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In this research, for the first time, a novel nanofabrication process is developed to produce graphene-based nanoparticles using mechanochemical principles. Utilizing strain energy at the interface of Si and graphite via the use of a tribometer, a reaction between nanometer sized graphite particles with a reducing agent (hydrazine) was initiated. This simple method demonstrated the synthesis of lamellar platelets (lamellae of ~2nm) with diameters greater than 100 micrometers and thicknesses less than 30 nm directly on the surface of a substrate under rubbing conditions. Spectroscopic evaluation of the particles verified them to be graphene-based platelets, with functionalized molecules including C-N and C-Si bonding. Furthermore, the size of the particles was shown to be highly correlated to the applied pressure at the point of contact, such that three-body friction (with intermediate particles) was shown to enhance the size effect, though with greater variation in size among a single test sample. A chemical rate equation model was developed to help explain the formation of the chemically modified graphene platelets, wherein the pressure applied at the surface can be used to explain the net energy supplied in terms of local flash temperature and strain energy. The activation energy calculated as a result of this method (~42kJ/mol) was found to be extraordinarily close to the difference in bond enthalpies for C-O and the C-N, and C-Si bonds, indicating the input energy required to form the platelets is equivalent to the energy required to replace one chemical bond with another, which follows nicely with the laws of thermodynamics. The ability to produce graphene-based materials using a tribochemical approach is a simple, one-step process that does not necessarily require specialized equipment. This development could potentially be translated into a direct-write nanopatterning procedure for graphene-based technologies, which promise to make electronics faster, cheaper and more reliable. The tribochemical model proposed provides insight into nanomanufacturing using a tribochemical approach, and suggests that further progress can be accomplished through the reduction of the activation energy required for graphene formation.

The chemical nature of the Transfer Film (T.F.) or Third-Body Layer (T.B.L.) formed at the friction interface of an automotive friction brake during off-brake motoring has been studied using Energy Dispersive X-ray (E.D.X.) analysis and Scanning Electron Microscopy (S.E.M.). Although these third-body layers are deposited on both mating surfaces of the friction couple, special attention has been paid to those formed on the disc brake rotor surface. Concurrently, detailed investigations have been undertaken examining the temperature-dependent, physico-chemical interactions of friction material constituents with each other, atmospheric oxygen and countermember materials using X-Ray Diffraction (X.R.D.).Evidence is presented relating the tribological performance of the friction pair to both the transfer film thermochemistry and the friction material composition. Among those characteristics describing the tribological performance of the friction couple, particular attention has been applied to the generation of Disc Thickness Variations (D.T.V.) induced by Off-Brake or Non-Braking Wear (O.B.W. or N.B.W.). The critical role of solid lubricants and abrasive friction modifiers and their effectiveness over a range of contact pressures / temperatures has received particular attention. Information obtained using various surface analytical techniques combined with detailed dimensional assessments of the affected triboelements has been used to show the considerable significance of abrasive particle size in determining the overall tribological behaviour of the friction pair, especially with respect to the wear regime and extent encountered at the surface of the countermember during O.B.W.Wear mechanisms are described for the generation of off-brake wear, these varying with friction material formulation. Dynamic and temperature-dependent influences on the level of in-service disc brake rotor runout are named as causes for particular forms of disc thickness variation generated by aggressive friction materials. Keywords: Third-body layer; Transfer film; Tribochemistry; Automotive Friction Braking; Cold Judder; Disc Thickness Variation; Disc Brake; Friction Material.

Parasitic friction and material wear exist in all moving parts, causing about 20% in global energy loss annually. Machinery startup accounts for a major portion of this loss. This issue involves a boundary lubrication problem, where rubbing surfaces are inadequately covered by lubricating oils. Lubricating oil fluids rely on tribochemical reactions to establish metalorganic tribofilms that protect the contacting surfaces. The improved oil lubrication mechanism can ensure smooth operation, improving efficiency, and extending the mechanical component lifetime. In this thesis, we study tribochemical reactions resulting from various fuel and oil blends. The interactions among blended additives are given particular attention. Lubrication phenomena are simulated using a ball-on-disk linear reciprocation configuration in a standardized tribological test rig, Optimol SRV5. The tribofilm growth patterns are investigated by measuring friction and electrical contact resistance (ECR), followed by a detailed surface analysis. The proposed lubrication mechanisms are verified with experimental and numerical simulation results. Fuel lubrication studies are conducted by investigating a) lubricity loss upon the addition of multiple oxygenated compounds, b) accelerated material wear rates observed in dieselethanol fuel blends, and c) enhanced lubrication performances with carbon-based nanofluid fuels. Lubricity loss is found to correlate with: ● Extended induction periods for ECR rises, ● Reduced average electrical contact resistance values, and ● Inhibitions of protective frictional species formations (e.g., iron oxides and graphite). The developed tribochemical reaction model advances the design of friction and extremepressure modifiers using tribo-active nanomaterials. For instance, adding carbon-based nanomaterials to fuels enhances lubrication performance by serving as tribo-active materials to accelerate tribofilm formation and by replenishing damaged surfaces. In engine oil systems, we demonstrated that the lubrication performance could be enhanced by formulating TiO2 nanoparticles modified by gallic acid esters, and polyether-based co(ter)polymers. Based on the tribochemical reaction mechanisms found in this study, we propose more designs of functionalized nanomaterials for advanced lubricant applications in future work.

