Tungsten (W) is listed among the European Union (EU) critical raw materials (CRMs) for its supply risk and economic importance. Primarily, tungsten is produced from scheelite and wolframite mineral ores with 0.08-1.5% tungsten trioxide (WO3) grade. However, as primary deposits for these resources are becoming less or lower in grade, alternative sources need to be explored. These alternative tungsten sources include scrap from end-of-life products, mine waste and rejects from the ore beneficiation processes (tailings). The latter alternative source is the focus within this thesis. Historical tailings repositories often pose environmental risks but may also become secondary sources of CRMs. This is because of relatively high minerals and metals content due to less efficient extraction methods and/or relatively low metal prices at the time of active mining. Therefore, reprocessing of such tailings is not only a supply risk-reducing measure but also an approach to remediation that contributes to the mining industry’s aim of moving towards a circular economy. The aim of this thesis has been to develop efficient methods for separating valuable minerals from the tailings in order to leave behind a stable and environmentally safe residue. Geometallurgical studies were conducted by collecting drill core samples from the Smaltjärnen tailings repository in Yxsjöberg, Sweden, for evaluating the potential of this repository for further processing. The tailings were originally produced from the ore that was mined by Yxsjö Mines while it was in operation from 1935 to 1963, with average ore grades of 0.3-0.4 wt.% WO3, 0.2 wt.% Cu and 5-6 wt.% fluorspar. The exploited minerals were scheelite for W, chalcopyrite for Cu and fluorspar. The tailings repository is estimated to have about 2.2 million tons of tailings covering an area of 26 hectares, with elemental concentrations of 1-2 wt.% S, 0.02-0.2 wt.% Cu, 0.02-0.3 wt.% W, 0.02-0.04 wt.% Sn and 0.02-0.03 wt.% Be. Sampling and characterization of the historical tailings were conducted based on geometallurgical units (i.e. a distinction between different layers and locations in the repository), followed by metallurgical test work. The tailings were characterized with regard to color and granulometry, particle size distribution, chemical composition, scheelite mineral occurrence, texture and mineral liberation, as well as mineralogical composition. Based on a comprehensive literature survey, tailings characteristics, and assessment of the earlier processes from which the Yxsjöberg tailings were produced, feasible separation methods were pre-selected involving dry low-intensity magnetic separation (LIMS) and high intensity magnetic separation (HIMS), enhanced gravity separation (EGS) using a Knelson concentrator, and batch froth flotation. The average WO3 and Cu concentration in these tailings based on the sampled locations was 0.15 % and 0.11 % respectively. Applying them to the estimated 2.2 million tons of tailings in this repository gives approximately 3300 tons of WO3 and 2512 tons of Cu. From the metallurgical test work, several feasible processing routes have been identified that need to be further assessed based on the economic and environmental criteria. / REMinE (Improve Resource Efficiency and Minimize Environmental Footprint)

