Wear 252 (2002) 361369

Sliding wear behavior of PTFE composites

Jaydeep Khedkar a , Ioan Negulescu b , Efstathios I. Meletis a,
a

Materials Science and Engineering Program, Department of Mechanical Engineering, Louisiana State University, Baton Rouge, LA 70803, USA b School of Human Ecology, Louisiana State University, Baton Rouge, LA 70803, USA Received 23 March 2001; received in revised form 25 June 2001; accepted 26 September 2001

Abstract The tribological behavior of polytetrauroethylene (PTFE) and PTFE composites with ller materials such as carbon, graphite, E glass bers, MoS2 and poly-p-phenyleneterephthalamide (PPDT) bers, was studied. The present ller additions found to increase hardness and wear resistance in all composites studied. The highest wear resistance was found for composites containing (i) 18% carbon + 7% graphite, (ii) 20% glass bers + 5% MoS2 and (iii) 10% PPDT bers. Scanning electron microscopy (SEM) was utilized to examine composite microstructures and study modes of failure. Wear testing and SEM analysis showed that three-body abrasion was probably the dominant mode of failure for PTFE + 18% carbon + 7% graphite composite, while ber pull out and fragmentation caused failure of PTFE + 20% glass ber + 5% MoS2 composite. The composite with 10% PPDT bers caused wear reduction due to the ability of the bers to remain embedded in the matrix and preferentially support the load. Differential scanning calorimetry (DSC) analysis was also performed to study the relative heat absorbing capacity and thermal stability of the various composites in an effort to correlate these properties to the tribological performance. The results indicated that composites with higher heat absorption capacity exhibited improved wear resistance. The dominant interactive wear mechanisms during sliding of PTFE and its composites are discussed in view of the present ndings. 2002 Published by Elsevier Science B.V.
Keywords: PTFE; Fillers; Wear; Friction; MoS2 ; PPDT; Carbon; Graphite; Differential scanning calorimetry

1. Introduction Polytetrauroethylene (PTFE) is currently nding increasing utility in high performance mechanical seals due to its unique properties like high chemical resistivity, low coefcient of friction and high temperature stability [1,2]. However, PTFE exhibits poor wear and abrasion resistance, leading to early failure and leakage problems in the seals. The wear resistance of PTFE can be signicantly improved by addition of suitable ller materials [3]. Besides the type, the shape and size of the materials added also inuence the tribological properties [4]. In the past, research in this area has been conned to the PTFE lled with conventional ller materials like glass bers, graphite, carbon bers, etc. However, with the growing demand for utilizing PTFE in a variety of applications, signicant effort is needed towards developing novel composite materials by adding one or more non-conventional ller materials possessing the potential of increasing the wear resistance. It is established that PTFE exhibits signicantly low coefcient of friction when sliding against steels. The low coefcient of friction results from the ability of its extended
Corresponding author. Tel.: +1-225-578-5806; fax: +1-225-578-5924. E-mail address: meletis@me.lsu.edu (E.I. Meletis).

chain linear molecules, (CF2 CF2 )n , to form low shear strength lms upon its surface and mating counter-faces during sliding [4,5]. However, this repetitive formation and destruction of the lm occurs at a high rate and results in unacceptable high rates of wear as shown by Steijn [6]. It was proposed by Lancaster [7] that addition of high aspect ratio ller materials (carbon bers, glass bers) to PTFE can improve its wear resistance due to preferential load supporting action by these bers. There have also been some reports on the use of particulate ller materials like MoS2 and graphite to modify the tribological properties of PTFE [810]. Tanaka and Kawakami [11] have studied the effect of incorporation of glass bers and MoS2 particulates separately on the friction and wear properties of PTFE. According to them, although the glass bers are effective in preventing the large-scale fragmentation of the PTFE, they tend to undergo fracture under heavy loading conditions and cause abrasion to the contact surfaces. It was also proposed that the addition of MoS2 alone does not impart a good wear resistance to PTFE, especially during severe conditions of sliding [9]. This is because the particulates are ineffective in carrying the load and, hence, result in higher wear rate. However, addition of lubricating MoS2 in the presence of a strengthening (glass bers) phase

