The Interrelated Effects of Temperature and Environment On Wear and Tribochemistry of An Ultra-Low Wear PTFE Composite

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Article
The interrelated effects of temperature and environment on
wear and tribochemistry of an ultra-low wear PTFE composite
Harman S Khare, Axel C Moore, Diana R Haidar, Liang
Gong, Jiaxin Ye, John Frank Rabolt, and David L. Burris
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.5b00947 • Publication Date (Web): 01 Jul 2015
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Page 1 of 30 The Journal of Physical Chemistry
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4 The Interrelated Effects of Temperature and Environment on Wear and
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6 Tribochemistry of an Ultra-Low Wear PTFE Composite
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9 H.S. Khare1+#, A.C. Moore2+, D.R. Haidar1, L. Gong3, J. Ye1, J.F. Rabolt3, D.L. Burris1,2*
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Department of Mechanical Engineering
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University of Delaware
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17 Newark, DE
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Department of Biomedical Engineering
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22 University of Delaware
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24 Newark, DE
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Department of Materials Science and Engineering
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31 Newark, DE
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36 Abstract
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38 A particular alumina-PTFE nanocomposite has distinguished itself with unusually large wear
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41 reductions at trace filler loadings. Recent studies have shown that the formation of carboxylic
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43 acid end groups in humid environments is a critical part of the wear reduction mechanism. This
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45 finding has significant implications for the utility of the material for space and high temperature
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48 applications. In this paper, wear rate, morphology, composition and chemistry of the wear
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50 surfaces were characterized as a function of environmental composition and surface temperature
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52 to better understand the environmental limitations of this solid lubricating system and the
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55 associated wear resistance mechanisms. The following results were found: (1) ultra-low wear
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57 rates were retained with increasing interface temperature up to 100°C, (2) carboxylates were
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ACS Paragon Plus Environment
The Journal of Physical Chemistry Page 2 of 30
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detected after sliding in dry environments despite high wear rates, (3) all samples ran-in to low
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6 wear regardless of the environmental conditions (dry conditions caused an eventual transition to
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8 high wear), (4) the amount of oxygen in the environment had no detectable effect on steady-state
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wear rates. Although high wear rates in dry environments were associated with reduced evidence
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13 of carboxylates, low wear rate interfaces at high temperatures produced even less evidence of
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15 carboxylates in the running films. Although the formation of carboxylic acid end groups almost
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18 certainly drives reduced wear rates by stabilizing the pin surface and anchoring transfer films,
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20 the results suggest that their presence or absence is not an independent predictor of wear
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22 performance.
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28 Keywords: polymer; transfer film; wear; solid lubricant; PTFE
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31 +equal contributors
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#current address
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36 Dept. of Mechanical Engineering and Applied Mechanics
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38 University of Pennsylvania
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41 Philadelphia, PA 19104
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43 *corresponding author
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45 David L. Burris, Ph.D.
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48 Dept. of Mechanical Engineering
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Newark, DE 19716
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55 dlburris@udel.edu
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57 (302) 831-2006
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1. Introduction
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7 Low friction coefficients, high thermal stability, and resistance to chemical attack 1-7 make
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9 Polytetrafluoroethylene (PTFE) an attractive solid lubricant candidate, but excessive wear rates 1,
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have limited its utility as a bearing material. Adding filler particles or fibers can reduce PTFE
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14 wear rates by an order of magnitude or more 3 due to the prevention of subsurface crack
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16 propagation, but typically also causes counterface abrasion and increased friction 9.
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19 In 2005, Burris and Sawyer 10 discovered that the addition of low loadings of a particular
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21 alumina (α-Al2O3) nanoparticle could reduce the wear rate of PTFE by nearly four orders of
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24 magnitude 11. This was the first study to demonstrate ultra-low wear (k < 5 x 10-7 mm3/Nm) of
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26 PTFE with filler loadings less than 5%. The small size and scarcity of these reinforcing particles
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suggested that mechanisms other than traditional mechanical reinforcement were at work 3, 12-13.
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31 Numerous independent investigations have since been conducted to elucidate the unique wear
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33 resistance mechanisms of this material 1, 3, 8, 13-15.
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36 There were early indications that chemistry played a role based on the observation that these
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ultra-low wear surfaces always exhibited a brown discoloration after transitioning to low wear 16-
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41 . Based on this observation alone, it is impossible to determine whether chemistry was the
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43 cause or consequence of low wear. Krick et al.18 and Pitenis et al. 19 provided compelling
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evidence that tribochemistry causes low wear; during experiments with varying humidity, they
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48 found that reduced humidity caused increased wear rates, counterface abrasion, patchy transfer
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50 films, and loss of the ‘brown’ discoloration. The beneficial effects of environmental moisture on
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53 wear rate strongly suggest a tribochemical mechanism 12, 20 of wear reduction.
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Onodera et al. 21-22 used computational simulations to elucidate the role of environment and
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6 chemistry on the tribological performance of this material system. They proposed that end-chain
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8 carboxyl groups (R-COOH) were likely formed in humid environments and suggested that these
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groups improve bonding of the PTFE to the counterface; stable and well-adhered transfer films
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13 reduce wear by preventing the need for subsequent transfer 1. Pitenis et al. 23 conducted
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15 spectroscopic studies of transfer film chemistry at various stages of sliding in air and observed
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18 increasing quantities of metal chelate salts of perfluorinated carboxylic acids with increased
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20 sliding distance and decreased wear rate. In a follow-up paper 24, they hypothesize the following
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22 three-steps: (1) polymer chains break during sliding to form perfluoroalkyl radicals, (2) radicals
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25 react with oxygen to form acyl fluoride end groups, (3) acyl fluoride end groups hydrolyze in
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27 ambient humidity to form carboxylic acids. The perfluorinated carboxylic acids chelate to the
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steel counterface and the alumina filler, effectively crosslinking the near surface and bonding the
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32 transfer film. To our knowledge, this is the first and only chemistry-driven wear resistance
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34 mechanism proposed for any polymer composite.
