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L’objectif de ce travail consiste à améliorer les propriétés mécaniques d’un acier faiblement allié à bas carbone (0,2%) sans recours à des procédés de métallurgie secondaire onéreux. Pour cela, un processus d’inoculation, déjà utilisé lors de l’élaboration des fontes, est transposé à notre nuance d’acier. Il consiste à ajouter des éléments en très faible quantité dans l’acier liquide pour en modifier le processus de solidification donc la microstructure et par conséquent les propriétés de l’acier, dont la résilience. L’ajout d’éléments en très faible quantité ne modifie pas la nuance d’acier. Ils doivent être ajoutés en fin de fusion du métal sous forme de poudre dans le jet de coulée. Les effets de ces éléments se verront sur la microstructure notamment au niveau des inclusions et de la taille des grains. Le « bon candidat » est un élément qui conduira à une répartition homogène d’inclusions de petites tailles et de forme sphérique. Il doit aussi permettre de réduire la taille des grains. Ces modifications de structure sont supposées améliorer les propriétés mécaniques de l’acier et notamment la résistance aux chocs. Une pièce de référence est réalisée pour pouvoir en étudier la microstructure. La forme retenue est un lingot parallélépipédique dimensionné à l’aide d’un logiciel de simulation de coulée afin de prévenir des principaux défauts de fonderie. La taille est adaptée à l’échelle laboratoire (capacité four 120 kg). Les charges de fusion correspondant à la nuance étudiée sont fournies par l’entreprise partenaire de la thèse, SAFE Metal. La première étape est d’obtenir un bain convenablement désoxydé ; c’est-à-dire ajouter de l’aluminium afin de piéger l’oxygène dissous pour l’évacuer. Pour mettre en évidence d’éventuels effets significatifs des différents inoculants testés, il faut partir d’un échantillon de référence contenant un nombre d’inclusions relativement élevé. Ceci est obtenu en ajoutant du soufre dans le bain liquide. Cet élément agit directement sur le nombre d’inclusions présentes dans l’acier en formant des sulfures. Pour passer à l’étape d’inoculation il a fallu créer un outillage spécifique pouvant s’adapter à l’échelle du laboratoire. Des essais sont ensuite réalisés avec différents produits à des concentrations variables. Les échantillons obtenus sont analysés par différentes techniques : analyse chimique de l’acier (spectrométrie étincelle et ICP), analyse de microstructure et de la taille de grains (par micrographie optique) et le comptage inclusionnaire. En ce qui concerne ce dernier point qui consiste à détecter les inclusions, à les compter et à les classer par leur nature, leur forme et leur taille, deux possibilités existent. Soit à l’aide d’un microscope optique mais les risques d’erreur sont importants et le processus est long et fastidieux, soit à l’aide d’un logiciel spécifique (AZtec) couplé à un microscope électronique à balayage (MEB). C’est ce choix qui a été fait, car outre le fait qu’il permette un gain de temps considérable grâce à une automatisation du processus, il est possible de connaître via une sonde EDS, la composition chimique de chaque particule. Pour tous les produits testés, il a été montré que l’inoculation n’avait que peu d’effet sur la taille des inclusions et qu’elles deviennent plus complexes en contenant plusieurs éléments chimiques. Pour certains produits, on voit apparaître des amas d’inclusions. Ces amas sont susceptibles de favoriser la fragilité de l’acier en formant des amorces de fissuration. Pour d’autres, les inclusions diminuent nettement, ont une forme globulaire et la taille des grains est affinée. Ces effets ont tendance à améliorer les propriétés mécaniques de ces aciers. La teneur d’introduction de l’inoculant est aussi déterminée pour un maximum d’efficacité. L’inoculant le plus important pourra être utilisé pour une possible industrialisation. / The objective of this work is to improve the mechanical properties of a low-carbon steel (0.2%) without the use of expensive secondary metallurgy processes. For this, a method of inoculation, already used during the development of the cast iron, is transposed to our steel grade. It consists in adding very small quantities in liquid steel in order to modify the solidification process, thus the microstructure and consequently the properties of the steel, especially resilience. The addition of elements in very small quantities does not modify the grade of steel. They must be added at the end of melting of the metal in the form of powder in the casting stream. The effects of these elements will be seen on the microstructure, particularly in terms of inclusions and grain size. The "good candidate" is an element that will lead to a homogeneous distribution of inclusions of small size and spherical shape. It must also make it possible to reduce the size of the grains. These structural modifications are supposed to improve the mechanical properties of the steel and in particular the impact resistance. A reference piece is made to study the microstructure. The retained shape is a parallelepiped ingot sized using a casting simulation software to prevent major foundry defects. The size is adapted to the laboratory scale (furnace capacity 120 kg). The load corresponding to the grade studied are provided by the SAFE Metal, the partner company. The first step is to obtain a suitably deoxidized bath; that means adding aluminum in order to trap the dissolved