Le composé intermétallique ordonné Ni3Al, de structure L12, présente une augmentation de contrainte d'écoulement avec la température, jusqu'à une température dite de "pic" au-delà de laquelle celle-ci décroit. Ce comportement, usuellement appelé anomalie de contrainte d'écoulement, est mis à profit dans les superalliages base nickel pour les applications hautes températures. Il a été étudiée de façon extensive ces trente dernières années et a donné lieu à de nombreuses modélisations. La plupart des modèles proposés considère qu'un processus thermiquement activé de glissement dévié des dislocations, à partir de leur plan de glissement primaire {111} sur le plan cubique de déviation {010}, joue un rôle clé dans la compréhension de l'anomalie. La distance de glissement dévié peut cependant fortement différer. Les traces de glissement laissées par l'émergence des dislocations mobiles à la surface d'échantillons déformés plastiquement permettent de visualiser les événements de déviations et de caractériser les mécanismes élémentaires de déformation plastique. Nous avons mesuré des paramètres essentiels pour modéliser la plasticité globale de l'intermétallique Ni3Al, comme : le nombre, la hauteur, la longueur des traces de glissement correspondant aux plans {111} et {010}. Ces paramètres qui caractérisent à la fois l'activité des sources et le libre parcours moyen des dislocations, suggèrent que l'anomalie s'accompagne d'un fort taux d'épuisement de la densité de dislocations mobiles. De nombreuses longues déviations dans les plans {010} ainsi que des doubles glissement dévié entre plans {111} adjacents, ont été mis en évidence. Ceci suggère deux processus de glissement dévié. / Ni3Al intermetallic compounds, that correspond to the strengthening phase of nickel-based superalloys, are well known to exhibit within a given range of temperature, an anomalous behaviour of flow strength. This positive temperature dependence of flow strength, called yield stress anomaly (YSA), has been the subject of extensive experimental studies concerning mechanical properties and dislocation microstructures, which have yielded several plausible models. Most of these models considers that a thermally activated cross-slip process, from the primary {111} onto the cube cross-slip {010} planes, plays a key role in the understanding of the YSA. However, the height of the cross-slipped segment in the {010} plane can be drastically different. The slip traces resulting from the emergence of moving dislocations at the surface in plastically deformed samples, allow us to visualize cross-slip events and to characterize the elementary mechanisms controlling plastic deformation. The number, height and length of slip traces corresponding to {111} and {010} planes, that are key parameters for modelling the plastic behaviour of Ni3Al intermetallic, are examined. These parameters reflect both the source activity and dislocation mean free path of dislocations; their values suggest that the YSA takes place with a strong exhaustion of mobile dislocations. Several larger deviations on the {010} planes, as well as double cross-slip between {111} neighbouring planes, are highlighted. These results suggest two different cross-slip process.

The diploma thesis deals with morphology of cobalt thin film on clean Si(111) and on silicon dioxide thin film on Si(111) studied by AFM and XPS. It is also study of selective growth of cobalt on lattice made by focused ion beam and electron lithography. In the last part, the growth of metals (Fe, Co) on surface oxide on Ni3Al(111) was studied.

