In comparison to traditionally fabricated steels that can undergo extensive processing to produce a complex-shaped component, the powder metallurgy (PM) technique can provide a more efficient approach as it is capable of producing intricately-shaped components that require little to no additional processing and machining [1], [2]. A key factor in being able to do so pertains to quenching and utilizing an appropriate quenching agent that can provide dimensional stability to the part being quenched [3], [4]. To ensure that a PM component can perform equally well when being quenched by a quenchant of reduced cooling capability, the PM component should be if not more, then just as hardenable. Steel hardenability can inevitably be improved with the increase of overall alloying content [5], however, if overall alloying content is to be kept at a minimum, the concept of lean PM steel design is one worth investigating; where a lean steel entails that each and every alloying addition is utilized to its maximum potential. This study evaluates the homogenization behaviour of alloying elements in PM steels during sintering as well as the efficiency of wide-spread industrial practices involving the use of various master alloys and ferroalloys, and investigates the realm of liquid phase sintering to understand and optimize the homogenization behaviour of alloying elements and mechanical properties of PM steels. In the context of this work, multi-component master alloys contain at least three of non-ferrous metals as alloying elements and ferroalloys are master alloys containing iron in addition to typically a maximum of two other non-ferrous alloying additions. Part one of this study discusses a combination of thermodynamic software (DICTRA and Thermo-Calc), incremental sintering experiments and scanning electron microscopy (SEM) - wavelength dispersive spectroscopy (WDS) that were used in order to form a deeper understanding of the homogenization behaviour of alloying elements within PM steel during sintering. Electron microscopy analyses on partially and industrially sintered components provide elemental maps to track the evolution of alloying elements as they relax to homogeneity. Electron microscopy analyses for this portion of the study were conducted on an industryproduced automotive component that was sectioned and sintered industrially as well as experimentally at 1280°C for 30 minutes and 13.4 hours. DICTRA simulations carried out for this research provide a 1-D insight into the evolution of concentration profiles and phases throughout various sintering times for systems involving Cr, Mn, C and Fe. DICTRA simulation results of alloying sources were studied alongside alloying element profiles obtained by compiling point quantification from wavelength dispersive spectroscopy maps for the sintered automotive component. Computational results provided conservative, semi-quantitative recommendations on optimal alloy addition forms that lead to an improvement in homogenization. Part two of this study involves the approach of fabricating and testing multi-component master alloy additions. As these materials are widely employed in PM and are typically fabricated by solidification, their states are non-equilibrium and therefore have regions containing phases precipitating in the beginning of freezing which have higher melting temperatures than regions with phases forming later on. During heating, it is hypothesized that Scheil’s solidification path backtracks and as a result, a fraction of liquid in the ferroalloy can be estimated at sintering temperature. If the fraction is significant, the utilization of this ferroalloy implies liquid phase sintering. Through a combination of Thermo-Calc and Fortran softwares, multi-component ferroalloys with promising compositions were discovered in Fe-C-Cr-Mn, Fe-C-Cr-Mn-Ni, FeC-Mn-Mo, Fe-C-Mn-Mo-Ni and Fe-C-Cr-Mn-Mo-Ni systems for low temperature liquid phase sintering. Those of the Fe-C-Cr-Mn-Mo, Fe-C-Cr-Mn-Mo-Ni and Fe-Mn-Mo-Ni system were fabricated and tried in practice. Compositional maps and mechanical properties of PM steels made with variations of this specially tailored multi-component master alloys were compared with those for which traditional alloy additions were used. / Thesis / Master of Applied Science (MASc)

著者名別形の記述を修正（2022-04-21） / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第16850号 / 工博第3571号 / 新制||工||1540(附属図書館) / 29525 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 河合 潤, 教授 酒井 明, 教授 大塚 浩二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