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has the potential to reduce the abrasion by the latter by maintaining a low friction lm. This lm would have been disrupted by the strengthening phase if only PTFE were present. Blanchet and Kennedy [12] have argued over the hypothesis by Tanaka and Kawakami [11] that the presence of transfer lms on the counter face to be the sole wear reducing mechanism for PTFE and PTFE composites. They proposed that the ller materials embedded in the PTFE matrix reduce the subsurface deformation and interrupt crack propagation. They suggest that the wear mechanism of the PTFE composites is entirely different from that of the bulk PTFE polymer. In the case of the composites, the ller materials obstruct the large-scale fragmentation of the PTFE, resulting in formation of small discontinuous fragments. This reduces the overall wear rate. Pocock and Cadman [13] used differential scanning calorimetry (DSC) to study the chemical reactions occurring between the llers and the polymer matrix at higher temperatures. Arkles and Schireson [14] have investigated the changes in the crystallinity of the wear debris as compared to the bulk PTFE polymer. All of the above research ndings suggest, that incorporation of two or more ller materials each having a distinct functionality (one providing wear resistance and the other a lower coefcient of friction), can result in a composite with the potential of enhancing tribological performance. The aspect ratio of the ller material seems to be a critical parameter for providing wear resistance under severe conditions of sliding. Polymer composites incorporating poly-p-phenyleneterephthalamide (PPDT) bers have shown to possess improved mechanical properties [15]. There is very limited previous work on the wear mechanisms of the PTFE composites, incorporating two or more llers. The purpose of the present investigation was to study the wear behavior and dominant mechanisms involved during the sliding wear of PTFE composites.

of each material are presented in Table 1. The materials were provided in the form of tubes (62.5 mm outer diameter and 10 mm thick) by Industrial Plastics and Machines Ltd. (Baton Rouge, Louisiana, USA). 2.2. Hardness measurements Hardness measurements were carried out on 6 mm thick specimens as per ASTM D224 standards on a shore D scale. Indentations were made at several locations for each specimen and the average hardness value was calculated. The indentation load for each measurement was 22.5 N and hold time was 15 s. The variation in the hardness values was within 10% of the average value. 2.3. Friction and wear testing Unidirectional sliding friction and wear tests were carried out in laboratory air (36% humidity) using a computer controlled pin-on-disc type tribometer. A 440C steel ball, 9 mm in diameter was used as a pin material. All the tests were conducted at a load of 5 N and a sliding velocity 0.1 m/s. The coefcient of friction (f) was monitored with the aid of a linear variable displacement transducer and was continuously recorded throughout the tests. Sliding wear and friction studies were carried out using all test specimens as disks. Prior to testing, it was ensured that all the specimens were polished to a desired surface roughness (R a 400 nm). = Two types of wear tests were performed in the present study. Preliminary tests were rst conducted on all materials for a sliding distance of 1 km. Based on these results, the composites exhibiting higher wear resistance were selected and further tested for a sliding distance of 5 km. In all tests, the ball wear was negligible and below detection limits using optical microscopy (50 magnication). Wear rate of the disc material was determined by conducting prolometry measurements in the wear track region. Four proles were taken for each wear track and the average values are reported. 2.4. Failure analysis Scanning electron microscopy (SEM) was employed to observe the changes in the wear track surface after testing,

2. Experimental 2.1. Materials Pure PTFE and six PTFE based composite materials were studied in the present work. The compositional details
Table 1 Composition (vol.%) of PTFE composites Materials Pure PTFE 75.0% PTFE 85.0% PTFE 75.0% PTFE 75.0% PTFE + 18% + 15% + 25% + 20% carbona E glass E glass E glass + 7% graphiteb bers bers bers + 5% MoS2 Designation A B C D E F G

Characteristics of ller materials 99% pure PTFE powder Carbon particulates 1025 m size + graphite akes 2550 m size 10 m diameter bers, 5075 m in length 10 m diameter bers, 5075 m in length Fibers 10 m diameter and 5075 m in length + small MoS2 particles with 810 m diameter Chopped bers 50100 m in length, 1012 m in diameter Chopped bers 50100 m in length, 1012 m in diameter

97.5% PTFE + 2.5% PPDT 90.0% PTFE + 10% PPDT

a b

Amorphous. Hexagonal.

