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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23196号 / 工博第4840号 / 新制||工||1756(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 田中 功, 教授 乾 晴行 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This thesis work deals with the volume changes during the solidification of cast irons and peritectic steels. The volume changes in casting metals are related to the expansion and/or contraction of the molten metal during solidification. Often, different types of shrinkage, namely macro- and micro-shrinkage, affect the casting quality. In addition to that, exposure of the metal casting to higher contraction or expansion during the solidification might also be related to internal strain development in samples, which eventually leads to surface crack propagation in some types of steel alloys during continuous casting. In consequence, a deep understanding of the mechanisms and control of the solidification will improve casting quality and production. All of the experiments during the entire work were carried out on laboratory scale samples. Displacement changes during solidification were measured with the help of a Linear Variable Displacement Transformer (LVDT). All of the LVDT experiments were performed on samples inside a sand mould. Simultaneously, the cooling curves of the respective samples during solidification were recorded with a thermocouple. By combining the displacement and cooling curves, the volume changes was evaluated and later used to explain the influence of inoculants, carbon and cooling rates on volume shrinkages of the casting. Hypoeutectic grey cast iron (GCI) and nodular cast iron (NCI) with hypo-, hyper- and eutectic carbon compositions were considered in the experiments from cast iron group. High nickel alloy steel (Sandvik Sanbar 64) was also used from peritectic steel type. These materials were melted inside an induction furnace and treated with different types of inoculants before and during pouring in order to modify the composition. Samples that were taken from the LVDT experiments were investigated using a number of different  methods in order to support the observations from the displacement measurements:  Differential Thermal Analysis (DTA), to evaluate the different phase present; Dilatometry, to see the effect of cooling rates on contraction for the various types of alloys; metallographic studies with optical microscopy; Backscattered electrons (BSE) analysis on SEM S-3700N, to investigate the different types of oxide and sulphide nuclei; and bulk density measurements  by applying Archimedes' principle. Furthermore, the experimental volume expansion during solidification was compared with the theoretically calculated values for GCI and NCI. It was found that the casting shows hardly any shrinkage during early solidification in GCI, but in the eutectic region the casting expands until the end of solidification. The measured and the calculated volume changes are close to one another, but the former shows more expansion. The addition of MBZCAS (Si, Ca, Zr, Ba, Mn and Al) promotes more flake graphite, and ASSC (Si, Ca, Sr and Al) does not increase the number of eutectic cells by much. In addition to that, it lowers the primary austenite fraction, promotes more eutectic growth and decreases undercooled graphite and secondary dendritic arm spacing (SDAS). As a result, the volume expansion changes in the eutectic region. The expansion during the eutectic growth increase with an increase in the inoculant weight percentage. At the same time, the eutectic cells become smaller and increase in number. The effect of the inoculant and the superheat temperature shows a variation in the degree of expansion/contraction and the cooling rates for the experiments. Effective inoculation tends to homogenize the eutectic structure, reducing the undercooled and interdendritic graphite throughout the structure. In NCI experiments, it was found that the samples showed no expansion in the transversal direction due to higher micro-shrinkages in the centre, whereas in the longitudinal direction the samples shows expansion until solidification was complete.   The theoretical and measured volume changes agreed with each other. The austenite fraction and number of micro-shrinkage pores decreased with increase in carbon content. The nodule count and distribution changes with carbon content. The thermal contraction of NCI is not influenced by the variation in carbon content at lower cooling rates. The structural analysis and solidification simulation results for NCI show that the nodule size and count distribution along the cross-sections at various locations are different due to the variation in cooling rates and carbon concentration. Finer nodule graphite appears in the thinner sections and close to the mold walls. A coarser structure is distributed mostly in the last solidified location. The simulation result indicates that finer nodules are