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37 These recent studies have convincingly revealed the likely chemical processes that enable the
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development of ultra-low wear rates for this material in ambient conditions. They strongly
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42 suggest that the loss of wear resistance in dry conditions occurs because the absence of humidity
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44 prevents carboxylic acid end groups from forming following chain scission. Additionally, wear
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rate can be expected to increase with interface temperatures due to desorption of water from the
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49 surfaces. To date, however, there have been no measurements of surface chemistry following
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51 high wear sliding under dry conditions and or of wear rates at temperatures above ambient. This
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54 paper aims to 1) establish thermal and environmental limitations of low wear for this material
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and 2) provide spectroscopic evidence that the loss of wear resistance corresponds to the
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6 chemical and compositional changes at the interface.
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9 2. Materials and Methods
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11 2.1 Materials and Sample Preparation
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The polymer matrix in this study is TeflonTM 7C from DuPont (40 µm particles). The filler,
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16 alpha-phase Al2O3 nanoparticles, is from Nanostructured & Amorphous Materials Inc. and has a
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18 reported particle size of 27-43 nm. This particular combination of materials has been the subject
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of several studies showing ultra-low wear behavior of the nanocomposite under ambient
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23 environments 11, 18, 25-29. Alumina nanoparticles (0.5 g) were added to the PTFE resin (9.5 g) in a
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25 PET container of about twice the volume of the powder ensemble to leave room for mixing. The
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28 container was immediately hand-shaken for 20 seconds to promote gross homogeneity of the
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30 mixture prior to ultrasonication. Anhydrous ethanol (80 ml) was added to the powder ensemble
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32 and pulsed using an ultrasonic horn at 360 W with a 50% duty cycle for 5 minutes. The bulk of
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35 the ethanol was removed using filter paper. The mixture was then placed in a heated vacuum
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37 desiccator for two hours at 110°C to evaporate the remaining ethanol. The dried powder was cold
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pressed into a cylindrical preform (25 mm long, 12.5 mm diameter) under a pressure of 170
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42 MPa. The pressure was held for 1 hour to eliminate porosity. The preform was then held at a
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44 pressure of 6 MPa, heated to 365°C over 3 hours, held at temperature for 3 hours and then cooled
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over another 3 hours in ambient lab air (35% RH, 25°C). After sintering, the cylindrical
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49 nanocomposite sample was CNC-machined into a pin measuring 6.4 mm × 6.4 mm in cross-
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51 section and 12 mm in length. The mass and dimensions were measured with an analytical
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54 microbalance and micrometer, respectively, to determine density. Five samples were used in this
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56 study to capture sample-to-sample variability.
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2.2 Temperature and Environment Control
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6 A PID-controlled thermal stage was used to directly heat the counterface to the prescribed
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9 temperature. The thermal stage consisted of an aluminum block of nominally identical
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11 dimensions as the steel counterface, but with cartridge heater inserts. The feedback thermocouple
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was attached to the surface of the steel counterface, which was attached on top of the thermal
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16 stage. The polymer sample was brought into contact and the test began once the temperature
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18 reached the target. During testing, the counterface temperature was held constant to ±1°C.
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21 Wear tests were conducted in a closed glove box (Vacuum Atmospheres Co.), as shown in
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24 Figure 1. A dry nitrogen (N2) environment was established by purging the glove box with
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26 99.998% pure dry N2, followed by closed-cycle recirculation through an activated charcoal
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purifier. A dry air environment (N2 + O2) was established by purging the glove box with lab air
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31 which had been passed through a desiccant filter, rated to a frost point of -80°C. By varying the
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33 duration of purge and purification, moisture content in both dry air and dry N2 was held at either
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36 ~15 parts per million (PPM) or ~150 PPM (equivalent to ~0.05% and ~0.5% room-temperature
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38 relative humidity, respectively). Ambient environment tests were conducted in lab air with
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40 moisture content of ~10,000 PPM, or ~1 part per hundred (PPH), equivalent to a relative
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43 humidity of ~35%.
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31 Figure 1. Schematic of the reciprocating pin-on-flat tribometer housed in an environmental
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33 glove box. A controlled bleed with varying amounts of dry nitrogen, desiccated air and
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humidified air was used to achieve the desired environmental composition. The inset illustrates
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38 the polymer pin, the stainless steel counterface, the transfer film, and the running film.
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41 2.3 Wear Testing
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44 A single 38 × 25.4 × 4 mm, 304 stainless steel counterface was lapped to an average surface
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roughness (Ra) of 35 nm prior to each test. Wear measurements were carried out on a custom-
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49 built pin-on-flat reciprocating tribometer (Figure 1) with a nominal normal load of 250 N, a
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51 mean contact pressure of 6 MPa (250N/6.4mm2), a reciprocation length of 25.4 mm and a sliding
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54 speed of 50.8 mm/s 28. The machined sample was loaded into the ante-chamber and pumped to
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56 rough vacuum before being introduced to the testing environment. The nanocomposite pin was
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then mounted in the tribometer and the surface was conditioned with three reciprocation cycles at
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6 2.5 MPa against 600 grit SiC paper to remove surface contamination and promote contact
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8 conformity. The total duration of sliding in the subsequent wear test did not exceed 50,000
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cycles (2.54 km), the test duration used by Krick et al. 18. Tests were interrupted periodically
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13 (including after conditioning) and the sample was removed from the environment for mass loss
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15 measurements (on a Mettler Toledo microbalance with a resolution of 10µg) and imaging of
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18 wear surface progression. Wear volume was calculated as the ratio of mass loss to density of the
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20 nanocomposite. From the wear-volume curve, the wear rate at any point was evaluated based on
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22 linear regression through the point of interest, the point before, and the point after.
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26 We define low wear here as an instantaneous wear rate (characterized by the regression of the
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28 wear measurements at, before, and after the point of interest) of k < 3×10-6 mm3/Nm; this wear
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30 rate was chosen because it is roughly one order of magnitude lower than those of other lightly-
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33 loaded PTFE nanocomposites 10-11, 30-32. With this definition, the general wear response of each
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35 sample can be characterized by three metrics. The transient wear volume is the measured
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37 volume loss before the sample reached low wear. The distance of low wear is the continuous
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40 distance for which the sample slides with low wear. The terminal wear rate is determined using
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42 the last two measurements of wear volume. These parameters are illustrated with a representative
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dataset in Figure 2.
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22 Figure 2. A representative wear curve plotted against sliding cycles for (a) wear volume, and (b)
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24 instantaneous wear rate, as determined from wear volume, as a function of sliding cycles. The
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29 <3×10-6 mm3/Nm. The distance of low wear corresponds to the total continuous sliding distance
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31 within the low wear region (k < 3×10-6 mm3/Nm). The terminal wear rate is the wear rate
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determined from the last two wear volume measurements.
