A systematic in-depth study has been undertaken to establish the corrosion mechanism of a Model 25Cr-35Ni-Fe alloy and four commercial alloys HP40Nb, AISI314, HP40Al and Alloy 800H in low oxygen, high sulphur and carbon containing environments typically found in coal gasification and fluidised bed combustion processes. A review of present knowledge of corrosion processes in purely oxidizing, sulphidizing and carburizing environments and multiple reactant carburizing/ oxidizing, carburizing/sulphizing and oxidizing/sulphidizing environments is given. The experimental programme was designed to establish the role of sulphur on the corrosion process by studying corrosion mechanisms in a sulphurfree H2-7%C0-1.5%H2o gas, a low sulphur H2-7%C0-1.5%H20-0.2%H 2 S gas (pS2_8= 10 bar), and a high sulphur H 2 -7%C0-1.5%H 2 0-0.6%H 2 S gas (pS = lO bar) at 800'C. All_21j_hree environments had a constant partiaf pressure of oxygen (po2 = 10 bar) and carbon activity (ac = 0.3). In the sulphur-free gas the Model alloy formed a thin uniform cr 2 o 3 layer which grew at a constant parabolic rate throughout the exposure period of 0 - 5000 hours. Surface working increased the growth rate and thickness of the Cr 2 o 3 layer but created a large number of cracks and pores which allowed carbon containing gaseous species to diffuse through the oxide to form carbide precipitates in the alloy substrata. Alloying additions of Si promoted the formation of an inner SiO layer which reduced the corrosion rate by cutting off the outward diffusion of Cr, Mn and Fe. Alloying additions of Mn promoted the formation of an additional outer (Mn, Fe )Cr 2o 4 layer. The 3. 5% Al content of the HP40Al was insufficient to form a complete Al 2 o3 layer. Alloy 800H was susceptible to localised internal oxidation. Adding a low level of sulphur (0.2% H 2 S) to the gas increased the corrosion rate of the Model alloy in the 1nitial stages. This rate gradually slowed down before becoming parabolic after 1000 - 2000 hours. This was due to the nucleation of sulphides in addition to oxides. The oxides and sulphides grew side by side until the oxides overgrew the sulphides to form a complete Cr 2o3 layer which cut off further ingress of sulphur from the gas. The entrapped sulphides promoted localized thickening of the oxide layer. Eventually the sulphur redistributed from the sulphides in the scale to internal sulphide precipitates in the alloy with the corrosion rate returning to that of the sulphur-fre,e gas for the rest of the exposure period (5000 hours total). In the commercial alloys the internal sulphide precipitates prevented the inner Si02 layer becoming complete. Sulphur doped the (Mn, Fe) Cr 2 0 4 outer layer ana the intermediate Cr 2o3 layer formed from the spinal layer, increasing the number of cation . vacancies and the growth rate of the scale. These factors caused a massive Cr depletion of the alloy substrata after several thousand hours. The internal carbides became unstable which led to a massive amount of internal attack and a dramatic increase (breakaway) in the corrosion rate. Due to its thickness and the presence of Si02 inner layer the external scale became susceptible to spallation. If this occurred the oxides and sulphides nucleated on the alloy surface again but sulphides. protective alloy. insufficient Cr was available for the oxides to overgrow the The sulphides therefore grew to form a fast growing nonsulphide scale which soon led to catastrophic failure of the Increasing the level of sulphur in the gas to 0.6% H2S caused oxides and sulphides to nucleate on the surface, but in this case the sulphides overgrew the oxides to form thick fast growing non-protective sulphide scales on all the alloys.

