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<p> The integration of silicon germanium (SiGe) in the base of heterojunction bipolar transistors (HBTs) has recently put the alloy into prominence to produce fast-switching transistors. However, the thin highly doped SiGe base makes the transistor susceptible to base dopant outdiffusion during device processing, which results in device performance degradation. Adding carbon to the base was shown to significantly suppress boron outdiffusion and help retain the narrow as-grown profile. Dopant behavior in the presence of various species needs to be well understood and modeled for two reasons: (1) to have accurate and predictive process simulators; and (2) to obtain insight into process development. </p> <p> Modeling carbon diffusion and its role in suppressing boron diffusion in silicon and SiGe has been studied by several groups. While boron diffusion is well-established, different modeling regimes have been developed for carbon diffusion. Each of the existing studies has focused on subsets of the available experimental data. We present a consistent and complete model that accounts for carbon and boron diffusion in silicon and SiGe, under equilibrium and non-equilibrium conditions. In our regime, carbon diffusion is modeled according to the kick-out and Frank-Tumbull mechanisms for diffusion; in addition, we incorporate the carbon clustering phenomenon. To completely model boron diffusion, we account for the boron-interstitial clustering (BICs) effect and the { 311} defects that are associated with boron transient enhanced diffusion (TED). In the developed model we make use of the well-established literature data for carbon diffusion, as well as boron diffusion and Si self-diffusion. The model was verified by simulating experiments that involve boron and/or carbon diffusion in silicon and SiGe and cover the complete temperature range of 750 - 1070 °C. The test structures include published experiments in addition to recent experimental results obtained through collaboration, and feature diffusion in inert and oxidizing ambients, under rapid thermal annealing (RTA) conditions, as well as in the presence of implant damage. We also investigated the validation of the model without the inclusion of either the clustering or the Frank-Turnbull reactions. </p> / Thesis / Master of Applied Science (MASc)

Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2007. / Includes bibliographical references (leaves 81-86). Also available in electronic version.

A carbon atom diffusion jump in iron austenite was considered as a subsequence of transformations between the cementite structure and the regular FCC packing. A model of this transformation was based on a 2D model of the elemental act of a polymorph transformation in metals. The energy threshold of this transformation has been calculated using the Morse pair potential. It occurs that the estimated enthalpy of the transformation is equal to 149±20 kJ/mole which is in satisfactory agreement with experimental data.

Static strain aging is an important concept in metalurgy that refers to the hardening of a material that has undergone plastic deformation and then is aged for a certain period of time. A theory proposed in the late 1940s by Cottrell and Bilby explains this phenomenon as being caused by the pinning of dislocations by impurities (e.g., carbon atoms in solid solution) that migrate to the vicinity of the line defect. In the course of this PhD work, the atomistic mechanism behind the static strain aging phenomenon in bcc iron has been studied by means of computer simulations. Given the fact that diffusion in the solid state proceeds slowly, thus preventing the use of molecular dynamics at low temperatures (when the effect of the dislocation stress field on carbon diffusion is more pronounced), we have preferentially employed a method coupling molecular statics with atomistic kinetic Monte Carlo. Three major points have been addressed by this thesis: (i) the effect of the stress field of an edge or screw dislocation on a carbon atom diffusing nearby; (ii) the diffusion of a carbon atom in the tight channel found in the dislocation core (pipe diffusion); and (iii) the equilibrium carbon distribution in a Cottrell atmosphere. The main effect of the dislocation stress field outside the dislocation core consists of biasing carbon diffusion, such that some transitions become more likely than others. This effect is expected to drive the early stages of Cottrell atmosphere formation, when the mutual interaction between carbon atoms is negligible. Right in the dislocation core, as expected, carbon was seen to diffuse faster than in the bulk. Carbon concentration in the neighborhood of an edge or a screw dislocation was modeled by an approach based in statistical physics using the binding energies calculated by molecular statics, revealing a good agreement with experimental data obtained by atom probe techniques.

This short communication is devoted to the room temperature processes of diffusion and redistribution of dissolved carbon atoms in martensite to the nanosegregation regions at dislocations and grain boundaries. It is related to the DF7 contribution of M. Lavrskyi et al. on the carbon kinetics in martensite [1] and to the DF7 contribution of Yu. Nechaev on the compound-like nanosegregation at dislocations and grain boundaries in metallic materials.

