In this thesis, research on synthesis, structure and characterization of amorphous carbide-based thin films is presented. Crystalline and nanocomposite carbide films can exhibit properties such as high electrical conductivity, high hardness and low friction and wear. These properties are in many cases structure-related, and thus, within this thesis a special focus is put on how the amorphous structure influences the material properties. Thin films within the Zr-Si-C and Cr-C-based systems have been synthesized by magnetron sputtering from elemental targets. For the Zr-Si-C system, completely amorphous films were obtained for silicon contents of 20 at.% or higher. Modeling of these films, as well as experimental results suggest that the films exhibit a network-type structure where the bond types influence the material properties. Higher hardness and resistivity were observed with high amounts of covalent Si-C bonds. Several studies were performed in the Cr-C-based systems. Cr-C films deposited in a wide composition range and with substrate temperatures of up to 500 °C were found to be amorphous nanocomposites, consisting of amorphous chromium carbide (a-CrCx) and amorphous carbon (a-C) phases. The carbon content in the carbidic phase was determined to about 30-35 at.% for most films. The properties of the Cr-C films were very dependent of the amount of a-C phase, and both hardness and electrical resistivity decreased with increasing a-C contents. However, electrochemical analysis showed that Cr-C films deposited at higher substrate temperature and with high carbon content exhibited very high oxidation resistance. In addition, nanocomposite films containing Ag nanoparticles within an amorphous Cr-C matrix were studied in an attempt to improve the tribological properties. No such improvements were observed but the films exhibited a better contact resistance than the corresponding binary Cr-C films. Furthermore, electrochemical analyses showed that Ag nanoparticles on the surface affected the formation of a stable passive film, which would make the Cr-C/Ag films less resilient to oxidation than the pure Cr-C films.

Élaborer et optimiser des nouveaux matériaux restent toujours parmi les enjeux liés à l'amélioration de la performance de la durabilité des matériaux.Le domaine des traitements de surface et plus particulièrement les nanotechnologies utilisées pour produire des revêtements en couches minces plus précisément les dépôts physiques en phase vapeur (PVD), permet de synthétiser des nouveaux matériaux qui peuvent résister dans des conditions sévères de diverses applications.L'industrie des outils de coupe et plus précisément le bois dans notre cas, nécessitent de plus en plus la synthèse des nouveaux matériaux et nanomatériaux pour améliorer la tenue en service des outils de coupe.L'objectif de ce présent travail est de développer et caractériser des revêtements dont le matériau de base est le chrome et/ou le silicium en vue de les optimiser. L'élaboration a été réalisée par différentes méthodes à savoir la pulvérisation cathodique magnétron radio fréquence ou encore en mode courant direct. En outre, la RGPP (reactive gas pulsing process) a été exploité pour la première fois dans ce travail dont le but est de surmonter les difficultés rencontrées avec la pulvérisation réactive.Les différentes caractéristiques mécaniques et tribologiques des couches ont été étudiées et corrélées avec les caractéristiques physicochimiques et microstructurales.Il s'avère que la pulvérisation cathodique en mode courant direct prouve son importance par l'obtention des couches de meilleure qualité que celles obtenues en mode radio fréquence. Pour des contenus d'azote similaires on obtient des propriétés mécaniques et tribologiques plus importantes. On note que les propriétés mécaniques réalisent un gain de 60 % par rapport à celles obtenues en mode RF. En outre l'ajustement des paramètres de la méthode RGPP (le rapport cyclique et la période des pulses) influe considérablement les caractéristiques des couches obtenues et on montre une amélioration de la performance des couches. A l'issue de l'injection pulsée du gaz réactif, on montre que l'alternance entre l'ouverture et la coupure de la vanne du gaz réactif est indispensable pour la déposition dans un milieu réactif afin d'éliminer les composés métalliques sur les cibles obtenus lors de dépôt.Enfin, l'ajout de silicium au CrN mène à obtenir des solutions solides ou une structure nanocomposite selon la teneur de silicium dans la couche ce qui implique une amélioration des caractéristiques mécaniques et par la suite celles tribologiques.L'apport de ce travail de thèse est de présenter une étude globale sur la performance des couches CrN et CrSiN en corrélant ses caractéristiques mécaniques et tribologiques avec les paramètres physiques de dépôt et en adoptant plusieurs méthodes d'élaboration.

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

Zugl.: Aachen, Techn. Hochsch., Diss., 2007

Zugl.: Aachen, Techn. Hochsch., Diss., 2008. / Hergestellt on demand.

Zugl.: Aachen, Techn. Hochsch., Diss., 2008.

Zugl.: Aachen, Techn. Hochsch., Diss., 2008. / Hergestellt on demand.

Stuttgart, Univ., Diss., 2004.

Zugl.: Bayreuth, University, Diss., 2009.

Aachen, Techn. Hochsch., Diss., 2004