High-performance materials such as stainless steels and nickel based super alloys are widely used in demanding applications where high mechanical and thermal properties are required. The applications of super alloys are mainly found in jet engines, power plants and gas turbines demanding high fatigue strength, corrosion and oxidation resistance as well as wear resistant properties. In order to use them, they go through various machining processes such as milling, turning, cutting, polishing etc. until the final product is achieved. Modern manufacturing industries employs various machining tools and technologies to improve the machining process of heat resistant super alloys. However, there are still challenges which needs to be addressed. Among them, adhesive wear of the machining tools is one of the main wear mechanism during the tribological interaction of tool and workpiece, preventing them to achieve the desired quality and surface finish of the end product. Moreover, it damages the tool reducing its lifecycle and in return, increasing the production cost. Among the cutting tools tungsten carbide (WC/Co) tools coated with TiAlN coating due to their good high temperature performance are extensively used. Nonetheless, these coatings still face issue like adhesive wear, abrasion, oxidation at higher temperature damaging the tools and subsequent machining. Therefore, it is imperative to understand the initiation mechanism of adhesive wear during the tribological interaction of super alloys and coated cutting tool material. In this research work, the tribological response of two coatings deposited by physical vapour deposition (PVD), having the composition Ti60Al40N and Ti40Al60N have been studied against two super alloys material, i.e. Inconel 718 and stainless steel 316L. A high temperature SRV (Schwingung (Oscillating), Reibung (Friction), Verschleiß (Wear)) reciprocation friction and wear test set up was employed to investigate the friction behaviour, wear rate and dominant wear mechanisms.  For Ti60Al40N coating, the experimental results revealed that generally, friction increases in case of sliding against Inconel 718 up to 400 °C and drops at 760 °C. A high wear volume at room temperature and a decrease to a minimum at 760 °C has been observed for Inconel 718. On the other side, Stainless steel 316L (SS 316L) faces a continuous rise in friction coefficient with highest value at 760 °C during sliding against Ti60Al40N coating. Wear is highest at 400 °C for SS 316L pin. The worn surfaces shows that both workpiece materials experience increase in material transfer due to adhesive wear with rise in temperature. At 400 °C, adhesion is the primary wear mechanism for both workpiece materials. A further rise in temperature to 760 °C promotes the adhesive wear through oxides formation on both material surfaces.  Similarly, Ti40Al60N coating shows the same friction behaviour with change in average steady state friction values for both material of Inconel 718 and SS 316L. Both workpiece materials responds in a similar way to wear volume loss, i.e. lowest at room temperature and highest at 760 °C. For Inconel 718, transfer of coating constituents on to the Inconel 718 pin surface was detected and associated with coating rupture and peeling, exacerbating with rise in temperature. Adhesion, abrasion, and oxidation are primary wear mechanisms at 400 °C and 760 °C. For SS 316L, coating transfer only happen at 400 °C. No damage of coating at 40 °C, a complete damage at 400 °C, and formation of dense porous oxides layers at 760 °C have been noticed. At 400 °C, adhesion, abrasion, and chipping while at 760 °C, adhesion, three body abrasion, ploughing and oxidation are the main wear mechanisms.