Replacement of cobalt in cemented carbides has gained in attention recently because threats of regulations due to health issues (cancerogenic effect), increased demand from the electric vehicle industry and the questionable extraction from countries like Democratic Republic of Congo. In this report the use of Ni-based binder as an alternative binder for cemented carbides has been explored. The design is based on producing a Ni-based superalloy binder which contains dispersed Ni3Al Gamma Prime (γ’) -phase precipitates in the binder matrix. The investigation focuses on the design of cemented carbide compositions and processes that ensures the formation of γ’- precipitates, the control of their morphology and distribution as well as the effect of heat treatment. To do this a Ni-Al master alloy has been designed that enables the formation of γ’-precipitates in WC-Ni-Al-X systems, produced by conventional powder metallurgy process including standard free sintering. Furthermore, the addition of usual elements in the cemented carbide industry (such as Ti, Cr, Ta, Nb) and their effect on the stability of γ’-precipitates has been investigated. A method to reveal the precipitates including ion-polishing and electro-etching has been developed. Basic mechanical properties such as hardness and toughness have been investigated, revealing particular crack propagation in Ni-based binder reinforced with γ’-precipitates. It was found that the common variables in cemented carbide manufacturing influence all aspects regarding the stability of γ’-phase. By varying the powder type, binder composition and content, the carbon balance, the WC grain size and the heating/cooling steps; the formation of γ’-precipitates (size, morphology, distribution, etc.) can be controlled to tailor the properties of the cemented carbide. / Att hitta en ersättning av kobolt i hårdmetall har nyligen uppmärksammats bl.a. eftersom regleringar hotar användning av ämnet pga. dess cancerogenitet, en ökande efterfrågan från elfordonsindustrin samt den moraliskt tvivelaktiga utvinningen som sker i länder som Demokratiska Republiken Kongo. I denna rapport har användningen av ett nickel-baserat bindemedel som ett alternativt bindemedel för hårdmetaller undersökts. Designen är baserad på att producera en nickel-baserad superlegering som bindemedel som innehåller dispergerad Ni3Al Gamma Prim (γ’) – fas utfälld i bindemedlet. Utredningen fokuserar på designen av hårdmetallskompositioner och processer som försäkrar formationen av γ’-utfällningar, kontroller av dess morfologi, distributionen samt hur värmebehandlingar påverkar. För att kunna göra detta har en Ni-Al masterlegering skapats som möjliggör γ’-utfällningar i ett WC-Ni-Al-X system, producerat med konventionell pulvermetallurgiprocess inkluderat standard fri sintring. Dessutom har tillsatsen av vanliga ämnen i hårdmetallindustrin (such as TI, Cr, Ta, Nb) samt deras effekt på stabiliteten hos γ’-utfällningarna undersökts. En metod för att upptäcka utfällningarna, som inkluderar jonpolering och elektroetsning har utvecklats. Grundläggande mekaniska egenskaper som hårdhet och seghet har undersökts, vilket har avslöjat en speciell sprickutbredning i den nickelbaserade bindaren förstärkt med γ’-utfällningar. Det visade sig att de vanliga variablerna förenade med tillverkning av hårdmetall påverkar samtliga aspekter gällande stabiliteten hos γ’-utfällningar. Genom att variera pulvertyp, bindemedelkomposition och innehåll, kolbalansen, WC-kornstorlek och uppvärmning samt kylningssteg så påverkas bildningen av γ’-utfällningar (storlek, morfologi, distribution, etc..) som kan kontrolleras för att skräddarsy egenskaperna för hårdmetallen.

The Si(100) surface and Ga surface phases up to 1 ML on their oxidation have been studied by XPS and LEED. The selective growth of Ga on the SiO2/Si structures fabricated by EBL has been analyzed using SEM and AFM methods. It was proved that Ga clusters grow in structures beside the oxide. The structure of alumina on Ni3Al(111) and NiAl(110) substrates was fully determined by combining the results of STM measurements and DFT simulations. It was determined the alumina/NiAl(110) does not form a suitable template for ordered Fe and Co clusters growth. However, the next research confirmed the alumina/Ni3Al(111) forms template appropriate to clusters growth purpose.

