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Polymer blends are also commonly termed as polyblends and they may be of the
following different kinds:
i. Mechanical polyblends,
v. 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.
It has been commonly observed that for a miscible polyblend, the following
arithmetical semiempirical rule4, 5 is obeyed by different physical properties:
(11.1)
(11.2)
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,
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.
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.
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.
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
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
A. Crystalline
PP 148 82 85 50
B. Amorphous
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.
Heat Stiffness
Nature of Tensile Flexural
distortion ratio
reinforcing strength modulus
temperature (Anisotropy
additive (MPa) (GPa)
(°C) Index)
Table 11.3. Properties of some materials; fibres, metals and alloys and
composites
Continuous
Short fibre
Matrix used No fibre length fibre
(30%)
(65%)
PP " 30 85 350
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.
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.
11.8. References
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.
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.
13. Ghosh, P., A.K. Sen and P. Ray, Polymer, 33 (1992) 744.
15. Mallick, P.K., Fibre Reinforced Composites, Marcel Dekker, New York, 1988.
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.
22. Ghosh, P. and N.R. Bose, J. Appl. Polym. Sci., 58 (1995) 2117.
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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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