Lead (Pb) is frequently used as an alloying element in brass to enhance machinability and castability. However, this element poses a significant risk to human health and the environment. The 2021 revision of the Drinking Water Directive imposed stricter limits on Pb content in brass, encouraging the development of lead-free brass. Several studies have identified tin (Sn) as a potential substitute for Pb in brass. This master’s thesis examines the thermodynamic description of the Cu-Zn-Sn ternary system, using the Swerim Cu database. The investigation involved casting five alloys in the Cu-rich corner, followed by heat treatment at 550 oC until homogenized, and quenching, after which the samples were analyzed to determine the bcc and fcc phase composition. The results were used to confirm the thermodynamic description, and the ternary parameters of the fcc and bcc phases were optimized to match the experimental results. After the optimization, a significant enhancement is achieved in the description of the Cu-Zn-Sn ternary system, which better fits the experimental data. / Bly  (Pb)  används  ofta  som  ett  legeringselement  i  mässing  för  att  förbättra bearbetbarheten och  gjutbarheten.    Detta  element  utgör  dock  en  betydande  risk för människors  hälsa  och miljön.   2021 års översyn  av  dricksvattendirektivet införde strängare  gränser  för  Pb-halten  i mässing,  vilket  uppmuntrade utvecklingen av blyfri mässing.    Flera  studier  har  identifierat tenn  (Sn)  som  ett potentiellt substitut  för  Pb i mässing.   Denna  masteruppsats  undersöker den termodynamiska beskrivningen  av det ternära  Cu-Zn-Sn-systemet  med  hjälp  av Swerim Cu-databasen.   Undersökningen innefattade  gjutning  av  fem  legeringar  i det  Cu-rika hörnet, följt av värmebehandling vid 550 oC tills de homogeniserades, och härdning, varefter proverna analyserades  för  att bestämma  bcc-  och  fcc-fassammansättningen.   Resultaten  användes  för att  bekräfta den  termodynamiska  beskrivningen,  och  de  ternära  parametrarna  för  faserna  fcc och bcc  optimerades  för  att  matcha  experiment resultaten.  Efter  optimeringen  uppnås  en betydande  förbättring  av  beskrivningen  av  det  ternära  Cu-Zn-Sn-systemet,  vilket bättre  passar experimentdata.

Thermo-Calc software AB develops high quality thermodynamic and kinetic databases to predict and simulate accurately multi-component phase behaviour in complex systems. One problem with their Ni-based alloys and superalloy solutions database (TCNI8) is poor description of tungsten partitioning for multi-component nickel based alloys. This work investigates the thermodynamic description of some lower-order systems i.e., Ni-W, Al-Ni-W and Cr-Ni-W by performing key experiments on three binary Ni-W alloys, and two ternary alloys (Al-Ni-W and Cr-Ni-W). Experiments at four different temperatures were carried out in which alloys were homogenized, equilibrated, quenched and investigated to determine the equilibrium solid/liquid compositions. Experimental results are used to validate the thermodynamic descriptions of the liquid and the fcc phase. Unlike ternary Al-Ni-W and Cr-Ni-W, binary Ni-W reproduced the experimental information in a satisfactory way. Ternary parameters for fcc are changed to fit the experimental results of this work. The findings of this work highlight that ternary parameters for the fcc of Al-Ni-W and Cr-Ni-W systems significantly effect the tungsten partitioning values in higher order systems. / Thermo-Calc Software AB utvecklar termodynamiska och kinetiska databaser av hög kvalitet för att korrekt kunna förutsäga och simulera jämvikter och fasomvandlingar i komplexa flerkomponentsystem. Ett problem med deras databas för Ni-baslegeringar och superlegeringar (TCNI8) är att beskrivning av volframpartitionering stämmer dåligt för nickelbaslegeringar. I detta arbete undersöktes den termodynamiska beskrivningen av vissa lägre system, dvs Ni-W, Al-Ni-W och Cr-Ni-W genom att utföra nyckelförsök på tre binära Ni-W-legeringar och två ternära legeringar (Al-Ni-W och Cr-Ni-W). Experimentvid fyra temperaturer utfördes i vilka legeringarna homogeniserades,jämviktsbehandlades, släcktes och undersöktes för att bestämma sammansättning för jämvikt fast fas/smälta. De erhållna experimentella resultaten användes för att validera den termodynamiska beskrivningen av smältan och fcc-fasen. Till skillnad från ternära Al-Ni-W ochCr-Ni-W, reproducerade den experimentella informationen den binära Ni-W-beskrivningen tillfredsställande. Ternära parametrar för fcc justerades efter de experimentella resultaten från detta arbete. Resultaten visar att de ternära parametrarna för fcc i Al-Ni-W och Cr-Ni-W systemen signifikant påverkar volframs fördelning mellan fast fas och smälta i nickelbaslegeringar.

