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Wear-resistance mechanisms in polytetrafluoroethylene (PTFE) based solid lubricants

University of Florida Institutional Repository

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WEAR RESISTANCE MECHANISMS IN POLYTETRAFLUOROETHYLENE (PTFE) BASED TRIBOLOGICAL NANOCOMPOSITES By DAVID BURRIS A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2006

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Copyright 2006 by David Burris

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This document is dedicated to the graduate students of the University of Florida.

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ACKNOWLEDGMENTS First I thank my parents who encouraged me to find my own path and follow it without restriction and opened every door they could for me. I would like to thank Jade for love and support of my graduate education. I would like to thank the Tribology Lab for thoughtful input on experimentation, help solving tough problems, hard work and friendship. I would like to thank Greg, for the opportunities he has given me and support in every aspect of my life whenever I need it. I would like to thank DuPont for a steady supply of Teflon 7C molding resin. Finally, I would like to acknowledge the financial support from the National Science Foundation grant no #CMS-0219889, GOALI: Collaborative Research: Tribology of Nanocomposites and AFOSR-MURI grant FA9550-04-1-0367. Any opinions, finding, conclusions or recommendations expressed in this material are those of the author and do not necessarily reflect the views of the National Science Foundation or the Air Force Office of Scientific Research. iv

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TABLE OF CONTENTS page ACKNOWLEDGMENTS .................................................................................................iv LIST OF TABLES ............................................................................................................vii LIST OF FIGURES .........................................................................................................viii CHAPTER 1 INTRODUCTION........................................................................................................1 Introduction to Solid Lubrication in Design.................................................................1 Polytetrafluoroethylene as a Solid Lubricant...............................................................3 PTFE Based Tribological Composites..........................................................................6 2 COMPARTMENTALIZATION MODELING..........................................................10 3 EXPERIMENTAL METHODS.................................................................................15 Materials and Processing............................................................................................15 Tribological Testing....................................................................................................19 4 DESIGN OF EXPERIMENTS...................................................................................29 The Effects of Surface Roughness on the Tribological Response of PTFE Nanocomposites......................................................................................................29 Varying Filler Loading and Surface Finish.........................................................31 Varying Filler Size and Surface Finish...............................................................33 The Effects of Particle Surface Characteristics on the Tribological Response of PTFE Nanocomposites............................................................................................34 Mechanical Modification of the Particle-Matrix Interface..................................35 Chemical Modification of the Particle-Matrix Interface.....................................37 5 RESULTS AND DISCUSSION.................................................................................39 The Effects of Surface Roughness on the Tribological Response of PTFE Nanocomposites......................................................................................................39 Varying Filler Loading and Surface Finish.........................................................39 Varying Filler Size and Surface Finish...............................................................43 v

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Transfer Film Examination..................................................................................47 The Effects of Nanoparticle Surface Characteristics on the Tribological Response of PTFE Nanocomposites.......................................................................................50 Mechanical Modification of the Particle-Matrix Interface..................................50 Chemical Modification of the Particle-Matrix Interface.....................................53 6 CONCLUSIONS........................................................................................................63 LIST OF REFERENCES...................................................................................................64 BIOGRAPHICAL SKETCH.............................................................................................67 vi

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LIST OF TABLES Table page 2-1. Definitions of variables used in compartmentalization model...................................12 4-1. Design of experiments: investigation of the coupled effects of counterface roughness and filler wt% on the tribological behavior of alumina-PTFE nanocomposites........................................................................................................32 4-2. Design of experiments: investigation of the coupled effects of counterface roughness and filler size on the tribological behavior of alumina-PTFE nanocomposites........................................................................................................34 4-3. Design of experiments: investigation of the effects of filler wt% on the tribological behavior of alumina-PTFE nanocomposites having irregular filler particle shape............................................................................................................37 5-1. Tribological results of an experimental matrix for tests varying filler loading and counterface surface finish.........................................................................................39 5-2. Tribological results of an experimental matrix for tests varying filler particle size and counterface surface finish. ...............................................................................43 5-3. Tribological results of an experimental matrix for tests varying filler particle loading for 80 nm alpha non-functional nanoparticles.............................................50 5-4. Tribological results for a 1 wt% functional alumina-PTFE nanocomposite.............53 vii

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LIST OF FIGURES Figure page 1-1. Results from wear tests for representative polymer matrix composites found in the literature................................................................................................................2 1-2. Schematic representation of the structure of PTFE at various length scales...............4 1-3. Schematic representations of the hypothesized transfer of PTFE in the mild (left) and severe (right) wear regimes.................................................................................5 2-1. Representation of the matrix and filler particles used in compartmentalization modeling...................................................................................................................11 2-2. Plot of required filler volume fraction plotted vs. the dimensionless diameter as calculated from Eq. 2-9............................................................................................14 3-1. Secondary electron images of Teflon 7C as received from DuPont..........................16 3-2. Schematic representation of the jet mill grinding apparatus.....................................17 3-3. Secondary electron mages of a 12.5 wt% alumina-PTFE powder ensemble after jet-milling.................................................................................................................18 3-4. Tribometer used for friction and wear testing...........................................................20 3-5. Model representation of misaligned measurement axes............................................23 4-1. Surface profilometry data from a scanning white-light interferometer (SWLI) with a 20x objective.................................................................................................31 4-2. TEM images of the two alumina particles evaluated................................................36 5-1. Average friction coefficients of all 40 nm delta:gamma non-functional composites plotted versus weight percent of filler particles....................................40 5-2. Average wear rates of all 40 nm delta:gamma non-functional composites plotted versus weight percent of filler particles...................................................................41 5-3. Average wear rates of the 40 nm delta:gamma non-functional nanocomposites plotted versus the RMS roughness of the counterfaces and R q /D f ...........................42 viii

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5-4. Average friction coefficients of the 5 wt% non-functional composites plotted versus the RMS roughness of the counterfaces........................................................44 5-5. Average wear rates of the 5 wt% non-functional composites plotted versus the RMS roughness of the counterfaces.........................................................................45 5-6. Left) Wear volume plotted vs. sliding distance for the 5 wt% 80 nm alpha non-functional nanocomposite on varying surface finish. Right) Initial wear rate plotted vs. counterface Rq........................................................................................46 5-7. Scanning white-light interferometry measurements of representative transfer films..........................................................................................................................48 5-8. Wear-rate and coefficient of friction plotted versus transfer film thickness.............49 5-9. Plots of friction coefficient as a function of sliding distance....................................51 5-10. Volume lost plotted versus sliding distance............................................................52 5-11. Friction coefficient plotted vs. sliding distance for a 1wt% 40 nm alpha functional nanocomposite........................................................................................54 5-12. Optical photograph of the wear track......................................................................55 5-13. Left) Plot of friction coefficient versus wear track position for a 1 wt% functional nanocomposite at various sliding distances. Right) Friction coefficient plotted versus the average transfer film thickness.................................56 5-14. Wear volume plotted vs. sliding distance for a 1wt% PTFE 40 nm functional alumina nanocomposite............................................................................................57 5-15. Left) friction coefficient plotted vs. sliding distance for 1 wt% alumina-PTFE nanocomposites with Fluorinated and un-Fluorinated irregular alumina filler. Right) wear volume plotted vs. sliding distance for 1 wt% alumina-PTFE nanocomposites with Fluorinated and un-Fluorinated filler....................................58 5-16. Volume fraction plotted versus the ratio of the filler particle diameter to the matrix particle diameter for the compartmentalization model as well as experimental data from these and previous studies..................................................60 5-17. Wear rate versus filler wt% comparing composites of the current study to those of past studies...........................................................................................................62 ix

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Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science WEAR RESISTANCE MECHANISMS IN POLYTETRAFLUOROETHYLENE (PTFE) BASED TRIBOLOGICAL NANOCOMPOSITES By David Burris May 2006 Chair: W. Gregory Sawyer Major Department: Mechanical and Aerospace Engineering This thesis presents an investigation of wear resistance mechanisms in PTFE based tribological nanocomposites. Tribological experiments are conducted on a linear reciprocating pin-on-flat tribometer with various PTFE-alumina nanocomposites. Variables in the experimental design include four counterface surface finishes, four filler particle loadings, three particle sizes and three filler particle surface conditions. In all cases the addition of nanoparticles to PTFE resulted in a substantial reduction in wear rate. In general, tribological properties of the nanocomposites were fairly insensitive to the counterface roughness from Rq =88 590 nm, but every composite, regardless of particle size, had lowest wear rates on a lapped counterface with Rq = 160 nm. The nature of the particle surface itself was found to have the greatest impact on the wear rate of the composite. Among 1 wt% nanocomposites, a spherical particle filled sample had the highest steady wear rate of k = 9000 x 10 -8 mm 3 /Nm, a sample with irregularly shaped filler particles had a steady wear rate of k = 19 x 10 -8 mm 3 /Nm and the sample with fluorine treated irregularly shaped nanoparticles had the lowest steady wear rate of k = 8 x 10 -8 mm 3 /Nm. x

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Very low wear rates (< k = 10 -5 mm 3 /Nm) were only attained after an initial high transient wear rate and the subsequent formation of a stable transfer film. The wear rate was found to decrease with decreased wear debris size and increased uniformity of the transfer film. Based on results of these studies, it is hypothesized that the nature of the filler/matrix interface, particle dispersion, and relative filler/matrix diameter all contribute in determining the efficiency of crack arresting, debris size reduction and the subsequent ease with which debris are removed from the counterface. These coupled phenomena are believed to govern the tribological response of the composite. xi

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CHAPTER 1 INTRODUCTION Introduction to Solid Lubrication in Design Solid lubrication is of great practical interest to mechanical design, being employed in a wide variety of applications ranging from frying pans to orthopedic implants to the deployment mechanisms of communications satellites. It can supplement other means of lubrication in rolling element bearings, metal forming/cutting, engine valve-trains and turbine foil air bearings. It can reduce cost, complexity, weight, and environmental impact by replacing the pumps, filters, pipes and waste management systems associated with fluid lubrication. Primarily, however, solid lubricants are used when other means of lubrication is precluded. This includes applications sensitive to contamination such as the conveyor bushings in the food industry, chemical processing, and space applications where extreme temperatures and vacuum can destroy liquid and grease lubricants. Despite the wide and expanding use of solid lubrication in engineering design, there is an increasing demand for new low friction, low wear materials to improve efficiency and operational life in various environments. As current states of their respective arts, artificial knee joints need replacement every 10-20 years on average and the thin MoS 2 films used in space applications cannot survive terrestrial testing and have limited lives in space operation. There are significant efforts dedicated to the research and development of such solid lubricants, with polymers and polymer composites comprising a large portion of the field (the state-of-the-art was reviewed by Zhang in 1

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2 1998 [1] and Friedrich et al. in 1995 [2]). Though not exhaustive, Figure 1-1 contains plots of wear rate versus filler wt% for representative polymer composites. Figure 1-1. Results from wear tests for representative polymer matrix composites found in the literature. Wear rate is plotted vs. filler weight percent: PTFE-FEP [3], PA6-HDPE [4], PA11-GF [5], PEEK-Si 3 N 4 [6], PTFE-ZnO [7], PTFE-CNT [8], PTFE-Al 2 O 3 [9], PTFE-B 2 O 3 [10], Epoxy-B 2 O 3 [10], and PEEK-PTFE [2]. Modern designs are becoming increasingly complex, imposing a larger number of functional requirements than those possessed by current solid lubricants. These requirements can include low friction, low wear, chemical resistance, environmental stability, high strength, variable modulus, and thermal and electrical conductivity, to name a few. At present, material discovery consists of an iterative process of guess and check, where every material combination imaginable is tested in search of a satisfactory candidate; a process which often results in failure. There is an obvious scientific need for a more fundamental understanding of the complex interactions within these tribological systems to enable the design highly functional tribological composites capable of excelling in modern machinery.

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3 Polytetrafluoroethylene as a Solid Lubricant Polytetrafluoroethylene (PTFE) typically consists of 10,000-50,000 mers, or repeating units, of tetrafluoroethylene (C 2 F 4 ) in a helix configuration. The carbon fluorine bond is very strong, and although the carbon backbone is single bonded, it is housed within a fluorine encasement which effectively shields it from chemical attack. High chemical stability and linear chain morphology gives PTFE many unique and desirable physical properties. Foremost, PTFE is distinguished as having the lowest coefficient of friction and chemical reactivity of any bulk polymer. PTFE also has a large useful temperature range (4-500 K), is biocompatible, is environmentally insensitivity and has a very low vapor pressure (low outgassing). Because of its unique combination of material properties, PTFE has received much attention for tribological use. Flom and Porile [11] performed some of the earliest tribological experiments with self-mated PTFE finding an abrupt increase in the friction coefficient at high speed (>10 mm/s) as the background temperature increased above a threshold value near room temperature. They hypothesized that this point increase is associated with the crystal phase transition between forms II and IV [12] at 19C as first reported by Rigby and Bunn [13]. They also noted a trend of increased friction coefficient with increased sliding velocity. McLaren and Tabor [14] systematically studied self mated PTFE varying sliding velocity at three background temperatures. They found a transition from low to high friction to occur at a critical speed that depended on the background temperature. As the temperature is increased, the critical speed increased, thus demonstrating the viscoelastic nature of PTFE in dry sliding. Makinson and Tabor [15] found evidence of strong adhesion to the counterface and a transition from mild to severe wear that accompanied the frictional transition above the critical speed. They combined

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4 the early structural work of Bunn, Cobold and Palmer [16], and Speerschnieder and Li [17] with their own tribological results and electron diffraction work to relate the tribological behavior of PTFE to its crystalline structure. A schematic representation of this hypothesized structure of PTFE is shown in Figure 1-2. Figure 1-2. Schematic representation of the structure of PTFE at various length scales:a) large deformable units such as particles or grains in sintered material b) Segmentation of crystalline and amorphous regions based on the work of Bunn, Cobold and Palmer [16] and Speerschneider and Li [17] c) strain of the amorphous region giving rise to intra-crystalline slip d) molecular structure deduced from electron diffraction by Makinson and Tabor [15]. Based on this structure, they conjectured that a transition in the relevant units of PTFE involved in shearing is responsible for the tribological transition. At low speeds and high temperatures, shearing occurs in the rate sensitive amorphous regions giving rise to a lamellar type response of crystals or molecules. As speed is increased and temperature decreased, the stresses required to shear the amorphous regions exceeds the stress required to shear larger units such as grain boundaries in the sintered material. Because they observed very low coefficients of friction with evidence of strong adhesion to the counterface, they suggested that van der Waals or electrostatic interactions within the PTFE itself dominate the tribological response. Steijn [18], Tanaka et al.[19],

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5 Blanchet and Kennedy [20], and McCook et al. [21] found independent sets of frictional data for PTFE to obey an Arrehnius dependence with activation energies consistent with van der Waals interactions. In the mild wear regime, the transfer of PTFE is characterized by thin, highly aligned, and well-adhered films [14-17, 22-25]. Friction coefficients are generally less than = 0.1 and wear rates can range from 1-10 x 10 -5 mm 3 /Nm. In the severe wear regime, the transferred material is thick and patchy, friction coefficients are increased and the wear rate, k, is over an order of magnitude greater than for mild wear. Figure 1-3 shows a schematic representation of the transfer of PTFE in these regimes as described by Makinson and Tabor [15]. Figure 1-3. Schematic representations of the hypothesized transfer of PTFE in the mild (left) and severe (right) wear regimes. At room temperature and speeds less than 10 mm/s the transfer is thin and aligned with <0.1. Above 10 mm/s thick platelets are transferred with >0.1. Blanchet and Kennedy [20] systematically studied the tribological behavior of PTFE as a function of speed and temperature and found similar results to those of McLaren and Tabor [14] and Makinson and Tabor [15], namely, increased friction coefficient with increased speed, and an increase in the critical speed with increased interface temperature. However, when the wear rate, k, was plotted versus the friction

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6 coefficient, a transition to severe wear was observed at = 0.1 for each background temperature tested. These results suggest that the severe wear transition is a response to the friction coefficient alone, while the friction coefficient is a function of speed and temperature. Several samples were microtomed perpendicular to the wear surface and in the direction of sliding after mild and severe wear had taken place. Cracks were found to propagate in the direction of sliding beneath a layer of worked material at subsurface depths consistent with observed debris thicknesses for severe wear samples. No such cracks were found in mild wear samples. They conjectured that defects in the sintered material act as initiated cracks. When speeds are low, the kinetic friction coefficient is low at the tribological interface, and the static friction coefficient between crack faces can fully support the surface tractions, relieving the crack tips from stress. However, when the kinetic coefficient of friction at the tribological interface exceeds the static coefficient of friction ( ~ 0.1), the crack tips must support shear, giving rise to mode II crack propagation. This leads to a progressive delamination wear process similar to that described in Suhs Delamination Theory of Wear [26]. PTFE Based Tribological Composites For decades, fillers have been added to PTFE to abate the onset of severe wear. The wear reducing mechanism of fillers in PTFE based composites remains a topic of debate. Lancaster [27] proposed the idea that the fillers, especially those with a high aspect ratio, preferentially support the load, thus lowering the wear rate of the composite. Sung and Suh [28] found that vertically oriented fibers were most effective in reducing wear, but suggested that the critical role of the filler was to arrest crack propagation through the matrix, rather than to support the load. Briscoe et al. [29] found that the wear

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7 rate of neat high density polyethylene (HDPE-another polymer with a linear molecular chain) on a pre-deposited composite transfer film was similar to that of a composite sample when tested against steel. Such improvements in wear resistance of the neat material were not observed when films were pre-deposited on glass counterfaces. They inferred that the wear reduction mechanism of the filler was to induce strong adhesion between the transfer film and a reactive counterface. On the contrary, Gong et. al. [30,31] found that the wear rate of PTFE was independent of chemical bonding based on XPS results and the metal fluoride content at the counterface, and concluded that cohesive failure within the PTFE governs its wear rate. Blanchet and Kennedy had similar findings with XPS analysis of PTFE and PTFE composites in dry sliding [32], and concluded that the wear reducing role of the filler is to slow primary removal of material from the bulk by arresting crack propagation rather than slowing secondary removal of material from the counterface via transfer film adhesion. Tanaka et al. [33] hypothesized that the filler interrupted the destruction of the banded structure of PTFE. Bahadur and Tabor [34] and Blanchet and Kennedy [32] saw direct relationships between wear rate, debris size and the ease with which debris are expelled from the contact. Small wear debris are hypothesized to be easily engaged into surface features, facilitating the formation of thin, uniform transfer films, and a reduced rate of wear. Despite the universal effectiveness of microscopic fillers in PTFE composites, conventional wisdom suggested that nanoscopic fillers would be ineffective. The wear reduction models proposed by Lancaster [27] and Tanaka and Kawakami [33], namely, preferential load support and prevention of large-scale destruction of the banded structure, predict nanoparticles to be ineffective fillers because they are too small to offer

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8 load support, and would not prevent the large-scale destruction of the banded structure, being swept away with the matrix by relatively large asperities. However, there are potential benefits of reduced filler size. The most obvious is reduced counterface abrasion. Traditional microcomposites require hardened shafts and counterfaces to reduce abrasion and third body debris that can accelerate wear. Less obvious is the high number density and surface area of the nanoparticles at low filler volume fractions. If Blanchet and Kennedys model of crack arresting [20] is assumed in favor of the theories of Lancaster [27] and Tanaka and Kawakami [33], nanoparticles have very promising attributes. Because cracks are arrested or deflected by the surfaces of interrupting particles or phases, composites with very high filler surface areas should have effective crack arresting characteristics. This would be especially helpful for materials like PTFE that wear by delamination. A nanocomposite is defined as a composite having filler particles with a characteristic dimension of less than 100 nm. Several investigators have successfully created nanocomposites, and contrary to the prevailing theories, improvements in wear resistance were found to be comparable to those of typical microcomposites. Li et al. [7] filled PTFE with nanometer ZnO, and found 15 wt.% (weight percent of fillers) to be the optimal filler content for reducing wear rate, while retaining a low friction coefficient. Chen et al. [8] created a nanocomposite with single-walled carbon-nanotubes (SWNT). They found that wear resistance was improved by more than two orders of magnitude over unfilled PTFE with limited reductions in the friction coefficient. The carbon-nanotubes were thought to strengthen the matrix, reducing wear of the PTFE. They hypothesized that the carbon-nanotubes provided additional self-lubrication of the

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9 composites by breaking off, becoming trapped in the contact and separating the surfaces. Sawyer et al. [9] made nanocomposites of PTFE with 38 nm Al 2 O 3 and found a 600x reduction in wear with 20 wt% filler concentration. Wear was reduced monotonically as filler concentration was increased to 20 wt%. Scanning electron microscopy (SEM) revealed that the PTFE particles were decorated by the nanoscopic alumina during a powder blending process that preceded compression molding. The resulting structure after molding is cellular with thin regions of highly concentrated PTFE-alumina material surrounding micrometer sized domains of PTFE. These concentrated regions act as barriers to crack propagation and reduce the delamination wear of PTFE. Further, it was offered that with increasing filler concentration, the number, size and possibly strength of the compartmentalizing regions increased. These results demonstrate the effectiveness of nanoscopic fillers in abating the severe wear mode of PTFE, and implicate the crack arresting model as the mechanism of wear resistance in filled PTFE systems. On the other hand, nanoscopic fillers have not been shown to provide any improvements (aside from reduced abrasion) over the more traditional fillers (Figure 1-1). To date, high wear resistance at low particle loading has not been achieved [7-9]. The goal of the present research is to study the frictional, wear and transfer responses of PTFE nanocomposites in greater detail in order to gain a more fundamental understanding of these complex systems. Such an understanding could facilitate the design of highly functional composite systems to benefit a wide spectrum of end use products.