oxygen and to evacuate it. To demonstrate any significant effects of the various inoculants tested, it is necessary to start from a reference sample containing a relatively high number of inclusions. This is achieved by adding sulfur to the liquid bath. This element acts directly on the number of inclusions present in the steel by forming sulphides. For the inoculation stage, it was necessary to create specific tools that could be adapted to the laboratory scale. Trials are then carried out with different products at varying concentrations. The samples obtained are analyzed by various techniques: chemical analysis of steel (spark spectrometry and ICP), microstructure and grain size analysis (optical micrograph) and inclusion counting. In order to detect inclusions, count and classify them by their nature, shape and size, two possibilities exist. Either using an optical microscope but the risks of error are significant and the process is long and tedious, either using a specific software (AZtec) coupled to a scanning electron microscope (SEM). It is this choice that was made, because besides the fact that it allows a considerable saving of time thanks to an automation of the process, it is possible to know via an EDS probe, the chemical composition of each particle. For all the products tested, it was shown that inoculation had little effect on the size of the inclusions and that they became more complex by containing several chemical elements. For some products, clusters of inclusions appear. These clusters are likely to promote the fragility of steel by forming cracking primers. For others, the inclusions decrease sharply, have a globular shape and the grain size is refined. These effects tend to improve the mechanical properties of these steels. The introductory content of the inoculant is also determined for maximum effectiveness. The most efficient inoculant can be used for a possible industrialization.

The microstructure of low alloy Transformation Induced Plasticity (TRIP) assisted steels has been systematically varied through the combination of computational and experimental methodologies in order to enhance the mechanical performance and to fulfill the requirement of the next generation Advanced High Strength Steels (AHSS). The roles of microstructural parameters, such as phase constitutions, phase stability, and volume fractions on the strength-ductility combination have been revealed. Two model alloy compositions (i.e. Fe-1.5Mn-1.5Si-0.3C, and Fe-3Mn-1Si-0.3C in wt%, nominal composition) were studied. Multiphase microstructures including ferrite, bainite, retained austenite and martensite were obtained through conventional two step heat treatment (i.e. intercritical annealing-IA, and bainitic isothermal transformation-BIT). The effect of phase constitution on the mechanical properties was first characterized experimentally via systematically varying the volume fractions of these phases through computational thermodynamics. It was found that martensite was the main phase to deteriorate ductility, meanwhile the C/VA ratio (i.e. carbon content over the volume fraction of austenite) could be another indicator for the ductility of the multiphase microstructure. Following the microstructural characterization of the multiphase alloys, two microstructural design criteria (i.e. maximizing ferrite and austenite, suppressing athermal martensite) were proposed in order to optimize the corresponding mechanical performance. The volume fraction of ferrite was maximized during the IA with the help of computational thermodyanmics. On the other hand, it turned out theoretically that the martensite suppression could not be avoided on the low Mn contained alloy (i.e. Fe-1.5Mn-1.5Si-0.3C). Nevertheless, the achieved combination of strength (~1300MPa true strength) and ductility (~23% uniform elongation) on the low Mn alloy following the proposed design criteria fulfilled the requirement of the next generation AHSS. To further optimize the microstructure such that the designed criteria can be fully satisfied, further efforts have been made on two aspects: heat treatment and alloy addition. A multi-step BIT treatment was designed and successfully reduced the martensite content on the Fe-1.5Mn-1.5Si-0.3C alloy. Microstructure analysis showed a significant reduction on the volume fraction of martensite after the multi-step BIT as compared to the single BIT step. It was also found that, a slow cooling rate between the two BIT treatments resulted in a better combination of strength and ductility than rapid cooling or conventional one step BIT. Moreover, the athermal martensite formation can be fully suppressed by increasing the Mn content (Fe-3Mn-1Si-0.3C) and through carefully designed heat treatments. The athermal martensite-free alloy provided consistently better ductility than the martensite containing alloy. Finally, a microstructure based semi-empirical constitutive model has been developed to predict the monotonic tensile behavior of the multiphase TRIP assisted steels. The stress rule of mixture and isowork assumption for individual phases was presumed. Mecking-Kocks model was utilized to simulate the flow behavior of ferrite, bainitic ferrite and untransformed retained austenite. The kinetics of strain induced martensitic transformation was modeled following the Olson-Cohen method. The developed model has results in good agreements with the experimental results for both TRIP steels studied with same model parameters.

