Additive manufacturing methods have been developed from rapid prototyping techniques and are now being considered as alternatives to conventional techniques of manufacturing. Stereolithography is one of the main additive methods and is considered highly accurate and consistent. Polymers are used as stereolithography materials and exhibit features such as high strength-to-weight ratio, corrosion resistance, ease of manufacturing and good thermal and electrical resistance properties. However, they are sensitive to environmental factors such as temperature, moisture and UV light, with moisture being identified as one of the most important factors that affect their properties. Moisture generally has an adverse effect on the mechanical properties of polymers. Investigation of the effects of moisture on polymers can be carried out using a number of experimental techniques; however, the benefits of the depth sensing indentation method over bulk tests include its ability to characterise various mechanical properties in a single test from only a small volume of material and the investigation of spatial variation in mechanical properties near the surface. The aim of this research was to investigate the effects of varying relative humidity on the indentation behaviour of stereolithography polymers and to develop a modelling methodology that can predict this behaviour under various humidities. It was achieved by a combination of experimental and numerical methods. Depth sensing indentation experiments were carried out at 33.5 %, 53.8 %, 75.3 % and 84.5 % RH (relative humidity) and 22.5 °C temperature to investigate the effects of varying humidity on the micron scale properties of the stereolithography resin, Accura 60. In order to minimise the effects of creep on the calculated properties, appropriate loading and unloading rates with suitable dwell period were selected and indentation data was analysed using the Oliver and Pharr method (1992). A humidity control unit fitted to the machine was used to condition the samples and regulate humidity during testing. Samples were also preconditioned at 33.5 %, 53.8 %, 75.3 % and 84.5 % RH using saturated salt solutions and were tested at 33.5 % RH using humidity control unit. It was seen that properties such as indentation depth increased and contact iv hardness and contact modulus decreased with increasing RH. The samples conditioned and tested using the humidity control unit at high RH showed a greater effect of moisture than the preconditioned samples tested at 33.5 % RH. This was because the samples preconditioned at high RH exhibited surface desorption of moisture when tested at ambient RH, resulting in some recovery of the mechanical properties. In order to investigate these further, tests were performed periodically on saturated samples after drying. Ten days drying of samples conditioned for five days at 84.5 % RH provided significant, though not complete, recovery in the mechanical properties. These tests confirmed that Accura 60 is highly hygroscopic and its mechanical properties are a function of RH and removal of moisture leads to a significant recovery of the original mechanical properties.

L’indentation instrumentée (nanoindentation) est une technique d’analyse des données expérimentales utilisées pour atteindre les propriétés mécaniques de matériaux (dureté H, module de Young E) pour lesquels les techniques classiques sont difficilement applicables voire non envisageables. Ces paramètres mécaniques sont issus de l’exploitation de la seule courbe expérimentale charge-décharge. L’analyse de cette dernière repose sur des nombreux modèles reportés dans la littérature (Oliver et pharr, Field et Swain, Doener et Nix, Loubet et al.) qui considèrent la décharge purement élastique. De nombreuses expériences que nous avons menées, sur divers types de matériaux massifs (aciers inoxydables AISI304, AISI316, AISI430; aciers rapides HSS652; verre de silice SiO2) et revêtus de films minces de TiN et TiO2 ont montré que les propriétés mécaniques (E et H), déduites de la méthode de Oliver et Pharr, dépendent du pourcentage de la courbe de décharge considéré, de la charge appliquée et du rayon de la pointe. De plus, pour un système film-substrat, la technique est en général utilisée pour atteindre les propriétés in-situ du film ou du substrat, alors que la méthode de dépouillement fournit des paramètres composites qu’il faut ensuite déconvoluer. Dans la recherche d’une stratégie simple, permettant d’accéder au module élastique d’un film « dur » pour les applications mécaniques, nous avons fait appel à la simulation numérique. Le code de simulation numérique utilisé, est basé sur la méthode des éléments de frontière. Nos investigations numériques utilisant l’indentation sphérique nous ont permis de mettre en évidence un certain nombre de résultats utiles pour l’analyse des données expérimentales. Nous avons commencé par montrer que aussi bien pour un matériau massif homogène élastoplastique que pour un système film dur – substrat élastoplastique, la relation [delta]=a2/R demeure valable (R étant le rayon de l’indenteur, a le rayon de l’aire projetée de contact). Cela permet de représenter les résultats de l’essai d’indentation sphérique par la courbe pression moyenne F/[pi]a2- déformation a/R . Au début du chargement, la pente cette courbe est proportionnelle au module de Young du film tandis que la pente initiale de la courbe de décharge est proportionnelle au module d’élasticité du substrat. Une relation entre le déplacement de l’indenteur et [delta] , puis une méthode d’analyse d’indentation ont été établies. Enfin, la procédure a été validée numériquement et expérimentalement sur les données issues de l’indentation de divers combinaisons film-substrat (TiN/AISI430, TiN/HSS652 et TiO2/HSS652) avec succès / Depth sensing Indentation (nanoindentation) is an experimental technique increasing retained for the assessment of the mechanical properties of materials (hardness H, Young's modulus E) for which common homogeneous mechanical tests can not be performed or are extremely difficult to perform. The mechanical parameters are obtained from the indentation curve (the plot of the load vs penetration depth during both load and unload). Usually, some methodology reported in the literature (Oliver and pharr, Field and Swain, Doener and Nix, Loubet and al.) are used in order to assess E and H. We have performed a number of experiments on homogeneous materials (stainless steel AISI304, AISI316, AISI430; high-speed steel HSS652; glass SiO2) as well as a film-substrate system (TiN/AISI430, TiN/HSS652, TiO2/HSS652). Applying the Oliver and Pharr methodology, E end H vary with the applied load as well as the percentage of used unload curve retained for the analysis, as reported in the literature. Besides, in the case of the film-substrate system, only composite parameters are obtained instead of the in-situ films properties. In order to establish a simple strategy for the determination of the elastic modulus of a hard coating, we have carried out many simulations using a boundary element based numerical tool. Then a number of useful results have been identified. The well known elastic relation [delta]=a2/R between the relative approach [delta], the projected contact radius a and the punch radius R, remain valid in the plastic range for homogeneous as well as film-substrate specimens. This allows data indentation to be represented in term of mean pressure F/[pi]a2 vs indentation strain a/R . The initial slope of the loading part of the latter curve is proportional to the elastic modulus of the film, while the slope of the initial part of the unloading curve is proportional to the substrate elastic modulus. Our indentation procedure anlysis has been validated experimentally on a number of samples (TiN/AISI430, TiN/HSS652, TiO2/HSS652) after having established a relation between the punch displacement and the relative approach [delta]

Thermoelectric (TE) ZrNiSn samples with a half-Heusler atomic structure were synthesized by mechanical alloying (MA) and consolidation by either Spark Plasma Sintering (SPS) or hot pressing (HP). X-Ray diffraction patterns of as milled powders and consolidated samples were compared and analyzed for phase purity. Thermal conductivity, electrical conductivity and Seebeck coefficient are measured as a function of temperature in the range 300 K to 800 K and compared with measurements reported for high temperature solid state reaction synthesis of this compound. HP samples, compared to SPS samples, demonstrate increased grain growth due to longer heating times. Reduced grain size achieved by MA and SPS causes increased phonon scattering due to the increased number of grain boundaries, which lowers the thermal conductivity without doping the base system with addition phonon scattering centers. Mechanical characterization of the samples by microindentation and depth sensing indentation for hardness and elastic modulus will be discussed.

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.