Polymer Blends and Composites

11. Polymer Blends and Composites

11.1. Polymer Blends

Mixing together of two or more different polymers or copolymers is known as

blending. Blending is a process somewhat similar to compounding. In a polymer
blend, the constituent polymers are usually present in significant weight or
volume proportions with respect to each other, but seldom all in equal
proportions. Blending of two or more different polymers is often viewed as similar
though not equal to alloying of two or more metals, the objective in either case
being development and production of new uniform materials having ranges of
properties far different from those of the constituents. In metal systems, the alloy
is a solid solution necessarily giving a homogeneous mass, while the polymer
blends or alloys are seldom homogeneous in that sense.

11.2. Consideration of Compatibility

The question of compatibility between polymers is a very important consideration

in making blends from them.1 In a very general manner it may be said that
polymer–polymer incompatibility is more a rule than the exception. Even if two
different polymers are by and large compatible under a specified condition, they
slowly develop incompatibility as they are put to use under a different set of
conditions. It is at the same time questionable if complete miscibility or
compatibility between the component polymers in a blend is at all the most
desired feature.

A useful blend has the characteristics of a uniform dispersion—fine discrete

particles of one component being uniformly dispersed through the medium or
matrix of the other component. It would be advantageous if the size and size
 distribution of the domains or the dispersed phase remain practically unaltered
over long time periods from the condition of blending to the condition under
which the blend is required to perform. Use of selected compatibilizers2,3 in the
form of appropriate block copolymers or coupling agents such as the silane or
titanate coupling agents may substantially help in dispersion of additives in
polymers by improving adhesion or by minimising phase separation in binary or
multicomponent polymer blends by playing the role of a surfactant.

11.3. Types of Polyblends

Polymer blends are also commonly termed as polyblends and they may be of the
following different kinds:

i. Mechanical polyblends,

ii. Chemical polyblends,

iii. Mechano-chemical polyblends,

iv. Solution cast polyblends, and

v. Latex polyblends.

11.3.1. Mechanical Polyblends

A mechanical polyblend is made by melt blending of the constituent polymers. In

the case of binary blends from two different amorphous polymers, the processing
temperature must at least be well above the glass transition temperature (Tg) of
both the constituting polymers and for blends of semicrystalline polymers, it must
be higher than the melting points of the two constituent polymers. Because of the
high heat input necessary to maintain a low melt viscosity and also because of
the high shearing rates needed for thorough mixing or blending, some degree of
chain branching or chain extension leading to formation of block and graft
copolymer structures, chain scission and even cross-linking may occur in the
polymers making the blend. Melt mixing is used for systems in which thermal
degradation does not ordinarily occur.

11.3.2. Chemical Polyblends and Mechano-chemical Polyblends

A chemical polyblend is given by polymeric systems in which long monomeric

sequences of one kind are chemically linked to similar long monomeric
sequences of a different kind in either the axial direction or in the cross direction
giving block copolymer or graft copolymer structures respectively. Selective or
random cross-linking of mechanical blends may ultimately lead to mutual
grafting, cocross-linking or intercross-linking resulting in formation of what may
be termed as mechano-chemical polyblends. The resultant polyblend may often
appear as an interpenet-rating polymer network (IPN) system of structurally
different polymers. Such polyblends are commonly characterized by a relatively
uniform phase morphology with remote chance for gross phase separation,
improved mechanical strength, thermal stability, chemical resistance and
durability.

11.3.3. Solution-cast Polyblends

In solution blending, selected diluents are used to dissolve the component

polymers; the diluents also lower the temperature and shear force necessary for
satisfactory and uniform mixing without having any degradative effect in the bulk
properties of the blend prepared. But removal of the diluents after solution
blending may ultimately lead to prominent and uncertain changes in the phase
morphology, thus weakening the blend and lowering its performance reliability.
Incomplete removal of solvent may further pose potential complication for lack of
reliability in performance at the desired level and uncertain failures.

11.3.4. Latex Polyblends

Latex mixing is one of the most important techniques for the preparation of
commercial polyblends. In a latex polyblend, polymers are present as suspended,
stabilized micropheres of a specific size and size distribution. Interactions
between the neighbouring particles are prevented by the stabilizers present in
the medium. When two different latexes are blended together, the mixture
contains a random suspension of dissimilar kinds of particles, each unaffected by
the presence of the others of like or unlike kinds. As the flocculation is entirely
contingent upon the emulsifier concentration and not on the polymer
characteristics, the coagulation is manifested as a random process. Blends thus
obtained on coagulation appear as relatively intimate mixtures of the constituent
polymers.