No presente trabalho foi avaliado o efeito da microestrutura e da capacidade de suportar carregamento de camadas nitretadas produzidas em aços ferramenta AISI H13 e AISI D2 sobre a aderência e a resistência ao desgaste microabrasivo de revestimentos de TiN-PVD. Em cada um desses aços, foram produzidas camadas nitretadas de diferentes estruturas e espessuras, e foram determinadas experimentalmente as curvas potencial início de formação de camada branca, para a nitretação a 520oC. Para o aço ferramenta AISI H13, o emprego de tempos de pré-tratamento de nitretação mais prolongados ( aproximadamente 11 h) foi necessário para aprofundar a camada nitretada e, conseqüentemente, aumentar a capacidade de suportar carregamento dos revestimentos, evitando a formação de bordas que provocam o lascamento e a escamação das camadas de TiN. Observou-se que esse tipo de falha persiste se a zona de endurecimento for pouco profunda, uma vez que a transição de propriedades mecânicas da camada de TiN para o núcleo não nitretado continua abrupta e a capacidade de suportar carregamento da camada nitretada ainda é baixa. Por outro lado, curtos tempos de nitretação (aproximadamente 42 min.) foram suficientes para aumentar a aderência das camadas de TiN ao aço ferramenta D2, pois o núcleo não nitretado desse aço possui uma capacidade de suportar carregamento razoável. Observou-se que a resistência ao desgaste microabrasivo e a aderência dos revestimentos são prejudicadas com a presença de uma camada preta na interface camada de TiN/camada nitretada. Quando a superfície dos revestimentos é carregada, falhas do tipo “casca de ovo" facilmente ocorrem. / In this work, the influence of both the microstructure and the load-bearing capacity of nitrided layers, formed on top of AISI D2 and AISI H13 tool steels, on adhesion and wear resistance of PVD-TiN coatings was studied. The threshold nitriding potential curves for the above mentioned steels and the optimum conditions of the pre-treatments which increased the adhesion as well as the wear resistance of the PVD-TiN were determined experimentally. By using longer nitriding times (about 11 h) and lower nitrogen contents in the gas mixture (about N2-5%vol.), it was possible to minimize the pile-up degree of the TiN/H13 nitrided substrates and, consequently, the occurrence of coatings chipping. This flaw persists when the nitrided layer is thin, due to an abrupt transition of mechanical properties at the TiN coating / steel core interface. Shorter nitriding times (about 42 min.) and lower nitrogen contents (about N2-5%vol.), on the other hand, are sufficient to guarantee a better adhesion of TiN coatings on AISI D2 tool steel, as the core of such steel possesses relatively better load-bearing capacity than the AISI H13 tool steel. The presence of a black layer at the TiN/nitrided layer interface was observed in all coatings deposited over nitrided layers produced above the threshold nitriding potential curves. This layer affects adversely the wear resistance and the adhesion of the TiN coatings. When higher loads are applied on the coated surface, “egg shell" type flaws easily occur.

No presente trabalho foi avaliado o efeito da microestrutura e da capacidade de suportar carregamento de camadas nitretadas produzidas em aços ferramenta AISI H13 e AISI D2 sobre a aderência e a resistência ao desgaste microabrasivo de revestimentos de TiN-PVD. Em cada um desses aços, foram produzidas camadas nitretadas de diferentes estruturas e espessuras, e foram determinadas experimentalmente as curvas potencial início de formação de camada branca, para a nitretação a 520oC. Para o aço ferramenta AISI H13, o emprego de tempos de pré-tratamento de nitretação mais prolongados ( aproximadamente 11 h) foi necessário para aprofundar a camada nitretada e, conseqüentemente, aumentar a capacidade de suportar carregamento dos revestimentos, evitando a formação de bordas que provocam o lascamento e a escamação das camadas de TiN. Observou-se que esse tipo de falha persiste se a zona de endurecimento for pouco profunda, uma vez que a transição de propriedades mecânicas da camada de TiN para o núcleo não nitretado continua abrupta e a capacidade de suportar carregamento da camada nitretada ainda é baixa. Por outro lado, curtos tempos de nitretação (aproximadamente 42 min.) foram suficientes para aumentar a aderência das camadas de TiN ao aço ferramenta D2, pois o núcleo não nitretado desse aço possui uma capacidade de suportar carregamento razoável. Observou-se que a resistência ao desgaste microabrasivo e a aderência dos revestimentos são prejudicadas com a presença de uma camada preta na interface camada de TiN/camada nitretada. Quando a superfície dos revestimentos é carregada, falhas do tipo “casca de ovo” facilmente ocorrem. / In this work, the influence of both the microstructure and the load-bearing capacity of nitrided layers, formed on top of AISI D2 and AISI H13 tool steels, on adhesion and wear resistance of PVD-TiN coatings was studied. The threshold nitriding potential curves for the above mentioned steels and the optimum conditions of the pre-treatments which increased the adhesion as well as the wear resistance of the PVD-TiN were determined experimentally. By using longer nitriding times (about 11 h) and lower nitrogen contents in the gas mixture (about N2-5%vol.), it was possible to minimize the pile-up degree of the TiN/H13 nitrided substrates and, consequently, the occurrence of coatings chipping. This flaw persists when the nitrided layer is thin, due to an abrupt transition of mechanical properties at the TiN coating / steel core interface. Shorter nitriding times (about 42 min.) and lower nitrogen contents (about N2-5%vol.), on the other hand, are sufficient to guarantee a better adhesion of TiN coatings on AISI D2 tool steel, as the core of such steel possesses relatively better load-bearing capacity than the AISI H13 tool steel. The presence of a black layer at the TiN/nitrided layer interface was observed in all coatings deposited over nitrided layers produced above the threshold nitriding potential curves. This layer affects adversely the wear resistance and the adhesion of the TiN coatings. When higher loads are applied on the coated surface, “egg shell” type flaws easily occur.

Sélectionner des traitements de surface pour l’industrie nécessite de prendre en compte : les propriétés à conférer au substrat, la nature et la géométrie de celui-ci et les caractéristiques du milieu extérieur. Certaines combinaisons de ces paramètres rendent difficile la sélection d’un traitement unique, d’où le recours à des multitraitements de surface. Dès lors, se posent les questions suivantes : - Utiliser des multitraitements de surface peut se faire en scindant les différentes requêtes en sous-ensembles, de manière à ce que chaque traitement réponde à l’un d’eux. Dans quel ordre ces requêtes doivent-elles être introduites par rapport au substrat ? - Comment sélectionner les traitements de surface répondant à chaque requête individuelle ? - Comment classer des multitraitements en termes d’adéquation au problème posé ? Dans ce travail, les première et troisième questions sont abordées, en explorant les requêtes concernant habituellement les dispositifs de moulage de l’aluminium : - Résistance aux contraintes d’origine thermique. - Résistance à la corrosion par les métaux fondus. - Résistance au frottement. L’analyse de la bibliographie relative aux traitements de surface utilisés dans ces systèmes a été analysée et des « architectures »-types ont été identifiées (chapitre 3). On prévoit, par exemple, un traitement conférant la résistance à la fatigue superficielle, ainsi qu’un revêtement étanche et résistant à l’aluminium fondu. Une barrière thermique est parfois préconisée. Pour chacune des architectures, des traitements de surface individuels peuvent être sélectionnés. Un « facteur de performance » permettant de classer les solutions par rapport au problème de la fatigue thermique a été construit (chapitre 4) et discuté dans deux situations : - Lorsqu’un revêtement est présent, et que les contraintes d’origine thermique (différence de dilatation thermique couche-substrat) menacent de le rompre lors de l’immersion dans un milieu corrosif à haute température. Des essais de corrosion dans de l’aluminium fondu ont été réalisés sur un acier revêtu par du nitrure de chrome dopé à l’aluminium, synthétisé par déposition physique en phase vapeur (chapitre 5 – collaboration : Inasmet). - Lorsque des variations thermiques rapides menacent de rompre le substrat et la (les) couches. Des essais de fatigue thermique ont été réalisés sur de l’acier à outils pour travail à chaud non traité, boruré ou recouvert d’un multitraitements (zircone yttriée / NiCrAlY / boruration / acier). Le revêtement en zircone yttriée a été obtenu par projection par plasma. L’essai de fatigue thermique a été modélisé et le facteur de performance, discuté (chapitre 6). Au chapitre 7, les architectures-types ont été introduites dans une méthodologie de sélection des multi-traitements de surface, qui a été appliquée dans deux cas : - Celui des moules de fonderie, devant résister à la fatigue thermique et à la corrosion par l’aluminium fondu. Le facteur de performance a été extrapolé à d’autres situations qu’aux chapitres 5 et 6. Les solutions habituellement proposées pour résoudre ce problème sont retrouvées. - Celui de deux pièces en acier frottant l’une contre l’autre en présence d’aluminium fondu. To select surface treatments, one must account for the required functional properties, the substrate features and the solicitations the substrate must endure. Certain combinations of these parameters make it difficult to select a single surface treatment, a reason why several successive treatments are preferred. To select them, one needs to determine: - How to divide the several requests into groups and how to stack up these groups from the substrate to the outer surface, so that each treatment deals with one specific group of requests/properties. - How to select individual layers for each group of properties. - How to rank the multi-treatments in terms of relevance for a given application. In this work, one tries to answer the first and the third questions, by studying the case of aluminium foundry, in