Orientador: Anselmo Eduardo Diniz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-09T18:35:54Z (GMT). No. of bitstreams: 1 Marques_DanielCirillo_M.pdf: 1133787 bytes, checksum: 7116947050a42005d85657f4c29da1a2 (MD5) Previous issue date: 2007 / Resumo: O objetivo deste trabalho foi estudar a influência do teor de níquel de ligas FeCrNi na vida da ferramenta de metal duro em processo de torneamento em acabamento. Para este estudo foram preparadas ligas com composição básica 18%Cr-0,01%C-0,2%Si-0,4%Mn e com teores de níquel variados (0, 10, 20, 30, 40, 50 e 60%). A medida que o teor de níquel subia, o teor de ferro diminuía na mesma proporção. Os ensaios foram realizados com pastilhas de metal duro classe M15 revestidas com TiC/Al2O3/TiN. Todos os materiais foram usinados nas mesmas condições (vc = 230 m/min, ap = 0,6 mm e f = 0,1 mm/volta), garantindo assim, como única fonte de variação, o teor de níquel. Os resultados mostram que a vida da ferramenta diminui com o aumento do teor de níquel e que o principal mecanismo de desgaste da ferramenta é a adesão e arrancamento de partículas da ferramenta. Uma exceção se deu com o material com 30% de níquel, que apesar de apresentar o mesmo mecanismo de desgaste, mostrouse mais fácil de usinar, gerando maior tempo de vida da ferramenta / Abstract: The aim of this work was to study the influence of nickel content in FeCrNi alloys on the coated cemented carbide tool life during the finish turning process. For this purpose 18%Cr-0,01%C-0,2%Si-0,4%Mn base composition and variable nickel content (0, 10, 20, 30, 40, 50 and 60 weight %) alloys were prepared. As the nickel content increased, the iron content decreased in the same proportion. Tests were carried out with coated cemented carbide inserts, M15 class with TiC/Al2O3/TiN coating. All alloys were machined on the same cutting conditions (vc = 230 m/min, ap = 0,6 mm and f = 0,1 mm/rev), in order to set nickel content as the only input variable. Results indicate that tool life decreases with the growth of nickel content, and the mainly tool wear mechanism is attrition. An exception was the material with 30% of nickel, that presented the same tool wear mechanism but showed out higher machinability, allowing longer tool life / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Spinodal decomposition is a phenomenon which hinders the usage of ferrite containing steels under certain conditions. With a better understanding and knowledge of spinodal decomposition new ferritic and duplex stainless steels could be designed. The project is divided into two parts, an experimental part and a theoretical part. The aim of the theoretical part was to compare simulated values of the amplitude and wavelength of spinodal decomposition, obtained from solving the Cahn-Hilliard equation with other experimental values. The experimental part is performed as to determine the chemical diffusion coefficient and the mobility of Fe and Cr in the binary Fe-Cr system for lower temperatures using the Boltzmann-Matano method from chemical profiles of different samples. Another purpose with the project is to determine if the methods and the approach which are taken is viable and useful for calculating diffusion coefficients and if it can be used in studies to come. The simulations were in good agreement with other data at higher time intervals, but deviates at lower times. The calculated interdiffusion coefficients were in all cases lower than the expected values and as such the conclusion that is drawn is that the methods which are used could need further development. / Spinodalt sönderfall är ett fenomen som hindrar användningen av stål som innehåller ferrit under vissa förutsättningar. Med en större förståelse och mer kunskap om spinodalt sönderfall så kan nya ferritiska och duplexa rostfria stål utformas. Projektet är uppdelat i två delar, en experimentell del och en teoretisk del. Syftet med den teoretiska delen var att jämföra simulerade värden av amplituden och våglängden för spinodalt sönderfall, vilka erhölls från att lösa Cahn-Hilliard ekvationen med andra experimentella värden. Den experimentella delen utförs för att bestämma kemiska diffusionskoefficienter för Fe och Cr i det binära Fe-Cr system för lägre temperaturer med hjälp av Boltzmann-Matano metod från kemiska profiler av olika prover. Ett annat syfte med projektet är att ta reda på om de metoder och tillvägagångssätt som tas är livskraftiga och användbara för beräkning av diffusionskoefficienter och om den kan användas i studier framöver. Simuleringarna var i god överensstämmelse med annan experimentel data vid högre tidsintervall, men avviker vid lägre tider. De beräknade Interdiffusion koefficienterna var i samtliga fall lägre än de förväntade värdena och som sådan, dras slutsatsen att de metoder som används kan förbättras.