11.4. Properties of Polyblends

 The behaviour of two polymers in a mixture or blend is not necessarily the same
as expected from the behaviour exhibited by them in their isolated/separate
forms. The ultimate behavioural pattern of polyblends is dependent on:

i. Extent of phase separation,

ii. Nature of the phase provided by the matrix material,

iii. Character of the dispersed phase,

iv. Interaction between the component polymers, etc.

It has been commonly observed that for a miscible polyblend, the following
arithmetical semiempirical rule4, 5 is obeyed by different physical properties:

(11.1)

where P is the property of interest, ϕ is the concentration and I is an interaction

term that can be positive, negative or zero. If I is zero, the rule of mixtures
(additivity principle) is observed. If it is positive, the polyblend property would be
higher than the weighted average of the constituent polymers and the polymers
produce a synergistic effect in the blend. If I is negative, the polyblend property
would be lower than what is expected from simple average and the blend system
is then referred to as antisynergistic.

For an immiscible polyblend giving a continuous phase (phase 1) and a dispersed

phase (phase 2), Eq. (11.1) is not tenable for property analysis. In such cases, the
semiempirical relationship to analyze the physical properties is given by Eq.
(11.2):

(11.2)

where ϕ 2 is the concentration of the dispersed phase constituent. The value of A

varies between zero and ∞ depending on the shape and orientation of the
dispersed phase as well as the nature of the interface. B depends on the relative
values of the properties P1 and P2 and A, and Ψ is a reduced concentration term
that is a function of the maximum packing fraction. It is a common experience
that for A → 0, the dispersed phase is soft and for A → ∞, the dispersed phase is
hard. Equation (11.2) is useful for analysis of almost all physical properties of
immiscible blends excepting the failure and toughness properties.

11.5. Glass Transition of Polyblends

The glass transition phenomenon characterizes almost all polymers. At glass

transition points, different polymers are said to exist in an isoviscous,
isoconfigurational and iso(free volume) state. A miscible polyblend exhibits a
single and sharp glass transition temperature (Tg), intermediate between those of
the constituent polymers6. However, polyblends showing gross phase
heterogeneity such as styrene-acrylonitrile (SAN) copolymer and grafted
polybutadiene7 exhibit glass transition for each constituent polymer present with
some shifting and broadening, however. The Tg method of characterizing blends
is limited by poor resolution particularly when the constituent polymers have Tgs
differing within 20°C.

11.6. Techno-commercial Consideration for Development of

Polymer Blends

Commercially available polyblends are either homogeneous or heterogeneous.

Plasticization of a given rigid polymer by blending with appropriate polymeric
plasticizers leads to homogeneous polyblends. In comparison with simple, low
molecular weight liquid plasticizers, polymeric plasticizers are relatively immobile
and show low or little volatility. Their effect on Tg is small and they yield blends
with reasonable or undiminished rigidity8 under ambient conditions and allow
measurable lowering in heat distortion temperature and melting temperature and
make the product flow at relatively low temperatures more readily during
processing. Incorporation of polymeric plasticizer renders the polyblend product
stable, free from proneness to migration or blooming of the plasticizer additive to
the surface of finished products. Use of polymeric plasticizers, therefore, often
yields blends endowed with energy saving processability. Thus, low molecular
weight poly(methyl vinyl ether) may be used to plasticize polystyrene, and
polyethylene glycols may be used to plasticize cellulose nitrate.

Heterogeneous polyblends possess unique and wide application potentials in the

field of high impact plastics. If a small to moderate proportion of a suitable rubber
(gum) is blended with a brittle plastic, a softer, low modulus material of improved
impact resistance results and if the rubber is appropriately cross-linked as the
blend is made, the resultant product would normally show much improved
toughness and impact resistance with measurably improved stiffness as well if
the uniform dispersion and prevalent size distribution of the dispersed rubber
phase are retained or they remain practically undisturbed on cross-linking.
Relevant feature is shown schematically in Fig. 11.1 for a styrene copolymer
(SAN) toughened with a diene rubber (NBR).

Figure 11.1. Toughening of SAN copolymer by rubber (NBR) and effect of

rubber cross-linking in imparting enhanced toughening or impact
resistance

Homogeneous, miscible polyblends from two different amorphous polymers

would mostly appear clear, showing in each such blend a single refractive index
that is intermediate between those of the constituent polymers. A heterogeneous
blend (discrete phase of one constituent dispersed or embedded in the matrix of
the other) usually scatters light according to the size of the dispersed particles
and would tend to appear opaque if the dispersed particles are large enough and
the films are thick enough to make the scattering extensive if not complete.