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37 2.4 Energy Dispersive X-Ray Spectroscopy (EDS)
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40 EDS measurements were made with a Zeiss AurigaTM 60 CrossbeamTM FIB-SEM/EDS after
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42 selected wear test interruptions to determine near-surface composition. EDS spectra were
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45 collected in a 115µm by 85µm sized-window using a 10keV accelerating voltage. Spectra were
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47 collected at 5 random locations on each sample to acquire statistics for spatial variability. Each
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49 spectrum was collected for 60 live-time seconds, with dead-times varying between 15% and 30%
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52 of the total clock time. Identical EDS acquisition parameters were used for transfer films and
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Table 1. Element ratios for the alumina powder, steel counterface, and unworn polymer
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6 nanocomposite. The ratios are given as the mean ± 95% confidence interval in atomic percent.
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9 Measured
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ratio (at.%)
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12 alumina powder N=5 O/Al 1.320 ± 0.050
13 steel counterface N=4 C/Fe 0.114 ± 0.006
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15 O/Fe 0.034 ± 0.005
16 F/Fe 0.021 ± 0.001
17 unworn nanocomposite N=4 C/F 0.780 ± 0.050
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19 O/F 0.020 ± 0.003
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23 Polished counterfaces and stock alumina powder were used as standards. EDS spectra were
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26 collected after lapping the counterface N=4 times (each average was obtained with spectra from
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28 five random locations). The resulting C/Fe, O/Fe, and F/Fe ratios of the counterface are given in
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30 Table 1. Spectra were collected for N=5 alumina powder samples. The measured O/Al ratio for
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33 the alumina is also given in Table 1. Figure 3(a) graphically depicts the atomic composition of
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35 the alumina powder and lapped steel counterface.
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38 To identify any processing related polymer degradation, i.e. degradation unrelated to wear, EDS
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41 spectra were also collected for the unworn nanocomposite. The results of EDS measurements on
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43 N=4 unworn nanocomposite samples are shown in Figure 3(b). To decouple the alumina filler
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45 (Al+O) and polymer (C+F+O) contributions we assume that alumina is the only possible source
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48 of Al in the system and the oxygen associated with alumina is calculated by the product:
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50 Alnanocomposite × O/Alstandard. The contribution of the filler in the unworn controls is shown in
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Figure 3(b) as light grey. These contributions were subsequently subtracted from the total signal
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55 to determine the relative amounts of fluorine, carbon, and oxygen in the polymer; the results are
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The constituents of worn samples were determined in the same manner as those of the controls.
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6 The only difference is that these measurements included possible contributions from the
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8 counterface due to abrasion. The Fe signal was used to subtract contributions from the
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counterface as before (the contribution never exceeded 0.01 at.% of the pin). Significant
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13 differences, P<0.05, are represented by non-overlapping 95% confidence intervals.
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36 N=4, and unworn polymer pin N=4). (a) The elemental at.% values are given for alumina powder
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39 and the steel substrate. (b) The elemental at.% values for the unworn nanocomposite. The
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41 contribution from the alumina filler (light grey) is subtracted from the dataset to establish the
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43 constituents of the polymer (dark grey). Error bars represent the 95% confidence interval for the
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46 population mean.
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49 2.5 Infrared Spectroscopy (IR)
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52 Infrared spectra of the nanocomposite pin and its running films were collected using a Nicolet
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54 Nexus 670 Fourier-transform infrared (FT-IR) spectrometer with a smart orbit attenuated total
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57 reflectance (ATR) accessory. Each spectrum consisted of 128 scans coaveraged at 4 cm-1 spectral
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resolution. Spectra were collected by loading the worn side in contact with the diamond ATR
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6 crystal. Between scanning individual samples, the diamond ATR crystal was mechanically
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8 cleaned by the shearing motion of a q-tip and acetone to remove any transferred PTFE. Then the
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window was further cleaned with a Kimwipe cloth and acetone. Subsequent measurements were
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13 only made after scans of the diamond window no longer revealed trace evidence of PTFE
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The IR spectra of the transfer films were collected using a NanoIR2TM AFM-IR (Anasys
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21 Instruments). The technique combines atomic force microscopy (AFM) and IR spectroscopy for
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23 nanoscale chemical characterization. Following tribological testing, the AFM tip was engaged in
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26 the center of the transfer film and a 100µm x 100µm region mapped. A representative location
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28 was then chosen for IR measurement. The NanoIR spectra were collected with a spatial
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30 resolution of ~50 nm and a spectral resolution of 2 cm-1, coaveraging 256 scans for each data
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33 point. Spectra were collected at morphologically different locations and averaged to obtain a
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35 single representative spectrum for each sample. More details about this technique are reported
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elsewhere33.
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41 Results
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44 3.1 Wear Results
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46 Wear volume is plotted versus sliding distance for tests conducted at 25°C in variable moisture
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49 air (~80% N2 and 20% O2) in Figure 4(a). The sample ran-in to low wear even in dry conditions.
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51 The transient wear volume ranged between 0.2 mm3 for highest humidity and 0.4 mm3 in the
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53 lowest humidity case. With increased moisture in the environment, the duration of low wear
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56 increased and the terminal wear rate decreased. For a decrease in moisture to trace amounts,
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there was a clear transition to a high steady-state wear rate, which is consistent with the results
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6 from Krick et al. 19, 34.
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9 Contrary to our hypothesis, sliding at 100°C did not drive away enough water to disrupt the
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11 transition to low wear (32X decrease in relative humidity at the counterface). Additionally, the
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14 run-in behavior at 100°C became less sensitive to humidity with transient wear volumes being in
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16 the vicinity of 0.1 mm3 for all moisture conditions (Figure 4b). As was the case at 25°C, the
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distance of low wear decreased and terminal wear rate increased with decreased humidity.
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32 Figure 4. Wear volume as a function of sliding distance in air of varying moisture content with
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35 surface temperatures of (a) 25°C and (b) 100°C. (c) The terminal wear rate decreased with
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37 increased moisture content and is insensitive to temperature. Note that at 100°C, the relative
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39 humidity at the counterface was 1/32 that of 25°C for the same moisture condition.
