Annexure II: Polymer Tribology

Polymers are used in various tribological applications such as seals, gears, bearings, brakes and
clutches, transmission belts, rollers, tank track pads, artificial joints, grinding mills, engines, space instruments,
office automation machinery, and audio-visual machinery [1]. In addition to the applications involving friction
and wear loading, new breed of polymers have found use in special tribological applications such as those
requiring high service temperatures [2]. Thus with the advent of new technologies owing to operational
conditions, automation and computerization, and miniaturization; more stringent requirement are laid on
tribological performance of each and every material [3].
Polymers have very specific structure and mechanical behaviour and hence are sensitive to the
factors such as mechanical stresses, temperature and chemical reactions, which are capable of causing a
change in polymer surface layers in contact region. More importantly, temperature at the contact region are
generally higher due to friction and also transient flashes or hot-spots at asperity level contacts, further
deteriorates the wear resistance of polymers [4].

Wear of Polymers
Wear debris formed during severe friction was studied and friction extrusion at the contacting region
was concluded to be the mechanism of wear debris generation in polymer composites [5]. In composites with
good ductility wear debris was in the form of complete unbroken wavelike ribbons and in flake form for
composites with poor ductility. In steel counterfaces, it has been observed that formation of transfer layer is a
mechanical process in which abraded fragments of material are deposited in the crevices between the
asperities on steel surface [1]. During and after the transfer layer deposition, compounds such as FeF 2, FeSO4
and FeS, which are formed near the interface, enhance the bonding between the transfer layer and the steel
counterface. A thin, uniform and tenacious transfer layer was found to be the reason to enhance the
tribological behaviour of PEEK composites filled with nano-meter sized Si3N4 and SiO2 particles during sliding
against a carbon steel ring [6], [7]. In case of polymers, general wear modes can be classified as follows;
(A) Abrasive Wear it can be either two-body or three-body in nature with microploughing (ridge formation
and no material loss) and microcutting (cutting of ridges as microchips) as the micromechanisms of the
wear process. Wear is manifested as scratches, gouges, scoring marks, or fine cutting chips at much finer
scale. In two-body abrasion, the attack angle of asperity and the interfacial shear strength (the ratio of
shear stress at the interface and the shear yield stress of plastically deformed material) decides the
effective wear micromechanisms: ploughing or cutting. One approach for modelling abrasive wear
considers geometric aspects of asperity while another considers that wear rates are proportional to
1/uu (Lancaster and Ratner model) [4], [8] where u is the ultimate tensile stress and u is the
corresponding strain.

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(B) Adhesion Wear consists of formation of junction, material transfer across the contacting solids, its
growth and fracture. It may be accompanied by other wear types such as abrasion, fatigue [9]. Though
the mechanism of friction transfer is observed in almost all the cases, e.g. metals, ceramics, polymers,
etc., in polymers it is significantly distinct [10]. The transfer layer formed on contacting steel surfaces may
either be held in place which is desirable or is carried away and a new layer is formed, resulting in
increased wear. Transfer of hard particles such as bronze particles is also known to occur in case of
polymers causing increased wear of polymers. The growth and steady condition for transfer layers in
polymer tribology is found to be dependent on test variables such as load and sliding velocity [11].
(C)

Fatigue Wear (Friction fatigue) like in fatigue, presence of frictional contact in polymers results in cyclic
stress during rolling and reciprocal sliding [9]. As a result asperities from friction surface experience
sequential loading from the asperities of counterface, generating stress fields. These stress fields causes
fatigue degradation of surface as well as subsurface layers and finally cracking at the areas experiencing
maximum tangential stress, generates wear particles. Fatigue cracks are also initiated at defects such as
scratches, dents, marks, pits.

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Influencing Factors in Polymer Tribology

Based on the detailed discussion and deliberations covered in previous paragraphs and following
sections, Fig. 1 gives an outline for the significant variables and factors which needs to be given a consideration
in order to arrive at definitive inter-relationships between the working conditions and desired combination of
properties in polymer composites for improved tribological performance.