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study the possible modes of failure and assess the role of individual ller elements in the modication of the tribological properties. Also, SEM was utilized to characterize the debris after wear testing. 2.5. DSC experiments DSC studies on the PTFE and PTFE composites were carried out using a SEIKO 6200 system coupled with a computer station (HP 712/60). The objective here was to study possible reactions taking place between the llers and the matrix at high temperatures and investigate the thermal stability of the present composites. All experiments were carried out in an oxygen atmosphere and at a heating rate of 5 C/min up to 400 C. The amount of heat absorbed by the materials during melting (i.e. heat of fusion in mJ/mg) was also estimated for each case by calculating the area of the melting peak. The results were obtained as input energy versus temperature.

Fig. 2. Frictional behavior of PTFE and PTFE composites (A: PTFE; B: 75% PTFE + 18% carbon + 7% graphite; C: 85% PTFE + 15% E glass bers; D: 75% PTFE + 25% E glass bers; E: 75% PTFE + 20% E glass bers + 5% MoS2 ; F: 97.5% PTFE + 2.5% PPDT bers; G: 90% PTFE + 10% PPDT bers).

PPDT bers to PTFE (composite G) also caused a signicant improvement in hardness. 3. Results 3.2. Friction and wear behavior 3.1. Hardness analysis Fig. 1 shows the comparative hardness values of the composites and the PTFE polymer. It can be seen that addition of ller materials to PTFE causes a signicant improvement in the hardness (up to 26% increase). In particular, composite B (PTFE + 18% carbon + 7% graphite) displayed the maximum hardness, which more than likely is due to the presence of the carbon particles. A considerable improvement in the hardness of glass ber lled PTFE was observed with an addition of MoS2 in small quantities. Addition of 3.2.1. Short duration tests Fig. 2 presents the variation of f with sliding distance of PTFE and PTFE composites for the 1 km tests. It is observed that after 1 km distance, f for all materials tested varied in the range 0.1 < f < 0.16. This is in agreement with the analysis made by Tanaka et al. [4], who have showed that the presence of transfer lms on the counter surface enables the same frictional characteristics to be maintained even with the presence of ller materials. The results presented in Fig. 3 show that the addition of ller materials

Fig. 1. Average hardness values of PTFE and PTFE composites (A: PTFE; B: 75% PTFE + 18% carbon + 7% graphite; C: 85% PTFE + 15% E glass bers; D: 75% PTFE + 25% E glass bers; E: 75% PTFE + 20% E glass bers + 5% MoS2 ; F: 97.5% PTFE + 2.5% PPDT bers; G: 90% PTFE + 10% PPDT bers).

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Fig. 4. Coefcient of friction of PTFE composites during long duration testing. Operating conditions: load 5 N, sliding velocity 0.1 m/s, environment laboratory air 36% relative humidity, sliding distance 5 km (B: 75% PTFE + 18% carbon + 7% graphite; E: 75% PTFE + 20% E glass bers + 5% MoS2 ; G: 90% PTFE + 10% PPDT bers). Fig. 3. Average wear rate of PTFE and PTFE composites (A: PTFE; B: 75% PTFE + 18% carbon + 7% graphite; C: 85% PTFE + 15% E glass bers; D: 75% PTFE + 25% E glass bers; E: 75% PTFE + 20% E glass bers + 5% MoS2 ; F: 97.5% PTFE + 2.5% PPDT bers; G: 90% PTFE + 10% PPDT bers).

can cause a dramatic improvement (up to one order of magnitude) in the wear resistance of PTFE. Composite B (PTFE + 18% carbon + 7% graphite) exhibited the highest wear resistance amongst all composites. This behavior can be attributed to the presence of hard carbon particles, which are embedded within the matrix and impart additional strength to the composite. Comparing the wear resistance of composites C and D (Fig. 3), it can be seen that increasing the percentage of the glass bers in the PTFE, increases the wear resistance. The results for composite E also suggest that glass bers with the presence of a small amount of MoS2 particulates (5%) in PTFE cause a signicant improvement in the wear resistance. Although, the percentage of glass ber in composite E (20% glass ber) is lower than that of composite D (25% glass ber), the addition of MoS2 particulates (composite E) enhances the wear resistance as seen in Fig. 3. This indicates that addition of MoS2 to glass ber PTFE composite is more effective than increasing the percentage of glass ber. Similarly, PPDT, a high strength and elastic modulus ber [14], when incorporated in signicant levels (10%) to PTFE (composite G) can cause a remarkable improvement in the wear properties of the composite. When present in low levels such as in composite F (PTFE + 2.5% PPDT), was not found to be as effective. 3.2.2. Long duration tests Composites B, E and G, which exhibited the highest wear resistance, were tested for a longer duration (5 km) in order to study the role of individual ller elements present in the composites. Fig. 4 shows the variation in the coefcient of friction with respect to sliding distance and the long duration wear rates are shown in Fig. 3. It is observed that f for