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43 The broader experimental design involved variable moisture content, oxygen content,
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45 temperature, and multiple samples, with replicate experiments of specific combinations thereof.
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47 The entire dataset is shown in Figure 5 for which the transient wear volume, distance of low
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50 wear, and terminal wear rate are plotted versus moisture, temperature, and oxygen of the sliding
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52 environment. The complete dataset suggests that the transient wear volume was not affected by
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moisture (R2=0.01, Figure 5a) or oxygen (R2=0.05, Figure 5c). There was evidence of a
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57 temperature-dependence (R2=0.73, Figure 5b). The most noteworthy result from Figure 5b,
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however, is the difference in variability between low and high temperatures. Transient wear
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6 volumes at 100°C were unusually repeatable; every value of transient wear volume recorded at
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8 100°C was less than every value recorded at 25°C.
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11 The distance of low wear tended to increase with increased moisture (R2=0.43, Figure 5d); it
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14 showed no clear trend with temperature or oxygen when controlled for humidity. Our experience
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16 suggests that the distance of low wear is more strongly correlated to moisture content than this
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coefficient suggests, but our experimental design prevented detection of stronger correlation.
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21 Many of the samples, especially in higher humidity environments, never exceeded the threshold
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23 for low wear and thus ran-out; 14% of low humidity samples ran-out, 66% of moderate humidity
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26 samples ran out, and 100% of high humidity samples ran out. Humidity clearly drives the speed
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28 of the transition to high wear and correlations would likely have been far stronger if tests were
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30 run long enough to reach a true steady state.
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The terminal wear rate did not depend on sliding temperature or oxygen (Figures 5h and 5i). Not
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36 surprisingly, it exhibited strong sensitivity to moisture (R2=0.71, Figure 5g). The terminal wear
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38 rate increased by three orders of magnitude for a three orders of magnitude reduction in moisture
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41 content.
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42 Figure 5. Correlations between dependent and independent variables: (a), (b), (c) - transient
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44 wear volume versus water content, temperature, and oxygen content; (d), (e), (f) - distance of
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47 low wear versus water content, temperature, and oxygen content; (g), (h), (i) - terminal wear rate
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49 versus water content, temperature, and oxygen content. Least-square fits used the better of linear
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51 and power-law functions. White data labels represent low humidity, gray data labels represent
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54 moderate humidity, and black data labels represent high humidity. R-square values are provided
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56 beside each fit. In the event that a metric correlates with water content with R2>0.05 (e.g.
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terminal wear rate), only dry data were used for subsequent correlations as a means to control for
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6 the humidity effect; these cases are marked by as asterisk. Arrows indicate run-out conditions.
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9 Representative transfer films are shown for 0, 3500, and 20500 sliding cycles for 1) low
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11 temperature + high humidity air, 2) low temperature + low humidity air, and 3) high temperature
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14 + high humidity air cases in Figure 6(a). In the low temperature + high humidity control, the
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16 transfer film had a relatively thick (~2 µm) and patchy morphology that became more complete
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19
with increased sliding; the terminal wear rate was 4×10-7 mm3/Nm for this system. When the
20
21 moisture was removed (low temperature + low humidity), the transfer film showed no obvious
22
23 reduction in coverage, but there was clear evidence of counterface abrasion; the terminal wear
24
25
26 rate in the dry environment was one order of magnitude higher for this specific sample (k =
27
28 2×10-6 mm3/Nm). During high temperature sliding in humid environments (high temperature +
29
30 high humidity), the transfer film became extremely thin with evidence of orientation in the
31
32
33 sliding direction; there was no detectable evidence of counterface abrasion in this case. The
34
35 terminal wear rate remained low for this sample (k = 2×10-7 mm3/Nm).
36
37
38 Representative running films on the surface of the pin are shown for the same conditions in
39
40
41 Figure 6(b). The characteristic ‘brown’ discoloration of the low temperature + high humidity
42
43 control running film was evident at 3,500 cycles and darkened with increased sliding. Similar
44
45 discolorations were present in the films of the low temperature + low humidity and high
46
47
48 temperature + high humidity environments after 3,500 cycles but with less intensity than that of
49
50 the control running film. The lightly discolored film persisted after 20,500 cycles in the high
51
52
temperature + high humidity case, but was largely removed by 20,500 cycles in the dry
53
54
55 environment.
56
57
58
59
60 16
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 6. Transfer film and running film morphology in the unworn, transition, and terminal
24
25
26 regions of wear tests. Humid corresponds to 1 PPH water in air and dry corresponds to 15 PPM
27
28 water in air. The images reveal that (a) transfer film coverage continues to increase even with
29
30
31
increasing wear rates and (b) transitions in the appearance of the ‘brown’ discoloration of the
32
33 running film appear to correlate with transitions in wear behavior.
34
35
36 3.2 EDS of Near-Surface Composition
37
38
The transfer film and near surface running film compositions are shown in Figure 7 for 1) low
39
40
41 temperature + high humidity + high oxygen (“ambient”), 2) high temperature + high humidity +
42
43 high oxygen (“100°C”), 3) low temperature + low humidity + high oxygen (“dry air”), and 4)
44
45
46
low temperature + low humidity + low oxygen (“N2”). Composition is broken into three
47
48 categories: alumina, fluorine, and oxygen content (at.%). Wear in dry environments was
49
50 insensitive to the presence of atmospheric oxygen (Figure 5) and Figure 7 demonstrates that filler
51
52
53 accumulation, fluorination, and oxidation were similarly insensitive. Sliding in both dry
54
55 environments was accompanied by filler accumulation (especially in the transfer film), increased
56
57 fluorine, and decreased oxygen. Sliding in the ambient control environment (humid, 25°C) was
58
59
60 17
1
2
3
accompanied by filler accumulation in the transfer film (but not the running film), defluorination,
4
5
6 and oxidation. Sliding at high temperature in humid conditions produced no evidence of filler
7
8 accumulation, less defluorination compared to ambient, and less evidence of oxidation.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Figure 7. EDS measurements of the alumina (Al+O), fluorine, and oxygen content in transfer
29
30 films and running films after 20500 cycles in ambient (25°C, 1 PPH water, k = 4×10-7
31
32
33 mm3/Nm), high temperature (100°C, 1 PPH water, k = 2×10-7 mm3/Nm), dry air (25°C, 15 PPM
34
35
water, k = 2×10-6 mm3/Nm) and dry nitrogen (25°C, 15 PPM water, k = 3×10-6 mm3/Nm).
