.A.C. 38, 47 Howland, C. 215, 240
Hashimoto, A.G. 136, 169 Hsieh, H.P. 149, 172
Hashin, Z. 147, 172 Hu, R. 84, 107
Hassager, O. 55, 59, 60, 67, 79, 83-5, Huang, C.R. 115, 124, 132
104, 105, 107, 108 Hudson, N.E. 136, 153, 169
Huget, E.F. 113, 132, 136, 169 Kambe, H. 138, 170
Hugill, H.R. 266, 267, 309 Kanno, T. 152, 173
Hunt, K.N 41, 51, 223, 224, 241, 243, Kasajima, M. 103, 110
266, 307, 312, 336, 338, 393, 395, Kataoka, T. 41, 48-50, 115, 132, 142,
413 143, 171, 223, 241, 243, 246, 248,
Huppler, J.D. 85, 108 249, 255, 257, 304-6, 308, 312,
Hutton, J.F. 41, 43, 47, 52, 67, 79, 105 333-5, 338, 346, 390-2, 395,
Hylton D.C. 130, 135 410-2
Katz, H.S. 10, 44
Ide, Y. 130, 135, 396, 403, 414 Kawasaki, H. 41, 49, 243, 273, 305, 312,
Immergut, E.H. 1, 44 334, 338, 391, 395, 411
Insarova, N.I. 165, 174 Kearsley, E. 72, 85, 106
Irving, H.F. 198, 240 Kendall, K. 190, 238
Ishida, N. 118, 133 Khadilkar, C.S. 41, 51, 136, 154, 157,
Ishigure, Y.41, 51, 243, 266, 307, 312, 168, 173, 232, 236, 237, 241, 243,
336, 338, 393, 395, 413 266, 307, 312, 336, 338, 393, 395,
Itadani, K. 41, 49, 243, 273, 305, 312, 413
334, 338, 391, 395, 411 Killman, E. 155, 173
Ito, K. 103, 110 Kim, D.H. 243, 303
Kim, K.U. 115, 124, 132
Jacobsen, P.H. 113, 131, 136, 169 Kim, K.Y. 43, 53, 113, 132
Jakopin, S. 186, 193, 196, 202, 227, 238 Kim, W.S. 208, 240
James, A.E. 81 44, 136, 169 Kim, Y.W. 395, 398, 402, 403, 414
Janacek, J. 286, 310 King, K.D. 136, 168
Janeschitz-Kriegl, H 41, 47, 117, 124, King, R.G. 115, 132
133, 134 Kirkwood, R.B. 136, 167
Janssen, L.P.B.M. 74, 106, 202, 214, 240 Kishimoto, J. 257, 308
Jarzebski, GJ. 247, 250, 308 Kitano, T. 41, 48-50, 115, 132,
Jastrzebski, Z. 151, 172 142, 143, 171, 223, 241, 243, 246,
Jeffrey, DJ. 136, 170 248, 249, 255, 257, 304-6, 308, 312,
Jeffrey, J.B. 143, 172 333-5, 338, 346, 390-2, 395,
Jepson, C.H. 175, 196, 237 410-2
Jerdrzejczyk, H. 136, 167 Kitchner, J.A. 156, 173
Jewmenow, S.D. 208, 240 Kizior, I.E. 165, 174
Jinescu, V. V. 103, 110, 136, 170 Klein, I. 194, 196, 238
Johnson, A.F. 396, 397, 414 Knappe, W. 121, 134
Johnson, C.F. 41, 51 Knudsen, J.G. 139, 171
Johnson, J.F. 100, 101, 104, 109, 111 Knutsson, B.A. 41, 49, 243, 292, 305,
Johnson, R.O. 41, 50, 279, 292, 310 312, 313, 315, 331, 334, 338, 391,
Jung, A. 103, 110 395, 411
Juskey, V.P. 41, 49, 243, 273, 305, 312, Kohan, M.I. 292, 311
334, 338, 392, 395, 411 Kolarik, J. 286, 310
Kondo, A. 124, 134
Kaghan, W.S. 100, 110 Kondu, AJ. 76, 107
Kaloni, P.N. 67, 79, 105 Koran, A. 136, 168
Kalousek, G.L. 113, 131, 136, 168 Korn, M. 155, 173
Kalyon, D.M. 189, 193, 201, 238, 240, Kosinski, L.E. 113, 132, 222, 241
338, 357, 390, 394, 395, 409 Kossen, N.W.F. 136, 168
Kamal, M.R.41, 50, 243, 307, 312, 336, Kraus, G. 18, 45, 104, 111
338, 393, 395, 413 Kremesec, VJ. 153, 173
Krieger, FM. 151, 153, 162, 173, 262, Litovitz, T. A. 103, 110
264, 309 Lobe, V.M. 41, 48, 115, 132, 243, 246,
Krotova, N.A. 186, 238 304, 312, 313, 317, 333, 338, 390,
Krumbock, E. 121, 134 395, 402, 410
Kruyt, H.R. 140, 171 Lockett, FJ. 396, 397, 414
Kubat, J. 397, 414 Lodge, A.S. 43, 52, 66, 72, 77, 104, 107
Kumins, C.A 38, 47 Loh, J. 136, 168
Kunio, T. 194, 239 Loppe, J.P.A. 41, 49, 143, 172, 243, 305,
Kuno, H. 264, 309 312, 334, 338, 391, 395, 411
Kurgaev, E.F. 138, 170 Lornsten, J.M. 98, 109, 130, 135
Kwei, T.K. 38, 47 Loshach, S. 104, 111
Luebbers, R.H. 148, 172
Lacey, P.M.C. 179, 180, 237 Luo, H.L. 41, 50, 243, 273, 306, 312,
Lakdawala, K. 282, 310 335, 338, 361, 392, 395, 412
Lamb, P. 74, 75, 106 Lyons, J. W., 43, 53, 113, 132
Lamoreaux, R. H. 103, 110
Landel, R.F. 14, 45, 99, 109, 153, 173, Macdonald, LF. 85, 108
400, 414 Macedo, P.B. 103, 110
Laskaris, A. 22, 46 MacGarry, FJ. 37, 46
Lau, H.C. 121 Mack, W.A. 189, 193, 238
Laude, R.F. 36, 46 Macosko, C.W. 130, 135
Lee, B.L. 115, 118, 132 Maddock, B.H. 194, 239
Lee, D.I. 264, 265, 309 Maheshri, J.C. 208, 240
Lee. KJ. 243, 303 Maine, F. W. 16, 45
Lee, M.C.H. 236, 241 Malkin, A. Y. 14, 41, 45, 47, 117, 133,
Lee, T.S. 41, 47, 115, 132, 151, 172, 243, 243, 307, 312, 319, 337, 338, 394,
246, 303, 312, 332, 338, 390, 395, 395, 413
407, 409 Mallouk, R.S. 196, 239