composite B (PTFE + 18% carbon + 7% graphite) exhibits a slight increase with sliding distance. On the contrary, composites E and G maintain a steady value of the coefcient of friction during the entire test. Even though composite B exhibited a slightly higher wear rate compared to composites E and G, the results show that all three-wear rates are within the same bulk gure. Also, the present behavior is in general agreement with that exhibited in the short duration tests. The latter rates, however, are somewhat higher since they are disproportionally affected by the break-in stage. 3.3. Microstructural analysis Fig. 5a and b are SEM showing surface morphology of composite B before and after long duration wear testing, respectively. Observations from the wear track revealed regions of localized wear along the sliding direction. High magnication observations indicated the presence of sharp, irregularly shaped particles on the wear tracks (Fig. 5c). Fig. 6a and b show the surface appearance of composite E before and after long duration wear testing, respectively. Glass bers with random orientation embedded within the PTFE matrix can be observed along with scattered agglomerated MoS2 particles. Examinations also revealed a higher percentage of glass bers on the wear track surface resulting from the sliding action. Observations on the wear track at high magnication showed de-bonding of glass bers along with ber fragmentation (Fig. 6c). 3.4. DSC analysis A DSC study was conducted on bulk PTFE and the three composites that exhibited the highest wear resistance (composites B, E and G). Thermal traces of the bulk PTFE and the three PTFE composites are shown in Fig. 7. Table 2 summarizes the heat of fusion values of bulk and wear debris (collected after 5 km of wear testing) from PTFE and the

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Fig. 5. SEM from 75% PTFE + 18% carbon + 7% graphite showing surface appearance (a) before wear testing, (b) after wear testing and (c) high magnication of wear track region (testing conditions: load 5 N, sliding velocity 0.1 m/s, environment laboratory air 36% relative humidity, sliding distance 5 km).

Fig. 6. SEM from75% PTFE + 20% glass ber + 5% MoS2 showing surface appearance (a) before wear testing, (b) after wear testing and (c) high magnication of the wear track region (operating conditions: load 5 N, sliding velocity 0.1 m/s, environment laboratory air 36% relative humidity, sliding distance 5 km).

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Fig. 7. Thermal traces of PTFE and PTFE composites using DSC (operating conditions: heating rate 5 C/min, atmosphere oxygen).

Table 2 DSC analysis (A: PTFE; B: 75% PTFE + 18% carbon + 7% graphite; E: 75% PTFE + 20% E glass bers + 5% MoS2 ; G: 90% PTFE + 10% PPDT bers) Material designation Material A Composite B Composite E Composite G
a b

Wear ratea (mm3 /N m) (105 ) 94 8.5 11.1 12.3

Average wear debris size ( m) 2000 125 500 100

Thermal conductivity (W/m C) 0.25 0.73 0.50 0.36

Peak melting temperature ( C) Bulk: 326, Bulk: 327, and 330 Bulk: 328, Bulk: 326, debris: 331 debris: 313 debris: 329 debris: 328

Heat of fusion (mJ/mg) Bulk: 18.0, debris: 39.5 Bulk: 21.5, debris: 17.0b Bulk: 27.9, debris: 24.2 Bulk: 25.4, debris: 36.0

Value is the total of two peaks of 12.9 and 4.1 mJ/mg. Based on 1 km sliding distance.

three PTFE composites. The heat of fusion, Hf , corresponds to the area of the melting peak (total heat input) divided by the mass of the sample (that has been corrected in the case of composites for the ller materials) and signies the amount of heat absorbed per unit mass of the matrix during melting. A comparison between the thermal traces of pure PTFE and composite materials shows no indication of any additional reaction between the ller materials and the matrix in the temperature range tested (from 30 to 500 C) and no major variation in the position of the transition-melting peak. The results show that Hf values of the bulk composites are signicantly greater than that of the bulk PTFE polymer. This indicates a higher thermal stability for the composites compared to the pure polymer. Amongst the composite materials, composite E (20% glass bers + 5% MoS2 ) exhibited the highest Hf value. The results of the DSC analysis on the wear debris (Table 2) show that in general the debris exhibited lower fusion heat values than its parent bulk material. The variation in the heat of fusion depends on the proportion of the ller materials present in the debris and these effects are discussed in Section 4.