36
37
38 Error bars represent the statistical 95% confidence interval for the mean; differences are
39
40 statistically significant with P<0.05 for all non-overlapping pairs of confidence intervals. The
41
42
43 95% confidence interval for the unworn controls is denoted by the grey band.
44
45
46 3.3 IR Spectroscopy
47
48 The IR spectra for transfer films and running films after 20,500 cycles in humid air (25°C), dry
49
50
51 N2 (25°C) and humid air (100°C) are shown in Figure 8. The peaks at 1660 and 1430 cm-1
52
53 correspond to the asymmetric and symmetric stretching vibrations of carboxylates 35,
54
55
respectively, while those at 1200 and 1150 correspond to the asymmetric and symmetric
56
57
58
59
60 18
1
2
3
stretching vibrations of the CF2, respectively 24, 36. In addition two medium bands were found at
4
5
6 1315 and 1360 cm-1 in the ambient running film; these have been shown to arise from an axial
7
8 component of the CF2 stretching vibrations and occur only when the fluorocarbon chains are
9
10
11
relatively short 37-38. As expected, the low temperature + high humidity air test displayed the
12
13 greatest evidence of carboxylates (1660 and 1430 cm-1) in transfer films and running films; these
14
15 results are consistent with increased oxygen and decreased fluorine in the EDS spectra. After
16
17
18 sliding in dry conditions, the transfer film showed no evidence of carboxylates but the running
19
20 film did. A new peak at 1260 cm-1 was found after sliding in ambient conditions and especially
21
22 so in dry conditions; because there is some uncertainty about the origins of this peak, we review
23
24
25 possible sources in the discussion. The high temperature transfer films and running films both
26
27 showed evidence of carboxylates, but concentrations were far less than for ambient conditions.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48 Figure 8. (a) IR spectra of transfer films and (b) running films after sliding for 20,500 cycles in
49
50 ambient (25°C, 1 PPH water, k = 4×10-7 mm3/Nm), high temperature (100°C, 1 PPH water, k =
51
52
53 2×10-7 mm3/Nm), and dry nitrogen (25°C, 15 PPM water , k = 2×10-6 mm3/Nm).
54
55
56 Discussion
57
58
59
60 19
1
2
3
This material achieved ultra-low wear in ambient conditions and spectroscopic studies confirmed
4
5
6 the presence of carboxylates in the running and transfer films, and filler accumulation in transfer
7
8 films only; our results support those from Pitenis et al. 23 and Harris et al. 24. Similarly, our
9
10
11
results show that the removal of environmental water disrupts the ultra-low wear mechanism,
12
13 which corroborates the results from Krick et al. 18 and Pitenis et al. 19. This study provides the
14
15 first direct evidence that dry environments do in fact impede the formation of carboxylates,
16
17
18 which supports the hypothesis that carboxylates are directly related to wear rate 23-24.
19
20
21 In addition to the PTFE and carboxylate peaks, we observed peaks at 1315 and 1360 cm-1 in the
22
23 running films and a peak at 1260 cm-1 in the transfer film. All three can be found in the spectra
24
25
26 from Pitenis et al. 23 and Harris et al. 24. While they do not comment on the higher wavenumber
27
28 peaks, they do explore the origin of the 1260 cm-1 peak. They observed this peak after a single
29
30 cycle of sliding and after static pull-off; both conditions are known to transfer exceedingly thin
31
32
33 and likely oriented polymer fibrils 4, 39-42; on the basis of these results and those from Moynihan
34
43
35 and Lauer et al. 42, they attribute this peak to the stretching mode of aligned chain fragments.
36
37 We observed the same peak in thick and well-developed transfer films. During IR studies with
38
39
40 fluoropolymer oligomers, Vanni et al. 37 found peaks at 1260, 1315, and 1360 cm-1; each peak
41
42 became more prominent as the chains shortened and as the ratio of CF3:CF2 increased. Since
43
44
45
there is evidence of a strong IR peak for CF3 at 1260 cm-1 44, this may be due to increased CF3
46
47 which would explain why EDS spectra show excessive fluorine in transfer films formed in dry
48
49 conditions (Figure 7). However, it may also be a consequence of shortened chain length. To our
50
51
52 knowledge, the peaks at 1315, and 1360 cm-1 can only be attributed to shortened chain-length,
53
54 which supports the hypothesis that chain scission is the initial step in the tribochemistry
55
56 responsible for ultra-low wear of PTFE 23-24.
57
58
59
60 20
1
2
3
The removal of oxygen had no detectable effect on any of the wear metrics of this study
4
5
6 (transient volume, low wear distance, terminal wear rate), which appears to conflict with the
7
8 proposed role of oxygen 24; however, since trace amounts were impossible to remove from our
9
10
11
system, its potential participation in generating acyl fluoride end groups cannot be ruled out.
12
13
14 Testing environment had no effect on the run-in wear behavior. All samples in all environments
15
16 tested ran-in to low wear with essentially the same characteristics. These low-wear surfaces post
17
18
19
run-in were brown (but of varying intensity) and appeared surprisingly similar in IR and EDS
20
21 spectra (results not shown). However, following run-in to low wear, whereas the carboxylate
22
23 peak intensified with sliding in humid air, it shrank with sliding as wear rate increased toward a
24
25
26 higher terminal value. Although the magnitude of the carboxylate peak from IR measurements
27
28 decreased with decreased humidity, we were unable to support the hypothesis that dry
29
30 environments prevent the formation of carboxylates during wear.
31
32
33
34
Several limitations may have prevented us from supporting this hypothesis. First, samples were
35
36 intermittently exposed to ambient conditions at interruptions; although pump-purge cycles were
37
38 used to remove contaminants prior to subsequent testing, it does not ensure complete removal of
39
40
41 contaminants. However, follow-up tests without interruption yielded comparable volume losses
42
43 in the low wear regime, which suggests that the interruptions did not significantly affect wear
44
45 behavior. Likewise, an uninterrupted 100,000-cycle test in 15 PPM N2 also produced significant
46
47
48 evidence of carboxylate salts despite having very high wear rates; this result suggests that the
49
50 carboxylates form with or without intermittent exposure to air. A second limitation is that IR
51
52
measurements were conducted in lab air, which prevented us from removing all water sources. It
53
54
55 is possible that radicals formed in the inert environment were stable until being eventually
56
57 exposed to air; this does not explain why the system transitioned to low wear and formed brown
58
59
60 21
1
2
3
surfaces early during sliding in dry conditions, however. We believe that trace contamination in
4
5
6 the environment or the sample must have provided enough fuel to start but the processes but not
7
8 enough fuel to sustain a low wear condition.
