08 Chapter1

CHAPTER
--
zi part of tfik cfiapter fias 6een communicate6 to:

JOo/jv?ierEngineerrigKeviews
1.1
Introductory remarks
rogress in the field of materials science and technology has given birth to
fascinating and wonderful materials known as coniposites. A composite
is a substa~lccthat is ma~lcup of a combination of two or morc different ~naterials. A composite n~atcrial can provide superior and tlniclue nicchanical and physical properties because it combines the most desirable properties of its constituents while suppressing their least desirable properties. Tlie opportunity to develop superior products for aerospace, autonlotive and recreational applications has sustained the interest in advanced composites. Curt-cntly co~uyositcs arc being considereel on n bronelcr basis-for applications that include civil engineering structures such as bridges and freeway pillar reinforcement and for biomedical products, sucll as prosthetic devices. Coniposite nlaterials usually consist of synthetic fibres entbedded within a matrix -a material that surrounds and is tightly bound to the fibres. 'I'he most wiciely used type of coniposite material is polymer matrix composites (PMCs). I'MCs consist of fibres made of a ceramic material such as carbon or glass embedded in a plastic matrix. l'ypically, the fibres make up by about 60 percent of a polymer 111atrix con~posite volume. Metal matrices or crrat~~ic itliill.iccs cat1 be substitulrd fol- the plastic miitrix to proviclcb tiiore
-
Chapter 1 General lntroduct~on
specialised composite systcnis called metal matrix composites (MMCs) and ceramic matrix conl posites (CMCs), respectively. The fibrous reinforcing coilstituent of composites may cotwist of thin continuous fibres or relatively sliort fibre segments. When using short fibre segnlelits, fibrcs with a high aspect ratio (length-to-diameter ratio) are used. Continuous-fibre reinforced composites are generally required for high performance structural applications. 'Ihe specific strength (strength-to-density ratio) and specific stiffness (elastic modulus-to-density ratio) of continuous carbon fibre reinforced conlposites can be superior to conventional metal alloys. Composites can also have other attractive properties, such as high tlierrrial or electrical conductivity and a low coefficient of thermal expansion. Also, depending on how the fibres are oriented or interwoven within the niatriu, cotiipositcs can bc fabricated into products that have structural properties sprcifirally tailored for a particular use. Although composite materials have certain advantages over
conventional materials, they have some disadvantages also. PMCs and other composite materials tend to be higldy anisotropic, i.e., their strength, stiffness and other engineering properties are different depending on the orientation of the composite material. These anisotropic properties pose a significant
challenge for the designer who uses composite materials in structures that place multidirectional forces on the structural members. Also, forming strong connections between separate coniposite material comgonents is difficult. 'I'lie broader use of advanced composites is inhibited by high manufacturing costs and labour-intensive problems. Elowever, as improved manufacturing techniques are developed, it will become possible to produce composite materials at higher volumes and at a lower cost than that is now possible, acct,lerating the wider exploitation of these materials.
Chapter 1: General Introduction
1.2
Classification of composites According t o tlie reinforcement used, composites are classified into
particulate, fibrous, laminate and hybrid composites' (Figure 1.1).
COMPOSITES
FIBROUS
PARTICULATE LAMINATE
HIRID
F u r 1.1.
Clnssificafiorr of conrposites
1.2. I Particulate reinforcement:
Particulate
fillers are employed
to iliiprove high-temperature
performance, reduce friction, increase wear resistance, iniprove machinability and reduce shrinkage'. In many cases, particulate fillers are used to reduce cost and as such their study is outside the scope of the present work. Under these conditions the additive is a filler, whereas when a considerable change in properties of the coniposite occurs, the additive is a reinforcc~nent. As a long dimension discourages the growth of incipient cracks normal to the reinforcement in a brittle matrix, a particle does not unprove the fracture toughness of such a matrix. The exception to this rule is when a rubber like substance is ciispersed in a brittle matrix. Uncier these conditions, considerable toughening occurs and this method is standard for improving tlie impact bel~aviourof thernioplastics. 'l'ypical exaniples are high-impact polystyrene and ABS. The particles wiU also share the load with the matrix, but to a le5ser extent than a fibre. A particulate reinforcer will, therefore, improve stiffnr,ss but will not generally strengthen. Ilard particles in a brittle matrix w~llcause locnlised stress concentrations in tlie matrix, which will reduce the overall impact strength.
Chapter 1 General lntroduct~on
1.2.2 Fibrous reinforcement
Fibre reinto~rrnlent represents a physical rather than a chemical means of changing a material to suit various engineering applications4, i.e.,far cheaper than rrdrsigning polymers by a chemical route. 'The measured strength of most materials is much less than that predicted by theory because flaws in the form of cracks perpendicular to the applied load are present in bulk materials. Fibres of non-polymeric materials have much higher longitudinal strengths in this form because the large flaws are not generally present in such small cross-sectional areas. However, these sn~all cross-sectional areas d o not permit the use of fibres alone in engineering applications. In the case of polymeric materials, such as Kevlar, the
orientation of the polymeric molecules along the long dimension produces model of a fibrous strength in that direction. Figure 1.2 shows the schen~atic con1positc?.
Matrix
Fibre
Figure 1.2. EIentertts o art idealised sliortfibre cor~rposite f
The fibres dispersed in the matrix may be confinuous, in which, it is easy to inlagine how the matrix transfers the load to them, or they may be short. In the latter case, the fibres must be of sufficient length to have the load transferred to them efficiently. 'Ihe fibre lengths are in the range of 0.125-0.5 cm. These short fibre reinforced elastomer co~npositeshave paramount
importance in replacing MMCs in applications requiring a combination of strength and lightness.
Chapter 1 General Introduction
1.2.3 Laminates
A laminate is fabricated by stacking a number of laminas in the
thickness (z) direction.* Figure 1.3 shows the schematic model of a laminate composite.
Figure 1.3. Sckenlatic nrodel o f a lnnrirrate conylosite
Generally, these layers are arranged alternatively for the better bonding between reinforcement and the polynier matrix. e.g. plywood, paper. These laminates can have uni- or bi-directional orientation of the libre reinforcement according to the end use of the composite. The different types of composite laminates are unidirectional, angle-ply, cross-ply and sym~iietric laminates. A hybrid laminate can also be fabricated by the use of different constituent materials or of the same material with different reinforcing pattern. I11 most of the applications of laminate composites, man-made fibres are used due to their good conibination of physico-mccha~iicalarid thermal behaviour.
1.2.4 Hybrid composites
Composite materials incorporated with two or more different types of fibres in a single matrix are comnionly known as hybrid composites'. By hybridisation, a new material with a new structure can be fabricated from the two or more component materials. The hybrid niaterial will retain all the advantages of its constituents. 'lhere are different types of liybricl coniposites, classified accordilig to the way ui which the component tnaterials are
Chapter 1: General Introdunion
incorporated. The following Figure 1.4 shows the schematic model of a hybrid composite.
Carbon Glass Carbon
Figure 1.4.
Sclterrralic rtrodel o a Itybrid laminate corrrpossile corrlrrirrirrg cnrborr f nrrcl glrrssjibres
llybricis are designated as (a) sandwich type (b) interply (c) intraply and (d) intimately mixed*. The sandwich hybrids, also known as coreshell are those in which one material is sandwiched between two layers of another whereas in inter ply, alternate layers of the two or more materials are stacked in regular manner. Tows of two or more constituents are arranged in a regular or randoni manner in intraply hybrids while in intimately mixed type, these constituents are made to mix as much as possible so that no concentration of either type are present ui the composite material.
1.3
Component materials
?'he component materials of a fibrous composite are fibre and matrix, ofcourse the interface comes between them.
1.3.1 Fibres
Fibres have a fine hair like structure, of aninial, vegetable, mineral, or synthetic origin'. Coniniercially available fibres have diameters ranging from less than 0.004 nlm to 0.2 mni and they collie in different fornis: short fibres (known as staple, or chopped), continuous single fibres (monofilament),
untwisted bundles of continuous filaments (tow) and twisted bundles of continuous filaments (yarn). Fibres are classified according to their origin and chemical s t r u c t ~ r e . ~ They can be braided into ropes and cordage, made into felts (also called non wovens), woven or knitted into textile fabrics, or, in the case of high-strength fibres, used as reinforcements in composites- that is, products made of two or more different materials. Fibres are broadly classified into two types, as natural and manmade. These two categories are further classified as shown in Figure 1.5. Natural fibres are classified into three major types as: (1)animal fibres, (2) vegetable fibres and (3) mineral fibres.
NATURAL
r
MANMADE Figure 1.5. General classijicatiorr oljibres
-.
VEGETABLE
<
m, .:,E /+
SYNTHETIC
ANIMAL
(a)
Animal fibres 1\11 animal fibres are c o n ~ ~ l e x proteins'. 'lhey are resistant to most
organic acids and to certain powerful mineral acids. 'l'he protein fibres can be damaged by mild alkalis and but, can be dissolved by strong alkalies such as NaOEl. Cldorine-based bleaches can also damage them and undiluted liquid
hypochloride bleach will dissolve wool or silk.
The classification and
properties of animal fibres are explained below (Figure 1.6).'
ANlvWL FIBRES
SILK
IWR
FUR
Figure 1.6. (i) Silk fibres
Classi'cafion o animalfibres f
The protein fibroin is the principal component of silk fibre'.
These
fibres are extruded in continuous filaments from the abdomens of various insects and spiders. It is the only natural filament that commonly reaches a length of more than 1000m. The natural silk used in commercial textiles is produced from the cocoons of the silkworm. Several silk filaments can be gathered to produce textile yarn and staple form is used to manufacture spun yarns. (ii)
Hair fibres
The protein keratin is the principal component of hair fibres. These
hairs may be as long as ninety-one cm. but are usually no more than forty-one cm. The fibres of hair and wool are not continuous and must be spun into yarn if they are to be woven or knitted into textile fabrics, or made into felt.
Hair fibres are marketed as wool or camel's hair.