O objetivo do presente projeto é a combinação de abordagens experimentais e teóricas para o desenvolvimento de bancos de dados termodinâmicos, visando o modelamento de aços e ligas de alto desempenho. Entre esses materiais estão as superligas fundidas por centrifugação para aplicações em fornos de reforma e pirólise, bem como aços-ferramenta reforçados por fases intermetálicas. Os métodos teóricos mencionados correspondem à combinação de cálculos de estrutura eletrônica e modelamento termodinâmico em temperaturas finitas, através do protocolo Calphad. Esta metodologia vem sendo aplicada com sucesso por vários grupos de pesquisa brasileiros e internacionais. Utilizando-nos de dados experimentais para o sistema Fe-Cr-Mo-C, obtidos recentemente em nosso laboratório, e cálculos de primeiros princípios para o sistema Ni-Nb-Si, aliados a outros resultados experimentais da literatura, aperfeiçoamos os bancos de dados termodinâmicos existentes para estes dois sistemas, minimizando as inconsistências quanto às evidências experimentais em relação aos campos de estabilidade e equilíbrio entre fases. No sistema Fe-Cr-Mo-C, utilizamo-nos de dados experimentais para uma reotimização da descrição termodinâmica. Adotamos novas descrições para os binários Cr-Fe, C-Cr e C-Fe, com novos modelos para as fases cementita no sistema C-Fe e sigma no sistema Cr-Fe. Com essas alterações, fomos levados a reavaliar todas as descrições dos ternários, reotimizando-os quando necessário (C-Cr-Fe) ou apenas revalidando os modelamentos pré-existentes (C-Cr-Mo). Por fim, reotimizamos o quaternário como um todo, chegando a resultados satisfatórios quando comparados a resultados experimentais. As propriedades termodinâmicas do sistema Nb-Ni-Si são pouquíssimo conhecidas. Por este motivo, não há dados suficientes na literatura para realizar um assessment completo deste sistema. Por isto, decidimos realizar cálculos de primeiros princípios de estrutura eletrônica, para a determinação de energias de formação dos compostos ternários presentes neste sistema. Os sistemas binários Nb-Ni, Nb-Si e Ni-Si, por outro lado, são bem conhecidos, cada um deles contando com diversas descrições termodinâmicas publicadas ao longo dos últimos anos. Por esta razão, adotamos as mais recentes descrições termodinâmicas dos binários como ponto de partida para o modelamento do sistema ternário. O resultado do modelamento, quando comparado aos poucos dados experimentais disponíveis, é bastante satisfatório. / The aim of this project is the combination of advanced experimental and theoretical approaches for the development of thermodynamic databases dedicated to modelling steels and high performance alloys. Examples of materials are centrifugally-cast superalloys designed for use in reforming and pyrolisis furnaces, as well as intermetallic-reinforced tool steels. The theoretical methods are the combination of electronic structure calculations and thermodynamic modeling at finite temperatures using the CALPHAD method. This methodology has been used by different scientific groups, both in Brazil and around the world. Using experimental data in the Fe-Cr-Mo-C sytem, recently determined in our laboratory, and first principles calculations in the Nb-Ni-Si system, together with other experimental results from the literature, we improved the existing thermodynamic databases for these two systems, minimizing discrepancies regarding the experimental evidence about phase stability fields and phase equilibria. In the Fe-Cr-Mo-C system, we employed experimental data for a reoptimization of the thermodynamic description. We adopted new descriptions for the binary Cr-Fe, C-Cr, and C-Fe systems, with new models for cementite in the C-Fe system, and sigma in the Cr-Fe system. Because of these alterations, a reevaluation of the ternary descriptions was necessary, reassessing them when required (C-Cr-Fe) or just revalidating existing models (C-Cr-Mo). After that, we re-optimized the quaternary system, arriving at satisfactory results, in comparison with experimental data. The thermodynamic properties of the Ni-Nb-Si system is almost completely unknown. For that reason, there are not enough data in the literature to perform a complete assessment of the system. With that in mind, we decided to perform first-principles electronic structure calculations, in order to determine the formation energies of the ternary compounds. The binary systems, on the other hand, are very well-known, each one of them with several published thermodynamic assessments during the last few years. For this reason, we adopted the most recent thermodynamic descriptions of the binaries as a starting point for the modelling of the ternary system. The result of the modelling is very satisfactory, in comparison with the few experimental information available.

