L'exploitation de revêtements micrométriques à base de carbone amorphe (les DLC) tend à se généraliser au sein des constructeurs automobiles afin d'améliorer le rendement des moteurs à combustion interne en réduisant les pertes mécaniques par frottement. Si ces revêtements exhibent généralement d'excellentes propriétés tribologiques et de très faibles taux d'usure, leur utilisation au sein des moteurs à combustion interne révèle que, soumis à des sollicitations complexes, de nombreux modes de dégradations sont observables. La propagation prématurée de ces dégradations sur l'intégralité des surfaces revêtues constitue un risque à maîtriser pour garantir la fonction des revêtements dans le temps. Cette maîtrise implique d'une part de connaître et de comprendre les mécanismes de dégradations probables des DLC appliqués aux composants du moteur et d'autre part de disposer d'outils de simulation de leur durée de vie, exploitables pour optimiser les systèmes tribologiques au plus tôt de leur conception. Les travaux présentés dans cette thèse ont été guidés par ces objectifs et rassemblent des expertises de composants revêtus, des développements d'analyses numériques, de protocoles d'essais simplifiés et des recherches de couplages entre modes de dégradations. Autant d'éléments qui permettent de répondre en partie aux questions initialement posées et de proposer, au final, un outil de simulation de durée de vie des DLC adapté aux applications moteur à combustion interne / The use of micrometric diamond-like carbon coatings (named DLC) are becoming widely used by automotive manufacturers in order to improve the efficiency of internal combustion engines by reducing the mechanical friction losses. Although DLC coatings generally exhibit excellent tribological properties and very low wear rates, their use in internal combustion engines shows that, subject to complex loadings, many degradation modes are observable. Untimely propagation of these latter upon the entire coated surfaces is a risk to control in order to guarantee the coating function over time. From one hand, this control implies to know and to understand all DLC degradation mechanisms when applied to engine components. On the other hand, it is necessary to possess lifetime simulation tools that can be used to optimize tribological systems in their early design. The work presented in this thesis has been guided by these goals and gathers experimental analyses of DLC-coated components, numerical analyzes, simplified testing protocols and coupling analyses of degradation processes. All these topics finally lead to the definition of a lifetime simulation tool adapted to DLC coated internal combustion engine applications

Wasserstofffreie tetraedrisch amorphe Kohlenstoffschichten, auch ta-C-Schichten, weisen aufgrund ihrer hohen Härte und Passivität überragende Reib- und Verschleißeigenschaften aus. In zahlreichen Anwendungen führen sie zu nennenswerter Reibungsminderung, höherer Verschleiß- und Fressbeständigkeit sowie besseren Notlaufeigenschaften. Sie sind kompatibel mit konventionellen Schmierölen, Wasser oder können auch trocken eingesetzt werden. In der vergleichsweise jungen Wissenschaft der Schichttribologie gibt es jedoch noch zahlreiche bemerkenswerte Phänomene, die bislang noch nicht ausreichend verstanden wurden. Hierzu zählt die Wechselwirkung von ta-C-Schichten mit fettsäurebasierten Schmierstoffen, welche aus Pflanzenölen gewonnen werden. Die vorhandenen Forschungsarbeiten berichten unter anderem von Supraschmierung (englisch Superlubricity), teilweise auch von starkem Verschleiß. Insbesondere der Supraschmiereffekt, bei dem die Reibungsverluste nahezu vollständig verschwinden, ist in Kombination mit nachhaltigen Schmierstoffen zum Erreichen aktueller klima- und umweltpolitischer Ziele von höchster Relevanz. In der vorliegenden Arbeit wird zunächst die Literatur zur Schmierstoffwechselwirkung von ta-C-Schichten umfassend aufgearbeitet. Anschließend wird die tribologische Interaktion speziell mit fettsäurebasierten Schmierstoffen anhand systematischer Experimente untersucht, wobei verschiedene Parameter, wie beispielsweise Schmiermittel, Temperatur, Flächenpressung und Gegenkörpermaterial eines oszillierenden Kugel-Scheibe-Modellsystems nacheinander variiert werden. Im Ergebnis werden Zustände des tribologischen Systems identifiziert, bei denen trotz höchster Härte der Oberfläche einer sehr starker Verschleiß auftritt. Dieses Phänomen wird als tribochemischer Verschleiß erkannt, von dem sonst sehr geringen abrasiven Verschleiß abgegrenzt und in Bezug auf die vorhandene Literatur eingeordnet. Unter anderen günstigen Umständen kann der Verschleiß an ta-C-Schichten unter der Messgrenze liegen und Supraschmierung auftreten. Sowohl für den tribochemischen Verschleiß als auch die Supraschmierung wird die Rolle der Kohlenstoff-Doppelbindung der Ölsäure herausgearbeitet, welche oft Hauptbestandteil fettsäurebasierter Schmierstoffe ist. Insgesamt können mit der Kombination von ta-C-Schichten und fettsäurebasierten Schmierstoffen verschiedene außergewöhnliche tribologische Eigenschaften erzielt werden. Eine dafür notwendige Systematisierung der möglichen Wechselwirkungen und erforderlichen Parameterfenster sind in dieser Arbeit dargelegt und bieten die Grundlage für eine zukünftige industrielle Anwendung von supraschmierenden Systemen.:Danksagung Abkürzungsverzeichnis 1. Einleitung 2. Grundlagen 2.1 Tetraedrisch amorphe Kohlenstoffschichten 2.1.1 Die Modifikationen des Kohlenstoffs 2.1.2 Klassifikation amorpher Kohlenstoffschichten 2.1.3 Wachstumsmechanismus 2.1.4 Beschichtungsverfahren 2.1.5 Eigenschaften und Struktur 2.1.6 Temperaturstabilität 2.1.7 Strukturaufklärung mit Raman-Spektroskopie 2.1.8 Technische Anwendung 2.2 Tribologie 2.2.1 Geschichte, Definition und Bedeutung 2.2.2 Beschreibung tribologischer Systeme 2.2.3 Reibung und Verschleiß 2.2.4 Schmierung und Stribeck-Kurve 2.2.5 Schmierstoffe 2.2.6 Tribologische Prüfung 2.2.7 Tribologie von Schichtsystemen 2.3 Superlubricity 2.3.1 Geschichte, Definition und aktuelle Bedeutung 2.3.2 Definition und Einteilung 2.3.3 Funktionsmodelle und Beispielsysteme 2.4 Tribologische Eigenschaften von ta-C-Schichten 2.4.1 Überblick 2.4.2 Eigenschaften der Oberfläche 2.4.3 Schmierung mit konventionellen Schmierstoffen und Additiven 2.4.4 Schmierung mit Gasen, feuchter Luft und Wasser 2.4.5 Superlubricity auf ta-C 2.4.6 Rehybridisierung und Grafitisierung 2.4.7 Verschleiß - Größenordnung und Mechanismen 2.4.8 Mechanisch dominierte Verschleißmechanismen 2.4.9 Tribochemische Prozesse 3. Arbeitsziele 4. Experimentelle Methoden 4.1 Tribologische Prüfung 4.1.1 Prüfkörpergeometrie und Flächenpressung 4.1.2 Werkstoffe und Beschichtungen 4.1.3 Verwendete Schmiermittel 4.1.4 Aufbau und Funktion des Tribometers 4.1.5 Versuchsdurchführung 4.1.6 Prüfparameter 4.1.7 Bestimmung der Reibung 4.1.8 Bestimmung des Verschleißes 4.1.9 Einordnung und Relevanz der untersuchten Systeme 4.1.10 Versuchsplanung 4.2 Raman-Spektroskopie 4.3 Mikroskopie 5. Ergebnisse 5.1 Tribochemischer Verschleiß 5.1.1 Referenzzustand 5.1.2 Schmierstoffeinfluss 5.1.3 Struktur der Kohlenstoffphase 5.1.4 Temperatureinfluss 5.1.5 Oberflächenzustand 5.1.6 Gegenkörpermaterial 5.1.7 Quantifizierung und Analyse des Verschleißmechanismus 5.2 Superlubricity 5.2.1 Schmierstoffeinfluss 5.2.2 Relative Schmierfilmhöhe 5.2.3 Rehybridisierung 5.2.4 Materialpaarung 6. Diskussion 6.1 Verschleiß an ta-C-Schichten 6.1.1 Abrasiver und tribochemischer Verschleiß 6.1.2 Tribochemischer Mechanismus 6.1.3 Verschleißkinetik 6.2 Reibungsminderung auf ta-C-Schichten 6.2.1 Ultra-low friction 6.2.2 Superlubricity 6.2.3 Glättung 6.2.4 Schmierungszustand 6.2.5 Bedeutung der Rehybridisierung für Superlubricity 6.3 Forschungsbedarf 7. Zusammenfassung und Ausblick Literaturverzeichnis / Hydrogen-free tetrahedral amorphous carbon coatings, called ta-C coatings, show superior friction and wear properties due to their high hardness and passivity. In numerous applications, they account for noteworthy friction reduction, increased wear and fretting resistance as well as improved emergency