(iii)
Woolfibres
The principal hair fibre used to produce textile fabrics is sheep's wool.
It also contains the component protein-keratin. The wild sheep's wool is short, where the soft under layer is protected by longer, coarser hair. But the wool is much longer in the case of domesticated sheep. Yarns made of wool are classified as either woolen or worsted. Longer fibres are used for the
smoother and firmer worsted yarns. Naturally crimped wool fibres produce air-trapping yarns that are used for insulating materials.
I'he protein keratin is the principal component of fur fibres. 'l'he fibres from animals such as mink and beavers are sometimes blended with other hairs t~ spin luxury yarns but are most often found as fur pelts.3 Horsehair and cow's hairs are used for felts and can be used to spun as yarn, particularly for upholstery and other applications for which durability is important. Even human hair has been spun into yarn and used for textiles. Other sources include hairs of camels, alpacas, guanacos, vicunas, rabbits, reindeer, angora goats and cashmere goats.
(b)
Vegetable fibres These fibres predominantly contain cellulose, which resists alkalies and
most of the organic acids, but can be destroyed by strong mineral acids. Now a days, the paper making industry uses vegetable fibres extensively. Cotton, flax, grasses, hemp and jute are used i the industry for making papers. ?he n newsprint and kraft papers are produced from wood fibre after appropriate chemical treatment. Wood fibre and bagasse (the fibre of sugarcane) are made into building board materials. The basic classification of vegetable fibres are shown below.3
VEGETABLE FIBRES
SEFD Figure 1.7.
7 FRUIT
Clossificnriorl of vegefnblejibres
Chapter 1 General Intoduction
10
I
.
.\ .. .~
(i)
Seedfibres
, . ..? I
;. .:\
c,,. , , ,
r'
; :.
)J
The soft hairs that surround the seeds of certain plan&
..',\
/;,,
e termed as
,. : .. /
.'-.i >.
,.
seed fibres, e.g., cotton and kapok. Cotton fibre is useful for the:manufacture of textiles. 'lhe different species of cotton plants produce fibres of different lengths. ?he long-staple fibres are spun into fine, strong yarns, which are then woven into betterquality fabrics while the short ones produce coarser yarns for durable fabrics. Cotton fibres can be dyed and printed easily to produce woven fabrics with a multitude of colours and designs. Kapok fibres are used in upholstery stuffing. Kapok is buoyant due to its hollow nature, which helped its use in flotation devices such as life preservers
(ii)
Bastfibres
These are the tough fibres that grow between the bark and stem of
many dicotyledonous plants. 'l'he different types of bast fibres are used in applications ranging from fine woven textiles to cordage. Linen cloth is made from flax. Coarser clothes and rope are produced from hemp, jute, ramie and sun hemp.
(iii)
Vascrrlar (grass-stenr) fibres

Vascular fibres are found in the leaves and stems of monocotyledons.
They include agave (sisal), henequen, manila hemp, pineapple and yucca. Entire stems of some grasses and straws, such as esparto, are woven as fibres for hats and matting. F1'hesefibres are used almost exclusively for making cordage and often used in textile industries.
These fibre types of limited utility, include strips of leaf skins, such as raffia; the fibre of fruit cases, such as coir; and palm fibres. The different species of coconut and palm plants produce fibres of different lengths. Coir and palm fibres can be dyed and printed easily to produce woven fabrics with
Chapter 1: General lnboduction
II
a multitude of colours and designs. The basic properties of vegetable fibres are given in 'I'able 1.1. Table I . I. I'rcqx-rlic,s Rfecharcicalproperlies of diJj2erenl vegetablefibres
-GiGFq - BSI:' -P A I ~ F ~- CI:F2 - ~ 1 . ~ 4

80-250 1.35 65 100460 1.15 43 0.15-0.25 45 20-80 1.44 100-200
I .45
~..
Diameter (prn) Density (g/cm3) Cellulose (%) HemiceUulose (%) Lignin (%)
150-250 1.51 65
81
78
'1 2
12
19
~~~~~~
12
Elastic modulus (GPa)
8-20
4-6
43 - 81
9-20 3-7 15
10-22
1 Elongation(%)
1-. 0.8 - 1.6 135

30
2-4 14 20 42 240-650
) Cost (Rs/Kg)
blicrci-fibrillar a11f;Ir
25 14-18 413-1627
4Sisal
(degrees) Tenacity (MN/m')
'Banana stem fibre, V o i r fruit fibre, bunch fibre
1 52:159 1
1
3'49 131-175
568-640
Tineapple leaf fibre,
leaf fibre, Wil
palm fruit
Source: Ref. I .
(c)
Mineral fibres
Glass fibre is the inorganic mineral fibre made kom silica sand, which is used in co~nmercialapplications.2 There are twd types of glass fibres: continuous and staple. The continuous glass fibre is made by drawing molten glass into threads, is used in textile materials. These fibres can be fabricated into mats or bulk-moulding and sheet-moulding compounds with the use of resins or organic binders. Quartz mineral is high-silica, high-purity glass that
is good for long-term use at temperatures as high as 1400" C. The basic

characteristics of glass fibres are given in Table 1.2.
12
Ceramic fibres such as aluminium oxide (Al203), silicon carbide (Sic) and boron carbide have been developed for heat-resistant composite materials2. The components of helicopters, military aircraft, civil aircraft, missiles and spacecraft including satellites and space shuttles, are made from these high-strength, lightweight composites. ceramic fibres are given in 'Table 1.2. (iii) Asbestosfibres These fibres are formerly used for insulation and fireproofing.3 Thin metal wires are used for the production of wire gauze. Chrysotile, the most common type represents more than 95% of world's asbestos production. Fibres coated with plastics possess a bright glitter and can be used in decorative yarns. They are found to be carcinogenic and are no longer used. I h e properties of these fibres are depicted in Table 1.2. The physical properties of
(d)
Synthetic fibres
Synthetic fibres developed from natural cellulose are known as rayons. Natural cellulose made from wood pulp is treated with chemicals to form a thick liquid. This liquid is then extruded as filaments into a weak acid bath that converts the filaments back into pure cellulose. Rayons come also under the category of regenerated fibres. Synthetic fibres such as acetates and triacetates are developed from cellulose acetate like rayon process.
Chapter 1: General lnhoduction
13
.l'he libres, which are derived from organic polymers are termed as organic synthetic fibres,3 e.g., nylon (polyamide), acrylic (polyacrylonitrile), aramid (aromatic polyamicie), olefins (PE and PP) etc. thermoplastic-i.e., Most of them are
they are softened by heat. During processing, a molten
polymer or polymer solution is extruded through tiny holes in a spinneret into an environment that causes the filaments to solidify. 'Ihe properties of these fibres depend on the base polymer, the spinning process and the postspinning treatment of the fibre, which can include drawing, annealing, applying a finish and coating. Fibre properties such as weight, abrasion resistance, heat resistance, chemical resistance, moisture resistance, strength, stiffness, elasticity and ease of dyeing and colouring can be optimised by such treatments. High-strength fibres such as aramid and polyethylene are also used in armour applications such as bullet-resistant garments, car doors and crew seats for military helicopters and aircraft.
Carbon and graphite fibres are high-strength materials that are used as reinforcing agents in composites.2 Chemically, carbon fibres are produced from rayon or acrylic fibre by thermal heating. Carbonisation occurs at temperatures of 1000 to 2500C in an inert atmosphere. Carbon fibres are converted to graphite at temperatures above 2500C. They can also be made from pitch, a residual petroleum product. The products that use carbon fibres include heat-shielding materials, aircraft fuelage and wings, spacecraft structures and sports equipment. The properties of some of the synthetic and mineral fibres are reported in Table 1.2.
14
r I
-
Table 1.2.
Mecltanicalpropertiesofmineral and syrtflteficfibres .. . Properties
Nylon 66 Kevlar 49
1.14 1.45 3.62 131 2.8
Carbon
1.76
3.20
228
1.4
iource: Ref. 2
1.3.2
Matrices
The classification of matrices of a composite is shown below:'
POL'IF/IERS
Polymers
CERAMICS
METALS
Figure 1.8. Clnssi~cafionf matrices. o
Polymers can be subdivided into three structural groups. They are linear, branched or crosslinked polymers."inear polymers consist of
nlolecules of long chaips of repeating units joined by bonds that are rigid to a certain degree- the monomers cannot rotate freely with respect to each other,
Chapter 1: General Intodudion
15
e.g., PE, PVA and PVC. ?'he number of repeating units in one large molecule
is called the degree of polymerisation. Materials with a very high degree of
polymerisation are called high polymers. Polymers consisting of only one

kind of repeating unit are called homopolymers. Copolymers are formed
from several different repeating units.

(i)
Structure o polymers f
Structure of different types of polymer are presented in Figure 1.9.4

-R-R-R-R-R-R-R-S-R-S-S-R-S-R-R-R-S-5-
Linear polymer
R
R
Random copolymer
-A-A-A-A-A-A-A-R-A-A-R-R-AI
R
-R-S-S-S-S-R-R-R-R-S-S-S-S-
Block copolymer
I R
Branched polymer
5 5 I
I
5
S
R-R-R-R-R I I
FFR-R-R-FR-kbCR-
I
-R-R-R-R-R-R-R-R-R-R-P-
R I
5 I
5 5
,
r
Crosslinked polymer
Graft copolymer
i
e 1.9.
Slruclures o d$fereni types o polymers f f
'Ihe above figure shows the polymer structure where R and S are the monomeric units5. Branched polymers have side chains that are attached to the chain molecule itself. The branching can be caused by impurities or by the presence of monomers that have several reactive groups.
Chapter 1: General Intoduction
16
In crosslinked polymers, two or more chains are joined together by

s side chains. With a small degree of crosslinking, a loose network i obtained
that is essentially two-dimensional. High degree of crosslinking result in a tight three-dimensional structure. Crosslinking is usually caused by chemical reactions, e.g., vulcanized rubber has a three-dimensional crosslinked structure, in which crosslinks are formed by sulphur atoms. Another example for highly crosslinked polymers is thermosetting plastics.
(a)
Plastics Organic polymeric materials consisting of giant organic molecules,
which can be formed into desired shapes through extrusion, moulding, casting, or spinning are termed as plastics. The molecules can be either natural- including cellulose and wax or synthetic -including polyethylene and nylon. [he stxting materials are resins in the form o f pcllets, powders, or solutions from these are formed the finished plastics. Basically, plastics are divided into two based on their structure and thermal behaviour. They are thermoplastics and thermosetting plastics'. l'he important properties of
plastic composite matrices are shown in Table 1.3.

Mecharticalyroperties of plastic composite matrices 'Thermosets -Thermoplastics . Properties Epoxy Polyimide I ' o l y s u l p h o n T F k ~ ~ Tensile modulus (GPa) 1 2.8 - 4.2 3.2 1 2.5 i 3.9 1 Tensile strength (hll'a) Table 1.3.
-.
~
. ~~. - - - - -~
. . .~.. ~
1.15-1.2 45-65
. .. . --- -
1.43
.. ..
1.24
'1.32
I'hermal expansion coefficient, loh per .C llermal conductivity,

W (mK)'
50
0.36
~-. 370 ~ . ~.
47 0.25
0.17-0.21
Source: Ref. 3
b,~ F)
- . -
~~~~
185
144
~
17
The techniques used for shaping and finishing plastics depend on three factors, (i) time, (ii) temperature and (iii) flow.1 Many of the processes are cyclic in nature, although some fall into the categories of continuous or semi-continuous operation. The different types of moulding techniques are given in Figure I . 1 U .
Compnssian Coldpnss cold itamping &ss nwuldimg

h j r s livrt
' i
kaciien injection Reinfnmed reaction injection Resin -6er
Pmrsure bag
Braiding
Figure 1.10. Moulding techniques