Lubrication of ceramics is a difficult and not completely solved problem. Ceramics do not respond to conventional lubricants which are designed to function by a chemical reaction with the surface. There is, accordingly, increased interest in the development of lubrication alternatives for ceramics, and in understanding the tribochemical fundamentals by which new lubrication processes can be designed and controlled. In particular, the mechanism of tribopolymerization for some addition-type monomers is thought to be initiated and controlled by triboemitted low-energy electrons. This Ph.D. dissertation presents the experimental work carried out at the Virginia Polytechnic Institute and State University for the characterization of charge intensity and energy distribution of charged-particles triboemitted from sliding contacts of ceramics. A review is presented of research work on tribochemistry and, in particular, on tribopolymerization as a lubrication mechanism. Relevant literature is also reviewed on the phenomena of exoemission, triboemission and fractoemission of charged-particles. The design, construction and development of a new instrument and data acquisition system to carry out triboemission measurements under high vacuum and for controlled load, sliding speed and retarding grid-voltage is described. The charge intensity is characterized of the particles triboemitted from two related ceramics, alumina and sapphire, and from one metallic material, i.e., aluminum, when scratched by a diamond pin. In the case of alumina, triboemitted-charge intensity also is studied by sliding contact of an alumina ball. Burst-type negatively-charged particle triboemission was observed from diamond-on-alumina, diamond-on-sapphire, and alumina-on-alumina sliding contacts. The different crystalline structure, i.e., of alumina and sapphire, does not appear to be a factor in electron triboemission. In general, large bursts of electron triboemission may appear superimposed on a constant lower level of small-burst emission. This constant level, being higher than background-noise, does not vary between different ceramic specimens, while maximum levels of triboemission-bursts differ by two orders of magnitude between different specimens. The characteristic decay-time of the triboemission bursts is found of about 100ms. Lower-level decaying post-contact emission of negatively-charged particles from ceramics is observed. Low negatively-charged triboemission was observed from diamond-on-aluminum sliding contacts. The positively-charged triboemission from these sliding material systems was also measured. Low positive-ion emission, barely above background level, was observed for the diamond-on-ceramics and alumina-on-alumina systems. The retarded-energy spectra of the negatively-charged particle triboemissions from ceramics were also obtained. Such spectra show decaying rates of triboemission for increasing minimum energy of the triboemitted particles: an important fraction of the total electron triboemission is produced in the zero to 5eVolts energy-range, with a decaying tail extending beyond the test maximum level of 48 Volts. These experimental measurements are discussed with a focus on the possible role of triboemitted charged-particles in tribopolymerization as a mechanism of ceramic lubrication. It is concluded that low-energy electrons are emitted in bursts from ceramics under sliding contact, the essential first step in the hypotheses of tribopolymerization of certain addition-type monomers, while positively-charged emission is negligible. These findings strongly support tribopolymerization results from previous research. A frequency domain analysis of the triboemission data is carried out. For the electron-triboemission outputs, a characteristic pattern is found for the experimentally estimated frequencies of occurrence of the triboemitted particles. A new probability distribution, called "Convoluted Poisson" is developed to describe this triboemission data. Good agreement is found between the probabilities of triboemitted-particle occurrence, as predicted by such distribution, and the experimental probabilities estimated from triboemission outputs. The significance of the two parameters defining this "Convoluted Poisson" distribution is explored and discussed with a focus on basic surface-change phenomena. / Ph. D.

<p>The present thesis thoroughly treats a special friction reduction phenomenon that may appear in boundary lubricated tribological contacts, of the type encountered in numerous mechanical components made of steel. The phenomenon involves the formation of a special type of tribofilm that offers very low coefficients of friction. Typically the friction level becomes halved when the film is formed, compared to when it is not formed. Since boundary lubricated mechanical components are so common in all sorts of machinery, the technical and economical potential of this phenomenon is gigantic.</p><p>The tribofilm is produced on the steel surface, resulting in friction coefficient reduction from typically 0.08–0.1 to 0.04–0.06. The tribofilm is formed from the metal in the carbon coating and sulfur in the oil additive. The main film studied was WS₂, which is a well-known low-friction material. It includes easy shearing atomic planes, in the same fashion as the solid lubricants MoS₂ and graphite. Virtually no carbon is present in the tribofilm, despite carbon being the main constituent of both the coating and the additive. No films form on the Me-DLC coated part.</p><p>It was also found that WSi₂-particles could result in the formation of WS₂-containing tribofilms. It was concluded that they, just as the W-DLC film, were sufficiently weak to mill down to very small particles, and chemically reactive in the prevailing tribological conditions. However, WC particles were too stable, both mechanically and chemically, to result in any film formation.</p><p>The chemical driving forces for formation of the tribofilms were analyzed using EkviCalc, a commercial software for thermodynamical calculations based on minimization of Gibbs free energy for a system as a function of temperature and pressure. The simulations indeed confirmed that both WS₂ and MoS₂ should be expected to be stable compounds, coexisting with FeS, in the studied environment. As a spin-off result, the thermodynamical calculations indicated that coatings of the Cr-C type should impose very little tribochemical wear of the uncoated steel surface, and even reduce the forma-tion of FeS (the “traditional” tribofilm) on the steel surface in S-containing environments. </p><p>As a final spin-off, the thermodynamical calculations indicate that the Ti-C coating should be very resistant to tribochemical wear in the S-containing environment. </p>

The present thesis thoroughly treats a special friction reduction phenomenon that may appear in boundary lubricated tribological contacts, of the type encountered in numerous mechanical components made of steel. The phenomenon involves the formation of a special type of tribofilm that offers very low coefficients of friction. Typically the friction level becomes halved when the film is formed, compared to when it is not formed. Since boundary lubricated mechanical components are so common in all sorts of machinery, the technical and economical potential of this phenomenon is gigantic. The tribofilm is produced on the steel surface, resulting in friction coefficient reduction from typically 0.08–0.1 to 0.04–0.06. The tribofilm is formed from the metal in the carbon coating and sulfur in the oil additive. The main film studied was WS2, which is a well-known low-friction material. It includes easy shearing atomic planes, in the same fashion as the solid lubricants MoS2 and graphite. Virtually no carbon is present in the tribofilm, despite carbon being the main constituent of both the coating and the additive. No films form on the Me-DLC coated part. It was also found that WSi2-particles could result in the formation of WS2-containing tribofilms. It was concluded that they, just as the W-DLC film, were sufficiently weak to mill down to very small particles, and chemically reactive in the prevailing tribological conditions. However, WC particles were too stable, both mechanically and chemically, to result in any film formation. The chemical driving forces for formation of the tribofilms were analyzed using EkviCalc, a commercial software for thermodynamical calculations based on minimization of Gibbs free energy for a system as a function of temperature and pressure. The simulations indeed confirmed that both WS2 and MoS2 should be expected to be stable compounds, coexisting with FeS, in the studied environment. As a spin-off result, the thermodynamical calculations indicated that coatings of the Cr-C type should impose very little tribochemical wear of the uncoated steel surface, and even reduce the forma-tion of FeS (the “traditional” tribofilm) on the steel surface in S-containing environments. As a final spin-off, the thermodynamical calculations indicate that the Ti-C coating should be very resistant to tribochemical wear in the S-containing environment.

In this study, we investigate the fundamental mechanisms defining the approach for addressing tribological challenges in mechanical systems via the use of the tribocatalytically active coating. The coating is designed using an electrodeposition process and consists of a hard amorphous cobalt-phosphorous matrix with the incorporation of tribocatalytically-active nickel and copper. Our focus is on understanding the effect of the tribocatalytic elements, Cu vs Ni, on the coating's performance in high-contact stress conditions, generating local heating, shear, and compression. By optimizing the relative composition and mechanical characteristics of the coating, we aim to enhance its tribological performance in the presence of a hydrocarbon environment. Through extensive characterization of the wear tracks using SEM/EDS and Raman analyses, we identify the formation of a protective carbon-based tribofilm on the coating's surface during sliding as the key factor behind its excellent performance. Our findings not only contribute to the understanding of material transformations in the contact but also offer a robust and versatile approach to addressing tribological challenges in mechanical systems. The development of this innovative coating opens up new possibilities for promoting the formation of protective tribofilms and improving the performance of mechanical components operating in low-viscosity fuels and synthetic oils.

