<p>The main focus in the present work concerns calculations on steel/slag equilibria. Thermodynamic software and databases are now powerful and accurate enough to give reliable results when applied to complex metallurgical processes. One example is the decarburization process of high alloyed steels. It is shown that using advanced thermodynamic models, without a complicated kinetic description of the system, reasonable agreement with experimental data is obtained. The calculations are performed using the Thermo-Calc software.</p><p>Within this work a Java interface for Thermo-Calc has been implemented. Java gives graphical possibilities and a graphical interface has been created that facilitates calculations that involve both metallic phases as well as oxides and make them feasible also for an industrial user.</p>

The main focus in the present work concerns calculations on steel/slag equilibria. Thermodynamic software and databases are now powerful and accurate enough to give reliable results when applied to complex metallurgical processes. One example is the decarburization process of high alloyed steels. It is shown that using advanced thermodynamic models, without a complicated kinetic description of the system, reasonable agreement with experimental data is obtained. The calculations are performed using the Thermo-Calc software. Within this work a Java interface for Thermo-Calc has been implemented. Java gives graphical possibilities and a graphical interface has been created that facilitates calculations that involve both metallic phases as well as oxides and make them feasible also for an industrial user. / QC 20101118

Haynes 282 is a gamma prime (𝛾′)-strengthened nickel base superalloy developed in 2005, exhibiting a good combination of high temperature properties and fabricability. Microstructural features such as 𝛾′ and carbides play an important role in deriving the mechanical properties of the alloy during heat treatment. As Haynes 282 is a relatively new alloy with insufficient literature availability, the present thesis is aimed at studying the evolution of microstructure for different heat treatment times and temperature with a special focus on 𝛾′ phase precipitation kinetics with different initial conditions for the material. The study is divided into two sections with objectives which are focused on the different ends to the heat-treatment time scales. The first objective of this study was to investigate γ' precipitation at short heat treatment times and develop Time-Temperature Precipitation (TTP) and Hardness (TTH) diagrams for Haynes 282 using a novel arc heat treatment. In this technique, a steady state temperature gradient, covering room temperature to liquidus, was created using stationary TIG arc on a disc mounted on a water-cooled chamber. Aged and solutionized samples were arc heat treated for 1.5 minutes, 30 minutes and 4 hours. The study was complemented with temperature modelling, thermodynamic calculations, and 𝛾′ precipitation simulation. A unique graded microstructure formed, consisting of dendritic region in fusion zone; dissolution area of all phases including MC carbides, grain boundary carbides, and 𝛾′; grain boundary carbide zone, 𝛾′ band; and base metal. 𝛾′ precipitate size increased with increasing time and temperature. 