Lee, W.K. 98, 109, 166, 174, 397, 414 Mangels, J.A. 41, 51, 52, 266, 267, 309
Lee, W.M. 41, 49, 243, 273, 305, 312, Manley, R.StJ. 140, 171
334, 338, 391, 395, 411 Mannell, W.R. 136, 168
Lefebvre, J. 136, 168 Mark, H. 140, 171
Leitlands, V. V. 130, 135 Markovitz, H. 43, 52, 66, 92, 104, 109
Lem, K.W. -41, 49, 243, 306, 312, 335, Maron, S.H. 255, 308
338, 392, 395, 412 Marrucci, G. 67, 79, 97, 105, 109, 142,
Lenk, R.S. 41, 47 171, 395, 414
Lens, W. 140, 171 Marsden, J.G. 35, 36, 46
Leonard, M.H. 14, 45 Martelli, F. 204, 240
Leonov, A.I. 121, 134 Maschmeyer, R.O. 145, 172
Lerner, I. 37, 46 Mason, S.G. 140, 146, 150, 171, 172
Lewellyn, M.M. 136, 168 Masuda, T. 86, 108
Lewis, H.D. 266, 267, 309 Matijevic, E. 262, 308
Liaw, T.F. 41, 49, 243, 273, 305, 312, Matsumoto, S. 149, 172
334, 338, 391, 395, 411 Matthews, G. 175, 237
Lightfoot, E.N. 136, 168 Maxwell, B. 103, 110, 118, 133
Lin, Y.H. 121, 134 McCabe, C.C. 14, 45
Linnert, E. 41, 49, 243, 273-5, 305, 312, McGeary, R.K. 139, 171
334, 338, 391, 395, 411 McGrath, J.E. 8, 44
Lipatov, Yu. S. 286, 310 McHaIe, E.T. 265, 309
Lippe, RJ. 113, 131 Mclntire, L.V. 120, 133
McKelvey, J.M. 180, 194, 196, 237, Mount III, E.M. 194, 239
239 Muchmore, C.B. 136, 168
Mead, W. T. 398, 414 Mueller, N. 14, 45
Meares, P. 1, 43 Mujumdar, A.N. 88, 90, 108
Medalia, A.L 14, 45, 319, 337 Mullins, L. 14, 38, 45, 47, 140, 171
Meissner, J. 55, 96, 100, 104, 109, 113, Munro, J.M. 136, 168
115, 128, 130, 132, 135 Munstedt, H. 117, 130, 133, 135
Meister, BJ. 91, 108 Murase, I. 41, 51, 243, 266, 307, 312,
Mendelson, R.A. 100, 109 336, 338, 393, 395, 413
Menges, G. 41, 48, 243, 292, 304, 312, Murty, K.N. 397, 414
333, 338, 390, 395, 410 Mutel, A.T. 41, 50, 243, 307, 312, 336,
Mennig, G. 41, 50, 121, 133, 243, 306, 338, 393, 395, 413
312, 335, 338, 392, 395, 412 Mutsuddy, B.C. 41, 50, 52, 243, 266,
Mertz, E.H. 86, 108 306, 312, 335, 338, 392, 395, 412
Metz, B. 136, 168
Metzner, A.B. 71, 79, 88, 90, 98, 105, Nadim, A. 136, 170
107-9, 136, 165, 170, 174, 332, Nadkarni, V.M. 11, 12, 41, 44, 50, 236,
337 237, 241, 243, 251, 252, 266, 273,
Mewis, J. 136, 165, 170, 174, 332, 337 276-8, 284, 287, 290, 292, 299, 306,
Middleman, S. 41, 47, 67, 79, 103, 105, 307, 310-2, 330, 335, 336, 338, 384,
110, 196, 239 392-5, 412
Mijovic, J.41, 50, 243, 273, 306, 312, Nagatsuka, Y. 41, 50, 243, 306, 312,
335, 338, 361, 392, 395, 412 335, 338, 392, 395, 412
Milewski, J. V. 10, 44, 268, 310 Nagaya, K. 41, 51, 243, 266, 307, 312,
Millman, R.S. 17, 45 336, 338, 393, 395, 413
Mills, NJ. 41, 47, 117, 133, 243, 246, Nakajima, N. 72, 105, 398, 414
303, 312, 332, 338, 345, 390, 395, Nakatsuka, T. 41, 49, 243, 273, 305,
409 312, 334, 338, 391, 395, 411
Minagawa, N. 41, 47, 115, 132, 243, Napper, D.H. 154, 156, 173
246, 277, 304, 312, 315, 317, 319, Nazem, F. 41, 47, 243, 304, 312, 333,
333, 338, 390, 395, 410 338, 390, 395, 402, 409
Minoshima, W. 86, 108, 316, 337 Nevin, A. 117, 133
Missavage, RJ. 136, 168 Newman, S. 123, 124, 134, 243, 307,
Mistry, D.B. 160, 173 312, 336, 338, 394, 395, 397, 413,
Mitsumatsu, F. 41, 51, 243, 266, 307, 414
312, 336, 338, 393, 395, 413 Newnham, R.E. 41, 52
Mizoguchi, M. 194, 239 Nguyen, Q.D. 136, 170
Modlen, G.F. 397, 414 Nichols, R. 213, 215, 240
Mohr, W.D. 175, 181, 183, 196, 237 Nicodemo, L. 153, 166, 167, 173, 174,
Mokube, V. 264, 309 395, 397, 414
Molau, G.E. 8, 44 Nicolais, L. 36, 46, 153, 166, 167, 173,
Monte, SJ. 41, 48, 243, 273, 275-8, 292, 174, 286, 310, 395, 397, 414
304, 310, 312, 333, 338, 390, 395, Nielsen, L.E. 14, 41, 45, 47, 51, 137,
410 147, 170, 172, 243, 257, 269, 307,
Mooney, M. 118, 133, 141, 149, 171 308, 312, 336, 338, 393-5, 413
Morawetz, H. 1, 44 Nikolayeva, N.E. 14, 45, 117, 133, 319,
Moreland, C. 148, 150, 172 337
Morgan, RJ. 158, 173 Nishijima, K. 41, 48, 115, 132, 142, 143,
Morley, J.G. 17, 45 171, 243, 246, 304, 312, 333, 338,
Morrison, S.R. 151, 172 390, 395, 410
Nishimura, T. 41, 48, 243, 246, 248, Pinder K.L. 113, 131
249, 255, 257, 304, 308, 312, 333, Pinto, G. 196, 240
338, 346, 390, 391, 395, 410 Pipkin, A.C. 97, 109
Nissan, A.H. 71, 105 Pisipati, R. 331, 337
Nitanda, H.41, 51, 243, 307, 312, 336, Platzer, N.A.J. 8, 44