An extruder is a device that pumps a plastic through a desired die or
shape. Extrusion products, such as pipes, have a regularly shaped crosssection. The extruder itself also serves as the means to cany out other operations, such as blow moulding and injection moulding. In extrusion blow moulding, the extruder fills the mould with a tube, which is then cut off and clamped to form a hollow shape called a parison. 'I'his hot, moltcn parison is then blown like a balloon and forced against the walls of the mould to form the desired shape. In injection moulding, one or more extruders are used with reciprocating screws that move forward to inject the melt and then retract to take on new molten.materia1 to continue the process. In injection blow
18
moulding, which is used in making bottles for carbonated beverages, the parison is first injection moulded and then reheated and blown. Compression moulding uses pressure to force the plastic into a given shape. Another process, transfer moulding, is a hybrid of injection and compression moulding. Here, the molten plastic is forced by a ram into the mould. Other finisling processes include calendering, in which plastic sheets are formed and sheet forming, in which the plastic sheets are formed into a desired shape. Some plastics, particularly those with very high temperature resistance, require special fabrication procedures, e.g., teflon.
(b)
Rubbers Rubber is a material, which is capable of recovering from large elastic
deformations quickly and forcibly, i.e., they can be stretched rapidly to very high elongation and they return to their original shape in a reversible way.5 Different types of elastomers are illusbated below.
Natural rubber is a high-molecular-weight polymer of isoprene, in which essentially all the isoprenes have the cis-l,4 configuration. In its very natural state, rubber exists as a colloidal suspension in the latex of rubberproducing plants- Hevea brasiliensis. The chemical formula of-natural rubber
is shown in Figure 1.11.
4 2
',El,
Figure I . 11. Structural formula of natural rubber
19
The analysis on natural rubber has shown that it contains the following components ('lhble 1.4).6
Ihble 1.4.
Ai&sis
of iralural rubber
I
1 Rubber hydrocarbon
1 Protein
Acetone extract Moisture
I 1
I
1 1
93.3
2.8
2.9
0.6
AS^
Source: Ref. 4
Latex is a polymer dispersed in water, which contains a white complex emulsion composed of varying proportions of gums, resins, tannins, alkaloids, proteins, starches, sugars and oils.6
Synthetic rubbers have become necessary materials in rubber goods manufacturing industry. Any synthetic polymeric substance that exhibits the properties of rubber, especially its elasticity and flexibility at room temperahue are termed as elastomers.
(i)
Types ofsynthetic rubbers

There are two broad classes of synthetic rubbers. These are:
(a) general purpose synthetic rubbers and rubbers.
(b) spycia1 purpose synthetic
(a)
Ger~eral pltr-pose syr~tiletic ruhhcrs (GPSRs)

The following are the important GPSRs listed under.
SBR (styrei~e-hutadie?re rubber):
It is a co-polymer of styrene and butadiene.
Butadiene is a gas, which boils at 50C. It is manufactured from petroleum products in most modern petrochemical plants. In most plants, butadienes are
20
produced by dehydrogenation at elevated temperature in presence of catalyst (Chromia-Alumina). Styrene is retained by dehydrogenating ethyl benzene obtained from benzene and ethylene in presence of AICb , by Friedel-Craft's reaction. Ethyl benzene so obtained is dehydrogented by Chromia-Alumina catalyst. 'I'he structural formula of styrene-butadiene copolymer is depicted in Figure 1.12.h
Figure 1.12. S~ructuralforn~ula styrene-butadiene rubber (SBR) o f
Polymerisation of styrene and butadiene is carried out in the ratio of 1:3 for yroducil~g SIjI<. I'olymerisation can be carried out cithcr in solution media or in aqueous emulsion of the monomers. Cold or hot conditions can also be selected for polymerisation depending on the recipe. A mutual recipe for making SBR at 50C is presented in Table 1.5.
Mutual recipe -
Parts by w e i g h t -
1 Styrene I Butadiene
Water
~
1 I
. -~
~ ~ ~ ~
25 75
180
~
j I 1
1
....
.....-
~~-
Fatty acid soap

.~
-
.~
5
0.50
.~
Lauryl mcrcnptan persulfate

Source: Ref. 6
SBR is now available in various tailor made forms like oil extended, carbon black filled etc. Different companies designate their products by different numbers. l'he International Institute for synthetic rubber producers
Chapter 1: General Introdunion
21
is now responsible for giving different numbers. SBR-1500 series is a cold polymer type and its properties are comparable to those of NR in many respects. In some properties like heat build up, tackiness, etc. SBR has inferior properties to those of NIZ. It is marketed generally at lower viscosity than NR and this permits its use in industry without premastication. Tendency to scorch is less in SBR when compared with that of NR. It has no good gum tensile strength unlike NR. But addition of reinforcing fillers adequately improves this property of the rubber. Abrasion resistance and resistance to degradation under heat are better for SBR than those of NR. SBR is slower curing than NR. So the content of accelerators in SBR compounding is generally more. The unsaturation of SBR is less active
chemically than that in the isoprenoid NR. The active methylene groups to the double bond in NR molecules are also instrumental in effecting more rapid cure especially in the presence of air. Hence scorch problems are less likely with SBR than with NlZ, especially in compounds containing furnace blacks. SBR can be used successfully in production of passenger car tyres, wires and cables, shoe soles and extruded goods.
BR (Polyh~itudiriu rubber): Polybutadiene is a homopolymer of butadiene

monomer. BR is cis-1,4-polybutadiene. Butadiene can be polymerised to form three other polymers also, which are not having industrial importance of the same order as that of BIZ. Both solution and emulsion polymerisation methods are used for commercial production. BR is prepared also as oil extended and black fi1led.h
BR is processed along with NR or SBR as it is a high molecular weight

product. BK has very good low temperature properties. It retains its
rubberiness for a wide range of temperature. As the trans content in the polymer increases, tendency for crystallisation also increases. BR has high air permeability, low heat build up, high resilience, better flex resistance, heat stability, etc. I'lus rubber is compatible in all proportions with NR, SBlZ and
22
neoprene. Cis-polybutadiene is used along with NR, in the ratio of 25:75. Higher proportions of I3R are also used in certain blends. Polybutadiene is mainly used in truck tyre treads because of its high resilience and low heat build up. Tyre treads designed with polybutadiene gives improved tread wear and reduced groove cracking. It is also used in manufacture of
mechanical goods and as modifier for plastics to improve impact resistance.
Ethylene propvlette rubbers (EPM/EPDM): Ethylene propylene rubbers are now

available in two types, EPM - the ethylene propylene co-polymers and EPDM
- the ethylene propylene diene monomers.6 The raw materials required in the
industry are ethylene, propylene and catalysts. The alternating distribution of monomers in the EPM and EPDM rubbers provide most amorphous or least crystalline rubber. In EPDM, a small amount of diene is used along with ethylene and propylene at the time of polymerisation. The unsaturated groups of such terpolymers occur as ligand groups in the polymer. Since unsaturation is thus occurring as ligand groups oxidation of residual unsaturation of the polymer will not affect properties of EPDM rubbers. This unsaturation is introduced in ethylene propylene rubbers to make it sulphur curable. ?'he cyclic dienes commonly used for polymerisation is dicyclopentadiene and its derivatives. The amount of unsaturation present in EPDM is in the range of 0.6 to 1.0 mole percent diene. These rubbers have a remarkable resistance to ozone and UV radiation. The combu~ation weather resistance, excellent electrical properties and the of ability to be cured rapidly with peroxide have made use of this rubber in production of good quality electrical cables. The outstanding weather
resistance provided by ethylene propylene rubbers is made use of in production of wind screen channels and window gaskets of automobiles. It i s
Chapter 1: General Intodudion
23
also used in production of seals of side door windows. EIJDM is a good material in production of radiator hoses. 13ousehold washing machine drain hose made of EPDM gives long service life and good resistance to damage by hot water detergent solutions.
lR(Po1visoprette rubber): In general, this rubber can be used in areas where NR

is used due to the inherent tack, high gum strength, good hysteresis, good hot tear and tensile properties. It is manufactured by solution polymerisation techniques.
IlR (Isobutyletre isoprene rubber-(butyl rubber)): Butyl rubber is prepared by

copolymerization of isobutylene with butadiene or isoprene. Chemical
m~thods and spectroscopy have revealed that mainly 1-4, addition is taking place in this polymerisation. Isoprene is also obtained from another source of petroleum cracking through an extractive distillation with aqueous acetone followed by distillation. Butyl rubber is not as resilient as natural rubber and other synthetics, it is extremely resistant to oxidation and the action of corrosive chemicals. Drcause of its low permeability to gas, butyl rubber is useci wiclely for inner tubes in automobile tyres. These rubbers have good heat, chemical, ozone and weather, abrasion resistance, low gas permeability and are non staining and non-discolouring.
(b)
Specinl purpose syntlzetic elnstotners