𝛾′ precipitation simulation model was developed, and it showed very good agreement with experimental results. Finally, the results were summarized in TTH and TTP diagrams. The second objective in this work was to study understand the coarsening behaviour of 𝛾′ phase with an initial pre-heat-treated GKN heat treatment using furnace heat treatment. Isothermal heat treatments for temperatures from 800°C to 1120°C and times from 30 seconds to 96 hours were performed. Morphological changes in 𝛾′ phase, particle size distribution, grain sizes and hardness on these isothermal heat-treated states are presented in this work. Additionally, A TC PRISMA precipitation model was evaluated to predict 𝛾′sizes and compare it with the measurements. It was concluded that complex initial microstructure, containing bimodal distribution of 𝛾′ precipitates, caused deviations between predicted and measured values, while the model, in the previous objective, predicted the sizes in close approximation to the experimental values. Therefore, further understanding and development of precipitation kinetics with the software should be done to achieve closer results to the experiment. / Haynes 282 är ett gamma prime (𝛾′) - förstärkt superlegering av nickelbas som utvecklades 2005 och uppvisar en god kombination av högtemperaturegenskaper och tygbarhet. Mikrostrukturella egenskaper såsom 𝛾′ och karbider spelar en viktig roll för att få de mekaniska egenskaperna hos legeringen under värmebehandling. Eftersom Haynes 282 är en relativt ny legering med otillräcklig litteraturtillgänglighet syftar den aktuella avhandlingen till att studera utvecklingen av mikrostruktur för olika värmebehandlingstider och temperatur med ett särskilt fokus på 𝛾′ fasutfällningskinetik med olika initiala förhållanden för materialet. Studien är uppdelad i två sektioner med mål som är inriktade på de olika ändarna på värmebehandlings tidsskalorna. Det första syftet med denna studie var att undersöka 𝛾′nederbörd vid korta värmebehandlingstider och utveckla Time-Temperature Precipitation (TTP) och Hardness (TTH) diagram för Haynes 282 med användning av en ny bågvärmebehandling. I denna teknik skapades en jämn temperaturgradient, som täcker rumstemperatur till liquidus, med användning av stationär TIG-båge på en skiva monterad på en vattenkyld kammare. Åldriga och lösningsbara prover bågvärmebehandlades under 1,5 minuter, 30 minuter och 4 timmar. Studien kompletterades med temperaturmodellering, termodynamiska beräkningar och 𝛾′utfällningssimulering. En unik graderad mikrostruktur bildad, bestående av dendritisk region i fusionszon; upplösningsområde för alla faser inklusive MC-karbider, korngränsande karbider och 𝛾′; korngränsen karbidzon, 𝛾′ band; och oädel metall. 𝛾′utfällningsstorlek ökade med ökande tid och temperatur. 𝛾′utfällningssimuleringsmodell utvecklades, och den visade mycket bra överensstämmelse med experimentella resultat. Slutligen sammanfattades resultaten i TTH- och TTP-diagram. Det andra syftet med detta arbete var att studera förstå det förgrovning beteendemönster hos 𝛾′ fasen med en initial förvärmebehandlad GKN-värmebehandling med ugnsvärmebehandling. Isotermiska värmebehandlingar för temperaturer från 800 ° C till 1120 ° C och gånger från 30 sekunder till 96 timmar utfördes. Morfologiska förändringar i 𝛾′fasen, partikelstorleksfördelning, kornstorlekar och hårdhet på dessa isotermiska värmebehandlade tillstånd presenteras i detta arbete. Dessutom utvärderades en TC PRISMA-nederbördsmodell för att förutsäga 𝛾′ storlekar och jämföra den med mätningarna. Det drogs slutsatsen att komplex initial mikrostruktur, innehållande bimodal fördelning av 𝛾′-fällningar, orsakade avvikelser mellan förutspådda och uppmätta värden, medan modellen i det tidigare målet förutspådde storleken i nära anpassning till experimentvärdena. Därför bör ytterligare förståelse och utveckling av utfällningskinetik med programvaran göras för att uppnå närmare resultat till experimentet.

This project is a feasibility study for Hydro Extrusion Sweden AB, a company that produces extruded aluminium profiles. The main purpose of this project was to analyse the difference of Mg2Si particle sizes in aluminium alloys when varying parameters, such as cooling rate and composition, in aluminium extrusion, particularly the EN AW 6082 alloy. The Mg2Si particles have a great impact on the product’s mechanical properties. This was done in order to investigate whether real-time process parameter control is possible or not. The main software used was Thermo-Calc and the add-on module DICTRA. Thermo-Calc was used to do equilibrium calculations and gather data for the alloy and its phases. Based on this information and data from Hydro, simulations in DICTRA could be performed. The results were then plotted with respect to time and radius. The findings indicate that the cooling rate significantly influences the particle size. As the process becomes more intricate and involves a greater number of trace elements, adjusting the cooling rate could potentially be employed as a means to address this issue. The results also showed that trace elements had a minimal effect on the particle size. However, this probably does not match the reality since other phases affect and block the growth of Mg2Si.The overall results indicate a positive outcome for using DICTRA in determining particle sizes. However, further research needs to be done in correlation with more experiments before this could be a viable research method for Hydro. / Det här projektet är en förstudie för företaget Hydro Extrusion Sweden AB som producerar extruderade aluminiumprofiler. Det huvudsakliga syftet med projektet var att analysera skillnaden på Mg2Si-partiklarnas storlek i aluminiumlegeringar när olika parametrar som kylhastighet och sammansättning användes vid aluminiumextrudering, mer specifikt legeringen EN AW 6082. Mg2Si partiklarna har stor betydelse för produktens mekaniska egenskaper. Syftet med detta var att undersöka huruvida det är möjligt att styra process parametrarna i realtid. Mjukvaran som användes var Thermo-Calc och tilläggsmodulen DICTRA. Thermo-Calc användes för att göra jämviktsberäkningar och samla in data för legeringen samt dess faser. Baserat på denna information och data från Hydro kunde simuleringar i DICTRA utföras. Resultaten plottades sedan med avseende på tid och radie. Partikelstorleken påverkas avsevärt av kylningshastigheten enligt resultaten. I framtiden, när processen blir mer avancerad med fler spårämnen, kan det vara möjligt att justera kylningshastigheten för att hantera detta. Resultaten visade också att spårämnen hade en mycket liten effekt på partikelstorleken. Detta stämmer dock förmodligen inte med verkligheten eftersom andra faser påverkar och blockerar tillväxten av Mg2Si. De övergripande resultaten pekar på ett positivt resultat för att använda DICTRA för att bestämma partikelstorlekar. Ytterligare forskning måste göras i samband med fler experiment innan detta kan vara en genomförbar forskningsmetod för Hydro.

For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason for using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is useful to support material designers. In this thesis some aspects of the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. amount and composition of phases, oxygen activity, heat capacity etc, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy as a function of composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. The elements included in the databse are: C, Fe, Cr, Nb, Ni, Mo, O, Si, Sn, and Zr + H, and the assessment performed under this thesis are: Cr-Sn, Mo-Zr, Sn-Zr, Fe-Nb-Zr and Nb-O-Zr. All the calculations have been made using Thermo-Calc software and the representation of the Gibbs energy obtained by applying Calphad technique with some use of ab initio calculations. / QC 20100902

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.

No description available.

<p>Combination of the Calphad method and theoretical calculations provides new possibilities for the study of materials science. This work is a part of the efforts within the CCT project (Centre of Computational Thermodynamics) to combine these methods to facilitate modeling and to extend the thermodynamic databases with critically assessed volume data. In this work, the theoretical calculations refer to first-principles and Debye-Grüneisen calculations. The first-principles (i.e. ab initio) electronic structure calculations, based on the Density- Functional Theory (DFT), are capable of predicting various physical properties at 0 K, such as formation energy, volume and bulk modulus. The ab initio simulation software, VASP, was used to calculate the binding curves (i.e. equation of state at 0 K) of metallic elements, cubic carbides and nitrides. From the binding curves, the equilibrium volumes at 0 K were calculated for several metastable structures as well as stable structures. The vibrational contribution to the free energy was calculated using the Debye-Grüneisen model combined with first-principles calculations. Two different approximations for the Grüneisen parameter, γ, were used in the Debye-Grüneisen model, i.e. Slater’s and Dugdale-MacDonald’s expressions. The thermal electronic contribution was evaluated from the calculated electronic density of states. The calculated thermal expansivities for metallic elements, cubic carbides and nitrides were compared with Calphad assessments. It was found that the experimental data are within the limits of the calculations using the two approximations for γ. By fitting experimental heat capacity and thermal expansivity around Debye temperatures, we obtained optimal Poisson’s ratio values and used them to evaluate Young’s and Shear moduli. In order to reach a reasonable agreement with the experiments, it is necessary to use the logarithmic averaged mass of the constitutional atoms. The agreements between the calculations and experiments are generally better for bulk modulus and Young’s modulus than that for shear modulus. A new model describing thermodynamic properties at high pressures was implemented in Thermo-Calc. The model is based on an empirical relation between volume and isothermal bulk modulus. Pure Fe and solid MgO were assessed using this model. Solution phases will be considered in a future work to check the model for compositional dependence.</p>

Combination of the Calphad method and theoretical calculations provides new possibilities for the study of materials science. This work is a part of the efforts within the CCT project (Centre of Computational Thermodynamics) to combine these methods to facilitate modeling and to extend the thermodynamic databases with critically assessed volume data. In this work, the theoretical calculations refer to first-principles and Debye-Grüneisen calculations. The first-principles (i.e. ab initio) electronic structure calculations, based on the Density- Functional Theory (DFT), are capable of predicting various physical properties at 0 K, such as formation energy, volume and bulk modulus. The ab initio simulation software, VASP, was used to calculate the binding curves (i.e. equation of state at 0 K) of metallic elements, cubic carbides and nitrides. From the binding curves, the equilibrium volumes at 0 K were calculated for several metastable structures as well as stable structures. The vibrational contribution to the free energy was calculated using the Debye-Grüneisen model combined with first-principles calculations. Two different approximations for the Grüneisen parameter, γ, were used in the Debye-Grüneisen model, i.e. Slater’s and Dugdale-MacDonald’s expressions. The thermal electronic contribution was evaluated from the calculated electronic density of states. The calculated thermal expansivities for metallic elements, cubic carbides and nitrides were compared with Calphad assessments. It was found that the experimental data are within the limits of the calculations using the two approximations for γ. By fitting experimental heat capacity and thermal expansivity around Debye temperatures, we obtained optimal Poisson’s ratio values and used them to evaluate Young’s and Shear moduli. In order to reach a reasonable agreement with the experiments, it is necessary to use the logarithmic averaged mass of the constitutional atoms. The agreements between the calculations and experiments are generally better for bulk modulus and Young’s modulus than that for shear modulus. A new model describing thermodynamic properties at high pressures was implemented in Thermo-Calc. The model is based on an empirical relation between volume and isothermal bulk modulus. Pure Fe and solid MgO were assessed using this model. Solution phases will be considered in a future work to check the model for compositional dependence.

Alumino-silicate systems are of great interest for materials scientists and geochemists. Thermodynamic knowledge of these systems is useful in steel and ceramic industries, and for understanding geochemical processes. A popular and efficient approach used to obtain a self-consistent thermodynamic dataset is called CALPHAD. It couples phase diagram information and thermochemical data with the assistance of computer models. The CALPHAD approach is applied in this thesis to the thermodynamic modelling and assessments of the CaO-Al2O3-SiO2, MgO-Al2O3-SiO2 and Y2O3-Al2O3-SiO2 systems and their subsystems. The compound energy formalism is used for all the solution phases including mullite, YAM, spinel and halite. In particular, the ionic two sub-lattice model is applied to the liquid solution phase. Based both on recent experimental investigations and theoretical studies, a new species, AlO2-1, is introduced to model liquid Al2O3. Thus, the liquid model corresponding for a ternary Al2O3-SiO2-M2Om system has the formula (Al+3,M+m)P (AlO2-1,O-2, SiO4-4,SiO20)Q, where M+m stands for Ca+2, Mg+2 or Y+3. This model overcomes the long-existing difficulty of suppressing the liquid miscibility gap in the ternary systems originating from the Al2O3-free side during the assessments. All the available and updated experimental information in these systems are critically evaluated and finally a self-consistent thermodynamic dataset is achieved. The database can be used along with software for Gibbs energy minimization to calculate any type of phase diagram and all thermodynamic properties. Various phase diagrams, isothermal and isoplethal sections, and thermochemical properties are presented and compared with the experimental data. Model calculated site fractions of species are also discussed. All optimization processes and calculations are performed using the Thermo-Calc software package. / QC 20100607