The excellent high temperature microstructure stability, high strength, and oxidation resistance of intermetallics has for long driven the development of intermetallic based alloys. More recent studies demonstrated attractive properties of eutectic intermetallic in the Ni-Al-Zr systems. This thesis deals with study of binary Ni3Al+Ni7Zr2, NiAl+Ni7Zr2 and Ni3Al+NiAl+Ni7Zr2 ternary intermetallic eutectic alloys in this system and includes the identification of compositions that would yield each eutectic structure and their microstructural characterization, mechanical and oxidation behavior. The thesis is divided into six chapters. Chapter 1 reviews the study on high temperature materials development and presents the objectives of work in the current thesis. Various experimental techniques used for alloy preparation (vacuum arc melting and vacuum suction casting), microstructural characterization (optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray Diffraction (XRD), electron probe micro analyzer (EPMA), differential scanning calorimetry (DSC)), compression tests, microhardness tests and thermo gravimetric analysis (TGA) are described in Chapter 2. The specific background of work related to each chapter together with experimental results and discussion are given in next three chapters. Chapter 3 reports the method of identification of the composition for each of the eutectic alloys referred to above. The identification of alloy compositions of binary eutectics Ni3Al+Ni7Zr2 (Ni-13.5Al-11Zr), NiAl+Ni7Zr2 (Ni-19Al-12Zr) and Ni3Al+NiAl+Ni7Zr2 ternary eutectic (Ni-18.4Al-11.6Zr) is carried out with the help of available liquidus projection of Ni-Al-Zr system, and the iterative melting of numerous compositions that were refined to define the critical compositions for each eutectic. The microstructural features of these alloys have been characterized using optical and electron microscopy. Phase identification is confirmed by X ray diffraction, EPMA and TEM. The microstructure of Ni3Al+Ni7Zr2 and Ni3Al+NiAl+Ni7Zr2 ternary eutectic alloy shows similar eutectic morphologies. The eutectic colony consists of lamellar plates at center and intermixed lamellar-rod irregular morphologies towards the boundaries of the colonies. However, the NiAl+Ni7Zr2 eutectic alloy shows a fine, lamellar plate morphology throughout the microstructure. The orientation relationship between eutectic phases is determined using TEM technique for each alloy composition. Onsets of melting and liquidus temperatures have been identified by Differential Scanning Calorimetry. Modified liquidus projections of Ni-Al-Zr system near the Ni3Al+NiAl+Ni7Zr2 ternary eutectic region have been derived from present experimental work. Chapter 4 focuses on understanding the mechanical behaviour of these individual eutectics at room temperature and high temperature. An attempt has been made to correlate the microstructure and mechanical properties of eutectics by measuring room temperature hardness, compressive yield strength at various temperatures, and examination of slip bands, crack initiation and fractography. It is observed that NiAl+Ni7Zr2 eutectic possesses the highest yield strength and hardness followed by ternary eutectic and then the Ni3Al+Ni7Zr2 eutectic. The yield strength of these eutectics decreases rapidly beyond 700oC and this decrease is accompanied by substantial increase in compressive ductility and steady state flow, with little work hardening. Chapter 5 explores the isothermal oxidation behavior at high temperatures of these eutectic alloys. Oxidation kinetics have been measured at various temperatures (900oC, 1000oC, 1050oC and 1100oC) are carried out using the thermo gravimetric analysis technique (TGA). The oxidation behavior has been characterized using TGA, X ray diffraction and EPMA. The Top surface of oxide layer shows compact, NiO layer with a fine grain size. The cross section of oxide samples shows five distinct microstructural and compositional layers at steady state. Attempt has been made to understand the oxidation mechanism, sequence of layer formation in correlation with microstructure and weight gains, rate constants and activation energy analysis. Finally Chapter 6 presents a summary of the current work and suggests for further work.