O chumbo é um metal muito tóxico e que tem ampla distribuição pela sua grande utilidade. Mesmo a exposição a baixos níveis (que não causam sintomas de intoxicação aguda) de chumbo é associada a desordens cognitivas e neurológicas. O osso é considerado o melhor marcador de exposição a chumbo. No tecido ósseo, vários elementos estão presentes, e alguns deles poderiam ter sua concentração modificada pela exposição a chumbo. Testou-se a hipótese de que haja variações nos elementos Zn e Mg nas tíbias de animais expostos a chumbo (por técnica de química analítica convencional). Testou-se também se variações em microelementos poderiam ser detectadas por técnicas semiquantitativas nas tíbias de controles e animais expostos a chumbo. O objetivo deste projeto foi caracterizar em animais expostos ao chumbo desde a gestação e controles as concentrações deste elemento no osso (tíbia) de animais de 28 e 60 dias. Além do chumbo, investigamos também a concentração de 2 outros microelementos no osso: zinco e magnésio. As medidas quantitativas de chumbo foram feitas no sangue total coletado ao final dos períodos. As medidas quantitativas de chumbo, cálcio, zinco e magnésio foram realizadas a partir de soluções ácidas obtidas pela dissolução total do osso, sendo estas utilizadas para quantificar por Espectrometria de Absorção Atômica no modo chama ou com Forno e Grafite. Mandíbulas foram análisadas em Microscopia Eletrônica de Varredura e utilizando os acessórios Eletron Dispersive Spectroscopy para os elementos mais abundantes e Wavelenght dispersive Spectroscopy para investigar por análise semiquantitativa os mais abundantes elementos inorgânicos no osso destes animais, como forma de verificar se há variações nestes microelementos nos animais expostos a chumbo em comparação com controles. Como o chumbo se concentra na superfície do esmalte, também analisou-se o esmalte de primeiros molares inferiores, a fim de verificar se era visto o sinal do elemento chumbo nestes dentes. Foram usados ratos Wistar machos de 28 e 60 dias divididos em 2 grupos: C 28D (n=5) e Pb 28D (n=5) e, C 60D (n=12) e Pb 60D (n=17). Em todas as medidas de chumbo dos grupos controle as concentrações obtidas foram próximas ao limite de detecção, e houve sempre diferença estatisticamente significante (P<0.0001) quando os controles foram comparados aos grupos expostos a chumbo. As concentrações de chumbo obtidas no sangue de animais do grupo Pb 28D foi de 8,0 ug/dl (± 1.1) e no grupo Pb 60D foi de 7,2 ug/dl (± 0.89). Houve diferença estatisticamente significante entre as massas das tíbias (aferidas em balança e também a partir da quantidade de cálcio dissolvida em solução) do grupo C 60D (0,86 g ± 0,13) e Pb 60D (0,61 g ±0,11)(p=0.0004). As concentrações de chumbo detectadas nos ossos do grupo Pb 28D foi 8,02 (± 1,12) e no grupo Pb 60D foi de 43,3ug/g (± 13,26). Concentração de zinco no osso do grupo C 60D foi 0,22 mg/g e no grupo Pb 60D foi 0,22 mg/g (p>0.05). A concentração de magnésio no osso do grupo C 60D foi de 4,89 mg/g ± 0,74 e no grupo Pb 60D foi de 4,98mg/g ±0,79 (p>0.05). Os microelementos mais abundantes detectados nas tíbias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações nestes elementos entre os grupos controle e expostos a chumbo de 60 dias. O chumbo foi detectado apenas na região cervical dos dentes molares por MEV-EDS, e, nesta posição, apenas na forma de óxido de chumbo (deposição extrínseca) que pode ser útil para fins forenses ou de determinação de contaminação desconhecida. As conclusões deste estudo são: Houve diferença estatisticamente significante entre as massas de osso do grupo Pb 60D e C 60D. Mesmo não havendo diferença entre as concentrações de chumbo no sangue total de animais de 28 e 60 dias, houve quantidade de chumbo 5 vezes maior nos animais Pb 60D. Não houve diferenças nas concentrações de zinco e magnésio entre controles e animais expostos a chumbo. Os microelementos mais abundantes detectados nas tibias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações semi-quantitativas nestes elementos. O chumbo não foi detectado nem nos grupos controle ou expostos por MEV, e nos molares só foi detectada no grupo exposto como uma deposição extrínseca. / Lead is a highly toxic metal that is ubiquitous do to its great usefulness. Exposure to even low levels of lead (which do not cause symptoms of acute poisoning) is associated with cognitive and neurological disorders. Bone is considered the best marker of exposure to lead. Several chemical elements are found in bone, and some of them may have a different concentration or distribution due to exposure to lead. We tested the hypothesis that there are variations in the elements zinc and magnesium in the tibia of animals exposed to lead (being those elements determined by a conventional analytic chemistry technique). It was also tested whether variations in microelements could be detected by semiquantitative microanalysis in tibias of controls and animals exposed to lead. The objective of this project was to determine the concentration of lead in bone (tibia) of animals exposed to lead from pregnancy to day 28 and day 60. Besides lead, zinc and magnesium were also determined. Lead was also determined in whole blood collected at the end of the 2 time points. Quantitative measurements of lead, calcium, zinc and magnesium have been made in solutions obtained by dissolution of the bone by Atomic Absorption Spectrometry using flame or Graphite Furnace. Tibias were analyzed by scanning electron microscopy using the accessories Electron Dispersive Spectroscopy and Wavelength dispersive Spectroscopy for semiquantitative analysis of inorganic elements in the bone and molars of these animals. Lower molars were also analyzed by these means. Male Wistar rats aged 28 and 60 days were used in these study. In both these ages there were animals in the control (C 28D, n = 5 and C 60D, n=12) and lead exposed group (Pb 28D, n = 5 and Pb 60D, n = 17). Lead concentrations found in control groups were close to the detection limit, and there was always statistically significant differences (P <0.0001) when control groups were compared with those exposed to lead. Blood lead of groups Pb 28D and Pb 60D was 8.0 ug/dl (± 1.1) and 7.2 ug/dl (± 0.89), respectively. There was a statistically significant difference between the masses of the tibia (measured in balance and also from the amount of calcium dissolved in solution): C 60D showing 0.86 g (± 0.13 g) and 0.61 g (± 0, 11) of the Pb 60D group (p = 0.0004). Lead concentrations increased five times when the Pb 28D group was compared with the Pb 60D (8.02 and 43.3 ug/g)(p<0.0001). Zinc concentrations were not different in the C 60D (0.22 mg/g) and in the Pb 60D group (0.22 mg/g)(p>0.05). Magnesium concentrations were 4.89 mg/g in the C 60D and 4.98 mg/g in the Pb 60D (p>0.05). The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium and no variations in these elements were detected between the control and lead exposed groups. Lead was detected only in the cervical region of molar teeth of the lead exposed groups by SEM-EDS. This finding revealed lead in the lead oxide (extrinsic deposition) which may be useful for forensic purposes or for determining unknown contaminations. Conclusions: There was a statistically significant difference between the bone masses of the Pb 60D and C 60D groups. While there is no difference between lead concentrations in whole blood of animals 28 and 60 days, the amount of lead was 5 times higher in animals Pb 60D. There were no differences in the concentrations of zinc and magnesium between controls and lead exposed animals. The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium, and no semi-quantitative variations in these elements were detected in relation to exposure to lead. Lead was not detected either in control or exposed groups by SEM, and in molars it was only detected in the exposed group as an extrinsic deposition.

O chumbo é um metal muito tóxico e que tem ampla distribuição pela sua grande utilidade. Mesmo a exposição a baixos níveis (que não causam sintomas de intoxicação aguda) de chumbo é associada a desordens cognitivas e neurológicas. O osso é considerado o melhor marcador de exposição a chumbo. No tecido ósseo, vários elementos estão presentes, e alguns deles poderiam ter sua concentração modificada pela exposição a chumbo. Testou-se a hipótese de que haja variações nos elementos Zn e Mg nas tíbias de animais expostos a chumbo (por técnica de química analítica convencional). Testou-se também se variações em microelementos poderiam ser detectadas por técnicas semiquantitativas nas tíbias de controles e animais expostos a chumbo. O objetivo deste projeto foi caracterizar em animais expostos ao chumbo desde a gestação e controles as concentrações deste elemento no osso (tíbia) de animais de 28 e 60 dias. Além do chumbo, investigamos também a concentração de 2 outros microelementos no osso: zinco e magnésio. As medidas quantitativas de chumbo foram feitas no sangue total coletado ao final dos períodos. As medidas quantitativas de chumbo, cálcio, zinco e magnésio foram realizadas a partir de soluções ácidas obtidas pela dissolução total do osso, sendo estas utilizadas para quantificar por Espectrometria de Absorção Atômica no modo chama ou com Forno e Grafite. Mandíbulas foram análisadas em Microscopia Eletrônica de Varredura e utilizando os acessórios Eletron Dispersive Spectroscopy para os elementos mais abundantes e Wavelenght dispersive Spectroscopy para investigar por análise semiquantitativa os mais abundantes elementos inorgânicos no osso destes animais, como forma de verificar se há variações nestes microelementos nos animais expostos a chumbo em comparação com controles. Como o chumbo se concentra na superfície do esmalte, também analisou-se o esmalte de primeiros molares inferiores, a fim de verificar se era visto o sinal do elemento chumbo nestes dentes. Foram usados ratos Wistar machos de 28 e 60 dias divididos em 2 grupos: C 28D (n=5) e Pb 28D (n=5) e, C 60D (n=12) e Pb 60D (n=17). Em todas as medidas de chumbo dos grupos controle as concentrações obtidas foram próximas ao limite de detecção, e houve sempre diferença estatisticamente significante (P<0.0001) quando os controles foram comparados aos grupos expostos a chumbo. As concentrações de chumbo obtidas no sangue de animais do grupo Pb 28D foi de 8,0 ug/dl (± 1.1) e no grupo Pb 60D foi de 7,2 ug/dl (± 0.89). Houve diferença estatisticamente significante entre as massas das tíbias (aferidas em balança e também a partir da quantidade de cálcio dissolvida em solução) do grupo C 60D (0,86 g ± 0,13) e Pb 60D (0,61 g ±0,11)(p=0.0004). As concentrações de chumbo detectadas nos ossos do grupo Pb 28D foi 8,02 (± 1,12) e no grupo Pb 60D