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CHAPTER 1
INTRODUCTION

In recent years, polymers form a very important class of tribo-engineering
materials and are invariably used in mechanical components such as gears, cams,
bearings, bushes, bearing cages and better wear resistance, where wear performance
in nonlubricated condition is a key parameter for the material selection However,
polymer is rarely used as bearing materials in its pure form, because neat polymer
could not satisfy the demands arising from the situations where a combination of good
mechanical and tribological properties is required. Fiber/filler loaded polymeric
composites are the most rapidly growing class of materials, due to their good
combination of high specific strength and specific modulus, are widely used for
variety of engineering applications. This chapter presents an overall view of
thermoplastic composite materials. Composite materials are among the most rapidly
growing classes of materials and are finding more applications in various fields. The
use of polymers and their composites are on the increase for improved performance in
many areas of applications including tribological purposes. This chapter covers the
motivation, objectives and scope of the present investigation.
1.1 Introduction to polymer composites
Polymeric materials such as plastics have become part and parcel of every
aspects of mankind. The unprecedented successes of polymers in various aspects of
human life are domestic consumer durables, electrical and electronic equipments,
automobiles; packaging, medical, aerospace and other engineering applications are
attributable to the novel inherent characteristics of plastics.
Polymers have generated wide interest in various engineering fields including
tribological applications, in view of their good strength and low density as compared
to metals and ceramics. Being lightweight with high specific strength, they are the
most suitable materials for weight sensitive uses. Composite materials (or composites
for short) are engineering materials made from two or more constituent materials that
remain separate and distinct on a macroscopic level while forming a single
component. There are two categories of constituent materials: matrix and
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reinforcement. The matrix material surrounds and supports the reinforcement
materials by maintaining their relative positions. The reinforcements impart their
special mechanical and physical properties to enhance the matrix properties. The
primary functions of the matrix are to transfer stresses between the reinforcing
fibers/particles and to protect them from mechanical and/or environmental damage
whereas the presence of fibers/particles in a composite improves its mechanical
properties such as strength, stiffness etc. A composite is therefore a synergistic
combination of two or more micro-constituents that differ in physical form and
chemical composition and which are insoluble in each other. The objective is to take
advantage of the superior properties of both materials without compromising on the
weakness of either. The synergism produces material properties unavailable from the
individual constituent materials. Due to the wide variety of matrix and reinforcement
materials available, the design potentials are incredible.
Composite materials have successfully substituted the traditional materials in
several light weight and high strength applications. The reasons why composites are
selected for such applications are mainly their high strength-to weight ratio, high
tensile strength at elevated temperatures, high creep resistance and high toughness.
Typically, in a composite, the reinforcing materials are strong while the matrix is
usually a ductile or tough material. If the composite is designed and fabricated
correctly it combines the strength of the reinforcement with the toughness of the
matrix to achieve a combination of desirable properties not available in any single 3
conventional material. In the advanced world, due to the better properties of fiber
reinforced thermoplastics and thermosets are used in many Engineering applications.
These materials play a key role in performance of the Engineering components in the
sectors like automobile industries, railways, defense, road transport, aeronautical
industries, electrical/electronic and construction. Further utilization of fibre reinforced
polymer composites are increasing rapidly due to its special properties namely high
strength-to-weight ratio, stiffness, corrosion resistance, dimensional stability under
humid and elevated temperature conditions, good fatigue strength, better surface
finish, good electrical and thermal insulation etc., Polymers and their composites
form a very important class of tribo-engineering materials and are invariably used in
mechanical components such as gears, cams, bearings, bushes, bearing cages, etc.,
where wear performance in non-lubricated condition is a key parameter for the
material selection [1].
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1.2 Tribology
Tribology is the science and engineering of interacting surfaces in relative
motion. It includes the study and application of the principles of friction, lubrication
and wear. Tribology is a branch of mechanical engineering. Most technical
universities have a group working on tribology, often as part of their mechanical
engineering departments. The limitations in tribological interactions are however no
longer mainly determined by mechanical designs, but rather by material limitations so
the discipline of tribology now counts at least as many materials engineers, physicists
and chemists as it does mechanical engineers.
Any product where one material slides or rubs over another is affected by
complex tribological interactions, whether lubricated like hip implants and other
artificial prostheses, or unlubricated as in high temperature sliding wear in which
conventional lubricants cannot be used but in which the formation of compacted
oxide layer glazes have been observed to protect against wear. Tribology plays an
important role in manufacturing. In metal-forming operations, friction increases tool
wear and the power required to work a piece. This results in increased costs due to
more frequent tool replacement, loss of tolerance as tool dimensions shift, and greater
forces required to shape a piece. A layer of lubricant which eliminates surface contact
virtually eliminates tool wear and decreases needed power by one third.
Abrasive wear occurs when hard asperities on one surface move across a
softer surface under load, penetrate, and remove material from the softer surface,
leaving grooves [2]. Most of the abrasive wear problems arise in gear pumps handling
industrial fluids, chute liners in power plants, mining, and earth moving equipments.
The need for the use of newer materials to combat wear situations has resulted
in the emergence of polymer based composite materials. Fiber reinforced polymeric
composites are the most rapidly growing class of materials, due to their good
combination of high specific strength and specific modulus. They are widely used for
variety of engineering applications. The importance of tribological properties
convinced many researchers to study the friction and wear behaviour and to improve
the wear resistance of polymeric composites. For fiber reinforced polymer matrix
composites the process of material removal in dry sliding condition is dominated by
four wear mechanisms, viz., matrix wear, fiber sliding wear, fiber fracture and
interfacial debonding [3].
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Tribologists often classify thermoplastic polymeric materials into three
distinct groups according to their friction and wear behaviour. These are: the normal
polymers: low-density polyethylene (LDPE), polypropylene (PP); the amorphous
polymers: polyvinyl chloride (PVC), polymethylmethacrylate (PMMA) and the-
smooth molecular profile- polymers: polytetrafluoroethylene (PTFE) and ultra high
molecular weight polyethylene (UHMWPE). Among them, the better frictional
performance of the smooth molecular profile polymers can be explained by the
easiness with which the long chain molecules shear across each other [4-5]. The
effects of fibrous fillers on wear characteristics of PTFE composites under dry or wet
conditions have reported by Wang et al [6].