These types of rubbers are used in specific applications which require
solvent resistance, fire resistance and resistance to temperature.7
These
include chloroprene rubbers, chlorosulphanated polyethylene rubbers, nitrile rubbers, polyacrylic rubbers, fluorocarbon rubbers, silicon rubbers,
polyurethane rubbers, polyether rubbers and polysulphide rubbers.
24
1.4
Fibre reinforced rubber composites
The rubber composites are classified into four types. The classification is shown below:'
composites
composites
composites
fibre composites
Figure 1.13. Classification o rubber composites f
1.4.1 Cellulose fibre reinforced rubber composites
Short cellulose fibres have been found to provide good reinforcement to the vulcanizates. The two advantages reported are their resistance to breakage during mixing and their rough surface, which can give rise to good bonding. Coodloe
ct
01.8
have used finely divided wood cellulose for
reinforcement in rubber.
Ihis is the earliest reported research work in the
field of cellulose fibre reinforcement. Hamed and Corany have reported that unregenerated wood cellulose fibres are highly reinforcing material for rubbers. Anthoine et nl.1" have reviewed the reinforcement of elastomers with discontinuous cellulose fibres. He has also reported the advantages of Santoweb D in reducing the die swell and in improving green strength. R Monsanto Co. owns a patent on discontinuous fibre reinforcement of rubber in which the advantages of using short fibres and in particular cellulose fibres have been discussed.
11 '2
In a preliminary report'', t3oustany and co-workers
have reported the advantages of treated, unregeneratrd cellulose fibres, called Santoweb". Cellulose f~bres have been found to provide good green strength and low die swell Thus the curing of these composites in an autoclave or by continuous vulcanization without much loss of dimensional stability becomes possible. While studying the flexing, swelling and extrudability of Santoweb HRfibres
25
in oil extended EPDM rubbers, Rahman and Hepburn" reported that flexing resistance reaches a maximum at 10 phr loading. It is reported that 20 phr loading of Santoweb ItRis optimum for the technical properties studied. ?he properties of diCfcrcnt types of crllulose fibrcs and their n~echanisni of reinforcement have been analysed by Goetler et a1.15 Ue and co-worhersl& 19have extensively studied the reinforcement of natural fibres with rubber matrices. Recently, Thomas and coworkers2n22 have carried out systematic studies on the reinforcement of short fibres with natural rubber and other elastomer matrices. 'lhe studies on the short sisal fibre reinforced natural rubber composites have been reported by Varghese et O[.~U.Geethamma et al.zlhave analysed the reinforcement of natural rubber with short coir fibres. Recently, Prasantha Kumar e t a1.22 have studied the mechanical properties of short fibre reinforced elaslonler con~yosites.
1.4.2 Glass fibre reinforced composites
Because of their high potentiality as reinforcing agents for plastics, their suitability for rubber reinforcement has been extensively studied. Lueers2Qas reviewed the glass fibre reinforcement. But the main
disadvantage faced is its breakage during mixing. Czarnechi and White?+eported the mechanism of glass fibre breakage and severity of breakage with time of mixing. They have observed that not I ,~ I with the only tlir fib~i. c I ~ ~butIalso the clistributiori of fibre Ir1igt11cliC~tiges time of mixing. 'I he fibre-matrix adhesion is also poor but can be improved by pretreatment of thc fibre. I)erringer?5has reported the advantages of short glass fibre reinforced rubber composites, which include high modulus, high resilience and low creep. Comparing the properties of vulcanizates reinforced with various types of short fibres, Monceau26 reported that glass fibres have a ~narkedlylower ri3inforcing capability than that of cellulose fibres but can
26
undergo higher elongations. In a patent to PI'G Inds27, it was reported that preirnpregnated glass fibres gave better reinforcement to rubbers.
1.4.3 Asbestos fibre reinforced composites
Asbestos fibres as reinforcing elements for rubber have been studied by Brokenbrow et
~1.2"
Bament" studied the use of asbestos fibre bonded
with polychloroprene to improve the dimensional stability of roofing sheet of unvulcanized chlorosulphonated polyethylene. Because of the hazards in using them and their poor properties, they have found little potential as reinforcing elements. But a patent to General Tyres and Rubber Co. claims good properties of asbestos-rubber composites when silica, 2,2,2-trimethyl, 2',4',7-trit~ydro flavan (a resorcinol donor) and 1-azo-5-methyl 3,7-dioxo bicyclo[3,3,61 octane (a methylene donor) are used as bonding agents.
1.4.4 Miscellaneous fibre reinforced composites
Aramid fibres have also been used to reinforcing rubber4". O'Connor?' has reported the high strength of aramid fibre composites. ?he high strength is n~ainlydue to the high fibre strength itself. ?he breakage resistance is reported to be better than that of glass fibres. Bagasse fibre reinforcement has been studied by Usmani et attention.
~1.3'.
Recently, carbon fibres are drawing good
llut thrir use is liniitcd due to their high, cost. Sieron'? have
observed that these fibres improve tensile properties in fluoro elastomers. Ecersley'J has also discussed the use of carbon fibre reinforcement. The applications of these fibres generally lie with the abrasion resistant composites. Grintbladt et
a1.35
have reported their effect on increasing the
strength, ageing resistance and resistance to con~pressionset of fluorine containing rubbers. Lewitt36 has reported recently the effect of carbon fibres on the properties of rubber vulcanizates. A new teclmology for developing
Chapter 1: General lntroduct~on
27
polytetrafluoro-ethylene fibrils in a rubber stock during compounding was

reported by Leonard'7.
1.5
Factors affecting the properties of the composite
By controlling the factors like the aspect ratio, orientation of fibres and by establishing a high degree of fibre dispersion and fibre-matrix adhesion, reasonably better rubber products can be fabricated using short fibres. The rubber compounds containing short fibres have been found to possess good dimensional stability and higher green strength. Several factors determine the properties of short fibre reinforced rubber composite. These include mixing, dispersion, fibre breakage and critical fibre length38.
1.5.1 Mixing of rubber compounds
The conventional mixers like Banbury and open mixing mill can be utilized for mixing short fibres with elastomers as described by Boustany and C ~ r a n ' ~h e mixing procedure may be distributive or dispersive which is l. adopted depending on the type of the fibre used. The distributive mixing increases the randomness of spatial distribution of the minor constituent within the major base material without further size reduction, while dispersive mixing serves to reduce the agglomerate size. Thus, brittle fibres such as glass or carbon, which break severely during mixing, require more distributive mixing, but for organic fibres such as nylon & silk and natural cellulosic fibres like jute and sisal, dispersive mixing is called for since these fibres tend to agglomerate during mixing procedure. Goettler and Lambrightlo have developed a technique for
controlling fibre orientation in extrusion by the use of an expanding mandrel

Chapter 1: General Intoduction
28
die. Calendering can also achieve the same level of fibre orientation in the machine direction".
1.5.2 Dispersion of short fibres
Good dispersion of the short fibres in the rubber con~pounds an is essential requisite for high performance composites. The major factors
associated with good dispersion of fibres are (a) level of fibre-fibre interaction and (b) fibre length. The naturally occurring cellulosic fibres tend to agglomerate during mixing due to hydrogen bonding.
A pretreatment of fibres is at times
necessary to reduce fibre-fibre interactions. Such treatments include making of predispersions and formation of a soft film on the surface. In the process of forulation of soft film on the surface even the bonding agents can be incorporated in the film and hence it is slightly advantageous over making of predispersions. Natural c~llulosefibres treated either with carbon black or with compositions containing latex were found to be dispersing well in the rubber matrix?7. The homogeneous predispersions of chopped polyester, glass and rayon fibres in neoprene latex and their dispersion in neoprene rubber was studied by Leo and Johansson'2. 'i'he fibre length has also a small effect to facilitate better dispersion. Derringer" has used the commercially available fibres such as nylon, rayon, polyester and acrylic flock cut into smaller fibre lengths of 9cm for better dispersion. The better dispersion of fibres can be achieved by adding fibres first in the masticating or mixing machine.
Cha~ter General Intoduction 1:
29
1.5.3 Fibre breakage

The importance of fibre length and its influence on the properties of the composite were studied by many researchers'4-47.
In a composite material,
fibre length is a critical one and it should not be too long so that they entangle with each other causing problems of dispersions. But a very small length of fibre does not offer sufficient stress transfer from matrix to fibre. The severity of fibre breakage depends mainly on the type of the fibre and its initial aspect ratio, e.g., the fibres like glass and carbon are brittle and they possess a low bending strength than the ductile fibres such as cellulose, which are more flexible and resistant to bending. For each type of fibre, depending on its resistance to bending there exist a certain aspect ratio below which no further breakage can occur. 'I'he aspect ratio of glass fibres was very low compared to the cellulose fibres. If the mix viscosity is high, more shear will be generated during mixing and thus exceeding the critical bending stress of the fibre which eventually results in severe breakage. O'Connory has reported the fibre breakage during mixing. The lower reinforcing ability of glass fibre has been attributed to the severe reduction in their length conlpared to cellulose fibres during mixing. ?'he mechanism of fibre damage using glass, aramid (KevlarR) and cellulose fibres in polystyrene melts has been reported by Czarnecki and White'-'. Studies on the effects of mastication time and mixing, on fibre damage was reported that the extent of breakage depends on the mastication time. l h e glass fibres wrre found to undergo a clean breakage whereas the aramid fibres break forming kinks occurring at every LUU~L~I. Murthy and DeIh suggeste~l that the breakage of fibres is due to buckling effect. De et ~ 1 . 1 7 - 1 9have studied the breakage of jute and silk fibres in natural rubber, XNBR and NBR and found that the breakage of silk fibres is less than that of jute fibres.
Chapter 1 General Inhaduction
30
Critical fibre length
In a perfectly oriented unidirectional fibre composite containing fibres of uniform radius, the rate of increase of fibre. stress is proportional to the interfacial shear stress. ?he interfacial shear stress
in a fibre reinforced elastomer composite will be significantly affected by