9
10
11 Interestingly, heating the interface to temperatures up to 100°C also attenuated the carboxylate
12
13
14 signal in the running film but without disrupting ultra-low wear. The films formed under high
15
16 temperature conditions were clearly very thin compared to those of ambient conditions. The lack
17
18
19
of carboxylate peak in the running film may reflect a reduction in the volume of material
20
21 involved in the wear process rather than the concentration of carboxylates in the volume. Unlike
22
23 the running film, however, the transfer film exhibited a significant carboxylate peak despite
24
25
26 being extremely thin. In general, the wear results of this study show better correlation with the
27
28 carboxylates in the transfer film than with those in the running film.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 9. Wear volume plotted against sliding cycles for three different initial conditions of the
54
55 sliding pair in room temperature air. The transient wear rate early in the experiment is typical
56
57
58 and often associated with the development of the transfer film. Running a worn pin against a
59
60 22
1
2
3
fresh counterface eliminates this transient. The result demonstrates that the transient is more
4
5
6 closely associated with run-in of the pin surface and the initiation of favorable tribochemistry.
7
8 Running a fresh pin on a pre-worn transfer film actually increased the severity of the run-in.
9
10
11 Whether the wear reduction mechanism of the carboxylates primarily involves the anchoring of
12
13
14 transfer films or the stabilization of the pin surface is a significant question. Our IR studies
15
16 suggest that only the chemistry of the transfer film is a predictor of wear performance. However,
17
18
19
Krick et al. 17 showed that wear transients in this system were better associated with the
20
21 stabilization or destabilization of the running films than they were with the transfer films, which
22
23 is consistent with our optical observations of running film and transfer film development.
24
25
26 Bahadur and Tabor 45 showed that the best pre-deposited transfer films had no wear reduction
27
28 effect on higher wear rate materials and concluded that transfer film quality of low wear
29
30 materials is a reflection of reduced debris size and not the cause of low wear. We found that a
31
32
33 pre-worn low wear nanocomposite exhibited an attenuated wear transient when tested against a
34
35 fresh counterface with no well-adhered transfer film (Figure 9). In fact, testing a fresh pin against
36
37 a low-wear transfer film actually increased the severity of the wear transient compared to the
38
39
40 control test. This suggests that the condition of the running film dominates the adhesion of the
41
42 transfer film in the reduction of wear rates.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 23
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 10. Wear volume plotted against sliding distance for a test in which the developing
33
34 transfer film was removed after cycle 43 and replaced with a fresh counterface. The results show
35
36
37
that the transfer film and wear rate develop as they would in an uninterrupted test, which
38
39 suggests that the transfer film develops in response to the developing surface properties of the
40
41 pin.
42
43
44
Our previous in-situ measurements showed that the wear transient of this system is associated
45
46
47 with monotonically reduced debris size and monotonically thinner transfer films 28. This is a
48
49 chicken-and-egg, cause-and-effect problem. Does reduced debris size produce thinner and more
50
51
52
uniform films during run-in or do thinner and more uniform films reduce debris size or does each
53
54 benefit the other? We tested this potential feedback mechanism by running in a sample and
55
56 replacing the counterface after 2.1 m of sliding, a point in the test known to be near the end of
57
58
59
60 24
1
2
3
the run-in period 28. The results, shown in Figure 10, demonstrate that debris size and wear rate
4
5
6 decrease whether or not the developing transfer film is present. This suggests that the appearance
7
8 of improving transfer film quality in the run-in is a consequence of reduced wear and not the
9
10
11
cause. More broadly, the results from Figures 9 and 10 suggest that the stability of the running
12
13 film is the primary driver of low wear in this system and that transfer film adhesion follows.
14
15
16 The idea that running films drive wear rates seems to conflict with the IR results since only the
17
18
19
carboxylate signal in the transfer film correlates with wear rate. We believe this is the case
20
21 because the carboxylate signal from the transfer film reflects the wear rate and is not itself the
22
23 cause. When debris are first deposited, a virgin surface becomes exposed to the sliding interface;
24
25
26 this new surface would have had insufficient time to produce a strong carboxylate signal 23 when
27
28 wear rates are high, debris are large, and turnover rates are rapid. Low wear rates produce small
29
30 debris that adhere long enough to accumulate detectable quantities of reaction products.
31
32
33
34
It was originally proposed that this particular filler reduces wear especially well because its
35
36 irregular shape promotes mechanical interactions with the inert polymer 11. It is now clear that
37
38 the idealization of PTFE as an inert material is false, particularly in sliding situations. Wear
39
40
41 involves bond breaking in material volumes (as opposed to the top few nanometers) and our EDS
42
43 and IR measurements show that sliding likely affects chemistry to significant depths in the pin.
44
45 As Harris et al. point out, the perfluorinated carboxylic acids that form in humid environments
46
47
48 will aggressively chelate to the alumina filler 24; this bond would directly reinforce the near-
49
50 surface, compartmentalize damage, and reduce wear rates with or without a transfer film
51
52
(Figures 9 and 10). The small degraded debris are better prepared to bond to the counterface,
53
54
55 which reduces surface energy, transfer film turnover, and overall wear rates.
56
57
58
59
60 25
1
2
3
Summary
4
5
6
7 1. Ultra-low wear was retained during sliding at high temperature in humid environments
8
9 despite a precipitous reduction in the presence of carboxylates in the running film.
10
11 2. Carboxylates were detected in significant quantities in the running films formed in dry
12
13
14 conditions despite the transition to elevated wear rates, but no evidence of carboxylates
15
16 was detected in the transfer films for these conditions.
17
18
19
3. During run-in, the wear behavior was insensitive to variations in the environmental
20
21 moisture; the volume of material lost in the transient ranged between 0.07 and 0.7 mm3 in
22
23 all combinations of conditions tested.