Afin d'améliorer la compréhension de l'évolution microstructurale des alliages Fe-Cr irradiés, alliages modèles des aciers ferrito-martensitiques (F-M) à haut Cr candidats comme matériaux de structure des réacteurs de génération IV, l'évolution de la microstructure a été étudiée à l'échelle nanométrique en fonction de la teneur en Cr et de la température d'irradiation. Deux séries d'expériences ont été réalisées: ● Des alliages modèles Fe-5%Cr, Fe-9%Cr et Fe-12%Cr irradiés aux neutrons à 300°C (température minimale de service pour les aciers F-M) jusqu'à 0.6dpa ont été analysés par sonde atomique 3D (3DAP). Ces analyses ont montré que les impuretés sont également impliquées dans l'évolution microstructurale de ces alliages sous irradiation. Deux familles indépendantes de clusters ont été observées : des clusters de NiSiPCr observés dans tous les alliages et des clusters riches en Cr correspondant à la phase α ' mais observés uniquement dans les alliages sursaturés en Cr (Fe-9%Cr et Fe-12%Cr). Ce travail a montré que l'apparition des clusters de NiSiPCr est induite par l'irradiation alors que celle des clusters riches en Cr est issue d'un processus accéléré par l'irradiation. Des enrichissements en Si, P et Cr ont été observés sur les lignes de dislocations ainsi que dans des joints de grain de faible et forte désorientation dans tous les alliages. ● Des alliages Fe-9%Cr et Fe-12%Cr ont été irradiés aux ions Fe + de 150 keV à 500°C (température maximale de service pour les aciers F-M). Des expériences de MET in situ entreprises jusqu'à une dose de 1.5 dpa, ont montré que le dommage apparaissait sous la forme de boucles de dislocations distribuées de façon homogène dans les grains. Dans les deux alliages modèles les boucles sont principalement du type <100>. L'analyse par 3DAP des mêmes alliages irradiés dans les mêmes conditions mais sous forme de pointes ne révèle aucune redistribution des espèces chimiques après irradiation.

Comprendre l'origine de la fragilisation des aciers austéno-ferritiques utilisés dans les coudes moulés des circuits primaires des centrales nucléaires est une étape clé pour l'anticipation de leur vieillissement. Cette prédiction nécessite une caractérisation et une compréhension du mécanisme de transformation de phase à l'origine de ce constat : la décomposition de la ferrite. Ainsi, de façon duale, des ferrites d'aciers vieillis plus de 20 ans, sur site ou en laboratoire ainsi qu'à différentes températures, ont été analysées par sonde atomique tomographique et un travail de simulation de la décomposition de la ferrite d'alliages modèles Fe-Cr a été initié. Afin de valider les paramètres utilisés en simulation Monte Carlo, une étude expérimentale de la démixtion d'un alliage Fe-20 % at. Cr vieilli à 500°C a été réalisée. Cette étude expérimentale a montré qu'un régime de germination non classique (GNC) intervient dans cet alliage. La simulation de la décomposition de la ferrite dans le même alliage, vieilli à la même température, n'a pas révélé l'enrichissement progressif des précipités de phase α' caractéristique de la GNC. L'étude d'aciers vieillis plus de 20 ans a permis de confirmer que les aciers vieillis en laboratoire sont représentatifs de ceux vieillis sur site (pour T < 350°C), que la phase G (précipitation intermétallique à l'interface des phases α/α') n'influence pas la fragilisation de la ferrite et que la différence de traitement thermomécanique n'est pas déterminante quant à l'écart de décomposition observé dans ces aciers.