The use of low-friction coatings on machine elements is steadily increasing, and they are expected to play an important role in the reduction of fuel consumption of future motorized vehicles. Many low-friction coatings function by transformation of the outermost coating layer into tribofilms, which then cover the coating surface and its counter surface. It is within these tribofilms that sliding takes place, and their properties largely determine the performance. The role of the coating is then not to provide low friction, but to supply support and constituents for the tribofilm. In this thesis, the formation of such tribofilms has been studied for a number of different low-friction coatings. The sensitivity of the tribofilm formation towards changes in the tribological system, such as increased surface roughness, varied surrounding atmosphere and reduced availability of the tribofilm constituents has been given special attention. For TaC/aC coatings, the formation of a functioning tribofilm was found to be a multi-step process, where wear fragments are formed, agglomerated, compacted and eventually stabilized into a dense film of fine grains. This formation is delayed by a moderate roughening of the coated surface. Coatings based on tungsten disulphide (WS2) are often able to provide exceptionally low friction, but their use is restricted by their poor mechanical properties and sensitivity to humidity. Large improvements in the mechanical properties can be achieved by addition of for example carbon, but the achievable hardness is still limited. When titanium was added to W-S-C coatings, a carbidic hard phase was formed, causing drastically increased hardness, with retained low friction. Titanium oxides in the tribofilms however caused the friction to be high initially and unstable in the long term. In a study of W-S-N coatings, the effects of humidity and oxygen were studied separately, and it was found that the detrimental role of oxygen is larger than often assumed. Low friction tribofilms may form by rearrangement of coating material, but also by tribochemical reactions between constituents of the coating and its counter surface. This was observed for Ti-C-S coatings, which formed WS2 tribofilms when sliding against tungsten counter surfaces, leading to dramatic friction reductions.

Lors du fonctionnement d'un turboréacteur, la rotation de l'axe du moteur induit une force centrifuge qui plaque les aubes contre les alvéoles du disque, le long de surfaces appelées « portées ». Au cours de la vie du moteur, des micro-glissements (« fretting ») sont générés au niveau des portées. Ce travail de thèse s'intéresse aux endommagements de type oligocyclique des portées aube/ disque du compresseur Haute Pression (HP) d'un turboréacteur civil. Afin de réduire le frottement et de protéger les pièces, les portées des aubes sont revêtues d'un dépôt épais de CuNiln sur lequel est appliqué un lubrifiant solide. Le système est soumis à des pressions fortes (600MPa) et à des températures élevées (500°C). Des expertises sur pièces ont permis d'identifier des usures importantes et des phénomènes de transfert. Pour simuler expérimentalement le contact, un moyen d'essai de fretting usure en température a été développé dans le cadre de cette thèse. A partir d'une géométrie de contact échelle 1 simplifiée, choisie pour représenter les champs de chargement moteur, le domaine des sollicitations a été balayé et les comportements tribologiques identifiés et caractérisés. L'étude tribologique a permis de mettre en évidence l'influence forte de la force normale sur les mécanismes d'endommagements, dont les scénarios de mise en place ont pu être explicités pour les deux domaines majeurs de sollicitations. Dans un deuxième temps, les endommagements ont été étudiés d'un point de vue physicochimique et le rôle tribochimique joué par les éléments environnementaux (0, N ... ) a été mis en évidence. Pour finir, la comparaison directe des mécanismes identifiés sur banc expérimental et sur le système industriel a permis d'aborder, d'un point de vue critique, l'importance des paramètres choisis pour les équivalences expérience / système industriel ; et de la dynamique de chargement pour garantir la représentativité d'un essai à l'échelle laboratoire. / In the blade/ disk contact of aero-engines, movements induced by the engine regime changes may lead to critical wear. In order to limit friction and protect components, motorists usually use a thick and soft CuNiin layer (150 !-lm) covered with a lubricant. This system is subjected to high contact pressure (upto 600 MPa) and high temperatures (up to 500 °C). In service observations of engine parts revealed significant wear and transfer phenomena. An experimental layout was designed to perform fretting wear tests in temperature on a punch/plane contact, representative of engine solicitation. Based on the tribological study performed, specified gradation mechanisms were identified and the evidence of a pressure threshold was demonstrated. Physicochemical analyses performed confirmed the role played by environment (0, N ... ) in fretting wear mechanisms and suggest that the tribochemical effects should be considered in the fretting wear models. Direct comparisons between degradation mechanisms identified on the experimental system, and on industrial parts, allow a critical review of parameters chosen to simulate the contact. Finally, the impact of loading dynamics was investigated in order to improve tests representativity at la bora tory scale.