La législation européenne sur les émissions des véhicules devient de plus en plus sévère et ceci afin de minimiser l'impact sur l'environnement de la pollution occasionnée par les moteurs à combustion interne. La réduction des pertes par frottement et une plus faible consommation du carburant représentent différents aspects sur lesquels il est possible d’intervenir dans ce sens. Pour diminuer les pertes par frottement, plusieurs approches ont été utilisées, soit au niveau du design des pièces mécaniques, soit au niveau de l’optimisation du lubrifiant pour un contact considéré. Le dithiocarbamate de molybdène (MoDTC) est l’un des additifs modificateur de frottement permettant d’atteindre les plus faibles coefficients de frottement pour un contact acier/acier lubrifié en régime limite. La molécule se décompose dans le contact à des températures et des pressions élevées, en formant des feuillets lamellaires de MoS2 sur les surfaces frottantes. Cependant, il est nécessaire d'optimiser la durée de vie de ces additifs, en empêchant leurs appauvrissements ou dégradations prématurés dans le lubrifiant. Il a été montré, en effet, que les performances du MoDTC sont sensibles au temps de fonctionnement du moteur et sont donc liées à sa dégradation. L'objectif principal de cette thèse était donc de mieux comprendre le comportement tribologique (frottement et usure) d’une huile de base contenant du MoDTC en fonction de la dégradation du lubrifiant pour des contacts acier/acier et DLC/acier. L’approche utilisée pour mieux comprendre le comportement du MoDTC lorsqu'il est soumis à une dégradation thermo-oxydative consiste à combiner des expériences tribologiques, à des caractérisations de surface (XPS, FIB / TEM / EDX, Raman, SEM) et à des caractérisations chimiques des huiles (chromatographie en phase liquide, spectroscopie de masse, FT-IR). Un lien direct et cohérent entre la composition du tribofilm et la voie de décomposition chimique de l'additif MoDTC proposée a été mise en évidence. Les additifs modernes sont conçus pour être utilisés sur des surfaces à base de fer. Il est donc essentiel d'optimiser simultanément les lubrifiants et les revêtements pour améliorer leurs performances. Dans cette thèse, un modèle d'usure du revêtement DLC hydrogéné lubrifié en présence de MoDTC a été proposé. Nous avons établi à l’aide de plusieurs techniques, que l’usure est due principalement à la formation de carbure de molybdène présent dans le tribofilm formé à la surface de l’acier. / European legislation on vehicle emissions continues to become more severe to minimize the impact of Internal Combustion Engines (ICE) on the environment. One area of significant concern in this respect is the reduction of friction losses resulting in reduced emissions and as well as higher fuel efficiency and lower fuel consumption. To decrease these losses, several approaches have been made particularly at design of mechanical parts stage and at experimental level to optimize lubricant components. A great contribution to solve the problem can be given by the optimization of the additives package blended into the engine lubricants. The molybdenum dithiocarbamate (MoDTC) is the additive showing the best tribological performance by acting as friction modifier. It decomposes under high temperatures and pressure, forming layered structures on the engine surfaces. However, the use of effective friction reducing additives to achieve low boundary friction coefficient is not enough to have great engine fuel efficiency. In addition, in fact, it is needed also to maximize their durability, preventing premature consumption or depletion of these additives. It has been shown, in fact, that the friction reduction performance of MoDTC is sensitive to engine operating time and that is related to the degradation of MoDTC itself. In the first part of my thesis we tried to get a good comprehension of the chemical mechanisms of MoDTC ageing and to study the impact on the tribological properties. The chemical bulk oil characterization of MoDTC blended into the base oil when subjected to thermo-oxidative degradation allowed to propose a new hypothetical chemical pathway followed by the friction modifier molecules during the ageing process. At the same time, these findings were linked to the impact of the MoDTC degradation on its tribological properties. As reported in literature, another MoDTC drawback is its strong antagonism with DLC coating. In fact, when DLC-involving contacts are lubricated by MoDTC-containing base oil, a catastrophic DLC wear is produced. For this reason, in the second part of the project a multi-techniques approach has been adopted to get a better understanding of this wear mechanism. The combination of all the findings allowed to propose for the first time a new wear mechanism based on the formation of molybdenum carbide species inside the contact. A strong chemical interaction between the molybdenum-based species formed on the steel counter-body and the carbon of the DLC material has been supposed, leading to the formation of MoC species. All the results found are discussed to clarify the correlation between degradation time, tribological performance and tribofilm characterizations in both steel/steel and DLC/steel contact.

Superfícies anisotrópicas lisas e rugosas foram usadas para avaliar o efeito da rugosidade e da direção de acabamento na formação de MoS2 a partir de MoDTC em ensaios tribologicos lubrificados com óleos de motor completamente formulados. Igualmente foi avaliada a resposta de atrito de lubrificantes de motor usados em carros de passageiros e em testes de dinamômetro abastecidos com etanol (E100) e gasolina (E22). Encontrou-se que tanto a direção de acabamento quanto a rugosidade foram fundamentais na reação MoDTC - MoS2. A direção de acabamento influenciou na medida que carregamentos tangenciais geram respostas diferentes nos ensaios quando são realizados paralelos e perpendiculares às linhas de acabamento, dado que para os últimos apresenta-se maior deformação plástica das asperezas, o qual favorece a obtenção de superfícies livres de óxidos, que tem sido indicada como uma condição necessário para que aconteça a reação MoDTC - MoS2. Por esta razão os valores de coeficiente de atrito próprios da formação de MoS2 foram obtidos somente nas superfícies rugosas ensaiadas perpendiculares às marcas de acabamento. Para superfícies com valores de índice de plasticidade superiores a 1 e nos quais não são formados filmes com boas capacidades redutoras de atrito, como é o caso de ensaios realizados com óleos base (livres de aditivos), o coeficiente de atrito não depende da rugosidade e da direção de acabamento. Nos ensaios lubrificados com óleos usado, encontraram-se valores de coeficiente de atrito similares aos obtidos nas condições de lubrificação com óleo livres de aditivos, devido provavelmente à redução do MoDTC no lubrificante como tem sido identificado por diferentes autores. Quando foram comparados os óleos usados contaminados com etanol com os óleos usados contaminados com gasolina, encontrou-se maior oxidação nestes últimos. Mesmo que estas diferenças de oxidação dos óleos não significaram diferenças em termos de atrito, estas podem ser importantes na medida em que óleos mais oxidados podem favorecer o desgaste oxidativo. / Smooth and rough anisotropic surfaces were used to evaluate the influence of surface roughnesss and lay direction on the in-situ formation of MoS2 from MoDTC in tribological tests. Also, this work evaluated the friction response of engine lubricants which were used in passenger cars and dynamometer tests fueled both with ethanol (E100) and gasoline (E22). It was found that both the lay direction as the surface roughness were critical for the MoDTC -MoS2 reaction. The lay direction influence due to tangential loads generate different responses when tests were conducted along and across the lay, since the latter showed higher asperities plastic deformation , which favors free oxides surfaces, which has been indicated as a condition for the sequence by MoDTC formed MoS2. For this reason the friction coefficient values related to MoS2 were obtained only for tests conducted on rough surfaces and across the lay. For surfaces with plasticity index values greater than 1 and which are not formed films with good friction-reducing capabilities, such as the tests lubricated with base oil (free aditives), the friction coefficient does not depends on the surface roughness and lay direction. For the tests conducted with used engine oils, the friction coefficient values were similar to those obtained on tests lubricated with free additives oils, this could be related by MoDTC depletion in the lubricants as have been identified by different authors. Comparing the used oils contaminated with ethanol with the used oils contaminated with gasoline, higher oxidation was founded in the latter. Even if these differences in oil oxidation not meant differences friction, these may be important as more oxidesed oils can promote oxidative wear.

Superfícies anisotrópicas lisas e rugosas foram usadas para avaliar o efeito da rugosidade e da direção de acabamento na formação de MoS2 a partir de MoDTC em ensaios tribologicos lubrificados com óleos de motor completamente formulados. Igualmente foi avaliada a resposta de atrito de lubrificantes de motor usados em carros de passageiros e em testes de dinamômetro abastecidos com etanol (E100) e gasolina (E22). Encontrou-se que tanto a direção de acabamento quanto a rugosidade foram fundamentais na reação MoDTC - MoS2. A direção de acabamento influenciou na medida que carregamentos tangenciais geram respostas diferentes nos ensaios quando são realizados paralelos e perpendiculares às linhas de acabamento, dado que para os últimos apresenta-se maior deformação plástica das asperezas, o qual favorece a obtenção de superfícies livres de óxidos, que tem sido indicada como uma condição necessário para que aconteça a reação MoDTC - MoS2. Por esta razão os valores de coeficiente de atrito próprios da formação de MoS2 foram obtidos somente nas superfícies rugosas ensaiadas perpendiculares às marcas de acabamento. Para superfícies com valores de índice de plasticidade superiores a 1 e nos quais não são formados filmes com boas capacidades redutoras de atrito, como é o caso de ensaios realizados com óleos base (livres de aditivos), o coeficiente de atrito não depende da rugosidade e da direção de acabamento. Nos ensaios lubrificados com óleos usado, encontraram-se valores de coeficiente de atrito similares aos obtidos nas condições de lubrificação com óleo livres de aditivos, devido provavelmente à redução do MoDTC no lubrificante como tem sido identificado por diferentes autores. Quando foram comparados os óleos usados contaminados com etanol com os óleos usados contaminados com gasolina, encontrou-se maior oxidação nestes últimos. Mesmo que estas diferenças de oxidação dos óleos não significaram diferenças em termos de atrito, estas podem ser importantes na medida em que óleos mais oxidados podem favorecer o desgaste oxidativo. / Smooth and rough anisotropic surfaces were used to evaluate the influence of surface roughnesss and lay direction on the in-situ formation of MoS2 from MoDTC in tribological tests. Also, this work evaluated the friction response of engine lubricants which were used in passenger cars and dynamometer tests fueled both with ethanol (E100) and gasoline (E22). It was found that both the lay direction as the surface roughness were critical for the MoDTC -MoS2 reaction. The lay direction influence due to tangential loads generate different responses when tests were conducted along and across the lay, since the latter showed higher asperities plastic deformation , which favors free oxides surfaces, which has been indicated as a condition for the sequence by MoDTC formed MoS2. For this reason the friction coefficient values related to MoS2 were obtained only for tests conducted on rough surfaces and across the lay. For surfaces with plasticity index values greater than 1 and which are not formed films with good friction-reducing capabilities, such as the tests lubricated with base oil (free aditives), the friction coefficient does not depends on the surface roughness and lay direction. For the tests conducted with used engine oils, the friction coefficient values were similar to those obtained on tests lubricated with free additives oils, this could be related by MoDTC depletion in the lubricants as have been identified by different authors. Comparing the used oils contaminated with ethanol with the used oils contaminated with gasoline, higher oxidation was founded in the latter. Even if these differences in oil oxidation not meant differences friction, these may be important as more oxidesed oils can promote oxidative wear.

De nos jours, afin de réduire le frottement et l'usure dans les moteurs thermiques et par voie de conséquence les émissions polluantes ainsi que la consommation énergétique, des revêtements APS (Atmospheric Plasma Spray) sont appliqués sur les chemises des cylindres. Le MoDTC (Di-ThioCarbamate de Molybdène), est un additif organométallique largement utilisé dans la lubrification automobile pour réduire le frottement grâce à la formation sur les surfaces frottantes de feuillets de MoS2. Ce travail de thèse porte sur l’étude de la réaction tribochimique du MoDTC avec le revêtement TiO2 APS dans des conditions de lubrification mixte / limite. Des poudres de TiO2 de taille micrométrique ont été utilisées pour obtenir un revêtement APS de TiO2 de 70 µm d'épaisseur. Différents tribomètres ont été utilisés pour effectuer des essais de frottement en présence d’une huile de base contenant du MoDTC. Les résultats obtenus pour un contact acier / TiO2 APS lubrifié avec du MoDTC présente une réduction significative du frottement par rapport au contact acier / acier (contact de référence). Les analyses de surface montrent que le tribofilm formé sur le plan de TiO2 APS est composé de MoS2 et de MoO3 tandis qu’il est constitué d’oxysulfure de molybdène, de MoS2 et de MoO3 sur le plan de référence en acier. De plus, les résultats indiquent que des phases Magneli résistantes à l'usure sont formées sur la surface du plan de TiO2 réduisant ainsi l'usure du contact lorsque celui-ci est uniquement lubrifié avec l'huile de base. L'impact de divers paramètres tels que la rugosité, la température d'essai, la pression de contact, la concentration en MoDTC et le remplacement des billes en acier par des billes en céramique sur le comportement tribologique du TiO2 APS a également été étudié. Les résultats ont été comparés avec ceux obtenus dans les mêmes conditions avec un contact acier / acier de référence et révèlent que le coefficient de frottement est toujours plus faible dans le cas des contacts impliquant un revêtement de TiO2 APS. Des résultats similaires à ceux obtenus avec le TiO2 APS (en termes de comportement tribologique et de composition chimique du tribofilm) ont été obtenus avec des nanoparticules de TiO2 mélangées dans l’huile de base avec du MoDTC dans le cas d'un contact acier / acier de référence. Dans les deux cas, une décomposition complète de MoDTC conduisant à la formation de MoS2 a été observée. Un phénomène de tribocatalyse a été suggéré comme pouvant être le mécanisme responsable de la décomposition du MoDTC en présence de matériaux à base de TiO2 comme le revêtement TiO2 APS et les nanoparticules de TiO2. / Nowadays to reduce friction and wear as well as gas emission and oil consumption of the passenger car engines, Atmospheric Plasma Spray (APS) coatings are used on cylinder liner. MoDTC (Molybdenum Di-Thiocarbamate), organometallic friction modifier has been previously used to reduce friction by formation of layered molybdenum disulphide flakes. This study focuses on tribochemical interaction of MoDTC with TiO2 APS coating under mixed / boundary lubrication conditions. Fused and crushed micron sized powders were used to obtain a 70 µm thick TiO2 coating. Various tribometers were used to carry out tribotests in presence of lubricant containing MoDTC. Steel / TiO2 APS contact showed significant friction reduction than steel / reference steel contact. It was shown that the tribofilm is composed of MoS2 and MoO3 on TiO2 APS flats while it is composed of Mo-oxysulphide, MoS2 and MoO3 on reference steel flats. It was shown that wear resistant Magneli phases are formed on the surface of TiO2 APS disc, decreasing wear when the contact was lubricated only with base oil. Impact of various parameters like roughness, test temperature, contact pressure, concentration of MoDTC and change of counterpart materials from steel balls to ceramic balls, on the tribological behavior of TiO2 APS was also studied. Results obtained were compared with contacts involving reference steel and it was confirmed that friction coefficient was always lower in case of contacts involving TiO2 APS coating. Similar tribological results and chemistry were obtained for TiO2 nanoparticles blended with MoDTC in case of steel / reference steel contact. Both the cases, TiO2 APS and TiO2 nanoparticles showed complete decomposition of MoDTC to form MoS2. Tribocatalysis was suggested as the mechanism responsible for complete decomposition of MoDTC in case of TiO2 based materials like TiO2 APS coating and TiO2 nanoparticles

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