Hard nanostructured TiAlN coatings have gained high importance in the field of protective tribological coatings. Nevertheless, their use regarding high temperature (>800°C) applications such as dry high speed machining still remains a challenge. Addition of elements such as Ta or Y has shown a beneficial impact on these properties. But for a better performance of these coatings, an in-depth understanding of their oxidation and wear mechanisms over a wider range of temperatures is needed which is currently unavailable in the literature. This work investigated the wear and oxidation properties of AlTiTaN hard coatings deposited by reactive magnetron sputtering at a substrate temperature of 250°C. Depending on process conditions, coatings with a preferential crystallographic orientation of cubic {111} or {200} with a columnar microstructure were observed. The oxidation and wear mechanisms for these coatings were investigated between 700°C and 950°C in air for various test durations. Further, the influence of Y doping in AlTiTaN coating was also studied.By combining Dynamic-Secondary Ion Mass Spectrometry ,X-ray diffraction (XRD) and Transmission Electron Microscopy measurements, it was demonstrated that a single amorphous oxide layer comprising of Ti, Al and Ta oxides formed at 700°C became a bilayer composed of a crystalline Al rich layer (protective Al2O3) and a Ti/Ta rich oxide layer at 900°C. The oxidation mechanism was governed primarily by inward diffusion of O at 700°C while from 800°C onwards outward diffusion of Al and inward diffusion of O controlled the reaction rate. A correlation between the oxidation kinetics and wear mechanism of AlTiTaN coatings, investigated at 700°, 800° and 900°C, was established. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Hartstoffschichten ermöglichen die Verbesserung bewährter und die Entwicklung neuartiger Produkte. Bei geringstem Materialaufwand lassen sich mit solchen Schichten Wirkungen erzielen, die auf eine andere Weise nicht erreichbar wären. Dünne Hartstoffschichten bis 10 µm werden seit Jahrzehnten zum Verschleißschutz von Werkzeugen und Bauteilen eingesetzt. Der zu den PVD-Verfahren zählende Vakuumbogenprozess (Arc-PVD) wird in der Industrie in großem Umfang zur Abscheidung nitridischer Hartstoffschichten eingesetzt. Als besonders vorteilhaft sind dabei die hohe Ionenenergie im fast vollständig ionisierten Plasma, die damit verbundenen hervorragenden Schichteigenschaften (Mikrohärte, Haftung, Struktur) und die relativ unkomplizierte, robuste und flexible Anlagentechnik anzusehen. Im Rahmen dieser Arbeit wurde ein nanostrukturierte AlCr(Si)N/TiN Hartstoffsystem entwickelt, welches sich mit dem Arc-PVD-Prozess homogen in Schichtdicken größer 50 µm aufbringen lässt und damit neue Einsatzbereiche für die Hartstoffbeschichtung eröffnet. Durch das definierte Schichtdesign im Nanometermaßstab kann einerseits das Eigenspannungsniveau stark abgesenkt werden und zusätzlich wird das Wachstum von Defektstrukturen unterdrückt. Die gewonnen Erkenntnisse bei der Herstellung dicker Schichten ermöglichen auch Verbesserungen der Eigenschaften dünner Schichten bis 10 µm.

