Secondary hardening ultra-high strength (SHUHS) steels possess a unique combination of strength, fracture toughness and stress corrosion cracking resistance, which makes them candidate materials for aircraft landing gear and armour applications. There is a sustained drive to develop stronger and tougher materials for such applications. The objectives of this thesis are two-fold: first, to develop a new SHUHS alloy that is stronger than the existing SHUHS steel developed at Defence Metallurgical Research Laboratory (DMRL), Hyderabad and second, to establish processing-structure-property correlations for the new alloy. Empirical design and development of these complex steels involves enormous effort, cost, time and materials resources. To avoid this, a semi-empirical approach was espoused in this thesis wherein thermodynamic calculations using ThermoCalc were conducted to computationally design a series of alloys with varying levels of Cr and Mo. The design space was constrained by two objectives related to M2C carbides which are the primary cause of secondary hardening in these alloys. The first objective was to increase the amount of M2C to increase the peak strength, while the second objective was to lower the Cr/Mo ratio of the M2C to control its over-ageing behavior. Two new alloys C23 (with 2Cr-3Mo, wt. %) and C55 (with 5Cr-5Mo, wt. %) and a base alloy akin to the DMRL SHUHS steel, C21 were selected for experimental validation. These alloys were melted, rolled and subjected to a battery of heat treatments. Austenitization studies revealed that the new alloys required higher austenitization temperatures to dissolve primary carbides. However such a treatment also resulted in an austenite composition that was not conducive for obtaining a fully martensitic microstructure on quenching. Based on these studies, the design space was modified to include additional criteria related to the Ms and precipitate dissolution temperatures. C55 failed to clear either criteria, while C23 cleared both, and so tempering studies were limited to C23. Isochronal tempering studies revealed that C23 in the peak aged condition was >10% stronger than C21 indicating that the alloy design objective of strength enhancement was achieved successfully. Microstructural characterization revealed that the strength enhancement was due to the higher number density and volume fraction of the M2C-like solute clusters in C23, which resist shearing in the under-aged condition and strengthen by Orowan mechanism in the over-aged condition. This thesis has successfully demonstrated that the design paradigm of enhancing strength by increasing the amount of M2C is justified and that ThermoCalc can be used to as an objective-oriented alloy design tool in this class of the steels.

Paper and pulp industry and steel industry are two major industries in Sweden, both of which are facing big challenges to treat their waste products properly. In this thesis work, initial evaluation of mechanical properties of briquettes made of waste products was performed. Three different CaO-containing waste products (Mesa, Kalk, Fly Ash) from Stora Enso and SCA were pressed with one kind of binding material (AOD slag) from Outokumpu. Drop tests were carried out to test the impact strength of the lab-made briquettes. Three different parameters were investigated of their influence on the impact strength of the briquettes: 1) Composition of briquettes 2) Heat treatment procedure 3) Exposure time to open air. A total of 97 briquettes were pressed. Drop test results show that for different material based briquettes, heat-treatment and exposure to open air had different influence on the final impact strength. In order to get best impact strength, MB briquettes (90% Mesa +10% AOD slag) heat treated at 850℃, KB briquettes (90% Kalk +10% AOD slag) heat treated at 850℃ and FC briquettes (80% Fly Ash + 20% AOD slag) exposed to open air for 20 days are recommended. Melting experiment was carried out to investigate the sulphur removal ability of the briquettes in metallurgical processes. Thermodynamic calculation of sulphide capacity was done. / Pappers-, massa och stålindustrin är två stora industrier i Sverige, vilka båda står inför stora utmaningar för att hantera sina avfallsprodukter på rätt sätt. I denna avhandling utfördes en första utvärdering av mekaniska egenskaper hos briketter av avfallsprodukter. Tre olika CaO- innehållande avfallsprodukter (Mesa, Kalk, Fly Ash) från Stora Enso och SCA pressades med ett   bindande   material   (AOD   slagg)   från   Outokumpu.   Dropptest   utfördes   för   att   testa slaghållfastheten hos de laboratoriegjorda briketterna. Tre  olika  parametrar  undersöktes  av  deras  påverkan  på  briketternas  slaghållfasthet:  1) Brikets sammansättning 2) Värmebehandlingsförfarande 3) Exponeringstid för friluft. Totalt 97 briketter pressades. Dropptestresultat visar att för olika materialbaserade briketter hade värmebehandling   och   exponering   för   utomhusluft   ett   annat   inflytande   på   den   slutliga slagstyrkan.  För  att  få  bästa  slaghållfasthet,  värmebehandlades  MB-briketter  (90%  Mesa  + 10% AOD-slagg) värmebehandlad vid 850 ° C, KB-briketter (90% Kalk + 10% AOD-slagg) vid 850  °  C  och  FC-briketter  (80%  Fly  Ask  +  20%  AOD  slagg)  utsatt  för  öppen  luft  i  20  dagar rekommenderas. Smältningsexperiment utfördes för att undersöka svavelfjernningsförmågan hos briketterna imetallurgiska processer. Termodynamisk beräkning av sulfidkapacitet gjordes.