running properties. They are compatible with conventional lubrication oils and water, or can be used without lubricant. In the comparably young science of coating tribology there are further noteworthy phenomena, which are not sufficiently understood. One of them is the interaction of ta-C coatings with fatty acid-based lubricants, which can be derived from vegetable oils. Among other, existing research reports superlubricity and sometimes very strong wear. Especially superlubricity, where friction losses nearly vanish and sustainable lubricants are used, is a topic of utmost relevance to achieve current climate political and environmental goals. In the presented work, the available literature to lubricant interaction of ta-C coatings is comprehensively reviewed. Then, tribological interaction with fatty acid-based lubricants in particular is investigated with systematic experiments, successively varying parameters like lubricant, temperature, contact pressure and counter body material in an oscillating ball-on-flat model system. As a result, conditions of the tribological system are identified in which strong wear occurs, despite highest hardness of the surface. The phenomenon is then attributed to tribochemical wear, distinguished from usually much lower abrasive wear and discussed with respect to existing literature. In other beneficial circumstances, wear decreases below measurability and superlubricity can occur. For both tribochemical wear and superlubricity the role of the carbon double bond in oleic acid is highlighted, which is the main component fatty acid-based lubricants. In summary, various exceptional tribological properties can be achieved when combining ta-C coatings and fatty acid-based lubricants. This work presents both a systematic categorization as well as parameter windows, and thus the foundation for future industrial application of superlubricious systems.:Danksagung Abkürzungsverzeichnis 1. Einleitung 2. Grundlagen 2.1 Tetraedrisch amorphe Kohlenstoffschichten 2.1.1 Die Modifikationen des Kohlenstoffs 2.1.2 Klassifikation amorpher Kohlenstoffschichten 2.1.3 Wachstumsmechanismus 2.1.4 Beschichtungsverfahren 2.1.5 Eigenschaften und Struktur 2.1.6 Temperaturstabilität 2.1.7 Strukturaufklärung mit Raman-Spektroskopie 2.1.8 Technische Anwendung 2.2 Tribologie 2.2.1 Geschichte, Definition und Bedeutung 2.2.2 Beschreibung tribologischer Systeme 2.2.3 Reibung und Verschleiß 2.2.4 Schmierung und Stribeck-Kurve 2.2.5 Schmierstoffe 2.2.6 Tribologische Prüfung 2.2.7 Tribologie von Schichtsystemen 2.3 Superlubricity 2.3.1 Geschichte, Definition und aktuelle Bedeutung 2.3.2 Definition und Einteilung 2.3.3 Funktionsmodelle und Beispielsysteme 2.4 Tribologische Eigenschaften von ta-C-Schichten 2.4.1 Überblick 2.4.2 Eigenschaften der Oberfläche 2.4.3 Schmierung mit konventionellen Schmierstoffen und Additiven 2.4.4 Schmierung mit Gasen, feuchter Luft und Wasser 2.4.5 Superlubricity auf ta-C 2.4.6 Rehybridisierung und Grafitisierung 2.4.7 Verschleiß - Größenordnung und Mechanismen 2.4.8 Mechanisch dominierte Verschleißmechanismen 2.4.9 Tribochemische Prozesse 3. Arbeitsziele 4. Experimentelle Methoden 4.1 Tribologische Prüfung 4.1.1 Prüfkörpergeometrie und Flächenpressung 4.1.2 Werkstoffe und Beschichtungen 4.1.3 Verwendete Schmiermittel 4.1.4 Aufbau und Funktion des Tribometers 4.1.5 Versuchsdurchführung 4.1.6 Prüfparameter 4.1.7 Bestimmung der Reibung 4.1.8 Bestimmung des Verschleißes 4.1.9 Einordnung und Relevanz der untersuchten Systeme 4.1.10 Versuchsplanung 4.2 Raman-Spektroskopie 4.3 Mikroskopie 5. Ergebnisse 5.1 Tribochemischer Verschleiß 5.1.1 Referenzzustand 5.1.2 Schmierstoffeinfluss 5.1.3 Struktur der Kohlenstoffphase 5.1.4 Temperatureinfluss 5.1.5 Oberflächenzustand 5.1.6 Gegenkörpermaterial 5.1.7 Quantifizierung und Analyse des Verschleißmechanismus 5.2 Superlubricity 5.2.1 Schmierstoffeinfluss 5.2.2 Relative Schmierfilmhöhe 5.2.3 Rehybridisierung 5.2.4 Materialpaarung 6. Diskussion 6.1 Verschleiß an ta-C-Schichten 6.1.1 Abrasiver und tribochemischer Verschleiß 6.1.2 Tribochemischer Mechanismus 6.1.3 Verschleißkinetik 6.2 Reibungsminderung auf ta-C-Schichten 6.2.1 Ultra-low friction 6.2.2 Superlubricity 6.2.3 Glättung 6.2.4 Schmierungszustand 6.2.5 Bedeutung der Rehybridisierung für Superlubricity 6.3 Forschungsbedarf 7. Zusammenfassung und Ausblick Literaturverzeichnis