associated with higher cooling rate and a lower degree of microsegregation, whereas the coarser nodules are related to lower cooling rate and a higher degree of microsegregation. As a result, this structural variation influences the micro-shrinkage in different parts. The displacement change measurements show that the peritectic steel expands and/or contracts during the solidification. The primary austenite precipitation during the solidification in the metastable region is accompanied by gradual expansion on the casting sides. Primary δ-ferrite precipitation under stable phase diagram is complemented by a severe contraction during solidification. The microstructural analysis reveals that the only difference between the samples is grain refinement with Ti addition. Moreover, the severe contraction in solidification region might be the source for the crack formation due to strain development, and further theoretical analysis is required in the future to verify this observation. / <p>QC 20170228</p>

For ecological reasons, the current main challenge of the automotive industry is to reduce the fuel consumption of vehicles and then emissions of greenhouse gas. In this context, steelmakers and automotive manufacturers decided for some years now to join their efforts to promote the development and use of advanced high strength steels such as TRIP steels. A combination of high strength and large elongation is obtained thanks to the TRansformation Induced Plasticity (TRIP) effect. However, improvement of the mechanical properties is still possible, especially by the refinement of the matrix. In this work, two main ways were followed in order to reach improved properties. The classical way consisting of the annealing of cold-rolled samples and an innovative way consisting of obtaining the desired microstructure by direct hot rolling of the samples. In the classical way, this refinement can be obtained by acting on the chemical composition (with such alloying elements like Cu and Nb). It was observed that complete recrystallisation of the ferrite matrix is quite impossible in presence of Cu precipitates. In addition, if the ferrite recrystallisation is not completed before reaching the eutectoid temperature, the recrystallisation will be slowed down by a large way. An innovative heat treatment consisting in keeping the copper in solid solution in the high-Cu steel was developed. Therefore, ferrite recrystallises quite easily and very fine ferrite grains (~1µm) were obtained. In the innovative way, the effects of hot-rolling conditions on TRIP-assisted multiphase steels are of major importance for industrial practice and could open new dimensions for the TRIP steels (i.e. thanks to precipitation mechanisms leading to additive strengthening). Impressive mechanical properties (true stress at maximum load of 1500 MPa and true strain at uniform elongation of 0.22) were obtained with a relatively easy thermomechanical process, the role played by Nb being essential.

This thesis describes the metallurgical and environmental factors that influence hydrogen embrittlement of super duplex stainless steels and presents a model to predict the rate at which embrittlement occurs. Super duplex stainless steel has an austenite and ferrite microstructure with an average fraction of each phase of approximately 50%. An investigation was carried out on the metallurgical and environmental factors that influence hydrogen embrittlement of super duplex stainless steels. Tensile specimens of super duplex stainless steel were pre-charged with hydrogen for two weeks in 3.5% NaCl solution at 50º C at a range of applied potentials to simulate the conditions that exist when subsea oilfield components are cathodically protected in seawater. The pre-charged specimens were then tested in a slow strain rate tensile test and their susceptibility to hydrogen embrittlement was assessed by the failure time, reduction in cross-sectional area and examination of the fracture surface. The ferrite and austenite in the duplex microstructures were identified by analysing their Cr, Ni, Mo and N contents in an electron microscope, as these elements partition in different concentrations in the two phases. It was shown that hydrogen embrittlement occurred in the ferrite phase, whereas the austenite failed in a ductile manner. An embrittled region existed around the circumference of each fracture surface and the depth of this embrittlement depended on the hydrogen charging time and the potential at which the charging had been carried out. The depth of embrittlement was shown to correlate with the rate of hydrogen diffusion in the alloy, which was measured electrochemically using hydrogen permeation and galvanostatic methods. A two-dimensional diffusion model was used to calculate the hydrogen distribution profiles for each experimental condition and the model could be employed to provide predictions of expected failure times in stressed engineering components.

A excelente resistência à corrosão dos aços inoxidáveis austeníticos é a principal característica de sua ampla gama de aplicações nas mais diversas indústrias. Entretanto, as limitadas propriedades mecânicas da austenita, restringem o uso dessas ligas em sistemas que requeiram melhor desempenho tribológico sem prejuízo de sua resistência à corrosão. Métodos de endurecimento superficial convencionais tendem a formar precipitados que reduzem a disponibilidade dos elementos responsáveis pela passivação da liga, favorecendo a ação de agentes corrosivos. A descoberta de uma fase supersaturada em intersticiais denominada austenita expandida, ou Fase-S, tem lançado novas perspectivas sobre as opções de endurecimento superficial dos aços inoxidáveis austeníticos. Produzida por modernas técnicas baseadas no emprego do plasma, a austenita expandida apresenta elevadíssima dureza, da ordem de 14 GPa, sem prejuízo de sua resistência à corrosão, uma vez que não ocorre precipitação observável por microscopia ótica ou de varredura. Caracterizações mecânicas das camadas de austenita expandida por ensaios que simulem situações mais próximas da real condição de trabalho do material fornecem um conjunto de dados empíricos relevantes para a compreensão e modelagem de fenômenos tribológicos atuantes em um dado sistema mecânico. Nesse sentido, a microesclerometria instrumentada aparece com excelente opção de ferramenta para os estudos direcionados à Engenharia de Superfície. O presente trabalho apresenta os resultados de uma série de ensaios de microesclerometria instrumentada realizados em amostras de aço AISI 316 nitretadas a plasma por 20 h em forno de corrente contínua, utilizando a tecnologia de tela ativa, temperatura de 400 ºC e atmosfera formada por três partes de nitrogênio para cada parte de hidrogênio (3N2:1H2), resultando na formação de austenita expandida na superfície. Também são discutidos a caracterização das amostras, o baixo coeficiente de atrito (< 0,1) verificado experimentalmente e a ausência de falha adesiva da camada durante o ensaio. / One of the main reasons for the common utilization of austenitic stainless steels by various industries remains on their great corrosion resistance. On the other hand, the poor mechanical properties of austenite restrict the use of these alloys in systems which require better tribological performance without decreasing their corrosion resistance. Conventional case hardening techniques promote precipitate formation, reducing availability of passivation elements in metallic matrix, what can ease the action of corrosive external agents. The discovery of a carbon and/or nitrogen supersaturated phase, called expanded austenite or S-phase, brought new perspectives over case hardening options for austenitic stainless steels. Obtained by recent techniques based on plasma, expanded austenite has very high hardness, around 14 GPa, without reducing corrosion resistance, since no precipitate is noticeable by optical or scanning electronic microscopy. Using testing apparatus that simulates real work conditions, mechanical characterization of expanded austenite layers gives an important set of empirical data. These data are useful for comprehension and modeling of tribological phenomena occurring in a given mechanical system. In this way, instrumented microscratch test appears as an interesting option to be used in studies oriented to the Surface Engineering field. This work presents results from a series of instrumented microscratch tests performed over AISI 316 stainless steel samples with an expanded austenite layer. Plasma nitriding surface treatment was carried out during 20 h, in an active screen DC reactor under 400 ºC and atmosphere compounded by three parts of nitrogen for each part of hydrogen (3N2:1H2). The tribological behavior of the expanded austenite layer was characterized in a series of linear scratch tests. The results show that in the beginning of the scratch test the coefficient of friction was kept smaller than 0,1. When the first cracks appear the apparent coefficient of friction steadily increases, indicating that cracking of the nitrided layer lead to an increase of the coefficient of friction. Although the expanded austenite layer cracks, no adhesive failure was observed, the hardened layer being preserved during the whole scratch test.

A austenita retida está sempre presente na microestrutura de camada cementada de aços, em maior ou menor quantidade. Como é uma fase dúctil comparada à martensita, sua presença tem sido alvo de muita controvérsia. Este trabalho apresenta um estudo sobre a influência da austenita retida na propagação de trincas curtas por fadiga em camada cementada de aço SAE 8620. Foram feitos ensaios de fadiga por flexão em quatro pontos, a temperatura ambiente, em corpos de prova sem entalhe com três níveis de amplitude de tensão e razão de tensões de 0,1. Através de diferentes ciclos de cementação e tratamentos térmicos, foram obtidas camadas cementadas com quatro níveis de austenita retida na microestrutura. O teor de austenita retida foi medido através da técnica de difração de Raios-X. Trincas superficiais foram monitoradas por meio da técnica de réplicas de acetato. Como resultados foram obtidos tamanho de trinca em função do número de ciclos e taxa de crescimento de trincas curtas. Corpos de prova com maiores níveis de austenita retida apresentaram maior vida em fadiga. / The retained austenite is always present in case carburized steel microstructure in small or high percentages. Since it is a ductile phase, its presence has long been a controversial subject. The influence of retained austenite on short fatigue crack propagation in case carburized SAE 8620 steel was studied in this work. Four-point-bend fatigue tests were carried out at room temperature in specimens without notch using three levels of stress range and a stress ratio of 0.1. Four different amount of retained austenite in the case carburized microstructure were obtained through different cycles of carburizing and heat treating. The retained austenite content was measured by X-ray technique, and the surface short crack growth was monitored by means of acetate replication technique. Crack length versus number of cycles and crack growth rate versus mean crack length were obtained as results. Specimens with higher levels of retained austenite in the carburized case showed longer fatigue life.