In the modern practice, a sustainable development strategy in a domain of wasteutilization is shifting its focus from a general completeness of recycling to a morespecific attention to efficiently utilize elements in the wastes. This is well-illustrated bythe steelmaking slag industries. The major waste product from the steelmaking practiceis slag and its main constituents are: CaO, SiO2, Al2O3, MnO, FeO and so on. The mainfield of application for the steelmaking slags is civil engineering, especially for road andwaterway construction. However, a significant amount of the slag remains in the dumps,damaging the environment as well as requiring a land for secure storage. Efficientrecycling of these materials is of increasing interest worldwide as a result of increasingsustainability in processes with respect to increasing raw material costs and wastereduction.In order to find a practical solution, joint efforts are currently made at the RoyalInstitute of Technology, Sweden and National Metallurgical Academy of Ukraine. Theconcept is based on transformation of non-magnetic wüstite (FeO) to magneticmagnetite (Fe3O4) using an oxidizing atmosphere was proposed.In order to verify the feasibility of the proposed way of slag utilization, experiments onthe ternary CaO-FeO-SiO2 and quaternary CaO-FeO-SiO2-MnO slags systems,accompanied by thermodynamic and kinetic modelling, were performed. The crystalprecipitation during synthetic slag oxidation was observed by Confocal Scanning LaserMicroscopy (CSLM). Precipitated phases were found to be magnetite and manganeseferrite in the spinel form.Obtained magnetite and manganese ferrite can be separated from the slag by magneticseparation.The formation of nanosize manganese ferrite from the CaO-FeO-SiO2-MnO slag systemduring oxidation was investigated. Experiments were conducted in a horizontalresistance furnace in an oxidizing atmosphere (air). The final product was analysed by Xraydiffraction (XRD). The particles size of the manganese ferrite was estimated by theScherrer formula and was found to be of the order of 23-25 nm. In order to get anunderstanding of the magnetic properties of the manganese ferrite recovered from slagtreatment, it was necessary to synthesize a reference compound from pure precursors.The MnFe2O4 nanopowder was synthesized by the oxalate route. The size effects on themagnetic properties of manganese ferrite particles were investigated.IIThe potential way of the magnetite particles separation from liquid slags was investigatedby cold model studies. The experimental technique of mobilising non-conducting,nonmagnetic particles in conducting liquid in crossed electric and magnetic fields wasinvestigated in order to find the way of the particle separation from the liquidsteelmaking slags. The effects of the current density, magnetic field, size and shape ofthe particle on the particle velocity under action of the electromagnetic buoyancy force(EBF) in the electrolyte were analyzed. / QC 20100916

This thesis deals with peritectic reactions and transformations that occur during the solidification of many alloys. Peritectics are believed to be a major cause of crack-formation in many steels, thus, good knowledge of the mechanisms by which these phenomena occur is essential for preventing such defects. The thesis also handles the behaviour of metals, in particular cast structures, during hot forming. Grain size and microstructure are of most importance in determining the strength, toughness and performance of a steel. For achieving enhanced mechanical and microstructural properties, good understanding of the phenomena occurring during hot forming is required. Peritectic reactions and transformations were studied in Fe-base and steel alloys through differential thermal analysis (DTA) experiments and micrographic investigation of quenched DTA samples. The effect of the ferrite/austenite interface strain during the peritectic reaction on equilibrium conditions was thermodynamically analysed, and the results were related to temperature observations from DTA experiments conducted on Fe-base alloys and low-alloy steels. Massive transformations from ferrite to austenite were observed in the micrographs of a number of quenched low-alloy steel samples and it was proposed that these transformations are uncontrolled by diffusion, and occur in the solid state as a visco-plastic stress relief process. DTA study of an austenitic stainless steel indicated that the alloy can exhibit primary precipitations to either ferrite or austenite. A continuously-cast breakout shell of the steel was analyzed and it was suggested that the observed irregularities in growth were due to alternating precipitations of ferrite and austenite; parts of the shell with higher ratios of primary-precipitated ferrite shrink in volume at the peritectic temperature and experience reduced growths. An experimental method for studying the behaviour of metals during hot forming developed, and hot compression tests were conducted on cast copper and ball-bearing steel samples. Flow stress curves were obtained at varying temperatures and strain rates, and the results showed good agreement with earlier observations reported in literature. Micrographic analysis of quenched samples revealed variations in grain size and a model was fitted to describe the grain size as a function of deformation temperature and strain. Solidification growth during continuous casting of stainless steel and copper was numerically modelled. A varying heat transfer coefficient was proposed to approximate the experimentally measured growth irregularities in the continuously-cast stainless steel breakout shell. Solidification growth of pure copper was also modelled in the Southwire continuous casting process. Temperature measurements from the chill mould were used to approximate the temperature gradient and the heat extraction from the solidifying strand, and the results were used in a two-dimensional model of solidification. / QC 20100803

