The discovery and subsequent synthesis of metal containing fullerenes- IFS (Inorganic Fullerene-like Structures) by R. Tenne et al. has generated considerable scientific interest with great potential impact in many industrial application areas such as lubrication. The lubrication mechanism (tribofilm formation) via exfoliation and deposition of the atomic layers from this cage-like IF-particles was revealed and demonstrated first by this research group. The incorporation of the nanoparticles into lubricants (oils, greases) is however not straightforward. When two surfaces are sliding against each other and a lubricant is used, a thin layer (tribofilm) is formed on the contact area. The friction reducing effects of the nanoparticles can be altered or hindered by certain additives that are used in lubricative oils. The effects of such additives on the tribological behavior of the nanoparticles are investigated by analyzing the tribofilms formed on the worn surfaces using energy-dispersive X-ray spectroscopy in a scanning electron microscope. Another challenge of nanoparticles in lubricants is the penetration of the nanoparticles into the contact zone. A possible solution of this problem is briefly discussed. A modified burnishing technique can be used to coat sliding metallic surfaces with a friction reducing tribofilm. The morphology and composition of these tribofilms was investigated with analytical electron microscopy techniques. In the second part of the thesis electron microscopy was used to investigate the material transfer. Titanium is an elements with high adhesive ability to the counter surface, it displays poor tribological properties in sliding metallic contacts. This can lead to material transfer and consequently severe surface damage. The cold formation and machining of titanium, thus can lead rapid tool wear and poor surface finish. Electron microscopy techniques were used to study the mechanism of titanium transfer to different counter surfaces.

Surfaces exposed to wear always transform and typically a layer of new structure and composition is formed. This layer, often called tribofilm, changes the friction and wear properties. Tribofilms formed on ceramic surfaces may consist of products from chemical reactions between the materials in contact and the environment or consist of compacted wear debris. In this thesis, focus has been to understand the friction and wear mechanisms of ceramic surfaces, as well as acquiring knowledge about the properties of the new surfaces created during wear. Ultimately, this understanding can be used to develop ceramic systems offering high or low friction, while the material loss in both cases should be minimised. Such ceramics could improve numerous tribological systems and applications, out of which ultrasonic motors, low-friction ceramic coatings and hip joint replacements have been treated in this thesis. Friction and wear tests, and subsequently various surface analyses have been essential for the knowledge about the friction, wear and tribofilm formation.  For ultrasonic motors of the studied type, the highest driving force is achieved when the friction is high between the alumina components in the friction drive system. The highest friction was here accomplished with a thick tribofilm on the surfaces. The formation of such tribofilms was favoured by dry conditions, and using an initially rough surface, which increased the initial generation of wear debris. In a detailed investigation of the importance of microtopography on tribofilm formation and friction behaviour, a low-friction, PVD coating of TaC/a-C was studied. This coating showed a very low, stable friction. High sensitivity to the microtopography was demonstrated, smooth coating exhibited a faster build-up of a dense tribofilm of fine ground material on the counter steel surface and subsequently a faster running in and friction decrease.  The life span for total hip joint replacements can be prolonged by minimising the wear particles that cause inflammation and subsequent implant loosening. In this work coatings of amorphous/nanocrystalline silicon nitride have shown low wear rate, and hence produce a minimum of wear particles. Furthermore, these particles that are expected to resorb in vivo. This system therefore has potential to reduce problems with inflammation and osteolysis connected to wear particles.

