Lubricants are used in numerous applications to control friction and protect moving parts from fatigue. These fluids consist of a variety of surface active chemistries competing for the surface to provide performance. In order to develop fluids that meet the ever-increasing requirements (from legislation and manufacturers), techniques that can provide insight into surface adsorption, in real time, and relate it back to performance are critical. The objective of this work is to determine if Quartz Crystal Microbalance with Dissipation (QCM-D) is an effective technique to investigate surfactant adsorption in regimes that are common to the transportation lubricant industry. QCM-D is employed to quantify the mass, characterize the morphology, and quantify the kinetics of adsorption of common friction modifiers. The adsorption information is then compared to macroscopic properties (friction and corrosion prevention) to determine if this technique can aid in formulating future lubricants.

Rail corrugation is a periodic wear pattern that develops on the wheel and rail contacting surfaces in railway systems. It is a commonly observed phenomenon worldwide and is a serious problem because it causes degradation of the track and its components and is a significant source of noise. Currently the only reliable method of ameliorating the negative effects of rail corrugation is to periodically regrind the rail surface to a smooth profile, at great expense to the railway operator. It is therefore of interest to investigate other possible control strategies to reduce corrugation growth through an understanding of the mechanism of corrugation formation. This thesis presents an investigation into the effect of speed variation on the corrugation formation mechanism. The research presented is intended to highlight the significant role that speed variation has on corrugation formation via a disruption of the feedback mechanism which leads to corrugation growth over successive train passages. This discovery motivates the investigation the feasibility of altered speed variation as a novel corrugation control method, due to the large effect that the variance of train speed has on corrugation growth rates. The effect of variable pass speed on corrugation formation has been investigated in this thesis through the use of efficient models of corrugation formation in straight track and cornering conditions. These models are simple enough to readily perform corrugation control studies without neglecting any relevant physics, obscuring the corrugation formation mechanism with overly detailed modelling or imposing a significant computational burden on performing control studies. These novel models have been outlined and their predictions elucidated in detail. A theoretical investigation into the effect of speed variation in the presence of a resonance free mechanism for corrugation growth via a contact filter has been performed and shown to only be important when the dynamic wavelength of formation approaches the size of the contact patch. The results of these corrugation models have been validated via test rig and field experiments. An investigation of the effectiveness of speed variation as a corrugation growth control measure has also been investigated via test rig experiments. The results of this thesis have formed the basis of an industry supported field trail of this technique for corrugation mitigation that is currently in progress.

Increasing environmental awareness has driven a lot of research to look into various environmentally friendly lubricants which can replace more conventional mineral oil based lubricants. This is true in particular for marine and hydropower applications where the risk of lubricant leakage can be damaging to the local environment. Glycerol is an organic compound produced as a byproduct when producing Biodiesel. It is environmentally friendly and has been used by the pharmaceutical and food industries for a long time. Recent research has shown that glycerol has very good tribological properties and can be used as a lubricant in some applications. However, its high viscosity and high static friction are disadvantageous and needs improvement. The purpose of this study is to investigate possible surface active environmentally adapted additives in glycerol and water solutions. 14 additives have been selected for testing and were tested in a pin-on-disc start-stop friction test to see their effect on the static and dynamic friction coefficients. From these 14 additives two were selected due to their superior performance and were further studied. The effect of concentration of water and additive in glycerol was also investigated using the same test conditions. A phosphor based additive has been found to be the best performing.

Le moteur à combustion, utilisé dans l’automobile est en perpétuelle évolution pour des raisons économiques et écologiques. Pour parvenir à de faibles consommations de carburant et émissions polluantes, l’un des axes étudiés est la réduction des pertes mécaniques par frottement du moteur qui constituent 15 à 20% de la consommation totale d’énergie du moteur. 50% de ces frottements proviennent des contacts Segment-Piston- Chemise et de la liaison Maneton-Bielle-Coussinet. De ce fait la compréhension de la tribologie de ce contact, l’optimisation de la lubrification et le vieillissement des lubrifiants deviennent primordiaux. L’objectif de cette thèse est d’étudier les mécanismes de lubrification de ces contacts segment/chemise et maneton/coussinet, et en particulier de comprendre l’influence du couplage additif, surface et matériau dans les différentes régimes de lubrification. Il s’agira de répondre à la question : comment maîtriser le frottement et l’usure en contrôlant la chimie du lubrifiant, la topographie et le matériau ? La démarche expérimentale choisie s’appuie sur l’analyse du comportement tribologique de deux additifs modificateurs de frottement sans cendres d’une part, puis sur l’impact du matériau et enfin sur l’influence de la topographie d’autre part. L’analyse de la cinétique d’évolution du coefficient de frottement et des traces d’usure en régime limite ont notamment permis d’identifier les mécanismes de réduction de frottement induits par les deux modificateurs étudiés. / The combustion engine used in automotive industry is constantly changing for economic and ecological reasons. To achieve low fuel consumption and pollutants emissions, one of research axes studied is the reduction of the mechanical friction loss of the motor which constitute 15-20 % of the total energy consumption of the engine. 50% of these come from friction contacts cylinder /piston rings and conrod bearing. Thereby understanding of tribology of the contact, optimizing lubrication and lubricants aging become paramount. The objective of this thesis is to study the mechanisms of lubrication of these contact (piston ring/cylinder and conrod bearing), and in particular to understand the influence of the additive coupling surface and material in the different lubrication regimes. This will answer the question : how to control the friction and wear by controlling the chemistry of the lubricant, the topography and the material ? The experimental approach chosen is based on the analysis of the tribological behavior of two friction modifiers additives ashless at first time, and on the impact of material and finally the influence of topography on the second time. XPS Analysis of the evolution of the coefficient of friction and wear track under boundary regime have enabled to identify mechanisms to reduce friction induced by the two modifiers studied.