The present work was initiated to investigate the surface- and interfacial phenomena for iron and slag/iron systems. The aim was to understand the mechanism of the effect of surface active elements on surface and interfacial properties. In the present work, the adsorption of oxygen and sulfur on iron surface as well as adatom surface movements were studied based on the ab initio method. BCC iron melting phenomena and sulfur diffusion in molten iron were investigated by Monte Carlo simulations. The impact of oxygen potential on interfacial mass transfer was carried out by X-ray sessile drop method. Firstly, the structural, electronic and magnetic properties as well as thermodynamic stability were studied by Density functional theory (DFT). The hollow site was found to be the most stable adsorption site both for oxygen and sulfur adsorbed on iron (100) surface, which is in agreement with the experiment. The relaxation geometries and difference charge density of the different adsorption systems were calculated to analyze the interaction and bonding properties between Fe and O/S. It can be found that the charge redistribution was related to the geometry relaxation. In addition, the sulfur coverage is considered from a quarter of one monolayer (1ML) to a full monolayer. It was found that the work function and its change Δφ increased with S coverage, in very good agreement with experiment. Due to a recent discussion regarding the influence of charge transfer on Δφ, it is shown in the present work that the increase in Δφ can be explained by the increasing surface dipole moment as a function of S coverage. S strongly interacts with the surface Fe layer and decreases the surface magnetic moment as the S coverage increases. Secondly, a two dimensional (2D) gas model based on density functional calculations combined with thermodynamics and statistical physics, was proposed to simulate the movement of the surface active elements, viz. oxygen and sulfur atoms on the Fe(100) surface. The average velocity of oxygen and sulfur atoms was found to be related to the vibration frequencies and energy barrier in the final expression developed. The calculated results were based on the density function and thermodynamics & statistical physics theories. In addition, this 2D gas model can be used to simulate and give an atomic view of the complex interfacial phenomena in the steelmaking refining process. A distance dependent atomistic Monte Carlo model was developed for studying the iron melting phenomenon as well as effect of sulfur on molten iron surface. The effect of boundary conditions on the melting process of an ensemble of bcc iron atoms has been investigated using a Lennard-Jones distance dependent pair potential. The stability of melting process was energetically and spatially analyzed under fixed wall and free surface conditions and the effects of short and long-range interactions were discussed. The role of boundary conditions was significantly reduced when long-range interactions were used in the simulation. This model was further developed for investigating the effect of sulfur on molten iron surface. A combination of fixed wall and free surface boundary condition was found to well-represent the molten bath configuration while considering the second nearest neighbor interactions. Calculations concerning the diffusion of sulfur on molten surface were carried out as a function of temperature and sulfur concentration. Our results show that sulfur atoms tended to diffuse away from the surface into the liquid bulk and the diffusion rate increased by increasing temperature. Finally, impact of oxygen potential on sulfur mass transfer at slag/metal interface, was carried out by X-ray sessile drop method. The movement of sulfur at the slag/metal interface was monitored in dynamic mode at temperature 1873 K under non-equilibrium conditions. The experiments were carried out with pure iron and CaO-SiO2-Al2O3-FeO slag (alumina saturated at the experimental temperature) contained in alumina crucibles with well-controlled partial pressures of oxygen and sulfur. As the partial pressure of oxygen increased, it was found that interfacial velocity as well as the oscillation amplitude increased. The thermo-physical and thermo-chemical properties of slag were also found to influence interfacial velocity. / QC 20101123

With the progress of high alloy steelmaking processes, it is essential to minimize the loss of valuable metals, like chromium and vanadium during the decarburization process, from both economic as well as environmental view points. One unique technique to realize this aim, used in the present work, is the decarburization of high alloy steel grades using oxygen with CO2 in order to reduce the partial pressure of oxygen. In the present work, the investigation on the oxidation of iron-chromium and iron-vanadium molten alloys under CO2-O2 mixtures was carried out and presented in this dissertation. For oxidation study on Fe-Cr molten alloy with CO2-O2 mixtures, on the basis of thermodynamic analysis, energy balance calculation and modeling results, experimental validation in laboratory was carried out, and later on, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts under controlled partial pressure of oxygen was investigated. Thermodynamics calculation and energy balance estimation demonstrated that, it is possible to use CO2 or CO2-O2 mixtures