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CHAPTER 2 COMPARTMENTALIZATION MODELING In order to slow or prevent the onset of severe wear, the mechanisms and properties contributing to the occurrence of severe wear must be identified and addressed. The following model is developed assuming that the severe wear mode of PTFE is one in which cracks pre-exist or are initiated and propagated to failure, a mode known as delamination wear [25]. Fillers are therefore assumed to play a crack arresting role [20]. Once these cracks encounter resistance (filler), they are arrested or are turned toward the surface to relieve a wear particle. For simplification, it is assumed that the rate of initiation is constant so that each wear particle represents an initiation point. Therefore, the smaller the wear particle at each initiation point, the lower the rate of wear. This is also the basis of the wear model presented by Bahadur and Tabor [34]. A few things should be kept in mind with this model: 1) the rate of initiation is probably faster in a filled system due to the addition of imperfections at the particle/matrix interfaces, 2) only cracks at depths of the same order of magnitude as the compartmentalized length can effectively be liberated as debris because of the surrounding material, and 3) the wear volume scales by R 3 where R is the characteristic compartment (matrix particle) radius. Point 2) likely counteracts the false assumption that the initiation rate is constant, and point 3) suggests that small matrix particles are desirable for reducing wear. With these ideas in mind, a simple model can be conceived for particulate systems where the matrix and filler particle sizes dictate the volume fraction of filler required for effective crack arresting. 10

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11 It is presumed that cracks are arrested most efficiently when each matrix particle is compartmentalized by a monolayer of filler; this corresponds to the least amount of filler required to effectively arrest a crack propagating through any matrix particle. At filler loadings less than the critical loading, the probability of arresting each crack is diminished. At some loading greater than the critical loading, there is insufficient matrix to effectively bind all of the particles diminishing the mechanical properties of the composite. The model system is shown schematically in Figure 2-1. Figure 2-1. Representation of the matrix and filler particles used in compartmentalization modeling. The model matrix particle and filler particles are treated as spheres. The volume fraction for complete coverage of the matrix by filler is solved for using various simplifying assumptions. Consider the matrix and filler particles to be spheres of characteristic diameter D m and D f respectively. In the closest packed configuration (2D-it is assumed that D f << D m ), the area fraction of the matrix particle surface that is covered by filler particles is 0.907. This packing factor will be treated as a variable, *. Also, since the matrix particles will likely deviate from spheres, a surface area correction factor, S*, will be considered, and is equal to the ratio of the surface area of the model sphere to the real surface area of the irregular matrix particle (the deviation of the filler particle from a

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12 sphere is insignificant). The ratio of the filler diameter to the matrix diameter is D*. Table 2-1 defines these and other variables used in the analysis. Table 2-1. Definitions of variables used in compartmentalization model. V Volume of any sphere S Surface area of any sphere Projected area of any sphere D m Diameter of model matrix sphere D f Diameter of model filler sphere D* Diameter ratio; Df/Dm 2-dimensional packing factor for filler D c Diameter of the sphere located at the centerline of the filler particles S c Surface area of the sphere located at the centerline of the filler particles S* Irregularity factor; Sm/real surface area A f Total projected area of the filler f Volume fraction of the filler For a monolayer of filler, the centers of the filler particles reside on a sphere of diameter equal to the sum of the diameters of filler and matrix. The surface area of this sphere is given by, 222442mfcmDDSRDD f Eq. 2-1 This surface area closely approximates the total projected area of filler particles when corrected by the packing factor *, and the irregularity factor S*, as 2***fcmASDDS f Eq. 2-2 The ratio between the volume and projected area of any sphere is given by, 32423232DVDAD Eq. 2-3

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13 The total volume of the filler is found by multiplying the total area of the filler by Eq. 2-3, 22*3*ffmfVDDDS Eq. 2-4 Applying the dimensionless diameter, D*, the volume of the filler becomes, 232**2***3*3*fmmmmDDVDDDDDDSS 2*1 Eq. 2-5 The volume of a single matrix particle is given by, 334326mmmDV D Eq. 2-6 The volume fraction of the filler required for monolayer coverage is therefore, 23222332**4***1(*1)3**4**2**(*1)1*1*3*6mfffmmmDDDDDVSSDDVVDDDDSS Eq. 2-7 If the ratio of the packing factor and the irregularity factor is approximately equal to unity, Eq. 2-7 becomes, 224*(*1)4*(*1)1fDDDD Eq. 2-8 If the model is restricted to cases where the filler is much smaller than the matrix, then D* is much less than 1. If second order terms are neglected, the volume fraction of the filler for monolayer coverage becomes, 4*4*1fDD Eq. 2-9 The filler volume fraction f is plotted vs. D* following Eq. 2-9 in Figure 2-2.

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14 Figure 2-2. Plot of required filler volume fraction plotted vs. the dimensionless diameter as calculated from Eq. 2-9. Nearly an order of magnitude reduction in required filler content is achieved by an order of magnitude reduction in filler diameter. This graph can be used as a simple tool for composite design, and is instructive in considering the advantages of nanocomposites over microcomposites. If the matrix and filler particles are of the same size (D*=1), the simplified model gives a required 80 vol% filler (this is underestimated by 15% due to the assumption that the filler is much smaller than the matrix). If the filler is 1/100 the size of the matrix (D*=0.01), the model predicts a required 3.8 vol% filler (1.9% underestimated). For D* = 0.001, as is typical for nanocomposites, 0.4 vol% filler is required for monolayer coverage. Hence, very effective damage compartmentalization in PTFE should be possible at very low filler volume fractions.

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CHAPTER 3 EXPERIMENTAL METHODS Materials and Processing The aforementioned model assumes perfect particle dispersion and neglects the obvious difficulties in obtaining such dispersions. With poor dispersion, some matrix particles will not be compartmentalized, and some will have thick boundaries of dense filler material. This can make the composite brittle and ineffective, especially when filler particles do not melt or bond in any way during polymer processing. An element that was briefly mentioned but not addressed by the compartmentalization model is the effect of matrix size. Assuming perfect compartmentalization, as the size of the matrix particle is decreased, the compartment size, debris size and wear rate are hypothesized to decrease, along with the filler size required to maintain D*. This suggests that low wear PTFE composites are most effectively obtained with micro-scale matrix particles and nano-scale fillers. DuPont 7C PTFE molding resin is used in these studies due to its combination of high molecular weight and small particle size. It has a molecular weight ranging from approximately 10 6 -10 7 Da and an average manufacturers claimed particle size of 35 m. As received, the particles are agglomerated, with agglomerates ranging from approximately 100 m 10 mm. The scanning electron microscopy shown in Figure 3-1 reveals that the particles have characteristic sizes on the order of 25 m and are irregular in shape. This shape irregularity tends to increase the required volume fraction of filler for monolayer coverage. 15

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16 Figure 3-1. Secondary electron images of Teflon 7C as received from DuPont. Agglomerations range from 100 m 10 mm. The average individual particles size is reported to be 35 m. This value is consistent with measurements made using scanning electron microscopy (SEM). The filler selected for use in this study is Al 2 O 3 or alumina. Alumina is very hard, wear resistant, chemically stable, and widely available as laboratory and commercial grade material with particle diameters ranging from tens of nanometers to millimeters. Variables related to the alumina in this study are, wt% of filler loading, average particle size (APS), crystalline phase, and surface chemistry. Values of filler weight percent (wt%) used are 0, 1, 2, 5, and 10. Possible values of APS are 40, 80, and 500 nm. Crystalline phase influences the shape of the particle, which is hypothesized to affect the mechanical compatibility of the filler/matrix interface. The phases used in this study are 70% delta: 30% gamma (referred to as delta:gamma) and 99% alpha (referred to as alpha), and have spherical and irregular particle shapes, respectively. Surface chemistry can be non-functional (as-received) or functional, a condition that results from a chemical treatment where fluorine groups are indirectly bonded to the alumina via silicon.

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17 In order to achieve effective particle compartmentalization, a technique is required to break apart agglomerations and then disperse the filler particles. A fluid energy jet mill, shown schematically in Figure 3-2, is used for this purpose. Figure 3-2. Schematic representation of the jet mill grinding apparatus. Fluid energy is used to impact and break the particles and agglomerations. Large particles are forced against the walls to be ground while small particles exit through the center into the collection chamber. Schematic obtained from www.sturtevantinc.com. The jet mill uses pressurized air to accelerate the powder ensemble into a grinding chamber. A pressurized manifold forces air through angled holes in the grind chamber to create a vortex within the chamber. This vortex accelerates the particles tangentially along the periphery of the chamber causing the particle/particle and chamber/particle impacts responsible for breaking apart agglomerations and dispersing the constituents. Larger particles are preferentially forced to the periphery for further grinding while smaller particles are displaced toward the center to be collected. This energetic technique results in a very high number of impacts and is thought to be a more effective particle dispersion technique than the more traditional mechanical mixing techniques. SEM

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18 images taken of a 12.5 wt% 40 nm alumina-PTFE powder ensemble after jet-milling are shown in Figure 3-3. Figure 3-3. Secondary electron mages of a 12.5 wt% alumina-PTFE powder ensemble after jet-milling. A PTFE particle with a 5 mm diameter is clearly compartmentalized by 40 nm alumina nanoparticles. The PTFE particle in the left image is approximately 5 m in diameter, and as shown in the right image, is completely covered or compartmentalized by nanoparticles. The jet mill has a maximum size limitation of 2 mm, so prior mechanical mixing of the powder ensemble is used. A rotating bar on a crank is used shear the biggest PTFE agglomeration through an elastic 10 mesh sieve (flour sifter). This technique allows the powder to be quickly classified to a size that is easily managed by the jet mill. After weighing and combining, the powder ensemble is roughly mixed by hand then jet-milled three times. The flow rate of the material on the first pass is low to avoid clogging the grind chamber while the biggest agglomerations are broken to a passable size. Next, the collection chamber is removed and the ensemble is mixed by hand. The powders are then given two additional passes at a higher flow rate.

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19 After jet-milling, the powder ensemble is placed in a mold and inserted into a compression molding station consisting of a hydraulic laboratory press with heaters and temperature control. The 7C PTFE used in these studies has a reported maximum initial melt temperature of 352C, and enters a viscous gel state rather than a liquid state. As the temperature is increased, the viscosity decreases until degradation begins above 400C. Once melted, subsequent melting occurs at 327C. Since the material is under pressure in the mold during processing, the actual temperature required for melting is likely a bit higher. The samples are created by cold pressing a cylindrical puck of material at 60 MPa for 15 minutes to evacuate the air from the powder. As the pressure is lowered to 6 MPa for the remainder of the processing, the temperature is increased to 380C at a rate of 2C/min. The material is pressurized during melt to evacuate volatiles from the powder ensemble. Upon reaching 380C, the temperature drops to 360C and is held for 3 hours. The temperature spike to 380C occurs due to the tuning of the PID controller (overshoot), and ensures initial melt is reached by the entire part. Once the hold schedule is complete, the mold is cooled at 2C/min. The compression molded puck is machined into a x x inch sample using computer numerical control. Dimensional measurements are made with a digital micrometer having a Type B uncertainty of 5 m (5X the reported repeatability) and the mass is measured on a precision analytical balance having a Type B uncertainty of 50 g. Tribological Testing A laboratory designed linear reciprocating pin-on-flat tribometer, shown schematically in Figure 3-4, is used to test the wear and friction of the samples. This testing apparatus and the uncertainties associated with the experimental measurements

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20 are described in detail in Schmitz et al. [35, 36]. Although open to the air, the entire apparatus is located inside a class 10,000 soft-walled cleanroom (for reduced particulate abrasion) with conditioned laboratory air at 25C and from 25-50% relative humidity. In all cases, the normal load is F n = 250 N, reciprocation length is S = 25.4 mm (50.8 mm/cycle), sliding speed is V = 50.8 mm/s, apparent contact area is A = 40 mm 2 and the nominal contact pressure is P 0 = 6.3 MPa. In general, the length of the test depends on the wear resistance of the material. Figure 3-4. Tribometer used for friction and wear testing. A pin of the bulk test material is pressed flat against a linearly reciprocating counterface. A 6-channel load cell reacts all of the loads incurred by the sample. The conditions are constant throughout the test i.e. as wear occurs. AISI 304 stainless steel is used as the counterface material; it is corrosion resistant and soft (measured hardness of 87 kg/mm 2 Rockwell B), and allows for easy detection of filler abrasion. New counterfaces are used for each experiment, so efforts were made to

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21 ensure that each nominally identical counterface sample was created under the same conditions. Prior to testing, the counterface and composite pin are cleaned with methanol, and dried with a laboratory wipe. The counterface surface roughness is a variable in this study, with possible values of 90 nm, 160 nm, 390 nm, and 580 nm, R q The composite samples are mounted directly to a 6-channel load cell which reacts all of the forces and moments on the pin sample. The counterface is mounted to a linear reciprocating stage beneath the pin sample. A pneumatic cylinder is used to apply a normal force. The load is continuously measured by the load cell and is computer controlled using an electro-pneumatic valve. A linear thruster isolates the pneumatic cylinder from frictional loads. Four 1 inch diameter rods located within an aluminum housing are guided by linear bearings and provide high stiffness in the transverse direction. An LVDT mounted to the thruster monitors pin displacement. A stepper motor is controlled within custom data acquisition software. The stepper motor drives the ball screw that drives the linear table. Another LVDT continuously measures the table position. Instantaneous data is collected for normal load, friction force, table position and pin position at 1000 Hz over 1 cycle at specified intervals. Data for one cycle is extracted using the positional LVDT. The instantaneous data are also averaged over two cycles and saved at a specified interval that depends on the length of the test. The primary function of this tribometer is to obtain values of friction coefficients and wear rates for different tribological systems of interest. Neither friction coefficient nor wear rate can be directly measured, so they must be calculated based on other measurable quantities. The uncertainties associated with the calculation of friction

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22 coefficient and wear rate based on this tribometer were analyzed by Schmitz et al. [35, 36]. The friction coefficient is defined as, fnFF Eq. 3-1 where F f and F n are the friction and normal forces, respectively. Often, the measurement axes, X and Y, are used to calculate an approximate friction coefficient, 'XY F F Eq. 3-2 where the measurement axes are not necessarily aligned with the normal and frictional axes. These misalignments inevitably arise from kinematic chains of imperfect machining and machine compliance. These misalignments can cause substantial errors in the calculation of friction coefficient if unaddressed, even in well designed machines. A simple model system can be constructed to illustrate these effects. The measurement axes, X and Y are assumed to be orthogonal and biased from the normal (N) and frictional (F) axes by an angle, as shown in schematically in Figure 3-5.

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23 Figure 3-5. Model representation of misaligned measurement axes. The measurement axes are assumed orthogonal and are rotated about the normal and frictional axes by an angle, The measured force responses to the tribological interactions are, cos()sin()cos()sin()cos()sin()xfnnnnFfffff Eq. 3-3 cos()sin()cos()sin()cos()sin()YnfnnnFfffff Eq. 3-4 resulting in, cos()sin()cos()sin()'cos()sin()cos()sin()nXYnfFFf Eq. 3-5 Defining an error fraction E as, 222'cos()sin()sin()(1)(1)1cos()sin()(cos()sin())E Eq. 3-6 The misalignment angle, can be found by monitoring the force response to a stationary loaded pin sample. Schmitz et al. [36] finds to be approximately 2 using this method. For a friction coefficient of = 0.1, the corresponding error using the X and Y axes

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24 measurements is 35%. Thus, the approximate friction coefficient is extremely sensitive to these misalignments. One could conceivably apply a coordinate transformation to force data with the measured value of and calculate the true value of but the angular measurement could vary from test to test, making this type of analysis very cumbersome. Instead, we can apply a reversal technique, and calculate the error in the approximate friction coefficient calculations. The aforementioned analysis will apply to the forward direction, so, 'cos()sin()cos()sin()f Eq. 3-7 Upon reversal, F xr =-f n cos()+f n sin()) and F yr =fncos()+sin(), and 'cos()sin()cos()sin()r Eq. 3-8 By subtracting r from f and dividing by two (average of absolute values), we obtain a new value of the approximate friction coefficient and the corresponding error, 2222cos()sin()cos()sin()cos()sin()cos()sin()'2cos() cos() Eq. 3-9 Using = 0.1 again, the corresponding error is 0.1%. This technique provides a robust method for estimating the friction coefficient from measurements along axes forming small angles with the normal and tangential directions, and is employed during testing. The uncertainties associated with this measurement were analyzed by Schmitz et al. [36] and include uncertainties in angular misalignment and uncertainties in the load measurements themselves. For a standard test of unfilled PTFE (~0.15), they

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25 determined the uncertainty in the friction coefficient for a 99% confidence interval to be approximately 2% of the nominal value. Thus, the uncertainty in friction coefficient is insignificant compared to the standard deviation of the measurement throughout the entirety of a test. The standard deviation is a more useful value to report, and confidence intervals on friction data will represent the standard deviation of averaged friction coefficient data. The volume of material lost during the wear process is generally proportional to the normal load and the sliding distance by a wear rate, k. The wear rate of a material can be used to determine component life and is defined as, nVk F D Eq. 3-10 Where V is the volume lost, F n is the normal load and D is the sliding distance. Often, wear volume is calculated by making displacement measurements of a given cross section or by measuring the mass before and after a test. In many polymer systems, specifically, for wear resistant polymers, creep and thermal expansion can become significant portions of the total volume calculation. Mass loss measurements become difficult in situations where environmental uptake is expected. Since PTFE is known to have a high creep rate and coefficient of thermal expansion, as well as low water uptake and outgassing, mass measurements are used to quantify wear in these studies. The volume lost is then, mV where 123im L LL The change in mass is m, is the density, m i is the initial mass, and L 1 L 2 and L 3 are the lengths of the rectangular solid sample. The sliding distance is 2 D SN where S is the reciprocation length (1/2 cycle)

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26 and N is the number of reciprocation cycles. The wear rate can be expressed in terms of the measured quantities as, 1232inmLLLkmFSN Eq. 13-11 The law of propagation of uncertainty can be applied to Eq. 3-11 to find the combined standard uncertainty or the expected dispersion of values obtained for the wear rate. The sensitivity of each measurement is calculated by taking the partial derivative of the measurand, k, with respect to the measurement. Each sensitivity term is then squared and multiplied by the square of the uncertainty in that measurement. These contributions are added to find the square of the combined standard uncertainty of the wear rate, as 322322221221222LuLKLuLKLuLKmumKKuc SuSKmumKFuFKiinN222222 Eq. 3-12 Evaluating the partial derivatives gives, 2223112232223212222LuSNmFLmLLuSNmFLmLmuSNmFLLLKuinininc nininFuSNmFLLmLLuSNmFLmL2223213222122 SuNSmFLLmLmuSNmFLLmLiniin22232122232122 Eq. 3-13 where nominal values of the measurements are used in numerical calculation. Determining the uncertainty of each measurement requires Type A or Type B evaluation

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27 consisting of either statistical methods or engineering judgment, respectively. A detailed analysis can be found in Schmitz et al. [35]. Briefly, the uncertainties of the sample length and mass measurements are taken conservatively as five times the manufacturers specified repeatability; 0.005 mm and 0.05 mg respectively. The uncertainty u(m) is calculated using the law of propagation of uncertainty. immm f Eq. 3-14 Taking the partial derivative of this function with respect to the measurements, m i and m f gives, 2222222211ifiifmmumumumumummm 2f Eq. 3-15 Since the initial and final masses are approximately the same, it is reasonable to assume that the uncertainties in these measurements are equal, and Eq. 3-15 becomes, 222iumum Eq. 3-16 and, 2iumum Eq. 3-17 The uncertainty in the normal load due to time dependent fluctuations was found to overwhelm angular misalignment errors and short term scatter, and the uncertainty is taken conservatively as u(Fn)=2N, twice the observed thermal drift of the load cell and electronics. The uncertainty in the number of cycles is zero and the uncertainty in the reciprocation length is u(S )= 0.2mm which results from a combination of an assumed angular misalignment of 2, and one standard deviation of measurements for commanded motions.

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28 Many materials exhibit initial wear transients, precluding the use of a single point mass measurement. Often, a least squares regression of the steady data is used to obtain a more representative value for the wear rate of a material. A modified numerical approach to the above uncertainty analysis is required for such regressions [35]. Interrupted measurements are made periodically during each test and are used to distinguish the steady region of wear from the transient region. A Monte Carlo simulation uses the uncertainty and nominal value of each measurement to calculate the average regression slope and standard deviation of the slopes of 1,000 simulated data sets, for wear rate and wear rate uncertainty, respectively. The uncertainty intervals on wear rate data represent the experimental uncertainty in the measurement.

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CHAPTER 4 DESIGN OF EXPERIMENTS The Effects of Surface Roughness on the Tribological Response of PTFE Nanocomposites The effectiveness of the filler has been hypothesized to decrease as the size scale of the asperities approach those of the filler based on the wear resistance models of preferential load support [27] and prevention of large scale destruction of the banded structure [33]. In this study, it is presumed that the role of the filler is to compartmentalize damage [9] by arresting crack propagation [20], and thus limiting the size and shape of the wear debris [34]. This model does not preclude the effectiveness of nanoparticles and conversely suggests that composites become more effective as the sizes of the matrix and filler particles decrease. This study investigates the tribological sensitivity of alumina-PTFE nanocomposites of varying filler size and wt% to varying counterface roughness. It has been shown that in many cases, tribological performance is most dependent on parameters such as skew, maximum peak height, average asperity slope and orientation of lay rather than the more commonly cited amplitude parameters (R a R q R t etc.) [34, 37, 38]. However, given the nature of the argument for the ineffectiveness of PTFE nanocomposites and the critical role of relative size of particles and asperities, an amplitude parameter is most appropriate for investigation. Efforts were made to keep other parameters as constant as possible. The amplitude parameter used in this study is R q (root-mean-squared roughness) and is given by, 29

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30 201()Lq R zxdxL Eq. 4-1 where z(x) is the height of a surface point at a location x along the surface. The counterface surfaces were prepared using 4 different traditional finishing processes, including: electro-polishing, lapping, wet-sanding, and dry-sanding. The electro-polished samples were prepared by wet-sanding with 600 grit silicon-carbide paper, followed by lapping, and finished by electro-polishing. Similarly, the lapped samples were initially wet sanded with the 600 grit silicon-carbide paper and then lapped. The wet-sanded samples were only exposed to the 600 grit silicon-carbide paper. The dry-sanded samples were initially wet sanded and then roughened with 80 grit coarse silicon-carbide paper. The samples were examined under a scanning white light interferometer with a 20x objective. Areas of 230m x 300m were measured on 5 different samples from each batch. A gray-scale contour plot with accompanying line scans, amplitude parameters R a (average roughness) and R q (root mean squared roughness), and histograms of the surfaces are shown in Figure 4-1. For these surfaces the average and standard deviation in R q between 5 samples was R q =88 nm =16 nm, R q =161 nm =35 nm, R q =390 nm =275 nm, and R q =578 nm =91 nm for the electro-polished, lapped, wet-sanded, and dry-sanded surfaces, respectively. The wet-sanded surfaces have a predominant orientation parallel to the direction of sliding, while the others have no predominant orientation. All of the surfaces except for the electro-polished surfaces have a negative skew.