Polymer
Material

Fibre
Reinforcement

Solid Fillers

Structure

Mechanical
Properties

Mechanical
Properties

Interface
Strength

Amount of
Lubricant

Sliding
velocity

Ductility

Weaving
Structure

Filler Critical
Packing

Temperature

Chemical
Compatibility

Wear
Mode

Toughness

Type of
Lubricant

Process
Characteristics
Load

Mechanical, Chemical & Physical

Compatibility with Filler-Fibre

Chemical
Reactions

Surface
Treatment

Surface
Roughness

Transfer Layer
Characteristics

Micro-roughness
of Asperities

Microstructure

Transfer Layer Bonding

with Counterface

Fig. 1: Significant variables and factors affecting wear polymer composites.

Views on the Project:

In light of the available previous studies discussed and above schematic, it can be seen that in
polymer tribosystem the wear response is material intensive, i.e. wear response of the polymer materials can
be significantly improved via polymer composite structure and ingredient modification/alteration. However, in
order to make a judicious decision on the structural configuration of a polymer composite for a specific
tribological application, it is extremely vital to know the performance characteristics of the decided composite
material in intended application environment and working conditions or an extensive study is to be
undertaken to define the limits and design the enhanced composite based on the experimental evidence thus
obtained. Help of wear modelling is of limited importance in case of polymer composites because of complex
nature of thermo-mechanical and chemical interactions occurring between the composite material and
counterfaces as well as amongst the ingredients (matrix-fibre-filler) of composite material.

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Structure and Properties of Polymer Composites

Like metallic materials, properties of polymer materials can be tailor made either through modifying
the structure of the polymer itself or introduction of additives such as solid lubricants and fibres, to aim for
certain desired properties. For example with increase in molecular weight depth wear rates are enhanced [12]
or by varying the volume proportions of ether and ketone groups in polymer chains, polyaryletherketones can
be altered to have higher glass transition and melting range [13]. In order to improve wear resistance of
polymers other alterable properties include degree of crystallinity, and preorientation [14]. Also tough matrix
polymers like PEEK perform better in wear when compared with brittle epoxy resins. Zhang et. al. [15] studied
the effect of plasms surface treatment on tribological behaviour of carbon fibre reinforced PEEK polymers.
Owing to enhancement in interface strength between the matrix and polymer, improved tribological
behaviour was observed. Yan et. al. [16] studied the inter-relationship between microstructure and wear
performance of graphite/PTFE composites. Presence of microscopic imperfections were analysed and wear
response corresponded well with the imperfections at a macro- and microscopic scale level and reflected by
the interfacial properties of crystalline and amorphous regions.
In polymers, addition of solid lubricants such as PTFE, graphite, and MoS2, reduces friction coefficient.
However, the role of fillers is slightly intricate than fibres in polymer composites. For example, addition of PTFE
powders in PEEK composites reduced both wear and friction coefficients when slid against tool steel, whereas
addition of CuS powders resulted in increase in coefficient of friction [17], [18]. Addition of solid lubricants
results in degradation in mechanical properties too. Bahadur and Gong [19] formulated a model for a critical
packing of inorganic filler powder proportion in polymer-based composites, giving maximum mechanical
strength and highest abrasion resistance. The degradation in mechanical properties due to the addition of
filling material can be compensated via fibre reinforcement which in addition enhance properties such as
stiffness, impact resistance, thermal conductivity, and creep resistance at elevated temperature [20]. Specific
wear rates are also significantly reduced with almost any type of fibre reinforcements when compared to
unreinforced polymers. When introduced in same volume fractions, carbon improves material wear resistance
by almost 5 times to that of glass [21], whereas performance of aramid fibres lies somewhere between the
above two [22], [23], [24]. Carbon fibres have been found to lower the friction coefficients in PEEK polymers
[1]. In another study [25], in a poly(vinyl butyral)-modified phenolic resin-matrix composites reinforced with
three different fibres (E-glass, high-strength carbon and Kevlar-49), Kevlar-49 exhibited the best wear
performance.
On the part of fibres, they should have less sensitivity with respect to the fibre-fibre friction and
hinder early breakage. Strong bonding with the matrix polymer also helps to preserve the broken fibres in the
matrix and thus avoid formation of third bodies between the contacting surfaces [26]. Fibre orientation with
respect to the sliding direction also plays an important role [27]. Carbon fibres parallel to the sliding direction
in PEEK matrix, offers better wear resistance than in normal position. However such an arrangement may work
well in unidirectional sliding. In case of multidirectional sliding conditions, additional fibres in antiparallel
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direction like a woven structure, causes multifold improvement in wear resistance probably on account of fibre
interlocking in the contact area. 3D hybridization has also been found to have extremely good wear response.
Kery et. al. [28] when reinforced amorphous polyamide with carbon and aramid fibres; and used them in
sliding against rotating steel rings, phenomenally superior wear resistance was observed. Addition of
lubricants as inclusions in such 3D fibre arrangement also has shown promising results [29].