As ligas de ferro fundido branco alto cromo (FFBAC) da norma ASTM A-532 são comumente utilizadas em peças que necessitam de elevada resistência ao desgaste. Tal escolha acontece devido à elevada dureza apresentada por tais materiais, o que propicia maior vida útil dos componentes. Entretanto, uma vez que o teor de cromo utilizado nos FFBAC possui grande influência no custo das peças, é importante garantir que os tratamentos térmicos (TOTO’s) aplicados estejam otimizados para cada composição de liga. Buscando atuar nesse sentido, esta dissertação analisou a utilização de diferentes tempos e temperaturas de patamar em TOTO’s de desestabilização da austenita para duas ligas da norma ASTM A-532 (ligas com 20% e 25%Cr). Após tais procedimentos, foram estudadas a dureza e a resistência ao desgaste, tanto para algumas das amostras tratadas quanto para seis amostras de FFBAC fornecidas por diversas fundições nacionais. Os resultados demonstraram a existência de uma temperatura que otimiza a dureza da liga, possibilitando incrementos desta propriedade nas amostras tratadas em valores de até 37% (considerando a dureza inicial na condição “bruto de fusão”). Com relação ao tempo de patamar, verificou-se que o mesmo apresentou pouca influência no incremento de dureza, apresentando variações máximas inferiores à 4% para tratamentos variando entre 30 minutos à 6 horas de duração, resultado que destoou daquele indicado pela literatura. Além disso, verificou-se que uma liga com 19,6 %Cr pode apresentar uma dureza até 11% maior do que o verificado para ligas comerciais Nesta comparação, apesar da liga comercial possuir menor teor de carbono, ficou evidenciado o indicativo de que as peças consideradas neste estudo e oriundas de fundições nacionais não otimizam os resultados de seus TOTO’s. A resistência ao desgaste, por sua vez, demonstrou não depender apenas da macrodureza das amostras, mas também de outras características como tamanho, distância e continuidade dos carbonetos primários, o que explica a obtenção de resultados similares de perda de massa no ensaio abrasivo para amostras que possuem durezas diferindo em cerca de 12% porém possuindo tamanho de microconstituintes similares. Por fim, observou-se que ligas com maiores teores de cromo e menores teores de carbono apresentam menores valores de dureza e resistência ao desgaste, o que viabiliza uma aplicação com maior vida útil e menor custo. / The high chromium white cast iron alloys from ASTM A-532 are commonly used in parts which wear resistance are required. This choice happens due the great hardness showed by these alloys, what propitiates a higher lifetime for the components. However, since chromium content has great influence in the cost of the parts, it is important ensure that the apply heat treatments are optimized for each alloy composition. Thus this dissertation analyzed the application of different heat treatment cycles on the austenite destabilization for two ASTM A-532 alloys (20%Cr and 25%Cr). After the heat treatment, hardness, wear resistance and microstructure were analyzed, both for some of the treated samples as for six samples provided by different manufactures in Brazil. The results showed the existence of a temperature that optimizes the alloy hardness, allowing increases on this property in values up to 37% (considering the initial hardness of the “as cast” condition) Concerning the time of heat treatment, was verified that this parameter has low influence in the increase on hardness, showing maximum variations lower than 4% in treatments with times coming from thirty minutes until six hours, results that does not match that one’s indicated by the literature. Besides that, it was verified that an alloy with 19,6%Cr can present a hardness 11% greater than that verified in commercial. In this comparation, although the commercial alloy having lower carbon content, was evidenced that the parts from the Brazilians companies which were considered in this study, does not have an optimum heat treatment. The wear resistance was not only depend of the sample hardness, but also of other characteristics as size, distance and continuity of the primary carbides, which explain the results of similar mass loss in the abrasive test for samples with hardness differing about 12%, but with similar size of microconstituents. Finally, it was observed that alloys with higher chromium and low carbon content shows lower hardness and wear resistance values than alloys with low percentages of chromium, what enable an application with larger lifetime and lower cost.