4. Discussion 4.1. Tribological behavior Composite B exhibited the highest wear resistance in the short duration testing (1 km) compared to PTFE and the rest of the composites in spite of its slightly higher coefcient of friction (Fig. 2). This behavior can be attributed to the presence of carbon and graphite akes, which act as effective barriers to prevent large-scale fragmentation of PTFE. This is also evident from the small size of the wear debris particles as determined by SEM analysis (Table 2). Several authors [8,9] have discussed the role of graphite as an effective ller material. The carbon particles act as effective dispersion strengthening elements, as is clearly demonstrated by the increase in the hardness values for composite B (Fig. 1) and in addition the graphite acts as a solid lubricant so together provide enhanced tribological behavior. Further more, this composite has the highest thermal conductivity amongst all materials tested that can result in better heat dissipation and lower prevailing temperatures at asperities. However, for longer sliding distances, the presence

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of carbon particles is not as effective on the improvement of the tribological properties, since a slight gradual increase in the coefcient of friction is observed (Fig. 4) and the wear rate increases above that of composites G and E (Fig. 3). It is proposed that this increase in the coefcient of friction could be due to the abrasive nature of carbon particles which when present at the sliding interface cause three-body abrasion. SEM observations of the worn surfaces of composite B (Fig. 7c) show the presence of sharp irregularly shaped particles, which more than likely are carbon particles. This indicates a strong possibility of abrasive wear, where the carbon particles plough the PTFE matrix and destroy the transfer lm formed on the counter-face. In addition, the absence of ller material with a high aspect ratio and the ineffectiveness of lamellar graphite to preferentially support the high contact stresses, causes some deterioration of the tribological properties. Hence, three-body abrasion seems to be the dominant wear mechanism in case of composite B. SEM also showed localized abrasion within the wear track (Fig. 5c), which further contributes to the above reasoning. Composite E (containing MoS2 and glass bers) exhibited somewhat different tribological characteristics. It has been reported [3,4] that glass bers suffer from poor abrasion resistance during sliding of PTFE composites. This is evident from the higher wear rates observed for composites C and D. However, the presence of MoS2 modies the tribological behavior of PTFE containing glass bers. Probably, the MoS2 particles, having a lamellar structure and being uniformly distributed prevent the direct contact between the glass bers and the counter surface. This causes the integrity of the transfer lm on the counter-face to be maintained and to lower f even for longer sliding distances. SEM analysis indicated an increase in the volume fraction of glass bers on the surface of the material after sliding. This is due to the preferential wear of the PTFE matrix during the tribological interaction. The glass bers, having a high aspect ratio reduce the wear rate of the material by preferential load supporting action while the presence of MoS2 helps in maintaining a lower coefcient of friction and prevents glass bers from causing abrasion. Moreover, from the SEM examination there was no indication of localized wear. However, examination at higher magnications (Fig. 6c) indicated de-bonding from the PTFE matrix along with fracture of the glass bers at selected locations. The dominant wear mechanism associated with composite E seems to be de-lamination along with micro-fracture of the glass bers at the interface. Tanaka and Kawakami [11] have reported that the aspect ratio of the ller materials is a very important parameter to be considered for evaluating the tribological properties of PTFE composites. A higher aspect ratio results in a better ability of the ber to resist contact stresses [10] and in better wear resistance. This seems to be the case of PPDT and glass bers incorporated into PTFE. Thus, in composites F and G (PTFE + PPDT bers) the higher aspect ratio along