Este trabalho traz contribuições à linha de pesquisa \'Nova Família de Ligas Baseada no Sistema Ni-Al-Cr-C Resistentes ao Desgaste em Elevadas Temperaturas\', estudando o comportamento mecânico, tribológico e a estabilidade superficial destas ligas. Esta família de ligas fundidas, denominada NICRALC - busca conjugar algumas características das superligas à base de níquel e dos ferros fundidos brancos, aliando ao comportamento mecânico anômalo do Ni3Al - aumento da resistência mecânica com a temperatura, até valores da ordem de 800°C - a uma dispersão de carbonetos de cromo de alta dureza. Desta forma, busca-se desenvolver uma alternativa às ligas ferrosas nas temperaturas acima das quais estas ligas perdem significativamente sua resistência mecânica (notadamente 600 °C), assim como uma alternativa mais econômica às ligas a base de cobalto resistentes ao desgaste, em virtude das altas cotações e instabilidades no preço deste elemento. Neste trabalho foram avaliadas as propriedades mecânicas em elevadas temperaturas (compressão e dureza), tenacidade à fratura na temperatura ambiente, comportamento tribológico (cavitação, abrasão, deslizamento e erosão) e a resistência à oxidação ao ar e à carburação em atmosfera redutora, em temperaturas elevadas, de ligas Ni-Al-Cr-C (NICRALC) fundidas. Ligas NICRALC fundidas com diferentes teores de carbono e submetidas a diferentes tratamentos tiveram seu comportamento mecânico e tribológico comparado ao comportamento do STELLITE 6 fundido, a uma liga NICRALC produzida por deposição por \'SPRAY\', a um ferro fundido branco alto cromo fundido convencionalmente e a um ferro fundido branco alto cromo depositado por \'SPRAY\'. Os ensaios de compressão confirmaram o comportamento anômalo da matriz ordenada Ni3Al. As ligas NICRALC apresentaram aumento ou manutenção da resistência ao escoamento com o aumento da temperatura de ensaio. A mesma tendência foi encontrada nos ensaios de dureza a quente. As demais ligas apresentaram tendência de queda da resistência ao escoamento e da dureza com o aumento da temperatura de ensaio. Esta tendência é mais acentuada na liga STELLITE, desta forma, as ligas NICRALC apresentaram em altas temperaturas maior resistência ao escoamento e maior dureza que o STELLITE. Os diferentes ensaios de desgaste mostraram, em geral, uma maior resistência do STELLITE em comparação com as ligas NICRALC na temperatura ambiente. Nestas condições verifica-se que a menor resistência mecânica da matriz ordenada nas ligas NICRALC é determinante para definir uma menor resistência ao desgaste na temperatura ambiente. Nos ensaios de erosão-oxidativa realizados a 600 e 800°C as ligas NICRALC mostraram perdas de massa menores que as experimentadas pelo STELLITE e pelos ferros fundidos. As ligas NICRALC com microestrutura de carbonetos mais homogênea, próxima do eutético, mostraram melhor comportamento sob desgaste abrasivo e erosivo se comparadas às ligas NICRALC 05 e 13. Os ensaios de resistência à oxidação mostraram que as ligas NICRALC são mais resistentes à oxidação que o STELLITE. Além disso, observou-se grande propensão ao destacamento dos filmes de óxidos formados nos STELLITES em temperaturas acima de 800°C. Os ensaios de resistência à carburação mostraram que no caso das ligas NICRALC ocorreu a precipitação de um depósito de grafita e, subjacente a esta, a formação de uma zona de fragmentação microestrutural, na qual se observa empobrecimento ora do Al ora do Cr, que aparentemente impede o avanço do processo. No caso do STELLITE verificou-se a ocorrência do aumento da fração volumétrica de carbonetos, típico dos casos clássicos de carburação. Os procedimentos de simulação termodinâmica utilizados indicam a necessidade de se implementar a descrição da solubilidade do carbono na fase ordenada de forma a permitir o pleno uso do software THERMOCALC no projeto e aprimoramento de ligas NICRALC. / This work contributes to the research line \'New Family of High Temperature Wear Resistant Alloys based on the Ni-Al-Cr-C System\', studying the mechanical and tribological behaviour and the surface stability of these alloys. This family of foundry alloys, called NICRALC, tries to unite some of the characteristics of the Ni based superalloys and the high-chromium-white-cast-irons, associating the anomalous behaviour of the ordered intermetallic phase Ni3Al - which increases its strength with the increase of temperature - with a dispersion of hard chromium carbides. The aim is to develop an alternative to iron-based wear resistant alloys at temperatures where they loose significantly their strength, as