The application of chemical additives, known as grinding aids (GA), dates back to 1930 in the cement industry. As opposed to the cement industry, where the use of GAs is on the final processing step, it could be one of the first process steps in ore beneficiation. A few investigations addressed the GA applications in ore dressing; therefore, further studies are required to better understand the GA effects on the product properties and downstream separation processes. This thesis undertakes a comparative study on the dry grinding of magnetite and the resulting product characteristics with and without GAs. The main aim is to reduce energy consumption and to address some of the challenges associated with dry processing.  The effects of GAs on the dry batch ball milling of magnetite were examined to analyze the energy consumption (Ec), particle size distribution, flow properties, bulk properties, surface morphology, particle fineness, and surface chemistry of products. Their effects on the ground product were systematically explored by sieve analysis, powder rheology, BET surface measurements, optical microscopy analysis, and zeta potential measurements. Compared with the absence of GAs, the dry grinding efficiency of magnetite increased after using GAs; however, an optimal dosage exists based on the GA type. Among GAs which considered in this investigation (Zalta™ GR20-587 (Commercial GA) and Zalta™ VM1122 (Commercial viscosity aid) as well as sodium hydroxide), Zalta™ VM1122, a polysaccharide-based additive, was the most effective GA where by using this GA; the Ec decreased by 31.1% from 18.0 to 12.4 kWh/t. The PSD became narrower and finer (P80 decreasing from 181 to 142 µm), and the proportion of the particles (38–150 µm) increased from 52.5 to 58.3%. In general, the results reveal that at sufficient GA dosages, they reduce the average particle size, increase the specific surface area, and narrow the particle size distribution. However, an excessive amount of GAs could be detrimental to the grinding performance.  Further studies on powder rheology indicated that the used GAs resulted in improved material flowability compared to grinding without additives (in the examined dosage range). The rheology measurements by the FT4 Powder Rheometer showed strong linear correlations between basic flow energy, specific energy, and the resulting work index when GAs was considered for grinding. There was a strong correlation between the grinding parameters and flow parameters (r > 0.93). These results confirmed the effect of GA on ground particles' flowability. Zalta™ VM1122 showed the best performance with 38.8% reduction of basic flow energy, 20.4 % reduction of specific energy, 24.6% reduction of aerated basic flow energy, and 38.3% reduction of aerated energy. The present investigation showed that the predominant mechanism of GAs is based on the alteration of rheological properties. Further investigation on the surface properties showed that using GAs could increase the surface roughness, which is beneficial for downstream processes such as froth flotation. Zalta™ VM1122 resulted in increased surface roughness and minimum microstructural defects from the optical microscope images. Furthermore, Zalta™ VM1122 (non-ionic) resulted in similar zeta potentials and pH values for the product compared to experiments without GA. These comparable product properties are advantageous as they minimize any potential negative effects on all possible downstream processes. / Kolarctic CBC (KO1030 SEESIMA)

Aluminium alloys have the possibility to be infinitely recycled. By only generating 5% of the emissions compared to primary aluminium, great CO2 savings can be made. One of the issues in manufacturing components entirely from post-consumer scrap is the presence of trace elements and impurities. Such elements can be Fe, Cu, Cr, P and Pb. In sheet metal manufacturing, these elements can also react with process agents such as Ti, B, Na and Sr and affect the recrystallization behavior and in turn mechanical properties.In this work, a derivative of the 3003 alloy made entirely from post-consumer scrap has been analysed. The alloy achieved insufficient formability due to lack of recrystallization and grain growth. With the use of scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) together with focused ion beam (FIB) lamella preparation, the microstructure was characterized.The characterization shows both larger particles of α-Al15Si2M4 (M=Mn,Fe,Cr) from solidification and dispersoids from heat treatment, pinning the grain boundary movement together with Q-AlCuMgSi. With the use of high throughput computational thermodynamics, Thermo-Calc was used to effectively screen compositions lowering the amount of α-Al15Si2M4 and removing the Q-AlCuMgSi phase. The new alloy was cast using directional solidification at different cooling rates to study the particle morphology, which in turn plays a role in the particle break up and distribution during cold working as the interparticle spacing affects the grain growth.Varying cooling rates was seen to affect morphology and distribution. Hot compression was utilized to examine the particle redistribution before cold work. It was however shown that hot compression was not sufficient in redistributing the particles as would be the case in rolling.

Heat transfer is key to understanding many processes in engineering. At a steel mill heat transfer is absolutely crucial to understanding most of the processes. One such a process is the pre-heating of a freshly relined ladle. The goal of this project was to develop code which could solve the diffusion equation, in an arbitrary three-dimensional geometry, subject to Dirichlet, Robin, Neumann, and certain kinds of non-linear boundary conditions. In order to approximate the solution the code uses a cell centred finite volume methodology. In order to verify the computational correctness of the code it was used on three simple cases where analytic solutions are known, a rarity for three-dimensional boundary value problems. A mathematical model for the heat conduction inside a ladle at Ovako’s site in Hofors was developed. The model was evaluated based on measurements on the outside of the ladle as well as from a temperature probe inside the bottom of the ladle. The model was found to adequately agree with the measured temperature. The code can thus be used to find a more optimal heating regiment of the ladle, possibly reducing emissions. / Värmeöverföring är nyckeln till att förstå många processer inom teknik. På ett stålverk är värmeöverföring helt avgörande för att förstå de flesta av processerna. En sådan process är förvärmning av en nymurad skänk. Målet med detta projekt var att utveckla en kod som kunde lösa diffusionsekvationen i en godtycklig tredimensionell geometri under Dirichlet-, Robin-, Neumann- och vissa typer av icke-linjära randvillkor. För att approximera lösningen använder koden en cellcentrerad finita volymmetodik. För att verifiera kodens beräkningsmässiga korrekthet användes den i tre enkla fall där analytiska lösningar är kända, vilket är en sällsynthet för tredimensionella randvärdesproblem. En matematisk modell för värmeledningen i en skänk vid Ovakos anläggning i Hofors utvecklades. Modellen utvärderades utifrån mätningar på utsidan av skänken samt från ett termoelement inuti botten av skänken. Modellen visade sig stämma väl överens med den uppmätta temperaturen. Koden kan därför användas för att hitta ett mer optimalt uppvärmningsschema för skänken, vilket eventuellt kan minska utsläppen från processen.

