L'objectif de ce travail de thèse a été de développer l'utilisation des isotopes du fer pour le traçage des métaux anciens, principalement ferreux. Notre approche méthodologique s'est articulée autour de trois axes majeurs. Le premier axe a consisté à étudier l'influence potentielle des processus métallurgiques sur la composition isotopique du fer des métaux produits. Pour cela, nous avons mesuré la composition isotopique du fer d'échantillons issus d'expérimentations de réduction de minerai de fer en bas fourneau, réalisées sur un site sidérurgique majeur de la période romaine (la Montagne Noire, Sud-Ouest de la France). Le second axe a eu pour objectif de valider ce nouveau traceur en mesurant la composition des isotopes du fer de minerais, scories et objets en fer issus d'un contexte archéologique connu et dont la provenance avait déjà été identifiée par des analyses élémentaires. Nous avons alors mesuré la composition des isotopes du fer de barres de fer principalement retrouvées dans des épaves romaines au large des Saintes-Maries-de-la-Mer (Bouches-du-Rhône, France). Enfin, le troisième axe a eu pour vocation d'estimer la pertinence, mais aussi les limites de ce nouvel outil en l'appliquant à deux terrains archéologiques très différents, où aucune étude de traçage classique n'avait été utilisée précédemment. Ces deux terrains concernaient la sidérurgie ancienne au Togo et la production de plomb argentifère médiévale au Maroc. Les résultats obtenus montrent que la composition isotopique du fer de la scorie et du métal produit est similaire à celle du minerai correspondant. Il n'y a donc pas de fractionnement des isotopes du fer tout au long de la chaîne opératoire de production de fer. De plus, et contrairement à certains traceurs élémentaires, les isotopes du fer ne sont pas contaminés par la paroi du four très pauvre en cet élément durant la réduction. Ceci permet ainsi d'établir des liens de provenance directs entre un objet en fer et un minerai. L'application de cette méthode de traçage à un contexte archéologique déjà largement étudié a permis de valider les hypothèses de provenance d'objets archéologiques. En outre, les isotopes du fer peuvent être plus discriminants que les éléments en trace car ils permettent notamment de différencier des productions de fer temporellement et géographiquement très proches. Le traçage est ainsi affiné. Enfin, nos résultats préliminaires suggèrent que les analyses des isotopes du fer pourraient également être appliquées à l'étude de la production de métaux non ferreux. Cette étude offre ainsi de nombreuses perspectives, telles que l'étude de la provenance de pièces de musée étant donné la faible quantité de matière nécessaire, l'établissement d'une base de données de composition isotopique du fer de minerais archéologiques et l'élaboration d'une méthode de traçage commune aux métaux ferreux et non ferreux. / The objective of this work was to develop the use of iron isotopes for ancient, essentially ferrous metal tracing. Our methodological approach was based on three major directions. The first one consisted in the assessment of the potential influence of metallurgical processes on iron isotope compositions of the reduction products. For this purpose, we measured the iron isotope composition of materials from experiments of iron ore reduction in bloomery furnace performed in a major site of iron production during the Roman period (Montagne Noire, SW France). The second direction aimed at validating this new tracer through the iron isotope measurement of ores, slags and iron artefact samples from a well-defined archaeological context, and whose provenance was previously investigated by elemental analyses. We thus measured the isotopic composition of iron bars discovered in Roman shipwrecks found offshore Les-Saintes-maries-de-la-Mer (Bouches-du-Rhône, France). Thirdly, we estimated the relevance and limitations of our new tracing approach by applying it to the study of two different archaeological fields, on which no previous provenance study had been performed. These were the ancient iron production from North East Togo and the Medieval lead-silver production in Morocco (Anti Atlas Massif). The results demonstrate that the isotopic composition of slags and metals produced reflect that of their corresponding ores because no iron isotope fractionation occurs along the entire chaîne opératoire of iron production. Moreover, and in contrast to several elemental tracers, iron isotopes are not impacted by iron contribution from the smelting device during the reduction process, which allows to establish provenance links directly between an iron artifact and a specific ore. The application of this tracing method in a well-studied archaeological context has allowed to validate the provenance assumption of several archaeological artifacts. Furthermore, iron isotopes may provide a more discriminative tracer than trace elements because a temporal and geographical distinction is possible between close iron production sites. The tracing is thus more precise. Finally, our results suggest that iron isotope analyses could also be used in the study of non-ferrous metal production. This work offers many perspectives in provenance studies of museum pieces given the very small amount of material needed, in the setup of a database of iron isotope compositions of archaeological iron ores and the establishment of a common tracing approach for both ferrous and non-ferrous metals.

The main objective of this industrially important work was to gain an increasing understanding of the properties of some industrially important materials such as CMSX-4 nickel base super alloy, 90Ti.6Al.4V alloy, 25Cr:6Ni stainless steel, 0.7% carbon steel, AISI 304 stainless steel-alumina composites, mould powder used in continuous casting of steel as well as coke used in blast furnace with special reference to the thermal diffusivities. The measurements were carried out in a wide temperature range covering solid, liquid, glassy and crystalline states. For CMSX-4 alloy, the thermal conductivities were calculated from the experimental thermal diffusivities. Both the diffusivities and conductivities were found to increase with increasing temperature. Microscopic analysis showed the presence of intermetallic phases γ´ such as Ni3Al below 1253 K. In this region, the mean free path of the electrons and phonons is likely to be limited by scattering against lattice defects. Between 1253 K and solidus temperature, these phases dissolved in the alloy adding to the impurities in the matrix, which, in turn, caused a decrease in the thermal diffusivity. This effect was confirmed by annealing the samples at 1573 K. The thermal diffusivities of the annealed samples measured at 1277, 1403 and 1531 K were found to be lower than the thermal diffusivities of non-annealed samples and the values did not show any noticeable change with time. It could be related to the attainment of equilibrium with the completion of the dissolution of γ´ phase during the annealing process. Liquid CMSX-4 does not show any change of thermal diffusivity with temperature. It may be attributed to the decrease of the mean free path being shorter than characteristic distance between two neighbouring atoms. Same tendency could be observed in the case of 90Ti.6Al.4V alloy. Since the thermal diffusivity increases with increasing temperature below 1225 K and shows slight decrease or constancy at higher temperature. For 25Cr:6Ni stainless steel, the thermal diffusivity is nearly constant up to about 700 K. Beyond that, there is an increase with temperature both during heating as well as cooling cycle. On the other hand, the slope of the curve increases above 950 K, which can be due to the increase of bcc phase in the structure. 0.7% carbon steel shows a decrease in the thermal diffusivity at temperature below Curie point, where the structure contains bcc+ fcc phases. Above this point the thermal diffusivity increases, where the structure contains only fcc phase. The experimental thermal conductivity values of these alloys show good agreement with the calculated values using Mills model. Thermal diffusivity measurements as a function of temperature of sintered AISI 304 stainless steel-alumina composites having various composition, viz, 0.001, 0.01, 0.1, 1, 2, 3, 5, 7, 8 and 10 wt% Al2O3 were carried out in the present work. The thermal diffusivity as well as the thermal conductivity were found to increase with temperature for all composite specimens. The thermal diffusivity/conductivity decreases with increasing weight fraction of alumina in the composites. The experimental results are in good agreement with simple rule of mixture, Eucken equation and developed Ohm´s law model at weight fraction of alumina below 5 wt%. Beyond this, the thermal diffusivity/ conductivity exhibits a high discrepancy probably due to the agglomeration of alumina particles during cold pressing and sintering. On the other hand, thermal diffusivities of industrial mould flux having glassy and crystalline states decrease with increasing temperature at lower temperature and are constant at higher temperature except for one glassy sample. The thermal diffusivity is increased with increasing crystallisation degree of mould flux, which is expected from theoretical considerations. Analogously, the thermal diffusivity measurements of mould flux do not show any significant change with temperature in liquid state. It is likely to be due to the silicate network being largely broken down. In the case of coke, the sample taken from deeper level of the pilot blast furnace is found to have larger thermal diffusivity. This can be correlated to the average crystallite size along the structural c-axis, Lc, which is indicative of the higher degree of graphitisation. This was also confirmed by XRD measurements of the different coke samples. The degree of graphitisation was found to increase with increasing temperature. Further, XRD and heat capacity measurements of coke samples taken from different levels in the shaft of the pilot blast furnace show that the graphitisation of coke was instantaneous between 973 and 1473 K. / QC 20100629

Today, there is a high demand on clean steel for high performance materialproperties. Thus, steel producers try to deliver a steel product with the highestquality and cleanliness to the market. The number of parameters that affect thesteel cleanliness may vary depending on the required material properties of thefinal product. However, the non-metallic inclusion characteristics represent one ofthe most important parameters. More specifically, the composition, size, numberand morphology affect steel cleanliness. In this work, selected parameters affectingthe inclusion characteristics were studied using the following methods: i)thermodynamic calculations (including computational thermodynamiccalculations), ii) inclusion determinations using a cross sectional (CS) method (2Dinvestigations) and iii) inclusion determinations using an electrolytic extraction(EE) method (3D investigations). The computational thermodynamic calculations of the slag-steel and inclusion-steelequilibriums were carried out using the Thermo-Calc software. With the help ofthese calculations, the influence of the slag carryover on the top slag, aluminumcontent in steel and sulfur distribution ratio as well as predictions of stable phasesof inclusions were studied. In addition, inclusion determinations of tool steel gradesamples collected during various stages of the ladle treatment in a scrap-based steelplant were carried out using both 2D and 3D methods. Furthermore, inclusiondeterminations of bearing steel grade samples from a runner system after ingotcasting were performed using a 2D metallographic method (CS-method). Also, theINCAFeature software was used, when using cross sectional method, in order tocollect more statistics of the inclusion characteristics. It was found that slag carryover has a large influence on the composition of theactual top slag as well as the aluminum content in the steel as well as the sulfurdistribution ratio. In addition, steel and slag were found to be in “near”-equilibriumconditions, after the completion of the vacuum degassing operation. Furthermore,the composition of small-size inclusions in samples taken from tool steel was foundto be very scattered. Moreover, the composition of the large-size inclusions wasfound to be less scattered. Furthermore, closer to the top slag composition insamples collected after vacuum degassing. Finally, the accuracy of the inclusioncomposition determinations of tool steel samples using the electrolytic extractionmethod was found to be better than for the cross sectional method. The worseaccuracy of the CS-method is due to a considerable effect of matrix elements oninclusion composition. / QC 20100709

In order to meet the need of metallurgical industry in the world, a new MgAlON-BN composite which can be used for example in special refractory nozzles, tubes and break rings for the continuous casting of steel was studied in the present thesis. The aim was to understand the mechanism of synthesis and their physicochemical properties during the application. Thus, the thermodynamic properties, synthesis process, mechanical properties, thermal shock behaviour, thermal diffusivity/conductivity as well as corrosion resistance to molten iron containing oxygen and molten slag of MgAlON and MgAlON-BN composites have been investigated. The Gibbs energy of formation of MgAlON was estimated using the method proposed by Kaufman. The phase stability diagram of Mg-Al-O-N-B was investigated, and consequently the synthesis parameters were determined. MgAlON and MgAlON-BN composites were fabricated by hot-pressing method. The composites obtained this way were characterized by XRD, SEM, TEM and HREM analyses. A Matrix-flushing method was employed in the quantitative XRD analysis for the multi-component samples to understand the mechanism of synthesis. The relationship between mechanical properties and microstructure of the composites was investigated. The experimental results indicated that BN addition has significant influence on the mechanical properties of the composites. These can be explained by the fact that BN has low Young’s modulus, density and non-reactive nature as well as considerable anisotropy of many properties such as thermal expansion, thermal diffusivity/conductivity. Thus, the addition of BN in MgAlON is likely to lead to the presence of microcracks caused by the mismatch of thermal expansion coefficient. The microcracks result in the enhancement of the strength at elevated temperature and thermal shock durability of the composites. Effective thermal conductivities were evaluated from the present experimental results of thermal diffusivities, heat capacity and density. A model suitable for present composites has been derived based on Luo’s model. The predicted lines calculated by the model were in good agreement with experimental results. The reactions between the composites and molten iron as well as the slag were investigated by ‘‘finger’’ experiments and sessile drop experiments. Both experimental results indicated that the BN addition has positive influence on the corrosion resistance. These are attributed to the excellent corrosion resistance of BN to molten iron and slag, such as the higher contact angle between BN substrate and liquid iron and molten slag compared with that obtained for pure MgAlON. / QC 20100929