Para transmitir o torque gerado pelo motor de combustão interna para a caixa de transmissão por meio da embreagem, seja em automóveis ou caminhões, é necessário que haja contato por deslizamento entre um material polimérico multifásico e um contracorpo metálico de ferro fundido cinzento. Além disso, os níveis do coeficiente de atrito entre esses materiais têem que ser suficientemente alto e estável, para proporcionar uma transmissão de torque regular e eficiente. Porém, durante o deslizamento, materiais são transferidos de uma superfície para outra, e alterações microestruturais e fisico-químicas ocorrem. Como consequência, uma nova superfície (denominada de tribofilme) se desenvolve, influenciando o desempenho funcional da embreagem. Dessa forma, compreender as suas características tem se tornado essencial para desenvolver sistemas de embreagens cada vez mais eficientes. No entanto, muitos ensaios são necessários para que se possa entender como uma ou várias matérias primas se comportam em relação aos aspectos tribológicos. Isso faz com que surja a necessidade de repetir os ensaios inúmeras vezes, para que se façam as escolhas mais assertivas tanto das matérias primas quanto dos processos envolvidos. Como alternativa, para reduzir tempo e custos, e ter um maior controle sobre as variáveis de ensaio, busca-se simular em laboratório, com equipamentos mais simples, a reprodução das interações tribológicas em condições reais. A primeira fase deste trabalho tem como objetivo apresentar os mecanismos de desenvolvimento do tribofilme para três níveis de severidade em condições reais de aplicação (ensaios mais demorados, complexos e mais caros, devido à necessidade da confecção completa dos protótipos), e posteriormente correlacionar esses mecanismos com os que foram simulados por meio de ensaios conduzidos num tribômetro de laboratório do tipo pino-disco (ensaios mais rápidos e mais simples, consequentemente menos complexos), variando o PV de 3,08 até 11,08 MPa ms-1. Foi constatado que as características do tribofilme dependem da severidade da aplicação. Além do que, o tribômetro pino-disco (amostra de 13 mm de diâmetro externo) consegue reproduzir os mecanismos identificados em campo, pois houve paridade na transferência das características do tribossistema do modelo de ensaio para o da condição real (430 mm de diâmetro externo). Na segunda fase, diferentes séries de ensaios tribométricos foram realizadas para investigar a influência do tribossistema no desempenho funcional do par tribológico (atrito e desgaste). Para os ensaios tradicionais, foi constatada um aumento na taxa de desgaste para temperaturas superiores a 250°C, revelando uma transição no regime moderado de desgaste para o severo. Quando os debris de desgaste foram removidos do meio interfacial, o nível do coeficiente de atrito aumentou e a taxa de desgaste reduziu. Já a adição de debris de desgaste ao meio interfacial contribuiu para aumentar a taxa de desgaste e reduzir drasticamente o nível do coeficiente de atrito. No entanto, quando os ensaios foram realizados empregando discos pré-condicionados, a taxa de desgaste e o nível do coeficiente de atrito foram otimizados, principalmente em níveis de severidade mais elevados (PV 10,09 MPa ms-1) indicando potencial ganho na eficiência do sistema embreagem. / Torque from an internal combustion-engine to a gear box, either in automobiles or trucks, is transmitted by a clutch system. In order to transmit torque from one side to the other, sliding contact between a multiphase friction material and a gray iron rotor is necessary. Torque transmission depends on the friction level among the tribological couples, and it have to be relatively high and most importantly stable to allow an efficient and regular performance. During the sliding between the coupling surfaces, material is transferred from one surface to the other causing microstructure and chemical changes. As consequence, a new surface, also known as tribofilm, is developed. This surface governs the clutch system performance and understanding the tribofilm characteristics is very important to improve the development of efficient clutch systems. For this, a large number of tests are necessary to understand the tribological behavior of the raw materials. Such investigation is highly empirical and in order to have a consistent data it\'s necessary to carry out several friction tests repetitions. Alternatively, to save time and money, and have better control over the test variables, the real tribological interactions can be simulated in laboratory by using simple equipment, pin-on-disc tribometer. The simplicity of this device allows evaluating a larger number of alternative materials. The first part of this work aims to investigate the tribofilm development mechanisms in three severity levels on the field application (those tests are more time-consuming, complex and expensive, because it is necessary to produce the entire prototype), and then correlate these mechanisms with those simulated in a pin-on-disc tribometer (faster and simpler test) by changing the PV level from 3.08 to 11.08 MPa ms-1. It was found that the tribofilm characteristics depend on the severity of application. In addition, the pin-on-disc tribometer (sample of 13 mm outside diameter) can reproduce the same mechanisms that were identified on the field, due to the parity between the tribosystem characteristics of test model and field condition (430 mm external diameter). In the second part of this work, different series of tribometer tests were performed to investigate the influences of tribosystem on tribological couple performance (friction and wear). Standard tribometer tests presented an increasing in the wear rate at temperatures of 250°C, revealing a transition from moderate to severe wear regime. When wear debris were removed from the interfacial contact, the friction coefficient level increased and wear rate reduced. On the other hand, when the wear debris were added, it contributed to increase the wear rate and to reduce the friction level dramatically. However, when the experiments were performed by using pre-conditioned discs, the wear rate and friction coefficient level has been optimized, particularly at higher severity levels (PV 10.09 MPa ms-1).

