In order to obtain a good performance and predict the properties of alloys, it is necessary to control the contents of alloying elements and to evaluate a largest inclusion in the product. Thus, improved techniques for both control of alloy elements and evaluation of the large inclusion in products will enable us to provide better qualities of the final products. In the case of one Ni alloy, (NW2201, >99 mass%Ni), the precise control technique of Mg content is important to obtain a good hot-workability. Hereby, the slag/metal reaction experiments in a laboratory have been carried out at 1873 K, so that the equilibrium Mg content and kinetic behavior can be understood. More addition of Al in the melt as well as higher CaO/Al2O3 value of slag resulted in higher amount of Mg content in Ni. For the same conditions of Al content and slag composition, the mass transfer coefficient of Mg in molten Ni was determined as 0.0175 cm/s. By applying several countermeasures regarding the equilibrium and kinetic process to the plant trials, the value of the standard deviation for the Mg content in an alloy was decreased till 0.003 from 0.007 mass%. The size measurements of largest inclusions in the various alloys (an Fe-10mass%Ni alloy, 17CrMo4 of low-C steel and 304 stainless steel) were carried out by using statistics of extreme values (SEV). In order to improve the prediction accuracy of this method, three dimensional (3D) observations were applied after electrolytic extraction. In addition, the relationship of extreme value distribution (EVD) in the different stages of the production processes was studied. This was done to predict the largest inclusion in the products at an early stage of the process. A comparison of EVDs for single Al2O3 inclusion particles obtained by 2D and 3D observations has clarified that 3D observations result in more accurate EVD because of the absence of pores. Also, it was found that EVD of clusters were larger than that of single particles. In addition, when applying SEV to sulfide inclusions with various morphologies, especially for elongated sulfides, the real maximum sizes of them were able to be measured by 3D observations. Geometrical considerations of these particles clarified the possibility of an appearance of the real maximum inclusion sizes on a cross section to be low. The EVDs of deoxidation products in 304 stainless steel showed good agreement between the molten steel and slab samples of the same heat. Furthermore, the EVD of fractured inclusion lengths in the rolled steel were estimated from the initial sizes of undeformed inclusions which were equivalent with fragmented inclusions. On the other hand, from the viewpoint of inclusion width, EVD obtained from perpendicular cross section of strips was found to be useful to predict the largest inclusion in the final product with less time consumption compared to a slab sample. In summary, it can be concluded that the improvement of the techniques by this study has enabled to precisely control of alloy compositions as well as to evaluate the largest inclusion size in them more accurately and at an earlier stage of the production process. / QC 20101222

The initial stage of liquid phase sintering, involving liquid penetration, agglomerate separation, particle spreading and growth has been investigated in experiments using tungsten heavy alloys. The particle composites used were produced by hot isostatic pressing (HIP) of pure powder mixtures of W-Ni-Fe-(Co). By using different HIP temperatures, volume fractions of tungsten, alloying elements like Cobalt and Sulphur or excluding Iron from the matrix, liquid penetration, agglomerate separation and particle growth conditions were affected. The investigations were performed mainly under microgravity (sounding rockets or parabolic trajectories by airplanes) but at high tungsten particle fractions, short sintering times or at infiltration of solid pure tungsten, they were performed at normal gravity. The liquid penetration of the tungsten agglomerates is explained by initial wetting under non-equilibrium conditions, due to the reaction between the liquid matrix and the particles, and a decrease of interfacial energy. The dissolving of tungsten gives a pressure drop in the penetrating liquid and a driving force for the liquid movement by a suggested parabolic penetration model. For cold worked tungsten, a penetration theory was proposed, where an internal stress release in the penetrated tungsten grains creates space for the advancing liquid. The spreading of the tungsten agglomerates is explained by an interagglomerate melt swelling due to a Kirkendall effect. The liquid matrix undergoes a volume increase since the diffusion rates of Ni-Fe are higher than for W and initial concentration gradients of W and Ni, Fe exists. The suggested model by Kirkendall are also used for an analysis of the interaction behaviour between solid particles and a solidification front and inclusion behaviour in iron base alloys during teeming and deoxidation. The average tungsten particles size decrease initially since part of the tungsten particles is dissolved when the non-equilibrium matrix phase is melting. When equilibrium is reached, the tungsten particles grow in accordance with the Ostwald ripening process by an approximately 1/3 power law. Larger particle fraction of particles showed a higher growth rate, due to shorter diffusion distances between the particles. Cobalt, Sulphur and absence of iron in the matrix were found to increase the growth rate of the tungsten particles due to a higher surface tension between the solid tungsten particles and the matrix melt. / QC 20100528