adhesion between fibre and matrix. Moreover, fibre ends in short fibre
composite play a major role in the determination of ultimate properties. Fibre length, over which the stress transfer allows the fibre to be stressed to its maximum stress or at which a n efficient fibre reinforcement can be achieved has been used to predict the strength of the material is termed as the critical fibre length of the composite. Brouhnan and Aggarwalt4 have done a theoretical analysis on the mechanism of stress transfer between fibres of uniform radius and length. 'The matrix gave the following expression for critical fibre length (L).
where, d, the diameter, o, , the ultimate fibre strength and, 2ry , is the matrix r, yield stress in shear.
1.6
Fibre orientation
Fibre orientation as well as fibre concentration has significant influence on the physico-mechanical properties of the natural fibre reinforced polymer composites.
31
The arrangement of fibres relative to one another determiries the utility of ccmposite as a structural material. With respect to orientation, three limits are explained as longitudinal orientation (along machine direction),
transverse oricwtaiion (across machine direction) anci ranciom orientation as shown in Figure 1.14.
FigureI.14. Sclrer~rntic represerrlfltiotr of (a) ~~orrgitrldillfl~/~~ aligrred (h) trnrrs~*ersely aligrced arrd (c) rar~dorrr orientntiort offlhres irr flce slrorl Jibre reitforced corrcposifes.
Longitudinally aligned composites 'l'hc lonj;itudinally oriented compositrs a r r inherc~ntly anisotropic. Sincc the cffectivc stress transfer from the matrix to t l ~ c fibre occurs in tL1c direction of fibrr alignment, thc ninxinium strength and rcinforrr.nlr,nt of co~nposites sIic~t\.n arc here (Figurc 1.14n). Cornpositcs containing uniaxirilly oriented fihrrs hnvc sho.rvcd greatw tcnsilr strctngth, hut its coniprcssivc strength is less d ~ to the buckling of thc ~ c
Chapter 1 General lnhodlictton
32
Transversely aligned coniposites In the transversely aligned composite, the fibre reinforcement is (1:ij;ure 1.14b)". The fracture of the sample occurs at virtually non-cxistt.~~t very low tensile stresses, which niay be equal or less tlian the strength of tlie matrix. 'lhus, the trarisvcrsc compressive strength is limited by the strength of the matrix and so is less than the longitudinal compressive strengthso. Randomly oriented composites Like the word random expounds the strength of randomly oriented composite shows variable values i.e., strength lies between the limits of longitudinally and transversely aligned composites (Figure 1.14~).These types of composites can be constructed by randomly orirnting fibres in a plane or by using multilayered laminates containing different orientations of fibres. 'I'hesr arc essentially isotropic in plane, i.~,.; tliry Ii.ivc ilcsirablr~ In randoni orientation also, the
properties in all directions in a plane.
niodulus increases \vith fibre concentrationfy. Fibre orientation in cliscontinuous fibre reinforced elastomer
composites is explained by means of following factors:
(a) effect of flow
behaviour, (b) determination of fibre orientation and (c) fibre orientation distribution.
1.6.1 Effectof flow behaviour
During mixing and subsecluent processing operatioris of short fibre reinforced rlastonicr cornpusitr~s, the fibres orirnt prc~lrrcritially ill one direction and the ultimate properties of the material depend mainly on the angle between the orientation and the direction of the applied stress. Fibres orient in a direction depending cln the nature of tlie flow
convergent,
divergent, sliear or elongational. If the flow is convergent type tlic fibres
Chapter 1: General lntrodi~cton
33
align themselves in the direction of flow and away from the direction of flow
if the flow is divergent.
During shear flow, the fibre orientation can be from random to unidirectional depending on the shear rate artd if the flow is of elongational type the fibre orientation takes place mainly in the direction and the rate of fibre rotation are controlled by the magnitude and direction of velocity gradient (i.e., +ve or -ve) which will be generated by normal forces occurring
in the flow resulting from the changes in the cross-sectional area of the
channel. In a convergent flow, the flow accelerates because of a reduction in the cross-sectional area of the channel, the velocity gradient becomes positive and the fibres tend to align in the direction of flow making a small angle with flow axis. Fibre orientation during mixing waS discussed by MogheS1. The effects of mill parameters such as number of passes, nip gap and mill roll speed ratio have been studied and it
iq
found that the nip gap has a significant effect on
the fibre orientation. The maximum fibre orientation takes place in the first pass itself. But the fibre orientation is controlled by the manner in which the mix sheet is folded and sufficient care should be ensured tn obtain maximum orientation along the machine direction.
1.6.2 Determination of fibre orientation
The maximum fibre orientation takes place in the machine direction. The tearing of the uncured sheet gives the preferential orientation as the tear proceeds easily in a direction parallel to the fibre alignment. But this method does not determine the fibre orientation distribution. Nowadays, contact micro radiography uses X-rays to detect fibre orientation distribution in short fibre reinforced plastic composites. Here, the difference between the X-ray absorption coefficients of fibre and matrix must
34
be high enough to give better contrast. So this method is applicable only to certain systems. Either a transmission elecbc>n/optical (magnification is limited) microscope can be used to determine the fibre orientation. Many reserarchers?[',
" have used SEM of fracture surfaces to determine the fibre
orientation due to the ease of sample preparation. Tensile strength of composites cannot give actual fibre orientation since the fibres orient themselves under large deformations at low fibre concentration. At higher volume fraction of fibres, the deformation problem does not arise due to the low elongation at break. The modulus at small
deformation, say 5% elongation, gives a clear idea about the preferential orientation. Ilecently, I honias et
a/.*'
have evaluated the extent of orientation from
the green strength measurements by using the following equation,
where S denotes the green strength of the composite and subscripts L,T & G denote longituclinal, transverse and gum compounds respectively. 'lhc swelling in the case of short fibrc elastomer composites is anisotropic. Anisotropy is due to thc preferential orientation of fibres and it is prominent at low strains and induces only small deformations in the composites. Many scientists have explained the fibrc orientation by means of anisotropic slvelling b e h a ~ i o u r ~ ~ ~ - ' .
1.6.3 Fibre orientation distribution
When all the fibre are aligned in one direction, there will bc a distribution of fibrc oricntiltion. The ccnt per ccnt c>ricntationis vcry difficult
Chapter 1 General lnboduction
35
to achieve in the case of natural/synthetic fibres. A maximum of 60-80% of fibres will orient witllin +10 degrees to the normal alignment directionss. McNally56 have reviewed the fibre orientation distribution and its effect on the properties of the corriposites. The mechanical performance of composites is greatly influenced by the fibre alignment. Ilence a theoretical prediction can also be considered for the evaluation of fibre orientation distribution. Swelling is a uniform restrictive force imposed on the fibre-reinforced composite"". 'Ihe modulus of the
composite can be related to the angle between the fibre orientation and the direction of applied stress by an equation, 57
where I?[. and 1;r are the moduli of the composite in longitudinal and transverse orientations respectively and 0 is the angle between the fibre orientation and the direction of applied stress. Halpin Tsai's equation
predicts the modulus of a unidirectionally oriented composite. Moghesx has taken two extremes as unidirectional and random orientations in his theory. He has also stated that the modulus of a perfectly oriented composite described in 1 lalpin-'I'sai's theory is six times that of a randomly oriented composite. The construction of balanced angle ply conlposites by overlapping method with short fibre compounds is another way of obtaining isotropic composites5V. Since the design affects the performance of the composite, care should be made to consider the thickness and width. It is concluded that even in the unidirectional composites with fibres oriented around the direction of applied load under tension, the fibres also rotate due to shear.
Chapter 1. General lnbodufl~on
36
1.7
Fibre-matrix adhesion
The behaviour of a composite material is explained on the basis of the combined behaviour of the reinforcing element, polymeric matrix and the fibre-matrix interface. ?he reinforcing element should not be weakened by surface or inlernal flaws and the applied load should be effectively transferred from the matrix to the fibre through the interface. The
con1ponerits of a con~posite system are chosen on the basis of their mechanical and physical characteristics in isolation. system in thern~odynamicequilibrium. The con~positewill rarely be a The process of fabrication of a
composite involves interfacial interactions and that can cause modifications in the interface structure.
1.7.1 Bonding at the interface
'Ihe fibre-matrix adhesion is evaluated at the interface of the composites. Interface is a bounding surface where a discontinuity of some kind occurs as sharp or gradual. It is an essentially bi-dimensional region through which material parameters such as concentration of an element, crystal structure, atomic regishy, elastic modulus, density and coefficient of thermal expansion, change from one side to another. There are two types of interface bonding in fibre reinforced composites. They are explained as (1) mechanical interface bonding and (2) chemical bonding at the interface.
(a)
Mecha~~ical bonding It is a simple mechanical anchoring between ttvo surfaces, which can
lead to a considerable degree of adhesion. Moreover, any coritraction of the polymeric matrix onto the fibre would result in a gripping of the fibre by the matrix.
Chapter 1 : General lnboduct~on
37
(b)
Chemical bonding at the interface It is found that two types of chemical bonding are involved at the fibre-
matrix interface by the chemical treatment. They are (a) dissolution and wettability bonding and (b) reaction bonding.
In this type of bonding, the interaction between the components (fibre and matrix) occurs on an electronic scale, i.e., these components come into an intimate contact on an atomic scale. Hence, both surfaces should be
appropriately wetted to remove any impurities.
In this type of bonding, a transport of atoms occurs from fibre, matrix or both to the interface. 'These polar surfaces can form bonding owing to the diffusion of matrix molecules to the molecular network of the fibre, thus forming tangled molecular bonds at the interface, e.g., reaction bonding by coupling agents like silane. Fibre-matrix adhesion has been explained by the evidences like (a) mechanism of dry bonding system b) fibre treatment and c) determination of adhesion level and optimisation. The dry bonding system, abbreviated as HRH, consisting of hydrated silica, resorcinol and hexamethylene tetramine is commonly used to create adhesion between fibre and.the rubber matrix. If the fibres are not properly bonded with the matrix, it will slide past each other under tension deforming the matrix to low strength. When the fibrematrix interface of a short fibre composite is sufficiently strong, the load will be effectively transferred to fibres to obtain a high performance composite. Hence the mechanism of load transfer may take place through the shear at fibre-niatrix interfacr.
Chapter 1General lnhoduction
38
1.7.2 Mechanism of dry bonding system
IlunnoniiA' has observed a marked difference in the adhesion level by adding silica to a compound containing resorcinol and hexa. Silica reduces the resin fornlation to a low molecular weight species and these low molecular weight species can dithse easily through the matrix thereby developing adhesionbl. I his mechanism is similar to IWL system. O'ConnorTl have studied the effect of three different bonding systems e.g., HRI-I system, RI-I system without silica and a resin bonding agent on NR composites containing 17 volume percent glass, carbon, aramid, cellulose and nylon fibres. Thomas et
a1.M
have successfully tried resorcinol and hexa
bonding system without silica in the recent work of short sisal fibre reinforced natural rubber con~posites.It is seen that the rate of resin formation and the rate of vulcanizatio~~ not same, i.e., the cure time has a sigruf~cant are effect on the adhesion.
1.7.3 Fibre treatment
Various oxidative or non-oxidative chemical treatments are available for natural and synthetic fibresfi6'. Asbestos fibres are hard to adhere with a rubber matrix but a treatment of the fibres with silane coupling agents and with isocyanate (Uesmodur) as 2% solution in dichlor~~methane found lo is improve the adhesion's. Glass fibres have drawn considerable attention and nowadays the trcatrnent is mainly with a silane coupling agenP5. Anthoi~lc ct a1.10 and Coran and Hamedg have reviewed the reinforcement of elastomers with treated discontinuous cellulose fibres and their mechanism of reinforcement. Recently carbon fibres are drawing considerable attention, even though their use i restricted due to their high cost. s
39
Several researchers have investigated the use of treated short natural fibres as reinforcing elements for polymer compositesT2, 671. These include bagasse'?, jute67, co*, cotton, flax, asbestos1<>, al.7uand Chand et on sisal fibres.
171.71 have
sisaPY etc.
Barkakaty
et
developed different types of chemical treatments
7.7.4 Determination of adhesion level and optimisation
A good amount of adhesion is required for high performance short
fibre reinforced composites. But high adhesions will adversely affect the composite by generating more heat at the interface and thereby weakening it. The main problem with the adhesion in short fibre rubber composites is that it can not be measured quantitatively. The adhesion level can be qualitatively assessed from the shapes of stress-strain curves and the study of fracture surfaces using SEM technique.
RES (restricted equilibrium swelling)
technique can also be used to evaluate adhesion5'. But t l measurement is ~ inaccurate since the restriction may be due to the presence of fibres and the adhesion cannot be separated out. In the case of visco elastic properties, a high shear at the interface, which increases with the increase in the level of adhesion, the mechanical loss associated with it also increases. At elevated temperatures, the interface deteriorates and the values decrease.
1.8
Theories of adhesion There are four theories of adhesion, w h c h is the basis of mechanism of
adhesion. '['hey are (1) mechanical, (2) adsorption, and (3) diffusion and (4) electrostatic theories.
Chapter 1 General lnhoduction
40
1.8.7 Mechanical theory
A rough surface will have a larger potential bonding area than a
smooth one. 'I'he adhesive interlocks seen around the pores of the substrate enhances the mechanical adhesion. E.g., the metal plating of acrylonitrilebutadiene styrene (ABS). In this method, a pre-treatment of the polymer with chromic acid dissolves rubber particles near the polymer surface. Thus a metal can be deposited from solution into the porous structure, which is developed on the polymer surface.
1.8.2 Adsorption theory
Ihis theory assunles a definite interface between the adhesive and adherent but the exact nature of the interactions at the interface is uncertain.
I he adhesive macromolecules get adsorbed over the surface of the substrate
by the action of various forces of attraction such as Van der Waals forces, hydrogen bonding, ionic or covalent bonds. The physical adsorption is
explained by the Van der Waal's forces while primary bonding is involved in the chen~isorption. Hydrogen bonding is explained in the bonding of lyre cords to rubber and in the self-adhesion of corona treated polyethylene (I'E)72,
73.
Kokta et n1.71 have also reported strong evidence for chemical bonding in
adhesion between isocyanate coupling agent and PE systems.
7.8.3 Diffusion theory
This theory is only applicable to the polymeric materials. 'l'he main requirement is that the macromolecules of the adhesive and adherent have sufficient chain mobility and are mutually soluble. IIere, the interface of the material is eliminated by the diffusion of adhesive macromolecules into the substrate. lhis theory is supportect by the experiments conductccl based on the bonding experimekts where the adhesive and substrate are identical75.
Chapter 1 General lnhoduct~on
41
Studies on the bonding of rubbers at elevated temperatures showed that the joint strength increases with increasing period of contact, temperature and pressure. The joint strength also increases with decreasing molecular weight, by the addition of suitable plasticizer and the cross-linking. When two pieces of same plastic sheet. are softened with chlorinated solvent and joined, the solvent welding of the plastic proceeds by diffusion mechanism.
1.8.4 Electrostatic theory
This theory of adhesion is explained due to the electrostatic forces, arising from the transfer of electrons from one material of an adhesive joint to another. It is observed that the parts of a broken adhesive joint are sometimes charged. Thus, the theory is explained by the experimental evidence'h. The strong peeling forces can be accounted by the Van der Waals forces or chemical bonds. This dependence on peel strength on testing speed is
explained by the said theoryn.
1.9
Interface modification
1.9.1 Surface treatment of polymers
'l'lie chemical modification of polymers is divided into chemical treatment, corona discharge treatment, UV radiation and plasma treatment.
(a)
Chromic acid treatment I'olar groups are introduced on the polymer surface when the
polymeric materials are treated with oxidative chemicals like cluomic acid/acetic acid or chromic acid/sulphuric acid'R79. The nascent oxygen
produced during the reaction oxidises the surface of the polymeric material.
K I C I - ' ~ ~I z S ( ~ I + 41
Cr2(SC)i), + K ~ S O + 41 1 2 0 + 3101 I
(1.4)
42
'She ptrlar groups lormcd on the surface of polyolefincs such as >C = 0,
-OH, -COOH and SO3H can be activated by chemical reaction to produce

good interfaces".
(b)
Corona discharge treatment Introduction of highly polar functional group like carbonyl group
(>C = 0)at the surface of the polynler is done by Corona discharge method.
l'hc improvcn~cnt properties of polynler material is due to the hydrogen of bonding or electric formation72~~1.
(c)
UV radiation
In UV radiation also, the surface modification is done by the introduction of functional groups. l'his method is applied in two ways: (i) UV light is applied on the material to oxidise the surface or the material is allowed to come into contact with a gas or sensitiser to cause a photochemical reaction and (ii) UV irradiation induced graft polymerisation at the surface of thc materi.11 could br effected. 'l'hcse reactions occur at ordinary temperature and pressurc and the selective reaction is possible by the light energy focussing on the surface of the matrix. Carboxylic acid group ( - O H ) can be introduced at the surface of the polynler by bringing double bonds through irradiation in acetylene followed by photo oxidations2.
(d)
Plasma treatment Non-equilibrium low tcnlperaturc plasma is used for the treatmen@'.
The energy of electrons is in the range of 1to 10 eV. Tlus energy converts the n~olecules a gas (A) to be ioniscd and excited. 'l'hus radicals and ions are of produced as shown in the following scheme.
Chapter 1 General inhoduct~on
43
Ionisation Excitation Radical dissociation I.un~inesccnce Electron addition
: : : :
A + q
*
AC+2e
A+er A* A* :A+e
A* + 2e A', + A . 2 A' + hu A-
The activated gaseous particles react with polymer material to produce polymer radicals on the surface layer. The surface layers are oxidised. The hee radicals are again polynierised and in the event the polymers of A coat the surface. CASING (Crosslinking by Activated Species of Inert Gases) is a new method developed with the plasma treatment to introduce crosslinking into the surface layers-'.
1.9.2 Surface treatment of fillers/fibres The physical and chemical methods are employed for the modification of fillers/ fibres.
(a)
Physical n~ethods
?he physical methods change the structural and surface properties of

fillers/fibres. They include corona discharge and cold plasnia treatment. In corona treatment, the surface activation is done by oxidation and thereby the surface energy of the filler changes. But plasma treatment depends on the nature of the gas used in the chamber. A variety of surface modifications like oxidation, CASING, etc. can be applied in the treatment to change the surface energy of the fillersnj.
(b)
Chemical methods There are different types of chemical modification methods reported
for fillers. Some of these are based on the action of coupling agents, dipping of fibres, grafting and chemical treatments.
Chapter 1 General In1roduct;on
44
(i)
Actioti of col~plillg ngrtlts Several mechanisms have been reported for coupling in composite
~ ~ ~ i l r i iC'o~~plinl; ~ l s ~ . .II;(-II~ is
ii
tii.il~rii~l, wliicl~ C.,III inll.otl~~cr co~~il)dlil)ilily
between two incompatible materials. The creation of compatibility is done by

(1)eliminating weak boundary layers, (2) producing a tough flexible layer, (3)
developing a highly crosslinked interface region, (4) improving the wetting between the polymer and substrate, (5) forming covalent bonds with both materials and (6) altering the acidity of the substrate surface. Silane coupling agents are the best known and have been used by the earlier researchers. They can be represented by a general formula: R-(CHz),Si(OR')>,whcrc n= 0-3; O R ' the hydrolysable alkoxy group and I<' the organic functional group which causes the reaction with polymers. Coupling agents impart hydrophilic properties to the interface by copolymerisation reaction or by the formation of an interpenetrating network86. (ii) Dipping of fibres Dipping of the reinforcing fibres with the polymer dispersions having low viscosity compatible with the polymer matrix enhances the strength of the compositex7. l'homas
e t n1. 8 have reported the enhancement of 8
.
mechanical properties in coir/NR composites by dipping of the coir fibre in natural rubber solution. (iii) Grnftirrg Graft co-polymerisation is a method of attaching polymer to the fibre/filler by hee radical initiation when exposed to a high-energy radiation. 'The cellulose molecule is treated with an aqueous solution and exposed to radiation. Thc molecule breaks and radical sites are formed. Then these sited are treated with n suit'~blesolvent compatible with the polynler matrix. I hus the grafting of cellulose fibres have been reported with vinyl monomerssy.
Chapter 1: General lntraduction
45
(iv)
Clterrricct 1 trcntrrrents Several rcscarcllcrs have applied different chemical treatnle~lts the to
fibres in order to enhance the mechanical strength.
A lot of chemical
treatments are reported in the case of natural fibres. Of these, acetylation of fibre is reported by Chand et
al.71.
The PMPPIC treated short cellulose fibres
have increased the mechanical strength of the sisal/PE compositem. In the case of PMPPIC treated FS/cellulose composites, the strong interaction exerted by the delocalised n-electrons present in the benzene rings of PMPPIC and PS creates a strong adhesion between them".
1.10 Measurement of interfacial strength