To enable a generic modelling tool for precipitation kinetics in non-homogeneous components, an efficient data-handling is required to facilitate the integration of models on different length scales, and to decrease the computational time and the use of resources. In this work an automated method to generate, curate and transform Calphad- based thermodynamic and kinetic data to facilitate precipitation models integrated in FEM codes is developed and tested. The open-source Python library, pycalphad, is employed to access Calphad databases. Python scripts are utilized to calculate the thermodynamic and kinetic parameters, required to supply a precipitation model. The obtained data is stored with an open-source software infrastructure. The Cu-Co binary is the chosen model alloy in this work and the corre-sponding parameters are calculated and stored. The obtained results show, that pycalphad can be used to supply the required thermodynamic and kinetic pa- rameters for a precipitation model. Further refinement of the presented sourcecode is required to enable application in the whole composition range. / För utveckling av ett generiskt modelleringsverktyg för utskiljningskinetiken i inhomogena komponenter krävs en effektiv databehandling som möjliggör integration av modeller för olika längdskalor och minskar beräkningstiden och resursförbrukningen. I denna avhandling utvecklas och testas en automatiserad metod för att generera, kurera och transformera termodynamisk och kinetisk Calphad-data. Detta möjliggör integration av utskiljningsmodeller i finita-element metodkoder. Pycalphad tillsammans med en öppen källkod används för att komma åt Calphad-databaser. Ett Python-skript används för att beräkna de termodynamiska och kinetiska parametrarna som används i utskiljningsmodellen. Uppgifterna sparas i en öppen källkodsinfrastruktur. Den utvecklade metoden demonstreras genom att generera, kurera och transformera information för det binära modellsystemet Cu-Co Resultaten visar att Pycalphad kan användas för att tillhandahålla de nödvändiga termodynamiska och kinetiska parametrarna för utskiljningsmodeller. En ytterligare förbättring av den presenterade källkoden är nödvändig för att möjliggöra applikationen inom hela sammansättningsområdet.

Fundamental studies on thermodynamic properties of vanadium-containing oxides systems are essential to understand practical vanadium metallurgical process. The CALPHAD technique is here applied to the thermodynamic modelling of the V-O, Ca-V-O and Ti-V-O systems. The compound energy formalism is used for all the solution phases. All optimization processes and calculations are performed using the Thermo-Calc software package. The present work attempts to develop a self-consistent thermodynamic database of all phases in the studied systems. The obtained datasets can be used to calculate thermodynamic properties, stable as well as metastable phase equilibria and driving forces for oxidation etc. Steelmaking slag is an important secondary source for vanadium extraction. The phase relationships and vanadium distribution in the CaO-SiO2-MgO-V2O3-Al2O3 synthetic slags, whose compositions were chosen based on the relevance to the steel producers, are also studied. Phase equilibria in the temperature range of 1773 to 1823 K at oxygen partial pressure of 10-10 bar and 0.21 bar were characterized. An investigation of the volatilization of vanadium oxide was also carried out in the present work. Isothermal evaporation of vanadium pentoxide in the temperature range between 1723 and 1873 K was investigated by Thermogravimetric Analysis under different oxygen partial pressures, viz. oxygen, air or CO2. The Arrhenius activation energy for the evaporation reaction in various atmospheres was calculated from the experimental results. A mathematical model was developed to describe the kinetics of the evaporation process. Evaporation coefficients and enthalpies in various atmospheres were also estimated. The present results may have some implications in recovering vanadium from different vanadium-bearing sources. / <p>QC 20161202</p>

L’étude menée sur le système Mo-Pt-Si vise à contribuer à la connaissance d’alliages métalliques complexes destinés à des applications à hautes températures rencontrées dans les industries aéronautiques ou verrières. Sa description d’un point de vue thermodynamique est rendu difficile par son caractère réfractaire lié à la présence du molybdène d’une part et à sa complexité due au nombre élevé de ses constituants (3 éléments) d’autre part. Seule une approche du problème par une modélisation thermodynamique de type CALPHAD permet d’aboutir à un résultat significatif. Comme l’impose l’établissement d’une modélisation d’un système ternaire, à savoir l’étude préalable des trois bordures binaires, le premier volet de ce travail a été consacré à l’étude des systèmes Pt-Si, Mo-Pt et Mo-Si. Parallèlement au travail d’optimisation, des mesures expérimentales réalisées dans le cadre de cette étude (radiocristallographie, analyse thermique, microsonde,….) ont permis de déterminer les équilibres entre phases, les enthalpies de formation des différents composés intermétalliques ainsi que les mécanismes structuraux responsables des grands domaines de stabilité observés pour certaines phases. La première approche du système ternaire Mo-Pt-Si, obtenue à partir de la banque de données intégrant les optimisations binaires, a permis de cibler et interpréter des expériences de contrôles des équilibres entre phases en condition isotherme et anisotherme. Un nouveau siliciure ternaire a ainsi été découvert et pris en compte dans le calcul. Enfin, à travers de nombreux exemples nous montrons la cohérence de la modélisation avec l’ensemble des données expérimentales. / The study on the Mo-Pt-Si system contributes to the knowledge of complex metal alloy, which are intended for applications at high temperatures in the aerospace or glass industries. Its thermodynamic description is difficult because its refractory character related to the presence of the molybdenum and to its complexity due to the high number of the constituents (3 elements). Only an approach of problem by a modelling thermodynamics of CALPHAD type gives to a significant result. As imposes the establishment of a modelling of a ternary system by the study of three binary borders, the first part of this work was devoted to the study of Pt-Si, Mo-Pt and Mo-Si systems. Along with the optimization, an experimental measurements used in this study (X-ray, thermal analysis, microprobe,….) allowed to determine the equilibria phases, the enthalpies of formation of the various intermetallic compounds as well as the structural mechanisms responsible for large domains of stability observed for some phases. The first approach of the Mo-Pt-Si ternary system obtained from the database including the binary optimisations, allowed to interpret the experiments of controls of equilibria phases in isotherm and anisotherm conditions. A new ternary silicide was discovered and took into account in calculation. Finally, through many examples we show the agreement of the modelling with all experimental data.

Cette thèse porte d'une part sur la conception et la caractérisation d'alliages métalliques pour des applications dans les domaines de la réfrigération magnétocalorique ou thermoélectrique ; ces alliages ont été conçus en tenant compte à la fois des critères dictés par l'application recherchée et des critères dictés par la nécessité de vitrifier l'alliage. Dans un deuxième temps, ce travail montre qu'il est en partie possible de prédire le domaine et l'aptitude de vitrification d'un système donné par une approche thermocinétique basée sur des données thermodynamiques.

The recent development of tool steels and high-speed steels has led to a significant increase in alloy additions, such as Co, Cr, Mo, N, V, and W. Knowledge about the phase relations in these multicomponent alloys, that is, the relative stability between different carbides or the solubility of different elements in the carbides and in the matrix phase, is essential for understanding the behaviour of these alloys in heat treatments. This information is also the basis for improving the properties or designing new alloys by controlling the amount of alloying elements. Thermodynamic calculations together with a thermodynamic database is a very powerful and important tool for alloy development of new tool steels and high-speed steels. By thermodynamic calculations one can easily predict how different amounts of alloying elements influence on the stability of different phases. Phase fractions of the individual phases and the solubility of different elements in the phases can be predicted quickly. Thermodynamic calculations can also be used to find optimised processing temperatures, e.g. for different heat treatments. Combining thermodynamic calculations with kinetic modelling one can also predict the microstructure evolution in different processes such as solidification, dissolution heat treatments, carbide coarsening, and the important tempering step producing secondary carbides. The quality of predictions based on thermodynamic calculations directly depends on the accuracy of the thermodynamic database used. In the present work new experimental phase equilibria information, both in model alloys containing few elements and in commercial alloys, has been determined and was used to evaluate and improve the thermodynamic description. This new experimental investigation was necessary because important information concerning the different carbide systems in tool steels and high-speed steels were lacking. A new thermodynamic database for tool steels and high-speed steels, TOOL05, has been developed within this thesis. With the new database it is possible to calculate thermodynamic properties and phase equilibria with high accuracy and good reliability. Compared with the previous thermodynamic description the improvements are significant. In addition the composition range of different alloying elements, where reliable results are obtained with the new thermodynamic database, have been widened significantly. As the available kinetic data did not always predict results in agreement with new experiments the database was modified in the present work. By coupling the new thermodynamic description with the new kinetic description accurate diffusion simulations can be performed for carbide coarsening, carbide dissolution and micro segregation during solidification. / QC 20100929

The purpose of this work is to optimize the chemical composition as well as the heat treatment for improving the mechanical performance of the TRIP steel by employing the theoretical models. TRIP steel consists of the microstructure with ferrite, bainite, retained austenite and minor martensite. Austenite contributes directly to the TRIP effect as its transformation to martensite under the external stress. In order to stabilize austenite against the martensitic transformation through the heat treatment, the two-step heat treatment is broadly applied to enrich the carbon and stabilize the austenite. During the first step of the heat treatment, intercritical annealing (IA), a dual phase structure (ferrite+austenite) is achieved. The austenite can be initially stabilized because of the low carbon solubility of ferrite. The bainite isothermal treatment (BIT) leads to the further carbon enrichment of IA-austenite by the formation of carbon-free ferrite. Comparing to the experiments, the thermodynamic and kinetic models are the lower and upper bounds of the carbon content of retained austenite. The mechanical properties are predicted using the swift model based on the predicted microstructure. In this work, a theoretical approach is coupled to a Genetic Algorithm-based optimization procedure to design (1) the heat treated temperatures to maximize the volume fraction of retained austenite in a Fe-0.32C-1.42Mn-1.56Si alloy and the chemical composition of (2) Fe-C-Mn-Si and (3) Fe-C-Mn-Si-Al-Cr-Ni alloy. The results recommend the optimum conditions of chemical composition and the heat treatment for maximizing the TRIP effect. Comparing to the experimental results, this designing strategy can be utilized to explore the potential materials of the novel alloys.

Le présent travail de recherche s’inscrit dans un projet global, dont le but est de comprendre et résoudre un problème de corrosion d’un acier dit T91 par un mélange métallique liquide de plomb et bismuth. Il présente un intérêt pour la communauté nucléaire qui envisage de développer une nouvelle génération de réacteurs dits ADS. Ce travail est une contribution à l’étude thermodynamique d’un système plus complexe composé de plusieurs éléments : Al, Bi, Pb, Fe, Cr et l’oxygène. Plus précisément, il a été focalisé sur les systèmes à base de mélanges d’oxydes Bi2O3 + PbO + Al2O3 et Bi2O3 + PbO + Fe2O3. Un travail expérimental a été accompli, au cours duquel ces mélanges à différentes proportions ont été recuits à une température supérieure à 600 °C pendant plusieurs jours, suivi de l’analyse des échantillons par des techniques de pointe. Il a permis de découvrir les différents produits formés dans les différentes conditions de température, de compositions et atmosphères. Les résultats ont permis de faire aussi une modélisation à l’aide d’un outil informatique. Tout cela aide à mieux comprendre et anticiper la formation des produits de corrosion de l’acier par le mélange métallique liquide / This research work takes part in a global project whose aim is to understand and solve a corrosion problem of a steel called T91 caused by a liquid mixture of lead-bismuth. It presents a great interest for the nuclear community who aims to develop a new generation of reactors called ADS. This study is a contribution to the thermodynamic study of a complex system involving several elements such as Al, Bi, Pb, Fe, Cr and oxygen. More precisely, it was focused on mixtures of the following oxides Bi2O3 + PbO + Al2O3 and Bi2O3 + PbO + Fe2O3. A long experimental work had been accomplished, in which mixtures of different proportions of these oxides were prepared and heated above 600 °C for several days, followed by samples analyses by use of accurate and advanced techniques. It allowed discovering the different products formed within the different experimental conditions. The results have been modeled using a computer tool. All this allowed a better understanding and anticipating the corrosion products formation of the T91 steel by the metallic liquid

This work deals with the effects of high temperature exposition of low alloyed creep resistant steels on their structural stability and structural stability of their weld joint. The theoretical part of this work gives an overview of creep resistant steels considering their chemical and phase composition and their connection to high temperature mechanical properties. The CALPHAD method is presented as generally accepted approach for equilibrated calculations and Thermo-Calc and DICTRA software packages are introduced as CALPHAD applications. Thermo-Calc software is used for calculation of phase composition of the examined materials and for calculation of the phase diagrams. Software DICTRA is used for simulations of diffusion controlled phase reactions in the analysed weld. Experimentally one weld joint of the steels 15 128 and 15 313 has been studied after four different annealing procedures. The experimental results include chemical profiles across the welds, microhardness profiles and metallographic analysis of significant regions of the welds. These experimental results are compared with the simulation results. The comparison shows a reasonable agreement between experimental and simulation data.