foi de 43,3ug/g (± 13,26). Concentração de zinco no osso do grupo C 60D foi 0,22 mg/g e no grupo Pb 60D foi 0,22 mg/g (p>0.05). A concentração de magnésio no osso do grupo C 60D foi de 4,89 mg/g ± 0,74 e no grupo Pb 60D foi de 4,98mg/g ±0,79 (p>0.05). Os microelementos mais abundantes detectados nas tíbias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações nestes elementos entre os grupos controle e expostos a chumbo de 60 dias. O chumbo foi detectado apenas na região cervical dos dentes molares por MEV-EDS, e, nesta posição, apenas na forma de óxido de chumbo (deposição extrínseca) que pode ser útil para fins forenses ou de determinação de contaminação desconhecida. As conclusões deste estudo são: Houve diferença estatisticamente significante entre as massas de osso do grupo Pb 60D e C 60D. Mesmo não havendo diferença entre as concentrações de chumbo no sangue total de animais de 28 e 60 dias, houve quantidade de chumbo 5 vezes maior nos animais Pb 60D. Não houve diferenças nas concentrações de zinco e magnésio entre controles e animais expostos a chumbo. Os microelementos mais abundantes detectados nas tibias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações semi-quantitativas nestes elementos. O chumbo não foi detectado nem nos grupos controle ou expostos por MEV, e nos molares só foi detectada no grupo exposto como uma deposição extrínseca. / Lead is a highly toxic metal that is ubiquitous do to its great usefulness. Exposure to even low levels of lead (which do not cause symptoms of acute poisoning) is associated with cognitive and neurological disorders. Bone is considered the best marker of exposure to lead. Several chemical elements are found in bone, and some of them may have a different concentration or distribution due to exposure to lead. We tested the hypothesis that there are variations in the elements zinc and magnesium in the tibia of animals exposed to lead (being those elements determined by a conventional analytic chemistry technique). It was also tested whether variations in microelements could be detected by semiquantitative microanalysis in tibias of controls and animals exposed to lead. The objective of this project was to determine the concentration of lead in bone (tibia) of animals exposed to lead from pregnancy to day 28 and day 60. Besides lead, zinc and magnesium were also determined. Lead was also determined in whole blood collected at the end of the 2 time points. Quantitative measurements of lead, calcium, zinc and magnesium have been made in solutions obtained by dissolution of the bone by Atomic Absorption Spectrometry using flame or Graphite Furnace. Tibias were analyzed by scanning electron microscopy using the accessories Electron Dispersive Spectroscopy and Wavelength dispersive Spectroscopy for semiquantitative analysis of inorganic elements in the bone and molars of these animals. Lower molars were also analyzed by these means. Male Wistar rats aged 28 and 60 days were used in these study. In both these ages there were animals in the control (C 28D, n = 5 and C 60D, n=12) and lead exposed group (Pb 28D, n = 5 and Pb 60D, n = 17). Lead concentrations found in control groups were close to the detection limit, and there was always statistically significant differences (P <0.0001) when control groups were compared with those exposed to lead. Blood lead of groups Pb 28D and Pb 60D was 8.0 ug/dl (± 1.1) and 7.2 ug/dl (± 0.89), respectively. There was a statistically significant difference between the masses of the tibia (measured in balance and also from the amount of calcium dissolved in solution): C 60D showing 0.86 g (± 0.13 g) and 0.61 g (± 0, 11) of the Pb 60D group (p = 0.0004). Lead concentrations increased five times when the Pb 28D group was compared with the Pb 60D (8.02 and 43.3 ug/g)(p<0.0001). Zinc concentrations were not different in the C 60D (0.22 mg/g) and in the Pb 60D group (0.22 mg/g)(p>0.05). Magnesium concentrations were 4.89 mg/g in the C 60D and 4.98 mg/g in the Pb 60D (p>0.05). The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium and no variations in these elements were detected between the control and lead exposed groups. Lead was detected only in the cervical region of molar teeth of the lead exposed groups by SEM-EDS. This finding revealed lead in the lead oxide (extrinsic deposition) which may be useful for forensic purposes or for determining unknown contaminations. Conclusions: There was a statistically significant difference between the bone masses of the Pb 60D and C 60D groups. While there is no difference between lead concentrations in whole blood of animals 28 and 60 days, the amount of lead was 5 times higher in animals Pb 60D. There were no differences in the concentrations of zinc and magnesium between controls and lead exposed animals. The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium, and no semi-quantitative variations in these elements were detected in relation to exposure to lead. Lead was not detected either in control or exposed groups by SEM, and in molars it was only detected in the exposed group as an extrinsic deposition.