with the high modulus of elasticity are probably the main factors responsible for the improved wear resistance. Additionally, more surface area of the ber is in contact with the matrix, which improves the adhesion of the ber to the matrix. The SEM debris analysis (Table 2) showed a small average particle size, which indicates the effectiveness of the llers to interrupt large-scale fragmentation of the polymer. In this case, the results suggest that increasing the volume fraction of bers is more effective in decreasing wear rate. The SEM analysis on pure PTFE indicated a large average wear particle size, which could be a result of removal of the nanometer-scale lm build up on the counter face during the wear action. This is in agreement with Blanchet et al. [5], who cite that the wear debris is generated due to the disruption of nanometer-scale transfer lms and thicker plates, lumps and slabs of polymer formed on the counter-face during the repetitive sliding action. However, in the case of the composites, the presence of the ller materials in the PTFE matrix impede the lm build up process resulting in a wear debris particle smaller in size than pure PTFE. 4.2. DSC analysis of bulk PTFE composites The increased heat absorbing capacity and thermal stability of the PTFE composites as compared to the bulk material can be attributed to effects by the presence of ller materials within the PTFE matrix. These effects can be two-fold. First, the matrix may form a strong bond with the ller materials increasing stability. Second, the presence of the latter may cause an increase in the degree of crystallinity of the matrix. Amongst the composite materials, composite E (containing 20% glass ber and 5% MoS2 ) absorbed the greatest quantity of heat suggesting that the addition of glass bers and MoS2 particulates induces higher levels of stability. For composite B, the addition of carbon and graphite causes a slight increase in the heat absorption capacity of the composite. In the case of composite G, PPDT is a synthetic polymer that belongs to the family of aromatic polyamides, which have excellent high temperature resistance and high levels of crystallinity. Moreover, it is a polymer liquid crystal, which when blended with PTFE, induces high levels of crystallinity in the resultant composite. In addition, the processing parameters and the properties of the ller materials play a signicant role in determining the nal properties of the composite. Probably, the processing at higher temperatures induces a kind of secondary bonding between the llers and the matrix, which in turn improves the thermal properties. 4.3. DSC analysis of the wear debris The observed signicant increase in the fusion heat of the PTFE debris (39.1 mJ/mg) as compared to bulk polymer (18 mJ/mg), indicates that a higher degree of crystallinity is present in the wear debris. It should also be noted that pure

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PTFE is essentially a semi-crystalline material, with selective amorphous regions between the crystalline regions. During sliding, the amorphous phase wears out leaving behind debris rich in the crystalline phase. It is also possible that the shearing action enhanced by the localized heating from friction causes the bers/fragments to orient in a particular direction thereby increasing the crystallinity. The combined effect of these two phenomena causes the increase in the fusion heat. In the case of composite B (18% carbon + 7% graphite), the mechanism of sliding wear was entirely different. Abrasion seems to be the dominant mode of failure due to the presence of carbon particles along the interface. The DSC curve for debris of the composite showed two distinct melting peaks, indicating the existence of two phases of PTFE, one crystalline and the other more than likely amorphous. This is also consistent with the observed peak melting temperatures. The crystalline phase (present in all materials tested) shows a melting temperature in the range of 326331 C whereas the second lower melting temperature (313 C) can be attributed to the amorphous phase. The presence of carbon and graphite in the material may have caused intermittent disruption of the fragmentation of the material along the boundaries of the amorphous and crystalline boundaries, thereby, resulting in the two phases. The heat of fusion shown in Table 2 refers to both phases (since it cannot be discriminated) and is lower than that of the bulk. This suggests that as a result of the wear process, a higher proportion of the ller particles is present in the debris compared to the bulk. The analysis of the wear debris for PTFE with MoS2 and glass ber also shows a decrease in the fusion heat compared to that of the bulk composite. It is well known that during sliding, the MoS2 particles accumulate on the surface and subsequently enter the wear debris. Moreover, there could be a small quantity of glass bers present in the debris, as evidenced by SEM analysis (Fig. 6b) reducing the weight fraction of the PTFE matrix. This combined effect can cause the fusion heat of the debris to decrease. For composite G (PTFE + 10% PPDT), the DSC analysis of the wear debris indicated an increase in the heat absorption capacity. It is well known that PPDT is a liquid crystal polymer (LCP) with higher toughness than glass ber [14]. Thus, during sliding, PPDT bers more than likely tend to remain embedded in the matrix and proportionally more PTFE matrix enters the debris. However, it should be noted that the debris is much ner in this case than in pure PTFE suggesting that the observed tribological behavior is also affected by the presence of the reinforcing phase as noted earlier. Overall, it can be deduced that the presence of excess ller particles in the wear debris compared to the ller content in the bulk (composites B and E), lowers the fusion heat as seen from the DSC analysis. On the contrary, if the strengthening phase remains in the matrix, the wear debris has higher fusion heat (composite G).