Two industrial studies and one set of lab scale trials have been done. In addition, a theoretical study has been done. The main focus has been on non metallic inclusion composition during the ladle refining operation in industrial steel production. Sampling has been done together with careful inclusion determination. The inclusion composition is related to different variables. In the industrial trials samples have been taken at different steps during the ladle refining period. Steel and slag composition as well as temperature and oxygen activity have been determined. The thesis is based on five supplements with different major objectives, all related to the inclusion composition. The equilibrium top slag-steel bulk and inclusions-steel bulk were investigated by comparison between calculated and measured oxygen activity values. The oxygen activity and relation to temperature has also been discussed as well as oxygen activity and temperature gradients. The effect of vacuum pressure on inclusion composition has been evaluated in a theoretical study as well as lab scale trials. The inclusion composition has been studied during the industrial ladle treatment process. The inclusion composition was related to top slag composition and other parameters during ladle treatment. The major findings in the thesis are the lack of equilibrium conditions with respect to top-slag and steel bulk before vacuum treatment. The inclusions have been found to be closer to equilibrium with the steel bulk. Al/Al2O3 equilibrium has been found to control the oxygen activity after Al-deoxidation. Evaluation of inclusion composition during the ladle refining has revealed that the majority of the inclusions showed a continuous composition change throughout the ladle refining process, from high Al2O3, via MgO-spinel to finally complex types rich in CaO and Al2O3. The final inclusion composition after vacuum treatment was found to be close to the top slag composition. Vacuum pressure has been found to have a theoretical effect on inclusion composition at very low pressures. / QC 20100712

The present thesis was to study non-metallic inclusions during vacuum degassing in ladle treatment. Emphasize was mostly given to liquid CaO-Al2O3 inclusions. A series of industrial experiments were carried out at Uddeholm Tooling AB, Hagfors, Sweden. To gain an insight into the industrial findings, laboratory investigations were also performed. Large number of steel samples were collected and examined. Liquid calcium aluminate inclusions with low SiO2 and high SiO2 were often found with spinel inclusions before vacuum degassing. Laboratory experiments showed that spinel would react with the dissolved Ca in the liquid steel forming calcium aluminate inclusions. This laboratory results agreed with the industrial observation that spinel phase was quite often found in the center of the calcium aluminate phase. After vacuum degassing, most of the inclusions were calcium aluminate liquid inclusions. When dissolved Al level was low, 2 types of liquid calcium aluminate inclusions with considerably different SiO2 contents were found to coexist even at the end of the process. In view of the lack of the thermodynamic data for SiO2 activities in the low silica region, thermodynamic measurements were conducted in the CaO-Al2O3-SiO2-MgO system. The experimental results could reasonably explain the coexistence of the two types of the liquid oxide inclusions. While the total number of inclusions decreased during vacuum degassing, the number of bigger inclusions (>11.3 μm) increased generally in used ladles. This finding was in accordance with the previous studies, wherein, ladle glaze was found to be responsible for the supply of bigger inclusions. The behaviors of several types of inclusions in liquid steel were examined using a laser scanning confocal microscope (LSCM). While alumina inclusions tended to impact on each other, agglomerate and grow very quickly, none of the other types of inclusions, such as spinel and calcium aluminate was observed to agglomerate. The results of LSCM study agreed well with the industrial observation. Examination on a huge number of inclusions did not show any indication of impact and physical growth of the inclusions, except the alumina inclusions. The removal of inclusions around open-eye in a gas-stirred ladle was experimentally studied by a cold model with oil and water. Most of the simulated inclusions were brought up to the oil phase by gas-water plume. Inclusion removal into oil layer took place when the inclusions passed through the sphere-bed of the oil layer around the open-eye. A calculation showed that the contribution of metal-gas plume in inclusion removal was much larger than that of buoyancy mechanism. The results of the industrial experiments revealed that the inclusions distribution strongly depended on stirring condition. When a ladle was stirred by both gas and induction, inclusion removal near slag layer was significant. / QC 20100803