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No description available.

Yes / To interpret nitrogen sintering of chromium and manganese steels without the formation of deleterious oxides, but with manganese and carbon modifying the local microclimate, the role of the volatile Mn and carbothermic reactions were considered. Reduction of Cr2O3 by Mn vapour is always favourable. CO is an effective reducing agent, however, whereas at atmospheric pressure it will reduce FeO at ~730°C, temperatures some 500 and 700°C higher, i.e. above those for conventional sintering, are necessary for reducing Cr2O3 and MnO, respectively. Accordingly partial pressures must be considered and the sintering process is modelled at a conglomerate of several surface oxidised alloy particles surrounding a pore with graphite present and a tortuous access to the nitrogen-rich atmosphere containing some water vapour and oxygen. The relevant partial pressures were calculated and reduction reactions become thermodynamically favourable from ~200°C. Kinetics, however, dictates availability of CO and the relevant reactions are the water-gas, C + H2O = CO + H2 from ~500°C and the Boudouard, C + CO2 = 2CO, from ~700°C. Discussion of sintering mechanisms is extended to processing in semi-closed containers, also possessing specific microclimates.

High alloy Fe-Cr-Ni-C austenitic stainless steels have become the principal alloys for use in steam-methane reforming furnaces within the petrochemical industry. Each furnace contains a large array of vertically oriented centrifugally cast tubes through which a mixture of methane and steam is flowed across a nickel-oxide catalyst in order to obtain a mixture of hydrogen, carbon monoxide and carbon dioxide and water commonly known as synthesis gas (or syngas). Generally, the tubes operate at temperatures between 850-1050°C, internal pressures between 1-3.5MPa and are expected to withstand service lives in excess of 100,000 hours. The combination of high temperatures and moderate stresses causes creep to be the dominant failure mechanism experienced by these tubes in service. The HP austenitic alloys are the latest in a series of heat resisting (H-series) stainless steels developed to provide high temperature strength, ductility, and corrosion resistance in the oxygen, carbon, and sulphur rich environments typical of these furnaces. Extensive work has been carried out to optimise HP alloys’ microstructure in order to maximise the alloy’s creep resistance. Strength increases have largely been realized through the use of niobium and/or titanium additions, which modify the primary precipitates (formed during solidification) and secondary precipitates (formed during exposure to the service temperatures). These strength increases have typically been observed during laboratory accelerated creep testing of the ‘modified’ HP alloys where the temperature and/or stress is increased to achieve failure of the material within reasonable time period (typically between 1000-2000 hours). However, since the duration of typical accelerated creep tests often represent less than 2% of the tubes’ actual service life, uncertainty surrounds the validity of using this testing method as the basis to predict the tubes actual service life. This uncertainty has largely arisen due to the significant microstructural evolution that occurs within these alloys during prolonged service exposure and is not captured within the typical accelerated testing time-frame. In the present work, the microstructures of HP alloys modified with a single addition of niobium (HP-Nb) and dual additions of niobium and titanium (HP-NbTi) have been characterized in the as-cast condition and after long-term (10,000 hours) isothermal laboratory ageing at 1000, 1050 and 1100°C. The main focus of this study is to provide further insight into the microstructural features that increase the HP-NbTi alloy’s creep resistance in comparison to the HP-Nb alloy when performing accelerated creep testing and determine if these microstructural features remain stable during long-term ageing. The microstructure and crystallography of the primary and secondary precipitates in each alloy have been studied in detail using light optical microscopy, high resolution scanning electron microscopy, transmission electron microscopy, various electron diffraction methods (EBSD, SAD and CBED), Powder X-ray Diffraction and energy dispersive X-ray spectroscopy. Specific attention has been paid to the niobium-rich and niobium-titanium-rich phases that form as a direct result of HP alloy’s modification with niobium and titanium. The current research is part of a wider project conducted in collaboration with Quest Integrity Group Ltd. (Wellington, New Zealand) that aims to characterize the microstructural and mechanical properties of the HP-Nb and HP-NbTi alloys during long-term service exposure. The microstructural characterization presented in this thesis will subsequently be used by Quest Integrity Group to build a comprehensive understanding of the relationship between HP-Nb and HP-NbTi alloy’s microstructure and creep properties. This understanding will allow Quest Integrity Group to more accurately predict the service life of HP-Nb and HP-NbTi alloy tubes within steam-methane reforming furnaces.