Piston rings cause significant friction losses within internal combustion engines. Especially the first compression ring, which is pressed onto the liner by high cylinder pressure, contributes significantly to the total friction loss of the piston assembly. The tribological behavior of the oil scraper ring is mainly related to the pretensioning force and can lead to high losses even at low and idle speed. Due to this, there is always a markable risk of wear for the contact surfaces of the piston rings and the cylinder. “Diamond-like carbon” coatings on the surface of the piston rings can prevent wear and are able to reduce friction in the ring-liner-contact. The purpose of this work was to investigate the tribological benefit of this coating-system on the compression and oil scraper ring. Experimental studies were carried out on a fired single-cylinder engine using the Indicated Instantaneous Mean Effective Pressure-method (IIMEP) for the crank angle-resolved detection of the piston assembly’s friction force. To be able to determine the component-related fractions of the friction loss and to quantify the hydrodynamic and asperity related parts locally and time dependent, an EHD/MBS model of the engine was created in AVL EXCITE and a simulative investigation was performed. This simulation was validated by the experimental work and provided detailed information about the individual contact conditions and gap height of each tribological contact of the piston group. The combined approach of measurement and simulation enabled the prediction of tribological aspects and performance in parameter studies on a virtual engine test bed.

Il est assez difficile pour la jeune génération d’électeurs démocrates qui ont contribué à porter Barack Obama au pouvoir en 2008 et 2012 d’imaginer l’état de déroute dans lequel se trouvait le parti démocrate après les victoires électorales de Ronald Reagan en 1980 et 1984. Obama doit sa double élection à la fois à l’efficacité de ses campagnes et aux changements qui ont affecté le parti démocrate depuis les années 1980. Certes, les élus démocrates n'avaient pas attendu l'échec humiliant de Jimmy Carter en 1980 pour engager un travail de réflexion mais c'est pendant les années Reagan que certains démocrates influents commencèrent à se mettre concrètement au travail. Le Democratic Leadership Council (DLC) fut la pièce maîtresse d'une sorte d'aggiornamento politique et idéologique qui permit au parti démocrate de reconstituer ses forces en moins de dix ans et de reconquérir la présidence en 1992 avec l’élection de Bill Clinton. Depuis le début des années 1980 jusqu’à sa disparition en 2011, le DLC se consacra à la modernisation idéologique du parti démocrate. / It is quite difficult for the young generation of Democratic voters who contributed to bring Barack Obama into power in 2008 and 2012 to imagine the electoral losing streak the Democratic Party endured after Ronald Reagan’s electoral victories in 1980 and 1984. Obama owes credit to both his efficient campaigns and the changes which have affected the Democratic Party since the 1980s for winning the executive office twice. The Democratic elected officials certainly had not waited for Jimmy Carter’s humiliating defeat in 1980 to reflect upon the situation but it is during the Reagan years that some Democratic influential members started taking action. The Democratic Leadership Council (DLC) became a key part of a sort of political and ideological aggiornamento which allowed the Democratic Party to rebuild its forces in less than ten years and to win back the executive office in 1992 with Bill Clinton’s election. From the early 1980s to its dissolution in 2011, the DLC devoted itself to the ideological modernization of the Democratic Party.

Die vorliegende Dissertation behandelt Charakterisierung, Modellbildung sowie Anwendung einer magnetfeldgestützten Hohlkathoden-Bogenentladung. Hohlkathoden sind seit den 1960er Jahren Gegenstand grundlagen- sowie anwendungsorientierter Forschung und werden seit 20 Jahren am Fraunhofer-Institut für Elektronenstrahl- und Plasmatechnik für die Anwendung auf dem Gebiet der Vakuumbeschichtung weiterentwickelt. Ziel dieser Arbeit ist es, die technologischen Fortschritte physikalisch zu verstehen und gezielte Weiterentwicklungen für spezifische Einsatzgebiete zu ermöglichen. In der untersuchten Hohlkathodenbauform ist das aus Tantal bestehende, vom Arbeitsgas Argon durchströmte Kathodenröhrchen koaxial von einer Ringanode sowie von einer Magnetfeldspule umgeben. Die Entladung wird durch Hochspannungspulse gezündet, worauf sich ein diffuser Bogen im Röhrchen (internes Plasma) ausbildet. Das Röhrchen wird von Plasmaionen auf hohe Temperaturen geheizt, die eine thermionische Emission von Elektronen ermöglichen, welche das Plasma speisen. Das technologisch nutzbare externe Plasma wird im Vakuumrezipienten durch Wechselwirkung der Gasteilchen mit Strahlelektronen aus der Kathode erzeugt. Bei starker Reduktion des Arbeitsgasflusses wird die Entladung durch das Magnetfeld der Spule stabilisiert. Der experimentelle Befund, dass dadurch Plasmadichte und -reichweite sowie ggf. die Ladungsträgerenergien im Rezipienten aufgrund des intensiveren Elektronenstrahls wesentlich gesteigert werden können, wird durch ortsaufgelöste Langmuir-Sondenmessung, optische Emissionsspektroskopie und energieaufgelöste Massenspektrometrie ausführlich belegt und nach der Lösung von Strom- und Wärmebilanzgleichungen durch die Verhältnisse im Kathodenröhrchen begründet. Neben Argon werden auch typische Reaktivgase der Vakuumbeschichtung im Hohlkathodenplasma betrachtet: zum einen Stickstoff und Sauerstoff, die in reaktiven PVD-Prozessen (physikalische Dampfphasenabscheidung) zur Beschichtung mit Oxid- bzw. Nitridschichten zum Einsatz kommen und durch Ionisation, Dissoziation und Anregung im Hohlkathodenplasma verbesserte Schichteigenschaften ermöglichen; zum anderen Azetylen, das bei PECVD (plasmagestützte chemische Dampfphasenabscheidung) von amorphen wasserstoffhaltigen Kohlenstoffschichten z. B. für tribologische oder biokompatible Beschichtungen genutzt wird. Azetylen wird durch Streuprozesse mit Elektronen und Ionen im Plasma aufgespalten, wodurch schichtbildende Spezies erzeugt werden, die am Substrat kondensieren. Durch die Wahl der Plasmaparameter sowie durch abgestimmte Substratbiasspannung und Substratkühlung lassen sich die Beschichtungsrate einstellen sowie polymer-, graphit- oder diamantartige Eigenschaften erzielen. Neben der Plasmadiagnostik mittels energieaufgelöster Massenspektrometrie werden die erzeugten Kohlenstoffschichten vorgestellt und hinsichtlich Härte, Zusammensetzung und Morphologie analysiert. / In the present thesis, characterization, modeling and application of a magnetically enhanced hollow cathode arc discharge are presented. Since the 1960s, hollow cathodes are being studied in basic and applied research. At Fraunhofer Institute for Electron Beam and Plasma Technology, further development concerning the application in vacuum coating technology has been carried out for about twenty years. The present work targets on physically understanding the technological progress in order to enable specific further development and application. In the investigated hollow cathode device, a ring-shaped anode and a magnetic field coil are arranged coaxially around the tantalum cathode tube, which is flown through by argon as the working gas. The discharge is ignited by high voltage pulses establishing a diffuse arc within the cathode tube (internal plasma). The cathode is being heated by the plasma ions to high temperatures, which leads to thermionic emission of electrons sustaining the plasma. The external plasma in the vacuum chamber, which can be used for technological applications, is generated by collisions of gas atoms with beam electrons originating from the cathode. In the case of strongly reduced working gas flow, the discharge is stabilized by the magnetic field of the coil; the related experimental findings such as significantly increased plasma density and range as well as higher charge carrier energies in the external plasma are extensively proved by spatially resolved Langmuir probe measurements, optical emission spectroscopy, and energy-resolved ion mass spectrometry. Furthermore, the results are correlated to the conditions within the cathode tube by solving the current and heat balance equations. Besides argon, typical reactive gases used in vacuum coating are examined in the hollow cathode plasma, too. First, nitrogen and oxygen, which are applied in PVD (physical vapor deposition) processes for the deposition of oxide and nitride layers, are ionized, dissociated, and excited by plasma processes. In the case of practical application, this plasma activation leads to improved film properties. Second, acetylene is used as a precursor for PECVD (plasma-enhanced chemical vapor deposition) of amorphous hydrogenated carbon films, e.g. for tribological or biocompatible applications. Acetylene is cracked by electron and ion scattering in the plasma providing film-forming species to be deposited on the substrate. The deposition rate as well as the polymeric, graphitic, or diamond-like properties can be controlled by plasma parameters, a defined substrate bias, and substrate cooling. The hollow cathode-generated acetylene plasma has been characterized by energy-resolved ion mass spectrometry, and the carbon films obtained are analyzed regarding hardness, film composition, and morphology.

Les organes de frottement en carbure de silicium répondent à des critères de fonctionnement exigeants grâce aux propriétés offertes par cette céramique. Son faible coefficient de dilatation thermique et sa bonne conductivité thermique la rendent moins sensible aux chocs thermiques que les autres céramiques et particulièrement, en frottement, où la génération locale de chaleur peut s’avérer importante. Ces performances tribologiques sont conditionnées par son environnement mécanique, par la nature de la face de frottement antagoniste et surtout par le comportement des éléments interfaciaux circulant dans le contact. Le frottement du couple homogène SiC/SiC dans une configuration anneau/anneau a tout d’abord été étudié et son mécanisme d’usure a été établi, montrant un glissement sec difficile et une usure prononcée. Des alternatives ont alors été étudiées : revêtement du carbure par du DLC ou remplacement de la contreface par une bague carbone-graphite. Les imprégnations des bagues carbone-graphites par différents composés, polymères avec la résine phénolique et le PTFE ou métallique avec l’antimoine permettent d’en façonner les propriétés et, par conséquent, la réponse tribologique. Les essais sont réalisés à l’aide d’un tribomètre en glissement rotatif et ont permis de caractériser ces comportements tribologiques en fonction de différentes conditions de pression de contact, de vitesse et de température. Une analyse thermique a également été développée grâce à l’utilisation d’une caméra thermique infrarouge et a permis d’identifier les flux thermiques et le champ de températures durant le frottement. Des analyses physico-chimiques par EDS et spectroscopie Raman ont permis de décrire les transferts de matière mis en jeu et ont mis en évidence des phénomènes locaux d’oxydation de l’interface. La forte participation des imprégnants du carbone-graphite à la formation du troisième corps a été montrée. La spectroscopie Raman a également permis d’étudier le caractère cristallin des surfaces et du troisième corps formé et de mettre en évidence des phénomènes de contraintes en surface à l’origine des mécanismes d’endommagement. Il a ainsi pu être reconstitué un scénario complet des différentes étapes du glissement en termes de bilans de matière et d’énergie dans le contact. / Silicon carbide friction bodies fulfill high operation criteria owing to the properties provided by this ceramic. Its low thermal expansion coefficient and good thermal conductivity make it less sensitive to thermal shocks than other ceramics and particularly in friction, where the local heat generation may be significant. These tribological performances are then conditioned by the mechanical environment, by the nature of the counterface and above all by the interfacial elements circulating inside the contact. The friction of the homogeneous SiC/SiC pair in a ring-on-ring configuration was first studied and its wear mechanism was redefined. A hard silicon carbide counterface showed a difficult dry sliding and a high wear, alternative materials were studied: DLC coating on silicon carbide rings or carbon-graphite rings. Impregnation of the carbon-graphite rings with different compounds, polymers with the phenolic resin and PTFE or metal with antimony, shaped its properties and therefore, the tribological behaviour. Friction tests are carried out using a rotary sliding tribometer. They characterized the tribological behaviour for different operating conditions of contact pressure, sliding velocity and temperature of the environment. In addition, a thermal analysis was also implemented by using an infrared thermal camera in order to identify heat flows in the system and the temperature field for the entire duration of the tests. Physico-chemical analysis using EDS and Raman spectroscopy permitted to describe the transfers of material which take place during the tests and highlighted the local oxidation phenomena of the interface. The strong contribution of the carbone-graphite impregnants to the formation of the third body was also shown. Raman spectroscopy was also used to examine the crystalline state of the surfaces and the third body. Raman spectroscopy highlighted also stresses which are the source of the damage mechanisms. The different stages of the phenomena taking place during sliding inside the contact in terms of material and energy balance were then described.

In this thesis Graphit-iC™, an amorphous carbon coating developed by Teer Coatings Ltd. was modified and deposited onto CoCr and WHMWPE substrates in order to improve the wear properties. It was identified that depositing a hard coating onto soft substrate would cause high stresses and lead to coating delamination. Consequently the polyethylene substrates were ion implanted with nitrogen to reduce the hardness differential at the substrate-coating boundary. The coating was characterised using a pin on disc method in order to determine wear and friction. Hardness and fatigue was characterised using nano-indentation and the coating adhesion was measured using scratch testing. Application of the coatings resulted in a significant reduction in wear. Wear factors as low as 3.65x10¯18m³/Nm were achieved for coated CoCr substrates compared to 3.53x10¯15m³/Nm reported in the literature for uncoated CoCr. The coating resulted in friction coefficients between 0.12 and 0.19 with hardness ranging from 6.65 and 15.63GPa. Similarly coating UHMWPE resulted in a reduction in the wear factor to less than 9.6x10¯17m³/Nm. It was concluded that the deposition of amorphous carbon coatings can improve wear of hip joint prostheses, although consideration must be made for the adhesion of the coating to the substrate so that it does not contribute to an early failure of the device. Improved adhesion can be achieved by reducing the hardness differential between the coating and adhesion, either through softening the coating or by using interlayers.

Neste trabalho é apresentado o estudo teórico-experimental a respeito das propriedades piezoresistivas de dois tipos de materiais com estrutura amorfa. O primeiro material estudado é o carbono semelhante ao diamante e o segundo é o óxido de estanho dopado com índio. O estudo compreende o levantamento bibliográfico sobre os materiais, projeto teórico e prático de estruturas individuais de testes e piezoresistores configurados em ponte completa, além da realização das caracterizações elétricas, mecânicas e térmicas de acordo com um arranjo experimental proposto. As caracterizações experimentais foram implementadas usando a técnica de flexão de uma viga engastada e a teoria das pequenas deflexões. Os diferentes materiais caracterizados e analisados apresentaram o efeito piezoresistivo e um sinal de sensibilidade mecânica condizente com as características esperadas para estes filmes. Ambos os filmes respondem as variações da temperatura de forma linear e apresentam uma direção de dependência com a temperatura. Os filmes de carbono amorfo hidrogenado livre de dopantes apresentam curvas de corrente e tensão características indicando um mecânismo de condução elétrica complexo devido a sua diversidade de microestruturas e relacionado aos parâmetros de processos de deposição. Os filmes com nitrogênio são mais estáveis termicamente com coeficientes da ordem de - 4900 ppm/ºC. Os resultados encontrados indicam a existência de dois tipos de portadores de cargas responsáveis pela mobilidade média, resistividade e efeito piezoresistivo. Os filmes de óxido de estanho dopado com índio livre e com 5 % e 10 % de oxigênio no plasma apresentam características de diminuição da resistência elétrica com o esforço mecânico e exibem efeitos de piezoresistividade na faixa de - 12 a - 23. Amostras destes filmes com oxigênio apresentaram um fator de sensibilidade mecânica muito baixa e são menos estáveis termicamente que as amostras livres de oxigênio. Os filmes estudados podem ser usados em aplicações envolvendo extensiometria ou mesmo em sensores de pressão piezoresistivos após adequação do processo de deposição e de recozimentos térmicos. / This tesis presents the piezoresistivity theoretical and experimental study for two materials with amorphous structure. The first material is the Diamond Like Carbon and the other is the Indium Tin Oxide. The work includes the bibliographic study, theoretical and practical design of structures for testing individual and piezoresistors configured in bridge, in addition to the completion of the characterizations electrical, mechanical and thermal according to a proposed experimental arrangement. The experimental characterizations have been implemented using the technique of cantilever and the theory of small deflections. The different materials analyzed showed the piezoresistive effect with some order of magnitude and a sign of sensitivity to mechanical stress of tension consistent with the characteristics expected for these types of films. Both films respond to changes in temperature in a very linear and have a direction of dependency with the temperature according to the literature. The films of free doping have curves of current and voltage characteristics for this type of material indicating a mechanism of electric conduction very complex because of its diversity of microstructures and processes related to the parameters of the deposition and films with nitrogen are more thermally stable with coefficients of order of - 4900 ppm/ºC. The results indicate the existence of two types of charge carriers responsible for the average mobility and hence the resistivity and the piezoresistive effect. The films of indium tin oxide free and with some oxygen content in plasma presents characteristics of decreased electrical resistance to mechanical stress and exhibit effects of piezoresistive in the range of - 12 to - 23. Samples of these films with oxygen showed a factor of very low mechanical sensitivity and are less stables to thermal effect the samples free of oxygen. The films studied can be used in certain applications such strain gauges or even in piezoresistive pressure sensors, after adequate process of deposition and thermal annealing.

Orientador: Jorge Muniz Júnior / Coorientadora: Andréia Maria Pedro Salgado / Banca: Arminda Eugênia Marques Campos / Banca: Adriana Leônidas de Oliveira / Resumo: A Qualidade de Vida no Trabalho (QVT) é uma área que vem crescendo muito nos últimos anos. As empresas vêm percebendo o quão importante é cuidar da qualidade de vida de seus funcionários e que este cuidado não traz benefícios apenas para o trabalhador, mas principalmente para os resultados da empresa. Este trabalho buscou comparar a QVT dos funcionários que trabalham na área administrativa com os que trabalham na área da produção e verificar possíveis indicadores de melhoria a serem sugeridos para essa empresa montadora automotiva. O trabalho explicita a importância da qualidade de vida, do bem-estar e da QVT dos funcionários para o crescimento e evolução da empresa em que estão inseridos. Trata-se de uma pesquisa com características aplicadas, na qual foi utilizado o questionário QWLQ-bref (com utilização da escala Likert) e posterior entrevista com o mesmo questionário (de forma discursiva). Foram questionados 64 funcionários, sendo 30 da área administrativa e 34 da linha de produção. Assim como 10 entrevistas, sendo 5 com funcionários da área administrativa e 5 da produção. Foi encontrado um nível de QVT de 3,73 (escala de 1 a 5) para a área administrativa contra um de 3,72 para a área da produção. A diferença mínima gerou a necessidade de se diferenciar a QVT para nível de escolaridade, idade, tempo de serviço e cargos. No fim encontraram-se as insatisfações das duas áreas, as quais o trabalho sugere que sejam feitas melhorias. Para a área administrativa constatou-se muit... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The Quality of Work Life (QWL) is an area that has very grown in recent years. Companies are realizing how important it is to take care of the quality of life of its employees and that this care does not bring benefits only to workers, but mainly to the company's results. This study aimed to compare the QWL of employees working in the administrative area with those who work in the production area and check for possible improvement of indicators to be suggested for this company automotive assembly plant. The paper explains the importance of quality of life, well-being and QWL of officials to the growth and evolution of the company to which they belong. This is a research with applied characteristics, which was used QWLQBREF questionnaire (with use of a Likert scale) and subsequent interview with the same questionnaire (discursive form). 64 employees were questioned, 30 of administrative and 34 production line. As well as 10 interviews, 5 with administrative workers and 5 production. QLW has found a level of 3.73 (scale from 1 to 5) for the administrative area from a production area to 3.72. The minimum difference generated the need to differentiate the QWL for education level, age, service time and positions. At the end of the dissatisfactions we met the two areas, which work suggests that improvements are made. For the administrative area found out a lot of dissatisfaction with the lack of training and the productive area dissatisfaction was found to the problems with sleep. ... (Complete abstract click electronic access below) / Mestre

<p>Recent developments in thin film synthesis of diamond have facilitated a host of new technical applications. These are motivated by the many attractive properties of diamond, for example high hardness, chemical inertness, transparency and heat conductivity. Unfortunately, these properties also make it difficult to fashion complex geometries. Other problems are the severely limited choice of suitable substrate materials and large surface roughness. To reduce these complications, a technology denoted <i>replication and bodybuilding</i> has been developed. The basic principle is to grow the diamond film onto a mold and then build a mechanical support on top of the diamond film. Then the mold is removed. Thereby, a diamond surface with the desired 3D geometry and the same surface roughness as the mold is created.</p><p>Three potential applications for devices built using the replication and bodybuilding concept have been explored. <i>Grinding tools for hard materials</i> have proved superior to conventional technology in rate of removal as well as in resulting surface finish. Diamond surfaces have also been crafted into <i>ultra-durable dies for injection molding</i> of hard particle reinforced polymers. Initial testing of an <i>abrasive diamond device</i>, intended to make CMP processes more economical and easier to control has successfully been carried out.</p><p>Diamond and diamond-like carbon is well-known for being “low-friction materials”, but are here demonstrated to actually be “high-friction materials” with the ability to disguise themselves in certain environments, most notably with the aid of water molecules. The mechanisms involved in these variations have been investigated. Using NEXAFS it is shown that high friction sliding is accompanied by changes in the material structure. These changes are induced by surface roughness as well as by strong adhesive forces.</p><p>Highly hydrogenated carbon coatings, on the other hand, affording super-low friction coefficients (<0.01) under certain circumstances, will suffer an increase in friction in the presence of water.</p>