Indirect additive processing of ferrous metals offers the potential to freeform fabricate parts with good surface finish and minimal dimensional variation from the computer solid model. The approach described here is to mix a ferrous powder with a transient binder followed by selective laser sintering (SLS) in a commercial polymer machine to create a “green” part. This part is post-processed to burn off the transient binder and to infiltrate the porous structure with a lower melting point metal/alloy. Commercially available SLSed ferrous components contain copper-based infiltrant in a ferrous preform. The choice of copper alloy infiltrant has led to inferior mechanical properties of these components limiting their use in many non-injection-molding structural applications, particularly at elevated temperature. In the present work, an attempt has been made to replace the copper-based infiltrant considering cast iron as a potential infiltrant because of its fluidity, hardness and stability at comparatively high temperature. A critical consideration is loss of part structural integrity by over-melting after infiltration as chemical diffusion of alloying elements, principally carbon, occurs resulting in a decrease in the melting temperature of tool steel preform. A predictive model was developed which defines the degree of success for infiltration based on final part geometry and depending on the relative density of the preform and infiltration temperature. The processing regime is defined as a function of controllable process parameters. An experimental program was undertaken using commercially available LaserForm[superscript tm] A6 tool steel that was infiltrated with ASTM A532 white cast iron. Guided by Ashby densification maps, pre-sintering of the A6 tool steel SLS part was performed to increase the part initial relative density prior to infiltration. The final infiltrated parts were analyzed for geometry, microstructure and hardness. The model may be extended to other ferrous powder and infiltrant compositions in an effort to optimize the properties and utility of the final infiltrated part. / text

Les liaisons bimétalliques entre acier faiblement allié et acier inoxydable sont nombreuses au sein des réacteurs nucléaires français où elles assurent la connexion entre les principaux composants et les tuyauteries du circuit primaire. Le revêtement interne de cuve réalisé par soudage feuillard-flux est un autre cas de soudure dissimilaire dont le rôle est d'assurer une bonne protection contre la corrosion. Ce travail de thèse a notamment pour but de comprendre la genèse des microstructures complexes se formant à l'interface entre les deux aciers pendant le soudage. Il étudie d'autre part leur évolution durant le traitement thermique post-soudage à 610°C ainsi que les conséquences de ces transformations sur le comportement mécanique du joint soudé. Partant du métal de base, on rencontre successivement une fine bande de martensite, une zone purement austénitique puis la microstructure biphasée δ/γ de l'acier inoxydable. Des techniques de microscopie (MEB, EDS, EBSD) combinées à des calculs thermo-cinétiques (modèle de Scheil-Gulliver, surfusion en pointe de dendrite) ont permis d'expliquer le gradient de microstructure et les raisons des transitions de phases observées. Au cours du traitement thermique de détensionnement à 610°C, le gradient de potentiel chimique du carbone à travers l'interface de fusion cause la dissolution de la cémentite et la croissance des grains du côté faiblement allié. On observe également la diffusion du carbone à travers l'interface et la précipitation de carbures riches en Cr dans le liseré martensitique et la zone austénitique. Une caractérisation détaillée des profils de composition et de la précipitation a été réalisée à différentes échelles (depuis le millimètre jusqu'au niveau atomique). Un modèle mésoscopique, s'appuyant sur des bases de données thermodynamiques et cinétiques, a été développé pour coupler la diffusion à longue distance dans un milieu multi-constitué à la germination et croissance des précipités (approche de type Kampmann-Wagner). Il a permis de prévoir la teneur en carbone ainsi que la fraction volumique et la distribution de taille des précipités en fonction de la distance à l'interface. Les conséquences de la forte variabilité de microstructure sur le comportement mécanique local ont été analysées dans la dernière partie de ce travail, en particulier les aspects de déformation localisée et de rupture ductile. Des lois de comportement élasto-plastique ont été déterminées pour chacune des régions de l'assemblage à l'état détensionné. L'étude des mécanismes de rupture ductile dans les zones les plus faibles de la soudure, c'est-à-dire le métal de base décarburé et les couches de revêtement austénitique a donné lieu à des observations in-situ et une modélisation de l'endommagement. / Dissimilar welds between low-alloy steel and stainless steel are numerous within the French nuclear power plants where they enable connecting the main components to the primary circuit pipes. The internal cladding (in stainless steel) of the pressure vessel (in bainitic steel) made by submerged arc welding is another case of dissimilar weld whose goal is the protection against corrosion. This PhD work aims at understanding the complex microstructures which form at the interface between both steels during welding together with their evolution during the post-weld heat-treatment at 610°C and their consequences on the mechanical behavior of the welded assembly. Starting from the base metal, one meets successively a thin layer of martensite, a fully austenitic zone and the two-phase δ/γ microstructure of the stainless steel. Microscopy techniques (SEM, EDS, EBSD) combined with thermo-kinetics calculations (Scheil-Gulliver model, dendrite tip undercooling) have allowed explaining the graded microstructure and the reasons for the observed phase transitions. During the post-weld heat-treatment, the large gradient of carbon chemical potential across the fusion line leads to cementite dissolution and grain growth on the low-alloyed side. Carbon diffusion through the interface and Cr-rich carbides precipitation in both the martensitic layer and the austenitic weld have also been observed. An in-depth characterization has been performed at different scales (from the millimeter to the atomic level) to quantify the extent of carbon diffusion and carbides precipitation during the phase transformations. A mesoscopic thermodynamic and kinetic model based on Calphad databases has been developed to fully couple long-range diffusion in a multi-component system with precipitates nucleation and growth (Numerical Kampmann-Wagner approach). It allowed a prediction of the carbon content, volume fraction and size distribution of the precipitates at any distance from the fusion line. The consequences of the high variability of microstructures on the local mechanical behavior have been examined in the last part of this work, in particular the localization of deformation and the ductile failure. Elasto-plastic constitutive laws were determined for each region of the dissimilar weld in the heat-treated state. Ductile failure mechanisms in the weak zones of the weld, namely the decarburized base metal and the stainless steel cladding layers, were investigated through in-situ observations and damage modeling.

L’allègement dans le secteur de l’automobile revête un enjeu important du fait de normes d’émission de CO2 de plus en plus drastiques, de la nécessité de réduire la consommation en carburant des véhicules et d’une aspiration sociétale à une économie « plus verte ». Pour répondre à ces défis et dans un souci de sécurité et de contrôle des coûts, l’industrie automobile étudie actuellement la possibilité de développer et de produire une 3ème génération d'aciers à très haute résistance. Ils résultent de traitements thermomécaniques généralement innovants, possèdent des microstructures complexes et des propriétés mécaniques améliorées. Le procédé de Quenching and Partitioning (Q&P) est le traitement le plus prometteur, il consiste en une trempe sous la température de début de transformation martensitique Ms, puis, d'un réchauffage et d'un maintien au-dessus de la température initiale de trempe (QT). L'étape de maintien est appelée "étape de partition", car un enrichissement en carbone de l'austénite est attendu. Les propriétés mécaniques exceptionnelles des aciers Q&P sont dues à leur microstructure duplexe complexe : de très fins îlots d'austénite résiduelle imbriqués dans une matrice martensitique revenue et/ou fraîche. Bien que les mécanismes d'enrichissement en carbone de l'austénite résiduelle lors de l'étape de partition soient encore débattus dans la littérature, il existe des preuves tangibles qui attestent d’un phénomène de partition du carbone de la martensite vers l’austénite. Cependant, la formation de bainite et de carbures dans la martensite soulève la question de l’influence de ces réactions et de leurs interactions sur les mécanismes et les cinétiques d’enrichissement en carbone de l'austénite. Il s'agit clairement d'un sujet d'intérêt puisque les propriétés mécaniques de ces aciers reposent principalement sur la teneur en carbone des îlots d’austénite.Cette thèse qui repose sur une approche expérimentale multi-échelle couplée à une approche théorique en champ moyen, a pour ambition d’apporter des éléments de réponse aux mécanismes d’enrichissement en carbone de l’austénite dans un aciers duplex Q&P à très haute résistance de composition Fe-0,3 C-2,5Mn-1,5Si... / The need to reduce the fuel consumption of vehicles while increasing safety led the automotive industry to develop a 3rd generation of Advanced High Strength Steels. Such steels combine innovative processing routes, complex microstructures, improved mechanical properties and are a possible response in vehicle lightweighting. The Quenching and Partitioning (Q&P) process is the most promising route and involves quenching below the martensite start temperature followed by a reheatingand ageing above the initial quench temperature (QT). The ageing step is termed “partitioning step” since carbon enrichment in austenite is expected to occur during this stage. The exceptional mechanical properties of Q&P steels come from their complex duplex microstructure: very fine austenite island retained at room temperature embedded in both recovered and fresh martensite. Although the mechanisms of carbon enrichment in retained austenite during the partitioning step are still debated,strong evidences of carbon partitioning from martensite to austenite exist. However, both the formation of bainite and carbides into martensite raise the question of the effects of competitive reactions on the carbon enrichment in austenite. It is clearly a topic of interest since the benefits of such a treatment in terms of improved mechanical properties depends strongly on the austenite stability and thus on the level of carbon enrichment in austenite during the partitioning step.This thesis aims at combining an innovative multiscale experimental methodology with an original theoretical approach providing a unique opportunity to give some clarifications regarding the microstructure evolution and the mechanisms of carbon enrichment into austenite. After having determined the optimum Q&P parameters using dilatometric and XRD measurements, a Q&P treatment at three different QT (260, 230 and 200°C) and at a partitioning temperature of 400°C was applied to a model Fe-0.3 C-2.5Mn-1.5Si steel. The dilatometric data combined with an SEM image analysis study showed that bainite forms during the partitioning step. The presence of bainite was also confirmed by in-situ High Energy X-Ray Diffraction. While bainite was shown to appear as carbide free laths, tempered martensite showed an advanced state of intra-lath precipitation. The combination of atom probe tomography (APT) and TEM technics showed that theses carbides are transitional andboth η and ε carbides were observed. Their carbon content ranged from 20.0 to 27.7 at.%. APT measurements also highlighted carbon segregation on martensite defects during the initial quench and calculation of the evolution of the carbon excess concentration on laths boundaries suggest that desegregation occurs along the Q&P treatment. In-situ HEXRD permitted to follow the austenite lattice parameter evolution and it was shown that austenite is subjected to a sequence of tensile andcompression state induced by the formation of martensite. A model for the coefficient of thermal expansion of austenite taking into account its stress state was successfully developed. The evolutions of carbon content into austenite for the three QT were determined. Surprisingly the carbon enrichment into austenite was shown not to depend on QT. It was also shown that the increase of carbon content in austenite results from both carbon partitioning and bainite contributions. Lastly, an originaltheoretical approach was developed. It was evidenced that bainite continues to form while partitioning process is rapidly completed, thus bainite transformation controls the maximum austenite carbon enrichment at 400°C, independently of QT. The contribution of partitioning from martensite was shown to be larger with decreasing QT. The developed model successfully described the experimentally observed phase transformations and austenite carbon enrichment by taking into account theinteractions between carbon partitioning, bainite transformation and carbide precipitation.

Le vieillissement statique est un concept important dans la métallurgie qui se réfère à un durcissement de la matière ayant subi une déformation plastique et est ensuite vieilli pendant une certaine période de temps. La théorie proposée dans les années 1940 par Cottrell et Bilby explique ce phénomène comme étant causé par l'épinglage des dislocations par les impuretés (par exemple, les atomes de carbone en solution solide) qui migrent au voisinage du défaut de ligne. Au cours de ce travail de thèse, le mécanisme atomistique responsable du phénomène du vieillissement statique dans le fer alpha a été étudié par des simulations numériques. Etant donné que la diffusion à l'état solide se déroule lentement, l'utilisation de la dynamique moléculaire à basse température (lorsque l'effet du champ de contraintes sur la dislocation de diffusion du carbone est plus prononcé) a été évitée, et nous avons utilisé préférentiellement le couplage de la statique moléculaire avec le Monte-Carlo cinétique atomistique. Trois points principaux ont été abordés dans cette thèse: (i) l'effet du champ de contraintes d'une dislocation coin ou vis sur un atome de carbone qui diffuse à proximité, (ii) la diffusion de l'atome de carbone dans le cour de la dislocation («pipe diffusion»), et (iii) la distribution d'équilibre des atomes de carbone dans une atmosphère de Cottrell. Le principal effet du champ de contrainte de la dislocation à l'extérieur du coeur est de biaiser la diffusion de l'impurité, de sorte que certains sauts (transitions) deviennent plus probables que d'autres. Cet effet va conduire aux premiers stades de la formation de l'atmosphère de Cottrell, lorsque l'interaction mutuelle entre atomes de carbone est négligeable. Au cœur de la dislocation, comme prévu, nos résultats indiquent que le carbone diffuse plus vite que dans le volume. La concentration de carbone dans le voisinage d'une dislocation coin ou vis a été modélisée par une approche de physique statistique en utilisant les énergies de liaison calculées par la statique moléculaire. Cette approche est en bon accord avec les données expérimentales. / Static strain aging is an important concept in metalurgy that refers to the hardening of a material that has undergone plastic deformation and then is aged for a certain period of time. A theory proposed in the late 1940s by Cottrell and Bilby explains this phenomenon as being caused by the pinning of dislocations by impurities (e.g., carbon atoms in solid solution) that migrate to the vicinity of the line defect. In the course of this PhD work, the atomistic mechanism behind the static strain aging phenomenon in bcc iron has been studied by means of computer simulations. Given the fact that diffusion in the solid state proceeds slowly, thus preventing the use of molecular dynamics at low temperatures (when the effect of the dislocation stress field on carbon diffusion is more pronounced), we have preferentially employed a method coupling molecular statics with atomistic kinetic Monte Carlo. Three major points have been addressed by this thesis: (i) the effect of the stress field of an edge or screw dislocation on a carbon atom diffusing nearby; (ii) the diffusion of a carbon atom in the tight channel found in the dislocation core (pipe diffusion); and (iii) the equilibrium carbon distribution in a Cottrell atmosphere. The main effect of the dislocation stress field outside the dislocation core consists of biasing carbon diffusion, such that some transitions become more likely than others. This effect is expected to drive the early stages of Cottrell atmosphere formation, when the mutual interaction between carbon atoms is negligible. Right in the dislocation core, as expected, carbon was seen to diffuse faster than in the bulk. Carbon concentration in the neighborhood of an edge or a screw dislocation was modeled by an approach based in statistical physics using the binding energies calculated by molecular statics, revealing a good agreement with experimental data obtained by atom probe techniques.