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Despite the high demand for press-hardenable steel (PHS) with coatings that provide sacrificial cathodic protection, Zn-based coatings have experienced limited use due to the significant challenges associated with avoiding liquid metal embrittlement (LME) while maintaining robust cathodic protection when using conventional PHS materials and processing techniques. The present research addresses these challenges by reducing the conventional direct hot press forming (DHPF) temperature to between 600–700 °C, such that forming and quenching occurs well below the Zn(Fe)liq → Г-Fe3Zn10 peritectic temperature of 782 °C, thereby removing the conditions necessary for LME to occur while allowing for formation of the cathodically-protective Г-Fe3Zn10 phase. The objective of this work was to define a process window for two galvanized prototype PHS alloys with compositions of 0.20C-2.01Mn-0.26Si-0.005B and 0.19C-2.5Mn-0.26Si-0.005B (wt%) that would result in fully martensitic microstructures, tensile strengths (TS) ≥ 1500 MPa, and robust cathodic protection, defined as attaining ≥ 15 vol% Г-Fe3Zn10 in the coating microstructure, while avoiding LME. Accomplishing this task involved characterizing both grades as a function of austenization time, stamping temperature, and strain imposed by the forming process in order to define process windows that resulted in parts that met the aforementioned property requirements. It was found that the approach of increasing the Mn content relative to conventional PHS grades was successful in improving the hardenability sufficiently to enable the formation of fully martensitic microstructures despite the lower effective cooling rates associated with the reduced DPHF temperatures. Microstructural imaging and tensile testing demonstrated that, for both prototype PHS grades, a process window exists for the production of parts that satisfy the targets of the formation of fully martensitic microstructures and TS ≥ 1500 MPa while exhibiting uniform elongation of about 0.05 followed by significant post-uniform elongation. The effect of DHPF temperature and strain imposed by the forming process on mechanical properties was found to be negligible. Tensile tests and fractography revealed that reducing the DHPF temperature to between 600–700 °C was successful in preventing LME, thereby allowing samples to fracture in a ductile manner. Micro-cracking in the coating of the DHPF part was observed; however, these cracks were arrested at the coating-substrate interface. For all tested conditions, the coating met the target of ≥ 15 vol% Г-Fe3Zn10, implying that robust cathodic protection is expected. Based on the results of these experiments, it was concluded that DHPF process windows that meet all of the property targets include austenization times and DHPF temperatures of 120–180 s and 600–700 °C, respectively, for the 2Mn grade, and 60–180 s and 600–700 °C, respectively, for the 2.5Mn grade. / Thesis / Master of Science (MSc)

Nous avons étudié la sensibilité du T91 à la fragilisation par le sodium liquide. Une procédure expérimentale a été mise en place afin de procéder à des essais mécaniques en sodium sous atmosphère inerte. Grâce à l’introduction d’une étape préliminaire d’exposition au sodium, la mouillabilité du T91 par le sodium liquide et la structure de l’interface sodium/acier ont pu être étudiés en fonction des différents paramètres d’exposition. Une réduction significative des propriétés mécaniques est observée quand le mouillage de l’acier par le sodium est bon. L’utilisation de différentes teneurs en oxygène et en hydrogène suggère que l’oxygène joue un rôle primordial dans l’amélioration de la mouillabilité du T91. La sensibilité du phénomène de fragilisation à la vitesse de sollicitation et à la température a été caractérisée. A partir de ces résultats, l’existence d’une transition fragile/ductile, fonction de ces deux paramètres a été mis en évidence. L’étude de cette transition suggère qu’une étape de diffusion du sodium dans les joints de grains du T91 est limitante pour la fragilisation. Des analyses en microscopie électronique en transmission et par cartographies d’orientation de fissures arrêtées ont également permis de constater que le mode de rupture est interlatte ou intergranulaire, fournissant ainsi une image cohérente du processus de fragilisation. La même méthodologie a été appliquée à l’acier non allié XC10. Les résultats montrent un comportement en tous points similaire à celui de l’acier T91 et suggèrent donc un mécanisme commun pour les aciers cubiques centrés. De plus, ils confirment que la transition fragile ductile observée semble la conséquence d’une vitesse de propagation de fissure fragile relativement limitée. Cette propagation est activée thermiquement avec une énergie d’activation d’environ 50 kJ/mol. Enfin, il a été montré que l’acier austénitique 304L est également sensible à la fragilisation par le sodium liquide. Certaines surfaces de rupture témoignent clairement d’une rupture intergranulaire, cependant des interrogations persistent à propos du chemin de fissuration. / We studied the sensitivity of T91 steel to embrittlement by liquid sodium. An experimental procedure was set up to proceed to mechanical testing in sodium under an inert atmosphere. The introduction of a liquid sodium pre-exposure step prior to mechanical testing enabled the study of both the wettability of T91 by sodium and the structure of the sodium steel/interface as a function of the exposure parameters. The mechanical properties of T91 steel are significantly reduced in liquid sodium provided the wetting conditions are good. The use of varying oxygen and hydrogen concentrations suggests that oxygen plays a major role in enhancing the wettability of T91. The sensitivity of the embrittlement to strain rate and temperature was characterized. These results showed the existence of a ductile to brittle transition depending on both parameters. Its characterization suggests that a diffusion step is the limiting rate phenomenon of this embrittlement case. TEM and EBSD analysis of arrested cracks enabled us to establish that the fracture mode is interlath or intergranular. This characteristic is coherent with the crack path commonly reported in liquid metal embrittlement. A similar procedure was applied to the unalloyed XC10 steel. The results show a behavior which is similar to the one of T91 steel and suggest a common mechanism for liquid sodium embrittlement of body centered cubic steels. Moreover, they confirm that the ductile to brittle transition seems associated with a limited crack propagation rate. The propagation is thermally activated with activation energy of about 50 kJ/mol. Finally, it was shown that 304L austenitic steel is sensitive to liquid sodium embrittlement as well. Some fracture surfaces testify of an intergranular fracture mode, but some questions still remain about the crack path.

L'objectif de cette thèse est de produire une avancée dans la compréhension du phénomène de fragilisation par les métaux liquide (FML), en nous appuyant sur l'étude expérimentale et numérique du couple cuivre/mercure. La fragilisation du cuivre pur OFHC (Oxygen Free High Conductivity) par le mercure liquide est mise en évidence et quantifiée par des mesures de ténacité. En outre, un procédé d'ingénierie des joints de grains est appliqué afin d'augmenter de façon importante la proportion de joints de grains spéciaux Σ3 dans le cuivre. Des essais de FML sont alors réalisés et permettent d'établir le rôle de ces joints de grains dans la fragilisation du cuivre par le mercure liquide. En parallèle, des modélisations de joints de grains spéciaux Σ3 et Σ5 sont réalisées par calcul basés sur la théorie de la fonctionnelle de la densité (DFT). Ces modélisations permettent à la fois de mettre en évidence une réduction des propriétés mécaniques de ces joints de grains en présence d'atomes de mercure, ainsi que de comprendre l'immunité des joints Σ3 observée expérimentalement. Cependant, ces modélisations ne permettent pas de rendre compte quantitativement des observations expérimentales. Pour améliorer cette description atomique de la FML, une contribution non locale est ajoutée, via l'utilisation d'un modèle de zone cohésive nourri par calcul DFT. Il est montré que le confinement du métal liquide en extrême pointe de fissure engendre une force normale aux parois de la fissure (l'origine physique de cette force est discutée), et que l'introduction de cette nouvelle composante permet de rendre compte des observations expérimentales de façon beaucoup plus quantitative. Ce dernier modèle est appuyé par la réalisation d'expériences de FML sous pression hydrostatique. / The aim of this thesis is to make an advance in the liquid metal embrittlement (LME) understanding, based on the experimental and numerical studies of the copper/mercury system. OFHC (Oxygen Free High Conductivity) copper embrittlement by liquid mercury is studied and quantified by toughness measures. Moreover, grain boundary engineering (GBE) is implemented in order to increase the proportion of special Σ3 grain boundaries. LME tests are performed and allow to establish the particular behaviour of the Σ3 grain boundaries in the copper embrittlement by liquid mercury. At the same time, modelling of special Σ3 and Σ5 grain boundaries based on density functional theory are performed. This allows to show the weakening of mechanical properties of both grain boundaries containing mercury atoms, and also to understand the immunity of Σ3 grain boundaries as observed experimentally. However, experimental observations can not been qualitatively explained by these modelling. In order to improve this description, a non-local contribution is introduced by means of a cohesive zone model. It is shown that the confinement of the liquid metal at the very crack tip produces a force normal to the surface of the solid (the origin of this force is discussed), and that the consideration of this force allows to describe more accurately experimental results. This model is supported by LME experiments under hydrostatic pressure.

High manganese TWIP (TWinning Induced Plasticity) steels are particularly attractive for automotive applications because of their exceptional properties of strength combined with an excellent ductility. However, as austenitic steels, they appear to be sensitive to liquid zinc embrittlement during welding, the liquid zinc arising from the melted coating due to the high temperatures reached during the welding process. In this framework, the cracking behaviour of a high manganese austenitic steel has been investigated in relation to the liquid metal embrittlement (LME) phenomenon by hot tensile tests carried out on electro-galvanized specimens using a Gleeble 3500 thermomechanical simulator. The influence of different parameters such as temperature and strain rate on cracking behaviour has been studied. Embrittlement appears within a limited range of temperature depending on experimental conditions. Conditions for which cracking occurs could be experienced during welding processes. The existence of a critical stress above which cracking appears has been evidenced and this critical stress can be used as a cracking criterion. Finally, the study of the influence of different parameters such as time of contact between steel and liquid zinc before stress application, coating and steel on LME occurrence provides understanding elements of LME mechanism and permits to suggest solutions for preventing cracking during spot welding of such steels.

L'objectif de cette étude est d'aboutir à une meilleure compréhension de la fragilisation par les métaux liquides (FML) à travers l'étude des systèmes T91/Pb-Bi et 316L/Pb-Bi et notamment d'en établir les mécanismes mis en jeu lors du contact entre ces aciers sous tension et le métal liquide. Ce travail s'inscrit dans le cadre du projet MEGAPIE-TEST mis en place pour étudier la faisabilité d'une cible de spallation au plomb-bismuth liquide. L'effet de l'eutectique plomb-bismuth liquide sur le T91 et le 316L a été étudié en fonction de la température et de la vitesse de déformation, en utilisant des éprouvettes CCT adaptées à l'étude de propagation de fissures. La présence de Pb-Bi modifie le mécanisme de rupture du T91 au détriment de la germination, croissance et coalescence des cavités. La rupture procède alors par décohésion des bandes de cisaillement. L'effet fragilisant du Pb-Bi est très marqué aux très faibles vitesses de déformation. Une transition fragile-ductile se produit aux grandes vitesses de déformation (~10-5 m.s-1 à 160°C). Les propriétés mécaniques du 316L ne sont pas autant affectées par la présence de Pb-Bi, toutefois une transition réelle est observée sur les faciès de rupture, où là également il y a compétition entre l'effet fragilisant du métal liquide et la rupture ductile. Le mécanisme suggéré dans ce travail est fondé sur la localisation de la déformation en pointe de la fissure combinée au phénomène de réduction d'énergie de surface induite par adsorption de métal liquide (effet Rebinder) et ne fait intervenir aucun processus diffusionnel en particulier aux joints de grains. / The aim of this work is to study liquid metal embrittlement (LME) on the T91/Pb-Bi and 316L/Pb-Bi systems. A particular attention is paid to obtain a better understanding of the mechanisms of fracture when steels are in contact with liquid metal. This work has been performed within the European projects MEGAPIE-TEST and EUROTRANS which aim to prove the feasibility of lead-bismuth nuclear systems such as spallation target and subcritical reactors. The effect of liquid Lead Bismuth Eutectic (LBE) on 316L and T91 steels has been studied in plane stress conditions as a function of temperature and strain rate, using a CCT geometry adapted for the study of crack propagation. The presence of LBE modifies the fracture mechanism of T91 and prevents fracture by growth and coalescence of cavities. Cracking proceeds by shear band decohesion. This embrittlement effect is very pronounced at low deformation rate whereas at the high strain rate range investigated, a brittle to ductile transition is observed. The temperature variation of the transition rules out LME mechanisms based on dissolution. A fracture mechanics analysis by the J-µa methodology allowed the quantification of the embrittlement degree which is estimated to 30% reduction in the energy required for crack propagation. The mechanical properties of the 316L steel are weakly affected by the presence of LBE, in spite of a change in the plastic deformation at the highest triaxiality point which strongly affecting fracture surfaces. The mechanism of this embrittlement seems to be based on the deformation localization at the crack tip combined with the phenomenon of surface energy reduction induced by the liquid metal adsorption. It does not involve any diffusion process. The deformation localization is confirmed by an electron microscopy study of the crack tip plasticity of 316L under the influence of a liquid metal.

Les aciers TWIP (TWinning Induced Plasticity) à haute teneur en manganèse sont particulièrement prometteurs pour les applications automobiles de par leur excellent compromis entre résistance mécanique et ductilité. Cependant, la microstructure austénitique leur confère une sensibilité à la fragilisation par le zinc liquide durant les procédés de soudage ; le zinc liquide provenant de la fusion du revêtement résultant de l’élévation de température à la surface de l’acier. Dans cette étude, la fissuration d’un acier austénitique à haute teneur en manganèse a été étudiée en rapport avec le phénomène de fragilisation par les métaux liquides par des essais de traction à chaud réalisés sur des éprouvettes électrozinguées au moyen d’un simulateur thermomécanique Gleeble 3500. L’influence de nombreux paramètres tels que la température et la vitesse de déformation sur la fissuration a été étudiée. La fragilisation apparaît dans un domaine de température limité qui dépend des conditions expérimentales. Les conditions pour lesquelles la fissuration apparaît peuvent être rencontrées durant les procédés de soudage. L’existence d’une contrainte critique pour laquelle la fissuration apparait a été mise en évidence et celle-ci peut être utilisée comme critère de fissuration. Enfin, l’étude de l’influence de différents paramètres tels que le temps de contact entre l’acier et le zinc liquide avant l’application des contraintes, le revêtement et l’acier sur l’apparition de la fragilisation apporte des éléments de compréhension du mécanisme de fissuration et permet de proposer des solutions pour éviter la fissuration durant le soudage par point de l’acier étudié. / High manganese TWIP (TWinning Induced Plasticity) steels are particularly attractive for automotive applications because of their exceptional properties of strength combined with an excellent ductility. However, as austenitic steels, they appear to be sensitive to liquid zinc embrittlement during welding, the liquid zinc arising from the melted coating due to the high temperatures reached during the welding process. In this framework, the cracking behaviour of a high manganese austenitic steel has been investigated in relation to the liquid metal embrittlement (LME) phenomenon by hot tensile tests carried out on electro-galvanized specimens using a Gleeble 3500 thermomechanical simulator. The influence of different parameters such as temperature and strain rate on cracking behaviour has been studied. Embrittlement appears within a limited range of temperature depending on experimental conditions. Conditions for which cracking occurs could be experienced during welding processes. The existence of a critical stress above which cracking appears has been evidenced and this critical stress can be used as a cracking criterion. Finally, the study of the influence of different parameters such as time of contact between steel and liquid zinc before stress application, coating and steel on LME occurrence provides understanding elements of LME mechanism and permits to suggest solutions for preventing cracking during spot welding of such steels.

[pt] A grande maioria dos componentes estruturais possui entalhes que concentram localmente as tensões em torno de suas pontas. O fator de sensibilidade ao entalhe q, muito usado para quantificar o efeito deles em fadiga, pode ser associado à geração de trincas não propagantes quando SL(R)/Kt < σn < SL(R)/Kf, onde SL(R) é o limite de fadiga do material em uma dada razão R = σmin/σmax; Kt = σmax/σn é o fator de concentração de tensões (SCF, de stress concentration factor) do entalhe; σn é a amplitude de tensão nominal aplicada; σmax é a máxima tensão na ponta do entalhe; e Kf = 1 + q(Kt – 1) é o fator de concentração de tensões à fadiga, que quantifica o efeito dos entalhes na resistência à fadiga do componente entalhado. Partindo desse comportamento, recentemente foi desenvolvido um modelo para calcular q considerando a influência do gradiente de tensões à frente da raiz do entalhe no comportamento à fadiga de trincas mecanicamente curtas, usando apenas técnicas apropriadas de análise de tensões e as resistências à fadiga do material: o limite de fadiga e o limiar de propagação de trincas longas. Este modelo, cujas previsões foram validadas por vários experimentos apropriados, considera assim todas as características da geometria do entalhe e do carregamento em q, sem precisar de nenhum parâmetro ajustável. Nesse trabalho, esse critério é estendido para tratar problemas de Trincamento Assistido por Meios Corrosivos (EAC), considerando apropriadamente parâmetros de análise de tensão. O efeito da corrosão é quantificado pela resistência do material ao trincamento por EAC, SEAC, e pelo limiar de propagação em condições de EAC, KIEAC, ambos medidos no ambiente agressivo em questão. Esse modelo em particular prevê a existência de uma sensibilidade ao entalhe qc em problemas de EAC quando SEAC/Kt < σmax < SEAC/[1 + qc(Kt - 1)], que pode ser mecanicamente quantificada por técnicas análogas àquelas utilizadas com sucesso para quantificar q em fadiga. Para comprovar experimentalmente a validade do modelo nestas condições, foi escolhido o par {Alumínio (Al) 2024 recozido – Gálio (Ga)} na temperatura de 35ºC, devido à rapidez da sua reação de trincamento sob EAC, a qual permite que suas propriedades básicas, SEAC and KIEAC, sejam determinados rapidamente. Usando somente a mecânica proposta neste novo modelo e as resistências básicas do material à EAC, 8 corpos de prova entalhados foram projetados para alcançar e suportar a máxima tensão na ponta de seus entalhes duas vezes maiores do que SEAC. O modelo prevê que isso é possível devido à interação do gradiente de tensões à frente da ponta do entalhe com a pequena trinca nele iniciada, que permanece não propagante nessas condições. Como nenhum dos corpos de prova assim projetados falhou nesses testes, pode-se concluir que aqueles ensaios suportam a eficácia do modelo, o qual pode ser bastante útil como ferramenta de dimensionamento mecânico no tratamento do efeito de entalhes em problemas de EAC. / [en] The vast majority of structural components have notches that locally concentrate stresses around their tips. The notch sensitivity factor q, widely used to quantify the effect of such notches on fatigue, can be associated with the generation of non-propagating cracks at the notch tips in fatigue tests when SL(R)/Kt < σn < SL(R)/Kf, where SL(R) is the fatigue limit of the material at a given R = σmin/σmax ratio; Kt = σmax/σn is the stress concentration factor (SCF) of the notch; σn is the amplitude of the nominal stress that loads it; σmax is the maximum stress at the notch tip; and Kf = 1 + q(Kt – 1) is the (effective) fatigue SCF, which quantifies the actual notch effect on the fatigue strength of the notched component. Based on this behavior, a model was recently developed to calculate q considering the influence of the stress gradient ahead of the notch tip on the fatigue behavior of mechanically short cracks, using only proper stress analysis techniques and the basic fatigue properties of the material, its fatigue limit and long crack propagation threshold. This model, whose predictions were validated by various appropriated experiments, considers the entire notch geometry and loading characteristics on q, without the need of any data-fitting parameter. In this study, this criterion is extend to properly treat environmentally assisted cracking (EAC) problems considering stress analysis issues. The corrosion effects are quantified by the material resistance to EAC, SEAC, and by its crack propagation threshold under EAC conditions, KIEAC, both measured in the aggressive environment in question. This model in particular predicts the existence of a notch sensitivity qc in EAC problems as well, when SEAC/Kt < σmax < SEAC/[1 + qc(Kt - 1)], which can be mechanically quantified by techniques analogous to those successfully used to quantify q in fatigue. To experimentally prove the validity of this model under EAC conditions, the pair material/aggressive medium chosen is an annealed 2024 Al alloy and Ga at 35oC, due to its very fast EAC reaction, which allows its basic properties, SEAC and KIEAC, to be quickly determined. Using only the mechanics proposed in this new model and the basic material resistances to EAC, 8 notched test specimens were designed to reach and survive to maxima stresses at the tip of their notches twice as large as SEAC. The model predicts that this is possible due to the interaction of the stress gradient ahead of the notch tip with the small crack initiated there, which is non-propagating under such conditions. Since none of the specimens failed in the designed tests, it can be concluded that they support the effectiveness of the model, which may thus be quite useful as a mechanical tool to treat notch effects in EAC problems.