Additive manufacturing (AM) processes may introduce large residual stresses in the as-built part, in particular the laser powder bed fusion process (L-PBF). The residual stress state is an inherent consequence of the heterogeneous heating and subsequent cooling during the process. L-PBF has become renowned for its “free complexity” and rapid prototyping capabilities. However, it is vital to ensure shape stability after the component is removed from the build plate, which can be problematic due to the residual stress inducing nature of this manufacturing process. Residual stresses can be analyzed via many different characterization routes (e.g. X-ray and neutron diffraction, hole drilling, etc.), both quantitatively and qualitatively. From an industrial perspective, most of these techniques are either prohibitively expensive, complex or too slow to be implementable during the early prototyping stages of AM manufacturing. In this work a deformation based method employing a specific geometry, a so called “keyhole”-geometry, has been investigated to qualitatively evaluate the effect of different stress relief annealing routes with respect to macroscopic part deformation, mechanical properties and microstructure. Previous published work has focused on structures with open geometry, commonly referred to as bridge-like structures where the deformation required for analysis occurs during removal from the build plate. The proposed keyhole-geometry can be removed from the build plate without releasing the residual stresses required for subsequent measurement, which enables bulk manufacturing on single build plates, prior to removal and stress relief annealing.  Two L-PBF manufactured austenitic stainless steel alloys were studied, 316L and 21-6-9. Tensile specimen blanks were manufactured and the subsequent heat treatments were carried out in pairs of keyhole and tensile blank. Both a contact (micrometer measurement), and a non-contact (optical profilometry) method were employed to measure the residual stress induced deformation in the keyholes. The annealing heat treatment matrix was iteratively expanded with input from the deformation analysis to find the lowest temperature at which approximately zero deformation remained after opening the structure via wire electrical discharge machining. The lowest allowable annealing temperature was sought after to minimize strength loss.  After stress relief annealing at 900 ℃ for 1 hour, the 316L keyhole-geometry was considered shape stable. The lateral micrometer measurement yielded a length change of 1 µm, and a radius of 140 m (over the 22 mm top surface) was assigned from curve fitting the top surface height profiles. The complementary microstructural characterization revealed that this temperature corresponded to where the last remains of the cellular sub-grain structures disappears. Tensile testing showed that the specimen subjected to the 900 ℃ heat treatment had a marked reduction in yield stress (YS) compared to that of the as-built: 540 MPa → 402 MPa, whereas ultimate tensile strength (UTS) only reduced slightly: 595 MPa → 570 MPa. The ductility (4D elongation) was found to be ~13 % higher for the specimen heat treated at 900 ℃ than that of the as-built specimen, 76% and 67% respectively.  For alloy 21-6-9 the residual stress induced deformation minimum (zero measurable deformation) was found after stress relief heat treatment at 850 ℃ for 1 hour. Slight changes in the microstructure were observable through light optical microscopy when comparing the different heat treatment temperatures. The characteristic sub-grain features associated with alloy 316L were not verified for alloy 21-6-9. Similar to the results for 316L, UTS was slightly lower for the tensile specimen subjected to the heat treatment temperature required for shape stability (850 ℃) compared to the as-built specimen: 810 MPa → 775 MPa. The measured ductility (4D elongation) was found to be approximately equal for the as-built (47%), and heat treated (48%) specimen. As-built material exhibited a YS of 640 MPa while the heat treated specimen had a YS of 540 MPa. For alloy 21-6-9, the lateral micrometer deformation measurements were compared with stress relaxation testing performed at 600 ℃, 700℃ and 800 ℃. Stress relaxation results were in good agreement with the results from the lateral deformation measurements.  The study showed that for both steel alloys, the keyhole method could be successfully employed to rapidly find a suitable stress relief heat treatment route when shape stability is vital.

Additive manufacturing (AM) techniques are being studied for their application in the aerospace industry. Numerous benefits come from the already in shape final piece, which needs reduced amount of prime material for its production and can have its shape numerically optimized for weight reduction. Austenitic stainless steels (AuSS) are widely used in aerospace and their manufacturing through AM is a popular research topic in order to accelerate their effective incorporation in air-crafts and spaceships. The special microstructures of AM has been observed with characterization techniques. The present work studies the high temperature stability of three AuSS (316L, MOD-316 and 21-6-9) considering two approaches; surface corrosion and microstructure evolution. First, for high temperature corrosion, thermogravimetric analysis has been performed from 850°C to 1150°C. From the results, kinetic analysis were performed and the activation energy was extracted from Arrhenius fits. Two mechanism were found for alloy 316L (first 435.41 kJ/mol and second 593.24 kJ/mol) and MOD-316 (first 740.01 kJ/mol and second 495.58 kJ/mol). Further SEM observations on the scales have shown Ni diffusion through the chromia scale in MOD-316 alloy, which could explain the higher oxidation rates at 1150°C. Alloy 21-6-9 has the best passivation behaviour with an activation energy of 190.47 kJ/mol. Secondly, long heat treatment (HT) at 725°C in air atmosphere has been performed, for 24 and 240h. Samples were initially as-built or annealed (900°C for 1h), to compare the effect of the HT on the microstructure evolution and precipitates formation. LOM observation showed preferable nucleation in grain boundaries (GB), an increment of the number of precipitates and a growth towards elongated shapes following GB with increased time. It was also observed a reduction in precipitates number with the annealing HT for all the alloys. XRD, SEM and EDS analysis has been carried out to identify the structure and composition of the precipitates. Various chromium, tungsten, copper, molybdenum and niobium carbides and oxides have been found in MOD-316. Higher porosity is observed in 21-6-9, that presented mainly chromium oxides, carbides and nitrides in GB and surrounding the AM defects. / SeSSA

In the past, the disagreement of near-threshold fatigue-crack growth (FCG) rate data generated from constant Kmax tests, high load ratio (minimum to maximum load) constant R tests, and ΔKeff based data was a mysterious issue. Because of the disagreement, a variety of test or analysis methods were created to correlate FCG rate data. It was suspected that the ASTM threshold test method using load reduction was inducing remote crack closure due to plastically deformed material, which caused elevated thresholds and slower rates than steady-state behavior. The first goal of this study was the development of a test method to eliminate remote closure during threshold testing. In order to avoid/minimize remote closure effect, compression-precracking methods were used to initiate a crack from a starter notch on compact specimens. Two materials with different fatigue crack surface profiles (flat or very rough) were tested and the results generated from the conventional ASTM precracking method and the compression-precracking test method were compared. In order to understand the disagreement of near-threshold data, crack-opening load measurements were performed from locally (near crack tip) installed strain gages instead of the remote gage (i.e., back face gage). Some careful specimen preparations were performed to avoid out-of-plane bending, to maintain straight crack fronts, and to ensure testing system linearity. It was known that remote gages, such as crack-mouth- opening-displacement-gages were insensitive to measuring load-strain records near threshold. By using local gages, the crack closure effects were clearly observed even in high load ratio (R) tests, like or higher than R = 0.7, and constant Kmax tests, which were believed to be crack closure free. By measuring load-reduced-strain records from local gages, crack-opening loads were able to correlate FCG rate data and showed that ΔKeff-rate data was unique for a wide variety of materials. By comparing (ΔKeff)th values, it may provide reasonable guidance for the material resistance against FCG. Because of “high R crack closure”, some theories considered in the past may need to be reconsidered. First, constant Kmax tests are not entirely crack-closure free. Second, there is no critical load ratio, Rc, to indicate the transition from crack-closure affected to crack-closure free data, and Kmax effects that appear in ΔKth-Kmax relations. Research has shown that the three dominate crack-closure mechanisms (plasticity-, roughness- and debris-induced crack closure) FCG rate behavior in the threshold regime from low to high load ratios.

Det här examensarbetet är baserat på en uppdragsbeskrivning från ventiltillverkaren ESBE. Företaget önskar utveckla livslängdsprovning av ventiler utifrån kemisk sammansättning hos tappvattnet och det finns ett intresse hos företaget kunna identifiera de faktorer som kan leda till haveri eller på annat vis inverka på ventilernas funktion. Syftet med arbetet har varit att sammanställa och utvärdera vilka kemiska komponenter och fysikaliska förhållanden som är relevanta för livslängdsprovning av blandningsventiler. Arbetet har annars främst grundat sig på litteraturstudier av vetenskapliga artiklar, relevant facklitteratur, diverse beräkningsmodeller samt en experimentell del. De två vanligaste problemen som kan uppstå i samband med att metall är i kontakt med vatten är: korrosion och bildning av oxider. I samband med accelererad korrosionsprovning har faktorer som temperatur, löst syre, pH, alkalinitet, hårdhet, klorid och sulfat visat sig vara de vattenparametrar som haft störst inverkan. Två olika förslag på testlösningar har tagits fram under arbetet. Båda optimerade för att vara effektiva för en accelererad provningsmetod. Den ena anpassad för att påskynda avzinkning, den andra för att påskynda oxidbildning. Det recept som har getts som förslag i detta arbete bör i ett nästa steg användas i nya enklare experiment och sedan utvärderas.

High chromium cast iron (HCCI) is considered as one of the most useful wear resistance materials and their usage are widely spread in industry. The wear resistance and mechanical properties of HCCI mainly depend on type, size, number, morphology of hard carbides and the matrix structure (γ or α). The Hypereutectic HCCI with large volume fractions of hard carbides is preferred to apply in wear applications. However, the coarser and larger primary M7C3 carbides will be precipitated during the solidification of the hypereutectic alloy and these will have a negative influence on the wear resistance. In this thesis, the Ti-added hypereutectic HCCI with a main composition of Fe-17mass%Cr-4mass%C is quantitatively studied based on the type, size distribution, composition and morphology of hard carbides and martensite units. A 11.2μm border size is suggested to classify the primary M7C3 carbides and eutectic M7C3 carbides. Thereafter, the change of the solidification structure and especially the refinement of carbides (M7C3 and TiC) size by changing the cooling rates and Ti addition is determined and discussed. Furthermore, the mechanical properties of hypereutectic HCCI related to the solidification structure are discussed. Mechanical properties of HCCI can normally be improved by a heat treatment process. The size distribution and the volume fraction of carbides (M7C3 and TiC) as well as the matrix structure (martensite) were examined by means of scanning electron microscopy (SEM) and electron backscattered diffraction (EBSD). Especially for the matrix structure, EBSD is a useful tool to classify the fcc (γ) and bcc (α) phases. In conclusion, low holding temperatures close to the eutectic temperature and long holding times are the best heat treatment strategies in order to improve wear resistance and hardness of Ti-alloyed hypereutectic HCCI. / <p>QC 20121130</p>

An induction setup for levitation studies of molten metals was built. The setup was used to levitate and heat stainless steel samples of 2.00 g to 1600 °C and subject them to different atmospheres. Changes in shape and temperature were recorded by video and infrared thermocouple. Oxide films forming on the droplets during levitation were observed. It was possible to notice an immediate surface reaction when the reaction gas was introduced. This reaction is concluded to influence the surface and bulk composition, and therefore have an effect on the shape evolution of the droplet. A more oxidizing atmosphere resulted in a more conical droplet shape; this is thought to be an effect of lowered surface tension and the conically shaped volumetric force caused by the magnetic field. Changes in temperature after the sample is molten are thought to be an effect of changes in emissivity, caused by surface oxidization. Post mortem analysis show a difference in surface morphology for samples subjected to different gases, as well as a difference in amount of oxidization.