O objetivo do presente projeto é a combinação de abordagens experimentais e teóricas para o desenvolvimento de bancos de dados termodinâmicos, visando o modelamento de aços e ligas de alto desempenho. Entre esses materiais estão as superligas fundidas por centrifugação para aplicações em fornos de reforma e pirólise, bem como aços-ferramenta reforçados por fases intermetálicas. Os métodos teóricos mencionados correspondem à combinação de cálculos de estrutura eletrônica e modelamento termodinâmico em temperaturas finitas, através do protocolo Calphad. Esta metodologia vem sendo aplicada com sucesso por vários grupos de pesquisa brasileiros e internacionais. Utilizando-nos de dados experimentais para o sistema Fe-Cr-Mo-C, obtidos recentemente em nosso laboratório, e cálculos de primeiros princípios para o sistema Ni-Nb-Si, aliados a outros resultados experimentais da literatura, aperfeiçoamos os bancos de dados termodinâmicos existentes para estes dois sistemas, minimizando as inconsistências quanto às evidências experimentais em relação aos campos de estabilidade e equilíbrio entre fases. No sistema Fe-Cr-Mo-C, utilizamo-nos de dados experimentais para uma reotimização da descrição termodinâmica. Adotamos novas descrições para os binários Cr-Fe, C-Cr e C-Fe, com novos modelos para as fases cementita no sistema C-Fe e sigma no sistema Cr-Fe. Com essas alterações, fomos levados a reavaliar todas as descrições dos ternários, reotimizando-os quando necessário (C-Cr-Fe) ou apenas revalidando os modelamentos pré-existentes (C-Cr-Mo). Por fim, reotimizamos o quaternário como um todo, chegando a resultados satisfatórios quando comparados a resultados experimentais. As propriedades termodinâmicas do sistema Nb-Ni-Si são pouquíssimo conhecidas. Por este motivo, não há dados suficientes na literatura para realizar um assessment completo deste sistema. Por isto, decidimos realizar cálculos de primeiros princípios de estrutura eletrônica, para a determinação de energias de formação dos compostos ternários presentes neste sistema. Os sistemas binários Nb-Ni, Nb-Si e Ni-Si, por outro lado, são bem conhecidos, cada um deles contando com diversas descrições termodinâmicas publicadas ao longo dos últimos anos. Por esta razão, adotamos as mais recentes descrições termodinâmicas dos binários como ponto de partida para o modelamento do sistema ternário. O resultado do modelamento, quando comparado aos poucos dados experimentais disponíveis, é bastante satisfatório. / The aim of this project is the combination of advanced experimental and theoretical approaches for the development of thermodynamic databases dedicated to modelling steels and high performance alloys. Examples of materials are centrifugally-cast superalloys designed for use in reforming and pyrolisis furnaces, as well as intermetallic-reinforced tool steels. The theoretical methods are the combination of electronic structure calculations and thermodynamic modeling at finite temperatures using the CALPHAD method. This methodology has been used by different scientific groups, both in Brazil and around the world. Using experimental data in the Fe-Cr-Mo-C sytem, recently determined in our laboratory, and first principles calculations in the Nb-Ni-Si system, together with other experimental results from the literature, we improved the existing thermodynamic databases for these two systems, minimizing discrepancies regarding the experimental evidence about phase stability fields and phase equilibria. In the Fe-Cr-Mo-C system, we employed experimental data for a reoptimization of the thermodynamic description. We adopted new descriptions for the binary Cr-Fe, C-Cr, and C-Fe systems, with new models for cementite in the C-Fe system, and sigma in the Cr-Fe system. Because of these alterations, a reevaluation of the ternary descriptions was necessary, reassessing them when required (C-Cr-Fe) or just revalidating existing models (C-Cr-Mo). After that, we re-optimized the quaternary system, arriving at satisfactory results, in comparison with experimental data. The thermodynamic properties of the Ni-Nb-Si system is almost completely unknown. For that reason, there are not enough data in the literature to perform a complete assessment of the system. With that in mind, we decided to perform first-principles electronic structure calculations, in order to determine the formation energies of the ternary compounds. The binary systems, on the other hand, are very well-known, each one of them with several published thermodynamic assessments during the last few years. For this reason, we adopted the most recent thermodynamic descriptions of the binaries as a starting point for the modelling of the ternary system. The result of the modelling is very satisfactory, in comparison with the few experimental information available.