24
25
26 4. Steady-state sliding at ambient temperature in humid environments always produced low
27
28 wear rates. In these cases, 1) polymer discoloration of the running film intensified with
29
30 sliding, 2) transfer films and running films exhibited significant evidence of carboxylates,
31
32
33 3) transfer films and running films were oxygen rich and fluorine deficient.
34
35 5. Decreased environmental humidity increased steady-state wear rates, caused significant
36
37 filler accumulation, and decreased the intensity of the carboxylate peak in IR
38
39
40 measurements.
41
42
43 Acknowledgements
44
45
46 The authors gratefully acknowledge the Air Force Office of Scientific Research (AFOSR YIP
47
48
49 FA9550-10-1–0295) for financial support of this work.
50
51
52
53
54
55
56
57
58
59
60 26
1
2
3
References
4
5
6 1. Blanchet, T.; Kennedy, F., Sliding Wear Mechanism of Polytetrafluoroethylene (Ptfe) and Ptfe
7 Composites. Wear 1992, 153, 229-243.
8 2. Bunn, C.; Cobbold, A.; Palmer, R., The Fine Structure of Polytetrafluoroethylene. J Polym Sci
9 1958, 28, 365-376.
10 3. Lancaster.Jk, Polymer-Based Bearing Materials - Role of Fillers and Fiber Reinforcement Tribol
11 Int 1972, 5, 249-255.
12
13
4. Makinson, K.; Tabor, D., The Friction and Transfer of Polytetrafluoroethylene. P Roy Soc A-Math
14 Phy 1964, 281, 49-61.
15 5. Mclaren, K.; Tabor, D., Visco-Elastic Properties and Friction of Solids - Friction of Polymers -
16 Influence of Speed and Temperature. Nature 1963, 197, 856-858.
17 6. Speerschneider, C.; Li, C., Some Observations on Structure of Polytetrafluoroethylene. J Appl
18 Phys 1962, 33, 1871-1875.
19
7. Tanaka, K., Transfer of Semi-Crystalline Polymers Sliding against a Smooth Steel Surface. Wear
20
21 1982, 75, 183-199.
22 8. Tanaka, K.; Uchiyama, Y.; Toyooka, S., Mechanism of Wear of Polytetrafluoroethylene. Wear
23 1973, 23, 153-172.
24 9. Burris, D. L.; Boesl, B.; Bourne, G. R.; Sawyer, W. G., Polymeric Nanocomposites for Tribological
25 Applications. Macromol Mater Eng 2007, 292, 387-402.
26 10. Burris, D.; Sawyer, W., Tribological Sensitivity of Ptfe/Alumina Nanocomposites to a Range of
27
Traditional Surface Finishes. Tribol T 2005, 48, 147-153.
28
29 11. Burris, D.; Sawyer, W., Improved Wear Resistance in Alumina-Ptfe Nanocomposites with
30 Irregular Shaped Nanoparticles. Wear 2006, 260, 915-918.
31 12. Briscoe, B., Wear of Polymers - an Essay on Fundamental-Aspects. Tribol Int 1981, 14, 231-243.
32 13. Sung, N.; Suh, N., Effect of Fiber Orientation on Friction and Wear of Fiber Reinforced Polymeric
33 Composites. Wear 1979, 53, 129-141.
34 14. Blanchet, T., A Model for Polymer Composite Wear Behavior Including Preferential Load Support
35
36
and Surface Accumulation of Filler Particulates. Tribol T 1995, 38, 821-828.
37 15. Tanaka, K.; Kawakami, S., Effect of Various Fillers on the Friction and Wear of
38 Polytetrafluoroethylene-Based Composites. Wear 1982, 79, 221-234.
39 16. Burris, D. L.; Santos, K.; Lewis, S. L.; Liu, X.; Perry, S. S.; Blanchet, T.; Schadler, L.; Sawyer, W. G.,
40 Polytetrafluoroethylene Matrix Nanocomposites for Tribological Applications. In Tribology of Polymeric
41 Nanocomposites, Friedrich, K., Ed. 2008.
42
17. Krick, B. A.; Ewin, J. J.; Mccumiskey, E. J., Tribofilm Formation and Run-in Behavior in Ultra-Low-
43
44 Wearing Polytetrafluoroethylene (Ptfe) and Alumina Nanocomposites Tribol T 2014, 57, 1058-1065.
45 18. Krick, B. A.; Ewin, J. J.; Blackman, G. S.; Junk, C. P.; Sawyer, W. G., Environmental Dependence of
46 Ultra-Low Wear Behavior of Polytetrafluoroethylene (Ptfe) and Alumina Composites Suggests
47 Tribochemical Mechanisms. Tribol Int 2012, 51, 42-46.
48 19. Pitenis, A. A.; Ewin, J. J.; Harris, K. L.; Sawyer, W. G.; Krick, B. A., In Vacuo Tribological Behavior of
49 Polytetrafluoroethylene (Ptfe) and Alumina Nanocomposites: The Importance of Water for Ultralow
50
Wear. Tribol Lett 2014, 53, 189-197.
51
52 20. Bahadur, S.; Gong, D., The Action of Fillers in the Modification of the Tribological Behavior of
53 Polymers. Wear 1992, 158, 41-59.
54 21. Onodera, T.; Kawasaki, K.; Nakakawaji, T.; Higuchi, Y.; Ozawa, N.; Kurihara, K.; Kubo, M., Effect of
55 Tribochemical Reaction on Transfer-Film Formation by Poly(Tetrafluoroethylene). J Phys Chem C 2014,
56 118, 11820-11826.
57
58
59
60 27
1
2
3 22. Onodera, T.; Kawasaki, K.; Nakakawaji, T.; Higuchi, Y.; Ozawa, N.; Kurihara, K.; Kubo, M.,
4
5
Chemical Reaction Mechanism of Polytetrafluoroethylene on Aluminum Surface under Friction
6 Condition. J Phys Chem C 2014, 118, 5390-5396.
7 23. Pitenis, A. A.; Harris, K. L.; Junk, C. P.; Blackman, G. S.; Sawyer, W. G.; Krick, B. A., Ultra-Low
8 Wear Ptfe and Alumina Composites: All About Tribochemistry. Tribol Lett 2015, 57, 626-631.
9 24. Harris, K. L.; Pitenis, A. A.; Sawyer, W. G.; Krick, B. A.; Blackman, G. S.; Kasprzak, D. J.; Junk, C. P.,
10 Ptfe Tribology and the Role of Mechanochemistry in the Development of Protective Surface Films.
11
Macromolecules 2015, 48, 3739-3745.