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31 Figure 4-1. Surface profilometry data from a scanning white-light interferometer (SWLI) with a 20x objective, clockwise from top left: electro-polished, lapped, dry-sanded and wet-sanded surfaces. It should be noted that the wet sanded counterface was tested in a direction parallel to the predominant orientation of the texture. The other surface did not have a predominant orientation. Varying Filler Loading and Surface Finish The alumina used in this study is from Nanophase. The particles have an (APS) of 40 nm, a crystalline phase of 70% delta 30% gamma, and are spherical in shape. Four alumina-PTFE nanocomposites, of 0, 1, 5, and 10 wt%, were processed following the standard processing techniques described in Chapter 3. The experimental design, shown

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32 in Table 4-1, consists of 4 counterface conditions and 4 particle loadings with repeat tests of unfilled PTFE and 5 wt.% alumina filled PTFE on the lapped counterface; this provides some indication of scatter in the data from processing variations. Experimental variations and uncertainties for friction coefficient and wear rate are discussed in detail in Schmitz et al. [35, 36]. These nanocomposites were observed to wear linearly, hence single point mass loss measurements are used to quantify wear. Table 4-1. Design of experiments: investigation of the coupled effects of counterface roughness and filler wt% on the tribological behavior of alumina-PTFE nanocomposites. Average particle size (APS), particle phase and surface chemistry of the alumina are held constant at 40 nm, spherical and non-functional, respectively. New counterfaces and individually made composite samples are used in each experiment. Sample Rq (nm) Filler wt% APS (nm) Phase 1 90 0 40 delta:gamma 2 90 1 40 delta:gamma 3 90 5 40 delta:gamma 4 90 10 40 delta:gamma 5a-5f 160 0 40 delta:gamma 6 160 1 40 delta:gamma 7a-7d 160 5 40 delta:gamma 8 160 10 40 delta:gamma 9 390 0 40 delta:gamma 10 390 1 40 delta:gamma 11 390 5 40 delta:gamma

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33 Table 4-1. Continued Sample Rq (nm) Filler wt% APS (nm) Phase 12 390 10 40 delta:gamma 13 580 0 40 delta:gamma 14 580 1 40 delta:gamma 15 580 5 40 delta:gamma 16 580 10 40 delta:gamma Varying Filler Size and Surface Finish The relative sizes of the nanoparticles and asperities are studied here using a dimensionless roughness parameter R q /D f (the ratio of the root-mean-squared roughness to the characteristic filler diameter). It is widely accepted that wear rate is a function of the counterface roughness, so in order to isolate the component due to particle size, this series of experiments varies the filler particle diameter. PTFE composites with characteristic filler diameters (APS) of 40 nm, 80 nm, and 500 nm are processed using the procedures outlined in Chapter 3, and are tested on each surface. Filler loading is held constant at 5 wt%. The 40 nm particles and the 500 nm particles are 70:30 delta:gamma phase and are spherical in shape, while the 80 nm particles are 99% alpha phase and are irregular in shape. The experimental design is given in Table 4-2.

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34 Table 4-2. Design of experiments: investigation of the coupled effects of counterface roughness and filler size on the tribological behavior of alumina-PTFE nanocomposites. Filler wt%, and surface chemistry of the alumina are held constant at 5 wt%, and non-functional, respectively. Crystalline phases are gamma:delta for 40 and 500 nm particles and alpha for 80 nm particles. New counterfaces and individually made composite samples are used in each experiment. Sample Rq (nm) Filler wt% APS (nm) Phase Functional 3 90 5 40 delta:gamma none 17 90 5 80 alpha none 18 90 5 500 delta:gamma none 7a-d 160 5 40 delta:gamma none 19 160 5 80 alpha none 20 160 5 500 delta:gamma none 11 390 5 40 delta:gamma none 21 390 5 80 alpha none 22 390 5 500 delta:gamma none 15 580 5 40 delta:gamma none 23 580 5 80 alpha none 24 580 5 500 delta:gamma none The Effects of Particle Surface Characteristics on the Tribological Response of PTFE Nanocomposites Contrary to conventional wisdom, PTFE nanocomposites have been found to have 100-1000X lower wear rates than unfilled PTFE. But, despite compartmentalization

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35 modeling predictions that optimum compartmentalization occurs in these systems at low filler wt%, these wear resistant nanocomposites are repeatedly optimized between 10 and 30 filler wt%, compositions comparable to those found for microcomposites [6, 7, 8, 9]. To date, a 100-1000X reduction in wear rate at low filler wt% (<5 wt%) has not been demonstrated. The inability to achieve this goal may be due to the more practical issues involved in nanocomposite synthesis that are not accounted for in the simple compartmentalization model. The first is particle dispersion. As particles become smaller, the ratio of the surface area to the volume, and hence, surface energy to inertial energy, increases. Because of this high surface energy, nanoparticles tend to agglomerate making dispersion of the particles difficult. Nanocomposites with poorly dispersed nanoparticle agglomerations may, in fact, behave as a microcomposite with the effective particle size being the characteristic size of the agglomerations. The other practical issue not dealt with in the model is the strength of the filler/matrix interface. The constituents used in these studies (PTFE and Al 2 O 3 ) are intentionally inert to reduce environmental sensitivity, and consequently, the interface between them is weak. Now consider a nanocomposite with 1 vol% 40 nm filler. For a basketball sized hunk of the material, the area of this inherently weak interface is 2.3 acres. For this reason, the nature of the interface is believed to have a substantial impact on the tribological properties of nanocomposites. This study focuses on improving the compatibility of the interface between the matrix and filler to help reduce the number of material defects and thus wear rate. All tests are performed on the lapped (160 nm R q ) counterface. Mechanical Modification of the Particle-Matrix Interface The two interfacial modifications considered here are mechanical and chemical. This study examines the effect of mechanical modification of the interface between the

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36 matrix and filler. Nanoparticles of Al 2 O 3 (alumina) from Alfa Aesar are used in this study. They have an alpha crystalline phase and were observed to be irregular in shape. It is hypothesized that an irregular nanoparticle shape will facilitate mechanical entanglement of the PTFE with the filler and increase the mechanical compatibility at the interface. The TEM micrographs shown in Figure 4-2 reveal the shape variation between the 40 nm nanoparticles of the aforementioned study and the more irregular 80 nm nanoparticles used in these experiments. Figure 4-2. TEM images of the two alumina particles evaluated. The manufacturer reported mean particle size is indicated on the upper left of each image. The crystal phase of the spherical 40nm particles is reported to be 70% delta and 30% gamma; the more irregular 80nm particles are reported to be 99% alpha. A series of tribological tests were conducted on alumina-PTFE nanocomposites with filler loadings of 1, 2, 5 and 10 wt% irregular 80 nm alumina. The particles are as received and are non-functional. The counterface surfaces have a lapped finish with an average RMS roughness of R q = 160 nm. Tests are interrupted periodically for mass measurement as these samples were observed to transition to a lower wear condition upon transfer film formation. The experimental design for this study is given in Table 4-3.

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37 Table 4-3. Design of experiments: investigation of the effects of filler wt% on the tribological behavior of alumina-PTFE nanocomposites having irregular filler particle shape. Counterface roughness, particle size, crystalline phase and surface chemistry of the alumina are held constant at 160 nm Rq, 80 nm, 99% alpha, and non-functional, respectively. New counterfaces and individually made composite samples are used in each experiment. Sample Rq (nm) Filler wt% APS (nm) Phase Functional 25 160 1 80 alpha none 26 160 2 80 alpha none 19 160 5 80 alpha none 27 160 10 80 alpha none Chemical Modification of the Particle-Matrix Interface A group at Rensselaer Polytechnic Institute (RPI) has created and characterized fluorinated (also referred to as functional) alumina. The additional fluorine atoms, which are chemically bonded via silicon atoms to the alumina, are thought to increase the chemical compatibility and strength of the alumina/PTFE interface, and the integrity of the composite. Particle dispersion may also be improved as a result of improved chemical compatibility through a reduced tendency of the unlike particles to segregate. A PTFE composite pin with 1 wt% functional alumina was created using the standard processing techniques outlined in Chapter 3. Filler particle diameter is 40 nm and the crystalline phase is 99% alpha. The counterface used is a lapped grade 304 stainless steel plate with a roughness of 160 nm R q Experiments are interrupted periodically and mass loss measurements are converted to wear volume loss as a function

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38 of the sliding distance. Uncertainty intervals shown on the wear volume and wear rate data are calculated following Schmitz et al. [35].

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CHAPTER 5 RESULTS AND DISCUSSION The Effects of Surface Roughness on the Tribological Response of PTFE Nanocomposites Varying Filler Loading and Surface Finish Results and organization of the experiments varying filler loading and surface roughness are shown in Table 5-1. Table 5-1. Tribological results of an experimental matrix for tests varying filler loading and counterface surface finish. New counterfaces and individually made composite samples with 40 nm delta:gamma non-functional filler are used in each experiment. The n represents mean values over n experiments, otherwise only a single experiment was run. The units on wear rate, k, are x10 -6 mm 3 /(Nm). weight percent of 40 nm delta:gamma non-functional alumina filler 0 % 1 % 5 % 10 % electro-polished 695K 0.165 174K 0.175 52K 0.191 75K 0.178 lapped 6586K 60.136 89K 0.174 466K 40.173 38K 0.184 wet sanded 770K 0.135 85K 0.172 99K 0.162 50K 0.163 counterface preparation dry sanded 634K 0.142 293K 0.159 294K 0.145 97K 0.183 The average friction coefficient data for these experiments are plotted in Figure 5-1 versus filler weight percent. The error-bar on a friction coefficient datum is the standard deviation of the friction coefficient data collected during the entire test. It is encouraging to note that the friction coefficient is not greatly affected by changes in composition or surface roughness. It has the general trend of increasing slightly with increasing filler 39

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40 concentration and decreasing surface roughness. Friction coefficient is thought to increase with the addition of the ceramic particles because the filler and counterface create a higher friction pair than the PTFE and counterface. A small abrasive component may also be present, though scratching of the counterface was not observed. Bahadur and Tabor [34] observed a similar trend of increased friction coefficients on surfaces with decreased roughness and suggested that adhesion dominated the friction coefficient. Figure 5-1. Average friction coefficients of all 40 nm delta:gamma non-functional composites plotted versus weight percent of filler particles. The normal load was 250N and the sliding speed was 50 mm/s (the sliding distances varied). The error bars represent the standard deviation of the friction coefficient during each test. The wear rates and uncertainties for these experiments were calculated using single point measurement of mass loss at the conclusion of the test; numerous interrupted experiments were conducted to support the reasonableness of this method (i.e. the interrupted measurements showed a linear trend of volume lost with sliding distance).

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41 These data are plotted in Figure 5-2 versus filler weight percent. The error-bar on a wear rate datum is the standard uncertainty of this measurement [35]. Figure 5-2. Average wear rates of all 40 nm delta:gamma non-functional composites plotted versus weight percent of filler particles. The normal load was 250N and the sliding speed was 50 mm/s (the sliding distances varied). The error bars represent the standard uncertainty of the measurement. The wear-rate decreased monotonically with increasing filler content; thus nano-fillers can provide substantial improvements in wear resistance, despite the large relative size of the asperities. Figure 5-3 shows wear rate data plotted versus roughness and the dimensionless roughness parameter R q /D f There is no monotonic relationship between wear-rate and the dimensionless roughness or counterface roughness, but the wear-rate appears to be minimized on the lapped counterface (R q /D f ~ 4). Since R q and R q /D f are directly proportional in the case of constant filler diameter, it is unclear which is dominating the tribological behavior.

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42 Figure 5-3. Average wear rates of the 40 nm delta:gamma non-functional nanocomposites plotted versus the RMS roughness of the counterfaces and R q /D f The normal load was 250N and the sliding speed was 50 mm/s (the sliding distances varied). The vertical error bars represent the standard uncertainty of the measurement and the horizontal error bars represent the standard deviation of the RMS roughness over 5 samples. Blanchet [39] observed filler accumulation at the sliding interface in PTFE-bronze microcomposites. Filler accumulation at the sliding interface occurs by a natural tendency for PTFE to be preferentially removed from the composite, and results in increased friction coefficients and decreased wear-rates with increasing sliding distance until a steady surface composition is reached. The wear volumes of the nanocomposites in this study are linear functions of sliding distance and wear rates are strongly dependant on filler wt%. These facts indicate that filler accumulation at the interface is not the wear reduction mechanism and that the surface composition is near steady-state at the onset of sliding.

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43 Varying Filler Size and Surface Finish The experimental design and results varying filler particle size and roughness holding filler loading constant are given in Table 5-2. Table 5-2. Tribological results of an experimental matrix for tests varying filler particle size and counterface surface finish. New counterfaces and individually made composite samples with 5 wt% non-functional alumina loading are used in each experiment. The n represents mean values over n experiments, otherwise only a single experiment was run. The units on wear rate, k, are x10 -6 mm 3 /(Nm). size of PTFE filler in 5 wt.% non-functional composites unfilled 40 nm (delta:gamma) 80 nm (alpha) 500 nm (delta:gamma) electro-polished 695K 0.165 52K 0.191 0.80K 0.191 70.3K 0.152 lapped 6586K 60.136 466K 40.173 0.84K 0.158 47.4K 0.174 wet sanded 770K 0.135 99K 0.162 28.74K 20.151 64.9K 0.168 counterface preparation dry sanded 634K 0.142 294K 0.145 0.95K 0.141 2664K 20.145 The average friction coefficient data for nanocomposites of varying particle size are plotted versus counterface R q in Figure 5-4.

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44 Figure 5-4. Average friction coefficients of the 5 wt% non-functional composites plotted versus the RMS roughness of the counterfaces. The normal load was 250N and the sliding speed was 50 mm/s (the sliding distances varied). The vertical error bars represent the standard deviation of the measurements and the horizontal error bars represent the standard deviation of the RMS roughness over 5 samples. There is no obvious correlation between friction coefficient and filler particle size. As in the previous study, friction coefficient is observed to decrease with increasing roughness. Unlike the previous study, steady-state wear rates were calculated from interrupted mass measurements because the 80 nm composites transitioned from an initial transient wear rate to a much lower steady state value of wear rate. This method of calculating wear rate and uncertainty is described by Schmitz et al. [35].

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45 Figure 5-5. Average wear rates of the 5 wt% non-functional composites plotted versus the RMS roughness of the counterfaces. The normal load was 250N and the sliding speed was 50 mm/s (the sliding distances varied). The vertical error bars represent the standard uncertainty of the measurement and the horizontal error bars represent the standard deviation of the RMS roughness over 5 samples. The results of these wear tests are plotted in Figure 5-5 versus the counterface R q The wear of unfilled PTFE is relatively insensitive to counterface roughness, varying by the scatter in the repeat experiments. The 5 wt% 40 nm and 500 nm (70:30 delta:gamma) composites in this study had comparable wear rates on all but the dry sanded counterface, despite the order of magnitude difference in particle size. This suggests that there is not a large effect due to the relative sizes of particles and asperities. The wear rate of the 5 wt% 80 nm alpha alumina nanocomposite was also lowest when tested against the lapped counterface, but had entirely different wear characteristics than the other particle filled composites. Considering the similarities of the 40 and 500 nm composites, the difference

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46 is attributed to the crystalline phase, and more specifically, the shape, rather than the size of the particles. Wear volume is plotted versus sliding distance in Figure 5-6 for the 5 wt% 80 nm alpha phase non-functional alumina nanocomposite against the varying counterface finishes. Initially, the wear rate of the nanocomposite is a strong function of the surface roughness, wearing most rapidly against rougher surfaces. The volume of wear debris produced during this initial period also correlates well with roughness and is proportional to the volume of material required to fill the surface roughness. After 100 m of sliding, samples tested against the polished (90 nm), lapped (160 nm) and dry-sanded (580 nm) counterfaces transitioned to nominally identical, very low steady state wear rates, while the sample tested against the wet-sanded (390 nm) surface retained a high rate of wear. The primary difference between these samples, aside from roughness, is texture, or direction of lay. The wet-sanded surface has a corrugated appearance in the direction of sliding, while the other surfaces have no predominant lay orientation. Figure 5-6. Left) Wear volume plotted vs. sliding distance for the 5 wt% 80 nm alpha non-functional nanocomposite on varying surface finish. The normal load was 250N and the sliding speed was 50 mm/s. The composite transitioned to very low steady wear rates on all but the wet sanded surface. Right) Initial wear rate plotted vs. counterface Rq. The initial wear rate is obtained using a single point measurement with the first measured data point.

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47 These results strongly support the model proposed by Bahadur and Tabor [34], which suggests that the wear rate of the composite is related to the size of the wear debris, engagement with the counterface asperities, and the ease with which they are removed from the contact. A steady transfer film does not form on the wet-sanded counterface because it is smooth in the direction of sliding providing little opportunity for mechanical interlocking with debris being easily pushed through the asperity corrugations. Transfer films do form and cover the asperities of the other surfaces, resulting in steady state wear rates that are independent of the initial roughness. In general, the wear debris of the 40 nm and 500 nm composites were much larger than for the 80 nm composite and did not form stable transfer films. It is hypothesized that the irregular shape of the alpha phase 80 nm nanoparticles facilitates entanglement between filler and matrix resulting in more efficient compartmentalization, smaller wear debris and the formation of stable transfer films. Transfer Film Examination The previous results suggest that the formation of a stable transfer film is a necessary condition to obtain very low wear rates. The characteristics of the transfer films, and specifically the thickness and coverage, were quantitatively analyzed using a scanning white-light interferometer (SWLI). Transfer films corresponding to the highest and lowest wear rates for the 5 wt% 40 nm, 80 nm and 500 nm alumina composites were measured and are shown in Figure 5-7.

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48 Figure 5-7. Scanning white-light interferometry measurements of representative transfer films; a) 5 wt% 40 nm composite on the lapped counterface, b) 5 wt.% 40 nm composite on the dry-sanded counterface, c) 5 wt.% 80 nm composite on the lapped counterface, d) 5 wt.% 80 nm composite on the wet-sanded counterface, e) 5 wt% 500 nm composite on the lapped counterface, f) 5 wt.% 500 nm composite on the dry-sanded counterface. The 40 and 500 nm nanoparticles are 70:30 delta:gamma phase while the 80 nm particles are 99% alpha phase. None of these particles are functional. It is evident from these scans that there is a direct relationship between the thickness of the transfer film and the wear-rate. Additionally, the thin transfer films appear more uniformly distributed across the counterface, while the thicker films are more banded in the direction of sliding for a given composite.

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49 Figure 5-8. Wear-rate and coefficient of friction plotted versus transfer film thickness. There is a correlation between wear rate and transfer film thickness. The friction coefficient shows no correlation. Figure 5-8 shows wear rate and friction coefficient plotted versus maximum transfer film thickness. The wear rate data follow a strong trend of decreased wear rates occurring on thinner transfer films. Although it seems counterintuitive that thin transfer films are more effective than thick transfer films in protecting the composite from asperity damage, thick films are easily removed by the pin and are therefore unstable, leaving bare counterface behind. The friction coefficient appears independent of the transfer film thickness and morphology.

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50 The Effects of Nanoparticle Surface Characteristics on the Tribological Response of PTFE Nanocomposites Mechanical Modification of the Particle-Matrix Interface Table 5-3 gives the results for steady state wear rate and average friction coefficient for nanocomposites with 80 nm alpha phase non-functional nanoparticles. Table 5-3. Tribological results of an experimental matrix for tests varying filler particle loading for 80 nm alpha non-functional nanoparticles. These alpha phase particles have an irregular or faceted shape which is hypothesized to improve mechanical compatibility of the particle/matrix interface. New counterfaces and individually made composite samples are used in each experiment. wt.% 80 nm alpha non-functional nanocomposites 1 2 5 10 71.910kx 7110ukx 73.410kx 70.410ukx 71.310kx 70.310ukx 72.110kx 70.210ukx Lapped counterface preparation 0.23 0.07 0.27 0.04 0.18 0.03 0.30 0.04 Figure 5-9 plots the friction coefficients of 1, 2, 5 and 10 wt% 80 nm alpha non-functional alumina-PTFE nanocomposites against a lapped counterface as functions of sliding distance under a normal load of 250 N.

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51 Figure 5-9. Plots of friction coefficient as a function of sliding distance. PTFE nanocomposite pins are filled with varying wt% irregularly shaped 80 nm filler. The experiments were run under a load of 250 N, a sliding speed of 50 mm/s, on a reciprocating pin-on-disk tribometer. The counterface was a lapped 304 stainless steel plate. The average friction coefficient over the entire experiment is given in the graph legend. Initially, the friction coefficient of each sample was low, ranging from =0.1-0.2. The friction coefficient of the 10 wt% sample quickly increased to a higher steady value of =0.32, while the 1 wt. % sample experienced nearly a kilometer of sliding distance before increasing to a similar value. Generally, the length of this transient period increased with decreased particle loading. This transient behavior is consistent with filler particle accumulation at the sliding interface [39]. It is interesting to note that the friction coefficient of the 5 wt% sample did not follow this trend, but stayed low at ~0.22 for the entire test. The steady values of friction coefficient for the 1, 2 and 10 wt% samples were similar at ~0.3.

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52 Figure 5-10. Volume lost plotted versus sliding distance. PTFE nanocomposite pins are filled with varying wt% irregularly shaped non-functional 80 nm filler. The experiments were run at a load of 250 N, and a sliding speed of 50 mm/s, on a reciprocating pin-on-disk tribometer. The counterfaces are lapped 304 stainless steel plates with roughness of Rq =160 nm. Error bars represent the experimental uncertainty The wear volume of each sample is plotted as a function of the sliding distance in Figure 5-10. The wear transient occurred in concert with the frictional transient for reach sample, and the wear rate and total wear volume during this transient period decreased with increasing filler concentration. Steady state wear rate was relatively insensitive to the filler loading, suggesting that filler accumulation occurred at the tribological interfaces until a steady surface composition is reached.

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53 Chemical Modification of the Particle-Matrix Interface The friction coefficient and wear rate results are given in Table 5-4. Table 5-4. Tribological results for a 1 wt% functional alumina-PTFE nanocomposite. Nanoparticles for this study were functionalized by bonding fluorine atoms to the alumina via silicon bonds, to improve the chemical compatibility at the filler/matrix interface. The particles in this study are 40 nm in diameter and 99% alpha in phase, and tests were performed against a lapped (160 nm Rq) counterface. 1 wt.% 40 nm alpha functional nanocomposite 88.0410kx 8.0410ukx lapped counterface preparation 0.21 0.02 The friction coefficient is plotted vs. sliding distance in Figure 5-11 for a nanocomposite with 1 wt% functional 40 nm alpha alumina against a lapped (Rq = 160 nm) counterface. The friction coefficient reaches a maximum value of = 0.25 after 15 km of dry sliding, and descends steadily for the remainder of the test. The average friction coefficient is approximately = 0.21 for this test and is obviously a strong function of the test length.