The imperatives that induces one to go for blending of polymers are: (a) to
maintain a more favourable cost-performance ratio, and (b) to achieve
reinforcement of a desired property. An expensive polymer whose property
spectrum is much higher than is needed for a specific application may be blended
with an inexpensive polymer having a property spectrum of a level that makes
the resulting polyblend exhibit an attractive cost/performance ratio for the
contemplated application. On the other hand, the demerits from a poor property
level of a polymer for a particular application may sometimes be effectively or
more than compensated by blending it with a second polymer which is rich in
that particular respect. Thus, the high level of performance demanded is often
satisfied by an appropriate blend of commercially available polymers without
having the need to develop a new polymer or to invest in a new plant.
Commercial polyblends are commonly of three types:

i. Elastomer–elastomer blends,

ii. Plastomer–plastomer blends, and

iii. Elastomer–plastomer blends.

11.6.1. Elastomer–Elastomer Blends

Such blends are widely made and used in view of the fact that a single elastomer
often fails to offer the desired balance of properties and overall cost advantage.
Natural rubber is selectively blended with synthetic rubbers to improve a range of
properties including tack, resilience, tear strength, heat-build-up and sometimes
fatigue resistance. Likewise, selected synthetic rubbers are blended with a
primarily natural rubber based compound to obtain advantages with respect to
wear or cracking resistance, bounce and cost-effectiveness. Sometimes different
synthetic rubbers are blended between themselves. Nitrile rubber (NBR) may be
blended with SBR, EPDM, polychloroprene and polysulphide rubbers to selectively
achieve advantages on cost, ozone resistance, oil and heat aging resistance and
low temperature flexibility.

11.6.2. Plastomer–Plastomer Blends

In the thermoplastic range, commercial polyblends include combination of

poly(methyl methacrylate), polystyrene, polycarbonates, nylons, polyethylene
(PE), polypropylene (PP), polyethylene terephthate (PET), polyimides,
thermoplastic polyurethanes, ionomers etc.

Poly(vinyl chloride), PVC, an inherently flame retardant, relatively low cost

thermoplastic resin has the disadvantage of being thermally unstable and
relatively brittle. The ABS plastics, on the other hand, are relatively ductile and
thermally stable but not flame retardant. When mixed appropriately, ABS and
PVC together yield polyblends with much improved heat stability, excellent
impact resistance and flame retardance. Such ABS–PVC polyblends are useful in
power tool handles, computer devices, communication relays, electrical terminal
blocks, kitchen appliances, housing for electronic gadgets, partition items and
furniture for the building and housing sector, etc. Polyblends based on ABS and
polycarbonate combine high impact strength excellent thermal resistance and
good processing characteristics with improved environmental stress cracking
resistance and cost advantage over use of only polycarbonates.

11.6.3. Elastomer–Plastomer Blends

General immiscibility of polymers has been turned into a unique advantage in the
development of rubber-toughened plastics4, 9 such as high-impact polystyrene
(HIPS). Such materials find applications in packaging, kitchen wares, toys,
appliances, furniture, electronic/electrical goods, etc.

Blending of an elastomer with a selected plastomer provides a convenient means

of making thermoplastic elastomers (TPE) of diverse nature. The olefinic class of
thermoplastic elastomers have been growing in use and acceptability. Polyolefin
thermoplastics, viz., polypropylene (PP) and polyethylene (HDPE) are blended
with such elastomers as EPR or EPDM and natural rubber (NR). To be widely
useful, the elastomer component should have a Tg <–50°C and the thermoplastic
polymer used must have a Tm >> the service temperature of the blend. EPR and
EPDM are preferable to NR and polybutadiene rubber (PBR) in this context.

The properties profile of TPEs from elastomer–plastomer blends is contingent

upon (i) the critical surface tension for wetting of each component, (ii) The weight
fraction of the crystallites in the hard phase providing the matrix, and (iii) the
strength and modulus of the hard phase. The elastomer component may be
cross-linked by use of selected curative under the influence of heating plus high
shearing action during blending by what is known as dynamic vulcanization or
cross-linking 10, or the vulcanization process may be accomplished statically in a
heated compression press as practised commonly.