338, 393, 395, 413 Plotnikova, E.P. 14, 45, 117, 133, 319,
Noll, W. 43, 52, 66, 67, 79, 104 337
Nomura, A. 194, 239 Plueddemann, E.P. 35, 36, 38, 46, 47,
Noshay, A. 8, 44 273, 277, 279, 310
Pokrovskii, V.N. 138, 143, 170, 172
Oda, K. 86, 108, 316, 337 Pollett, W.F.O 115, 132
Ojama, T. 103, 110 Porter, R.S. 100, 101, 103, 104, 109-11,
Okubo, S. 74, 106 126, 134, 299, 311, 398, 414
Onogi, S. 86, 108 Poslinski, AJ. 41, 51, 83, 107, 143, 171,
Opsahl, D.G. 136, 167 243, 250, 255, 257, 264, 269, 307,
Orenski, P.I. 35, 46 308, 312, 317, 319, 321, 336-8,
Ostwald, W. 80, 107 345-8, 353, 355, 393, 395, 413
Oswald, G.E. 136, 168 Powell, R.L. 41, 50, 243, 306, 312, 335,
Otabe, S. 41, 51, 243, 266, 307, 312, 336, 338, 393, 395, 412
338, 393, 395, 413 Powers, J.M. 136, 169
Ouchiyama, N. 268, 310 Pritchard, J.H. 299, 311
Overbeek, J. 163, 173 Prokunin, A.N. 130, 135
Oyanagi, Y. 41, 48, 75, 106, 163, 166,
173, 243, 248, 249, 255, 292, 304, Rabinowitsch, B. 121, 133
312, 315, 333, 338, 390, 391, 395, Radushkevich, B.V. 97, 109, 128, 135
405, 410 Raible, T. 130, 135
Rajaiah, J. 247, 308
Padget, J.C. 292, 311 Rajora, P. 74, 106
Palmgren, H. 183, 238 Ramamurthy, A. V. 121, 134
Pao, Y.-H. 91, 108 Ramney, M. W. 35, 46
Papkov, S. 140, 171 Rauwendaal, CJ. 189, 200, 202, 214,
Parish, M. V. 272, 310 238, 240
Park, C.S. 243, 303 Reddy, K.R. 73, 106
Park, HJ. 243, 303 Reiner, M. 54, 80, 104, 138, 141, 170,
Parkinson, C. 149, 172 401, 414
Patel, R.D. 41, 49, 243, 273, 277, 278, Revankar, V.V.S. 262, 263, 309
305, 312, 334, 338, 391, 395, 411 Rhi-Sausi, J. 130, 135
Paul, D.R. 75, 106, 243, 307, 312, 336, Richardson, CJ. 98, 109
338, 394, 395, 413 Richardson, J.F. 136, 151, 169
Payne, A.R. 38, 47 Richardson, P.C.A. 113, 131, 136, 169
Pearson, J.R.A. 43, 52, 72, 106, 200, 240 Rideal, G.R. 292, 311
Penwell, R.C. 103, 110 Rieger, J.M. 166, 174
Petrie, CJ.S. 43, 52, 65, 73, 104, 106, Riseborough, B. E. 16, 45
130, 135 Rodriguez, F. 41, 50, 243, 306, 312, 335,
Pett, R.A. 266, 268, 309 338, 392, 395, 412
Peyser, P. 286, 310 Roff, WJ. 1, 44
Philippoff, W. 100, 109, 113, 122, 124, Rogers, B.A. 136, 168
131, 134 Rogers, M.G. 126, 134
Pickthall, D. 36, 46 Romanov, A. 384, 394
Pierce, P.E. 255, 308 Rosen, M.R. 67, 79, 105
Rosevear, J. 41, 49, 243, 305, 312, 334, Scheffe, R.S. 265, 309
338, 391, 395, 411 Scheiffele, G.W. 41, 51, 136, 154, 157,
Roteman, J. 38, 47 168, 232, 236, 237, 241, 243, 266,
Rubio, J. 156, 173 307, 312, 336, 338, 393, 395, 413
Ruckenstein, E. 74, 106 Schenkel, G. 207, 240
Rudd, J.F. 100, 110 Schmidt, L.R. 41, 47, 123, 124, 134, 243,
Rudraiah, N. 67, 79, 105 304, 312, 333, 338, 345, 390, 395,
Rumpf, H. 272, 310 410
Runt, J.P. 41, 52 Schmitz, A.O. 125, 134
Rush, O.W. 30-33, 46, 243, 273, 304, Schooten, J.V. 163, 173
312, 333, 338, 390, 395, 410 Schott, H. 100, 110, 120, 133
Russel, W.B. 136, 170 Schowalter, W.R. 43, 52, 67, 79, 105,
Russell, RJ. 71, 105 121, 134
Rutgers, LR. 138, 170 Schrader, M.E. 37, 46
Ryan, M.E. 41, 51, 83, 107, 143, 171, Schramm, G. 67, 105, 113, 132
243, 250, 255, 257, 264, 269, 307, Schreiber, H.P. 72, 74, 105, 106
308, 312, 317, 319, 321, 336-8, Schubert, H. 272, 310
345-8, 353, 355, 393, 395, 413 Schultz, J.M. 1, 43
Schurtz, J.F. 41, 52
Saarnak, A. 136, 169 Schwartz, H.S. 20, 45
Sabia, R. 100, 110 Schwartz, R.T. 20, 45
Sabsai, O.Yu 14. 45, 117, 133, 319, 337 Scott, J.R. 1, 44
Sacks, M.D. 41, 51, 136, 154, 157, 158, Scott Blair, G.W. 43, 52
168, 173, 229, 232, 236, 237, 241, Sebastian, D.H. 194, 239
243, 266, 307, 312, 336, 338, 349, Segre, G. 150, 172
357, 370, 371, 393, 395, 413 Sellers, J.W. 18, 45
Saechtling, H. 1, 44 Sergeeva, L. M. 286, 310
Saini, D.R. 11, 12, 41, 44, 47, 50, 82, 87, Seshadri, S.G. 41, 51, 83, 107, 143, 171,
90, 92, 93, 100-2, 108-10, 115, 126, 243, 250, 255, 257, 264, 268, 269,
132, 134, 236, 237, 241-3, 251, 252, 307, 308, 310, 312, 317, 319, 321,
257, 258, 266, 273, 276-8, 284, 287, 336-8, 345-8, 353, 355, 393, 395,
290, 292, 300, 301, 306-8, 310-2, 413
330, 335, 336, 338, 340-3, 372, 373, Severs, E.T. 41, 47, 141, 171
375, 381, 383-5, 392-5, 412, 413 Seyer, F.A. 165, 174
Saito, N. 140, 171 Shaheen, EJ. 148, 172