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54 Figure 5-11. Friction coefficient plotted vs. sliding distance for a 1wt% 40 nm alpha functional nanocomposite. The alumina surfaces have been functionalized with fluorine groups to enhance compatibility with the matrix. The experiments were run under a load of 250 N, and a sliding speed of 50 mm/s, on a reciprocating pin-on-disk tribometer. The counterface was a lapped 304 stainless steel plate. The grey region at the beginning of the test is enlarged with greater data density. An optical photograph of the transfer film with accompanying SWLI topography and thickness measurements are shown in Figure 5-12. It is immediately obvious that the transfer is very thick at the reversals; SWLI measurements indicate that thicknesses in these regions range from 10-20 m. Inside the reversals, the transfer film is thin with thickness ranging from 1-3 m, and becomes less uniform toward the center of the wear track. It is interesting to note that the color of the film is brown while the color of the composite is grey. This transfer film discoloration is consistently observed in PTFE

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55 based composites when the wear rate is less than k = 1 x 10 -6 mm 3 /Nm, and its origin is a current topic of investigation. Figure 5-12. Optical photograph of the wear track. Thick transfer at reversal points and thin patchy transfer in the center of the wear track are key features. SWLI topographical images and film thickness measurements are included for various points along the track length. Friction coefficients are plotted versus track position for a completer cycle in Figure 5-13 at various sliding distances during the test. At 500 m, the friction coefficient is low and constant along the wear track in both directions. At 5 km, the positional data is not constant across the wear track but begins increasing in the center. After 18 km of dry sliding, the friction coefficient is at its highest and is spatially dome-shaped. At 140 km, the friction coefficient appears as a truncated triangle. It should be noted that the velocity is constant after 1.4 mm, and this dependence is therefore not due to velocity. The friction coefficient during the last cycle of sliding is plotted versus the average transfer film thickness at points of SWLI measurement on the right hand side of Figure 5

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56 13. This graph confirms a trend of increasing friction coefficient with decreased thickness and uniformity. This is in direct contrast to the results of the other nonfunctional composites, which showed no correlation between friction coefficient and transfer film thickness and uniformity. The friction coefficient of this composite appears to be a strong function of both. Preliminary XPS results suggest that the transfer films of functional and nonfunctional composites have radically different chemistries, with the functional composite having substantially higher silicon content (from the fluorinated filler) in the transfer film than in the bulk, while the transfer films of the nonfunctional composites are believed to be PTFE rich. Figure 5-13. Left) Plot of friction coefficient versus wear track position for a 1 wt% functional nanocomposite at various sliding distances. Right) Friction coefficient plotted versus the average transfer film thickness. This average thickness reflects thickness as well as coverage. Wear volume is plotted versus sliding distance in Figure 5-14. There is a decrease in wear rate with increased sliding distance with k = 10 x 10 -8 mm 3 /Nm immediately following the transient region and k = 6 x 10 -8 mm 3 /Nm at the end of the test. This dependence of wear rate on sliding distance may be due to increased transfer film uniformity or the result of decreased traction stresses at the interface. The average wear

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57 rate of the material is calculated to be k = 8.0 x 10 -8 mm 3 /Nm with an uncertainty u(k) = 4 x 10 -10 mm 3 /Nm. Figure 5-14. Wear volume plotted vs. sliding distance for a 1wt% PTFE 40 nm functional alumina nanocomposite. The experiments were run under a load of 250 N, and a sliding speed of 50 mm/s, on a reciprocating pin-on-disk tribometer. The counterface was a lapped 304 stainless steel plate. It was hypothesized that Fluorinating the nanoparticles would result in improved properties at the filler/matrix interface and reduced wear rates. We can study the effects of particle fluorination by comparing the tribological properties of the 1 wt% 40 nm irregular functional and 1 wt% 80 nm irregular non functional nanocomposites. The functional composite had a wear rate of k = 8 x 10 -8 mm 3 /Nm, while the non-functional composite had a wear rate of k = 19 x 10 -8 mm 3 /Nm. It is unclear if this improvement is due to the reduced particle size or the particle fluorination, or whether the improvement is even significant. Despite the arguably similar steady wear rates of these functional and

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58 non-functional irregular samples, other tribological characteristics of these systems appear fairly distinctive and warrant further analysis. Qualitatively, the transfer films of these samples were very dissimilar with the transfer film of the non-functional sample being very thin (~2 m) and uniform, while the transfer film of the functional sample was much more variable in thickness and coverage across the wear track. Figure 5-15 shows friction coefficient and wear volume plotted versus sliding distance for the 1 wt% functional (irregular 40 nm particles) and the 1 and 10 wt% non-functional (irregular 80 nm particles) alumina-PTFE nanocomposites. It should be kept in mind that this graph represents a very small fraction of the total sliding distance from the functional nanocomposite; since it was tested 50X longer, the data are compared to the end of the non-functional experiments. Figure 5-15. Left) friction coefficient plotted vs. sliding distance for 1 wt% alumina-PTFE nanocomposites with Fluorinated and un-Fluorinated irregular alumina filler. Right) wear volume plotted vs. sliding distance for 1 wt% alumina-PTFE nanocomposites with Fluorinated and un-Fluorinated filler. The results of the 10 wt% non-functional sample are also included for comparison. The 10 wt% non-functionalized nanocomposite experienced an increase in friction coefficient almost immediately. The 1 wt% non-functional sample behaved identically, having the same steady friction coefficient of = 0.3 and wear rate of k = 2 x 10 -7

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59 mm 3 /Nm after a delay of 1 km. The similarities in steady tribological properties of the 1 and 10 wt% composite are likely due to filler accumulation [39] at the tribological interface; a process that occurs due to the preferential removal of PTFE and the resulting particle enrichment of the surface. The friction coefficient of the functionalized composite remained low for 4 km of sliding before beginning to transitioning to a higher value (Figure 5-11). While the non-functional composites remained steady after the initial transient, the friction coefficient and the wear rate of the functional composite decreased steadily for the remainder of the test (Figures 5-11 and 5-14). This reduction in the friction coefficient is not characteristic of filler accumulation at the tribological interface, and suggests that the frictional response was driven by the development of the transfer film. The transient volume loss of the 1 wt% functional composite was much less than that of the 1 wt% non-functional composite, being 0.5 and 1.75 mm 3 respectively. The extended sliding length and decreased wear volume of the transient region for the functional sample suggests that the functional composite had a more wear resistant initial state that is independent of transfer films. A strong dependence of wear rate on transfer films was noted earlier, which suggested that among similar systems, thin, uniform transfer films facilitate low wear sliding. Since the functional sample achieved a 2X lower wear rate on a thicker, less uniform transfer film, as compared to the non-functional sample, the improved wear resistance of the functional sample is attributed to improved composite integrity, and to a lesser extent, the lower traction stresses at the interface. The compartmentalization model of Chapter 2 predicts optimum composition at low filler loading which is in contrast to the results of previous nanocomposite studies.

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60 The results of the studies by Chen et al. [7] and Sawyer et al.[9] are plotted with the results of the irregular particle filled composites in this study against the compartmentalization model in Figure 5-16. Figure 5-16. Volume fraction plotted versus the ratio of the filler particle diameter to the matrix particle diameter for the compartmentalization model as well as experimental data from these and previous studies. Experimental data are recorded based on the optimized composition and the reported particle sizes. All of the microcomposites reported in the literature are in general agreement with the model. As the filler particles become smaller however, results diverge from the model and composites are optimized at much higher loadings than the model would predict. This is clearly illustrated in Figure 5-16 with the results of the previous experiments with spherical filler particles. It is thought that this divergence is due to the difficulty in dispersing the nanoparticles, and the inherently weak interface between the two inert constituents. However, the results of both irregular nanocomposites in this study are in agreement with the model having optimized wear rates at compositions close to the predicted values based only on the relative particle sizes. The difference may be

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61 due to the particle shape and the increased mechanical interaction of the filler and matrix at the interface. There are a number of models describing the role of filler in PTFE-based composites, each supporting one of two conclusions regarding nanoparticle inclusion within a PTFE matrix. The first is that nanoparticles are ineffective in reducing wear, the second that the filler content required for high wear resistance is reduced with reduced particle size. In practice, nanoparticles have been found effective in reducing wear, but only at loadings comparable to those of microcomposite systems. To the authors knowledge, this study is the first to demonstrate the capability of a PTFE nanocomposite to attain high wear resistance at a low loading (<5 wt. %). Wear rate is plotted versus filler wt% for several nanocomposites in Figure 5-17. This graph clearly illustrates the bifurcated wear characteristics of nanocomposites with filler particles believed to be spherical in shape to those of composites with irregularly shape filler particles. In the main, PTFE composites and nanocomposites with a wide variety of chemistry, size, processing and testing, behave very similarly having increased wear resistance with increased particle loading (until a saturation point is reached-composites typically become brittle), and tend to have optimized wear rates on the order of k = 1 x 10 -6 mm 3 /Nm. Both 1 wt% nanocomposites with irregular particles (functional 40 nm and non-functional 80 nm), achieved 10X the wear resistance of other highly filled and optimized PTFE-based systems. Comparing wear rates of 1 wt% nanocomposites, the irregular nanoparticle filled systems had 100-1000X lower wear rates than spherical nanoparticle filled systems.

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62 Figure 5-17. Wear rate versus filler wt% comparing composites of the current study to those of past studies. Squares and stars denote samples from this study and circles denote those of past studies. The open circles and squares are both spherical 40 nm (measured 38 and 44 nm, respectively) alumina nanoparticles with reported crystal phases of 70% delta and 30% gamma, and represent different batches of a single process. The 38 nm particles were used in a previous study; the 44 nm particles were used in this study. The solid stars are the irregular 80 nm alumina nanoparticles that are reported to be 99% alpha phase. The open star is the functionalized irregular 40 nm alumina nanocomposite. The closed square corresponds to the 500 nm spherical alumina composite. The light gray circles are from Li et al. [7] and are uncharacterized ZnO nanoparticles with a reported particle size of 50 nm. Uncertainty intervals are based on 95% confidence and are calculated based on the procedure discussed in Schmitz et al. [35]. It is evident based on these results that the surface condition of the nanoparticle fillers has a profound impact on the tribological properties of the composite, either enabling or precluding the development of a stable transfer film, and steady low wear sliding. It is unclear whether particle fluorination is the cause of higher steady wear resistance in the functional composite since particle size was also variable. However; the transient data suggest that there is a fundamental difference in the wear mechanism of the two composites which is unlikely to be the result of decreased particle size alone.

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CHAPTER 6 CONCLUSIONS 1. The inclusion of alumina nanoparticles into a PTFE matrix resulted in reduced wear rates in all cases. Abrasion of the counterfaces by the nanoparticles was not observed. 2. The steady state wear rate of PTFE was reduced by 3000X with the addition of 1 wt% (~0.5 vol%) 80 nm alpha alumina. It was reduced by 7500X with the addition of 1 wt% 40 nm alpha functional (fluorinated) alumina. 3. Among 1 wt% nanocomposites, the functional irregular 40 nm particle filled sample had the lowest steady wear rate of k = 8 x 10 -8 mm 3 /Nm, the nonfunctional irregular 80 nm particle filled sample had a steady wear rate of k = 19 x 10 -8 mm 3 /Nm and the nonfunctional spherical 40 nm particle filled sample had the highest steady wear rate of k = 9000 x 10 -8 mm 3 /Nm. 4. The functional nanocomposite was the only sample to exhibit a strong dependence of friction coefficient on wear track position. Friction coefficient was observed to be highest at points of low transfer film coverage. The friction coefficient (high dependence) and wear rate (low dependence) decreased as the transfer film coverage increased with sliding distance. 63

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LIST OF REFERENCES [1] Zhang, S. (1998). "State-of-the-art of polymer tribology." Tribology International 31(1-3): 49-60. [2] Friedrich, K., Z. Lu and A. Hager. (1995). "Recent advances in polymer composites' tribology." Wear 190(2): 139-144. [3] Blanchet, T. and Y. Peng (1998). "Wear resistant irradiated FEP unirradiated PTFE composites." Wear 214(2): 186-191. [4] Palabiyik, M. and S. Bahadur (2000). "Mechanical and tribological properties of polyamide 6 and high density polyethylene polyblends with and without compatibilizer." Wear 246(1-2): 149-158. [5] Bahadur, S. and V. Polineni (1996). "Tribological studies of glass fabric-reinforced polyamide composites filled with CuO and PTFE."Wear 200(1-2): 95-104. [6] Wang, Q., J. Xu, W. Shen and W. Liu. (1996). "An investigation of the friction and wear properties of nanometer Si3N4 filled PEEK." Wear 196(1-2): 82-86. [7] Li, F., K. Hu, J. Li and B. Zhao. (2001). "The friction and wear characteristics of nanometer ZnO filled polytetrafluoroethylene." Wear 249(10-11): 877-882. [8] Chen, W. X., F. Li, G. Han, J. Xia, L. Wang, J. Tu and Z. Xu. (2002). "Tribological behavior of carbon-nanotube-filled PTFE composites." Tribology Letters 15. [9] Sawyer, W. G., K. D. Freudenburg, P. Bhimaraj and L.Schadler. (2003). "A Study on the Friction and Wear of PTFE filled with alumina nanoparticles." Wear 254(5-6): 573-580. [10] Burroughs, B., J. Kim, T. Blanchet. (1999). "Boric acid self-lubrication of B2O3-filled polymer composites." Tribology Transactions 42(3): 592-600. [11] Flom, D. and N. Porile (1955). "Friction of Teflon sliding on Teflon." Journal of Applied Physics 26(9): 1088-1092. [12] Clark, E. (1999). "The molecular conformations of Polytetrafluoroethylene: forms II and IV." Polymer 40(16): 4659-4665. 64

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65 [13] Rigby, H. and C. Bunn (1949). "A room temperature transition in Polytetrafluoroethylene." Nature 164(4170): 583-583. [14] Mclaren, K. and D. Tabor (1963). "Visco-elastic properties and friction of solids friction of polymers influence of speed and temperature." Nature 197(487): 856-&. [15] Makinson, K. and D. Tabor (1964). "Friction + transfer of Polytetrafluoroethylene." Nature 201(491): 464-&. [16] Bunn, C., A. Cobbold, and R. Palmer. (1958). "The fine structure of Polytetrafluoroethylene." Journal of Polymer Science 28(117): 365-376. [17] Speerschneider, C. and C. Li (1962). "Some observations of structure of Polytetrafluoroethylene." Journal of Applied Physics 33(5): 1871-&. [18] Steijn, R. (1968). "Sliding experiments with Polytetrafluoroethylene." ASLE Transactions 11(3): 235-&. [19] Tanaka, K., Y. Uchiyama and S. Toyooka. (1973). "Mechanism of wear of Polytetrafluoroethylene." Wear 23(2): 153-172. [20] Blanchet, T. and F. Kennedy (1992). "Sliding wear mechanism of Polytetrafluoroethylene (PTFE) and PTFE composites." Wear 153(1): 229-243. [21] McCook, N.L., D.L. Burris, P.L. Dickrell and W.G. Sawyer. (2005). "Cryogenic friction behavior of PTFE based solid lubricant composites." Tribology Letters 20(2): 109-113. [22] Pooley, C. and D. Tabor (1972). "Friction and Molecular Structure Behavior of Some Thermoplastics." Proceeding of the Royal Society of London Series A-Mathematical and Physical Sciences 329(1578): 251-&. [23] Beamson, G., D. Clark, D.E. Deegan, N.W. Hayes, D.S.L. Law, J.R. Rasmusson and W.R. Salanek. (1996). "Characterization of PTFE on silicon wafer tribological transfer films by XPS, imaging XPS and AFM." Surface and Interface Ananlysis 24(3): 204-&. [24] Breiby, D., T. Solling, O. Bunk, R. Nyberg, K. Norman and M. Nielsen. (2005). "Structural surprises in friction-deposited films of poly(tetrafluoroethylene)." Macromolecules 38(6): 2383-2390. [25] Wheeler, D. (1981). "The transfer of Polytetrafluoroethylene studied by x-ray photoelectron spectroscopy." Wear 66(3): 355-365. [26] Suh, N. (1973). "Delamination theory of wear." Wear 25(1): 111-124.

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66 [27] Lancaster, .JK (1968). "Effect of carbon fiber reinforcement on friction and wear of polymers." Journal of Physics D-Applied Physics 1(5): 549-&. [28] Sung, N. and N. Suh (1979). "Effect of fiber orientation on friction and wear of fiber reinforced polymeric composites." Wear 53(1): 129-141. [29] Briscoe, B., A. Pogosian and D. Tabor. (1974). "Friction and wear of high-density polythene action of lead oxide and copper oxide fillers." Wear 27(1): 19-34. [30] Gong, D., B. Zhang, Q. Zue and H. Wang. (1990). "Effect of tribochemical reaction Polytetrafluoroethylene transferred film with substrates on its wear behavior." Wear 137(2): 267-273. [31] Gong, D., Q. Xue and H. Wang. (1991). "ESCA study on tribochemical characteristics of filled PTFE." Wear 148(1): 161-169. [32] Blanchet, T., F. Kennedy, and D. Jayne. (1993). "XPS analysis of the effect of fillers on PTFE transfer film development in sliding contacts." Tribology Transactions 36(4): 535-544. [33] Tanaka, K. and S. Kawakami (1982). "Effect of various fillers on the friction and wear of polytetrafluoroethylene-based composites." Wear 79: 221-234. [34] Bahadur, S. and D. Tabor (1984). "The wear of filled Polytetrafluoroethylene." Wear 98(1-3): 1-13. [35] Schmitz, T. L., W. G. Sawyer, J. Action and J. Ziegert. (2003). "Wear rate uncertainty analysis." Journal of Tribology. 126(4): 802-808. [36] Schmitz, T., W. Sawyer, J. Action and J. Ziegert. (2005). "The difficulty of measuring low friction: uncertainty analysis for friction coefficient measurements." Tribology Transactions 127(3): 673-678. [37] Wieleba, W. (2002). "The statistical correlation of the coefficient of friction and wear rate of PTFE composites with steel counterface roughness and hardness." Wear 252(9-10): 719-729. [38] Franklin, S. E. and A. de Kraker (2003). "Investigation of counterface surface topography effects on the wear and transfer behaviour of a POM-20% PTFE composite." Wear 255: 766-773. [39] Blanchet, T. A. (1995). "A model for polymer composite wear behavior including preferential load support and surface accumulation of filler particulates." Tribology Transactions 38(4): 821-828.

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BIOGRAPHICAL SKETCH David Burris graduated from Lemon Bay High School in Englewood, Florida, in June of 1998. He commenced his higher education at the University of Florida that summer. In the spring of 2002, he joined the Tribology Laboratory at the University of Florida and began work in the field of tribology. The following spring he received his bachelors degree and began his graduate studies. Upon receiving the degree of Master of Science, David will begin work on his doctorate degree. 67


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Permanent Link: http://ufdc.ufl.edu/UFE0014207/00001

Material Information

Title: Wear-resistance mechanisms in polytetrafluoroethylene (PTFE) based solid lubricants
Physical Description: xi, 67 p.
Language: English
Creator: Burris, David Lawrence ( Dissertant )
Sawyer, Wallace G. ( Thesis advisor )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2006
Copyright Date: 2006

Subjects

Subjects / Keywords: Mechanical and Aerospace Engineering thesis, M.S   ( local )
Dissertations, Academic -- UF -- Mechanical and Aerospace Engineering   ( local )

Notes

Abstract: This thesis presents an investigation of wear resistance mechanisms in PTFE based tribological nanocomposites. Tribological experiments are conducted on a linear reciprocating pin-on-flat tribometer with various PTFE-alumina nanocomposites. Variables in the experimental design include four counterface surface finishes, four filler particle loadings, three particle sizes and three filler particle surface conditions. In all cases the addition of nanoparticles to PTFE resulted in a substantial reduction in wear rate. In general, tribological properties of the nanocomposites were fairly insensitive to the counterface roughness from Rq =88 - 590 nm, but every composite, regardless of particle size, had lowest wear rates on a lapped counterface with Rq = 160 nm. The nature of the particle surface itself was found to have the greatest impact on the wear rate of the composite. Among 1 wt% nanocomposites, a spherical particle filled sample had the highest steady wear rate of k = 9000 x 10⁻⁸ mm³/Nm, a sample with irregularly shaped filler particles had a steady wear rate of k = 19 x 10⁻⁸ mm³/Nm and the sample with fluorine treated irregularly shaped nanoparticles had the lowest steady wear rate of k = 8 x 10⁻⁸ mm³/Nm. Very low wear rates (< k = 10⁻⁵ mm³/Nm) were only attained after an initial high transient wear rate and the subsequent formation of a stable transfer film. The wear rate was found to decrease with decreased wear debris size and increased uniformity of the transfer film. Based on results of these studies, it is hypothesized that the nature of the filler/matrix interface, particle dispersion, and relative filler/matrix diameter all contribute in determining the efficiency of crack arresting, debris size reduction and the subsequent ease with which debris are removed from the counterface. These coupled phenomena are believed to govern the tribological response of the composite.
Subject: composite, friction, lubricant, lubrication, nanocomposite, polymer, solid, tribology, wear
General Note: Title from title page of source document.
General Note: Document formatted into pages; contains 78 pages.
General Note: Includes vita.
Thesis: Thesis (M.S.)--University of Florida, 2006.
Bibliography: Includes bibliographical references.
General Note: Text (Electronic thesis) in PDF format.

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0014207:00001

Permanent Link: http://ufdc.ufl.edu/UFE0014207/00001

Material Information

Title: Wear-resistance mechanisms in polytetrafluoroethylene (PTFE) based solid lubricants
Physical Description: xi, 67 p.
Language: English
Creator: Burris, David Lawrence ( Dissertant )
Sawyer, Wallace G. ( Thesis advisor )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2006
Copyright Date: 2006

Subjects

Subjects / Keywords: Mechanical and Aerospace Engineering thesis, M.S   ( local )
Dissertations, Academic -- UF -- Mechanical and Aerospace Engineering   ( local )

Notes

Abstract: This thesis presents an investigation of wear resistance mechanisms in PTFE based tribological nanocomposites. Tribological experiments are conducted on a linear reciprocating pin-on-flat tribometer with various PTFE-alumina nanocomposites. Variables in the experimental design include four counterface surface finishes, four filler particle loadings, three particle sizes and three filler particle surface conditions. In all cases the addition of nanoparticles to PTFE resulted in a substantial reduction in wear rate. In general, tribological properties of the nanocomposites were fairly insensitive to the counterface roughness from Rq =88 - 590 nm, but every composite, regardless of particle size, had lowest wear rates on a lapped counterface with Rq = 160 nm. The nature of the particle surface itself was found to have the greatest impact on the wear rate of the composite. Among 1 wt% nanocomposites, a spherical particle filled sample had the highest steady wear rate of k = 9000 x 10⁻⁸ mm³/Nm, a sample with irregularly shaped filler particles had a steady wear rate of k = 19 x 10⁻⁸ mm³/Nm and the sample with fluorine treated irregularly shaped nanoparticles had the lowest steady wear rate of k = 8 x 10⁻⁸ mm³/Nm. Very low wear rates (< k = 10⁻⁵ mm³/Nm) were only attained after an initial high transient wear rate and the subsequent formation of a stable transfer film. The wear rate was found to decrease with decreased wear debris size and increased uniformity of the transfer film. Based on results of these studies, it is hypothesized that the nature of the filler/matrix interface, particle dispersion, and relative filler/matrix diameter all contribute in determining the efficiency of crack arresting, debris size reduction and the subsequent ease with which debris are removed from the counterface. These coupled phenomena are believed to govern the tribological response of the composite.
Subject: composite, friction, lubricant, lubrication, nanocomposite, polymer, solid, tribology, wear
General Note: Title from title page of source document.
General Note: Document formatted into pages; contains 78 pages.
General Note: Includes vita.
Thesis: Thesis (M.S.)--University of Florida, 2006.
Bibliography: Includes bibliographical references.
General Note: Text (Electronic thesis) in PDF format.

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0014207:00001


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Full Text












WEAR RESISTANCE MECHANISMS IN POLYTETRAFLUOROETHYLENE
(PTFE) BASED TRIBOLOGICAL NANOCOMPOSITES
















By

DAVID BURRIS


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

UNIVERSITY OF FLORIDA


2006





























Copyright 2006

by

David Burris

































This document is dedicated to the graduate students of the University of Florida.















ACKNOWLEDGMENTS

First I thank my parents who encouraged me to find my own path and follow it

without restriction and opened every door they could for me.

I would like to thank Jade for love and support of my graduate education.

I would like to thank the Tribology Lab for thoughtful input on experimentation,

help solving tough problems, hard work and friendship.