1.3 Fundamentals of wear
Wear is defined as damage to a solid surface generally involving progressive
loss of material due to relative motion between that surface and contacting substance
or substances. Main types of wears are abrasive wear, adhesive wear, corrosive wear,
erosion wear and fatigue wear, which are commonly observed in practical situation.
The process of `wear may be variously defined but most generally it is
quantitatively measured in terms of the mass, or volume, loss from a sliding or
eroding contact. The sequence of events is invariably as follows. Mechanical forces,
frictional work, impact forces, contact fatigue stress, cavitation forces and so on
induce damage in the contact members. Eventually, or may be also immediately, the
surfaces lose mechanical cohesion and debris is produced. Chemical wear has a
similar character but on a smaller scale. Subsequently, perhaps immediately, this
debris is expelled from the contact zone and the process of wear is observed.
When material is removed by contact with hard particles, abrasive wear
occurs. The particles either may be present at the surface of a second material (two-
body wear) or may exist as loose particles between two surfaces (three-body wear).
Adhesive wear is also known as scoring, galling or seizing. It occurs when two solid
surfaces slide over one another under pressure. Surface projections or asperities are
plastically deformed and eventually welded together by the high local pressure. As
sliding continues, these bonds are broken, producing cavities on the surfaces,
projections on the second surface, and frequently tiny, abrasive particles, all of which
contribute to future wear of surfaces. Often referred to simply as corrosion or
corrosive wear is deterioration of useful properties in a material due to the reactions
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with its environment. Surface fatigue is a process by which the surface of a material is
weakened by cyclic loading, which is one type of general material fatigue.
Wear can also be divided into sliding wear, which occurs in the absence of
hard particles, and abrasive wear, which occurs in their presence. Under some
conditions sliding wear can generate debris which then causes further wear by
abrasion; it must therefore always be borne in mind that the boundary between
different types of wear is not a rigid one.
Abrasive wear can be further subdivided into two-body and three-body
abrasive wear. Two-body wear is caused by hard protuberances on the counter face,
while in three-body wear hard particles are free to roll and slide between two, perhaps
dissimilar, sliding surfaces. These types of wear are illustrated below in Figure 1.1.

Figure 1.1. Schematic diagram of two body and three body abrasion.

In three body abrasion, the loose abrasive particles abrade the solid surfaces
between which they are situated only about 10% of the time, remaining 90% of the
time in rolling. Most of the abrasive wear problems which arise in industrial
equipment are three body, while two body abrasion is encountered primarily in
material removal operation. The rate of material removal in three body abrasions is
lower than that of two body abrasion [7].
Abrasive wear is the most important among all the forms of wear because it
contributes almost 63% of the total cost of wear [8]. Abrasive wear is caused due to
hard particles or hard protuberances that are forced against and move along a solid
surface [9]. In two-body abrasion, wear is caused by hard protuberances on one
surface which can only slide over the other. Polymer and their composites are finding
ever increasing usage for numerous industrial applications such as bearing material,
rollers, seals, gears, cams, wheels, clutches etc., [10]. Different types of polymer
show different friction and wear behaviour. However, neat polymer is very rarely
used as bearing materials and wear-resistant materials because unmodified polymer
could not satisfy the demands arising from the situations wherein a combination of
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good mechanical and tribological properties is required [11]. Among the wear types,
abrasive wear situation encountered in vanes and gears, in pumps handling industrial
fluids, sewage and abrasive-contaminated water, roll neck bearings in steel mills
subjected to heat, shock loading; chute liners abraded by coke, coal and mineral ores;
bushes and seals in agricultural and mining equipment, have received increasing
attention [12]. The bi-directional fabric reinforcement offers a unique solution to the
ever increasing demands on the advanced materials in terms of better performance
and ease in processing [13].
1.3.1 Sliding wear
Sliding wear may be defined as wear due to localized bonding between
contacting solid surface leading to material transfer between the two surfaces or loss
from either surface. Specific wear rate is the measure of the wear loss per unit
distance and per unit load. The coefficient of friction is the ratio of frictional load to
the normal load applied. For the applications like gears, bearings and cams, low
specific wear rate and low coefficient of friction is essential parameters. But for
components like clutches and brakes low specific wear rate and high coefficient of
friction is required. However, in both the cases thermal conductivity of the material is
essential property.
Most commonly used matrix materials are polymeric. The reason for this are
two fold. In general the mechanical properties of polymers are inadequate for many
structural purposes. In particular their strength and stiffness are low compared to
metals and ceramics. These difficulties are overcome by reinforcing other materials
with polymers. Secondly the processing of polymer matrix composites need not
involve high pressure and does not require high temperature. Also equipments
required for manufacturing polymer matrix composites are simpler. For this reason
polymer matrix composites developed rapidly and soon became popular for structural
applications. Composites are used because overall properties of the composites are
superior to those of the individual components for example polymer/ceramic.
New requirement and new product has led to drive for more and better
polymer composites. Lightweight high performance engineering plastics had replaced
metals in many applications as polymers are relatively cheap and large volume
structural materials. The wide application of polymer composites ranges from the
manufacturing of engineering structures such as tanks, pipes, aircraft interior
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furnishings and support beams, to the making of leisure and sporting items such as
golf clubs and balls, skis, racquets and boats.
1.3.2 Wear behaviour of polymers and their composites
Composites have diverse range of mechanical and tribological properties that
can be obtained using different types of reinforcements in different orientations with
different volume fractions. Generally frictional properties of polymer composites are
different from that of metals. In contrast to metals polymers deform at higher loads.
The friction at the mating surfaces is characterized by adhesion and deformation. As a
result the coefficient of friction decreases as the load increases.
Polymer based materials are finding increasing use in many engineering
applications owing to their flexible chemistry and availability of wider choice of
systems [3]. One of the areas where their use has been found to be particularly
advantageous is the situation involving contact wear. Due to the low coefficient of
friction and also the ability to maintain loads, some specific grades of polymer are
used in place of the traditional metal based materials in recent times [14,15]. It is
therefore, imperative to give greater thrust to the examination of this aspect through
increased research activities in the materials. One such possible method to widen the
approach is to adopt fillers/whiskers into the polymeric matrix systems. A second
method would be to resort to the use of continuous fibrous//woven cloth/and high
performance fiber cloths like carbon, aramid and basalt in many forms as
reinforcement and study its response to wear and friction. In view of above two
methods, many researchers have been conducted with various shapes, sizes, types and
compositions of fibers and fillers in number of matrices [1626].