Les amines grasses sont présentes dans la formulation de lubrifiants automobiles, en tant que modificateurs de frottement organiques (MFO), afin d'atténuer les effets négatifs entraînés par le frottement et l'usure induits au sein des pièces sujettes aux conditions limites (c'est-à-dire, sous haute pression et basse vitesse de glissement). Outre leurs propriétés de lubrification, ces additifs présentent l'avantage d'être compatibles avec les systèmes de dépollution des gaz d'échappement, puisque leur composition organique est exempte d'éléments nocifs, tels que le soufre, le phosphore et certains métaux. Ainsi, un protocole de calcul en dynamique moléculaire classique a été mis en place et utilisé pour étudier, à l'échelle moléculaire, les propriétés des surfactants. En particulier, trois mécanismes d'action ont été considérés, à savoir : leur diffusion dans un milieu liquide, leur adsorption sur des substrats solides, et leur comportement en frottement. Dans ce contexte, différents facteurs associés à la structure des constituants des lubrifiants ont été analysés, notamment leur effet sur la performance des MFO. Les simulations révèlent que : (i) Diffusion – le coefficient de diffusion des composés aminés sont considérablement impactées par les caractéristiques de l'huile de base (exemple: leur polarité et masse moléculaire), sachant que les modèles de solvant les plus polaires et les plus lourds provoquent le ralentissement du flux diffusif des MFO ; par ailleurs, la structure des additifs jouent également un rôle dans leur diffusion, où les molécules les plus petites et les moins polaires s'avèrent relativement les plus mobiles. (ii) Adsorption – les amines primaires réagissent chimiquement avec une surface d'oxyde de fer, en formant des monocouches auto-assemblées, dont l'organisation et l'épaisseur augmentent avec leur taux de recouvrement. (iii) Frottement – les films adsorbés contenant d'amines constituées d'une chaîne hydrocarbonée C18 linéaire et saturée sont capables de réduire le frottement d'un système modèle représentant un nano-contact en régime limite ; en plus, leur efficacité dépend de la microstructure développée par les amines adsorbées sur les substrats sous compression et cisaillement ; d'ailleurs, les films permettant la formation de(s) plan(s) de glissement bien défini(s) entre les molécules organiques confinées sont davantage disposés à diminuer la résistance de glissement. Par conséquent, ces études ont permis de confirmer l'intérêt de l'apport d'une approche numérique complémentaire aux techniques expérimentales dans le but de comprendre les phénomènes élémentaires des systèmes tribologiques. / Fatty amines and their derivatives are employed as organic friction modifiers (OFM) in lubricant oils in order to mitigate the negative effects of friction and wear, both induced by the moving and rubbing components of an internal combustion engine that are subjected to boundary lubrication conditions (i.e., high contact pressure and low sliding velocity). In addition to their tribological performance, these additives exhibit the benefit of being compatible with exhaust aftertreatment systems that equip the current light-duty vehicles, owing to their sulfur- and phosphorus-free chemical composition. For these reasons, we have developed a computational protocol, composed of equilibrium and non-equilibrium (classical) molecular dynamics simulations, in order to gain a deeper understanding into their mechanisms of action at nanoscale, and in particular into their diffusion, adsorption and friction behaviors. In this context, the influence of different molecular structure factors – related to lubricant constituents – on OFM working performance were investigated. The obtained results have shown that: (i) Diffusion – OFM diffusivity is substantially affected by the base oil structure and chemistry (e.g., polarity and molar mass), where solvents with relatively larger and higher polar groups tend to slow down their diffusive rate; besides, the OFM dynamics in liquid phase is also impacted by their own composition, being the molecules with relatively smaller and less polar structure the most mobile additives. (ii) Adsorption – primary alkyl amines do chemisorb onto iron-oxide substrates, thereby forming molecular films whose packing order and thickness increase with increasing surface coverage. (iii) Friction – adsorbed layers containing primary amines with linear, saturated, C18 hydrocarbon tails are able to reduce friction in a single-asperity, boundary nano-contact model, where their efficiency is dependent on their molecular ordering under confinement and shear; in addition, the organic films allowing the formation of well-defined slippage interface(s) with little molecular interdigitation are more prone to diminish the sliding resistance of solid substrates in relative motion.Therefore, those findings are expected to foster the exploration and development of computational simulation approaches, as a complement of experimental techniques, to investigate the fundamental phenomena present in tribological-relevant engineering systems.