Deformation and Friction in Polymer Tribosystems

In recent times, a review was performed on tribological behaviour of polymers covering adhesion at
interface, friction, wear and subsequent mass transfer [9]. It was suggested that friction involves three basic
elements;
(i)

interfacial adhesive bonds, their type and strength,

(ii)

deformation and fracture within and around interacting layer,

(iii) real contact area.

Attraction and repulsive forces are generated between the atoms and molecules of the material,
when brought in contact. The interfacial bonds are followed by junctions at contact spots, which are sheared
on application of tangential forces, resulting in the frictional force. The nature of surfaces in contact, surface
chemistry, and loading conditions in the interacting layer governs the formation, growth and fracture of
interfacial junctions.
Deformation in the interaction volume of the contacting materials is another source of frictional
force. Mechanical energy expended is dissipated including deformation in various forms depending on
deformation mode, sliding conditions, rubbing materials, scale level of mechanical properties, and
environment [9]. The deformed layers and fracture products are regarded as the third body owing to their
properties in variance with the bulk polymer properties [30], [31]. Ploughing contributes to friction when hard
surface asperities plough the softer body in sliding friction condition [32]. Though very small; this component
often increases friction when combined with adhesion and subsequent microcutting. Other forms of energy
dissipation include hysteresis loss in case of viscoelastic polymers [32], [33]; and in the form of elastic waves
owing to nucleation and development of microcracks in material [34], [35].
When two surfaces approach each other closely, their asperities of maximum height come into
contact forming contact spots and overall area of these spots is called as real contact areas (RCA) [9].
Temperature of the contacting surfaces affects the RCA [9] and using Greenwood-Williamsons approach [36]
RCA was found to decrease with temperature. Thus temperature-dependent RCA may pass through a
minimum with rise in temperature. However its existence and minimum value depends on the thermal and
mechanical properties of the contacting materials.

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Friction Effect of Test Parameters

In highly elastic and smooth surfaces, the basic mechanism of friction is adhesion, while transition into
other friction mechanism occurs when polymer transforms into glassy state [9]. In glassy state, more
mechanical energy is expended in plastic deformation of surface layers on polymer. These mechanisms were
observed for both amorphous as well as crystalline polymers [37]. Effect of testing conditions on friction
during wear is different for different polymers which is as detailed below.
(i) Load - Under certain contact conditions, some polymers exhibit exception to the first law of friction
which tells that friction force is proportional to the normal applied load [9]. As a function of load,
friction coefficient in polymers passes through a minimum owing to a transition from elastic contact
to a plastic contact [30], [38], [39], [35], [40].
(ii) Sliding velocity - Relationship between sliding velocity and frictional force is complicated due to the
change in contact temperatures and interface behaviour [9], [41]. Within a limited range of velocities
(0.01-1.0 cm/s), an independent relationship is observed [42], [43]. In low range of velocities, viscous
flow increases the friction [44], [45], [46] whereas at higher velocities elastic behaviour of polymers
either affects only slightly or decreases the friction force [47], [48].
(iii) Polymers as viscoelastic materials are very sensitive to frictional heating [9]. Friction dissipates up to
almost 90-95% of total mechanical energy as heat. Other mechanisms of mechanical energy
dissipation include plastic deformation of material, hysteresis, dispersion and viscous flow. Increase in
test temperature increases specific wear rates and lowers friction coefficients [1]. Effect of
temperature on friction is believed to be dependent on the changes in the mechanical properties of
polymers with temperature. A relationship of coefficient of friction was established with hardness and
shear strength for some polymers [49], [50] [51]. However effect of temperature on adhesion is not
considered in these correlations [37].

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