which the industrial devices frequently face the following solicitations: - Thermal stress (thermal fatigue, thermal expansion mismatch). - Presence of corrosive molten metal. - Sliding wear. In the literature, several “standard” architectures are proposed (chapter 3), like a diffusion layer reducing superficial fatigue plus a corrosion barrier layer. A thermal barrier coating is also sometimes proposed. For each of these architectures, one can select individual treatments. To rank them, one devised a “performance index” for thermal stress (chap.4), which is discussed for two cases: - For large differences between layer and substrate thermal expansion coefficients, when both are put into contact with a high temperature corrosive medium, the layer may be damaged. One discusses this case by examining the corrosion caused by molten aluminium for a steel substrate coated by anticorrosive chromium nitride doped with aluminium. The layer is produced by physical vapour deposition (chap. 5 – cooperation: Inasmet). - Repeated fast surface temperature transients can also damage the substrate and/or the layer by thermal fatigue. One conducted thermal fatigue tests with samples of hot work tool steel, respectively untreated, simply borided and protected by a multilayer. In the last case, top coat is yttria stabilised zirconia, followed by a nickel superalloy and then a borided layer (undercoat). One synthesized the zirconia coating by plasma spray and one modelled the thermal fatigue (chap. 6). In chap. 7, architectures from chap. 2 are introduced in a multi-treatment selection routine, which is applied in two cases: - Foundry moulds for molten aluminium, withstanding both thermal fatigue and corrosion. The devised performance index is extrapolated beyond the tests of chap. 5 and 6 to treatments for this industrial application, thereby quantifying their respective merits. - A foundry device exposed to molten metal and sliding wear.

Sélectionner des traitements de surface pour l’industrie nécessite de prendre en compte :les propriétés à conférer au substrat, la nature et la géométrie de celui-ci et les caractéristiques du milieu extérieur. Certaines combinaisons de ces paramètres rendent difficile la sélection d’un traitement unique, d’où le recours à des multitraitements de surface. Dès lors, se posent les questions suivantes :<p>- Utiliser des multitraitements de surface peut se faire en scindant les différentes requêtes en sous-ensembles, de manière à ce que chaque traitement réponde à l’un d’eux. Dans quel ordre ces requêtes doivent-elles être introduites par rapport au substrat ?<p>- Comment sélectionner les traitements de surface répondant à chaque requête individuelle ?<p>- Comment classer des multitraitements en termes d’adéquation au problème posé ?<p>Dans ce travail, les première et troisième questions sont abordées, en explorant les requêtes concernant habituellement les dispositifs de moulage de l’aluminium :<p>- Résistance aux contraintes d’origine thermique.<p>- Résistance à la corrosion par les métaux fondus.<p>- Résistance au frottement.<p>L’analyse de la bibliographie relative aux traitements de surface utilisés dans ces systèmes a été analysée et des « architectures »-types ont été identifiées (chapitre 3). On prévoit, par exemple, un traitement conférant la résistance à la fatigue superficielle, ainsi qu’un revêtement étanche et résistant à l’aluminium fondu. Une barrière thermique est parfois préconisée.<p>Pour chacune des architectures, des traitements de surface individuels peuvent être sélectionnés. Un « facteur de performance » permettant de classer les solutions par rapport au problème de la fatigue thermique a été construit (chapitre 4) et discuté dans deux situations :<p>- Lorsqu’un revêtement est présent, et que les contraintes d’origine thermique (différence de dilatation thermique couche-substrat) menacent de le rompre lors de l’immersion dans un milieu corrosif à haute température. Des essais de corrosion dans de l’aluminium fondu ont été réalisés sur un acier revêtu par du nitrure de chrome dopé à l’aluminium, synthétisé par déposition physique en phase vapeur (chapitre 5 – collaboration :Inasmet).