The fibre matrix interface strength is characterised by different evaluations. Some of them are detailed below:
1.fU. 1 Sirlgle fib! c tesfs
A single fihlt, is rnrbcdtlcd in a m a t ~ i x and the stress necessary to pull
the fibre out is calculated as interfacial strength.
'I'l~c transverse strc~igtlr tllc conipositc 111alerialcan be ~ncasured of by this method. In this test, fibres are aligned perpendicular to the specimen lengtl~as one of the variants. 'I'he stress, a , in the outer surface of the specimen is obtained from the relation,
where p is the applietl load, t, thickness, 11, height and s, span of the bend specimen.
Chapter 1: General lnhoduction
46
II I Interface characterisation
The structure of the interface is characterised by different methods. Some of them are ESCA (electron spectroscopy for chemical analysis), AES (auger electron spectroscopy), IR (infrared spectroscopy), FTIR (fourier transform infrared spectroscopy), SIMS (secondary ion mass spectroscopy,
SEM (scanning electron microscopy), IGC (inverse gas chromatography), etc. ESEM (environmental scanning electron microscopy) technique is used to
observe the oily or wet specimens without gold coating. It is also useful for evaluating wood polymer interactions in WPC(wood polymer composites). EDAX (energy dispersive analysis of X-rays) is used for elemental composition and for measuring the depth of penetration of a chemical used for wood treatment in WIJCs. Solid state C-NMW2 spectroscopy is also used for characterising wood and WI'Cs.
1.12
Properties of short fibre composites
I he mechanical properties of short fibre composites are intermediate
between
those
containing cords and
particulate
filled
composites.
Christenen93 has reported that short fibres are nearly identical to continuous fibres in their transverse properties. The use of particulate fillers in elastomer reinforcement is reported by Boonstrag'. On analysing the dynamic
propertics of visco-clnstic conrpositcs, it has bren rc,pol trd that the cotiipositc. plays a frequency dependent responses'. 'Ihe factors affecting the mechanical fibre co~npositcsare related to the aspect ratio, volun~e properties of s h o ~ t fraction, fibre orientation, state of dispersion and the degree of adhesion to the matrix. Iliese factors are again influenced by the additives or bonding system. Aleksandrovys has reported on the fibrous composites of NR and synthetic rubbers. 7 he physico-mechanical properties of EPUM rubber cellulose fibre composites have been reported by Hamed et 01.9
Chapter 1 General lnlroduct~on
47
'l'he important
technical properties of
fibrc reinforced
rubber
coniposites are: (a) modulus and elongation at break, (b) tensile strength, (c) tear strength, (c) crecp and (e) fatigue propcrties.
1.12.1 Modulus and elongation at break
The incorporation of short fibres to elastomers increases the modulus of the composite material%. 7'he modulus of a fibre reinforced rubber composite can be expressed as a following relation97. G = G,, (1 + 0.67fc + 1.62f'c?) (1.6)
where, G,, is the modulus of unfilled vulcanizatr, C , volume fraction of the fibre and, f, length to diameter ratio of the fibrc. If there is good adhesion betwccn fibt-c, and matrix and the value of 'f ' is in the range of 10-50, moduli between 102-10' can be achieved for the composite. The rapid loss of elongation with increased fibre loading is due to good fibre-matrix adhesion. Derringer?5suggested that the value of elongation is a good index of fibre-matrix adhesion in the composite. In the case of glass, carbon, kevlar, cellulose and nylon reinforced rubber composite, O'Connorq1 has observed that the elongation at break can be reduced in the range of 16-
17%volume of fibres.
1.12.2 Tensile strength
I h e theories as applied to particulate filler reinforced rubber composites can also be applied to short fibre composites. In these theories, the elastomrr matrices can be considered as a special case9"-99 "Ihe factors, which influence the stress-strain properties of the short fibre-composite, are fibre concentration, fibre aspcct ratio, fibrc orientation anti fibrc-matrix adhesion.
Chapter 1 General lnhoduction
48
The rule of mixtures is applicable to a perfectly aligned and bonded unidirectional continuous fibre composite. The relation is given by,
strength, sf, ultimate fibre strength, on,, where, o,,,is the ultimate con~posite matrix strength at the maximum fibre stress, vr , volume fraction of fibres and v,, , volume fraction of matrix. But for short fibres, the fibres cannot be stressed to their maximum because of the ineffective stress transfer near the ends. ?he commonly used theory to explain the mechanism of stress transfer
is the shear-lag analysis given by Rosen47. Then the strength of continuous
fibre reinforcement becomes,
Rosen's theorydl does not include the stress concentrations arising out of fibre-fibre interactions. Chow and Kardosl~l"'have quantified the extent of reduction in composite strength due to fibre-fibre interaction. They have also given a good review of models for predicting the elastic moduli as a function of the shape of the reinforcing particle. 'lhese theoretical analyses can also be applied to short fibre composites. The strength of the unfilled matrix is poor in the case of noncrystallising rubbers like SllR. 'I'llc presence of evc~ti s111all fraction of fibre a increases the overall strength of the composite. Dzyural0* and Del"3 have reported that the tensile strength does not drop in the case of non-strain hardening SBR. Derringer13 has postulated certain empirical equations for tensile strength, modulus and elongation at break to be related to volume fraction of fibres and fibre aspect ratio. There are many references regarding the effect of angle between the principal fibre direction and the direction of applicatiun of stress. The
Chapter 1 General introduction
49
theoretical cor~sidcrations hold good for unidirectional and randomly oriented fibre composites when the load is applied along the direction of principal fibre orientation. But in the transverse direction, the fracture of the composites takes place mainly through the matrix and the fibres do not affect the strength properties significantly. The maximuni composite strength can be achieved if the angle is 00 and it decreases as the angle increases from 0 to
YW' giving the minimum value of the composite strength at 90". Moghel("
gave the expression for the strength of the composite in which orientation paranleter had been taken into consideration. 'l.he ultimate coniposite strength is given by,
,is where, o~,, the ultimate fibre strength, vr , volume fraction of the fibre, o n , ,
matrix strength at the maximum fibre stress, orientation parameter and 1, length of the fibre. the According to the additivity rule proposed by D ~ y u r a ' ~ ~ , true influence of the matrix can be considered only by the introduction of adhesion and orientation coefficients. Kelly and 'I'yson"J5 explained the dependence of composite strength on the filler loading by computing the efficiency of filamentary reintorcen~entof metals. 'lhis is used to express the strength of the fibre rubber conlposite as,
, critical fibre length, C, ,
where a, , is the composite strength,
01
, strength of the fibre, vr , volunle ,
fraction of fibre, o,,, strength of the matrix at its maximum attainable , deformation, L, length of the fibre, K, coefficient of fibre orientation and L, the ineffective length of the fibre. 'l'l~e incffcctivc lPngtll of thr lil>rcis ralculatc.d o n tllc. cclndition tlliit the force required for breaking the fibre is equal to the maximunl shear force on the fibre-rubber bonding. l'he expression i given as, s
Chapter 1 General Introduct~on
50
Of
d (1.11)
Li
= -
2r where d, is the diameter of the fibre and r
, the minimum shear stress on
boundary. 'lhe orientation coefficient depends not only on the method of processing but also on the fibre concentration and is different for different fibre-rubber compositions. The ultimate composite strength was reported to be dependant not on the matrix strength(^,,,) but on its stretching resistance at the maximuni cornpusite deformation(^',,,). IIigher o',,, cr,,, ratio suggests / in that tliere exists a ~ninimurli tensile strength vs fibre co~~ccritration.
1.12.3 Tear strength
Generally, the tear resistance of short fibre rubber coniposites is higher than that of other composites. When the fibres are aligned perpendicular to the direction of propagation of the tear, the tear proceeds through matrix. It either deviates or stops when it conies in contact with the fibre. When the tear proceeds parallel to the fibre alignment, the tear strength will not be influenced considerably by the ilbres as they do riot obstruct the tear pltlr. 'Ihe short fibres cause an increase in tear strength of the composite at low levels of fibre loading(<5%)and decreases at higher loading'5. Ile cjt
111.l" c"'.
1"'
have pointed that the tear strength increases up to a
certain loading of fibre beyond which fibre does not exert significant influence on the strength. 'Ihe increase in tear strength of the composite improves the resistance to chipping and chunking in tyre tread applications.
1.12.4 Creep
Creep is clr.firiccl a s thr iricrrasr in strain \\.it11 tinic, at a constant strcss level. In creep tests, a constant stress is maintained on a cor~rposite spccirl~en while its deformation(strain) is monitr~redas function of tin~e. 111 polynicrs,
Chapter 1 General lnboduct!on
51
creep occurs because of a cornbination of elastic dc,tornlation and viscous flow, commonly known as visco-elastic deformation. When the stress is
applied, the resulting creep strain increases nonlinearly witli increasing time. When the stress is released after a period of time, the elastic deformation is immediately recovered. The deformation caused by the viscous flow recovers value, called the recovery strain. slowly to an asyn~ptotic Creep strain in polymers and polymeric conipusites depends on the stress level and temperature. Many umeinforced polymers exhibit large
creep strains at roonl te~nperature and at low stress levels. 'l'lie creep of the composites compared to that of unfilled should be reduced by about the same factor as the ratio of the two moduli of the materials. 'I llr incorporation of short fibres to an elastomer reduces the creep behaviourlM. Moghel07 has discussed the time dependant failure of short fibre rubber co~nposites under cyclic strain conclitions.
1.12.5 Fatigue properties