Les vis à rouleaux satellites (VAR) équipent certains actionneurs électromécaniques du secteur aéronautique, et permettent de transformer un mouvement de rotation en un mouvement de translation. Ces systèmes sont constitués d’aciers inoxydables martensitiques trempés, et sont habituellement lubrifiés à la graisse. Comme pour beaucoup d’autres pièces de roulement, l’adhésion-grippage peut survenir bien avant la durée de vie théorique calculée en fatigue de roulement. La charge actionnée par la vis est portée par un ensemble de contacts entre les filets de la vis, des rouleaux et de l’écrou. Chaque contact peut être décrit comme un contact de type ellipsoïde sur plan soumis à de fortes pressions de contact (3-4 GPa), et à une cinématique de roulement associée à une composante de glissement transverse (jusqu’à 10 % de taux de glissement). L’objectif de la thèse est de comprendre les mécanismes d’endommagement dans les VAR, d’étudier l’influence des paramètres de design et d’utilisation sur ces mécanismes au travers de paramètres tribologiques, et de proposer une ou plusieurs solutions permettant d’améliorer le comportement et la durée de vie. Le contact est simulé expérimentalement par un galet torique en roulement sur un disque plan. Un tribomètre rotatif est utilisé pour reproduire la cinématique de contact avec un glissement perpendiculaire au roulement. L’effort tangentiel transverse lié au glissement est mesuré, ainsi que la vitesse de roulement du galet. Une caméra et un microscope installés au-dessus du disque permettent de réaliser un film image par image de l’évolution de la piste usée au cours des essais. Le comportement du contact acier / acier sans lubrification est d’abord étudié, et montre une usure adhésive catastrophique dès les premiers cycles. Plusieurs aspects du comportement en contact lubrifié à la graisse sont alors étudiés, en particulier les mécanismes d’alimentation spécifiques liés au glissement transverse, ainsi que les degrés d’instabilité de la sous-alimentation qui peuvent être cartographiés en fonction des paramètres d’entrée (pressions, vitesse, taux de glissement). Un revêtement couche mince du type WC/C est également étudié en remplacement de la graisse. L’étude de son comportement montre une étape de rodage importante puis une phase de bas frottement, qui se termine par une phase d’endommagement par usure abrasive. Un endommagement secondaire du revêtement lié à la fatigue de contact a également été identifié, et les conditions de son apparition par rapport aux conditions de sollicitation ont été cartographiées. L’analyse des résultats expérimentaux obtenus permet de proposer des pistes pour le design et le choix des matériaux pour améliorer le comportement et la durabilité des VAR. / The planetary roller screw (PRS) mechanism is used in the aeronautics industry for electro-mechanical actuators application. It transforms a rotational movement into a translation movement, and it is designed for heavy loads. The main components are made of martensitic stainless steels, and lubricated with grease. Like most usual rolling mechanisms, smearing and jamming can occur before the theoretical fatigue lifetime, especially in poor lubrication conditions. The actuated load is carried by small contacts between the threads of the screw, the rollers and the nut. The static single contact can be described as an ellipsoid on flat contact with high contact pressure (3-4 GPa). The motion consists of rolling with spin associated with side slip (up to 10 %). The aim of this PhD work is to investigate the wear behavior for different operating and design parameters of PRS such as load, speed, slip ratio, lubrication and material structure, in order to improve behavior and lifetime of PRS. The contact is experimentally simulated by a free rolling roller loaded on a rotating disk. A specific tribometer is used to create a contact with a side slip component, i.e. perpendicular to the rolling direction. The roller rolling speed and the tangential force generated by the slip ratio are measured. Also, an optical device is set on the tribometer to make a film of the evolution of the track outside of the contact. Steel on steel wear behavior is first presented. Then, several aspects of the greased lubricated contact are studied such as the feeding mechanisms related to the specific kinematics, and susceptibility to smearing in relation with tests input parameters. The feeding mechanisms are mapped as a function of input parameters (contact pressure, rolling speed, and sliding ratio). The wear behavior of hard carbon-based coatings with and without grease is also investigated. It shows good performance for the roller-screw application. The coating lifetime is governed by a three-body wear mechanism, but the experiments also reveal a progressive cracking in the rolling direction, i.e. perpendicular to the sliding direction. Lastly, a wear mode map is proposed to illustrate the competition between the two damage modes depending on the tests input parameters. The analysis of experimental results allows us to propose ways to improve the design and the selection of materials in order to increase the behavior and the durability of PRS.

