The high temperature microstructure of the solid phases within the electric arc furnace (EAF) slag has a large effect on the process features such as foamability of the slag, chromium recovery, consumption of the ferroalloys and the wear rate of the refractory. The knowledge of the microstructural and compositional evolution of the slag phases during the EAF process stages is necessary for a good slag praxis. In supplement 1, an investigation of the typical characteristics of EAF slags in the production of the AISI 304L stainless steel was carried out. In addition, compositional and microstructural evolution of the slag during the different EAF process stages was also investigated. Computational thermodynamics was also used as a tool to predict the equilibrium phases in the top slag as well as the amount of these phases at the process temperatures. Furthermore, the influence of different parameters (MgO wt%, Cr2O3 wt%, temperature and the top slag basicity) on the amount of the spinel phase in the slag was studied. In supplement 2, a novel study to characterize the electric arc furnace (EAF) slags in the production of duplex stainless steel at the process temperatures was performed. The investigation was focused on determining the microstructural and compositional evolution of the EAF slag during and at the end of the refining period. Slag samples were collected from 14 heats of AISI 304L steel (2 slag samples per heat) and 7 heats of duplex steel (3 slags sample per heat). Simultaneously with each slag sampling, the temperature of the slag was measured. The selected slag samples were studied both using SEM-EDS and LOM. In some cases (supplement 2), X-ray diffraction (XRD) analyses were also performed on fine-powdered samples to confirm the existence of the observed phases. It was observed that at the process temperature and at all process stages, the stainless steel EAF slag consists mainly of liquid oxides, magnesiochromite spinel particles and metallic droplets. Under normal operation and at the final stages of the EAF, 304L steelmaking slag contains 2-6 wt% magnesiochromite spinel crystals. It was also found that, within the compositional range of the slag samples, the only critical parameter affecting the amount of solid spinel particles in the slag is the chromium oxide content. Petrographical investigation of the EAF duplex stainless steelmaking showed that, before FeSi-addition, the slag samples contain large amounts of undissolved particles and the apparent viscosity of the slag is higher, relative to the subsequent stages. In this stage, the slag also includes solid stoichiometric calcium chromite. It was also found that, after FeSi-injection into the EAF and during the refining period, the composition and the basicity of the slag in the EAF duplex steelmaking and EAF stainless steelmaking are fairly similar. This indicates that, during the refining period, the basic condition for the utilization of an EAF foaming-slag praxis, in both austenitic and duplex stainless steel cases, is the same. Depending on the slag basicity, the slag may contain perovskite and/or dicalcium silicate too. More specifically, the duplex stainless steel slag samples with a higher basicity than 1.55 found to contain perovskite crystals. / QC 20110413

This thesis is concerned with theoretical concepts of phenomenological and statistical thermodynamics and their computational realization. The main goal of this thesis is to provide efficient workflows for an accurate description of thermodynamic properties of molecules and solid state materials. The Cp-MD workflow developed within this thesis is applied to characterize binary battery materials, such as lithium silicides.This workflow enables a numerically efficient description of macroscopic thermodynamic properties. For battery materials and metal-organic frameworks, it is shown that some macroscopic properties are dominantly controlled by microscopic properties. These microscopic properties are well described by respective small clusters or molecules.Given their reduced size, these systems can be calculated using more accurate and numerically more demanding methods. Standard density functional theory (DFT) and the so called Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method are used for further investigations. It will be shown that SIC is able to overcome some of the problems of DFT. Given further workflows, it is demonstrated how a combination of different computational methods can speed up thermodynamic calculations and is able to deepen the understanding of the driving forces of macroscopic thermodynamic properties.:1 Introduction 2 Open-source and open-science I Theoretical basics 3 Computational methods 4 Computation of thermodynamic properties II Thermodynamics of solid state systems 5 Methodical developments 6 Lithium silicides 7 Metal-organic frameworks III Thermodynamics of nuclei and electrons 8 Electrons and bonding information 9 Thermodynamic properties IV Summary 10 Conclusion 11 Outlook V Appendix / Diese Arbeit befasst sich mit theoretischen Konzepten der phänomenologischen und statistischen Thermodynamik und deren numerischer Umsetzung. Das Hauptziel dieser Arbeit ist es, Arbeitsabläufe für die akurate Beschreibung von thermodynamischen Eigenschaften von Molekülen und Festkörpern zur Verfügung zu stellen. Der während dieser Arbeit entwickelte Cp -MD Arbeitsablauf wird angewandt um binäre Batteriemateralien, wie Lithiumsilizide, zu charakterisieren. Dieser Arbeitsablauf ermöglicht eine numerisch effiziente Beschreibung von makroskopischen thermodynamischen Eigenschaften. Für Batteriemateralien und metallorganische Gerüstverbindungen wird gezeigt, dass einige makroskopische Eigenschaften hauptsächlich von mikroskopischen Eigenschaften kontrolliert sind. Diese mikroskopischen Eigenschaften können mittels zugehöriger Cluster oder Moleküle beschrieben werden. Aufgrund ihrer reduzierten Größe können diese Systeme mit genaueren und numerisch aufwendigeren Methoden berechnet werden. Standard Dichtefunktionaltheorie (DFT) und die Fermi-Löwdin-Orbital Selbstwechselwirkungskorrektur (FLO-SWK) werden für weitere Untersuchungen verwendet. Es wird gezeigt, dass die SWK einige Probleme der DFT überwinden kann. Anhand weiterer Arbeitsabläufe wird gezeigt, wie eine Kombination von verschiedenen numerischen Methoden thermodynamische Berechnungen beschleunigen kann und in der Lage ist das Verständnis der Triebkräfte von makroskopischen thermodynamischen Eigenschaften zu vertiefen.:1 Introduction 2 Open-source and open-science I Theoretical basics 3 Computational methods 4 Computation of thermodynamic properties II Thermodynamics of solid state systems 5 Methodical developments 6 Lithium silicides 7 Metal-organic frameworks III Thermodynamics of nuclei and electrons 8 Electrons and bonding information 9 Thermodynamic properties IV Summary 10 Conclusion 11 Outlook V Appendix

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.