well as substituting cobalt based high temperature wear resistant alloys, which suffer from the instability and high cost of the Co metal. The high temperature mechanical properties (hardness and compression), room temperature fracture toughness, tribological behaviour (cavitation, abrasion, sliding and erosion) and resistance to high temperature oxidation and carburization of cast Ni-Al-Cr-C (NICRALC) alloys are studied. Cast NICRALC alloys with different C contents and different heat treatments were compared with a cast STELLITE 6, a conventionally cast high chromium white cast iron, a spray formed high chromium white cast iron and a spray formed NICRALC. Mechanical tests in compression confirmed that NICRALC alloys share the anomalous behaviour of the ordered intermetallic phase Ni3Al, increasing or maintaining their yield strength with increased testing temperature. The same occurred with hot hardness tests. STELLITE and all other alloys showed loss of strength with increased testing temperatures. Thus NICRALC alloys showed higher strength and hardness than STELLITE at high temperatures. All wear tests showed a higher wear resistance of STELLITE in comparison with NICRALC at room temperature. This result can be explained by the higher matrix hardness of STELLITE at room temperature. Oxidative-erosion tests run at 600 and 800° C showed that NICRALC suffered smaller mass loss than STELLITE and the white cast irons. NICRALC alloys with more homogeneous carbide distributions (eutectic alloys) obtained the best results under severe oxidation-erosion conditions. NICRALC alloys were more oxidation resistant than STELLITE alloy, which tended to break and detach the oxide layer formed above 800°C under air. During carburization essays in a reducing atmosphere the NICRALC alloys tended to form a coke-like graphite layer, over a layer with a fragmented microstructure depleted alternatively in chromium and aluminum, which effectively stopped the advance of the process. The STELLITE alloy suffered an increase in carbide volume fraction, a classic carburizing behaviour. The thermodynamic simulation results show that it is still needed to introduce the solubility of carbon on the ordered Ni3Al phase in the model in order to be able to fully calculate the NICRALC phase diagrams.

Este trabalho traz contribuições à linha de pesquisa \'Nova Família de Ligas Baseada no Sistema Ni-Al-Cr-C Resistentes ao Desgaste em Elevadas Temperaturas\', estudando o comportamento mecânico, tribológico e a estabilidade superficial destas ligas. Esta família de ligas fundidas, denominada NICRALC - busca conjugar algumas características das superligas à base de níquel e dos ferros fundidos brancos, aliando ao comportamento mecânico anômalo do Ni3Al - aumento da resistência mecânica com a temperatura, até valores da ordem de 800°C - a uma dispersão de carbonetos de cromo de alta dureza. Desta forma, busca-se desenvolver uma alternativa às ligas ferrosas nas temperaturas acima das quais estas ligas perdem significativamente sua resistência mecânica (notadamente 600 °C), assim como uma alternativa mais econômica às ligas a base de cobalto resistentes ao desgaste, em virtude das altas cotações e instabilidades no preço deste elemento. Neste trabalho foram avaliadas as propriedades mecânicas em elevadas temperaturas (compressão e dureza), tenacidade à fratura na temperatura ambiente, comportamento tribológico (cavitação, abrasão, deslizamento e erosão) e a resistência à oxidação ao ar e à carburação em atmosfera redutora, em temperaturas elevadas, de ligas Ni-Al-Cr-C (NICRALC) fundidas. Ligas NICRALC fundidas com diferentes teores de carbono e submetidas a diferentes tratamentos tiveram seu comportamento mecânico e tribológico comparado ao comportamento do STELLITE 6 fundido, a uma liga NICRALC produzida por deposição por \'SPRAY\', a um ferro fundido branco alto cromo fundido convencionalmente e a um ferro fundido branco alto cromo depositado por \'SPRAY\'. Os ensaios de compressão confirmaram o comportamento anômalo da matriz ordenada Ni3Al. As ligas NICRALC apresentaram aumento ou manutenção da resistência ao escoamento com o aumento da temperatura de ensaio. A mesma tendência foi encontrada nos ensaios de dureza a quente. As demais ligas apresentaram tendência de queda da resistência ao escoamento e da dureza com o aumento da temperatura de ensaio. Esta tendência é mais acentuada na liga STELLITE, desta forma, as ligas NICRALC apresentaram em altas temperaturas maior resistência ao escoamento e maior dureza que o STELLITE. Os diferentes ensaios de desgaste mostraram, em