Orientador: Juno Gallego / Resumo: O desgaste abrasivo é uma das causas de falhas em equipamentos e responsável por prejuízos nos processos industriais. Uma técnica capaz de minimizar os efeitos deste fenômeno é a aplicação de revestimentos duros nas superfícies críticas. Recentemente foram desenvolvidos revestimentos contendo carbonetos de titânio formados pela fusão de misturas contendo cavacos das ligas ASTM F67 e ASTM F136 sobre peças de aço-carbono ASTM A-36. Após a aplicação do processo de soldagem GTAW obteve-se significativa fração volumétrica de TiC grosseiro com elevada dureza. No presente trabalho foi investigada a refusão dessas soldas pelo processo de soldagem a Laser Nd:YAG pulsado. A microestrutura das amostras foi analisada por difração de raios-X (DRX), microscopia eletrônica de varredura (MEV) e microdureza Vickers. A caracterização microestrutural mostrou que houve refinamento dos carbonetos de titânio (TiC) na matriz ferrítica refundida com o Laser, cujo principal efeito foi um endurecimento do metal de solda. A caracterização mecânica demonstrou um aumento na microdureza da superfície do material. Este comportamento favorece o uso da refusão a Laser para a melhoria da qualidade das superfícies que demandam maior resistência ao desgaste abrasivo. / Mestre

Submitted by GABRIEL INÁCIO PONTIN null (gabrielguaira@hotmail.com) on 2017-08-15T18:00:10Z No. of bitstreams: 1 Dissertação Final - Gabriel Inacio Pontin.pdf: 2725651 bytes, checksum: f1433687bb33e3c16dd042c87cb686db (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-08-22T17:44:39Z (GMT) No. of bitstreams: 1 pontin_gi_me_ilha.pdf: 2725651 bytes, checksum: f1433687bb33e3c16dd042c87cb686db (MD5) / Made available in DSpace on 2017-08-22T17:44:39Z (GMT). No. of bitstreams: 1 pontin_gi_me_ilha.pdf: 2725651 bytes, checksum: f1433687bb33e3c16dd042c87cb686db (MD5) Previous issue date: 2017-07-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O desgaste abrasivo é uma das causas de falhas em equipamentos e responsável por prejuízos nos processos industriais. Uma técnica capaz de minimizar os efeitos deste fenômeno é a aplicação de revestimentos duros nas superfícies críticas. Recentemente foram desenvolvidos revestimentos contendo carbonetos de titânio formados pela fusão de misturas contendo cavacos das ligas ASTM F67 e ASTM F136 sobre peças de aço-carbono ASTM A-36. Após a aplicação do processo de soldagem GTAW obteve-se significativa fração volumétrica de TiC grosseiro com elevada dureza. No presente trabalho foi investigada a refusão dessas soldas pelo processo de soldagem a Laser Nd:YAG pulsado. A microestrutura das amostras foi analisada por difração de raios-X (DRX), microscopia eletrônica de varredura (MEV) e microdureza Vickers. A caracterização microestrutural mostrou que houve refinamento dos carbonetos de titânio (TiC) na matriz ferrítica refundida com o Laser, cujo principal efeito foi um endurecimento do metal de solda. A caracterização mecânica demonstrou um aumento na microdureza da superfície do material. Este comportamento favorece o uso da refusão a Laser para a melhoria da qualidade das superfícies que demandam maior resistência ao desgaste abrasivo. / The abrasive wear is one of the causes of failures in equipment and responsible for damages in industrial processes. A technique capable of minimizing the effects of this phenomenon is the application of hard coatings on critical surfaces. Recently, coatings containing titanium carbides produced by melting mixtures containing ASTM F67 and ASTM F136 chip blends on ASTM A-36 carbon steel parts have been developed. After an application of the GTAW get process, an important volumetric fraction of coarse TiC with high hardness was obtained. In the present work the remelts is investigated for welds by the pulsed Nd: YAG Laser process. A microstructure of the samples was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Vickers microhardness. The microstructural characterization showed that there was a refinement of the titanium carbides (TiC) in the ferritic matrix remelt with the Laser, whose main effect was a hardening of the weld metal. The mechanical characterization showed an increase in the microhardness of the material surface. This behavior favors the use of laser cladding to improve the quality of surfaces that require high abrasive wear resistance.

With the amalgamation of hard coating in cutting tools industries for three decades now, a stage with proven performance has been reached. Today, nearly 40% of all cutting tools used in machining applications are sheltered with coatings. Coatings have proven to dramatically improve wear resistance, increase tool life and enable use at higher speed. Over the years TiN, TiAlN and TiC have emerged as potential materials to coat machining tools. Chemical vapor deposition was the first technology to be used to deposit these coatings followed by physical vapor deposition. Currently, extensive use is being made of cathodic arc evaporation and sputtering for coatings components. The principal limiting factor in the performance of these cutting tools lies in their failure due to the brittleness of these coatings. These hard coatings, usually coated on soft steel substrates, are subjected to contact damage during service. This contact damage is driven by mismatch strain between the elastically deforming film on a plastically deforming substrate. Understanding of the contact damage is the key parameter for improvement in the coating design. Contact damage involves initiation of cracks and subsequent propagation within coating. Multiple cracking modes are seen in nitride coatings on soft substrate and mutual interaction of cracks may lead to spallation of the coating, exposing the substrate to extreme service conditions. Hence visualization of subsurface crack trajectories facilitates the classification of benign and catastrophic modes of failure, which consequently allows us to tailor the coating architecture to eliminate catastrophic failure. Multilayers have shown to perform better then monolayer coatings. In multilayer coatings, application specific particular properties can be engineered by alternately stack-ing suitable layers. The multilayer utilizes benefits of interfaces by crack deflection, crack blunting and desirable transition in residual stress across the interface. Hence, designing interfaces is the key parameter in the multilayer coating. However, very few studies exist that describe experimental visualization of deformation modes in multilayer coatings with different types of interfaces, e.g. nitride/nitride and nitride/metal. Thus the prime objective of the present study is to comprehend the influence of different interface structures as well as its architecture on the various contact damage modes in these coatings. TiAlN/TiN has shown better tribological properties compared to its constituent monolayers. There is an order of magnitude augmentation in loads for cracking without any hardness enhancement relative to monolayers of constituents, with the additional feature that both constituents exhibit similar hardness and modulus. The resistance to cracking is seen to increase with increase in number of interfaces. Hence this uniqueness in toughening without drastic reduction in mechanical properties provides the motivation for understanding the fundamental mechanisms of toughening provided by the interfaces in these hard/hard coatings. Another combination for the present study is with interfaces between hard-soft phases ZrN/Zr, a composite that seeks to compromise hardness in order to achieve greater toughness. The selected combination has potential of providing a model system without any substoichiometric nitrides influencing the interfacial structure. There is a great need to optimize the metal fraction/thickness for exploiting the benefits of toughening without much compromise on hardness and stiffness, since the principal applications of these coatings lies in preventing erosive and corrosive wear. As all the deformation modes in theses coatings are stress driven, the influence of different variables on stress field would dictate the emerging damage. To understand the role of stress fields on contact damage, finite element method and an analytical model was used to predict the stress field within the coating. The TiAlN/TiN coatings were deposited by cathodic arc evaporation, while sputtering was employed to procure the ZrN/Zr multilayer coatings with much finer layer spacing. Microstructural characterization of the as received coatings was done by XRD, scanning electron microscopy, focused ion beam cross section machining and transmission electron microscopy. Mechanical properties like hardness and modulus were evaluated by nanoindentation with restricted penetration depths to allow measurements that were not influenced by the substrate. Contact damage was induced by micro indentation at high loads. Indentations were examined from plan view as well as cross section for getting details of crack nucleation as well as propagation trajectories. Focused ion beam was used to examine cross sections of indents as well as to prepare electron transparent thin foils for transmission electron microscopy examination of subsurface damage induced by indentation. To emphasize specific issues in detail, the present work is divided into four sections: 1 Microstructure and mechanical characterization of the as deposited coatings of ZrN/Zr multilayer (while that of TiAlN/TiN has been reported elsewhere) 2 Details of contact damage in ZrN/Zr coating 3 Resolution of micro mechanistic issues in TiAlN/TiN coating utilizing detailed microscopy 4 The effect of change in architecture through heat-treatment of ZrN/Zr multilayer coatings on the mechanical behavior and contact damage Detailed microstructural, compositional and mechanical characterization was done on ZrN/Zr as received multilayer coatings. Thickness of metal layer was seen to influence the texture in the nitride, thick metal acquiring basal texture in turn inducing (111) texture in the nitride to reduce interfacial energy. Microstructure revealed that the nitride grows with interrupted columnar grains, renucleating at each metal/nitride interface. Presence of both phases was confirmed at even very low bilayer spacing, with slight changes in multilayers architecture, from planar interfaces