Fe-Cr based steels, i.e. stainless steels, possessing a combination of excellent corrosion resistance and good mechanical properties, have indispensable applications ranging from low-end cooking utensils, to sophisticated components for nuclear power plants. However, the bcc/bct phase containing stainless steels which have a miscibility gap (MG) suffer from the so-called “475 oC embrittlement” leading to hardness increase and toughness deterioration. It occurs due to demixing of Fe and Cr leading to the formation of Fe-rich (α) and Cr-rich (α′) regions in bcc/bct phases. The demixing is referred to as phase separation (PS). The goal of this work was to study PS in ferrite containing stainless steels mainly by small-angle neutron scattering (SANS). Firstly, the application of different experimental techniques for the study of phase separation in Fe-Cr based steels was reviewed and supplemented by new measurements. SANS was shown to be very sensitive to the nanostructure change caused by PS and capable of characterizing the early stages of PS in Fe-Cr alloys. However, atom probe tomography and transmission electron microscopy are complementary to SANS. Therefore, in order to have a more complete view of the microstructure, the combination of these techniques should be pursued. Secondly, the factors affecting the initial microstructure prior to aging treatment and the effect of the resulted initial microstructure on PS were systematically investigated using binary Fe-Cr model alloys. The critical temperature of the MG was determined to be located between 560 and 580 oC in binary Fe-Cr. The results indicate that the solution treatment temperature above the MG and the cooling rate after solution treatment have significant effects on the initial microstructure and thus on PS during subsequent aging. The mechanisms responsible for the changed aging behavior are Cr clustering, quenched-in vacancy and decomposition during cooling. Therefore, computational simulations should take into account these factors and the initial microstructure to make predictions that are more accurate. Thirdly, the study was extended to PS in commercial duplex stainless steels (DSSs) which are of practical importance in various industries, e.g., nuclear power. It is found that alloying elements have an important effect on PS in DSSs. The grade 2507 (25 %Cr, 7 %Ni) experiences stronger PS than grade 2205 (22 %Cr, 5 % Ni) for the same heat treatment. Moreover, the fracture mechanisms as well as the mechanical properties depend on the extent of PS.  Finally, the fundamental aspects regarding the neutron scattering behavior for Fe-Cr alloys were examined. The results show that the nuclear and magnetic scattering of neutrons depend on the evolution of the nanoscale compositional fluctuation in Fe-Cr alloys. The ratio of the magnitude of nuclear scattering versus magnetic scattering varies with the extent of PS. / Stål baserade på Fe-Cr systemet, det vill säga rostfria stål, som har en kombination av utmärkta korrosionsegenskaper och bra mekaniska egenskaper, har många tillämpningar; allt från köksredskap, till sofistikerade komponenter för kärnkraftverk. Rostfria stål som innehåller Bcc / bct-fasen och som således har en blandningslucka, är känsliga för den så kallade "475 °C försprödningen" som leder till en hårdhetsökning men kraftigt försämrad slagseghet. Detta uppstår på grund av en uppdelning av Fe och Cr som leder till bildandet av Fe-rika (a) och Cr-rika (a’) regioner i bcc / bct-fasen. Denna uppdelning brukar kallas fasseparation. Målet med detta arbete var att studera fasseparationen i ferrit-innehållande rostfria stål främst genom lågvinkel-spridning av neutroner (SANS). Till att börja med studerades och jämfördes olika experimentella tekniker för undersökning av fasseparation i Fe-Cr-baserade stål med nya SANS- mätningar. SANS visade sig vara mycket känslig för förändringar på nano-skala orsakad av fasseparation och tekniken visade sig även kapabel att karakterisera de tidiga stadierna av fasseparation i Fe-Cr-legeringar. För att få en mer fullständig bild av mikrostrukturen efter fasseparation, bör emellertid en kombination av SANS och komplementära tekniker, såsom atomsond och transmissions-elektronmikroskopi, användas. Vidare undersöktes de faktorer som påverkar den ursprungliga mikrostrukturen före åldringsbehandling, och effekten av den initiala mikrostrukturen på fasseparation studerades systematiskt med användning av binära modell-legeringar av Fe-Cr. Den kritiska temperaturen för blandningsluckan i Fe-Cr bestämdes vara belägen mellan 560 och 580 °C. Resultaten indikerar