An experimental investigation of the binary system Co-Cr and the ternary system C-Co-Cr has been carried out in the present thesis. The experimental strategy adopted for the binary system was to measure the thermodynamic activities of Cr, the molar heat capacity as function of time, the phase transformation temperatures with corresponding enthalpies, the Curie transition temperature as well as melting temperatures with corresponding enthalpies. In the ternary system the strategy was to determine the solubility of Co in the Cr7C3 phase as well as the C and Cr contents in the Co rich (fcc) binder phase. The experimental results were compared with atomistic simulations of the solubility of Co in the Cr7C3 phase. Solid state galvanic cell measurements were conducted with both ZrO2-7.5 mol % CaO and CaF2 as the solid electrolyte. In view of possible errors in the measurements with ZrO2-7.5 mol % CaO, as a result of electronic contributions to the conduction of the solid electrolyte, new measurements were conducted with CaF2 as the solid electrolyte. The results indicated that the measured EMF values showed trends which were contrary to the thermodynamic behaviour expected from phase diagram considerations. It was concluded that further detailed experimentation was necessary in order to throw more light on the thermodynamic behaviour of the Co-Cr system. Two different series of DSC measurements were conducted, i.e. one in an atmosphere of pure hydrogen and another in pure argon. In the first investigation, conducted in an atmosphere of pure hydrogen in the temperature interval 318-1660 K, evidence was obtained for the existence of a phase transformation around 900 K in the compositional range 20.7-67.1 wt.% Cr. No indications of such a phase transformation had earlier been seen. In the second investigation, conducted in an atmosphere of pure argon in the temperature interval 298-1823 K, special attention was given to alloys in the Co rich corner of the phase diagram, i.e. 0-10 wt.% Cr. This investigation verified earlier findings of a phase transformations around 900 K in the compositional range 20.7-67.4 wt.% Cr. The magnetic transition temperatures for alloys low in Cr content were also obtained. With the use of the DTA technique the melting temperatures with corresponding enthalpy values for alloys in the compositional range 0.9-7.7 wt.% Cr were obtained. The three-phase triangle fcc+Cr7C3+graphite was investigated at 1373 K, 1423 K and 1473 K. The obtained results showed that the solubility of cobalt in the Cr7C3 phase was significantly higher than previously predicted by thermodynamic calculations. / QC 20100930

The objective of this research work was to develop a methodology for experimentally estimating the interfacial properties at slag-metal interfaces. From previous experiments carried out in the division, it was decided to use surface active elements like sulfur or oxygen to trace any motion at the interface. For this purpose the following experimental investigations were carried out. Firstly the density of slag was estimated using the Archimedes Principle and the Sessile Drop technique. The density of the slag would give the molten slag height required for the surface active element to travel before reaching the slag-metal interface. Diffusivity measurements were uniquely designed in order to estimate the sulfur diffusion through slag media. It was for the first time that the chemical diffusivity was estimated from the concentration in the metal phase. Experiments carried out validated the models developed earlier. The density and diffusivity value of sulfur in the slag was used to accurately capture the time for sulfur to reach the slag-metal interface. The oscillations were identified by calculating the contact angle variations and the interfacial velocity was estimated from the change in the surface area of the liquid iron drop. The interfacial tension was estimated from the contact angles and the interfacial dilatational modulus was calculated. Based on cold model experiments using water as well as mercury, an equation of the dependence of the interfacial shear viscosity on the interfacial velocity and interfacial tension was established. This paved way for the estimation of the interfacial shear viscosity at the slag-metal interface. The present study is expected to have a strong impact on refining reactions in pyometallurgical industries where slag/metal interfaces play an important role. From a fundamental view point, this provides a deeper insight into interfacial phenomena and presents an experimental technique to quantify the same. / QC 20101130

<p>The present dissertation describes part of the efforts directed towards the development of computational tools to support process modeling. This work is also a further development of the Thermoslag software developed in the Division of Materials Process Science, KTH.</p><p>The essential parts of the thesis are</p><p>a) development of a semi-empirical model for the estimation of the molar volumes/densities of multicomponent slags with a view to incorporate the same in the model for viscosities and</p><p>b) further development of the viscosity model for application towards fluorid- containing slags, as for example, mould flux slags.</p><p>The model for the estimation of molar volume is based on a correlation between the relative integral molar volume of a slag system and the relative integral molar enthalpies of mixing of the same system. The integral molar enthalpies of the relevant systems could be evaluated from the Gibbs energy data available in the Thermoslag software. The binary parameters were evaluated from experimental measurements of the molar volumes. Satisfactory correlations were obtained in the case of the binary silicate and aluminate systems. The model was extended to ternary and multi component systems by computing the molar volumes using the binary parameters. The model predictions showed agreements with the molar volume data available in literature. The model was used to estimate the molar volumes of industrial slags as well as to trace the trends in molar volume due to compositional variations. The advantage of the present approach is that it would enable prediction of molar volumes of slags that are compatible with the thermodynamic data available.</p><p>With a view to extend the existing model for viscosities to F--containing slags, the viscosities of mould flux slags for continues casting in steel production have been investigated in the present work. The measurements were carried out utilizing the rotating cylinder method. Seven mould fluxes used in the Swedish steel industry and the impact of Al₂O₃pick up by mould flux slags on viscosities were included in the study. The results showed that even relatively small additions of Al₂O₃ are related with a significant increase in viscosity</p>

<p>The fluid flow in the mold during up-hill teeming is of great importance for the quality of the cast ingot and therefore the quality of the final steel products. At the early stage of the filling of an up-hill teeming mold, liquid steel enters, with high velocity, from the runner into the mold and the turbulence on the meniscus could lead to entrainment of mold flux. The entrained mold flux might subsequently end up as defects in the final product. It is therefore very important to get a mild and stable inlet flow in the entrance region of the mold. It has been acknowledged recently that swirling motion induced using a helix shaped swirl blade, in the submerged entry nozzle is remarkably effective to control the fluid flow pattern in both the slab and billet type continuous casting molds. This result in increased productivity and quality of the produced steel. Due to the result with continuous casting there is reason to investigate the swirling effect for up-hill teeming, a casting method with similar problem with turbulence.</p><p>With this thesis we will study the effect of swirling flow generated through a swirl blade inserted into the entry nozzle, as a new method of reducing the deformation of the rising surface and the unevenness of the flow during filling of the up-hill teeming mold. The swirling blade has two features: (1) to generate a swirling flow in the entrance nozzle and (2) to suppress the uneven flow, generated/developed after flowing through the elbow. The effect of the use of a helix shaped swirl blade was studied using both numerical calculations and physical modelling. Water modelling was used to assert the effect of the swirling blade on rectifying of tangential and axial velocities in the filling tube for the up-hill teeming and also to verify the results from the numerical calculations. The effect of swirl in combination with diverged nozzle was also investigated in a similar way, i. e. with water model trials and numerical calculations.</p>

<p>Fatigue and ductility properties in various tool steels, produced by powder metallurgy, spray forming or conventionally ingot casting, have been analysed experimentally and successfully compared to developed models. The models are able to predict the fatigue limit and cause for fatigue fracture, and strain- and stress-development until fracture during the ductile fracture process respectively. Total fracture in a tool steel component, both in fatigue and ductility testing, is caused by a propagating crack initiated by particles, i.e. carbides or non-metallic inclusions. The models are based on experimentally observed size distributions.</p><p>The axial fatigue strength at two million cycles was determined for various tool steels. The fracture surface of each test bar broken was examined in SEM to determine the cause for fatigue failure, i.e. a single carbide or inclusion particle or a cluster of carbides, and the size of the particle. The particles act as stress concentrators where a crack is easily initiated when the material is subjected to alternating stresses. The developed models calculate the probability that at least one particle will be present in the material which is larger than the threshold level for crack initiation at a certain stress range.</p><p>The ductility testing was performed on various tool steels by four-point bending under static load. The load and displacement until total fracture were recorded and the maximum strain and stress acting in the material were calculated. The fracture surface of each broken test bar was examined in SEM, though the crack initiating area appears different compared to a fatigue failure. Ductile fracture is caused by a crack emanating from voids nucleated around many particles in a joint process and then linked together. By finite element modelling of void initiation and propagation in 2D of an experimentally observed carbide microstructure for each tool steel, successful comparisons with experiments were performed. Carbides were modelled as cracked when larger than a certain size, based on fracture surface observations, and the matrix cracked above a pre-defined plastic deformation level. The stresses and strains at total failure were in good agreement between model and experiments when evaluated.</p><p>The use of these developed models could be a powerful tool for optimisation of fatigue and ductility properties for tool steels. With good fatigue and ductility properties normal failures appearing during operation of a tool steel product could be minimised. By theoretical tests in the developed models of various carbide microstructures the optimum mechanical properties could be achieved with a minimum of experiments performed.</p>

<p>In the present work, the thermodynamic activities of chromium and vanadium oxide in CaO-SiO2-MgO-Al2O3 slags were measured using gas-slag equilibration technique. The slag was equilibrated with a gas mixture of CO, CO2 and Ar gases enabling well-defined oxygen partial pressures in the gas mixture (PO2=10-3,10-4,10-5 Pa) at temperatures 1803, 1823K, 1873, 1923 K. The slags were kept in Pt crucibles during the equilibration and the duration of which was 20 h. From a knowledge of the thermodynamic activity of chromium and vanadium in Cr or V in Pt alloy, obtained from literature, and the oxygen partial pressure in the gas stream calculated by Thermo Calc software, the thermodynamic activity of chromium, vanadium oxide in the slags could be observed.An assessment of the experimental studies in earlier works reveal that, the activities of chromium at low chromium contents and vanadium in their respective alloys in platinum exhibits a strong negative deviation from ideality, the logarithms of activity coefficient of these elements were found to increase with increasing mole fractions of these metals in the Pt-alloys.Regarding the slag phase, all the chromium in the slags was assumed to be present in the divalent state in view of the low Cr contents and the low oxygen potentials employed in the present studies. Analogously, vanadium in the slag was assumed to be in the trivalent state in view of the low vanadium contents in the slag and the low oxygen partial pressure in the gas phase. Activity of chromium oxide, CrO decreases with increasing temperature and decreasing content of chromium oxide in slag and oxygen partial pressure in the gas phase. Activity of vanadium oxide, VO1.5 in slag phase shows a negative deviation from ideality. Activity coefficient of vanadium oxide shows a decrease with basicity of slag and the “break point” occurs at about slag basicity of 1 under the oxygen partial pressure of 10-3 Pa and temperature of 1873 K.A relationship for estimating the actual content of chromium, vanadium in slag as a function of activities of chromium or vanadium, temperature, oxygen partial pressure and slag basicity were developed from the present results, the agreement between the estimated and experimental values is satisfactory, especially at lower oxygen partial pressure.</p>