I would like to thank Greg, for the opportunities he has given me and support in

every aspect of my life whenever I need it.

I would like to thank DuPont for a steady supply of Teflon 7C molding resin.

Finally, I would like to acknowledge the financial support from the National

Science Foundation grant no #CMS-0219889, GOALI: Collaborative Research:

Tribology of Nanocomposites and AFOSR-MURI grant FA9550-04-1-0367. Any

opinions, finding, conclusions or recommendations expressed in this material are those of

the author and do not necessarily reflect the views of the National Science Foundation or

the Air Force Office of Scientific Research.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TABLES ............... ................... ..................... .... .. .. ............. vii

LIST O F FIG U R E S ......... .......................... .. .............. ........................ .. .. viii

CHAPTER

1 IN TR OD U CTION ............................................... .. ......................... ..

Introduction to Solid Lubrication in Design..... .......... .................... .................
Polytetrafluoroethylene as a Solid Lubricant ........................................ ....................3
PTFE Based Tribological Com posites...................................... ........................ 6

2 COMPARTMENTALIZATION MODELING.....................................................10

3 EXPERIM ENTAL M ETHODS ........................................ ........................... 15

M materials and Processing .......................................................................... 15
T ribological T testing ........... ...... ........................................ .............. .......... .. 19

4 DESIGN OF EXPERIM ENTS ............................................................................29

The Effects of Surface Roughness on the Tribological Response of PTFE
N anocom posites .................................. .. .................... .. ... ........ .. .......... 29
Varying Filler Loading and Surface Finish ................................................31
V arying Filler Size and Surface Finish ...................................................... .... 33
The Effects of Particle Surface Characteristics on the Tribological Response of
PTFE N anocom posites....................................................................................... 34
Mechanical Modification of the Particle-Matrix Interface...............3...............5.
Chemical Modification of the Particle-Matrix Interface.............. ................ 37

5 RESULTS AND DISCU SSION ........................................... .......................... 39

The Effects of Surface Roughness on the Tribological Response of PTFE
N anocom posites .................................. .. .................... .. ... ........ .. .......... 39
Varying Filler Loading and Surface Finish ................................................39
Varying Filler Size and Surface Finish .................................... ............... 43









Transfer Film Exam ination............... ........... ............ ...............................47
The Effects of Nanoparticle Surface Characteristics on the Tribological Response
of PTFE N anocom posites ................................. ........... ......... ................. 50
Mechanical Modification of the Particle-Matrix Interface..............................50
Chemical Modification of the Particle-Matrix Interface...............................53

6 C O N C L U SIO N S ..................... .... .......................... ........ ........ ...... ........... 63

L IST O F R EFE R E N C E S ............................................................................ .............. 64

B IO G R A PH IC A L SK E TCH ..................................................................... ..................67
















LIST OF TABLES


Table page

2-1. Definitions of variables used in compartmentalization model. ............................. 12

4-1. Design of experiments: investigation of the coupled effects of counterface
roughness and filler wt% on the tribological behavior of alumina-PTFE
nanocom posites. ........................................................................32

4-2. Design of experiments: investigation of the coupled effects of counterface
roughness and filler size on the tribological behavior of alumina-PTFE
nanocom posites. ........................................................................34

4-3. Design of experiments: investigation of the effects of filler wt% on the
tribological behavior of alumina-PTFE nanocomposites having irregular filler
p article sh ap e ........................................................................................... 3 7

5-1. Tribological results of an experimental matrix for tests varying filler loading and
counterface surface finish ........... ................. ............................ ............... 39

5-2. Tribological results of an experimental matrix for tests varying filler particle size
and counterface surface finish. ................................ .. .................................. 43

5-3. Tribological results of an experimental matrix for tests varying filler particle
loading for 80 nm alpha non-functional nanoparticles...........................................50

5-4. Tribological results for a 1 wt% functional alumina-PTFE nanocomposite. ............53
















LIST OF FIGURES


Figure page

1-1. Results from wear tests for representative polymer matrix composites found in
the literature .......................... ...... ..................... ............. ..........2

1-2. Schematic representation of the structure of PTFE at various length scales ..............4

1-3. Schematic representations of the hypothesized transfer of PTFE in the mild (left)
and severe (right) w ear regim es. ........................................ .......................... 5

2-1. Representation of the matrix and filler particles used in compartmentalization
m modeling ......... ......... ......... .................................... ...........................11

2-2. Plot of required filler volume fraction plotted vs. the dimensionless diameter as
calculated from Eq. 2-9. .............................. ................ ................ ............. 14

3-1. Secondary electron images of Teflon 7C as received from DuPont.....................16

3-2. Schematic representation of the jet mill grinding apparatus. ............................... 17

3-3. Secondary electron mages of a 12.5 wt% alumina-PTFE powder ensemble after
jet-m killing ............................................................................18

3-4. Tribometer used for friction and wear testing. .................................. ............... 20

3-5. Model representation of misaligned measurement axes......................... .........23

4-1. Surface profilometry data from a scanning white-light interferometer (SWLI)
w ith a 20x objective. ................. .................. .................. ............. 1

4-2. TEM images of the two alumina particles evaluated. ........................... 36

5-1. Average friction coefficients of all 40 nm delta:gamma non-functional
composites plotted versus weight percent of filler particles. ...............................40

5-2. Average wear rates of all 40 nm delta:gamma non-functional composites plotted
versus weight percent of filler particles. ...................................... ............... 41

5-3. Average wear rates of the 40 nm delta:gamma non-functional nanocomposites
plotted versus the RMS roughness of the counterfaces and Rq/Df .......................... 42









5-4. Average friction coefficients of the 5 wt% non-functional composites plotted
versus the RM S roughness of the counterfaces......................................................44

5-5. Average wear rates of the 5 wt% non-functional composites plotted versus the
RM S roughness of the counterfaces. ......................... .......... ............. .................. 45

5-6. Left) Wear volume plotted vs. sliding distance for the 5 wt% 80 nm alpha non-
functional nanocomposite on varying surface finish. Right) Initial wear rate
plotted vs. counterface R q ............................................... ............................. 46

5-7. Scanning white-light interferometry measurements of representative transfer
film s ............................................................................ .4 8

5-8. Wear-rate and coefficient of friction plotted versus transfer film thickness ............49

5-9. Plots of friction coefficient as a function of sliding distance. ..................................51

5-10. Volume lost plotted versus sliding distance. ................................ ..................52

5-11. Friction coefficient plotted vs. sliding distance for a lwt% 40 nm alpha
functional nanocom posite. ............................................. .............................. 54

5-12. Optical photograph of the wear track. ........................................ ............... 55

5-13. Left) Plot of friction coefficient versus wear track position for a 1 wt%
functional nanocomposite at various sliding distances. Right) Friction
coefficient plotted versus the average transfer film thickness. .............................56

5-14. Wear volume plotted vs. sliding distance for a lwt% PTFE 40 nm functional
alum ina nanocom posite ............................................................................ .... ..... 57

5-15. Left) friction coefficient plotted vs. sliding distance for 1 wt% alumina-PTFE
nanocomposites with Fluorinated and un-Fluorinated irregular alumina filler.
Right) wear volume plotted vs. sliding distance for 1 wt% alumina-PTFE
nanocomposites with Fluorinated and un-Fluorinated filler. ..................................58

5-16. Volume fraction plotted versus the ratio of the filler particle diameter to the
matrix particle diameter for the compartmentalization model as well as
experimental data from these and previous studies.............................................60

5-17. Wear rate versus filler wt% comparing composites of the current study to those
of past studies. ...................... ..... ............ ............. ..... ............ 62









Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science

WEAR RESISTANCE MECHANISMS IN POLYTETRAFLUOROETHYLENE
(PTFE) BASED TRIBOLOGICAL NANOCOMPOSITES

By

David Burris

May 2006

Chair: W. Gregory Sawyer
Major Department: Mechanical and Aerospace Engineering

This thesis presents an investigation of wear resistance mechanisms in PTFE based

tribological nanocomposites. Tribological experiments are conducted on a linear

reciprocating pin-on-flat tribometer with various PTFE-alumina nanocomposites.

Variables in the experimental design include four counterface surface finishes, four filler

particle loadings, three particle sizes and three filler particle surface conditions. In all

cases the addition of nanoparticles to PTFE resulted in a substantial reduction in wear

rate. In general, tribological properties of the nanocomposites were fairly insensitive to

the counterface roughness from Rq =88 590 nm, but every composite, regardless of

particle size, had lowest wear rates on a lapped counterface with Rq = 160 nm. The

nature of the particle surface itself was found to have the greatest impact on the wear rate

of the composite. Among 1 wt% nanocomposites, a spherical particle filled sample had

the highest steady wear rate of k = 9000 x 10-8 mm3/Nm, a sample with irregularly

shaped filler particles had a steady wear rate of k = 19 x 10-8 mm3/Nm and the sample

with fluorine treated irregularly shaped nanoparticles had the lowest steady wear rate of k

= 8 x 10- mm3/Nm.









Very low wear rates (< k = 10i5 mm3/Nm) were only attained after an initial high

transient wear rate and the subsequent formation of a stable transfer film. The wear rate

was found to decrease with decreased wear debris size and increased uniformity of the

transfer film. Based on results of these studies, it is hypothesized that the nature of the

filler/matrix interface, particle dispersion, and relative filler/matrix diameter all

contribute in determining the efficiency of crack arresting, debris size reduction and the

subsequent ease with which debris are removed from the counterface. These coupled

phenomena are believed to govern the tribological response of the composite.














CHAPTER 1
INTRODUCTION

Introduction to Solid Lubrication in Design

Solid lubrication is of great practical interest to mechanical design, being employed

in a wide variety of applications ranging from frying pans to orthopedic implants to the

deployment mechanisms of communications satellites. It can supplement other means of

lubrication in rolling element bearings, metal forming/cutting, engine valve-trains and

turbine foil air bearings. It can reduce cost, complexity, weight, and environmental

impact by replacing the pumps, filters, pipes and waste management systems associated

with fluid lubrication. Primarily, however, solid lubricants are used when other means of

lubrication is precluded. This includes applications sensitive to contamination such as

the conveyor bushings in the food industry, chemical processing, and space applications

where extreme temperatures and vacuum can destroy liquid and grease lubricants.

Despite the wide and expanding use of solid lubrication in engineering design,

there is an increasing demand for new low friction, low wear materials to improve

efficiency and operational life in various environments. As current states of their

respective arts, artificial knee joints need replacement every 10-20 years on average and

the thin MoS2 films used in space applications cannot survive terrestrial testing and have

limited lives in space operation. There are significant efforts dedicated to the research

and development of such solid lubricants, with polymers and polymer composites

comprising a large portion of the field (the state-of-the-art was reviewed by Zhang in










1998 [1] and Friedrich et al. in 1995 [2]). Though not exhaustive, Figure 1-1 contains

plots of wear rate versus filler wt% for representative polymer composites.

1 /-^ A


IU


.
64

x







-7 I I *
7, ,.


matrix-filler
PTFE-FEP
PA6-HDPE
PA11-GF
PEEK-Si3N4
PTFE-ZnO
PTFE-CNT
PTFE-A1203
PTFE-B203
Epoxy-B203
PEEK-PTFE


0 5 10 15 20 25 30
wt% filler

Figure 1-1. Results from wear tests for representative polymer matrix composites found
in the literature. Wear rate is plotted vs. filler weight percent: PTFE-FEP [3],
PA6-HDPE [4], PA11-GF [5], PEEK-Si3N4 [6], PTFE-ZnO [7], PTFE-CNT
[8], PTFE-A1203 [9], PTFE-B203 [10], Epoxy-B203 [10], and PEEK-PTFE
[2].

Modem designs are becoming increasingly complex, imposing a larger number of

functional requirements than those possessed by current solid lubricants. These

requirements can include low friction, low wear, chemical resistance, environmental

stability, high strength, variable modulus, and thermal and electrical conductivity, to

name a few. At present, material discovery consists of an iterative process of guess and

check, where every material combination imaginable is tested in search of a satisfactory

candidate; a process which often results in failure. There is an obvious scientific need for

a more fundamental understanding of the complex interactions within these tribological

systems to enable the design highly functional tribological composites capable of

excelling in modern machinery.


E
S10-
E

S10-
4-,
I-

10-



in-









Polytetrafluoroethylene as a Solid Lubricant

Polytetrafluoroethylene (PTFE) typically consists of 10,000-50,000 mers, or

repeating units, of tetrafluoroethylene (C2F4) in a helix configuration. The carbon

fluorine bond is very strong, and although the carbon backbone is single bonded, it is

housed within a fluorine encasement which effectively shields it from chemical attack.

High chemical stability and linear chain morphology gives PTFE many unique and

desirable physical properties. Foremost, PTFE is distinguished as having the lowest

coefficient of friction and chemical reactivity of any bulk polymer. PTFE also has a large

useful temperature range (4-500 K), is biocompatible, is environmentally insensitivity

and has a very low vapor pressure (low outgassing). Because of its unique combination

of material properties, PTFE has received much attention for tribological use.

Flom and Porile [11] performed some of the earliest tribological experiments with

self-mated PTFE finding an abrupt increase in the friction coefficient at high speed (>10

mm/s) as the background temperature increased above a threshold value near room

temperature. They hypothesized that this point increase is associated with the crystal

phase transition between forms II and IV [12] at 190C as first reported by Rigby and

Bunn [13]. They also noted a trend of increased friction coefficient with increased

sliding velocity. McLaren and Tabor [14] systematically studied self mated PTFE

varying sliding velocity at three background temperatures. They found a transition from

low to high friction to occur at a critical speed that depended on the background

temperature. As the temperature is increased, the critical speed increased, thus

demonstrating the viscoelastic nature of PTFE in dry sliding. Makinson and Tabor [15]

found evidence of strong adhesion to the counterface and a transition from mild to severe

wear that accompanied the frictional transition above the critical speed. They combined










the early structural work of Bunn, Cobold and Palmer [16], and Speerschnieder and Li

[17] with their own tribological results and electron diffraction work to relate the

tribological behavior of PTFE to its crystalline structure. A schematic representation of

this hypothesized structure of PTFE is shown in Figure 1-2.

amorphous
grain boundaries

crystalline rate dependent
amorphous crystalline
\ \slice



S5.7A

200A
b)




Figure 1-2. Schematic representation of the structure of PTFE at various length scales:a)
large deformable units such as particles or grains in sintered material b)
Segmentation of crystalline and amorphous regions based on the work of
Bunn, Cobold and Palmer [16] and Speerschneider and Li [17] c) strain of the
amorphous region giving rise to intra-crystalline slip d) molecular structure
deduced from electron diffraction by Makinson and Tabor [15].

Based on this structure, they conjectured that a transition in the relevant units of

PTFE involved in shearing is responsible for the tribological transition. At low speeds

and high temperatures, shearing occurs in the rate sensitive amorphous regions giving

rise to a lamellar type response of crystals or molecules. As speed is increased and

temperature decreased, the stresses required to shear the amorphous regions exceeds the

stress required to shear larger units such as grain boundaries in the sintered material.

Because they observed very low coefficients of friction with evidence of strong adhesion

to the counterface, they suggested that van der Waals or electrostatic interactions within

the PTFE itself dominate the tribological response. Steijn [18], Tanaka et al. [19],









Blanchet and Kennedy [20], and McCook et al. [21] found independent sets of frictional

data for PTFE to obey an Arrehnius dependence with activation energies consistent with

van der Waals interactions.

In the mild wear regime, the transfer of PTFE is characterized by thin, highly

aligned, and well-adhered films [14-17, 22-25]. Friction coefficients are generally less

than [t = 0.1 and wear rates can range from 1-10 x 10-5 mm3/Nm. In the severe wear

regime, the transferred material is thick and patchy, friction coefficients are increased and

the wear rate, k, is over an order of magnitude greater than for mild wear. Figure 1-3

shows a schematic representation of the transfer of PTFE in these regimes as described

by Makinson and Tabor [15].





g0.1

PTFE slider PTFE slider
highly oriented [t 5-30 pm > lOmm/s
VV > 10 mm/s
t-10snm V < <10mm/s
countrfa crystalline sce counterface
1 counteractc amorphous material

Figure 1-3. Schematic representations of the hypothesized transfer of PTFE in the mild
(left) and severe (right) wear regimes. At room temperature and speeds less
than 10 mm/s the transfer is thin and aligned with p<0.1. Above 10 mm/s
thick platelets are transferred with t>0.1.

Blanchet and Kennedy [20] systematically studied the tribological behavior of

PTFE as a function of speed and temperature and found similar results to those of

McLaren and Tabor [14] and Makinson and Tabor [15], namely, increased friction

coefficient with increased speed, and an increase in the critical speed with increased

interface temperature. However, when the wear rate, k, was plotted versus the friction









coefficient, [t, a transition to severe wear was observed at [t = 0.1 for each background

temperature tested. These results suggest that the severe wear transition is a response to

the friction coefficient alone, while the friction coefficient is a function of speed and

temperature. Several samples were microtomed perpendicular to the wear surface and in

the direction of sliding after mild and severe wear had taken place. Cracks were found to

propagate in the direction of sliding beneath a layer of worked material at subsurface

depths consistent with observed debris thicknesses for severe wear samples. No such

cracks were found in mild wear samples. They conjectured that defects in the sintered

material act as initiated cracks. When speeds are low, the kinetic friction coefficient is

low at the tribological interface, and the static friction coefficient between crack faces can

fully support the surface tractions, relieving the crack tips from stress. However, when

the kinetic coefficient of friction at the tribological interface exceeds the static coefficient

of friction ([t 0.1), the crack tips must support shear, giving rise to mode II crack

propagation. This leads to a progressive delamination wear process similar to that

described in Suh's Delamination Theory of Wear [26].

PTFE Based Tribological Composites

For decades, fillers have been added to PTFE to abate the onset of severe wear.

The wear reducing mechanism of fillers in PTFE based composites remains a topic of

debate. Lancaster [27] proposed the idea that the fillers, especially those with a high

aspect ratio, preferentially support the load, thus lowering the wear rate of the composite.

Sung and Suh [28] found that vertically oriented fibers were most effective in reducing

wear, but suggested that the critical role of the filler was to arrest crack propagation

through the matrix, rather than to support the load. Briscoe et al. [29] found that the wear









rate of neat high density polyethylene (HDPE-another polymer with a linear molecular

chain) on a pre-deposited composite transfer film was similar to that of a composite

sample when tested against steel. Such improvements in wear resistance of the neat

material were not observed when films were pre-deposited on glass counterfaces. They

inferred that the wear reduction mechanism of the filler was to induce strong adhesion

between the transfer film and a reactive counterface. On the contrary, Gong et. al.

[30,31] found that the wear rate of PTFE was independent of chemical bonding based on

XPS results and the metal fluoride content at the counterface, and concluded that

cohesive failure within the PTFE governs its wear rate. Blanchet and Kennedy had

similar findings with XPS analysis of PTFE and PTFE composites in dry sliding [32],

and concluded that the wear reducing role of the filler is to slow primary removal of

material from the bulk by arresting crack propagation rather than slowing secondary

removal of material from the counterface via transfer film adhesion. Tanaka et al. [33]

hypothesized that the filler interrupted the destruction of the banded structure of PTFE.

Bahadur and Tabor [34] and Blanchet and Kennedy [32] saw direct relationships between

wear rate, debris size and the ease with which debris are expelled from the contact. Small

wear debris are hypothesized to be easily engaged into surface features, facilitating the

formation of thin, uniform transfer films, and a reduced rate of wear.

Despite the universal effectiveness of microscopic fillers in PTFE composites,

conventional wisdom suggested that nanoscopic fillers would be ineffective. The wear

reduction models proposed by Lancaster [27] and Tanaka and Kawakami [33], namely,

preferential load support and prevention of large-scale destruction of the banded

structure, predict nanoparticles to be ineffective fillers because they are too small to offer









load support, and would not prevent the large-scale destruction of the banded structure,

being swept away with the matrix by relatively large asperities.

However, there are potential benefits of reduced filler size. The most obvious is

reduced counterface abrasion. Traditional microcomposites require hardened shafts and

counterfaces to reduce abrasion and third body debris that can accelerate wear. Less

obvious is the high number density and surface area of the nanoparticles at low filler

volume fractions. If Blanchet and Kennedy's model of crack arresting [20] is assumed in

favor of the theories of Lancaster [27] and Tanaka and Kawakami [33], nanoparticles

have very promising attributes. Because cracks are arrested or deflected by the surfaces

of interrupting particles or phases, composites with very high filler surface areas should

have effective crack arresting characteristics. This would be especially helpful for

materials like PTFE that wear by delamination.

A nanocomposite is defined as a composite having filler particles with a

characteristic dimension of less than 100 nm. Several investigators have successfully

created nanocomposites, and contrary to the prevailing theories, improvements in wear

resistance were found to be comparable to those of typical microcomposites. Li et al. [7]

filled PTFE with nanometer ZnO, and found 15 wt.% (weight percent of fillers) to be the

optimal filler content for reducing wear rate, while retaining a low friction coefficient.

Chen et al. [8] created a nanocomposite with single-walled carbon-nanotubes (SWNT).

They found that wear resistance was improved by more than two orders of magnitude

over unfilled PTFE with limited reductions in the friction coefficient. The carbon-

nanotubes were thought to strengthen the matrix, reducing wear of the PTFE. They

hypothesized that the carbon-nanotubes provided additional self-lubrication of the









composites by breaking off, becoming trapped in the contact and separating the surfaces.

Sawyer et al. [9] made nanocomposites of PTFE with 38 nm A1203 and found a 600x

reduction in wear with 20 wt% filler concentration. Wear was reduced monotonically as

filler concentration was increased to 20 wt%. Scanning electron microscopy (SEM)

revealed that the PTFE particles were decorated by the nanoscopic alumina during a

powder blending process that preceded compression molding. The resulting structure

after molding is cellular with thin regions of highly concentrated PTFE-alumina material

surrounding micrometer sized domains of PTFE. These concentrated regions act as

barriers to crack propagation and reduce the delamination wear of PTFE. Further, it was

offered that with increasing filler concentration, the number, size and possibly strength of

the compartmentalizing regions increased.

These results demonstrate the effectiveness of nanoscopic fillers in abating the

severe wear mode of PTFE, and implicate the crack arresting model as the mechanism of

wear resistance in filled PTFE systems. On the other hand, nanoscopic fillers have not

been shown to provide any improvements (aside from reduced abrasion) over the more

traditional fillers (Figure 1-1). To date, high wear resistance at low particle loading has

not been achieved [7-9]. The goal of the present research is to study the frictional, wear

and transfer responses of PTFE nanocomposites in greater detail in order to gain a more

fundamental understanding of these complex systems. Such an understanding could

facilitate the design of highly functional composite systems to benefit a wide spectrum of

end use products.














CHAPTER 2
COMPARTMENTALIZATION MODELING

In order to slow or prevent the onset of severe wear, the mechanisms and properties

contributing to the occurrence of severe wear must be identified and addressed. The

following model is developed assuming that the severe wear mode of PTFE is one in

which cracks pre-exist or are initiated and propagated to failure, a mode known as

delamination wear [25]. Fillers are therefore assumed to play a crack arresting role [20].

Once these cracks encounter resistance (filler), they are arrested or are turned toward the

surface to relieve a wear particle. For simplification, it is assumed that the rate of

initiation is constant so that each wear particle represents an initiation point. Therefore,

the smaller the wear particle at each initiation point, the lower the rate of wear. This is

also the basis of the wear model presented by Bahadur and Tabor [34]. A few things

should be kept in mind with this model: 1) the rate of initiation is probably faster in a

filled system due to the addition of imperfections at the particle/matrix interfaces, 2) only

cracks at depths of the same order of magnitude as the compartmentalized length can

effectively be liberated as debris because of the surrounding material, and 3) the wear

volume scales by R3, where R is the characteristic compartment (matrix particle) radius.

Point 2) likely counteracts the false assumption that the initiation rate is constant, and

point 3) suggests that small matrix particles are desirable for reducing wear. With these

ideas in mind, a simple model can be conceived for particulate systems where the matrix

and filler particle sizes dictate the volume fraction of filler required for effective crack

arresting.









It is presumed that cracks are arrested most efficiently when each matrix particle is

compartmentalized by a monolayer of filler; this corresponds to the least amount of filler

required to effectively arrest a crack propagating through any matrix particle. At filler

loadings less than the critical loading, the probability of arresting each crack is

diminished. At some loading greater than the critical loading, there is insufficient matrix

to effectively bind all of the particles diminishing the mechanical properties of the

composite. The model system is shown schematically in Figure 2-1.

filler
monolayer coverage by filler
centerline sphere
D Dc
matrix



model system






0* = 0.907
Figure 2-1. Representation of the matrix and filler particles used in compartmentalization
modeling. The model matrix particle and filler particles are treated as spheres.
The volume fraction for complete coverage of the matrix by filler is solved for
using various simplifying assumptions.

Consider the matrix and filler particles to be spheres of characteristic diameter Dm

and Df, respectively. In the closest packed configuration (2D-it is assumed that Df <<

Dm), the area fraction of the matrix particle surface that is covered by filler particles is

0.907. This packing factor will be treated as a variable, 0*. Also, since the matrix

particles will likely deviate from spheres, a surface area correction factor, S*, will be

considered, and is equal to the ratio of the surface area of the model sphere to the real

surface area of the irregular matrix particle (the deviation of the filler particle from a









sphere is insignificant). The ratio of the filler diameter to the matrix diameter is D*.

Table 2-1 defines these and other variables used in the analysis.

Table 2-1. Definitions of variables used in compartmentalization model.
V Volume of any sphere
S Surface area of any sphere
A Projected area of any sphere
Dm Diameter of model matrix sphere
Df Diameter of model filler sphere
D* Diameter ratio; Df/Dm
0* 2-dimensional packing factor for filler

D, Diameter of the sphere located at the
centerline of the filler particles
Sc Surface area of the sphere located at the
centerline of the filler particles
S* Irregularity factor; Sm/real surface area
Af Total projected area of the filler
Vf Volume fraction of the filler


For a monolayer of filler, the centers of the filler particles reside on a sphere of

diameter equal to the sum of the diameters of filler and matrix. The surface area of this

sphere is given by,


Sc = 4rR2 = 4 2 = (D, +Df)2


Eq. 2-1


This surface area closely approximates the total projected area of filler particles when

corrected by the packing factor 0*, and the irregularity factor S*, as


0* 2
Af =0*S,= (D,,,+Df
S *


Eq. 2-2


The ratio between the volume and projected area of any sphere is given by,


V 3 2
A D
2


Eq. 2-3


2
3









The total volume of the filler is found by multiplying the total area of the filler by Eq. 2-

3,

2 0* 2
V D zT (D, +D,)2 Eq. 2-4
3 *

Applying the dimensionless diameter, D*, the volume of the filler becomes,

V,- D*O* (D +D*Dm)2 D*O*D3(D*+1)2 Eq. 2-5
f 3 S* 3 S*

The volume of a single matrix particle is given by,

34
Vm (m 4 m3 Eq. 2-6
3 2 6

The volume fraction of the filler required for monolayer coverage is therefore,

2QTTD* 0* 2 4D*0*
TD 3 (D* +1)2 4D*O*(D* +1)2
f vf 3S* m S* Eq. 2-7
V +V m 2xCD** 2 BD 4D*0*
S2 D *(D*+1)2 + D3 (D*+)2+1
S3S* 6 m S*

If the ratio of the packing factor and the irregularity factor is approximately equal to

unity, Eq. 2-7 becomes,

4D*(D*+1)2
Uv = *(* Eq. 2-8
f 4D*(D*+1)2 +1

If the model is restricted to cases where the filler is much smaller than the matrix, then

D* is much less than 1. If second order terms are neglected, the volume fraction of the

filler for monolayer coverage becomes,

4D*
Vf = 4Eq. 2-9
S4D *+1

The filler volume fraction vf is plotted vs. D* following Eq. 2-9 in Figure 2-2.






14


1 0-




10-1
<4- -^


10-2-


3x 10 -3 ...... ...... ......
10-3 10-2 10-1 100

Df/Dm
Figure 2-2. Plot of required filler volume fraction plotted vs. the dimensionless diameter
as calculated from Eq. 2-9. Nearly an order of magnitude reduction in
required filler content is achieved by an order of magnitude reduction in filler
diameter.

This graph can be used as a simple tool for composite design, and is instructive in

considering the advantages of nanocomposites over microcomposites. If the matrix and

filler particles are of the same size (D*=I), the simplified model gives a required 80 vol%

filler (this is underestimated by 15% due to the assumption that the filler is much smaller

than the matrix). If the filler is 1/100 the size of the matrix (D*=0.01), the model predicts

a required 3.8 vol% filler (1.9% underestimated). For D* = 0.001, as is typical for

nanocomposites, 0.4 vol% filler is required for monolayer coverage. Hence, very

effective damage compartmentalization in PTFE should be possible at very low filler

volume fractions.














CHAPTER 3
EXPERIMENTAL METHODS

Materials and Processing

The aforementioned model assumes perfect particle dispersion and neglects the

obvious difficulties in obtaining such dispersions. With poor dispersion, some matrix

particles will not be compartmentalized, and some will have thick boundaries of dense

filler material. This can make the composite brittle and ineffective, especially when filler

particles do not melt or bond in any way during polymer processing.

An element that was briefly mentioned but not addressed by the

compartmentalization model is the effect of matrix size. Assuming perfect

compartmentalization, as the size of the matrix particle is decreased, the compartment

size, debris size and wear rate are hypothesized to decrease, along with the filler size

required to maintain D*. This suggests that low wear PTFE composites are most

effectively obtained with micro-scale matrix particles and nano-scale fillers.

DuPont 7C PTFE molding resin is used in these studies due to its combination of

high molecular weight and small particle size. It has a molecular weight ranging from

approximately 106-107 Da and an average manufacturers claimed particle size of 35 jtm.

As received, the particles are agglomerated, with agglomerates ranging from

approximately 100 |tm 10 mm. The scanning electron microscopy shown in Figure 3-1

reveals that the particles have characteristic sizes on the order of 25 jtm and are irregular

in shape. This shape irregularity tends to increase the required volume fraction of filler

for monolayer coverage.





















200 Xm 20 pjm

Figure 3-1. Secondary electron images of Teflon 7C as received from DuPont.
Agglomerations range from 100 ptm 10 mm. The average individual
particles size is reported to be 35 |tm. This value is consistent with
measurements made using scanning electron microscopy (SEM).

The filler selected for use in this study is Al203, or alumina. Alumina is very hard,

wear resistant, chemically stable, and widely available as laboratory and commercial

grade material with particle diameters ranging from tens of nanometers to millimeters.

Variables related to the alumina in this study are, wt% of filler loading, average particle

size (APS), crystalline phase, and surface chemistry. Values of filler weight percent

(wt%) used are 0, 1, 2, 5, and 10. Possible values of APS are 40, 80, and 500 nm.

Crystalline phase influences the shape of the particle, which is hypothesized to affect the

mechanical compatibility of the filler/matrix interface. The phases used in this study are

70% delta: 30% gamma (referred to as delta:gamma) and 99% alpha (referred to as

alpha), and have spherical and irregular particle shapes, respectively. Surface chemistry

can be non-functional (as-received) or functional, a condition that results from a chemical

treatment where fluorine groups are indirectly bonded to the alumina via silicon.









In order to achieve effective particle compartmentalization, a technique is required

to break apart agglomerations and then disperse the filler particles. A fluid energy jet

mill, shown schematically in Figure 3-2, is used for this purpose.



Feed Funnel ,$


Compressed Feed Outlet
Air inlet Vortex
.sen gnder

1,'Grinding

Compressed Grind Cambe
Air Inlet



Alumina Liner Grind Air Manifold

Figure 3-2. Schematic representation of the jet mill grinding apparatus. Fluid energy is
used to impact and break the particles and agglomerations. Large particles are
forced against the walls to be ground while small particles exit through the
center into the collection chamber. Schematic obtained from
www. sturtevantinc.com.

The jet mill uses pressurized air to accelerate the powder ensemble into a grinding

chamber. A pressurized manifold forces air through angled holes in the grind chamber to

create a vortex within the chamber. This vortex accelerates the particles tangentially

along the periphery of the chamber causing the particle/particle and chamber/particle

impacts responsible for breaking apart agglomerations and dispersing the constituents.

Larger particles are preferentially forced to the periphery for further grinding while

smaller particles are displaced toward the center to be collected. This energetic technique

results in a very high number of impacts and is thought to be a more effective particle

dispersion technique than the more traditional mechanical mixing techniques. SEM









images taken of a 12.5 wt% 40 nm alumina-PTFE powder ensemble after jet-milling are

shown in Figure 3-3.















5 .m 200 nm

Figure 3-3. Secondary electron mages of a 12.5 wt% alumina-PTFE powder ensemble
after jet-milling. A PTFE particle with a 5 mm diameter is clearly
compartmentalized by 40 nm alumina nanoparticles.

The PTFE particle in the left image is approximately 5 jtm in diameter, and as

shown in the right image, is completely covered or compartmentalized by nanoparticles.

The jet mill has a maximum size limitation of 2 mm, so prior mechanical mixing of the

powder ensemble is used. A rotating bar on a crank is used shear the biggest PTFE

agglomeration through an elastic 10 mesh sieve (flour sifter). This technique allows the

powder to be quickly classified to a size that is easily managed by the jet mill.

After weighing and combining, the powder ensemble is roughly mixed by hand

then jet-milled three times. The flow rate of the material on the first pass is low to avoid

clogging the grind chamber while the biggest agglomerations are broken to a passable

size. Next, the collection chamber is removed and the ensemble is mixed by hand. The

powders are then given two additional passes at a higher flow rate.









After jet-milling, the powder ensemble is placed in a mold and inserted into a

compression molding station consisting of a hydraulic laboratory press with heaters and

temperature control. The 7C PTFE used in these studies has a reported maximum initial

melt temperature of 352C, and enters a viscous 'gel' state rather than a liquid state. As

the temperature is increased, the viscosity decreases until degradation begins above

400C. Once melted, subsequent melting occurs at 327C. Since the material is under

pressure in the mold during processing, the actual temperature required for melting is

likely a bit higher. The samples are created by cold pressing a cylindrical puck of

material at 60 MPa for 15 minutes to evacuate the air from the powder. As the pressure

is lowered to 6 MPa for the remainder of the processing, the temperature is increased to

380C at a rate of 2C/min. The material is pressurized during melt to evacuate volatiles

from the powder ensemble. Upon reaching 380C, the temperature drops to 360C and is

held for 3 hours. The temperature spike to 380C occurs due to the tuning of the PID

controller (overshoot), and ensures initial melt is reached by the entire part. Once the

hold schedule is complete, the mold is cooled at 2C/min. The compression molded puck

is machined into a 1/ x 1/ x 12 inch sample using computer numerical control.

Dimensional measurements are made with a digital micrometer having a Type B

uncertainty of 5 jtm (5X the reported repeatability) and the mass is measured on a

precision analytical balance having a Type B uncertainty of 50 |tg.

Tribological Testing

A laboratory designed linear reciprocating pin-on-flat tribometer, shown

schematically in Figure 3-4, is used to test the wear and friction of the samples. This

testing apparatus and the uncertainties associated with the experimental measurements










are described in detail in Schmitz et al. [35, 36]. Although open to the air, the entire

apparatus is located inside a class 10,000 soft-walled cleanroom (for reduced particulate

abrasion) with conditioned laboratory air at 250C and from 25-50% relative humidity. In

all cases, the normal load is Fn = 250 N, reciprocation length is S = 25.4 mm (50.8

mm/cycle), sliding speed is V = 50.8 mm/s, apparent contact area is A = 40 mm2 and the

nominal contact pressure is Po = 6.3 MPa. In general, the length of the test depends on

the wear resistance of the material.

pneumatic cylinder
LVDT for displacement pneumatic cylinder
measurements of pin



thruster with linear
rolling element
bearings
e arnd b r l computer data acquisition

6 channel loa
load cell
(Fx, Fy, Fz, --
Mx, My, Mz)


unloading pin I/LZ | 2'
electro- counter- sample
pneumatic valve face
sample oo



5 loading
stepper motor LVDT for measurement electro-pneumatic
and ball-screw linear table of table position valve

Figure 3-4. Tribometer used for friction and wear testing. A pin of the bulk test material
is pressed flat against a linearly reciprocating counterface. A 6-channel load
cell reacts all of the loads incurred by the sample. The conditions are constant
throughout the test i.e. as wear occurs.

AISI 304 stainless steel is used as the counterface material; it is corrosion resistant

and soft (measured hardness of 87 kg/mm2 Rockwell B), and allows for easy detection of

filler abrasion. New counterfaces are used for each experiment, so efforts were made to









ensure that each nominally identical counterface sample was created under the same

conditions. Prior to testing, the counterface and composite pin are cleaned with

methanol, and dried with a laboratory wipe. The counterface surface roughness is a

variable in this study, with possible values of 90 nm, 160 nm, 390 nm, and 580 nm, Rq.

The composite samples are mounted directly to a 6-channel load cell which reacts

all of the forces and moments on the pin sample. The counterface is mounted to a linear

reciprocating stage beneath the pin sample. A pneumatic cylinder is used to apply a

normal force. The load is continuously measured by the load cell and is computer

controlled using an electro-pneumatic valve. A linear thruster isolates the pneumatic

cylinder from frictional loads. Four 1 inch diameter rods located within an aluminum

housing are guided by linear bearings and provide high stiffness in the transverse

direction. An LVDT mounted to the thruster monitors pin displacement. A stepper

motor is controlled within custom data acquisition software. The stepper motor drives

the ball screw that drives the linear table. Another LVDT continuously measures the

table position.

Instantaneous data is collected for normal load, friction force, table position and pin

position at 1000 Hz over 1 cycle at specified intervals. Data for one cycle is extracted

using the positional LVDT. The instantaneous data are also averaged over two cycles

and saved at a specified interval that depends on the length of the test.

The primary function of this tribometer is to obtain values of friction coefficients

and wear rates for different tribological systems of interest. Neither friction coefficient

nor wear rate can be directly measured, so they must be calculated based on other

measurable quantities. The uncertainties associated with the calculation of friction









coefficient and wear rate based on this tribometer were analyzed by Schmitz et al. [35,

36]. The friction coefficient is defined as,

F
= Eq. 3-1


where Ff and Fn are the friction and normal forces, respectively. Often, the measurement

axes, X and Y, are used to calculate an approximate friction coefficient,


/ = Eq. 3-2
FY

where the measurement axes are not necessarily aligned with the normal and frictional

axes. These misalignments inevitably arise from kinematic chains of imperfect

machining and machine compliance. These misalignments can cause substantial errors in

the calculation of friction coefficient if unaddressed, even in well designed machines. A

simple model system can be constructed to illustrate these effects. The measurement

axes, X and Y are assumed to be orthogonal and biased from the normal (N) and

frictional (F) axes by an angle, a, as shown in schematically in Figure 3-5.










N (normal)


pin sample


Figure 3-5. Model representation of misaligned measurement axes. The measurement
axes are assumed orthogonal and are rotated about the normal and frictional
axes by an angle, a.

The measured force responses to the tribological interactions are,

Fx = f cos(a) + f, sin(a) = pf, cos(a) + f, sin(a) = f, (p cos(a) + sin(a)) Eq. 3


F, = f, cos(a)- f- sin(a) = f, cos(a) pf, sin(a) = f, (cos(a) sin(a)) Eq. 3

resulting in,

SF f, (u cos(a) + sin(a)) (u cos(a) + sin(a))
pE =-- Eq. 3-5
F, f, (cos(a) -u sin(a)) (cos(a) -u sin(a))

Defining an error fraction E as,

E p'-/= / cos(a)+ sin(a) sin(a)(l+/ 2) a(l+/'2)
P/ / (cos(a) -/u sin(a)) /U(cos(a) -/ sin(a)) u -2a En


-3


-4


-6


The misalignment angle, a, can be found by monitoring the force response to a stationary

loaded pin sample. Schmitz et al. [36] finds a to be approximately 20 using this method.

For a friction coefficient of [t = 0.1, the corresponding error using the X and Y axes









measurements is 35%. Thus, the approximate friction coefficient is extremely sensitive

to these misalignments. One could conceivably apply a coordinate transformation to

force data with the measured value of a and calculate the true value of [t, but the angular

measurement could vary from test to test, making this type of analysis very cumbersome.

Instead, we can apply a reversal technique, and calculate the error in the approximate

friction coefficient calculations. The aforementioned analysis will apply to the forward

direction, so,

S(u cos(a) + sin(a))
p =- Eq. 3-7
S(cos(a) -u sin(a))

Upon reversal, Fxr=-tfncos(a)+fnsin(a)) and Fyr=fncos(a)+[tsin(a), and

(-/u cos(a) + sin(a))
(cos(a) + u sin(a))

By subtracting C'r from ['f and dividing by two (average of absolute values), we

obtain a new value of the approximate friction coefficient [' and the corresponding error,


(u cos(c) + sin(a)) (u cos(a) sin(c))
- (cos(a) sin(a)) (cos(a)+u sin(a))


&~ P n 1-Q


S2 U2 cos(a)2 2 + cos(aa)2 4

Using [t = 0.1 again, the corresponding error is 0.1%. This technique provides a

robust method for estimating the friction coefficient from measurements along axes

forming small angles with the normal and tangential directions, and is employed during

testing.


The uncertainties associated with this measurement were analyzed by Schmitz et al.

[36] and include uncertainties in angular misalignment and uncertainties in the load

measurements themselves. For a standard test of unfilled PTFE (~t-0.15), they


J









determined the uncertainty in the friction coefficient for a 99% confidence interval to be

approximately 2% of the nominal value. Thus, the uncertainty in friction coefficient is

insignificant compared to the standard deviation of the measurement throughout the

entirety of a test. The standard deviation is a more useful value to report, and confidence

intervals on friction data will represent the standard deviation of averaged friction

coefficient data.

The volume of material lost during the wear process is generally proportional to the

normal load and the sliding distance by a wear rate, k. The wear rate of a material can be

used to determine component life and is defined as,

V
k= Eq. 3-10
FnD

Where V is the volume lost, Fn is the normal load and D is the sliding distance.

Often, wear volume is calculated by making displacement measurements of a given cross

section or by measuring the mass before and after a test. In many polymer systems,

specifically, for wear resistant polymers, creep and thermal expansion can become

significant portions of the total volume calculation. Mass loss measurements become

difficult in situations where environmental uptake is expected. Since PTFE is known to

have a high creep rate and coefficient of thermal expansion, as well as low water uptake

and outgassing, mass measurements are used to quantify wear in these studies. The

Am m
volume lost is then, V = -, where p = The change in mass is Am, p is the
p LL2L3

density, mi is the initial mass, and L1, L2 and L3 are the lengths of the rectangular solid

sample. The sliding distance isD = 2SN, where S is the reciprocation length (1/2 cycle)








and N is the number of reciprocation cycles. The wear rate can be expressed in terms of

the measured quantities as,

k AmLLL
2mk= N Eq. 13-11
2mFSN

The law ofpropagation of uncertainty can be applied to Eq. 3-11 to find the

combined standard uncertainty or the expected dispersion of values obtained for the wear

rate. The sensitivity of each measurement is calculated by taking the partial derivative of

the measurand, k, with respect to the measurement. Each sensitivity term is then squared

and multiplied by the square of the uncertainty in that measurement. These contributions

are added to find the square of the combined standard uncertainty of the wear rate, as



uc 2 u ( ) + u (L ) u (L )+ u2 (L3)+
ucO(K) Am) L+ 1 L2) I L3)

/\ 2 / \ 2 8 8 2, ( ,2
K u 2 )+ K u 2 (m,)+ u2(S) Eq. 3-12
8aFN a)m, 8as

Evaluating the partial derivatives gives,

2 L( L 2(A \LL L AmL L >3 A mL, L 2
uc (K)= u (m)+ u (L,)+ + (u (L2)+
( 2F, m, SN 2Fm, SN) 2F, m, SN

2 2
AmL1L2 2(L) AmLL2L3 u FQ) +
2FimSN) 2F 2m,SN
2 2
AmL1L23 2()+ u L (S) Eq. 3-13
2Fm, SN 2F ,m,S N



where nominal values of the measurements are used in numerical calculation.

Determining the uncertainty of each measurement requires Type A or Type B evaluation









consisting of either statistical methods or engineering judgment, respectively. A detailed

analysis can be found in Schmitz et al. [35]. Briefly, the uncertainties of the sample

length and mass measurements are taken conservatively as five times the manufacturers'

specified repeatability; 0.005 mm and 0.05 mg respectively. The uncertainty u(Am) is

calculated using the law ofpropagation of uncertainty.

Am = m -mf Eq. 3-14

Taking the partial derivative of this function with respect to the measurements, m, and mf

gives,


u2 m 2 \ U(mJ + A u2(m) (1)2 u(m,)+(1)2 u2() 2 Eq. 3-15


Since the initial and final masses are approximately the same, it is reasonable to

assume that the uncertainties in these measurements are equal, and Eq. 3-15 becomes,

u2 (Am)= 2u2 (m) Eq. 3-16

and,

u(Am)= 2.-u(m) Eq. 3-17

The uncertainty in the normal load due to time dependent fluctuations was found to

overwhelm angular misalignment errors and short term scatter, and the uncertainty is

taken conservatively as u(Fn)=2N, twice the observed thermal drift of the load cell and

electronics. The uncertainty in the number of cycles is zero and the uncertainty in the

reciprocation length is u(S)= 0.2mm which results from a combination of an assumed

angular misalignment of 2, and one standard deviation of measurements for commanded

motions.









Many materials exhibit initial wear transients, precluding the use of a single point

mass measurement. Often, a least squares regression of the steady data is used to obtain a

more representative value for the wear rate of a material. A modified numerical approach

to the above uncertainty analysis is required for such regressions [35]. Interrupted

measurements are made periodically during each test and are used to distinguish the

steady region of wear from the transient region. A Monte Carlo simulation uses the

uncertainty and nominal value of each measurement to calculate the average regression

slope and standard deviation of the slopes of 1,000 simulated data sets, for wear rate and

wear rate uncertainty, respectively. The uncertainty intervals on wear rate data represent

the experimental uncertainty in the measurement.