4.4. Tribological mechanism Tribological behavior of polymers and polymer composites can in general be associated to their visco-elastic and temperature related properties. Sliding contact of two materials results in heat generation at asperities and, hence, increase in temperature at the interface. Thus, the adhesive wear resistance of the material depends upon the quantity of the heat generated, the way this heat is dissipated and the ability of the material to maintain its integrity at the resultant temperature. Differences in heat generation would be expected mainly as a result of differences in f. In view of the present results, the major factors inuencing the tribological behavior become the thermal stability and thermal conductivity. Composites B, E and G exhibited the largest heat of fusion, possess higher thermal conductivity than PTFE and exhibited the highest wear resistance. Composite B has the highest thermal conductivity and exhibited the highest wear resistance in the short duration tests (1 km) suggesting that thermal conductivity may have a major effect at the initial stages of wear. However, long duration tests show that in addition to the thermal conductivity, factors like thermal stability and ller material characteristics have a signicant effect on the tribological properties. For example, the SEM analysis and wear test results (5 km) show that the abrasive nature of the carbon particles has a detrimental effect on the tribological properties of composite B. Also, the desired properties and higher aspect ratio of the PPDT bers improve the wear resistance of composite G. Additionally, the smaller size of the wear debris produced for all composites demonstrates the role of the llers in impeding the large-scale fragmentation process. The higher Hf values exhibited by the composites more than likely depend on factors such as increased bonding strength between the matrix and ller materials and higher degree of crystallinity induced by the ller material. This results in higher stability at a given temperature as developed during sliding at the interface thereby reducing adhesive wear. The DSC analysis of the wear debris suggests that a smaller proportion of pure PTFE is present in the wear debris and, thus, the presence of ller materials modies the wear process. A possibility is that the PTFE at the matrix/ller interface deforms and wears out preferentially due to the strain incompatibility with the harder ller. This process would result in more ller content as compared to the matrix and ne PTFE particles in the debris (Table 2).

5. Conclusions The following conclusions can be drawn from the present study. 1. Addition of ller materials such as carbon, graphite, glass bers and PPDT to PTFE causes an increase in

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2. 3.

4.

5.

hardness and wear resistance, while the coefcient of friction is slightly affected and remains low. Filler materials in general are effective in impeding large-scale fragmentation of PTFE, thereby reducing the wear rate. DSC studies suggest a correlation between heat of fusion and wear resistance. In the presence of a strengthening phase such as glass bers, MoS2 particles were found to be very effective in improving the wear properties of the composite. PPDT bers were found to be the most effective llers in interrupting large-scale fragmentation more than likely due to their high aspect ratio and desirable mechanical properties. The wear process in the composites depends mainly on three factors: thermal stability, thermal conductivity, and the characteristics of the ller materials.

References
[1] M.W.J. Lewis, Lubric. Eng. 42 (1986) 152158. [2] T.A. Blanchet, F.E. Kennedy, Tribol. Trans. 34 (3) (1991) 327334. [3] L. Huang Lee, in: M.J. Comstock (Ed.), Polymer Wear and its Control, American Chemical Society, Washington, DC, 1985, pp. 2739. [4] K. Tanaka, Y. Uchiyama, S. Toyoka, Wear 23 (1973) 153172. [5] T.A. Blanchet, Y. Peng, S.V. Nablo, Tribol. Lett. 4 (1998) 8794. [6] R.P. Steijn, Wear 130 (1985) 93101. [7] J.K. Lancaster, J. Appl. Phys. 1 (1968) 549. [8] B.J. Briscoe, M.D. Steward, Wear 42 (1977) 99107. [9] J. Bijwe, C.M. Logani, U.S. Tewari, Wear 138 (1990) 7792. [10] S. Bahadur, D. Tabor, Wear 98 (1984) 113. [11] K. Tanaka, S. Kawakami, Wear 79 (1982) 221234. [12] T.A. Blanchet, F.E. Kennedy, Wear 152 (1992) 229243. [13] G. Pocock, P. Cadman, Wear 37 (1976) 129141. [14] B.C. Arkles, M.J. Schireson, Wear 39 (1976) 177180. [15] A. Matthews, R.D. Rawlings, Composite Materials: Engineering and Science, Chapman and Hall, London, 1994, pp. 371377.