geral, uma maior resistência do STELLITE em comparação com as ligas NICRALC na temperatura ambiente. Nestas condições verifica-se que a menor resistência mecânica da matriz ordenada nas ligas NICRALC é determinante para definir uma menor resistência ao desgaste na temperatura ambiente. Nos ensaios de erosão-oxidativa realizados a 600 e 800°C as ligas NICRALC mostraram perdas de massa menores que as experimentadas pelo STELLITE e pelos ferros fundidos. As ligas NICRALC com microestrutura de carbonetos mais homogênea, próxima do eutético, mostraram melhor comportamento sob desgaste abrasivo e erosivo se comparadas às ligas NICRALC 05 e 13. Os ensaios de resistência à oxidação mostraram que as ligas NICRALC são mais resistentes à oxidação que o STELLITE. Além disso, observou-se grande propensão ao destacamento dos filmes de óxidos formados nos STELLITES em temperaturas acima de 800°C. Os ensaios de resistência à carburação mostraram que no caso das ligas NICRALC ocorreu a precipitação de um depósito de grafita e, subjacente a esta, a formação de uma zona de fragmentação microestrutural, na qual se observa empobrecimento ora do Al ora do Cr, que aparentemente impede o avanço do processo. No caso do STELLITE verificou-se a ocorrência do aumento da fração volumétrica de carbonetos, típico dos casos clássicos de carburação. Os procedimentos de simulação termodinâmica utilizados indicam a necessidade de se implementar a descrição da solubilidade do carbono na fase ordenada de forma a permitir o pleno uso do software THERMOCALC no projeto e aprimoramento de ligas NICRALC. / This work contributes to the research line \'New Family of High Temperature Wear Resistant Alloys based on the Ni-Al-Cr-C System\', studying the mechanical and tribological behaviour and the surface stability of these alloys. This family of foundry alloys, called NICRALC, tries to unite some of the characteristics of the Ni based superalloys and the high-chromium-white-cast-irons, associating the anomalous behaviour of the ordered intermetallic phase Ni3Al - which increases its strength with the increase of temperature - with a dispersion of hard chromium carbides. The aim is to develop an alternative to iron-based wear resistant alloys at temperatures where they loose significantly their strength, as well as substituting cobalt based high temperature wear resistant alloys, which suffer from the instability and high cost of the Co metal. The high temperature mechanical properties (hardness and compression), room temperature fracture toughness, tribological behaviour (cavitation, abrasion, sliding and erosion) and resistance to high temperature oxidation and carburization of cast Ni-Al-Cr-C (NICRALC) alloys are studied. Cast NICRALC alloys with different C contents and different heat treatments were compared with a cast STELLITE 6, a conventionally cast high chromium white cast iron, a spray formed high chromium white cast iron and a spray formed NICRALC. Mechanical tests in compression confirmed that NICRALC alloys share the anomalous behaviour of the ordered intermetallic phase Ni3Al, increasing or maintaining their yield strength with increased testing temperature. The same occurred with hot hardness tests. STELLITE and all other alloys showed loss of strength with increased testing temperatures. Thus NICRALC alloys showed higher strength and hardness than STELLITE at high temperatures. All wear tests showed a higher wear resistance of STELLITE in comparison with NICRALC at room temperature. This result can be explained by the higher matrix hardness of STELLITE at room temperature. Oxidative-erosion tests run at 600 and 800° C showed that NICRALC suffered smaller mass loss than STELLITE and the white cast irons. NICRALC alloys with more homogeneous carbide distributions (eutectic alloys) obtained the best results under severe oxidation-erosion conditions. NICRALC alloys were more oxidation resistant than STELLITE alloy, which tended to break and detach the oxide layer formed above 800°C under air. During carburization essays in a reducing atmosphere the NICRALC alloys tended to form a coke-like graphite layer, over a layer with a fragmented microstructure depleted alternatively in chromium and aluminum, which effectively stopped the advance of the process. The STELLITE alloy suffered an increase in carbide volume fraction, a classic carburizing behaviour. The thermodynamic simulation results show that it is still needed to introduce the solubility of carbon on the ordered Ni3Al phase in the model in order to be able to fully calculate the NICRALC phase diagrams.