Le dialkyldithiophosphate de zinc ( ZDDP ) est un additif anti-usure habituellement utilisé dans les lubrifiants moteurs. Dans des conditions sévères de frottement, les molécules de ZDDP forment sur les surfaces métalliques un film, appelé tribofilm, qui protège ces surfaces de l'adhésion et de l'abrasion. Les tribofilms sont principalement composés de polyphosphates de zinc dont la longueur des chaînes varie progressivement sur la hauteur du film. On trouve les chaînes de phosphate les plus courtes à la surface du métal et les chaînes de phosphate les plus longues au sommet du film. Plusieurs études ont été menées afin de comprendre le mécanisme par lequel l'additif peut conduire à la formation de ce gradient de phosphate. Pour améliorer la compréhension de ce mécanisme, nous nous concentrons dans cette étude sur l'influence de la pression, du cisaillement, de la nature des surfaces et de la température sur des composés de type orthophosphate de zinc et métaphosphate de zinc, utilisés pour modéliser le tribofilm de ZDDP. Des tests tribologiques ont été réalisés en régime de lubrification limite à partir de dispersions de ces polyphosphates de zinc dans de l'huile de base. L'effet de la pression seule a été étudié à l'aide d'une cellule à enclumes de diamant (CED) afin de découpler son effet de celui du cisaillement. La spectroscopie Raman a été utilisée pour suivre in-situ ou ex-situ, les changements de structures des poudres de polyphosphate de zinc. Ces expériences ont été réalisées sur ces composés afin d'identifier précisément la contrainte qui conduit à ce gradient de phosphate au sein d'un tribofilm. La pression seule, à induit uniquement des désordres structurels au sein des polyphosphates de zinc. Une dimérisation mineure a été observée pour l'orthophosphate de zinc mais, est peu significative pour expliquer les changements structurels observés dans un tribofilm. Lors des tests tribologiques, les phosphates ont montré une capacité à former des tribofilms. Une dépolymérisation du métaphosphate de zinc à été observée a l'issue de ces tests. Les grandes contraintes et conditions de déformation des essais tribologiques sont nécessaires pour induire une réaction tribochimique entre le métaphosphate de zinc et l'oxyde de fer conduisant à une dépolymérisation du phosphate dans le tribofilm. La réaction anti-usure et la formation de tribofilm est favorisée par les hautes températures (120 * C), et par certaines formes d'oxydes de fer.

Grâce à ses propriétés d'antioxydant, d'anti-usure et éventuellement d'extrême pression le dithiophosphate de zinc (ZDDP) fait partie des additifs les plus utilisés dans les lubrifiants pour moteurs thermiques. De nos jours, dans un souci de respect de l'environnement, de nouveaux lubrifiants possédant de bonnes performances en lubrification (frottement faible et usure limitée) sont développés en prenant compte des limitations d'utilisations actuelles du ZDDP. L'idée étant de réduire dans ceux-ci les teneurs en phosphore et soufre (Normes euros VI), éléments essentiels du ZDDP qui endommagent les pots catalytiques. L'objectif de cette thèse est l'étude du comportement tribologique du phosphate de zinc di alkyl (ZP) en comparaison avec le ZDDP. La méthodologie expérimentale étudiée pour comprendre le mécanisme d'action de ces additifs, associe des essais de frottement à descaractérisations physico-chimiques des surfaces frottantes après essais.Cette comparaison a été effectuée en fonction de la température (25°C et 100°C), la vitesse de glissement (25, 50 et 100 mm/s) et la concentration en additif (200 et 600 ppm dephosphore). Les meilleures actions anti-usure sont obtenues avec le ZDDP pour une température de 100°C et une vitesse de glissement de 100 mm/s et le ZP pour une température de 25°C et une vitesse de glissement de 25 mm/s. Les analyses de surface XPS, AES, XANES et MET-EDX ont permis de mettre en évidence la présence d'un film protecteur constitué principalement de phosphate de zinc, ceci pour les deux additifs.Une synergie de comportement tribologique a été mise en évidence avec un lubrifiantconstitué de ZP (usure faible) et d'oléate d'urée (frottement faible). Des essais complémentaires sur un tribomètre dynamique ont permis d'étudier le niveau de frottement du tribofilm formé à partir du ZDDP. Le caractère visqueux du tribofilm de ZDDP a été mis en évidence.

Pour répondre aux problématiques d'usure précoce des pièces mécaniques causée par des pressions et températures élevées d'utilisation, des nanolubrifiants constitués de nanocarbones fluorés, connus pour leurs faibles coefficients de frottement et haute stabilité thermique ont été synthétisés. Pour améliorer ces propriétés, des précurseurs nanocarbonés de dimensionnalités différentes, et des procédés de synthèse gaz-solide variés ont été employés. Ainsi, une structure fermée comme les nanofibres de carbone NFCs (1D, tubulaire), ouverte comme le mélange nanodisques / nanocônes de carbone NDCs (majoritairement 2D, discotique) et intermédiaire avec les noirs de carbone graphitisés NCGs (0D, sphérique) ont été fluorés, d'une part avec le fluor moléculaire gazeux et d'autre part avec le fluor atomique produit par décomposition thermique d'un agent solide. Les mécanismes de fluoration / défluoration ont été proposés à l'aide de différentes techniques de caractérisation complémentaires (RMN du solide, MEB, MET, AFM, DRX) pour l'ensemble des matrices étudiées. Des matériaux présentant un gain de stabilité thermique de plusieurs dizaines de degrés comparativement aux matériaux fluorés de la littérature ont été élaborés, et une nouvelle méthode de synthèse dite " fluoration flash " a été mise au point pour étendre encore cette tenue en température. Les bonnes propriétés tribologiques de ces matériaux ont également été démontrées, notamment à 160°C et ceci quel que soit le mode de fluoration. Par la suite, des vernis à base de résines siliconées et chargés en nanofibres de carbone fluorées ont été formulés. Le revêtement composite présente une stabilité thermique supérieure à 400°C comme démontré par l'étude de son mécanisme de dégradation en température, notamment par couplage ATG-FTIR. D'un point de vue tribologique, les coefficients de frottement mesurés à température ambiante et 160°C sont inférieurs à 0,1 et les tribofilms obtenus ont été caractérisés par analyse MEB et EDX.

Para transmitir o torque gerado pelo motor de combustão interna para a caixa de transmissão por meio da embreagem, seja em automóveis ou caminhões, é necessário que haja contato por deslizamento entre um material polimérico multifásico e um contracorpo metálico de ferro fundido cinzento. Além disso, os níveis do coeficiente de atrito entre esses materiais têem que ser suficientemente alto e estável, para proporcionar uma transmissão de torque regular e eficiente. Porém, durante o deslizamento, materiais são transferidos de uma superfície para outra, e alterações microestruturais e fisico-químicas ocorrem. Como consequência, uma nova superfície (denominada de tribofilme) se desenvolve, influenciando o desempenho funcional da embreagem. Dessa forma, compreender as suas características tem se tornado essencial para desenvolver sistemas de embreagens cada vez mais eficientes. No entanto, muitos ensaios são necessários para que se possa entender como uma ou várias matérias primas se comportam em relação aos aspectos tribológicos. Isso faz com que surja a necessidade de repetir os ensaios inúmeras vezes, para que se façam as escolhas mais assertivas tanto das matérias primas quanto dos processos envolvidos. Como alternativa, para reduzir tempo e custos, e ter um maior controle sobre as variáveis de ensaio, busca-se simular em laboratório, com equipamentos mais simples, a reprodução das interações tribológicas em condições reais. A primeira fase deste trabalho tem como objetivo apresentar os mecanismos de desenvolvimento do tribofilme para três níveis de severidade em condições reais de aplicação (ensaios mais demorados, complexos e mais caros, devido à necessidade da confecção completa dos protótipos), e posteriormente correlacionar esses mecanismos com os que foram simulados por meio de ensaios conduzidos num tribômetro de laboratório do tipo pino-disco (ensaios mais rápidos e mais simples, consequentemente menos complexos), variando o PV de 3,08 até 11,08 MPa ms-1. Foi constatado que as características do tribofilme dependem da severidade da aplicação. Além do que, o tribômetro pino-disco (amostra de 13 mm de diâmetro externo) consegue reproduzir os mecanismos identificados em campo, pois houve paridade na transferência das características do tribossistema do modelo de ensaio para o da condição real (430 mm de diâmetro externo). Na segunda fase, diferentes séries de ensaios tribométricos foram realizadas para investigar a influência do tribossistema no desempenho funcional do par tribológico (atrito e desgaste). Para os ensaios tradicionais, foi constatada um aumento na taxa de desgaste para temperaturas superiores a 250°C, revelando uma transição no regime moderado de desgaste para o severo. Quando os debris de desgaste foram removidos do meio interfacial, o nível do coeficiente de atrito aumentou e a taxa de desgaste reduziu. Já a adição de debris de desgaste ao meio interfacial contribuiu para aumentar a taxa de desgaste e reduzir drasticamente o nível do coeficiente de atrito. No entanto, quando os ensaios foram realizados empregando discos pré-condicionados, a taxa de desgaste e o nível do coeficiente de atrito foram otimizados, principalmente em níveis de severidade mais elevados (PV 10,09 MPa ms-1) indicando potencial ganho na eficiência do sistema embreagem. / Torque from an internal combustion-engine to a gear box, either in automobiles or trucks, is transmitted by a clutch system. In order to transmit torque from one side to the other, sliding contact between a multiphase friction material and a gray iron rotor is necessary. Torque transmission depends on the friction level among the tribological couples, and it have to be relatively high and most importantly stable to allow an efficient and regular performance. During the sliding between the coupling surfaces, material is transferred from one surface to the other causing microstructure and chemical changes. As consequence, a new surface, also known as tribofilm, is developed. This surface governs the clutch system performance and understanding the tribofilm characteristics is very important to improve the development of efficient clutch systems. For this, a large number of tests are necessary to understand the tribological behavior of the raw materials. Such investigation is highly empirical and in order to have a consistent data it\'s necessary to carry out several friction tests repetitions. Alternatively, to save time and money, and have better control over the test variables, the real tribological interactions can be simulated in laboratory by using simple equipment, pin-on-disc tribometer. The simplicity of this device allows evaluating a larger number of alternative materials. The first part of this work aims to investigate the tribofilm development mechanisms in three severity levels on the field application (those tests are more time-consuming, complex and expensive, because it is necessary to produce the entire prototype), and then correlate these mechanisms with those simulated in a pin-on-disc tribometer (faster and simpler test) by changing the PV level from 3.08 to 11.08 MPa ms-1. It was found that the tribofilm characteristics depend on the severity of application. In addition, the pin-on-disc tribometer (sample of 13 mm outside diameter) can reproduce the same mechanisms that were identified on the field, due to the parity between the tribosystem characteristics of test model and field condition (430 mm external diameter). In the second part of this work, different series of tribometer tests were performed to investigate the influences of tribosystem on tribological couple performance (friction and wear). Standard tribometer tests presented an increasing in the wear rate at temperatures of 250°C, revealing a transition from moderate to severe wear regime. When wear debris were removed from the interfacial contact, the friction coefficient level increased and wear rate reduced. On the other hand, when the wear debris were added, it contributed to increase the wear rate and to reduce the friction level dramatically. However, when the experiments were performed by using pre-conditioned discs, the wear rate and friction coefficient level has been optimized, particularly at higher severity levels (PV 10.09 MPa ms-1).

An environmentally sustainable production of electrical power is important for preserving the earth’s natural resources. In order to utilize this power as efficiently as possible, it is of great importance to minimize the losses, for example in sliding electrical contacts. A sliding electrical contact is where current is transferred from one rotating to one stationary component and power is lost due to friction and contact resistance. Also in some signal applications, high performance sliding contacts are crucial to ensure stable signal transfer with low noise. Although sliding electrical contacts are primarily designed for good electrical performance, the system will benefit also from optimization of the tribological properties. The aim of this thesis is to increase the fundamental knowledge of the tribological and electrical performance of metal-graphite composite materials for sliding electrical contacts. The influence of mechanical and electrical load was investigated. Different stationary materials, from pure copper to nanocomposite coatings, were tested against copper- and silver-graphites. Two complementary test setups were used, one with reciprocating and one with unidirectional sliding. Surface analysis was essential to gain deepened understanding of the influence of the interaction on the surfaces. Especially my novel imaging of cross-sections has advanced the level on knowledge in this research field. On the stationary material surface, a tribofilm forms with constituents from the metal-graphite and the surrounding atmosphere. Cross-sectioning reveals a material flow that indicates turbulence. Furthermore, the presence of oxides in the tribofilm is not necessarily detrimental for the contact resistance as long as there is also pure metal available. The presence of graphite is vital for low friction and wear. It is shown that the tribological and electrical behaviour of this system is only marginally influenced by the material selection of the stationary contact. Increasing the metal content in the composite, on the other hand, greatly reduces the contact resistance while there is no significant impact on friction and wear. The mechanical load has to be optimized to compromise between low wear (achieved with low load) and low contact resistance (achieved with high load). Pure mechanical tests show a lower friction and higher wear rate in comparison to tests with a five ampere current.

Different lubricant additives such as dialkyldithiophosphates (DTPs) of different metals have been extensively used as multifunctional additives to control wear and friction in mechanical systems. These additives can produce protective films on steel rubbing surfaces and, therefore, control friction and reduce wear. On the other hand, these additives contain large amounts of metals, phosphorus and sulfur, which can adversely affect the environment by degrading catalytic converters in automobiles. Boron based additives are recognized as friction modifiers, corrosion inhibitors, antioxidants, and effective antiwear additives. These additives are emerging as attractive alternatives for the additives already used in lubricants. The aim of the project is to investigate the tribological performance of some novel alkylborate dithiocarbamates.This project was performed in the following steps:1- Chemical synthesis of three different borated dialkyl dithiocarbamate additives with alkyl chains of different lengths.2- Tribological tests of novel compounds using a four ball tribometer.3- Surface analysis using an optical profiler (Veeco WYkO NT 1100) and Scanning Electron Microscopy coupled with X-ray Energy Dispersive Spectroscopy (SEM/EDS).The effect of the alkyl chain length in both DTC and the borate molecular moities of three B-DTC compounds on the tribological performance was studied. An increase in the alkyl chain length at the borate side improves antiwear properties in steel-steel contact. It was found that cyclo-N,N-alkylenedithiocarbamato-S-alkyl-di-n-alkyl-borate previously synthesized and studied [1], has the best antiwear performance compared with the other compounds synthesized in this work. All the novel additives were able to stabilize friction coefficient over a wide concentration range of the additives in the base oil. B-DTC additives with long alkyl chains show greater reduction in friction compared to the one with short alkyl chains. A possible explanation of this phenomenon is that longer chains have improved deposition process of additives on surfaces leading to a thicker and more stable tribofilm. EDS spectra show the presence of sulfur atoms on the rubbing surfaces lubricated by the base oil with B-DTC additives. / <p>Validerat; 20111001 (anonymous)</p>