as decarburizers during EAF process and high initial carbon contents in the steel can be adopted at the beginning in order to reduce the cost. A generic model has been developed to describe the overall process kinetics prevailing in metallurgical reactors containing liquid metal and gas bubbles. This model is general and can be extended further to consider any gas liquid reactions in any chemical engineering reactor, and especially the metallurgical ones, like AOD. In the present dissertation, the model is applied in predicting the evolution of Cr and C contents in a Fe-C-Cr melt during injection of different O2-CO2 mixtures. The related simulation results illustrated that CO2 is efficient in Cr retention. In order to verify the modeling results, 1kg induction furnace experiments were carried out in the present laboratory. The results indicated that the predictions of the model are in good agreement with the experimental results. Meanwhile, the experimental results indicated that the Cr-losses can be significantly lowered by replacing the oxygen with CO2 in the injected gas, specifically for Fe-Cr-C melts with carbon levels higher than about 0.8 mass%. Subsequently, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts was investigated under different CO2-O2 mixtures. It is indicated that, the oxidation rate is controlled by the chemical reaction at the initial stage and the reaction rate can be expressed as  at the Cr range of 11-21 mass% in the Fe-Cr melt. For oxidation study on Fe-V liquid alloy, the investigation of the oxidation kinetics was carried out under CO2-O2 mixtures, which is followed by the study on thermodynamic properties of vanadium containing slags. During oxidation of Fe-V melt, in the case of alloys with vanadium contents exceeding 10 mass%, there exists an incubation period before the chemical reactions prevail the process. In addition, the ‘incubation time’ increased with the increase of temperature and the vanadium content, whereas it decreased with the increase of oxygen partial pressure in the oxidant gas. High-temperature mass spectrometric method was used to determine the activity of the vanadium oxide in CaO-MgO-Al2O3-SiO2-V2O3 slags, whereas, the oxidation states of vanadium in the CaO-MgO-Al2O3-SiO2-VOxslag system was studied by XANES method. The results indicated that, higher basicities stabilize higher vanadium oxidation state, whereas, higher temperature stabilizes lower vanadium oxidation state. The present work, which was carried out within the ECO-STEELMAKING project funded by MISTRA via Jernkontoret is expected to lead to implementation of some modifications in high alloy steel production based on fundamental concepts towards more environment-friendly steel processing. / <p>QC20100628</p>

Duplex stainless steels can be very attractive alternatives to austenitic grades due to their almost double strength at equal pitting corrosion resistance. When welding, the duplex alloys normally require addition of filler metal, while the commodity austenitic grades can often be welded autogenously. Over-alloyed consumables are used to counteract segregation of important alloying elements and to balance the two phases, ferrite and austenite, in the duplex weld metal. This work focuses on the weldability of the recently-developed lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101). The pitting corrosion resistance of this grade is better than that of austenitic AISI 304 (EN 1.4307) and can reach the level of AISI 316L (EN 1.4404). The austenite formation is rapid in LDX 2101 compared to older duplex grades. Pitting resistance tests performed show that 1-2.5 mm thick laser and gas tungsten arc (GTA) welded LDX 2101 can have good corrosion properties even when welding autogenously. Additions of filler metal, nitrogen in the shielding gas, nitrogen-based backing gas and use of laser hybrid welding methods, however, increase the austenite formation. The pitting resistance may also be increased by suppressing formation of chromium nitrides in the weld metal and heat affected zone (HAZ). After thorough post-weld cleaning (pickling), pitting primarily occurred 1-3 mm from the fusion line, in the parent metal rather than in the HAZ. Neither the chromium nitride precipitates found in the HAZ, nor the element depletion along the fusion line that was revealed by electron probe microanalysis (EPMA) were found to locally decrease the pitting resistance. The preferential pitting location is suggested to be controlled by the residual weld oxide composition that varies over the surface. The composition and thickness of weld oxide formed on LDX 2101 and 2304 (EN 1.4362, UNS S32304) were determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean duplex grades proved to contain significantly more manganese than what has been reported for standard austenitic stainless steels in the AISI 300 series. A new approach to heat tint formation is presented; whereby evaporation of material from the weld metal and subsequent deposition on the already-formed weld oxide are suggested to contribute to weld oxide formation. This is consistent with manganese loss from the weld metal, and nitrogen additions to the GTA shielding gas enhance the evaporation. The segregation of all elements apart from nitrogen is low in autogenously welded LDX 2101. This means that filler wire additions may not be required as for other duplex grades assuming that there is no large nitrogen loss that could cause excessive ferrite contents. As the nitrogen appears to be controlling the austenite formation, it becomes essential to avoid losing nitrogen during welding by choosing nitrogen-containing shielding and backing gas. / QC 20101213