<p>- Lorsque des variations thermiques rapides menacent de rompre le substrat et la (les) couches. Des essais de fatigue thermique ont été réalisés sur de l’acier à outils pour travail à chaud non traité, boruré ou recouvert d’un multitraitements (zircone yttriée / NiCrAlY / boruration / acier). Le revêtement en zircone yttriée a été obtenu par projection par plasma. L’essai de fatigue thermique a été modélisé et le facteur de performance, discuté (chapitre 6).<p>Au chapitre 7, les architectures-types ont été introduites dans une méthodologie de sélection des multi-traitements de surface, qui a été appliquée dans deux cas :<p>- Celui des moules de fonderie, devant résister à la fatigue thermique et à la corrosion par l’aluminium fondu. Le facteur de performance a été extrapolé à d’autres situations qu’aux chapitres 5 et 6. Les solutions habituellement proposées pour résoudre ce problème sont retrouvées.<p>- Celui de deux pièces en acier frottant l’une contre l’autre en présence d’aluminium fondu.<p><p>To select surface treatments, one must account for the required functional properties, the substrate features and the solicitations the substrate must endure. Certain combinations of these parameters make it difficult to select a single surface treatment, a reason why several successive treatments are preferred. To select them, one needs to determine:<p>- How to divide the several requests into groups and how to stack up these groups from the substrate to the outer surface, so that each treatment deals with one specific group of requests/properties.<p>- How to select individual layers for each group of properties.<p>- How to rank the multi-treatments in terms of relevance for a given application.<p>In this work, one tries to answer the first and the third questions, by studying the case of aluminium foundry, in which the industrial devices frequently face the following solicitations:<p>- Thermal stress (thermal fatigue, thermal expansion mismatch).<p>- Presence of corrosive molten metal.<p>- Sliding wear.<p>In the literature, several “standard” architectures are proposed (chapter 3), like a diffusion layer reducing superficial fatigue plus a corrosion barrier layer. A thermal barrier coating is also sometimes proposed.<p>For each of these architectures, one can select individual treatments. To rank them, one devised a “performance index” for thermal stress (chap.4), which is discussed for two cases:<p>- For large differences between layer and substrate thermal expansion coefficients, when both are put into contact with a high temperature corrosive medium, the layer may be damaged. One discusses this case by examining the corrosion caused by molten aluminium for a steel substrate coated by anticorrosive chromium nitride doped with aluminium. The layer is produced by physical vapour deposition (chap. 5 – cooperation: Inasmet).<p>- Repeated fast surface temperature transients can also damage the substrate and/or the layer by thermal fatigue. One conducted thermal fatigue tests with samples of hot work tool steel, respectively untreated, simply borided and protected by a multilayer. In the last case, top coat is yttria stabilised zirconia, followed by a nickel superalloy and then a borided layer (undercoat). One synthesized the zirconia coating by plasma spray and one modelled the thermal fatigue (chap. 6).<p>In chap. 7, architectures from chap. 2 are introduced in a multi-treatment selection routine, which is applied in two cases:<p>- Foundry moulds for molten aluminium, withstanding both thermal fatigue and corrosion. The devised performance index is extrapolated beyond the tests of chap. 5 and 6 to treatments for this industrial application, thereby quantifying their respective merits.<p>- A foundry device exposed to molten metal and sliding wear.<p><p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished