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