Sakai, T. 41, 48, 243, 248, 249, 255, 257, Sharma, Y.N. 41, 49, 243, 273, 277, 278,
304, 308, 312, 333, 338, 346, 391, 305, 312, 334, 338, 391, 395, 411
395, 410 Shaw, H.M. 41, 51, 243, 266, 307, 312,
Sakamoto, K. 118, 133 336, 338, 393, 395, 413
Salovey, R. 282, 310 Shenoy, A. V. 11, 12, 41, 44, 47, 50, 51,
Sanchez, LC. 103, 110 81, 82, 86, 87, 90, 92, 93, 100-2,
Sandford, C. 41, 48, 243, 273, 276-8, 107-10, 115, 126, 132, 134, 136,
292, 304, 312, 315, 333, 338, 390, 154, 157, 168, 229, 232, 236, 237,
395, 407, 410 241-3, 251, 252, 257, 258, 266, 273,
Sarmiento, G. 113, 131 276-8, 284, 287, 290, 292, 299,
Sasahara, M. 41, 48, 115, 132, 142, 143, 300-2, 306-8, 310-2, 330, 335-8,
171, 243, 246, 248, 249, 255, 304, 340-3, 349, 357, 370-3, 375, 381,
312, 333, 338, 390, 391, 395, 410 383-5, 392-5, 412, 413
Saxton, R.L. 175, 196, 198, 237, 240 Shenoy, U. V. 81, 82, 86, 87, 107, 301,
Schaart, B. 214, 240 302, 311
Sherman, P: 136, 149, 168, 172 Swanborough, A. 189, 190, 193, 238
Shete, P. 41, 49, 243, 273, 276, 277, 305, Sweeny, K.H. 265, 269, 309
312, 313, 319, 323, 334, 338, 391, Szalanczi, A. 397, 414
395, 411 Szczesniak, A.S. 136, 168
Sheu, R.S. 41, 51, 136, 154, 157, 168,
232, 236, 237, 241, 243, 266, 307, Tadmor, Z. 59, 104, 180, 183-5, 194,
312, 336, 338, 393, 395, 413 196, 217, 237-40
Shida, M. 72, 105 Tadros, Th.F. 136, 154-6, 169, 173
Shinya, S. 194, 239 Tager, A. 1, 43
Shirata, T. 41, 49, 142, 143, 171, 243, Takahashi, M. 41, 51, 86, 108, 243, 307,
305, 312, 334, 338, 391, 395, 411 312, 336, 338, 393, 395, 413
Silberberg, A. 150, 172 Takano, M. 166, 174
Simha, R. 138^1, 147, 170-2 Takserman-Krozer, R. 166, 174
Simon, R.H.M. 100, 110 Tammela, V. 41, 48, 243, 259, 304, 312,
Siskovic, N. 115, 124, 132 333, 338, 390, 395, 398, 410, 414
Skatschkow, W. W. 208, 240 Tan, C.G. 10, 44, 262, 263, 309
Skelland, A.H.P. 67, 79, 105 Tanaka, H. 41, 48, 49, 243, 244, 246,
Slattery, J.C. 153, 173 247, 248, 268, 292, 305, 308, 310,
Smilga, V.P. 186, 238 312, 313, 315, 317, 323, 334, 337,
Smith, J.H. 136, 167 338, 344, 391, 395, 396, 400, 403,
Smits, C.T. 136, 169 404, 407, 411, 414
Smoluchowsky, M. 163, 173 Tanford, C. 1, 43
Snyder, J.W. 14, 45 Tanner, R.I. 43, 52, 67, 72, 73, 79, 97,
Sobajima, A. 41, 51, 243, 266, 307, 312, 104, 105, 106, 109
336, 338, 393, 395, 413 Taylor, R. 118, 133
Somcynsky, T. 138, 139, 171 Taylor, N.H. 292, 311
Soni P.L. 103, 110 Teutsch, E.G. 41, 50, 279, 292, 310
Soppet, F.E. 266-8, 309 Theberge, J. E. 16, 45
Southern, J.H. 75, 103, 106, 110 Thiele, J. L. 400, 414
Spencer, R.S. 74, 106, 120, 133 Thomas, D.G. 138-42, 170
Spriggs, T.W. 91, 92, 97, 108, 109 Thomson, J.B. 16, 45
Spruiell, J.E. 86, 103, 108, 111, 316, 337 Thurgood, J.R. 136, 168
Stade, K. 189, 201, 238 Thurston, G.B. 136,167
Stamhuis, J.E. 41, 49, 143, 172, 243, Ting, A.P. 148, 172
305, 312, 334, 338, 391, 395, 411 Tiu, C. 81, 107
Steingiser, S. 104, 111 Tobolsky, A. V. 8, 44, 117, 133
Stephenson, S.E. 130, 135 Todd, D.B. 189, 208, 228, 238, 240
Sterman, S. 35, 46 Tolstukhina, F.S. 14, 41, 45
Stevenson, J.F. 128, 135 Tomkins, K.L. 41, 51, 243, 266, 307,
Stober, W. 10, 44, 262, 263, 309 312, 336, 338, 393, 395, 413
Stover, BJ. 141, 171 Tordella, J.P. 73, 75, 106, 120, 133
Studebarker, M. L. 14, 45 Travers, A. 22, 46
Suetsugu, Y. 41, 50, 243, 246, 273, 306, Trela, W. 41, 52, 266, 267, 309
312, 335, 338, 392, 395, 412 Tremayne, P. 41, 49, 243, 305, 312, 334,
Sugerman, G.T. 41, 48, 243, 273, 275-8, 338, 391, 395, 411
292, 304, 310, 312, 333, 338, 390, Trementozzi, Q.A. 123, 124, 134, 397,
395, 410 414
Sundstrom, D.M. 194, 239 Trottnow, R. 72, 106
Suzuki, S. 41, 51, 243, 307, 312, 336, Trouton, F.T. 93, 109
338, 393, 395, 413 Truesdell, C. 66, 67, 79, 104
Tsao, I. 88, 90, 108 Warren, R.C. 113, 132, 136, 169
Tsutsui, M. 103, 110 Wasiak, A. 103, 110
TuR, P. 113, 131 Waston, W.F. 18, 45
Turcotte, G. 136, 168 Watson, C.A. 179, 237
Turetsky, S. B. 226, 241 Watson III, J.G. 194, 239
Turnbull, D. 103, 110 Weidenbaum, S.S. 180, 237
Tusim, M.H. 194, 239 Weill, A. 74, 106
Weinberger, C.B. 165, 174
Uebler, E.A. 79, 107 Weiss, Y. 8, 44
Uhland, E. 74, 106, 121, 133 Weissenberg, K. 71, 105, 115, 121, 132,
Uhlherr, P.H.T. 81, 107, 113, 131 133
Umeya, K. 152, 173 Werner, H. 208, 240
Usagi, R. 82, 107 Westman, A.E.R. 266, 267, 309
Utracki, L. A. 41, 43, 49, 52, 103, 110, Westover, R.F. 299, 311
136, 170, 243, 305, 312, 334, 338, Whalen, TJ. 266, 268, 309
392, 395, 411 Whelan, J.P. 41, 51, 292, 299, 311
White, J.L. 14, 41, 45, 47-50, 75, 76, 85,
Van Buskirk, P. R. 226, 241 86, 103, 106-8, 111, 115, 118, 120,
VanderWeghe, T. 41, 49, 243, 273, 276, 124, 130, 132-5, 163, 166, 173, 243,
277, 305, 312, 313, 319, 323, 334, 244, 246-8, 273, 277, 292, 304-6,
338, 391, 395, 411 308, 312, 313, 315-7, 319, 323, 331,
Van Doren, R.E. 136, 168 333-5, 337, 338, 344, 390-2, 395,
Van Suijdam, J.C. 136, 168 396, 400-5, 407, 410-2, 414
Van Wazer, J.R. 43, 53, 113, 132 Whiting, R. 113, 131, 136, 169
Vand, V. 140, 171 Whitmore, R.L. 148, 150, 172, 264, 309
Veal, CJ. 136, 168 Whittaker, R.E. 38, 47
Vermeulen, J.R. 194, 239 Whorlow, R. W. 43, 53, 113, 132, 154,
Vermilyea, S.G. 113, 132, 136, 169 173
Verreet, G. 136, 169 Wigotsky, V. 200, 240
Vervoorn, P.M.M. 136, 169 Wildemuth, C.R. 143, 172
Vinogradov, G.V. 14, 41, 45, 47, 97, Wilkinson, W.L. 67, 79, 104
109, 117, 128, 133, 135, 243, 307, Willard, H. 136, 167
312, 319, 337, 338, 394, 395, 413 Willermet, P.A. 266, 268, 309
Virbsom, L. 217, 240 Williams, D.J.A. 136, 169
Vlachopoulos, J. 194, 239 Williams, M.C. 136, 143, 168, 172
Volpe, A.A. 37, 47 Williams, M.L. 99, 109
Von Mises, R. 401, 414 Williams, R.M. 41, 52, 266, 267, 309
Willmouth, P.M. 103, 110
Wagner, A.H. 395, 409 Winning, M.D. 151, 173
Wagner, M.H. 84, 85, 108, 343, 394 Winter, H.H. 131, 135
Wagnes, M.P. 18, 45 Wissbrun, K.F. 41, 47, 98, 109, 299, 311
Wales, J.L.S. 117, 121, 124, 133, 134 Withers, V.R. 136, 168
Walk, C. 215, 240 Wolf, R.F. 18, 45
Walker, J. 66, 104 Wong, W.M. 41, 49, 243, 273, 306, 312,
Wall, D.R. 136, 168 335, 338, 360, 361, 387, 388, 392,
Walters, K. 41, 43, 47, 52, 53, 67, 71, 394, 395, 412
79, 84, 105, 107, 113, 116-8, 132 Wood, R. 189, 238
Wang, R.H. 179, 237 Woodthorpe, J. 41, 51, 223, 224, 241,
Warburton, B. 160, 173 243, 266, 307, 312, 336, 338, 393,
Ward, S.G. 148, 150, 172, 264, 309 395, 413
Wright, B. 100, 109 Young, C.C. 194, 239
Wright, C.H. 139, 171 Youngblood, E.L. 136, 168
Wu, S. 41, 48, 243, 292, 304, 312, 333,
338, 391, 395, 410 Zahorski, S. 43, 52
Wyman, C.E. 208, 240 Zaikov, G.E. 41, 51, 243, 308, 312, 337,
338, 394, 395, 414
Yamada, M. 299, 311 Zakharenko, N.V. 14, 41, 45, 285,
Yamashita, S. 41, 49, 243, 273, 305, 312, 310
334,338,391,395,411 Zapas, L. 72, 85, 106
Yanovsky, Yu.G. 41, 51, 243, 308, 312, Zhao, G.Y. 262, 263, 309
337, 338, 394, 395, 414 Ziabkki, A. 103, 110, 166, 174
Yao, J. 215, 240 Ziegel, K.D. 147, 172, 384, 394
Yazici, R. 395, 409 Ziemanski, L.P. 35, 46
Yoo, HJ. 41, 48, 243, 273, 276-8, 292, Zingel, U. 41, 48, 243, 292, 304, 312,
304, 312, 315, 333, 338, 390, 395, 333, 338, 390, 395, 410
407, 410 Zisman, W.A. 19, 45
Index
Index terms Links
A
Activation energy 100
Alumina filled
polyethylene 349 353 358 362 370
388
Amorphous polymer
definition 5
Antistatic agent 23
Aramid fiber filled
polystyrene 245 314
Arrenhius-Eyring equation 99
Azidosilanes 26 28
B
Bagley correction 121
Barium sulfate filled
polyethylene 274
Barium ferrite filled
polyester elastomer 253
polyethylene 253 286 374 377 381
polyurethane thermoplastic elastomer 253
styrene-isoprene-styrene block copolymer 254 277 286 374 377
381 384 385 387
This page has been reformatted by Knovel to provide easier navigation. 469
470
Index terms Links
Batch mixers 189
Biaxial
extension 64
extensional viscosity 65
Blending
definition 175
Block copolymer 7
Branched polymer 3
C
Calcium carbonate filled
polyethylene 249 274 293
polypropylene 249 259 274 276 282
294 319 325 328
polystyrene 245 295 314 324 397
407
Carbon black filled
polyethylene 287
polystyrene 245 260 283 295 314
316 397 401 404
Carbon fiber filled
polyethylene 249
Cauchy stress tensor 57
Cellulose fiber filled
polystyrene 245 314
Central tube effect 150
Characteristic time 54
Chemical bonding theory 37
Chemical additives 160
Chlorinated paraffins 28

471
Index terms Links
Chrome complexes 25
Commodity plastics 6
Complex viscosity 60
Complex modulus 61
Compounding
definition 175
process tasks 188
techniques 175
variables 221
chamber loadings 231
mixer type 223
mixing temperature 232
mixing time 225
order of ingredient addition 236
ram pressure 229
rotor geometry 224
rotor speed 229
Constitutive equation 57
Constrained recoil 62
Contact angle 19 20
Continuous compounders 192
Copolymer
definition 7
Coupling agent
characteristics 29
mechanism 35
Cox-Mertz method or rule 86
Creep compliance 62
Creep 61

472
Index terms Links
Crystalline polymer
definition 5
D
Deborah number
definition 54
Deformable layer theory 37
Dilatant behavior 152
Dispersive mixing 184
Distributive mixing 183
Dolomite filled
polyethylene 262
Draw resonance 73
Dump criteria 218
Dynamic
loss modulus 60
storage modulus 60
viscosity 60
E
Effect of filler agglomerates
steady shear
elastic 321
viscous 272
unsteady shear
viscoelastic 356
Effect of filler concentration
extensional 402
steady shear
elastic 317

473
Index terms Links
Effect of filler concentration (Continued)
viscous 248
unsteady shear
viscoelastic 345
Effect of filler size
extensional 400
steady shear
elastic 315
viscous 246
unsteady shear
viscoelastic 344
Effect of filler size distribution
steady shear
elastic 321
viscous 262
unsteady shear
viscoelastic 350
Effect of filler surface treatment
extensional 405
steady shear
elastic 323
viscous 273
unsteady shear
viscoelastic 360
Effect of filler type
extensional 396
steady shear
elastic 313
viscous 244
unsteady shear

474
Index terms Links
Effect of filler type (Continued)
viscoelastic 344
Effect of matrix additives
unsteady shear
viscoelastic 387
Effect of polymer matrix
steady shear
elastic 330
viscous 279
unsteady shear
viscoelastic 372
Einstein equation 138
Elastic solid
description 39 54
Elastic energy 122
Elastomers
definition 2
examples 2 6
Electroviscous effect 163
Ellipsoidal particles 143
Engineering thermoplastics
examples 7
Entry flow 75
Extension
biaxial 64
planar 65
uniaxial 62
Extensional viscometer
extrusion method 130

475
Index terms Links
Extensional viscometer (Continued)
filament stretching 128
Extensional viscosity
biaxial 65
planar 65
uniaxial 65
Extensional rate
biaxial 64
planar 65
uniaxial 63
Extensional flow 55 62 65 164
Extra stress tensor 57
Extrudate swell 71
F
Filled polymer
definition 11 13
examples 13
Filled polymer rheology
definition 54
Filler
cost-effectiveness 15
definition 9
ellipsoidal 10 11
fibrous 10 11
flexible 10
geometry 19
inorganic 11
organic 11
platelike 10 11

476
Index terms Links
Filler (Continued)
rigid 10
selection 13
spherical 10 11
surface 19
surface treatment 21
types 10
Filler-polymer interactions 16 17
Finishes 22
Flocculation 151
Flow curve
ideal unfilled 40
filled 42
Flow
curve 40 42
entry 75
extensional 55 62
shear 55
Fluids
Newtonian 66 67 77 78
non-Newtonian 66 77 78
pseudoplastic 67 68
thixotropic 67 68 70
viscoelastic 67 77 78
Franklin fiber filled
polystyrene 245 314
G
Glass bead/sphere filled
polypropylene 123 327 340

477
Index terms Links
Glass bead/sphere filled (Continued)
polystyrene 245 314
Glass transition temperature
definition 5
Glass bead/sphere filled
polybutene 256 270 318 322 347
355
styrene acrylonitrile 123
thermoplastic polymer 251 256 318 347
Glass fiber filled
nylon 280 296 330
polycarbonate 261 281 298 331
polyether ether ketone 300
polyetherimide 281 299
polyethylene 249 408
polyethylene terephthalate 261 280 297
polystyrene 245 295 314 317 322
Graft copolymer 7
H
Homopolymers 6
Hooke's law in shear 122
I
Intensity of segregation 181
Interface
definition 16
Interfacial
energy 20

478
Index terms Links
Interfacial (Continued)
region 16
Internal mixers 190
Interphase
definition 16
L
Liquid crystalline polymer 9
Loss tangent 60
Lubricant 23
M
Matrix additives
examples 43
Melt flow index 127
Melt flow indexer 126
Melt fracture 73
Melting temperature
definition 5
Mica filled
polyethylene 263
polypropylene 275 294
polystyrene 245 314
Mixing
definition 175
goodness 175
index 179
mechanisms 183
temperature 232

479
Index terms Links
Mixing
devices in single-screw systems 198
dispersive 184
distributive 183
pins 198
sections 199
time 225
variables 221
Modulus
complex 61
dynamic loss 60
dynamic storage 60
Molecular weight
description 39
distribution 39
N
Network polymer 3 4
Newtonian fluids
behavior 77 78
description 66
generalized 67
Non-Newtonian fluids
behavior 77 78
description 66 67
Normal stress
components 58
difference
cone and plate 117
definition 59

480
Index terms Links
Normal stress (Continued)
parallel-disk 118
Nylon
glass fiber filled 280 296 330
O
Open mills 189
P
Packing of filler 139
Particle size distribution 147
Particle surface effect 150
Planar
extension 65
Plasticizer 23
Plate separation 77
Poly (vinyl chloride)
fine particles filled 103
Polybutene
glass bead/sphere filled 256 270 318 322 347
355
Polycarbonate
glass fiber filled 261 281 298 331
Polyester elastomer
barium fernte filled 254 286 374 377 381
unfilled 285 380
Polyether ether ketone
glass fiber filled 300

481
Index terms Links
Polyetherimide
glass fiber filled 281 299
Polyethylene
alumina filled 349 353 358 362 370
388
barium ferrite filled 253 286 374 377 381
barium sulfate filled 274 286
calcium carbonate filled 249 274 293 359
carbon black filled 287
carbon fiber filled 249
dolomite filled 262
glass fiber filled 249 408
mica filled 263
quartz filled 258 293
silica filled 359
silicon filled 89
steel sphere filled 340 353
talc filled 262
titanium dioxide filled 320
unfilled 285 293 380
zirconia filled 354
Polyethylene terephthalate
glass fiber filled 261 280 296
Polymeric esters 27 28
Polymerization
addition 1
condensation 1
Polypropylene
calcium carbonate filled 249 259 274 276 282
294 319 325 328

482
Index terms Links
Polypropylene (Continued)
glass bead/sphere filled 123 327 346
glass fiber filled 187 249 294 329
mica filled 275 294
talc filled 249 294
unfilled 294
Polystyrene
aramid fiber filled 245 314
calcium carbonate filled 245 295 314 324 397
407
carbon black filled 245 260 283 295 314
316 397 401 404
cellulose fiber filled 245 314
Franklin fiber filled 245 314
glass bead filled 245 314
glass fiber filled 245 295 314 317 332
mica filled 245 314
titanium dioxide filled 245 260 295 314 316
320 397 401 406
unfilled 403
Polyurethane thermoplastic elastomer
barium ferrite filled 253
Pressure hole error 77
Purely elastic solid
definition 54
Purely viscous liquid
definition 54

483
Index terms Links
Q
Quartz filled
R
Rabinowitsch-Weissenberg correction 121
Random copolymer 7
Residence time 227
Resitols 4
Resols 4
Restrained layer theory 37 38
Reversible hydrolyzable bond theory 38
Rheological models
Carreau 81
complex viscosity 86
dynamic modulus 90
Ellis 80
general 81
Herschel-Bulkley 83
modified Carreau 86 87
modified Herschel-Bulkley 83
normal stress difference 84
power-law 80
steady shear viscosity 79
Rheology
definition 39
Rheometer (see also Viscometer)
capillary type 113 114 118
definition 112

484
Index terms Links
Rheometer (Continued)
rotational-type 113
types 114
Rheometry
definition 12
Rod-shaped particles 144
Rotational viscometer 113
S
Scale of segregation 181
Scale of scrutiny 183
Segregation
intensity 181
scale 181
Self-cleaning time 228
Semi-crystalline polymer
definition 5
Shear flow
extensional 55
steady simple 55
unsteady simple 55 59
Shear stress
capillary 124
components 58
Shear rate
capillary 124
cone and plate 116
definition 56
Silanes 25