Dynamic vulcanization effectively enhances the elastomeric properties of the

blend while enhancing processing advantage and recycling potential by retaining
thermoplastic processability. The advantage of dynamic vulcanization can be
drawn to full potential on allowing adequate cross-linking of the elastomeric
phase. Even when the rubber is the major component of the blend, it gets
dispersed in the form of discrete particles or domains in the thermoplastic matrix
under heat and shear action in a shear mixer 10, thus conferring the thermoplastic
processing character to the blend. Such dynamically cross-linked elastomer–
plastomer blends are also called thermo-plastic vulcanizates (TPVs).
11.6.4. Formation of Interpenetrating Polymer Network (IPN)

Due to very small entropy of mixing and positive heat of mixing, phase separation
during mixing or shortly or long after mixing is more common in two-component
polymer blends even in systems where the component polymers are very close in
solubility parameter. Even though limited phase separation is necessary or
desirable for proper balancing of properties between the constituent polymers
making the blend, uncontrolled or large-scale phase separation is altogether
undesirable. Domain size (of the dispersed phase, elastomer or plastomer) is
viewed as important in determining the physical and mechanical behaviours of
elastomer–plastomer blends.

Interpenetrating polymer network (IPN)9–13 is a good example of controlled

morphology chemical polyblend. The IPNs are novel blends of network and linear
polymers of two or more polymer networks that are held together with prominent
resistance to gross phase separation such as a consequence of stable or
permanent chain entanglements or catenation than by establishment of mutual
covalent bonds, i.e. by grafting of one polymer or the other. IPNs where only one
polymer component is selectively cross-linked leaving the other component
uncross-linked are known as semi-IPNs or pseudo-IPNs. Full-IPNs are blend
networks where the constituent polymers are all selectively crosslinked either
simultaneously (giving simultaneous IPNs) or sequentially (giving sequential
IPNs). Control of morphology including domain size and domain distribution and
prevention of gross phase separation is often better achieved due to some
degree of unavoidable mutual grafting during network formation or due to
controlled grafting induced by design, more so, in full IPNs than in semi IPNs.
Figures 11.2 and 11.3 showing SEM micrographs, highlight the differences in
phase morphology for (i) semi and full IPNs from nitrile rubber (NBR)–poly(vinyl
chloride) (PVC) blends, and for (ii) polyethylene (PE)-EPDM semi IPNs where the
EPDM was vulcanized statically and dynamically using accelerator-sulphur
curative system.
Figure 11.2. SEM micrographs of NBR–PVC (70 : 30) blends: (a) uncured
blend, (b) semi IPN (only NBR component cross-linked using TMTD-Sulphur
combination as the curative, and (c) full IPN (both NBR and PVC
components simultaneously cross-linked using a combination of ethylene
thiourea (ETU) and sulphur as the curative)

Figure 11.3. SEM micrographs of PE–EPDM (30 : 70) blends (semi IPNs)
cross-linked by TMTD–MBTS–Sulphur curative system: (a) Statically cured
(showing flaky, layered phase morphology) and (b) dynamically cured
(cocontinuous phase morphology), showing fine threads or fibrils of PE
passing through the cores of the doughnut-like clustered beads of EPDM

11.7. Polymer Composites

11.7.1. Historical Background

The course of development of composite materials runs parallel to the course of

transformation of our civilized society over the ages. Complex combination of
materials was used by man even in the early periods of history for housing and
hunting purposes. Mud and clay are being used for building walls for thousands of
years. It was realised even in the early stage of development of the mud-walls
that use of chopped straw and strips or mats of bamboo, canes or the like
imparted higher strength, safety and durability to the mud walls. Uses of papyrus
reinforced bitumen in building fishing boats and of shellac as a stiff matrix
material with reinforcements based on fibrous materials collected from forest
were known to people in ancient Babylonia, Egypt and India. At a much later date,
composites such as linoleum, asbestos cement items, and reinforced concrete
grew into prominence and universal acceptance. More recent developments are
the high performance composite materials such as glass fibre reinforced plastic
(FRP) composites, carbon-black or carbon fibre reinforced polymer/resin based
composites and plastic or rubber based composites reinforced with natural or
synthetic fibres or fibrics, steel cords, and fibres from some other metal,
nonmetal or ceramic items.

11.7.2. Definition and Basic Concepts

The word composite, as technically defined, means a macroscopic combination of

two or more distinct materials having an identifiable interface between them, but
more pointedly, the definition is confined to only such materials as would contain
a fibrous or particulate reinforcement supported by a binder or matrix material.
The discontinuous phase constituted of the fibre or particulate reinforcement is
commonly stiffer and stronger than the continuous (matrix) phase. In most cases,
a substantial volume fraction (> 10%) of the discontinuous phase is necessary
just to achieve significant reinforcement. The difference between a composite
and a filled system lies in the fact that while in a composite the discontinuous
phase imparts significant mechanical reinforcement, it only plays the role of a
loading agent or diluent without property enhancement or reinforcement in what
is called a filled system. Fillers may, however, impart many advantages such as
fire/flame retardancy, shrinkage control, improved thermal/electrical conductivity
and above all, cost benefit. One may also have composites where the stiff
component may constitute the major, continuous phase such as the rubber
modified (toughened) plastics.