att temperaturen för upplösningsbehandling ovanför blandningsluckan och kylhastigheten har en signifikant inverkan på den initiala mikrostrukturen och därmed på fasseparationen under efterföljande åldring. Mekanismerna som är ansvariga för det förändrade åldringsbeteendet är: Cr-klustring, insläckta vakanser och fasseparation under kylning. Simuleringar av fasseparationen bör därför ta hänsyn till dessa faktorer och den ursprungliga mikrostrukturen för att göra mer exakta förutsägelser av hur mikrostrukturen utvecklar sig med åldringstiden. Fasseparationen i kommersiella duplexa rostfria stål (DSS), som är av stor praktisk betydelse i olika branscher, t ex kärnkraft, studerades också med SANS. Det visade sig att mängden av olika legeringselement har en viktig effekt på graden av fasseparation i DSS. Legeringen 2507 uppvisade en tydligare fasseparation jämfört med legering 2205 för samma värmebehandling. Brottmekanismerna såväl som de mekaniska egenskaperna visade sig bero på omfattningen av fasseparationen. Slutligen undersöktes de grundläggande aspekterna hos neutronspridnings-beteendet för binära Fe-Cr-legeringar. Resultaten visade att kärn- och magnetisk spridning av neutroner beror på utvecklingen av sammansättningsfluktuationerna på en nanoskala i Fe-Cr-legeringar. Förhållandet mellan magnetisk- och kärnspridning varierar med omfattningen av fasseparationen. / <p>QC 20171117</p>

Spinodal decomposition is a phase separation mechanism within the miscibility gap. Its importance in case of Fe-Cr system, the basis of the whole stainless steel family, stems from a phenomenon known as the “475oC embrittlement” which results in a ruin of mechanical properties of ferritic, martensitic and duplex stainless steels. This work is aimed at a better understanding of the phase separation process in   the Fe-Cr system. Alloys of 10 to 55 wt.% Cr , each five percent, were homogenized to achieve fully ferritic microstructure and then isothermally aged at 400, 500 and 600oC for different periods of time ranging from 30min to 1500 hours. Hardness of both homogenized and aged samples were measured by the Vickers micro-hardness method and then selected samples were studied by means of Transmission Electron Microscopy (TEM).  It was observed that hardness of homogenized samples increased monotonically with increasing Cr content up to 55 wt.% which can be attributed to solution hardening as well as higher hardness of pure chromium compared to pure iron.  At 400oC no significant change in hardness was detected for aging up to 1500h, therefore we believe that phase separation effects at 400oC are very small up to this time. Sluggish kinetics is imputed to lower diffusion rate at lower temperatures. At 500oC even after 10h a noticeable change in hardness, for alloys containing 25 wt.% Cr and higher, was observed which indicates occurrence of phase separation. The alloy with 10 wt.% Cr did not show change in hardness up to 200h which suggests that this composition falls outside the miscibility gap at 500oC. For compositions of 15 and 20 wt.% Cr only a small increase in hardness was detected even after 200h of aging at 500oC, which could be due to the small amounts of α´ formed. However, it means that alloys of 15 wt.% Cr and higher are suffering phase separation. For compositions inside the miscibility gap, hardening effect is a result of phase separation either by nucleation and growth or spinodal decomposition. To distinguish between these two mechanisms, TEM studies were performed and we found evidence that at 500oC the Fe-25 wt.% Cr sample decomposes by nucleation  and growth  while that of 35 wt.% Cr  shows characteristics of the spinodal mechanism. For compositions inside the miscibility gap, with increasing Cr content up to 40% the change in hardness generally increased and for 45% and higher it always decreased. This suggests that the composition range corresponding to the spinodal region at 500oC is biased towards the Fe-rich side of the phase diagram. At 600oC only samples of 25, 30 and 35 wt.% Cr were studied because according to the previous studies, the spinodal boundary is most probably located in this composition range. However, no change in hardness was observed even up to 24h. We believe that this means the miscibility line lies below 600oC for alloys containing 35 wt.% Cr and lower. Further investigations are needed to confirm and explain this result.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20363号 / 工博第4300号 / 新制||工||1666(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 安田 秀幸, 教授 辻 伸泰, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM