Contribution à l'étude de la solidification et à la description thermodynamique des équilibres de phases du système quaternaire Fe-Al-Ti-Zr

La première partie de ce manuscrit est consacrée à l étude des microstructures et des microségrégations, héritées de la solidification des alliages ternaires Fe-Al-Ti, Fe-Al-Zr et quaternaires Fe-Al-Ti-Zr. Pour améliorer la compréhension des phénomènes ayant lieu au cours de la solidification et disposer d un outil permettant de prédire les phases formées au cours de la solidification, une description thermodynamique du coin riche en fer du système quaternaire Fe-Al-Ti-Zr est proposée dans une seconde partie. A partir de l ensemble des données expérimentales et bibliographiques disponibles concernant les équilibres de phases dans les différents systèmes ternaires, une description thermodynamique de chacun des systèmes ternaires est effectuée. Les systèmes Fe-Al-Zr et Fe-Ti-Zr ont été complètement décrits à l aide du logiciel ThermoCalc. Le système ternaire Fe-Al-Ti a fait l objet d une description partielle. Les résultats obtenus permettent de proposer une première description thermodynamique du coin riche en fer du système quaternaire Fe-Al-Ti-Zr. Des séquences de solidification ont également été calculées à partir de cette description pour les alliages ternaires Fe-Al-Zr et quaternaires Fe-Al-Ti-Zr et comparées aux résultats expérimentauxThe first part of this work deals with the study of the microstructures and micro-segregations phenomena, inherited from the solidification on Fe-Al-Ti, Fe-Al-Zr and Fe-Al-Ti-Zr alloys. To improve our understanding of the phenomena occurring during the solidification process and to dispose of a predictive tool of the phases formed during the solidification process, a thermodynamic modeling of the iron rich corner of the Fe-Al-Ti-Zr quaternary system is proposed on a second part. From the data available in this work and in the literature, a thermodynamic modeling of each of the constituting ternaries systems is performed. Fe-Al-Zr and Fe-Ti-Zr ternaries systems were fully modeled using the ThermoCalc software. The Fe-Al-Ti ternary system is only partially modeled. These results allowed us to propose a first description of the iron rich corner of the Fe-Al-Ti-Zr quaternary system. Solidification sequences were calculated from this thermodynamic model for Fe-Al-Zr ternaries and Fe-Al-Ti-Zr quaternaries alloys and compared to our experimental resultsNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF

Influence de l'oxygène sur le comportement à la solidification d'aluminiures de titane binaires et alliés au niobium basés sur le composé intermétallique [gamma]-TiAI

Cette étude s inscrit dans le cadre du projet européen IMPRESS, "Intermetallic Materials Processing in Relation to Earth and Space Solidification". Elle porte sur la compréhension des mécanismes fondamentaux qui contrôlent la solidification de l alliage Ti-46Al-8Nb envisagés pour le développement d aubes de turbines. La première partie de cette étude caractérise l influence de l oxygène sur le comportement à la solidification d alliages de base TiAl coulés et contenant de 40 a 48 at.% d aluminium. L addition d oxygène augmente la fraction volumique de phase [alpha] formée pendant la solidification péritectique et conduit au changement de la phase primaire de solidification de la phase [bêta] à la phase [alpha] dans les alliages ternaires Ti-44,3Al-1,5O, Ti-47,7Al-0,8O et Ti-47,3Al-1,5O (at.%). Les coefficients de partage pour l aluminium et l oxygène kAl[alpha]/l= 0,9 et kO[alpha]/l = 1,29, ont été déterminés pour l alliage ayant [alpha] comme phase primaire de solidification. Dans un deuxième temps, l étude du comportement à la solidification de l alliage Ti-46Al-8Nb, est décrite en portant une attention particulière sur les effets de la contamination et des conditions de croissance sur la formation des microstructures et des microségrégations. Deux comportements différents ont été mis en évidence : dans la phase primaire de solidification [alpha] rencontrée pour des hauts niveaux de contamination en oxygène, une très faible rétrodiffusion est observée. Pour de faibles quantités d oxygène, la phase primaire de solidification est la phase [bêta]. Dans ce cas la présence d oxygène induit une augmentation de l amplitude de ségrégation malgré une forte rétrodiffusion dans la structure cubique centréeThis study was performed in the framework of the IMPRESS, "Intermetallic Materials Processing in Relation to Earth and Space Solidification", and is dedicated to the understanding of the fundamental mechanisms that control solidification in a Ti-46Al-8Nb alloy selected for TiAl-based alloy turbine blade development. The first part of this work is devoted to study the influence of oxygen on the solidification behaviour of cast TiAl-based alloys containing from 40 to 48 at.% of Al. Increasing the oxygen content affects significantly the macrostructure of the as-cast ingots, increases volume fraction of the phase formed during the peritectic solidification and leads to a change of the [bêta] primary solidification phase to the [alpha] phase in the ternary Ti-44.2Al-1.4O, Ti-47.3Al-0.9O and Ti-47.2Al-1.5O (at.%) alloys. When [alpha] is the primary solidification phase, the partition coefficients has been determined as kAl[alpha]/l= 0,9 and kO(alpha]/l = 1,29. In a second part, the solidification behaviour of Ti-46Al-8Nb alloy is investigated, with a particular attention to the contamination and growth conditions effects on microstructures and microsegregation formations. For high contamination levels, the solidification phase is [alpha] where oxygen reduces solute mobility, leading to limited backdiffusion. In low oxygen containing alloys, [bêta] is the primary solidification phase, and oxygen leads to an extent of the segregation amplitude despite high level of back-diffusion in the bcc structureNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF

Formation des microstructures dans la fonte à graphite spheroïdal aux premiers instants de la solidification

Les conditions thermiques et le traitement du métal liquide pour la coulée centrifuge des tuyaux de canalisation permettent d'obtenir une solidification sous forme de graphite sphéroïdal sur l'ensemble de l'épaisseur. Il est parfois observé en peau des zones solidifiant selon le mode blanc qui peuvent induire des différences de réponses métallurgiques problématiques. La caractérisation de tuyaux de différents diamètres montre qu'une compétition entre la croissance de l'eutectique métastable et la germination et croissance de l'eutectique stable existe dès le tout début de la solidification. Pour préciser les conditions thermiques de cette compétition un dispositif de chute de goute sur substrat a été utilisé pour lequel la solidification rapide et dirigée se déroule avec mesure de l?évolution de la température aux premiers moments de la solidification (t<200 ms). La caractérisation des microstructures à l'état brut de coulée et après traitement thermique a montré que ce dispositif permettait de reproduire les conditions thermiques de la peau des tuyaux et de figer la structure précurseur de celle obtenue par coulée centrifuge. Un modèle physique décrivant les premiers instants de la solidification sous très fort gradient thermique d'une fonte inoculée et traitée au Mg est présenté, prenant en compte la cinétique de germination et croissance des nodules de graphite en compétition avec la solidification de l'eutectique métastable. La comparaison entre les résultats du modèle et les caractérisations microstructurales permet de préciser les scénarios de formation des microstructures en découplant l'influence du gradient thermique et de la vitesse de solidificationThe thermal conditions and the treatment of the liquid metal for centrifugal casting of pipes lead to the solidification of the melt in the form of spheroidal graphite (SG) iron throughout the thickness. However it is sometimes observed zones that are solidified within the white mode (eutectic austenite / cementite) mainly in the skin of the product. These areas lead to differences which could be problematic. Further characterization of the microstructure of pipes shows that competition between the nucleation and growth of stable and metastable eutectic growth exists from the beginning of solidification. To clarify the thermal conditions of this competition an experimental device has been used. Liquid metal droplet fall on a cold substrate. Rapid directionnal solidification occurs and the temperature evolution of the lower surface of the droplet is recorded during the very first moment of solidification (< 200 ms). Characterization of droplet microstructures obtained in as-cast state and after heat treatment showed that the device is able to froze the solidified microstructure in an earlier stage of formation than in the as cast pipe. A physical model describing the first instants of the solidification under very high thermal gradient of a cast iron which is inoculated and treated with Mg is presented, taking into account the kinetics of nucleation and growth of graphite nodules in competition with the solidification of the metastable eutectic. The comparison between the calcluated results and microstructural characterizations allows to specify microstructures devlopment scenarios by decoupling the influence of the thermal gradient and solidification rateMETZ-SCD (574632105) / SudocNANCY1-Bib. numérique (543959902) / SudocNANCY2-Bibliotheque electronique (543959901) / SudocNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF

Effect of Inoculant Alloy Selection and Particle Size on Efficiency of Isomorphic Inoculation of Ti-Al

International audienceThe process of isomorphic inoculation relies on precise selection of inoculant alloys for a given system. Three alloys, Ti-10Al-25Nb, Ti-25Al-10Ta, and Ti-47Ta (at %) were selected as potential isomorphic inoculants for a Ti-46Al alloy. The binary Ti-Ta alloy selected was found to be ineffective as an inoculant due to its large density difference with the melt, causing the particles to settle. Both ternary alloys were successfully implemented as isomorphic inoculants that decreased the equiaxed grain size and increased the equiaxed fraction in their ingots. The degree of grain refinement obtained was found to be dependent on the number of particles introduced to the melt. Also, more new grains were formed than particles added to the melt. The grains/particle efficiency varied from greater than one to nearly twenty as the size of the particle increased. This is attributed to the breaking up of particles into smaller particles by dissolution in the melt. For a given particle size, Ti-Al-Ta and Ti-Al-Nb particles were found to have a roughly similar grain/particle efficiency

In-situ observations of solutal melting using laser scanning confocal microscopy: The Cu/Ni model system

International audienceSolutal melting was investigated in-situ by means of high temperature laser scanning confocal microscopy. This technique enabled us to track the motion of the solid-liquid interface in order to determine the evolution of the interfacial velocity. The Cu-Ni binary system was chosen as a model case and concentric samples were fabricated from both pure metals. Two holding temperatures above the melting point of Cu were investigated, i.e., 1115 and 1145 degrees C. As the average composition of the mounted samples was chosen to lie within the solid solution region, the reaction occurred via the following steps: i) thermal melting of Cu, ii) solutal melting of Ni, and iii) resolidification. A smooth and regular s-1 interface was observed during solutal melting, except during a short period at 1145 degrees C where an irregularity briefly appeared. At 1115 degrees C, the dissolution of Ni was completed in less than 3 min and the total thickness dissolved was in the range 40-50 mu m. At 1145 degrees C, the dissolution did not last much longer but the total thickness dissolved was significantly larger: approximately 180 mu m. At both temperatures, the velocity first increased, then reached a maximum value after 20-30 s (0.6-0.8 mu m/s at 1115 degrees C and 4.8 mu m/s at 1145 degrees C), and finally tends progressively to zero. Post-mortem observations showed that the Ni was homogeneously dissolved over the entire sample height at 1115 degrees C, which excludes any effects of convection on the velocities that we measured. On the contrary, at 1145 degrees C, the dissolution was more important in the upper part of the sample and the interface appeared curved. The total thickness dissolved was in both cases larger than the predicted theoretical values and the melting velocities were also larger than the values obtained from finite difference calculations. The discrepancies are more pronounced at higher temperature

Three Dimensional Methodology to Characterize Large Dendritic Equiaxed Grains in Industrial Steel Ingots

International audienceThe primary phase grain size is a key parameter to understand the formation of the macrosegregation pattern in large steel ingots. Most of the characterization techniques use two-dimensional measurements. In this paper, a characterization method has been developed for equiaxed dendritic grains in industrial steel castings. A total of 383 contours were drawn two-dimensionally on twelve 6.6 cm 2 slices. A three-dimensional reconstruction method is performed to obtain 171 three-dimensional grains. Data regarding the size, shape and orientation of equiaxed grains is presented and thereby shows that equiaxed grains are centimeter-scale complex objects. They appear to be a poly-dispersed collection of non-isotropic objects possessing preferential orientations. In addition, the volumetric grain number density is 2.2 × 10 7 grains/m 3 , which compares to the 0.5 × 10 7 grains/m 3 that can be obtained with estimation from 2D measurements. The 2.2 × 10 7 grains/m 3 value is ten-times smaller than that previously used in the literature to simulate the macrosegregation profile in the same 6.2 ton ingot

Microsegregation Model Including Convection and Tip Undercooling: Application to Directional Solidification and Welding

International audienceThe microsegregation behavior of alloy filler metal 52 (FM 52) was studied using microprobe analysis on two different solidification processes. First, microsegregation was characterized in samples manufactured by directional solidification, and then by gas tungsten arc welding (GTAW). The experimental results were compared with Thermo-Calc calculations to verify their accuracy. It was confirmed that the thermodynamic database predicts most alloying elements well. Once this data had been determined, several tip undercooling calculations were carried out for different solidification conditions in terms of fluid flow and thermal gradient values. These calculations allowed the authors to develop a parametrization card for the constants of the microsegregation model, according to the process parameters (e.g., convection in melt pool, thermal gradient, and growth velocity). A new model of microsegregation, including convection and tip undercooling, is also proposed. The Tong-Beckermann microsegregation model was used individually and coupled with a modified Kurz-Giovanola-Trivedi (KGT) tip undercooling model, in order to take into account the convection in the fluid flow at the dendrite tip. Model predictions were compared to experimental results and showed the microsegregation evolution accurately

Microstructural and micro-electrochemical study of a tantalum-titanium weld interface

International audienceLaser welding offers an array of advantages compared to conventional fusion welding techniques, such as a higher welding speed and lower thermal distortion. However, information about the key aspects of the welding of dissimilar materials remains limited. Therefore, we chose to study the weld interface between tantalum and Ti-6Al-4V, which have good metallurgical compatibility but highly different thermophysical properties that can lead to pronounced chemical heterogeneities. An SEM analysis of the microstructure clearly revealed the formation of an unmixed zone in the melted area and a DRX analysis highlighted the presence of a beta(Ta,Ti) solid solution, tantalum islets and possibly alpha'-titanium where betagenic tantalum was absent. In terms of electrochemical behaviour, the titanium content was the main indicator of oxidation phenomena: a content greater than 50% resulted in a stable passive film, while lower Values led to an oxidation peak at approximately 1.7V vs Ag/AgCl. These results suggest that a reliable laser welding process.must promote a high titanium content in the melted area. This may be achieved through am optimized process with a heat source that shifts away from the tantalum in order to minimize tantalum levels in the melted area