Composites, in general, and fibre reinforced plastics (FRP) or glass fibre

reinforced plastics (GRP) in particular, have been developed out of sheer
necessity imposed by the stringent requirements of modern technology. The
demand of the automotive and particularly of the aerospace community
prompted developments in reinforced composites which combine light weight
and high strength of Aluminium and Al-alloys and excel them in respect of
chemical resistance, corrosion/weather resistance and dent resistance (good
recovery of deformation). Composites are in growing demand from architects and
construction engineers in the transport, sports, aerospace, defence, building and
many other sectors. Composites have been developed because no homogeneous
structural material could offer all the desired attributes for a given application.

11.7.3. Prospects and Limitations

As materials of construction in automotive and aerospace sectors, plastics are

undoubtedly growing in acceptance. Even then, in engineering status, simple
plastics still find their place at or near the bottom; but they hold high potential for
a much brighter future through material development in the form of FRP
composites. In many cases, there are clear objections to use of plastics on
consideration of demands on thermal and aging resistance and lack of confidence
centering limitations in a desired balance of thermal and mechanical properties.
The best way to overcome these limitations and constraints to enable plastics to
not only compete with or even overshadow light metals and alloys in stress and
safety-sensitive engineering applications is to make composites 14 through fibre
reinforcement of prospective polymers coupled with judicious cross-linking of the
polymer matrix.

The chemical, thermal and often the electrical performance of composites are
controlled by the polymer or the matrix material while the mechanical
performance within the polymer's ultimate temperature capability is dictated by
effectiveness of the reinforcement. Each polymer has basic attributes that no
amount of incorporation of reinforcing or other additives of different dose levels
and varieties can disguise; no plastic can reliably function even briefly at a
temperature above the softening or heat distortion temperature of the base
polymer. However, the heat distortion temperature and mechanical (tensile)
strength of selected polymers may be substantially enhanced through judicious
incorporation of a reinforcing fibre such as glass fibre and by cross-linking. Data
in Table 11.1 will substantiate this point. With appropriate support and fibre-
reinforcement, the polymer or the matrix material enables us to partly realise the
inherent high strength and stiffness of the reinforcing fibre material. The principal
benefits of fibre reinforcements are: improved resistance to hot deformation,
lowering or avoidance of low temperature embrittlement, higher strength,
modulus, rigidity and stiffness, improved creep resistance and hence improved
dimensional stability.

Table 11.1. Effect of glass fibre reinforcement (30% w/w) of some crystalline
and amorphous polymers: data listed highlight actual heat distortion
temperature (HDT) and tensile strength (TS) and enhancement effected due
to fibre reinforcement

[HDT (°C)] [TS (MPa)]

Matrix [HDT (°C)] [TS (MPa)]
Enhancement Enhancement
material in Actually Actually
on fibre on fibre
composite observed observed
reinforcement reinforcement

A. Crystalline

Nylon 66 248 150 180 100

PEEK 300 145 175 75

PBT 210 140 135 75

Nylon 6 210 130 135 100

PP 148 82 85 50

Acetal 164 55 140 70

B. Amorphous

PES 215 16 145 55

PPO 140 15 125 60

PC 140 10 120 52

ABS 100 10 90 40
The discovery of light-weight, strong and stiff carbon fibres in the mid 1960s
proved to be a turning point in the development of high performance plastic
composites offering serious threats to the light alloys in their traditional use as
materials of construction in the aerospace sector. A chain of further
developments in strong stiff, light weight synthetic fibres, particularly the
aromatic polyamides popularly known as aramid fibres and by the trade name
Kevlar, and also developments in aromatic resins and other engineering polymers
(as matrix materials) suitable for use in the design of high performance FRP
composites followed in the wake of developments of carbon fibres (short fibres
and continuous filaments).15 With the developments in high performance
aromatic polymers, the old division between the functional and processing
potentials of thermoplastics and thermosets is getting blurred progressively.
Thermosets, however, commonly exhibit lower shrinkage, improved chemical
resistance and thermal performance, while thermoplastics give advantages in
higher outputs, better design of parts over and above their recycling potential.

Amorphous thermoplastics such as ABS, poly(phenylene oxide) (PPO),

polycarbonate etc. are valued for low shrinkage and good impact behaviour, even
though their fatigue resistance is rated low and on fibre reinforcement, they offer
low or limited benefits; crystalline polymers on the other hand exhibit higher
shrinkage and are dimensionally affected more on heating but they are
characterized by substantial improvements in heat distortion temperature and
tensile/flexural strength on fibre reinforcements. (see Table 11.2).
Table 11.2. Properties of nylon 66 composites: effect of incorporation of
particulate and fibrous reinforcing agents

Heat Stiffness
Nature of Tensile Flexural
distortion ratio
reinforcing strength modulus
temperature (Anisotropy
additive (MPa) (GPa)
(°C) Index)

1. None 85 2.5–3.0 95–100 1.0

2. Particulate 95 5.6–6.0 130–170 1.0–1.2

(50%)

3. Particulate 125 6.0–7.0 220–230 1.4–1.5

(35%) and
Fibrous
(15%)

4. Fibrous 200 9.0–9.5 240–250 1.7–1.8

(50%) (Glass
Fibre)

A composite is viewed as a laminate if the reinforcing fibres are arranged in

layered fashion such as in the form of webs, fabrics or mats, Fig. 11.4(a); mixing
of the matrix resin with randomly oriented short fibres, Fig. 11.4(b); allows the
resin fibre mix or the dough to be injection moulded or compression moulded with
or without the presence of a particulate filler and such dough-like short fibre resin
mixes are commonly known as dough moulding compound. Short fibres are not
necessarily randomly arranged. Maximum strength and stiffness are obtained
when continuous fibres/filaments are aligned parallel to the applied load. Such
unidirectionally aligned fibres in resin matrix, Fig. 11.4(c), can be most efficiently
achieved by such methods as pultrusion (combining pulling with extrusion).
Figure 11.4. Diagrams showing different arrangements of short (– –) and
long (—) fibres in composite making

11.7.4. Controlling Features and Property Demands

An unfavourable competitive position of a plastic object vis-a-vis a metal

component may originate from incompetent processing and from bad part design
or the designer's ignorance of the plastic conversion process. Unknown features
and uncontrolled factors relating to thermal or thermomechanical history and
flow geometry of the tool, particularly in injection moulding may be the root
cause of performance shortcomings and unexpected failures. Improved flow
geometry coupled with controlled rate of cooling from moulding temperature may
give substantial advantages in having a good to excellent balance of properties
and performance stability to moulded parts.

High performance applications frequently call for fibre reinforcements for

thermoplastic or thermosetting resins or elastomers. For thermoplastics, the flow
geometry of tool is critical. Stiffness ratio (ratio of modulus in machine direction
to modulus on cross direction) or anisotropy index is also an important
consideration and this parameter would also largely depend on particulate or
fibrous nature of the reinforcing agent, Table 11.2. In respect of anisotropy index
commonly observed, the positioning of the reinforcing agents will be in the order
fibrous >> particulate > none. Equally if not more important considerations are
the fibre length or more intrinsically the fibre aspect (length/diameter) ratio and
bond strength (inter laminar shear strength, ILSS) between the fibre and the
matrix material or the contact angle between the reinforcing fibres and matrix
resin indicating extent of wetting of the fibre with resin (a lower contact angle
indicating better wetting). Fibre-resin or filler-resin interactions and wetting may
be improved substantially by treating the fibre or filler system with what is known
as a coupling or compatibilising agent.16–18 A long range of silicones have been
developed as coupling agents for this purpose. The nature of dependence of
composite strength on length of the given reinforcing fibre (i.e. on aspect ratio)
and on use of a coupling agent is shown schematically in Fig. 11.5. For a fine fibre
of a given diameter a fibre length of 8–10 mm appears to impart the upper
limiting reinforcing effect. For a given fibre length, the strength of composite is
higher for use of a suitable coupling agent. Table 11.3 lists specific gravity and
mechanical property levels of some fibres, metals or alloys and FRP composites.
Data in Table 11.4 highlight the level of reinforcements possible for use of fibres
(short or continuous length) in different weight proportions in the composite for
use of a number of thermoplastic matrix resins.

Figure 11.5. Effect of variation of fibre length (aspect ratio), nature of

polymer (polymer A and polymer B) and of use of a coupling agent for a
given polymer (polymer B) on the strength properties of FRP composites

Table 11.3. Properties of some materials; fibres, metals and alloys and
composites

Tensile Tensile Specific Specific

Specific Strength Modulus Strength Modulus
Materials
Gravity lb/in2 × lb/in2 × lb/in2 × lb/in2 ×
10–5 10–6 10–5 10–6

S-glass 2.49 6.5 12.45 2.61 5.02

Fibre

B-fibre 2.69 4.5 35.5 1.67 17.1

C-fibre 2.00 2.5 55.0 1.25 27.5

(high-
modulus)
C-fibre 1.74 4.5
Tensile 35.0
Tensile 2.70
Specific 20.1
Specific
(high- Specific Strength Modulus Strength Modulus
Materials
strength) Gravity lb/in × lb/in × lb/in × lb/in ×
10 10 10 10
Aramid 1.44 4.0 19.0 2.77 13.2
fibre

Al-alloy 2.77 0.59 10.0 0.23 3.59

(RR-58)

Ti-alloy (Ti- 4.50 1.50 16.0 0.33 3.55

6Al-4V)

Steel (FV 7.80 1.55 28.0 0.198 3.59

520)

S-glass- 2.08 2.60 7.6 1.25 3.65

epoxy
composite

C-fibre 1.67 1.50 30 0.93 18.7

(high
modulus)-
epoxy
composite

Aramid 1.38 2.0 11 1.44 7.97

fibre-epoxy
composite

B-fibre- 1.97 1.95 39 0.99 19.8

epoxy
composite
Table 11.4. Flexural strength of some FRP composites

Polymer Fibre Flexural Strength, MPa

Continuous
Short fibre
Matrix used No fibre length fibre
(30%)
(65%)

None Glass – – 3400*

PP " 30 85 350

Nylon 66 " 80 180 600

PET " 60 140 800

PES " 90 145 500

PEEK " 91 150 780

PEEK C-fibre 90 250 1100

*
Tensile strength

11.7.5. Mixing or Impregnation

It is difficult to mix fibres with a viscous polymer. Crude mixing is of little practical
advantage. The entire surface of all the fibres must be forced into close contact
with the polymer. A low initial matrix viscosity is helpful for mixing and
impregnation. Molecular weight must either be low initially or a solvent/diluent
that would finally turn into an integral part of the matrix must be used. Use of a
simple thinner poses more problems than it solves.

The rise in viscosity of the initial low viscous resin system on curing or chain
extension, which is guided by what is known as chemorheology, is important for
moulding or shaping of parts of intricate shapes. Orientational effects are
important in reinforced plastics and this is still one of the least understood
features of FRP composites. Designers are required to view loaded or reinforced
parts in terms of stress–strain–time–temperature–orientation relationships.

The easiest way to achieve a composite with long continuous fibres with high
axial orientation is to allow continuous impregnation followed by shaping into
profiles by pultrusion technique (extrusion with pull in the machine direction).
Such impregnated systems have the added advantage of providing very high
reinforcing fibre content with near 100% orientation in the finished composite in
the machine direction.

11.7.6. Scope for Use of Natural or Man-made Fibres in Composite

Making

In many applications, use of very high-cost glass fibres, aramid fibres or carbon
fibres in composite making is not necessary or essential. Relatively low-cost
natural fibre substitutes such as jute and synthetic fibre substitutes such as
rayon, nylon or polyester fibres are considered promising with respect to energy
and property advantages. Use of rayon, nylon and polyester cords in construction
of tyres, beltings and hoses is well known. Technologies based on use of steel
cords in constructing high speed radial tyres have been developed and are in the
process of developing into higher sophistications.

Use of jute and allied fibres as reinforcing agents in place of traditional glass
fibres in different forms partly or fully in composite making stems from higher
specific modulus and lower specific gravity of jute (40 GPa and 1.29 respectively)
compared with those of glass fibre (30 GPa and 2.5 respectively). Besides, much
lower cost, and renewable nature of jute and much lower requirement of energy
for production and processing of jute (only 2% of that required for glass) make it
attractive as a reinforcing fibre in resin-based composites. Properties of jute fibre
reinforced plastic (JRP) composites may be substantially improved by minor
chemical modification of jute by grafting of polyacrylonitrile (PAN) and related
polymer and by incorporation of phenolic resins.19 Only 10–20% acrylic polymer-
grafting on jute may impart up to 30% improvements in flexural strength and
flexural modulus of polyester resin based JRP composites. Likewise, phenolic resin
binding (4% resin uptake) on jute fibre may impart up to 40% improvement in
flexural strength of such JRP composites. Improvements in mechanical properties
due to modification of jute as referred to above is a consequence of better
wetting and hence improved bonding between the matrix resin and the
reinforcing (jute) fibres. This has been evidenced by results of (i) measurements
of contact angle between the fibres (modified and unmodified) and the matrix
resin, (ii) resistance to hydrothermal aging of the respective composites, and (iii)
examination of tension fractured surfaces of the different composites by scanning
electron microscopy. 21,22
Properties of FRP composites, more importantly, their dynamic mechanical
properties are likely to depend as much on the nature and distribution of the
matrix materials and the reinforcing fibres as on the nature of the fibre-matrix
interfaces and of the interfacial regions.20–27 Even a small change in the chemical
and physical nature of the fibre for a given matrix resin and in relative weight
proportions of fibre and matrix may result in notable changes in the overall
properties of the composite. Subtle variations in reinforcing fibre selection or
combinations of different fibres in hybrid composites and in processing conditions
may lead to uncertain presence of voids, odd thermal effects due to odd
differences in the expansion coefficients of the main phases, and hence odd
variations in static and dynamic mechanical properties,27 more so, for hybrid
composites consequent to uncertain nature and degrees of interactions at the
different fibre-matrix interfaces.

Proximity of the stiff fibre and preferential adsorption of readily diffusable

constituents (usually low molecular weight curatives) on the fibre surface may
impose a relatively high cross-link density and hence lead to development of a
more than expected stiffness level at the fibre-matrix interface. This may, at the
same time, lead to some softening of the matrix in the zone next to the interface
due to notable depletion of the curative. There is a common unmistakable
general trend in having a progressively lower loss modulus value with
progressive replacement of glass fibre with jute fibre starting with all-glass
unitary composite and finally ending with all jute unitary composite and giving
different glass jute hybrid compositions in between. Fibre reinforcement in
general causes lowering in the damping parameter (tan δ) value of the resin
matrix.27

11.8. References

1. Schultz, A.R., Polymer Preprints, 8 (1967) 1455.

2. Coran, A.Y. and R. Patel, Rubber Chem. Technol, 56 (1983) 1045.

3. Asaletha, R., S. Thomas and M.G. Kumaron, Rubber Chem. Technol, 66 (1995)
671.

4. Nielson, L.E., Predicting the Properties of Mixtures, Marcel Dekker, New York,
1978, p. 13.

5. Hill, R., J. Mech. Phys. Solids, 13 (1965) 189.

 6. Bikales, N.M, Ed., Encyclopedia of Polymer Science and Technology, Wiley
Interscience, New York, 1969, Vol. 10, p. 701, 703.

7. Uemura, S. and N. Takayahagi, J. Appl. Polym. Sci., 10 (1966) 113.

8. Hopff, H. in Plasticization and Plasticizer Process, R.F. Gould Ed., Advances in

Chemistry Series, Amer. Chem. Soc., Washington, D.C., 1965, No. 48, p. 87.

9. Ghosh, P. and P. Ray, Rubber Reporter, 14 (1989).

10. Ghosh, P., B. Chattopadhyay and A.K. Sen, Polymer, 35 (1994) 3958.

11. Ghosh, P. and P. Ray, Polymer Science, Contemporary Themes, S. Sivaram Ed.,
Vol. 2, pp. 871–876, Tata McGraw-Hill, New Delhi, 1991.

12. Ghosh, P. and P. Ray, J. Mater. Sci., 26 (1991) 6104.

13. Ghosh, P., A.K. Sen and P. Ray, Polymer, 33 (1992) 744.

14. Ghosh, P., Rubber Reporter, 17 (1992) 25.

15. Mallick, P.K., Fibre Reinforced Composites, Marcel Dekker, New York, 1988.

16. Pluedemann, E.P. et al., Modern Plastics, 39 (1962) 135.

17. Clark, H.A. and E.P. Pluedemann, Modern Plastics, 40 (1963) 133.

18. Wu, S.,Polymer Interface and Adhesion, Marcel Dekker, New York, 1982.

19. Ghosh, P. and P.K. Ganguly, Plastics, Rubbers and Composites—Processing and
Application, 20 (1993) 171.

20. Jang, B.Z., Composite Sci. Technol., 44 (1992) 333.

21. Ghosh, P. and N.R. Bose, J. Mater. Sci., 20 (1991) 4759.

22. Ghosh, P. and N.R. Bose, J. Appl. Polym. Sci., 58 (1995) 2117.

23. Jinen, E., Composite Sci. Technol., 33 (1988) 19.

24. Ide., S., T. Takahashi and A. Shimamoto in Controlled Interphases in Composite

Materials, H. Ishida Ed., Elsevier, London, 1990.

25. Kardos, J.I., In Molecular Characteristics of Composite Interfaces, H. Ishida and

G. Kumer Ed., Polymer Sci. and Tech. Series, Plenum Press, New York, 1985,
Vol. 27.
26. Nielsen, L.E. and R.F Landel, Mechanical Properties of Polymers and
Composites, 2nd Ed., Marcel Dekker, New York 1994, 131.

27. Ghosh, P. et al., J. Appl. Polym. Sci., 64 (1997) 2467.

Citation
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Dr Premamoy Ghosh, Ph.D.: Polymer Science and Technology: Plastics, Rubbers,
Blends and Composites, Third Edition. Polymer Blends and Composites, Chapter
(McGraw-Hill Professional, 2011), AccessEngineering

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