485
Index terms Links
Silica filled
polyethylene 359
Silicon filled
polyethylene 89
Single screw extruders
conventional 193
modified 198
Single screw kneaders 201
Small-amplitude oscillatory flow 59 60
Specialty polymers
examples 7
Spherical particles 137
Steady state compliance 86
Steady shear viscosity unification 287
Steady simple shear flow 55
Steel sphere filled
Stick-slip phenomenon 121
Stress relaxation 61
Stress
growth 61
normal 58
relaxation 61
shear 56 58
Striation thickness 181 196
Styrene acrylonitrile
glass bead filled 123

486
Index terms Links
Styrene-isoprene-styrene block copolymer
barium ferrite filled 254 277 286 374 377
381 384 387
unfilled 285 380
Surface wettability theory 37
Surface modifiers
effects 160
examples 26 27
mechanism 35
silane treated
alumina 362 367
barium ferrite 277
calcium carbonate 325
glass beads 327
mica 275 294
suggested 34
titanate treated
alumina 362 366
barium ferrite 277
calcium carbonate 276 294 328
glass fibers 329
Surface treatment
effect 30
method 24 25
Suspension
concentrated 139
definition 136
dilute 137
rheology 136

487
Index terms Links
T
Talc filled
polyethylene 262
polypropylene 249 294
Thermoplastic polymer
glass/sphere filled 251 256 318 347
Thermoplastics
definition 1
examples 2
Thermosets
definition 2
examples 2
Time
characteristics 54
residence 227
scale of deformation 54
self-cleaning time 228
Titanates 26 28
Titanium dioxide filled
polyethylene 320
polystyrene 245 260 295 314 316
320 397 401 406
Trouton viscosity 95
Tubeless siphon 78
Twin screw extruders 202
classification 205
intermeshing
co-rotating 207
counter-rotating 21
non-intermeshing

488
Index terms Links
Twin screw extruders (Continued)
counter-rotating 214
Two-roll mill 189
U
Uebler effect 79
Uniaxial
extension 62
Unification of steady shear viscosity 287
Uniform copolymer 7
Unsaturated polyester
clay filled 274
mica filled 274
silica filled 274
talc filled 274
wollastonite filled 274
Unsteady simple shear flow 55
V
Viscoelastic fluid behavior 77 78
Viscoelastic effects 71
Viscoelasticity
description 54
Viscometer (see also Rheometer)
cone and plate 115
extensional 128
parallel-disc 117
Viscometric functions 59

489
Index terms Links
Viscosity
complex 60
definition 59
dynamic 60
extensional 65
function 59
shear 57 58
Viscous liquid
description 39 54
W
W-L-F equation 99
Wall slip (see Stick-slip phenomenon)
Wall effect 150
Weissenberg effect 71
Wettability 19
Wetting 185
Wollastonite filled
polyethylene 274
Z
Zirconia filled
polyethylene 354

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Published by Kluwer Academic Publishers

Sold and distributed in North, Central and South America

In all other countries, sold and distributed

Printed on acid-free paper

All Rights Reserved

Printed in Great Britain

Polymeric materials have been replacing other conventional materials

This page has been reformatted by Knovel to provide easier navigation. v

1.5 Rheology ...................................................................... 39

2. Basic Rheological Concepts .................................. 54

This page has been reformatted by Knovel to provide easier navigation.

3. Rheometry ............................................................... 112

4. Constitutive Theories and Equations for

This page has been reformatted by Knovel to provide easier navigation.

4.2.5 Effect of Flocculation ................................... 151

5. Preparation of Filled Polymer Systems ................ 175

This page has been reformatted by Knovel to provide easier navigation.

6. Steady Shear Viscous Properties .......................... 243

7. Steady Shear Elastic Properties ............................ 312

8. Unsteady Shear Viscoelastic Properties .............. 338

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8.8 Effect of Matrix Additives ............................................. 387

9. Extensional Flow Properties .................................. 395

10. Concluding Remarks .............................................. 416

Appendices .................................................................... 425

Author Index .................................................................. 455

Index ............................................................................... 469

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1.1.1 THERMOPLASTICS, THERMOSETS AND ELASTOMERS

Thermosets are materials that have undergone a chemical reaction,

1.1.2 LINEAR, BRANCHED OR NETWORK POLYMERS

HIGH PRESSURE LDPE

LOW PRESSURE LLDPE

Figure 1.1 Comparison of structures of HDPE1 LDPE, and LLDPE.

ethylene (LDPE) has a branched structure and a density ^0.92g/cm3,

Resols on further heating change into resitols, a three-dimensional

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

1.1.3 CRYSTALLINE, SEMI-CRYSTALLINE OR AMORPHOUS POLYMERS

when R = H, then the result is the homopolymer polyethylene (PE);

1,4 addition 3,4 addition 1,2 addition

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

1.1.5 COPOLYMERS AND TERPOLYMERS

1.1.6 LIQUID CRYSTALLINE POLYMERS

1.2.1 RIGID OR FLEXIBLE FILLERS

1.2.2 SPHERICAL, ELLIPSOIDAL, PLATELIKE OR FIBROUS FILLERS

Fillers can be classified based on their physical form and shape as

3-dimensional 2-dimensional 1-dimensional

Spherical Ellipsoidal Flakes Platelets Fibers Whiskers

Glass beads Wood flour Mica Clay Glass fibers Wollastonite

1.2.3 ORGANIC OR INORGANIC FILLERS

1.3 FILLED POLYMERS

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

Table 1.6 Reasons for the use of fillers in thermoplastics

1. Cost and availability

1.4 FILLER-POLYMER INTERACTIONS

Filled polymer theology is basically concerned with the description of

2.1 FLOW CLASSIFICATION

2.1.1 STEADY SIMPLE SHEAR FLOW

6. Shear-stress and extra stress tensor

f =-pf + f + ijv[trl5]I (2.3)

f = ri(l H, IH)H (2.5a)

f= T21 T22 O (2.6)

V1 = E3X1; V2 = 632; ^3 = -2eB3 (2.27)

(,,-„) -(- >=SH^g) M