to curved interfaces. The chosen system proved to be an ideal system for multilayer study without formation of secondary nitrides. Residual stress and hardness reduced with increase in metal layer thickness, whereas modulus was seen to follow the rule of mixture value. Detailed contact damage study of ZrN/Zr is reported in section two with influence of volume fraction and metal layer thickness. All the experimental results were corroborated with finite element methods. A comparative study of contact damage of multilayer with monolayer was carried out with cross section as well as plan view of indents. Metal plasticity was able to distribute damage laterally as well as vertically, hence reducing the stress concentration. There lies an optimum thickness of the metal providing maximum toughening by increasing the threshold load required for edge cracking. The sliding of columns is resisted by the metal. However, thick metal layers promote microcracking in individual nitride layers. Cracking is restricted to within individual nitride layers, eliminating through thickness cracking. The intermediate metal thickness was able to provide a mechanism of laterally distributing sliding and hence a higher tolerance level of the indentation strain that can be accommodated without cracking. Thin metal multilayers were seen to show delamination, strongly influenced by the multilayer architecture. We use the finite element method to understand the influence of stress fields in driving these various modes of damage for varying volume fraction and metal layer thicknesses. It is demonstrated how metal plasticity results in stress enhancement in the nitride layer compared to a monolayer and reduces the shear stress, which is the driving force for columnar sliding. The micro cracking to columnar shearing transition with metal thickness was explained with the help of average shear and normal stress across the multilayer which could explain the transition from cracking and sliding to interfacial delamination in thin metal layer multilayers with enhancement in interfacial shear stress. TiAlN/TiN multilayer allowed to exploit a form of compositional contrast to measure the strain with respect to depth. Layers acting as strain markers quantify the amount of sliding in terms of the offset in layers with respect to depth within the coating. We illustrate with transmission electron micrographs, the flaw generation that occurs as a result of sliding of misaligned column boundaries. These boundary kinks,upon further loading, may lead to cracks running at an angle to the indentation axis in an otherwise dense, defect free, as deposited coating. A previous study illustrates the increase in resistance of multilayers to multiple modes of cracking that are seen in the monolayer nitride coatings on steel substrates. We provide evidence of the enhanced plasticity, seen as macroscopic bending, which in reality is column sliding in a series of distributed small steps. We discuss the role of misfit dislocations in spreading the material laterally to accommodate the constraints during indentation and lattice bending. Interfacial sliding is seen to reduce the stress concentration by distributing the vertical column sliding and accommodating the flaws generated by the sliding of misaligned column boundaries. Some preferred boundaries with special orientation relations do slide, while near the substrate, the sliding is facilitated by the relaxation in intrinsic residual stresses. An analytical model which was formulated earlier is used to support our experimental findings. Investigations of the plausible reasons for the naturally occurring multilayer mollusc sea shells to reach stiffnesses equal to the upper bound of the rule of mixture value have concluded that its brick and mortar organization is responsible for its exceptional mechanical properties. Inspired by the same model, heat treatment was used to change the architecture of the soft-hard metal/nitride combination from that of the planar interface of the as deposited multilayer to a brick and mortar arrangement. Such an interconnected ZrN microstructure was successfully achieved and the stiffness and hardness were both seen to increase relative to the as received coatings. The possible reasons for this enhancement are discussed in term of this newly emerged architecture ,change in residual stress as well as changes in stoichiometry after heat treatment. The contact damage, though, was found to be more catastrophic relative to the as deposited coating with increased propensities for edge and lateral cracking. This was attributed to the interconnected nitrides formed in the brick and mortar architecture as well as residual stress changes due to the dissolution of Zr in ZrN to form off-stoichiometric nitrides. The cracks feel the presence of the metal and deviate from the otherwise smooth trajectory and take a path along the interface of the metal packet and the interconnected nitride. Summarizing, the present study clearly illustrates the fact that interfaces play an important role in damage control under contact loading. Fracture and deformation are either controlled by metal plasticity, distributing the column sliding in metal/nitride multilayers or by interfacial sliding mediated by interfacial misfit dislocations in case of the nitride/nitride multilayer coatings. The effective role of interfaces is to distribute damage laterally as well as horizontally to relieve stresses and hence enhance the damage tolerance under indentation. Optimum metal layer thickness has been proposed for maximum toughening in the metal/nitride multilayer coating and the role of interfaces in providing modes of plasticity is presented for the nitride/nitride multilayer coatings by use of extensive transmission electron microscopic investigations. A new interconnected architecture coatings provides a unique way of combining stiffness and toughness along with scope for further developing such configurations with improved mechanical properties.