CHAPTER 4
DESIGN OF EXPERIMENTS

The Effects of Surface Roughness on the Tribological Response of PTFE
Nanocomposites

The effectiveness of the filler has been hypothesized to decrease as the size scale of

the asperities approach those of the filler based on the wear resistance models of

preferential load support [27] and prevention of large scale destruction of the banded

structure [33]. In this study, it is presumed that the role of the filler is to

compartmentalize damage [9] by arresting crack propagation [20], and thus limiting the

size and shape of the wear debris [34]. This model does not preclude the effectiveness of

nanoparticles and conversely suggests that composites become more effective as the sizes

of the matrix and filler particles decrease. This study investigates the tribological

sensitivity of alumina-PTFE nanocomposites of varying filler size and wt% to varying

counterface roughness.

It has been shown that in many cases, tribological performance is most dependent

on parameters such as skew, maximum peak height, average asperity slope and

orientation of lay rather than the more commonly cited amplitude parameters (Ra, Rq, Rt,

etc.) [34, 37, 38]. However, given the nature of the argument for the ineffectiveness of

PTFE nanocomposites and the critical role of relative size of particles and asperities, an

amplitude parameter is most appropriate for investigation. Efforts were made to keep

other parameters as constant as possible. The amplitude parameter used in this study is

Rq (root-mean-squared roughness) and is given by,










R = z(x)dx Eq. 4-1


where z(x) is the height of a surface point at a location x along the surface.

The counterface surfaces were prepared using 4 different traditional finishing

processes, including: electro-polishing, lapping, wet-sanding, and dry-sanding. The

electro-polished samples were prepared by wet-sanding with 600 grit silicon-carbide

paper, followed by lapping, and finished by electro-polishing. Similarly, the lapped

samples were initially wet sanded with the 600 grit silicon-carbide paper and then lapped.

The wet-sanded samples were only exposed to the 600 grit silicon-carbide paper. The

dry-sanded samples were initially wet sanded and then roughened with 80 grit "coarse"

silicon-carbide paper. The samples were examined under a scanning white light

interferometer with a 20x objective. Areas of 230pm x 300ipm were measured on 5

different samples from each batch. A gray-scale contour plot with accompanying line

scans, amplitude parameters Ra (average roughness) and Rq (root mean squared

roughness), and histograms of the surfaces are shown in Figure 4-1. For these surfaces

the average and standard deviation in Rq between 5 samples was Rq=88 nm o-=16 nm,

Rq=161 nm o =35 nm, Rq=390 nm o =275 nm, and Rq=578 nm o =91 nm for the

electro-polished, lapped, wet-sanded, and dry-sanded surfaces, respectively. The wet-

sanded surfaces have a predominant orientation parallel to the direction of sliding, while

the others have no predominant orientation. All of the surfaces except for the electro-

polished surfaces have a negative skew.












300 um


height z
-1 ( m)
M- n0.3


U0 b 1OU 150u ZO (gm)
0.3 x-direction
40

" 0.3


.03 y-direction
.J-0.3


300 gm


count


1_ 1-0.31
Ra = 88 nm
Rms= 111 nm


304 stainless steel
electropolished

5 Samples
mean RMS= 88 nm
st.dev.= 16 nm


height z
- (sm .


E UU

I1 -1.0


' -2.0
0 50 100 150 200 (1m)
S. . Ra = 302 nm
E i x-direction Rms= 404 nm

P 304 stainless st
"-i1 wet sanded wit


S j y-direction
i'to -- -r
P


ount


eel
h 600


grit paper
5 Samples
mean RMS= 390 nm
st.dev.= 27 nm


300 um


U 0U 1UU 1U50 2U (pm)
-0.5 x-direction
0


-05

|- i Uy-direction


300 Igm


0 50 100 150 200 (prm)
?E 1 x-direction


.
=L
1' y-direction
. -2L
!W_2 Vycf


height z
i_ ( count




0.0 ----- -



-0.5
Ra = 142 nm
Rms=186nm

304 Stainless Steel
lapped finish

5 Samples
mean RMS= 161 nm
st.dev.= 35 nm
height z


Ra = 457 nm
Rms= 606 nm

304 stainless steel
dry sanded "coarse" grit
abrasive cloth
5 Samples
mean RMS = 578 nm
st.dev.=91 nm


Figure 4-1. Surface profilometry data from a scanning white-light interferometer (SWLI)
with a 20x objective, clockwise from top left: electro-polished, lapped, dry-
sanded and wet-sanded surfaces. It should be noted that the wet sanded
counterface was tested in a direction parallel to the predominant orientation of
the texture. The other surface did not have a predominant orientation.


Varying Filler Loading and Surface Finish


The alumina used in this study is from Nanophase. The particles have an (APS) of


40 nm, a crystalline phase of 70% delta 30% gamma, and are spherical in shape. Four


alumina-PTFE nanocomposites, of 0, 1, 5, and 10 wt%, were processed following the


standard processing techniques described in Chapter 3. The experimental design, shown


c









in Table 4-1, consists of 4 counterface conditions and 4 particle loadings with repeat tests

of unfilled PTFE and 5 wt.% alumina filled PTFE on the lapped counterface; this

provides some indication of scatter in the data from processing variations. Experimental

variations and uncertainties for friction coefficient and wear rate are discussed in detail in

Schmitz et al. [35, 36]. These nanocomposites were observed to wear linearly, hence

single point mass loss measurements are used to quantify wear.

Table 4-1. Design of experiments: investigation of the coupled effects of counterface
roughness and filler wt% on the tribological behavior of alumina-PTFE
nanocomposites. Average particle size (APS), particle phase and surface
chemistry of the alumina are held constant at 40 nm, spherical and non-
functional, respectively. New counterfaces and individually made composite
samples are used in each experiment.


Sample Rq (nm) Filler wt% APS (nm) Phase

1 90 0 40 delta:gamma

2 90 1 40 delta:gamma

3 90 5 40 delta:gamma

4 90 10 40 delta:gamma

5a-5f 160 0 40 delta:gamma

6 160 1 40 delta:gamma

7a-7d 160 5 40 delta:gamma

8 160 10 40 delta:gamma

9 390 0 40 delta:gamma

10 390 1 40 delta:gamma

11 390 5 40 delta:gamma









Table 4-1. Continued

Sample Rq (nm) Filler wt% APS (nm) Phase

12 390 10 40 delta:gamma

13 580 0 40 delta:gamma

14 580 1 40 delta:gamma

15 580 5 40 delta:gamma

16 580 10 40 delta:gamma



Varying Filler Size and Surface Finish

The relative sizes of the nanoparticles and asperities are studied here using a

dimensionless roughness parameter Rq/Df (the ratio of the root-mean-squared roughness

to the characteristic filler diameter). It is widely accepted that wear rate is a function of

the counterface roughness, so in order to isolate the component due to particle size, this

series of experiments varies the filler particle diameter. PTFE composites with

characteristic filler diameters (APS) of 40 nm, 80 nm, and 500 nm are processed using

the procedures outlined in Chapter 3, and are tested on each surface. Filler loading is

held constant at 5 wt%. The 40 nm particles and the 500 nm particles are 70:30

delta:gamma phase and are spherical in shape, while the 80 nm particles are 99% alpha

phase and are irregular in shape. The experimental design is given in Table 4-2.












Table 4-2. Design of experiments: investigation of the coupled effects of counterface
roughness and filler size on the tribological behavior of alumina-PTFE
nanocomposites. Filler wt%, and surface chemistry of the alumina are held
constant at 5 wt%, and non-functional, respectively. Crystalline phases are
gamma:delta for 40 and 500 nm particles and alpha for 80 nm particles. New
counterfaces and individually made composite samples are used in each
experiment.


Sample Rq (nm) Filler wt% APS (nm) Phase Functional

3 90 5 40 delta:gamma none

17 90 5 80 alpha none

18 90 5 500 delta:gamma none

7a-d 160 5 40 delta:gamma none

19 160 5 80 alpha none

20 160 5 500 delta:gamma none

11 390 5 40 delta:gamma none

21 390 5 80 alpha none

22 390 5 500 delta:gamma none

15 580 5 40 delta:gamma none

23 580 5 80 alpha none

24 580 5 500 delta:gamma none



The Effects of Particle Surface Characteristics on the Tribological Response of
PTFE Nanocomposites

Contrary to conventional wisdom, PTFE nanocomposites have been found to have

100-1000X lower wear rates than unfilled PTFE. But, despite compartmentalization









modeling predictions that optimum compartmentalization occurs in these systems at low

filler wt%, these wear resistant nanocomposites are repeatedly optimized between 10 and

30 filler wt%, compositions comparable to those found for microcomposites [6, 7, 8, 9].

To date, a 100-1000X reduction in wear rate at low filler wt% (<5 wt%) has not been

demonstrated. The inability to achieve this goal may be due to the more practical issues

involved in nanocomposite synthesis that are not accounted for in the simple

compartmentalization model. The first is particle dispersion. As particles become

smaller, the ratio of the surface area to the volume, and hence, surface energy to inertial

energy, increases. Because of this high surface energy, nanoparticles tend to agglomerate

making dispersion of the particles difficult. Nanocomposites with poorly dispersed

nanoparticle agglomerations may, in fact, behave as a microcomposite with the effective

particle size being the characteristic size of the agglomerations. The other practical issue

not dealt with in the model is the strength of the filler/matrix interface. The constituents

used in these studies (PTFE and A1203) are intentionally inert to reduce environmental

sensitivity, and consequently, the interface between them is weak. Now consider a

nanocomposite with 1 vol% 40 nm filler. For a basketball sized hunk of the material, the

area of this inherently weak interface is 2.3 acres. For this reason, the nature of the

interface is believed to have a substantial impact on the tribological properties of

nanocomposites. This study focuses on improving the compatibility of the interface

between the matrix and filler to help reduce the number of material defects and thus wear

rate. All tests are performed on the lapped (160 nm Rq) counterface.

Mechanical Modification of the Particle-Matrix Interface

The two interfacial modifications considered here are mechanical and chemical.

This study examines the effect of mechanical modification of the interface between the









matrix and filler. Nanoparticles of A1203 (alumina) from Alfa Aesar are used in this

study. They have an alpha crystalline phase and were observed to be irregular in shape.

It is hypothesized that an irregular nanoparticle shape will facilitate mechanical

entanglement of the PTFE with the filler and increase the mechanical compatibility at the

interface. The TEM micrographs shown in Figure 4-2 reveal the shape variation between

the 40 nm nanoparticles of the aforementioned study and the more irregular 80 nm

nanoparticles used in these experiments.


40 nm .__. 80 nni










100 nm 100 nm


Figure 4-2. TEM images of the two alumina particles evaluated. The manufacturer
reported mean particle size is indicated on the upper left of each image. The
crystal phase of the spherical 40nm particles is reported to be 70% delta and
30% gamma; the more irregular 80nm particles are reported to be 99% alpha.

A series of tribological tests were conducted on alumina-PTFE nanocomposites

with filler loadings of 1, 2, 5 and 10 wt% irregular 80 nm alumina. The particles are as

received and are non-functional. The counterface surfaces have a lapped finish with an

average RMS roughness ofRq = 160 nm. Tests are interrupted periodically for mass

measurement as these samples were observed to transition to a lower wear condition

upon transfer film formation. The experimental design for this study is given in Table 4-

3.









Table 4-3. Design of experiments: investigation of the effects of filler wt% on the
tribological behavior of alumina-PTFE nanocomposites having irregular filler
particle shape. Counterface roughness, particle size, crystalline phase and
surface chemistry of the alumina are held constant at 160 nm Rq, 80 nm, 99%
alpha, and non-functional, respectively. New counterfaces and individually
made composite samples are used in each experiment.


Sample Rq (nm) Filler wt% APS (nm) Phase Functional

25 160 1 80 alpha none

26 160 2 80 alpha none

19 160 5 80 alpha none

27 160 10 80 alpha none



Chemical Modification of the Particle-Matrix Interface

A group at Rensselaer Polytechnic Institute (RPI) has created and characterized

fluorinated (also referred to as functional) alumina. The additional fluorine atoms, which

are chemically bonded via silicon atoms to the alumina, are thought to increase the

chemical compatibility and strength of the alumina/PTFE interface, and the integrity of

the composite. Particle dispersion may also be improved as a result of improved

chemical compatibility through a reduced tendency of the unlike particles to segregate.

A PTFE composite pin with 1 wt% functional alumina was created using the

standard processing techniques outlined in Chapter 3. Filler particle diameter is 40 nm

and the crystalline phase is 99% alpha. The counterface used is a lapped grade 304

stainless steel plate with a roughness of 160 nm Rq. Experiments are interrupted

periodically and mass loss measurements are converted to wear volume loss as a function






38


of the sliding distance. Uncertainty intervals shown on the wear volume and wear rate

data are calculated following Schmitz et al. [35].














CHAPTER 5
RESULTS AND DISCUSSION

The Effects of Surface Roughness on the Tribological Response of PTFE
Nanocomposites

Varying Filler Loading and Surface Finish

Results and organization of the experiments varying filler loading and surface

roughness are shown in Table 5-1.

Table 5-1. Tribological results of an experimental matrix for tests varying filler loading
and counterface surface finish. New counterfaces and individually made
composite samples with 40 nm delta:gamma non-functional filler are used in
each experiment. The ( ) represents mean values over n experiments,
otherwise only a single experiment was run. The units on wear rate, k, are
x10-6 mm3/(Nm).

weight percent of 40 nm delta:gamma non-functional alumina filler
0% 1% 5% 10%


electro-
Spolished

lapped

wet
$ sanded
dry
sanded


The average friction coefficient data for these experiments are plotted in Figure 5-1

versus filler weight percent. The error-bar on a friction coefficient datum is the standard

deviation of the friction coefficient data collected during the entire test. It is encouraging

to note that the friction coefficient is not greatly affected by changes in composition or

surface roughness. It has the general trend of increasing slightly with increasing filler


K = 695 K =174 K =52 K =75
S= 0.165 p = 0.175 p = 0.191 = 0.178

K)6 = 586 K 89 (K)4 = 66 K 38
(P)6 0.136 = 0.174 (/)4 =0.173 p = 0.184
K 770 K =85 K =99 K =50
p = 0.135 p = 0.172 p = 0.162 = 0.163
K = 634 K = 293 K = 294 K =97
p = 0.142 p = 0.159 p = 0.145 = 0.183










concentration and decreasing surface roughness. Friction coefficient is thought to

increase with the addition of the ceramic particles because the filler and counterface

create a higher friction pair than the PTFE and counterface. A small abrasive component

may also be present, though scratching of the counterface was not observed. Bahadur

and Tabor [34] observed a similar trend of increased friction coefficients on surfaces with

decreased roughness and suggested that adhesion dominated the friction coefficient.


0.20



0.15 -
o


0.10-



V electropolished
0.05 a lapped
A wet sanded
A dry sanded

0-
0% 1% 5% 10%
weight % of filler
Figure 5-1. Average friction coefficients of all 40 nm delta:gamma non-functional
composites plotted versus weight percent of filler particles. The normal load
was 250N and the sliding speed was 50 mm/s (the sliding distances varied).
The error bars represent the standard deviation of the friction coefficient
during each test.

The wear rates and uncertainties for these experiments were calculated using single

point measurement of mass loss at the conclusion of the test; numerous interrupted

experiments were conducted to support the reasonableness of this method (i.e. the

interrupted measurements showed a linear trend of volume lost with sliding distance).










These data are plotted in Figure 5-2 versus filler weight percent. The error-bar on a wear

rate datum is the standard uncertainty of this measurement [35].

1x10 3 V electropolished
El lapped
A wet sanded
A dry sanded





E
E
~ 1x10 4
S,-4i








1x10-5
0% 1% 5% 10%
weight % of filler
Figure 5-2. Average wear rates of all 40 nm delta:gamma non-functional composites
plotted versus weight percent of filler particles. The normal load was 250N
and the sliding speed was 50 mm/s (the sliding distances varied). The error
bars represent the standard uncertainty of the measurement.

The wear-rate decreased monotonically with increasing filler content; thus nano-

fillers can provide substantial improvements in wear resistance, despite the large relative

size of the asperities. Figure 5-3 shows wear rate data plotted versus roughness and the

dimensionless roughness parameter Rq/Df. There is no monotonic relationship between

wear-rate and the dimensionless roughness or counterface roughness, but the wear-rate

appears to be minimized on the lapped counterface (Rq/Df 4). Since Rq and Rq/Df are

directly proportional in the case of constant filler diameter, it is unclear which is

dominating the tribological behavior.










RMS roughness/filler particle diameter
2.3 4.2 10.3 15.2
1x10i i
1x0" r---------------------






E
S1x10-4

So 0 wt%
1 wt%
S5 wt%
10wt%

electropolished lapped wetsanded drysanded
<88nm> <161 nm> <390 nm> <578nm>
1x10-5 I I I I I
0 100 200 300 400 500 600 700
RMS roughness (nm)
Figure 5-3. Average wear rates of the 40 nm delta:gamma non-functional
nanocomposites plotted versus the RMS roughness of the counterfaces and
Rq/Df. The normal load was 250N and the sliding speed was 50 mm/s (the
sliding distances varied). The vertical error bars represent the standard
uncertainty of the measurement and the horizontal error bars represent the
standard deviation of the RMS roughness over 5 samples.

Blanchet [39] observed filler accumulation at the sliding interface in PTFE-bronze

microcomposites. Filler accumulation at the sliding interface occurs by a natural

tendency for PTFE to be preferentially removed from the composite, and results in

increased friction coefficients and decreased wear-rates with increasing sliding distance

until a steady surface composition is reached. The wear volumes of the nanocomposites

in this study are linear functions of sliding distance and wear rates are strongly dependant

on filler wt%. These facts indicate that filler accumulation at the interface is not the wear

reduction mechanism and that the surface composition is near steady-state at the onset of

sliding.









Varying Filler Size and Surface Finish

The experimental design and results varying filler particle size and roughness

holding filler loading constant are given in Table 5-2.

Table 5-2. Tribological results of an experimental matrix for tests varying filler particle
size and counterface surface finish. New counterfaces and individually made
composite samples with 5 wt% non-functional alumina loading are used in
each experiment. The ( )n represents mean values over n experiments,
otherwise only a single experiment was run. The units on wear rate, k, are
x10-6 mm3/(Nm).


size of PTFE filler in 5 wt.% non-functional composites


40 nm
(delta:gamma)


80 nm
(alpha)


500 nm
(delta:gamma)


The average friction coefficient data for nanocomposites of varying particle size are


plotted versus counterface Rq in Figure 5-4.


unfilled


electro-
polished

lapped

wet
sanded

dry
sanded


K = 695 K = 52 K = 0.80 K = 70.3
p = 0.165 p = 0.191 p = 0.191 p = 0.152

(K)6 = 586 (K)4 =66 K =0.84 K =47.4
(/)6= 0.136 (p)4 =0.173 p =0.158 p =0.174
K 770 K =99 (K)2 =8.74 K = 64.9
S= 0.135 = 0.162 /p)2 =0.151 = 0.168

K = 634 K = 294 K = 0.95 (K)2 = 664
S= 0.142 = 0.145 = 0.141 (p)2 =0.145










0.22

-o- unfilled PTFE
0.2 -- 40 nm alumina-5 wt%
-- 80 nm alumina-5 wt%
500 nm alumina-5 wt%

'Z 0.18 .
FE

0 0.16 :

4--
0.14 _


0.12


0.1
eectropolished lapped wet sanded dry sanded
<88 nm> <161 nm> <390nm> <578 nm>

0 100 200 300 400 500 600 700
Rq (nm)

Figure 5-4. Average friction coefficients of the 5 wt% non-functional composites plotted
versus the RMS roughness of the counterfaces. The normal load was 250N
and the sliding speed was 50 mm/s (the sliding distances varied). The vertical
error bars represent the standard deviation of the measurements and the
horizontal error bars represent the standard deviation of the RMS roughness
over 5 samples.

There is no obvious correlation between friction coefficient and filler particle size.

As in the previous study, friction coefficient is observed to decrease with increasing

roughness. Unlike the previous study, steady-state wear rates were calculated from

interrupted mass measurements because the 80 nm composites transitioned from an initial

transient wear rate to a much lower steady state value of wear rate. This method of

calculating wear rate and uncertainty is described by Schmitz et al. [35].












/





E unfilled PTFE
E -- 40 nm alumina-5 wt%
S--*- 80 nm alumina-5 wt%
S10.- 5-- 500nmalumina-5wt%





10-6

electropolised lapped wet sanded drysanded
<88nm> <161 nm> <390nm> <578nm>

0 100 200 300 400 500 600 700
Rq (nm)
Figure 5-5. Average wear rates of the 5 wt% non-functional composites plotted versus
the RMS roughness of the counterfaces. The normal load was 250N and the
sliding speed was 50 mm/s (the sliding distances varied). The vertical error
bars represent the standard uncertainty of the measurement and the horizontal
error bars represent the standard deviation of the RMS roughness over 5
samples.

The results of these wear tests are plotted in Figure 5-5 versus the counterface Rq.

The wear of unfilled PTFE is relatively insensitive to counterface roughness, varying by

the scatter in the repeat experiments. The 5 wt% 40 nm and 500 nm (70:30 delta:gamma)

composites in this study had comparable wear rates on all but the dry sanded counterface,

despite the order of magnitude difference in particle size. This suggests that there is not a

large effect due to the relative sizes of particles and asperities. The wear rate of the 5

wt% 80 nm alpha alumina nanocomposite was also lowest when tested against the lapped

counterface, but had entirely different wear characteristics than the other particle filled

composites. Considering the similarities of the 40 and 500 nm composites, the difference










is attributed to the crystalline phase, and more specifically, the shape, rather than the size

of the particles.

Wear volume is plotted versus sliding distance in Figure 5-6 for the 5 wt% 80 nm

alpha phase non-functional alumina nanocomposite against the varying counterface

finishes. Initially, the wear rate of the nanocomposite is a strong function of the surface

roughness, wearing most rapidly against rougher surfaces. The volume of wear debris

produced during this initial period also correlates well with roughness and is proportional

to the volume of material required to fill the surface roughness. After 100 m of sliding,

samples tested against the polished (90 nm), lapped (160 nm) and dry-sanded (580 nm)

counterfaces transitioned to nominally identical, very low steady state wear rates, while

the sample tested against the wet-sanded (390 nm) surface retained a high rate of wear.

The primary difference between these samples, aside from roughness, is texture, or

direction of lay. The wet-sanded surface has a corrugated appearance in the direction of

sliding, while the other surfaces have no predominant lay orientation.

3.5 initial wear rate 10-4
steadywear rate
3.0- wet sanded f,
E 2.5 z
E 0
S2.0-
S15 drysanded 0
: 1.0- / o -
/ kl.Fn -'
0.5 lapped
S"- polished
0.0 10-6
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600
sliding distance (m) Rq (nm)


Figure 5-6. Left) Wear volume plotted vs. sliding distance for the 5 wt% 80 nm alpha
non-functional nanocomposite on varying surface finish. The normal load
was 250N and the sliding speed was 50 mm/s. The composite transitioned to
very low steady wear rates on all but the wet sanded surface. Right) Initial
wear rate plotted vs. counterface Rq. The initial wear rate is obtained using a
single point measurement with the first measured data point.









These results strongly support the model proposed by Bahadur and Tabor [34],

which suggests that the wear rate of the composite is related to the size of the wear

debris, engagement with the counterface asperities, and the ease with which they are

removed from the contact. A steady transfer film does not form on the wet-sanded

counterface because it is smooth in the direction of sliding providing little opportunity for

mechanical interlocking with debris being easily pushed through the asperity

corrugations. Transfer films do form and cover the asperities of the other surfaces,

resulting in steady state wear rates that are independent of the initial roughness.

In general, the wear debris of the 40 nm and 500 nm composites were much larger

than for the 80 nm composite and did not form stable transfer films. It is hypothesized

that the irregular shape of the alpha phase 80 nm nanoparticles facilitates entanglement

between filler and matrix resulting in more efficient compartmentalization, smaller wear

debris and the formation of stable transfer films.

Transfer Film Examination

The previous results suggest that the formation of a stable transfer film is a

necessary condition to obtain very low wear rates. The characteristics of the transfer

films, and specifically the thickness and coverage, were quantitatively analyzed using a

scanning white-light interferometer (SWLI). Transfer films corresponding to the highest

and lowest wear rates for the 5 wt% 40 nm, 80 nm and 500 nm alumina composites were

measured and are shown in Figure 5-7.







48


mm3/(Nm)
a) K=6.61x10'5 g=0.173 18 pm
b) K=2.94x10-4 g=0.145 9 pm 17
c) K=8.35x10"7 R1=0.158 8
8 16
d) K=8.75x10-6 g=0.141
e) K=4.74x10'5 g=0.174 7 15
f) K=6.64x10-4 1g=0.145 6 14
5 13
a) 4 b) 4
35 m






1 0 bmd- 22 pm
220








6 9m 18
5 -5 17



1,250_







films; a) 5 wt% 40 nm composite on the lapped counterface, b) 5 wt.% 40 nm
composite on the dry-sanded counterface, c) 5 wt.% 80 nm composite on the
lapped counterface, d) 5 wt.% 80 nm composite on the wet-sanded
counterface, e) 5 wt% 500 nm composite on the lapped counterface, f) 5 wt.%
500 nm composite on the dry-sanded counterface. The 40 and 500 nm
nanoparticles are 70:30 delta:gamma phase while the 80 nm particles are 99%
alpha phase. None of these particles are functional.

It is evident from these scans that there is a direct relationship between the

thickness of the transfer film and the wear-rate. Additionally, the thin transfer films


appear more uniformly distributed across the counterface, while the thicker films are


more banded in the direction of sliding for a given composite.











10-3 -0.2



10-4
E
z o
mE
E
S10-5- 0.1 =


g/ k =1.6 x 10-7*(t3)

10-6 0 k
0 g



10-7 I 0.0
1 10 100
maximum transfer film thickness, t (gm)


Figure 5-8. Wear-rate and coefficient of friction plotted versus transfer film thickness.
There is a correlation between wear rate and transfer film thickness. The
friction coefficient shows no correlation.

Figure 5-8 shows wear rate and friction coefficient plotted versus maximum

transfer film thickness. The wear rate data follow a strong trend of decreased wear rates

occurring on thinner transfer films. Although it seems counterintuitive that thin transfer

films are more effective than thick transfer films in protecting the composite from

asperity damage, thick films are easily removed by the pin and are therefore unstable,

leaving bare counterface behind. The friction coefficient appears independent of the

transfer film thickness and morphology.









The Effects of Nanoparticle Surface Characteristics on the Tribological Response of
PTFE Nanocomposites

Mechanical Modification of the Particle-Matrix Interface

Table 5-3 gives the results for steady state wear rate and average friction coefficient

for nanocomposites with 80 nm alpha phase non-functional nanoparticles.

Table 5-3. Tribological results of an experimental matrix for tests varying filler particle
loading for 80 nm alpha non-functional nanoparticles. These alpha phase
particles have an irregular or faceted shape which is hypothesized to improve
mechanical compatibility of the particle/matrix interface. New counterfaces
and individually made composite samples are used in each experiment.


wt.% 80 nm alpha non-functional nanocomposites
1 2 5 10

k = 1.9x107 k = 3.4x107 k =1.3x107 k = 2.1x107
S u (k) =lx10 u(k)=0.4x107 u(k)=0.3x107 u(k)=0.2x107


S p = 0.23 p = 0.27 p = 0.18 p = 0.30
o- = 0.07 o-= 0.04 o-= 0.03 o-= 0.04



Figure 5-9 plots the friction coefficients of 1, 2, 5 and 10 wt% 80 nm alpha non-

functional alumina-PTFE nanocomposites against a lapped counterface as functions of


sliding distance under a normal load of 250 N.










0 1 wt% g=0.23
0.35 A 2 wt% g=0.27

.. 0.30 A Ao 5 wt% g=0.18
A ^^A A AA6A~GO0000
-A A 0 0- o Aa 10 wt% 9L=0.30
u A 0 A
E 0.25 A 0o
Q) A 0 00
o o ,
| 0.20




0.10
o >ofoo0


0.10 0 ,-
0 1 2 3 4 5
sliding distance (km)

Figure 5-9. Plots of friction coefficient as a function of sliding distance. PTFE
nanocomposite pins are filled with varying wt% irregularly shaped 80 nm
filler. The experiments were run under a load of 250 N, a sliding speed of 50
mm/s, on a reciprocating pin-on-disk tribometer. The counterface was a
lapped 304 stainless steel plate. The average friction coefficient over the
entire experiment is given in the graph legend.

Initially, the friction coefficient of each sample was low, ranging from i=0.1-0.2.

The friction coefficient of the 10 wt% sample quickly increased to a higher steady value

of i=0.32, while the 1 wt. % sample experienced nearly a kilometer of sliding distance

before increasing to a similar value. Generally, the length of this transient period

increased with decreased particle loading. This transient behavior is consistent with filler

particle accumulation at the sliding interface [39]. It is interesting to note that the friction

coefficient of the 5 wt% sample did not follow this trend, but stayed low at t-0.22 for the

entire test. The steady values of friction coefficient for the 1, 2 and 10 wt% samples were

similar at t-0.3.






52


2.0 r 1.9x10-7
00



4- 0 3.4x 10-
I1.0 -
o o 1 wt%

S -A- -1.3x10-7 A 2wt%
S0.5 -
o '- -- *---- 5wt%

S- 2.1xI0 A 10 wt%
0 1 2 3 4 5
sliding distance (km)

Figure 5-10. Volume lost plotted versus sliding distance. PTFE nanocomposite pins are
filled with varying wt% irregularly shaped non-functional 80 nm filler. The
experiments were run at a load of 250 N, and a sliding speed of 50 mm/s, on a
reciprocating pin-on-disk tribometer. The counterfaces are lapped 304
stainless steel plates with roughness of Rq =160 nm. Error bars represent the
experimental uncertainty

The wear volume of each sample is plotted as a function of the sliding distance in

Figure 5-10. The wear transient occurred in concert with the frictional transient for reach

sample, and the wear rate and total wear volume during this transient period decreased

with increasing filler concentration. Steady state wear rate was relatively insensitive to

the filler loading, suggesting that filler accumulation occurred at the tribological

interfaces until a steady surface composition is reached.









Chemical Modification of the Particle-Matrix Interface

The friction coefficient and wear rate results are given in Table 5-4.

Table 5-4. Tribological results for a 1 wt% functional alumina-PTFE nanocomposite.
Nanoparticles for this study were functionalized by bonding fluorine atoms to
the alumina via silicon bonds, to improve the chemical compatibility at the
filler/matrix interface. The particles in this study are 40 nm in diameter and
99% alpha in phase, and tests were performed against a lapped (160 nm Rq)
counterface.


1 wt.% 40 nm alpha functional
nanocomposite
o k = 8.04x10 8
Su (k) =.04x108
oc3
3 -p = 0.21
So- = 0.02



The friction coefficient is plotted vs. sliding distance in Figure 5-11 for a

nanocomposite with 1 wt% functional 40 nm alpha alumina against a lapped (Rq =160

nm) counterface. The friction coefficient reaches a maximum value of [t = 0.25 after 15

km of dry sliding, and descends steadily for the remainder of the test. The average

friction coefficient is approximately [t = 0.21 for this test and is obviously a strong

function of the test length.









0.25
0.20

0.25 0.15
0 2 0.10
0.24 Q
00 0.05
0.23 O 0
O 0.00oo .. -.. .. .
0.22- 0 0 2 4 6 8

2 0.10- o
S0,21 0
0 o
0 0
C 0.19 8

o 0.18- 0

0.17
0.16

0.15 -
0 20 40 60 80 100 120 140 160 180

sliding distance (kn)

Figure 5-11. Friction coefficient plotted vs. sliding distance for a lwt% 40 nm alpha
functional nanocomposite. The alumina surfaces have been functionalized
with fluorine groups to enhance compatibility with the matrix. The
experiments were run under a load of 250 N, and a sliding speed of 50 mm/s,
on a reciprocating pin-on-disk tribometer. The counterface was a lapped 304
stainless steel plate. The grey region at the beginning of the test is enlarged
with greater data density.

An optical photograph of the transfer film with accompanying SWLI topography

and thickness measurements are shown in Figure 5-12. It is immediately obvious that the

transfer is very thick at the reversals; SWLI measurements indicate that thicknesses in

these regions range from 10-20 |tm. Inside the reversals, the transfer film is thin with

thickness ranging from 1-3 pm, and becomes less uniform toward the center of the wear

track. It is interesting to note that the color of the film is brown while the color of the

composite is grey. This transfer film discoloration is consistently observed in PTFE-







based composites when the wear rate is less than k = 1 x 10-6 mm3/Nm, and its origin is a
current topic of investigation.


m


reversal area reversal area


Figure 5-12. Optical photograph of the wear track. Thick transfer at reversal points and
thin patchy transfer in the center of the wear track are key features. SWLI
topographical images and film thickness measurements are included for
various points along the track length.
Friction coefficients are plotted versus track position for a complete cycle in
Figure 5-13 at various sliding distances during the test. At 500 m, the friction coefficient
is low and constant along the wear track in both directions. At 5 km, the positional data
is not constant across the wear track but begins increasing in the center. After 18 km of
dry sliding, the friction coefficient is at its highest and is spatially dome-shaped. At 140
km, the friction coefficient appears as a truncated triangle. It should be noted that the
velocity is constant after 1.4 mm, and this dependence is therefore not due to velocity.
The friction coefficient during the last cycle of sliding is plotted versus the average
transfer film thickness at points of SWLI measurement on the right hand side of Figure 5-


MM-1 JLMJ


Ai"


Mm-


I m- 5p







56


13. This graph confirms a trend of increasing friction coefficient with decreased

thickness and uniformity. This is in direct contrast to the results of the other

nonfunctional composites, which showed no correlation between friction coefficient and

transfer film thickness and uniformity. The friction coefficient of this composite appears

to be a strong function of both. Preliminary XPS results suggest that the transfer films of

functional and nonfunctional composites have radically different chemistries, with the

functional composite having substantially higher silicon content (from the fluorinated

filler) in the transfer film than in the bulk, while the transfer films of the nonfunctional

composites are believed to be PTFE rich.

o 0.5 km
0.3 5 km 0.20
**e o 18km
0.2 *- oo 140km 0.18
S0.18
S0.1 -
U 0.16
S0.0
U 0.14
.2 -0.1 -
-0.2 0 0 0.12

-0.3 ****SSS*060 0.10
0 5 10 15 20 25 0 3 6 9 12 15 18
track position (mm) average film thickness (lim)

Figure 5-13. Left) Plot of friction coefficient versus wear track position for a 1 wt%
functional nanocomposite at various sliding distances. Right) Friction
coefficient plotted versus the average transfer film thickness. This average
thickness reflects thickness as well as coverage.

Wear volume is plotted versus sliding distance in Figure 5-14. There is a decrease

in wear rate with increased sliding distance with k = 10 x 10-8 mm3/Nm immediately

following the transient region and k = 6 x 10-8 mm3/Nm at the end of the test. This

dependence of wear rate on sliding distance may be due to increased transfer film

uniformity or the result of decreased traction stresses at the interface. The average wear









rate of the material is calculated to be k = 8.0 x 10-8 mm3/Nm with an uncertainty u(k) =

4 x 10-10 mm3/Nm.



Fn = 250 N
4-
k = 8.0 x 10-8 mm3/Nm

u(k)= 4 x 10-0 mm3/Nm

E


0 3









0 I I I I I I I I I I
0 20 40 60 80 100 120 140 160 180
sliding distance (km)

Figure 5-14. Wear volume plotted vs. sliding distance for a lwt% PTFE 40 nm
functional alumina nanocomposite. The experiments were run under a load of
250 N, and a sliding speed of 50 mm/s, on a reciprocating pin-on-disk
tribometer. The counterface was a lapped 304 stainless steel plate.

It was hypothesized that Fluorinating the nanoparticles would result in improved

properties at the filler/matrix interface and reduced wear rates. We can study the effects

of particle fluorination by comparing the tribological properties of the 1 wt% 40 nm

irregular functional and 1 wt% 80 nm irregular non functional nanocomposites. The

functional composite had a wear rate of k = 8 x 10- mm3/Nm, while the non-functional

composite had a wear rate of k = 19 x 10-8 mm3/Nm. It is unclear if this improvement is

due to the reduced particle size or the particle fluorination, or whether the improvement is

even significant. Despite the arguably similar steady wear rates of these functional and










non-functional irregular samples, other tribological characteristics of these systems

appear fairly distinctive and warrant further analysis. Qualitatively, the transfer films of

these samples were very dissimilar with the transfer film of the non-functional sample

being very thin (-2 [tm) and uniform, while the transfer film of the functional sample was

much more variable in thickness and coverage across the wear track. Figure 5-15 shows

friction coefficient and wear volume plotted versus sliding distance for the 1 wt%

functional (irregular 40 nm particles) and the 1 and 10 wt% non-functional (irregular 80

nm particles) alumina-PTFE nanocomposites. It should be kept in mind that this graph

represents a very small fraction of the total sliding distance from the functional

nanocomposite; since it was tested 50X longer, the data are compared to the end of the

non-functional experiments.

0.35
10 wt alumina-PTFE A A A AA A 1 wt% alumina-PTFE
Swt% aluA AA- A1A A 2.0 1.9x107 mm3/Nm
0.30 AA -o- 8. .

SA A 1.5
u 0.25 1 wt% alumina-PTFE
IE A E
S1 wt% functionalized alumina-PTFE
0.20 O oOoooooo 0 8.0x 0 8 mm3/Nm
4t 0
0 0.5 . . o . .
0.15 686 1 wt% functionalized alumina-PTFE wt% alumina-PTF
0 2.1 x10"7 mm3/Nm-
0.10' 0.0 A'
0 1 2 3 4 0 1 2 3 4 5
sliding distance (km) sliding distance (km)

Figure 5-15. Left) friction coefficient plotted vs. sliding distance for 1 wt% alumina-
PTFE nanocomposites with Fluorinated and un-Fluorinated irregular alumina
filler. Right) wear volume plotted vs. sliding distance for 1 wt% alumina-
PTFE nanocomposites with Fluorinated and un-Fluorinated filler. The results
of the 10 wt% non-functional sample are also included for comparison.

The 10 wt% non-functionalized nanocomposite experienced an increase in friction

coefficient almost immediately. The 1 wt% non-functional sample behaved identically,

having the same steady friction coefficient of [t = 0.3 and wear rate ofk = 2 x 10-7









mm3/Nm after a delay of 1 km. The similarities in steady tribological properties of the 1

and 10 wt%/ composite are likely due to filler accumulation [39] at the tribological

interface; a process that occurs due to the preferential removal of PTFE and the resulting

particle enrichment of the surface. The friction coefficient of the functionalized

composite remained low for 4 km of sliding before beginning to transitioning to a higher

value (Figure 5-11). While the non-functional composites remained steady after the

initial transient, the friction coefficient and the wear rate of the functional composite

decreased steadily for the remainder of the test (Figures 5-11 and 5-14). This reduction

in the friction coefficient is not characteristic of filler accumulation at the tribological

interface, and suggests that the frictional response was driven by the development of the

transfer film. The transient volume loss of the 1 wt% functional composite was much

less than that of the 1 wt% non-functional composite, being 0.5 and 1.75 mm3

respectively. The extended sliding length and decreased wear volume of the transient

region for the functional sample suggests that the functional composite had a more wear

resistant initial state that is independent of transfer films. A strong dependence of wear

rate on transfer films was noted earlier, which suggested that among similar systems,

thin, uniform transfer films facilitate low wear sliding. Since the functional sample

achieved a 2X lower wear rate on a thicker, less uniform transfer film, as compared to the

non-functional sample, the improved wear resistance of the functional sample is

attributed to improved composite integrity, and to a lesser extent, the lower traction

stresses at the interface.

The compartmentalization model of Chapter 2 predicts optimum composition at

low filler loading which is in contrast to the results of previous nanocomposite studies.









The results of the studies by Chen et al. [7] and Sawyer et al. [9] are plotted with the

results of the irregular particle filled composites in this study against the

compartmentalization model in Figure 5-16.

100

model curve
spherical nanoparticles

10-1
4- ; Lietal.50nmZnO
SSawyer etal. 38 nm A203

10-2 L nonfunctional irregular 80 nm A1203
i4 functional irregular 40 nm Al203
3x1 0-3 irregular nanoparticles
I I 11111 I I I 111111 1 1 1 111. I
10-3 10-2 10-1 100

Df/Dm

Figure 5-16. Volume fraction plotted versus the ratio of the filler particle diameter to the
matrix particle diameter for the compartmentalization model as well as
experimental data from these and previous studies. Experimental data are
recorded based on the optimized composition and the reported particle sizes.

All of the microcomposites reported in the literature are in general agreement with

the model. As the filler particles become smaller however, results diverge from the

model and composites are optimized at much higher loadings than the model would

predict. This is clearly illustrated in Figure 5-16 with the results of the previous

experiments with spherical filler particles. It is thought that this divergence is due to the

difficulty in dispersing the nanoparticles, and the inherently weak interface between the

two inert constituents. However, the results of both irregular nanocomposites in this

study are in agreement with the model having optimized wear rates at compositions close

to the predicted values based only on the relative particle sizes. The difference may be









due to the particle shape and the increased mechanical interaction of the filler and matrix

at the interface.

There are a number of models describing the role of filler in PTFE-based

composites, each supporting one of two conclusions regarding nanoparticle inclusion

within a PTFE matrix. The first is that nanoparticles are ineffective in reducing wear, the

second that the filler content required for high wear resistance is reduced with reduced

particle size. In practice, nanoparticles have been found effective in reducing wear, but

only at loadings comparable to those of microcomposite systems. To the authors'

knowledge, this study is the first to demonstrate the capability of a PTFE nanocomposite

to attain high wear resistance at a low loading (<5 wt. %). Wear rate is plotted versus

filler wt% for several nanocomposites in Figure 5-17.

This graph clearly illustrates the bifurcated wear characteristics of nanocomposites

with filler particles believed to be spherical in shape to those of composites with

irregularly shape filler particles. In the main, PTFE composites and nanocomposites with

a wide variety of chemistry, size, processing and testing, behave very similarly having

increased wear resistance with increased particle loading (until a saturation point is

reached-composites typically become brittle), and tend to have optimized wear rates on

the order of k = 1 x 10-6 mm3/Nm. Both 1 wt% nanocomposites with irregular particles

(functional 40 nm and non-functional 80 nm), achieved 10X the wear resistance of other

highly filled and optimized PTFE-based systems. Comparing wear rates of 1 wt%

nanocomposites, the irregular nanoparticle filled systems had 100-1000X lower wear

rates than spherical nanoparticle filled systems.









o 44 nm spherical A1203
* 500 nm spherical A1203
o 50 nm ZnO
o 38 nm spherical A1203
* 80 nm irregular AI203
a 40 nm irregular functionalized A1203


52 wt%
o0-


E 104
Z

E


L0.


Figure 5-17. Wear rate versus filler wt% comparing composites of the current study to
those of past studies. Squares and stars denote samples from this study and
circles denote those of past studies. The open circles and squares are both
spherical 40 nm (measured 38 and 44 nm, respectively) alumina nanoparticles
with reported crystal phases of 70% delta and 30% gamma, and represent
different batches of a single process. The 38 nm particles were used in a
previous study; the 44 nm particles were used in this study. The solid stars are
the irregular 80 nm alumina nanoparticles that are reported to be 99% alpha
phase. The open star is the functionalized irregular 40 nm alumina
nanocomposite. The closed square corresponds to the 500 nm spherical
alumina composite. The light gray circles are from Li et al. [7] and are
uncharacterized ZnO nanoparticles with a reported particle size of 50 nm.
Uncertainty intervals are based on 95% confidence and are calculated based
on the procedure discussed in Schmitz et al. [35].

It is evident based on these results that the surface condition of the nanoparticle

fillers has a profound impact on the tribological properties of the composite, either

enabling or precluding the development of a stable transfer film, and steady low wear

sliding. It is unclear whether particle fluorination is the cause of higher steady wear

resistance in the functional composite since particle size was also variable. However; the

transient data suggest that there is a fundamental difference in the wear mechanism of the

two composites which is unlikely to be the result of decreased particle size alone.


6.2 x 103


*



01 5 10 20 3(
filler wt%


P a
QQ r% {














CHAPTER 6
CONCLUSIONS

1. The inclusion of alumina nanoparticles into a PTFE matrix resulted in reduced

wear rates in all cases. Abrasion of the counterfaces by the nanoparticles was not

observed.

2. The steady state wear rate of PTFE was reduced by 3000X with the addition of 1

wt% (-0.5 vol%) 80 nm alpha alumina. It was reduced by 7500X with the

addition of 1 wt% 40 nm alpha functional (fluorinated) alumina.

3. Among 1 wt% nanocomposites, the functional irregular 40 nm particle filled

sample had the lowest steady wear rate of k = 8 x 10-8 mm3/Nm, the nonfunctional

irregular 80 nm particle filled sample had a steady wear rate of k = 19 x 10-8

mm3/Nm and the nonfunctional spherical 40 nm particle filled sample had the

highest steady wear rate of k = 9000 x 10-8 mm3/Nm.

4. The functional nanocomposite was the only sample to exhibit a strong

dependence of friction coefficient on wear track position. Friction coefficient was

observed to be highest at points of low transfer film coverage. The friction

coefficient (high dependence) and wear rate (low dependence) decreased as the

transfer film coverage increased with sliding distance.















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BIOGRAPHICAL SKETCH

David Burris graduated from Lemon Bay High School in Englewood, Florida, in

June of 1998. He commenced his higher education at the University of Florida that

summer. In the spring of 2002, he joined the Tribology Laboratory at the University of

Florida and began work in the field oftribology. The following spring he received his

bachelor's degree and began his graduate studies. Upon receiving the degree of Master

of Science, David will begin work on his doctorate degree.