The aim of this thesis work is to increase the knowledge of inclusion behavior at the steel-slag interface by mathematical modeling and in-situ Confocal Scanning Laser Microscope experiments. Mathematical models based on the equation of motion predicting liquid and solid inclusion behavior was first investigated. Four main forces, the buoyancy force, the added mass force, the rebound force and the drag force, act on the inclusion as it crosses the interface. There are three types of behavior an inclusion at the steel-slag interface can adopt. These are a) pass, which means that the inclusion is separated to the slag, b) remain, where the inclusion stays at the interface without being fully transferred to the slag or c) oscillate, and the inclusion rises and descends at the interface until the motion is dampened out by the interfacial forces. The studies showed the importance of accurate experimental physical property data. Application of the models to industrial conditions illustrated that useful plots could be made showing the industry how to optimize their interfacial properties in the ladle and tundish to obtain maximum inclusion separation. In-situ Confocal Scanning Laser Microscope (CSLM) experiments were carried out in order to study agglomeration of liquid and semi liquid inclusions at the steel-gas and steel-slag interfaces and in the slag. Liquid-liquid inclusion agglomeration at steel-gas and steel-slag interfaces was seen to not occur without using force. However, when already transferred to the slag the inclusions agglomerated freely due to a higher free energy force. Comparison of experimental and theoretical agglomeration force showed good agreement between experiments and theory. The main conclusion of this work is that inclusion separation is a complex field of study and there exist no model that takes everything into account. Here the tendency for inclusion transfer and how to manipulate the physical properties for inclusion separation together with agglomeration experiments have been studied. For the future maybe coupling of models for computational fluid dynamics, agglomeration, inclusion separation, dissolution and slag entrainment in addition with experimental physical property data can provide a better overview and understanding. / QC 20100823

The objective of this research is to increase the understanding of the solidification behaviour of some industrially important wrought aluminium alloys. The investigation methods range from direct investigations of as-cast ingots to laboratory-scale techniques in which ingot casting is simulated. The methods span from directional solidification at different cooling rates to more fundamental and controlled techniques such as DTA and DSC. The microstructure characteristics of the castings have been investigated by optical and Scanning Electron microscopy. Hardness tests were used to evaluate the mechanical properties. The effects of adding alloying elements to 3XXX and 6XXX aluminium alloys have been studied with special focus on the effects of Zn, Cu, Si and Ti. These elements influence the strength and corrosion properties, which are important for the performance of final components of these alloys. Solidification studies of 0-5wt% Zn additions to 3003 alloys showed that the most important effect on the microstructure was noticed at 2.5 wt% Zn, where the structure was fine, and the hardness had a maximum. Si addition to a level of about 2% gave a finer structure, having a relatively large fraction of eutectic structure, however, it also gave a long solidification interval. The addition of small amounts of Cu, 0.35 and 1.0 wt%, showed a beneficial effect on the hardness. Differences have been observed in the ingot surface microstructures of 6xxx billets with different Mg and Si ratios. Excess Si compositions showed a coarser grain structure and more precipitations with possible negative implications for surface defect formation during DC casting. The comparison of alloys of different Ti content showed that the addition of titanium to a level of about 0.15 wt% gave a coarser grain structure than alloys with a normal Ti content for grain refinement, i.e. < 0.02 wt%, although a better corrosion resistance can be obtained at higher Ti contents. The larger grain size results in crack sensitivity during DC casting. A macroscopic etching technique was developed, based on a NaOH solution, and used in inclusion assessment along DC cast billets. Good quantitative data with respect to the size and spatial distribution of inclusions were obtained. The results from studied billets reveal a decreasing number of inclusions going from bottom to top, and the presence of a ring-shaped distribution of a large number of small defects in the beginning of the casting. The present study shows how composition modifications, i.e. additions of certain amounts of alloying elements to the 3xxx and 6xxx Al alloys, significantly change the microstructures of the materials, its castability, and consequently its mechanical properties / QC 20100901

The present work was initiated to investigate the stability, structural and thermodynamic properties of transition metal carbides, nitrides and carbo-nitrides by atomistic simulations and experimentations. The interatomic pair potentials of Cr-Cr, Mn-Mn, Fe-Fe, C-C, Cr-C, Mn-C, Fe-C, Cr-Fe, Cr-N and Mn-N were inverted by the lattice inversion method and ab initio cohesive energies, and then employed to investigate the properties of Cr-, Mn- and Fe-carbides by atomistic simulations in this work. For the binary M7C3 carbide, the structural properties of M7C3 (M = Cr, Mn, Fe) were investigated by atomistic simulations. The results show that the stable structure for these compounds is hexagonal structure with P63mc space group. The cohesive energy of M7C3 calculated in this work indicates that the stability of carbides decreases with the increasing in metal atomic number. Further, the vibrational entropy of Cr7C3 was calculated at different temperatures and compared with the entropy obtained by experimentations. The comparison demonstrates that the main contribution to the entropy is made by the vibrational entropy. For the binary τ-carbides, the structural properties of Cr23C6 and Mn23C6, as well as the vibrational entropy of Cr23C6 were computed. Further, the site preference of ternary element Fe among 4a, 8c, 32f and 48h symmetry sites in Cr23-xFexC6 was studied. It has been seen that Fe atoms would firstly occupy 4a sites and then 8c sites. The lattice constant and stability of Cr23-xFexC6 were also computed with different Fe content. In order to understand the relative stability of the transition metal carbides and nitrides, the standard formation Gibbs energies of carbides and nitrides for Cr, Mn and Fe were compared. The order of carbon and nitrogen affinities for Cr, Mn and Fe was further clarified by the comparison of the interatomic pair potentials among Cr-C, Mn-C, Fe-C, Cr-N and Mn-N. It was found that Cr-N interaction was very strong in comparison with other binary interactions above and consequently, nitrogen addition would lead to a strong decrease in the thermodynamic activity of chromium in Cr-containing alloys. This was confirmed by the investigations of thermodynamic activities of Cr in the Fe-Cr-N and Fe-Cr-C-N alloys. The activities were measured in the temperature range 973-1173 K by solid-state galvanic cell method involving CaF2 solid electrolyte under the purified N2 gas. In addition, the analysis of nitrogen content and phase relationships in the Fe-Cr-N and Fe-Cr-C-N alloys equilibrated at 1173 K were carried out by inert-gas fusion thermal conductivity method, X-ray diffraction and scanning electron microscopy technique. The experimental results show that the solubility of nitrogen in the alloys decreases with the decreasing chromium content, as well as the increasing temperature. The addition of nitrogen to the alloys was found to have a strong negative impact on the Cr activity in Fe-Cr-N and Fe-Cr-C-N systems. / QC 20100929

QC 20100927

The key to the understanding of the mechanical behavior of dual phase (DP) steels is to a large extent to be found in the microstructure. The microstructure is in its turn a result of the chemical composition and the process parameters during its production. In this thesis the connection between microstructure and mechanical properties is studied, with focus on the microstructure development during annealing in a continuous annealing line. In-line trials as well as the lab simulations have been carried out in order to investigate the impact of alloying elements and process parameters on the microstructure. Further, a dislocation model has been developed in order to analyze the work hardening behavior of DP steels during plastic deformation. From the in-line trials it was concluded that there is an inheritance from the hot rolling process both on the microstructure and properties of the cold rolled and annealed product. Despite large cold rolling reductions, recrystallization and phase transformations, the final dual phase steel is still effected by process parameters far back in the production chain, such as the coiling temperature following the hot rolling. Lab simulations showed that the microstructure and consequently the mechanical properties are impacted not only by the chemical composition of the steel but also by a large number of process parameters such as soaking temperature, cooling rate prior to quenching, quench and temper annealing temperature. / QC 20101004

The present study was carried out to investigate the formation and evolution of non-metallic inclusions during ingot casting. Emphasize have been on understanding the types of inclusions formed and developed through the casting process and on the development of already existing inclusions carried over from the ladle during casting. Industrial experiments carried on at Uddeholm Tooling together with laboratory work and Computational Fluid Dynamics (CFD) simulations. Ingots of 5.8 tons have been sampled and the types of inclusions together with their distribution within the ingot have been characterized. Two new types of inclusions have been found. Type C1 is found originated from casting powder and in the size from a few μm to 30 μm. Type C2 is of macro inclusion type sizing up to 70 μm. The presence of C2 inclusions are few but very detrimental for the quality of the steel. Both types, C1 and C2 consist of alumina, indicating that reoxidation is the main reason for their existence. The protecting argon shroud has been studied by the use of a 1:1 scaled 2D model. Both flow pattern and oxygen measurement have been carried out. CFD has also been used as an auxiliary tool. It has been found that the oxygen pickup through argon gas shroud depends mostly on the distance between the ladle and the collar placed on top of runner. Further increase of gas flow rate above 2.5 m3.h-1 had very little effect on the oxygen distribution since both the flushing effect and the entraining effect with respect to oxygen are enhanced by further increase of inert gas flow rate. In the case of dual gas inlet, the flow in the shroud was found much less diffused compared with either vertical or horizontal injection system. The oxygen content in this arrangement was also greatly reduced. Studies of the runner after casting revealed a sparse non-metallic network structure around the periphery of the steel rod remained in the runner. The surface of the refractory had been severely attacked by the mechanical force from the streaming steel. The erosions of the centre stone and the end stone were on the other hand negligible. CFD calculations showed that the flow at those locations is almost stagnant. The surface of the refractory in contact with the steel was found to have an increased content of alumina. The source for the alumina could come from either exchange reaction of dissolved aluminium replaces the silica or reoxidation products origin from oxygen pick up during the transfer from the ladle to the vertical runner. Inclusions were also found entrapped in the steel refractory interface. It was also found that a formation of a liquid slag film as early as possible during casting would increase the possibility to remove inclusions and especially inclusions generated by the casting powder. / QC 20100617