12
13 25. Blanchet, T. A.; Kandanur, S. S.; Schadler, L. S., Coupled Effect of Filler Content and
14 Countersurface Roughness on Ptfe Nanocomposite Wear Resistance. Tribol Lett 2010, 40, 11-21.
15 26. Burris, D. L.; Zhao, S.; Duncan, R.; Lowitz, J.; Perry, S. S.; Schadler, L. S.; Sawyer, W. G., A Route to
16 Wear Resistant Ptfe Via Trace Loadings of Functionalized Nanofillers. Wear 2009, 267, 653-660.
17 27. Mcelwain, S.; Blanchet, T.; Schadler, L.; Sawyer, W., Effect of Particle Size on the Wear
18 Resistance of Alumina-Filled Ptfe Micro- and Nanocomposites. Tribol T 2008, 51, 247-253.
19
20
28. Ye, J.; Khare, H. S.; Burris, D. L., Transfer Film Evolution and Its Role in Promoting Ultra-Low
21 Wear of a Ptfe Nanocomposite. Wear 2013, 297, 1095-1102.
22 29. Ye, J.; Khare, H. S.; Burris, D. L., Quantitative Characterization of Solid Lubricant Transfer Film
23 Quality. Wear 2014, 316, 133-143.
24 30. Chen, W.; Li, F.; Han, G.; Xia, J.; Wang, L.; Tu, J.; Xu, Z., Tribological Behavior of Carbon-
25 Nanotube-Filled Ptfe Composites. Tribol Lett 2003, 15, 275-278.
26
31. Li, F.; Hu, K.; Li, J.; Zhao, B., The Friction and Wear Characteristics of Nanometer Zno Filled
27
28 Polytetrafluoroethylene. Wear 2001, 249, 877-882.
29 32. Vail, J. R.; Burris, D. L.; Sawyer, W. G., Multifunctionality of Single-Walled Carbon Nanotube-
30 Polytetrafluoroethylene Nanocomposites. Wear 2009, 267, 619-624.
31 33. Dazzi, A.; Prater, C. B.; Hu, Q. C.; Chase, D. B.; Rabolt, J. F.; Marcott, C., Afm-Ir: Combining
32 Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization. Appl
33 Spectrosc 2012, 66, 1365-1384.
34
34. Krick, B. A.; Ewin, J. J.; Blackman, G. S.; Junk, C. P.; Gregory Sawyer, W., Environmental
35
36 Dependence of Ultra-Low Wear Behavior of Polytetrafluoroethylene (Ptfe) and Alumina Composites
37 Suggests Tribochemical Mechanisms. Trib Int 2012, 51, 42-46.
38 35. Wang, Y. C.; Du, X. Z.; Guo, L.; Liu, H. J., Chain Orientation and Headgroup Structure in Langmuir
39 Monolayers of Stearic Acid and Metal Stearate (Ag, Co, Zn, and Pb) Studied by Infrared Reflection-
40 Absorption Spectroscopy. J Chem Phys 2006, 124, 134706-134706.
41 36. Liang, C. Y.; Krimm, S., Infrared Spectra of High Polymers .3. Polytetrafluoroethylene and
42
43
Polychlorotrifluoroethylene. J Chem Phys 1956, 25, 563-571.
44 37. Vanni, H.; Rabolt, J. F., Fourier-Transform Infrared Investigation of the Effects of Irradiation on
45 the 19-Degrees-C and 30-Degrees-C Phase-Transitions in Polytetrafluoroethylene. J Polym Sci Pol Phys
46 1980, 18, 587-596.
47 38. Lenk, T. J.; Hallmark, V. M.; Hoffmann, C. L.; Rabolt, J. F.; Castner, D. G.; Erdelen, C.; Ringsdorf,
48 H., Structural Investigation of Molecular-Organization in Self-Assembled Monolayers of a
49
Semifluorinated Amidethiol. Langmuir 1994, 10, 4610-4617.
50
51 39. Beamson, G.; Clark, D.; Deegan, D.; Hayes, N.; Law, D.; Rasmusson, J.; Salaneck, W.,
52 Characterization of Ptfe on Silicon Wafer Tribological Transfer Films by Xps, Imaging Xps and Afm. Surf
53 Interface Anal 1996, 24, 204-210.
54 40. Breiby, D.; Solling, T.; Bunk, O.; Nyberg, R.; Norrman, K.; Nielsen, M., Structural Surprises in
55 Friction-Deposited Films of Poly(Tetrafluoroethylene). Macromolecules 2005, 38, 2383-2390.
56
57
58
59
60 28
1
2
3 41. Krick, B. A.; Hahn, D. W.; Sawyer, W. G., Plasmonic Diagnostics for Tribology: In Situ
4
5
Observations Using Surface Plasmon Resonance in Combination with Surface-Enhanced Raman
6 Spectroscopy. Tribol Lett 2013, 49, 95-102.
7 42. Lauer, J. L.; Bunting, B. G.; Jones, W. R., Investigation of Frictional Transfer Films of Ptfe by
8 Infrared-Emission Spectroscopy and Phase-Locked Ellipsometry. Tribol T 1988, 31, 282-288.
9 43. Moynihan, R. E., The Molecular Structure of Perfluorocarbon Polymers - Infrared Studies on
10 Polytetrafluoroethylene. J Am Chem Soc 1959, 81, 1045-1050.
11
44. Miller, F. A.; Kiviat, F. E., Infrared and Raman Spectra of (Cf3)2c=C=O, (Cf3)2c=N=N and
12
13 (Cf3)2c=Nh. Spectrochim Acta A-M 1969, A 25, 1577-1588.
14 45. Bahadur, S.; Tabor, D., The Wear of Filled Polytetrafluoroethylene. Wear 1984, 98, 1-13.
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The Interrelated Effects of Temperature and Environment On Wear and Tribochemistry of An Ultra-Low Wear PTFE Composite

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The Interrelated Effects of Temperature and Environment On Wear and Tribochemistry of An Ultra-Low Wear PTFE Composite

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The Journal of Physical Chemistry C is published by the American Chemical Society.

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