V
~il,~t~~i,~ls are subjected to cyclic n ~ ' c l ~ ~ ~ n istresses, most of cal
them fail at a stress considerably lower than that rccluired causing rupture in
a single stress cycle, tertned as latigue.
Fatigue or hysteresis properties of
short fibre rubber composites are associated with crack generation and its propagation in the matrix followed by dewetting and destruction of the fibrematrix bond. Ijue to the increased stiffness associated with the concentration of fibres, the fatigue properties of tlie fibre filled composite are poor. When the fibres are oriented transversely, the flex cracking resistance is slightly improved"'8. Boustany et
n1.U"
have observed tliat the fatigue property
exhibited by the cellulose fibre-rubber composites is due to the repeated Ioatli~r~; tcansicin and conlprc~ssiori. Gc-tic-rally, a 1 it~[-t.c.;isc,i n tllc* fi1)i.v in 1 loading increases the heat buildup. I leat buildup of these colliposites is also
Chapter 1 Genera! Intraduc!ion
52
higher than the urlfilled vulcanizateslw. The mechanical loss or damping near the fibre-matrix interface accounts for the higher heat buildup and low fatigue life of composites.
1.13 Applications of composite materials

Bone is a simple example of a natural composite material having the best properties of its constituents. l'he organic component consists of
carbohydrates, fats and proteins while calcium phosphate is the inorganic component. Bone is strong and rigid due to the inorganic component, yet flexible enough to resist breaking under normal use because of the organic components. Composite materials have been in use since biblical times when chopped straw was added to brick to make building materials. The age of modern composite materials began with the introduction of particulate or fibrous reinforcement material in the early 1900s. Much of the early impetus to the development of composite materials was on account of needs of military aircraft during the World War 11. 'lhe emergence of composites has had tremendous impact on transportation, marine engineering, chemical equipment and machinery, sports goods, electronic ecluipment and even the aerospace and defence industries. Composite materials are generally costlier as compared to conventional materials. But their use is becoming increasingly popular because of the innumerable advantages they possess. Composite materials possess a unique combination of properties such as lightness in weight, toughness, fatigue resistance ancl stiffness, better corrosion surface, weathering and fire resistance, electrical insulation, anti-friction, translucency (85%) ease of fabrication or versatility of fabrication methods, better durability and low maintenance cost.
53
These properties have stimulated a tremendous interest i n composite materials for application in various fields. Their applications range from a simple washbasin to high tech application such as in space shuttles. The potential of composites in increasing the fuel economy reduced the weight of vehicles in the automobile and transportation industry. Composite materials have been used in wide variety of structural and non-structural marine applications almost from the time of their introduction as commercial materials and their use fur such application is constantly growing. Another area of interest, wluch is considered to be a boon to mankind,
is the use of composites in making artificial joints.
Many designers are
turning to composite materials as means of producing furniture, which is considered better than conventional or traditional materials. Composite
materials also find application in a big a way in sports goods where their superior properties conlpensate for any additional cost.
1.14
Scope of the present work and objectives
One of the important discoveries in the field of rubber technology is the rcinfol-ccmctlt of rubber by particulate fillers s11c11as carbon l h c k ant1 silica. However, the reinforcement by particulate fillers alone is not sufficient in certain rubber products. ?he cluest for alternate reinforcing agents
produced a new type of reinforcement using continuous fibre to meet certain specific requirements of rubber products such as tyres, hoses, conveyor belts and V-belts. But several problems are associated with the use of continuous fibres. Continuous fibre reinforcement requires extra processing operations such as dipping, coating with rubber, wrapping, braiding and ply making. A search for a suitable replacelnent of a continuous fibre resulted in the enle~gence sllort lib~cs. 01
Chapter 1. General lntroduct~on
54
The tern1 short fibre means fibre with a critical length to diameter ratio, which is not too high so that individual fibres do not entangle with each other and wluch, is not too small so that it affects the reinforcing action. Short fibre reinforcement of rubber is in its infancy and details on adhesion fracture criteria and flow properties are still unexplored. Many authors have studied the mechanical properties of short fibre reinforced elastomer composites using nylon, rayon, glass and carbon. Because of the uncertainties prevailing
in the supply and rise of petroleum waste products, there is every need to
study the naturally occurring alternatives. Among the naturally occurring fibres, only cellulose has been studied extensively. The use of short cellulose fibre as filler for synthetic rubber has not been studied in detail. Fibre length or aspect ratio, fibre-matrix adhesion and fibre orientation controls the ultimate properties of fibre-rubber composites. In a short fibrerubber composite, mainly, the tricomponent dry bonding system is used to produce adhesion between fibre and rubber. 'l'he mechanism of dry bonding system and the role of silica are not clearly understood. The role of silica and
of the rrplacr~nic~nt silica by carbon black in devc,lopinp, adlirsion have* brrn
studied for asbestos and glass fibre reinforced rubber composites. question remains unanswered for sisal and other fibre reinforced rubbers.
The
'1he.level of adhesion in the case of short fibre reinforcement of rubber quantita\ivcly ancl hence a clualitativc asscssnlent of cannot be n~casur(*d adhesion must be made. Besides the mechanical properties, adhesion affects visco-elastic properties of the conlposites greatly. l~lowever,there are sonle conflicting views regarding the effect of adhesion on visco-elastic properties. The actual effect of adhesion is still not clear. 'Ihe development of a rubber product will be difficult unless the factors contributing to the failure of the product are thoroughly understood. 1:ailure analysis is thus a subject of great importance. In the case of short fibre reinforced composites the failure may be due to the weak fibre-matrix
55
adhesion, premature fibre failure due to insufficient quantity of fibres or due to fibre breakage. Lately, Ue and co workers have used scanning electron microscope as a useful tool to study the fracture mechanisms of rubber composite. However, a detailed study on the fracture of short fibre reinforced SBR composite is lacking. With the advent of new processing machinery, which is mainly extrusion oriented, the quest for the knowledge of rheological behaviour of composites has increased. ?'he studies on the rheological behaviour of fibre and particulate filler filled polymer melts and particulate filler filled rubber compounds are very important as far as their processing is concerned. The short fibre reinforced rubber compounds have found application in products like hoses and V-belts but, no detailed study on the rheological behavivur of short natural fibre filled synthetic rubber compounds has been made till date. The influence of various chemical treatment of the cellulose fibre on the properties of the composites is not explained in detail. Therefore, a detailed and in-depth investigation has been undertaken on the properties of short sisal librc rcinlorced styrrne-hulatiirnc rubber conipositi-s. 'l'he important objectives of the present study are: Preparation of cost effective composites of sisal and SBR. Analysis of niechanical properties, adhesion and failure criteria. Evaluation of the effect of surface modification of fibres and incorporation of bonding agent on the mechanical properties, adhesion and failure behaviour of short sisal fibre reinforced SHK composites. Measurement of the rheological and extrusion characteristics of short sisal fibre lilled SI3K compuuncts
-
Effect of ternperaturc, chemical
treatment and nature of bonding agcnt. Studies of the interfacial adhesion of sisal/Sl3lZ coniposites by restricted ecluilibrium technique.
Chapter 1 General lnhoductton 56
Evaluation of dielectric properties of short sisal fibre reinforced SBR composites Dynamic mechanical thermal analysis of styrene-butadiene rubber reinforced with short sisal fibres. Thermal analysis a n d kinetic investigation of the degradation of sisal/SBR composites by TGA and DSC.
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Chapter 1 : General Introduction
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Chapter 1: General lnlroduct~on
61

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CHAPTER

zi part of tfik cfiapter fias 6een communicate6 to:

fascinating and wonderful materials known as coniposites. A composite

Chapter 1 General lntroduct~on

Chapter 1: General Introduction

particulate, fibrous, laminate and hybrid composites' (Figure 1.1).

1.2. I Particulate reinforcement:

fillers are employed

Chapter 1 General lntroduct~on

1.2.2 Fibrous reinforcement

Figure 1.2. EIentertts o art idealised sliortfibre cor~rposite f

importance in replacing MMCs in applications requiring a combination of strength and lightness.

Chapter 1 General Introduction

A laminate is fabricated by stacking a number of laminas in the

Figure 1.3. Sckenlatic nrodel o f a lnnrirrate conylosite

1.2.4 Hybrid composites

Chapter 1: General Introdunion

Carbon Glass Carbon

Sclterrralic rtrodel o a Itybrid laminate corrrpossile corrlrrirrirrg cnrborr f nrrcl glrrssjibres

Chapter 1: General Introduction

Chapter 1: General Introduction

hypochloride bleach will dissolve wool or silk.

The classification and

properties of animal fibres are explained below (Figure 1.6).'

Figure 1.6. (i) Silk fibres

The protein fibroin is the principal component of silk fibre'.

Hair fibres are marketed as wool or camel's hair.

Chapter 1: General Introduction

SEFD Figure 1.7.

Chapter 1 General Intoduction

The soft hairs that surround the seeds of certain plan&

Vascrrlar (grass-stenr) fibres

Chapter 1: General lnboduction

-GiGFq - BSI:' -P A I ~ F ~- CI:F2 - ~ 1 . ~ 4

Elastic modulus (GPa)

1-. 0.8 - 1.6 135

(degrees) Tenacity (MN/m')

'Banana stem fibre, V o i r fruit fibre, bunch fibre

Tineapple leaf fibre,

leaf fibre, Wil

is good for long-term use at temperatures as high as 1400" C. The basic

Chapter 1: General lnhoduction

they are softened by heat. During processing, a molten

Chapter 1: General lnboduction

Mecltanicalpropertiesofmineral and syrtflteficfibres .. . Properties

1.14 1.45 3.62 131 2.8

Figure 1.8. Clnssi~cafionf matrices. o

polymerisation are called high polymers. Polymers consisting of only one

from several different repeating units.

Structure of different types of polymer are presented in Figure 1.9.4

Slruclures o d$fereni types o polymers f f

Chapter 1: General Intoduction

In crosslinked polymers, two or more chains are joined together by

Plastics Organic polymeric materials consisting of giant organic molecules,

plastic composite matrices are shown in Table 1.3.

I'hermal expansion coefficient, loh per .C llermal conductivity,

Chapter 1: General Introduction

Compnssian Coldpnss cold itamping &ss nwuldimg

kaciien injection Reinfnmed reaction injection Resin -6er

Figure 1.10. Moulding techniques

Chapter 1: General Introduction

Rubbers Rubber is a material, which is capable of recovering from large elastic