Major consumers of plastics have become more quality and performance
oriented on account of global competition. The synthesis and characterization of new
polymers would require an exhaustive research work which will be time consuming
and more expensive than development of new polymers [27].
Composites provide the designer, fabricator, equipment manufacturer and
consumer with sufficient flexibility to meet the demands presented by different
environments and special requirements. Thus they often eliminate the crippling
necessity faced by the designers of restricting the requirements of designs to
traditional experience. The goal in creating the composite is to combine similar or
dissimilar materials in order to develop specific properties that are related to desired
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characteristics. Since composites can be designed to provide an almost unlimited
selection of characteristics, they are employed practically in all industries.
Composites are used in a variety of economically efficient and sophisticated field of
application ranging from low cost building materials, aircraft application, automobile
parts, goods, sound insulation shields, miniature printed circuits for space crafts and
furniture industries.
However, the use of polymeric composites is still limited by tribological
performance, requiring metal inserts or other provisions, which usually negate most
of the weight and fabrication benefits gained by using the composite. It is possible
that with a better understanding of the tribological properties of composites
they can be designed intelligently to overcome these difficulties. Numerous
studies over the past few decades have investigated the tribological properties of
many types of composite materials. The effects of matrix type, fiber/filler type, fiber
orientation, load, speed, lubrication, and lubricating fillers have been experimentally
studied and modeled.
1.3.3 Influence of various parameters on abrasive wear performance
The wear behaviour of a tribological material is characterized based on
number of results of wear parameter and their interdependence obtained in a given
environment under certain operating conditions such as load, speed, sliding distance,
type of motion with different mating materials. Commonly used wear parameters
which give quantitative/qualitative estimate of different aspects of wear are wear
length, wear area, wear volume (weight loss), wear velocity, wear rate, wear
coefficient, wear depth, surface roughness and surface deterioration [28-30].
However, all these wear parameters may not be of relevance in all the tribological
situations. Wear length which represents the one dimensional change in the geometry
of tribological material is simple to measure. However, it is considered less important
as compared to wear area which represents a two dimensional change of the cross
section of a tribological material, when variations in cross- sections is an indicative of
performance degradation. A still better measure of wear in most tribological
situations is the wear volume which represents a three dimensional change in the
geometry of the tribological materials involved. Wear volume is connected via
density or specific gravity with wear mass, wear weight or weight loss. When time
variations of wear are required, wear velocity measurement may be of prime
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importance. Similarly, material loss per unit sliding distance is also representative of
wear measure [29, 31].
In particular, the usage of glass epoxy composites as an engineering material
is increasing day by day due to low cost and special properties and design freedom. In
recent days the application has increased in automobiles, engineering machinery
components, electrical and electronic parts because of its noncorrosive and good
insulation property [32-34]. Due to essential relative motion between the parts
required to fulfill the functional requirement, in many such parts while working in
systems is subjected to rubbing action. Example: relative motion between parts in
automobile, in switch gears; contactors etc. In such situation along with the existing
advantageous properties of glass epoxy composites need good tribological properties
also. Hence, it is very important to study the tribological properties of glass epoxy
composites with different parameters.

1.4 Literature survey
The tribological performance of composite materials is usually related with
the properties of their reinforcement. One of the traditional concepts to improve the
friction and wear behaviour of polymeric materials is to enhance their hardness,
stiffness and compressive strength and to reduce their adhesion to the counter part
material [35-36]. A notable advance in the polymer industries has been the use of
fiber and particulate fillers as reinforcement in polymer matrix. However, the matrix
materials also play an important role as is the case for thermoset resin matrix
composites which can be designed for specific applications by properly selecting the
polymer. Some of the commonly used polymers include PTFE, polyetheretherketone
(PEEK), polyamide, polyethylene, phenolic, vinyl ester, unsaturated polyester, epoxy
etc. [37-40]. Epoxy resins are basically the thermosetting resins. One of the most
prominent characteristics of these materials is the ability to adhere to the metallic and
non-metallic surfaces. On the other hand, advanced epoxy resins are characterized
with some of the features such as outstanding mechanical and electrical structure,
superior size stability, and high resistance against heat and chemical effects. Also
epoxies in moulded or cast form have excellent dimensional stability and low
shrinkage. Further, it has been reported that epoxies reinforced with fillers and fibers
possess very good mechanical and tribological properties. In recent years, much
research has been devoted to exploring the potential advantage of thermoset matrix
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for composite applications. Many investigations have shown that the incorporation of
fiber reinforcement improved the wear resistance and reduced the coefficient of
friction [41]. In most cases, carbon fiber proves better in this respect than the more
abrasive glass fiber. The lubricating function of the graphitized carbon is thought to
be responsible for the reduction of friction coefficient and wear rate as the composites
slide against the mating surface. Besides the lubricating function, carbon fiber also
enhances the thermal conductivity and the mechanical properties of the polymer
matrix, which is believed to be beneficial to the wear resistance as well. Chauhan et al
[42] have investigated on sliding wear behaviour of vinylester and its composites under
dry and water lubricated sliding conditions.
Thermoplastic composite materials are being widely used in machine
elements such as gears and bearings due to its excellent wear resistance and intrinsic
lubrication characteristics. The ease and economics of manufacturing complex parts
by injection molding, excellent strength-to-weight ratio, tailorable properties of
thermoplastic composites are well recognized [43-44]. Due to the chemical inertness
of the base polymer, these materials find applications where harsh environments, such
as aqueous, corrosive chemical environments, etc., prevail. The continuous drive to
improve technology in all areas of manufacturing, processing and transportation is
placing increasing demands upon the materials to operate in special environments and
under adverse conditions. Chen et al studied the effect of different metallic
counterface materials on the wear and friction of polyamide 66 and its composite
[45]. Very recently the sliding friction of thermoplastic polymer composites has been
reported by many scientists [46-48]. Recently, Xie et al have investigated the
tribological behaviour of PEEK/PTFE composites reinforced with potassium titanate
whiskers [49].
The modification of tribological behaviour of fiber-reinforced polymers by the
addition of filler material has been reported [50-53] to be quite encouraging. Most
studies on the influence of filler material, in the case of polymer composites sliding
against metallic counterfaces have reported on the reduction of wear rate and
coefficient of friction. In addition to the higher mechanical strength obtained due to
the addition of fillers in polymeric composites, there is direct cost reduction due to
the less consumption of resin material. Various researchers [54-57] have reported that
the wear resistance of polymers is improved by the addition of fillers. Some of the
fillers which are effective in reducing friction and wear are MoS
2
, CuO, CuS, Al
2
O
3
,
11
etc. Kishore et al [58] have analyzed the influence of sliding speed and load on the
friction and wear behaviour of glass reinforced polymer composite, filled with either
rubber or aluminium oxide particles, wherein it is reported that the wear loss
increases with increase in load/speed. The use of graphite as a filler material is known
to improve the mechanical and tribological properties of polymer matrix composites
[59]. Recent studies using a sliding-wear tester have demonstrated that variations in
test parameters can profoundly alter the wear behaviour of polymer composites.
A literature survey indicated that the short fiber reinforcement, in general, led
to the deterioration in the abrasive wear resistance of the matrix [60]. Fabric
reinforcement, on the other hand, improved the abrasion resistance of the polymers
[61]. Many researchers studied the two-body wear behaviour for polymers in general
and polymer composites in particular [62-63]. Cirino et al [63] investigated the
sliding and abrasive wear behaviour of PEEK with different continuous fibers and
reported that the wear rate decreases with increase in the fiber content. The abrasive
wear behaviour of short carbon/glass fiber reinforced with PEEK/polyphenylene
sulphide (PPS) thermoplastic polymers were studied by Lhymn et al [64]. The results
showed that the addition of ultra high molecular weight polyethylene (UHMWPE)
reduced the wear rate. Friedrich [65] investigated the abrasive wear behaviour of
epoxy reinforced with carbon, glass and aramid fabrics and reported the wear
performance of the fabrics in the order Aramid > glass > carbon.
1.4.1 Thermoplastics
Thermoplastics have replaced metals in many light duty load bearing
applications because of their lightweight, economic fabrication and good chemical
resistance. Polymers exhibit low coefficient of friction compared with metals due to
their low interfacial adhesion energy [66]. The mechanical strength, modulus and
wear resistance of polymers largely determine the suitability of these materials for
applications like gears, bearings, cams, etc. Furthermore polymer gears and bearings
can accommodate shock loading, shaft misalignment and bending better than metal
parts. Polyamides and polyacetals are widely used thermoplastic polymers for
structural applications. Friction and wear behaviour of unreinforced nylon is widely
reported in literature [6770]. The friction behaviour of commercial polymer based
bearing materials were studied using by sliding against steel surface. It was reported
that the friction and wear behaviour of nylon was fairly satisfactory under dry sliding
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conditions and lubrication was found necessary at higher speeds. Watanabe and
Yamaguchi [67] investigated the effect of temperature, load and sliding speed on the
coefficient of friction and wear behaviour of nylon. Viscoelastic property of nylon
influences the tribological behaviour. Friction and wear experiments were conducted
on 18 polymers when slid against steel in air and water by Mens and de Gee [68]. It
was reported that addition of PTFE with the base polymers lowers the wear rate when
tested under unlubricated dry conditions [71]. The roughness and the lay orientation
influence the wear rate of polymers. Polymers are reinforced with fibres to improve
the strength and stiffness of the matrix. Glass and carbon fibres are the most widely
used reinforcing agents in nylon matrix. These fibres are usually sized to permit good
bonding with the matrix, producing a material of high flexural and tensile strength.
Addition of reinforcements in nylon not only affects the mechanical but also the
tribological properties [72-73]. Tribological properties of glass fabric reinforced
polyamide composites filled with CuO and PTFE were reported by Bahadur and
Polineni [70]. With the glass fabric reinforcement the steady state wear rate of nylon
was found reduced. The mechanical and tribological properties of polyamide 6 (PA6)
with HDPE polyblends with and without compatibilizer were also reported [73].
Addition of reinforcements will affect the friction and wear properties of nylon and
the effect needs to be clearly understood for better utilization and widening
application of nylon based polymer composites.
Thermoplastic material responds to induced stress by two mechanisms,
viscous flow and elastic deformation. Viscous flow dissipates the applied mechanical
energy as frictional heating and results in permanent material deformation. Elastic
deformation stores the applied mechanical energy as completely recoverable material
deformation. The service temperature, duration and magnitude of stress decide the
failure mechanism of composite materials [74].
Recently, there has been a considerable amount of research directed towards
acquiring a comprehensive understanding of the tribological behaviour of these
materials [75-76]. There have been numerous reports of the tribological behaviour of
fibre glass reinforced polymers because of the possibility of using polymer
composites for wear resistive applications [77-78]. Wear tests [79] conducted on the
wear of several polymers sliding against steel showed the specific wear rate
decreasing with increasing sliding distance. For glass fibre reinforcing polymer
matrix [80-81] the process of material removal in dry sliding is dominated by four
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mechanisms (i) matrix wear, (ii) fibre sliding wear, (iii) fibre fracture and (iv)
interfacial debonding.
Polymers and polymer-based composites are widely used because of the
combination of good mechanical and tribological properties, especially in dry friction
conditions where lubricants cannot be used [8284]. It is often found that such
properties are not attainable with a homopolymer. The methods of polymer
modification include copolymerizing, reinforcing and blending.
The friction between polymers can be attributed to two main mechanisms:
adhesion and deformation [8587]. Erhard [86] found that the friction coefficient of
polymerpolymer combination increased with the increasing adhesive work between
them. Czichos [87] also attributed the majority of friction between polymerpolymer
sliding to adhesion effect. Israelachvili and co-workers [88] pointed out that friction
force of polymerpolymer combination was correlated with the adhesion hysteresis
between two shearing polymer surfaces. Chen et al [89] stated that the population of
chain ends at surfaces was the most important factor that determined the adhesion,
friction and wear between two polymer surfaces. Dry sliding of polymerpolymer
combinations always produced intermittent motion and seizure or stickslip [90-91]
due to adhesion, while the adhesion might be considerably influenced or changed by
some ways. The rough-on-rough surface sliding combinations had lower friction
coefficients than those of smooth-on-smooth surface combinations, frictional
hardening or orientation [92] and adding solid lubricants to polymer matrix [93-97]
could decrease adhesion of two sliding surfaces while grafting acid polar groups to
polymer surface would increase adhesion and friction coefficients of polymer
polymer combinations [96]. It is generally known that external lubrication is a useful
method to reduce adhesion of two sliding surfaces.
Components made from injection-moulded PA66 and PA66 composites
running in nonconformal rolling-sliding contact are widely used in engineering.
Typical examples include gears, cams and rolling element bearings. PA66 has been
reported to have superior wear resistance to other polymers due to its ability to form a
thin and uniform transfer film while sliding against steel counterparts [98]. Clerico et
al [99] reported that there were no substantial differences in the wear rate of particle
filled PA66 running against bronze and glass-fibre reinforced PA66 composite
running against steel when in rolling-sliding contact. It has also been shown that the
transfer of film from the polymer to the steel counterface reduces both the friction and
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the wear rate due to a change in the sliding conditions from polymer sliding on metal
to that of polymer sliding on polymer. The friction and the wear behaviour of the
polymeric material depends on the nature, thickness and stability of the transfer film
that is formed and on the properties of the metallic counterface material. However,
relatively little research has been carried out when both PA66 and PA66 composite
run against different grades of steel with different surface treatments as well as
different counterface materials in non-conformal rolling-sliding contact [100-107].
Experiments were carried out either at different slip ratios under a given normal load
or at different loads with a given slip ratio. With this method the typical loading and
sliding conditions of engineering components in non-conformal, rolling-sliding
contact can be simulated [106-108].
Polyamides most favoured class of engineering materials, are preferred as
materials for bearing, gears etc., by virtue of their easy availability, appreciably good
combination of strength properties along with tribo-performance (in composite form)
and cost. Since this class of polymers is known for high friction coefficient (l - 0.6),
they are not used in virgin form. A number of research papers are available reporting
on the improvement in wear resistance of various PAs such as PA6, PA66, PA11,
PA46, PA1010 etc., with the help of various fillers and reinforcements such as PTFE,
graphite, MoS
2
, glass fibers (GF), carbon fibers (CF) etc., [109111]. Reinforcement
preferentially enhances the wear resistance while solid lubricants reduce the friction.
However, efforts to optimize the combination of these fillers to boost the strength and
tribo-performance of PAs in different wear modes are not reported and hence,
required especially in the background of such papers available for other polymers and
composites [112].
A notable advance in the polymer industry has been the use of fiber and
particulate fillers as reinforcements in polymer matrix [113-114]. Particulate fillers
are of considerable interest, not only from an economic point of view but also as
modifiers especially in respect to physical properties of the polymer. It is well
documented in the literature that majority of fillers have a positive influence on
mechanical properties [115- 116]. Furthermore, it is known that the shape, size, and
volume fraction of any filler will influence this modifying effect on the properties
[117122]. Rajesh et al [119] reported abrasive wear of various polyamides. Cai et al
[120] studied the tribological properties of Al
2
O
3
-polyimide nanocomposites. A dry
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sand/rubber wheel abrasion test was used investigate the three-body wear behaviour
of polyaryletherketone composites [121].
Tewari et al have observed that wear rates increased rapidly with increasing
fibre concentration [122]. A combination of particulate filler (PTFE) and carbon fibre
proved to be very detrimental to abrasive wear resistance. In most cases, the specific
wear rate decreased with an increase in load. Except for bronze-filled PTFE, all the
fillers (carbon, graphite, PTFE and MoS
2
) as well as short glass fibres increased
abrasive wear [123].
Kukureka et al [124] reported a comparative study of effect of reinforcement
of three types of short fibres- aramid, carbon and glass on the friction and wear of
nylon 66. Tayeb et al [125] have undertaken an experimental investigation to study
the effect of fibre orientation on tribological performance of polymer composites. The
abrasive nature of glass fibres was reported by Hasim and Nihat [126] in a study on
block on ring wear tester at higher loads and higher speeds. This is in good agreement
with the recent findings on the influence of fibre orientation on the friction and wear
of polymer composites.
1.4.2 Effect of fillers
Use of low cost, easily available fillers is therefore useful to bring down the
cost of component. Study of the effect of such filler addition is necessary to ensure
that the mechanical properties of the composites are not affected adversely by such
addition. Available references suggest a large number of materials to be used as fillers
in polymers [127]. The purpose of use of fillers can therefore be divided into two
basic categories; first, to improve the mechanical, thermal or tribological properties
and second, to reduce the cost of the component. There have been various reports on
use of materials such as minerals and inorganic oxides, such as alumina and silica
mixed into widely employed thermoplastic polymers like polypropylene (PP) [128-
129] and polyethylene (PE) [130- 131]. But very few attempts have indeed been made
to utilize cheap materials like industrial wastes in preparing particle-reinforced
polymer composites. A key feature of particulate reinforced polymer composites that
makes them so promising as engineering materials is the opportunity to tailor the
materials properties through the control of filler content and matrix combinations and
the selection of processing techniques. A judicious selection of matrix and the
reinforcing solid particulate phase can lead to a composite with a combination of
16
strength and modulus comparable to or even better than those of conventional
metallic materials [132]. Hard particulate fillers consisting of ceramic or metal
particles and fiber fillers made of glass are being used these days to dramatically
improve the wear resistance of composites, even up to three orders of magnitude
[133]. Various kinds of polymers and polymer matrix composites reinforced with
metal particles have a wide range of industrial applications such as heaters, electrodes
[134], composites with thermal durability at high temperature [135] etc. These
engineering composites are desired due to their low density, high corrosion
resistance, ease of fabrication, and low cost [136-137].
Polyamides such as nylon 6 and nylon 66 are engineering thermoplastics
which have found great attractions in wide variety of engineering applications due to
their desirable mechanical properties, suitable tribological characteristics and ease of
processing. These properties can also be improved further when suitable particulates,
short fibers or special additives are incorporated into the nylons. However, the type
and content of the additives depend on the final usage of the product. The good wear
resistance and self-lubricating characteristics as well as good strength and stiffness of
nylons make these thermoplastics promising candidate in the bearing applications
where two different bodies are in contact at severe sliding conditions [138-139].
However, further improvement is still required to meet more demanding applications.
In order to enhance the tribological characteristics of nylons efficiently, the solid
lubricants may be added into the polymer matrix. The solid lubricants often lead to
decrease of friction coefficient and wear rate through the reduction in adhesion with
the counterface or creation a transfer film with low shear strength at the interface
[140-141].
Polytetrafluoroethylene so called teflon, is a well-known anti-adhesive
material for tribological applications [142]. However, due to its poor processability
with the commercial processing equipments such as extruder and injection moulding
machines and relatively weak mechanical properties, the widespread usage of teflon
as anti-friction materials is restricted. Alternatively, teflon can act as an efficient solid
lubricant when it is added into the nylons matrix so that the nylon/teflon composites
take the advantages of good mechanical properties and processability of the nylons
and very low friction coefficient and good wear resistance of teflon. The results have
indicated that the teflon decreases friction coefficient and wear rate of the nylons
while the mechanical properties are reduced due to the weaker mechanical properties
17
of teflon with respect to neat nylons [143-146]. However, incorporation of teflon can
improve the mechanical properties of nylons at wetted conditions because of the
reduction in the water absorptivity of nylons.
1.4.3 Inorganic particles with other fillers
A traditional route to achieve high wear resistant polymer composites is the
combination of various functional fillers [147148]. In order to reduce the adhesion
of polymers to metallic counterparts, internal lubricants such as PTFE powders and
graphite flakes are frequently incorporated. In a PEEK matrix, PTFE powders were
applied as additional filler together with micron size CuS particles [149] or SiC
nanoparticles [150], respectively. Two opposite trends were observed. In the first
case, the addition of PTFE contributed to a reduction of both the wear rate and the
frictional coefficient. However, in the latter case, PTFE brought a negative effect to
the tribological properties, which was believed by the authors to be due to a chemical
reaction between the SiC nanoparticles and the PTFE. In other studies of the Bahadur
et al [151,152], micron size CuS or CuO particles together with PTFE powders were
added into short carbon fibre or glass fabric reinforced polyamide (PA). Neither CuS
nor CuO alone contributed to the development of a good transfer film when being put
together with the fibres. However, the further incorporation of PTFE was very
effective in the reduction of wear.
There are more and more technical applications in which friction and wear are
critical issues. Polymer composites containing different fillers and/or reinforcements
are frequently used for these purposes. In particular, they are now being used as
sliding elements, which were formerly composed of metallic materials only.
Nevertheless, new developments are still under way to explore other fields of
application for these materials and to tailor their properties for more extreme loading
and environmental temperature conditions. One example for automotive applications
is the new generation of control arm mountings or ball joints in the car chassis
technology, in which higher loads and temperature are acting on a tribo-couple. In
this case, polymer composites will be operated at relatively high environmental
temperature, e.g., 120
0
C, and the demand for high wear resistance becomes
increasingly important. To understand these properties at severe operating conditions
is directly related to the safety and service life of the technical components
considered.
18
Inorganic particles are well known to enhance the mechanical properties of
polymers, which has been widely investigated in the past decades. It has been found
that the size of the particles plays an important role to improve, in particular, stiffness
and toughness simultaneously. Reducing the particle size to a nanoscale level is
assumed to reach a significant efficiency. Nanoparticle filled polymers, so-called
polymer nanocomposites, are very promising materials for various applications. They
are expected to replace polymers, polymer blends and their traditional composites in
products produced by melt processing techniques. This prediction is justified by the
improvements in properties without sacrificing the melt rheological properties. The
major feature of polymer nanocomposites is their huge interfacial surface area, which
may result in a peculiar physical network structure of three-dimensional interphase
[153]. Nano-fillers are also expected to be able to strongly influence the wear
performance of polymers and composites. By the way, how these materials must
exactly be designed depends on the requirement profile of the particular application.
That means the tribological characteristics, i.e., the friction coefficient and the wear
resistance, is no real material properties, but depends on the system in which these
materials have to function. Sometimes, a high coefficient of friction, coupled with
low wear, is required (e.g., for brake pads or clutches). In most of the cases, however,
it is of primary concern to develop polymeric composites that possess low friction
and low wear properties under dry sliding conditions against smooth metallic
counterparts (e.g., as gears or bearings).
1.4.4 Fibre reinforced composites
There are a wide range of applications for polymers in wear-related situations
such as bearings, gears, sprockets, sleeves, valve guides, seals, brakes etc. The
attraction of polymers for these applications lies in their high specific strength, low
coefficient of friction, favourable wear characteristics, ease of processing and
economic feasibility [154]. A number of material-processing strategies have been
used to improve the wear performance of polymers. These include the incorporation
of organic and inorganic fillers as well as the addition of glass, carbon or aramid
fibers. The addition of these second-phase materials results not only in improved
tribological properties but also in superior physical and mechanical properties.
Because of the technological importance of composite materials, the friction and wear
behaviour of reinforced polymers has been actively investigated [155-156]. The wear
19
process for these materials is fairly complex. The interaction of the matrix and fiber
materials, and in some cases the coupling agent as well, complicates the fracture
process which results in the formation of wear particles. It has been reported [157-
159] that the coefficient of friction and the wear rate of reinforced polymers depend
on the fiber orientation, with superior wear resistance when the axis of the fibers is
normal to the plane of sliding. This is presumably so because the fibers in this
orientation are in the best position to support load and resist detachment from the
matrix. The magnitude of the effect of orientation on wear decreases as the fiber
content increases.
Short fibre reinforced thermoplastics have been used in the automotive
industry for many years and there has been a strong growth in the use of polyamide
based materials in under the hood applications. More recently there has been an
increasing growth in the use of long fibre thermoplastic composite systems in semi-
structural and engineering applications. It is interesting to note that the growth rates
for polypropylene based long fibre compounds has far exceeded that of the other long
fibre thermoplastic systems over the last decade. This has occurred despite the fact
that many of the early developments and long fibre thermoplastic products were
based on polyamide resins. It may well be the part of the background to this
phenomenon lies in the excellent levels of profitability, processability and
performance of these materials are now utilized for numerous tribological purposes,
such as seals [160-161], gears [162-163], bearings [164-173], brakes and clutches
[174], transmission belts [175], rollers [176], tank track pads [177-180], artificial
joints [181-185], grinding mills [186], engines [187], space instruments [188], office
automation machinery [189] and audio-visual machinery [190]. A summary of the
tribological applications of plastics and rubbers is given by Uchiyama [191].
The influence of fibers and/or fillers on the abrasive wear resistance of neat
polymer is more complex and unpredictable and mixed trends are reported [190196].
Lancaster [192] studied 13 polymers reinforced with 30% short carbon fiber and
reported that reinforcement enhanced the wear performance of seven composites
while that of six composites deteriorated. Sole et al [193] studied the effect of mineral
fillers such as talc, CaCO
3
, BaSO
4
, and fly ash on abrasive wear of resistance of PP.
They reported that the addition of mineral fillers to the PP matrix decreases the wear
resistance under severe abrasion conditions. However, under mild abrasion conditions
the shape and size of the reinforcing filler influences the wear performance. Briscoe
20
et al [194], however, reported mixed trend for the abrasive wear of polyether ether
ketone (PEEK)-filled PTFE and PTFE-filled PPE. Incorporation of PEEK in PTFE
reduced the wear rate of PTFE while the wear rate increased in the later case, though
the extent of influence depended on the polymers and the type of fillers. Lu et al
[195], for instance, investigated the abrasion resistance of earth moving equipment
components made up of alumina + PTFE + PPS and reported that the wear
performance continuously increased up to 20% filler concentration. Beyond that it
worsened drastically.
1.4.5 Internal lubricants and short fibres
A comprehensive comparative study of four different internal lubricants
(PTFE, graphite, MoS
2
and SnS
2
) on the sliding wear of composites was reported by
Jacob et al [196]. Xintao et al [197] observed that 5-25 wt.% PTFE and 5-30 wt.%
Graphite contributes to improved tribological performance PTFE filled PEEK
composites. The beneficiary effect of using PTFE is also reported by Babu et al [198].
Xiubing et al [199] emphasized the friction and wear behaviour mechanism of
graphite and MoS
2
filled composites. A recent study by Valeria et al [200] indicated
that MoS
2
particles were found to improve the wear resistance of UHMWPE in both
adhesive and abrasive mode.
In order to improve the friction and wear behaviour of polymeric materials,
one typical concept is to reduce their adhesion to the counterpart material and to
enhance their hardness, stiffness and compressive strength. This can be achieved
quite successfully by using special fillers. To reduce the adhesion, internal lubricants
such as PTFE and graphite flakes are frequently incorporated. One of the mechanisms
of the corresponding reduction in the coefficient of friction is the formation of a
PTFE-transfer film on the surface of the counterpart [201]. Short aramid (AF), glass
(GF) or carbon (CF) fibres are used to increase the creep resistance and the
compressive strength of the polymer matrix system used [202206]. Normally the
matrix should possess a high temperature resistance and have a high cohesive
strength. However, sometimes it is also advantageous to have a PTFE based matrix in
which a stiffer and more wear resistant polymer phase along with other fillers provide
more optimum conditions for the tribological situation under particular consideration,
e.g., its use at cryogenic temperatures [207]. Additional fillers that enhance the
thermal conductivity are often of great advantage, especially if effects of temperature
21
enhancement in the contact area must be avoided in order to prevent an increase in
the specific wear rate. It should also be noted, that not all the fillers are of benefit to
the wear performance of composites. The wear resistance is increased when fillers
decompose and generate reaction products which enhance the bonding between the
transfer film and the counterface [206], whereas other fillers decrease the wear
resistance because they generate more discontinuities in the material. It is thus
important to understand the growth, bonding and loss of transfer films, which are
strongly related to the wear mechanisms. It should also be noted that chemical and
mechanical interactions of transfer films are very complicated, therefore, further
efforts to understand these relationships in more detail are still a subject of current
and future studies [210-211].
Influence of toughness on friction and wear characteristics of polycarbonate
(PC) have been reported by Mergler et al [208]. Recently the influence of ZnO
nanoparticles on the thermal, mechanical and tribological properties of PC has been
investigated by Carrion et al [209]. PP is an extensively used thermoplastic in the
industry because it is an inexpensive material, with relatively good performance in
terms of strength and easily processability. Polypropylene-based lining materials are
being used in industry due to its high chemical and wear resistance, etc [214]. Navin
and Dwivedi have investigated the abrasive wear behaviour of chopped jute fibre-
reinforced PP composites [211]. Byett and Allen have studied the reciprocating dry
sliding wear behaviour of PA66 and PC containing glass fibres, ultra high molecular
weight polyethylene (UHMWPE) and PTFE/2% Si oil. It has been shown that
additions of 1015% of filler/reinforcement lead to greatly improved sliding wear
behaviour [212]. The UHMWPE reinforced with carbon fibers (CF) in different
contents was studied and the effect of CF content on hardness and tribological
properties of the materials were studied. The results show that the hardness and wear
resistance of CF-reinforced UHMWPE composites increased with CF content [213].
Hashmi et al have investigated Sliding wear behaviour of wear resistant polymer,
UHMWPE/PP blends in different proportions at different pressures and sliding
speeds. The wear volume of PP reduces significantly on the addition of UHMWPE.
Reduction in wear loss of UHMWPE filled PP blend has been attributed to the
reduction in temperature at contact surface of UHMWPE filled PP blend significantly
low as compared to PP [214].
22
1.4.6 Solid lubricants
A solid lubricant is defined as a material that provides lubrication, under
essentially dry conditions, to two surfaces moving relatively to each other. A solid
lubricant material is used as powder or thin film to provide protection from damage
during relative movement and to reduce friction and wear. Other terms commonly
used for solid lubrication include dry lubrication, dry-film lubrication, and solid-film
lubrication. Although these terms imply that solid lubrication takes place under dry
conditions, fluids are frequently used as a medium or as a lubricant with solid
additives. The desirable properties of a solid lubricant [215-218] are to (a) provide
low, constant and controlled friction between two bearing surfaces, (b) be chemically
stable over the required temperature range, and not to attack or damage the bearing
material, (c) preferably adhere strongly to one or both bearing surfaces so that it is not
rapidly lost from the bearing, (d) have sufficient resistance to wear to provide a useful
life, (e) be non-toxic and economical. These requirements are so demanding that most
substances are ruled out for one reason or another and the vast majority of solid
lubrication involves only few substances like graphite, MoS
2
and PTFE.
The solid lubricants often lead to decrease of friction coefficient and wear rate
through the reduction in adhesion with the counterface or creation a transfer film with
low shear strength at the interface [219-220]. Solid lubricants, e.g. PTFE, MoS
2
and
graphite flakes, have been proved very helpful in developing a continuous transfer
film between the two counterparts and can drastically reduce the wear rate of the
composites [221222].
Recently, nano-scale inorganic particles are under consideration. Attempts
give special hints that this method is promising for new routes of wear resistant
materials even at very low filler content (about 14 vol%) [223-224]. The effect of
nanoparticles on the sliding wear of polymer composites have been reported by [225-
226]. However, the mechanisms by which nanoparticles in modifying the tribological
performances in polymer composites are not fully understood.
A number of research papers are available on the improvement in wear
resistance of various nylons such as nylon 66, nylon 6, nylon 11, nylon 46, etc., with
solid lubricants such as PTFE, graphite (Gr) and MoS
2
[227-228].
The external variables that affect the tribological properties are many, among
which are applied loads, sliding distance, running speed, counter-surface topography,
23
working temperature and many other physico-mechanical properties of the
counterparts [142-146]. Studying the effects of such parameters is of a continued and
common interest [229-234]. However, in spite of the considerable attention spent on
the tribological behaviours of materials in general, the share of polymers was
somewhat less. Among the very poor attendant parameters that affect the tribological
properties of polymers is the impact force. The phenomenon of impact as a collision
of two moving bodies where we have active and reactive forces of large magnitude is
commonly encountered in machines such as automobiles, construction machinery and
equipment, and many others [235-238].
1.5 Scope of the present investigation
The polymer composites clearly exhibit the properties which are advantageous
in comparison to both their conventional filler/fibre counterparts and base polymer.
Properties which have been shown to undergo substantial improvements include
mechanical properties, decreased permeability to gases, water and hydrocarbons,
thermal stability and heat distortion temperature (HDT), chemical resistance and
electrical conductivity.
The good wear resistance and self-lubricating characteristics as well as good
strength and stiffness of PAs and PC make these thermoplastics promising candidate
in the bearing applications where two different bodies are in contact at severe sliding
conditions. However, further improvement is still required to meet more demanding
applications. In order to enhance the tribological characteristics of PA 66, PA 6 and
PC efficiently, the solid lubricants may be added into the polymer matrix. The solid
lubricants often lead to decrease of friction coefficient and wear rate through the
reduction in adhesion with the counterface or creation a transfer film with a low shear
strength at the interface.
Polymer composites operate in applications where fluid and grease lubricants
fail, and have superior tribological performance to traditional polymer composites.
Particulate fillers or fibres or solid lubricants have been a part of notable reductions in
the wear rate of the polymer matrix at very low loading, and there exists a wide scope
on the development of polymer composites on the tribological behaviour. The main
goal is to achieve a comprehensive understanding of the tribological aspects of the
prepared polymer composites and their uses.
24
The research programme involves the investigation of the effect of the type
and content of solid lubricant fillers such as PTFE, MoS
2
and graphite on the physico-
mechanical properties and the wear mechanisms of polymer composites were studied.
The developed polyamide/polycarbonate composites will find applications in
automobile/electrical sectors respectively.
1.6 Background and motivation of the investigation
The engineering plastic composites technology has been the subject of intense
research in both academic and industrial aspects. Use of thermoplastic composite
material for load bearing components is increasing due to economical processing of
complicated shapes in large quantities. Addition of fibre improves the strength and
modulus of composites. Although the tribo-behaviour of thermoplastic composites
was investigated, the friction and wear mechanisms are not yet fully understood.
With the enlargement of application fields of polymers and their composites,
it is essential to study the tribological behaviours as well as the mechanisms of
polymermetal sliding combinations. So PTFE, nylon 66, nylon 6 and polycarbonate
(PC) are promising sliding materials, which are selected in this research programme.
The solid lubricants are added to these polymers because our attention is paid on the
effect of antiwear additives (in single and in mixture) on the tribological behaviours
of engineering composites. The purpose of this research work is to gain some insight
into the wear mechanisms of polymer compositesmetal combinations. It is expected
that this study may be helpful to widen the application range of engineering plastic
composites sliding combinations in practice.
1.7 Objectives of this study
The current research programme involves the investigation of the effect of the
type and content of solid lubricant filler (PTFE, MoS
2
, graphite and UHMWPE) on
the physico-mechanical properties like density, tensile, impact behaviours, thermal
and the wear mechanisms of engineering thermoplastics composites such as nylon 66,
nylon 6, PP and PC. Addition of fillers/additives/reinforcements will affect the
friction and wear properties of engineering plastics. The effect needs to be clearly
understood for better utilization and widening applications of engineering plastics
(nylon and PC) based polymer composites. This thesis focuses on the tribo-behaviours
of anti-wear additives filled nylon 66, nylon 6, PP and PC composites. The wear
25
mechanisms of these polymer composites in the thesis are discussed. Also to generate
the wealth of sliding wear data on thermoplastic composites, this may be useful for
young academicians and researchers.
1.8 Present research problem
The main goal of the present research work is to achieve a comprehensive
study and understanding of the effect of solid lubricants on the mechanical and wear
characteristics of engineering plastic composites for automotive applications.
Thermoplastic composite technology is simple, flexible and inexpensive
method to generate newer materials with tailor made properties by changing the
composition and morphology of the components. There is an ample scope to continue
research on the modifications of polymer composites using different antiwear
additives to meet the demand of newer applications in many engineering sectors.
The nylon 66, nylon 6, PC and PP have been fabricated by melt mixing
method using extrusion with different solid lubricants and their influence on the
properties have been interpreted in this thesis. The prepared thermoplastic
composites were characterized by physico-mechanical properties, thermal (TGA,
DSC and DMA) behaviours, wear characteristics and laser etching. Scanning electron
microscopy and optical microscopy were used to probe the morphology of the worn
surface and laser etched surface features of polymer composites and to understand the
mechanisms involved in the sliding wear analysis. The generated results are expected
to be beneficial to tailor made applications as sought by material and polymer
technologists.
The results of this research investigation have been systematically presented
and analyzed. Since experimental methods are very important for understanding the
results, their description has been included. The details of the experimental works
carried out are presented in Chapter 2. With the understanding of the experimental
equipments, procedures and methods of measurements (characterizations) on
engineering thermoplastic plastic composites, the experimental data are presented in
the forthcoming chapters.


26
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