<p>This study has been triggered by the fact that stainless steel is being increasingly used in new applications, where possible environmental effects may be a matter of concern. When stainless steel is exposed to a given environment, a key issue is the release of small amounts of the main alloying elements iron, chromium, nickel and molybdenum. Published release rate data of these elements turned out to be sparse. Furthermore, only little was known about the role of different parameters that may affect the release rate, such as degree of alloying, exposure time and surface finish. Hence, the aim of this study was to develop methodological means and to provide accurate metal release rates of alloying constituents from different grades of stainless steels- austenitic, ferritic and duplex- when exposed to selected environments: artificial rain and synthetic body fluids. The results and discussion have been summarised in this thesis by formulating and answering ten questions, all believed to be crucial for the understanding of possible environmental effects of stainless steels.</p><p>Some common conclusions could be drawn, independent of stainless steel grade and exposure condition. Iron was always preferentially released, and the release rates of chromium, nickel and molybdenum (when measured) were significantly lower than of iron, also when considering the bulk proportion of these elements. The release rate of all elements was initially high and decreased with exposure time, mainly because of an observed enrichment of chromium in the passive film formed.</p><p>The release rates of iron (2 μgcm^-2week^-1) and nickel (0.08 μgcm-²week-¹) from stainless steel from grades 304 and 316 exposed to artificial rain were much lower than corresponding rates for the pure metals (750 μgcm-²week^-1 released Fe and 15 μgcm^-2week^-1 released Ni), whereas chromium exhibited similar release rates from stainless steel and the pure metal (0.1 μgcm^-2week^-1). This implies that the common procedure to calculate release rates, based on the pure metals and the nominal steel composition, significantly overestimates release rates of iron and nickel from stainless steel, but not of chromium.</p><p>Total release rates from seven stainless steel grades in synthetic body fluid were found to decrease with increasing alloy content in the following release rate order: grade 409 >> grade 430 > grades 316L ≈ 201 ≈ 2205 ≈ 304 > grade 310. The release rate was highly sensitive to pH of the synthetic body fluid but only slightly sensitive to stainless steel surface finish.</p>

<p>Ionic conductivity of metal oxides is critical for the function of a broad range of different components, such as electrolytes in solid oxide fuel cells and alloys designed for high temperature applications. In both cases the ionic conductivity can be studied by in situ impedance spectroscopy, which is also able to reveal information on the dielectric properties of the metal oxides, and in some cases the influence of their microstructure. The focus of this thesis is on impedance spectroscopy measurements of α-alumina in the temperature range 400-1000 °C. This metal oxide has found extensive use as the protective scale on heat resistant alloys. Some unpublished work on oxygen ion conductivity of yttria-stabilized zirconia is also included.</p><p>The low electrical conductivity of α-alumina can be a source for errors and misinterpretations during impedance spectroscopy measurements. A major disturbance originates from leakage currents that appear in the experimental setup. These leakage currents are due to conduction through the gas phase around the sample, conduction on the sample surface, or poor insulation in the sample holder. It was shown that below 700 °C, conduction on the sample surface could severely distort the measurement. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements.</p><p>Conductivity of metal oxides is known to be dependent on their microstructure. Generally it is believed that ionic conductivity is favoured along grain boundaries and dislocations. The influence of microstructure on conductivity was studied for α-alumina in the temperature range 400-1000 °C. The conductivity of a series of highly pure and dense samples with narrow grain size distributions was measured by impedance spectroscopy. It appeared that the activation energy for conduction increased with decreasing grain size.</p><p>Results based purely on impendence spectroscopy have some inherently weaknesses. For instance no information on the nature of the charge carrier can be found. Therefore the charge transport in single crystalline α-alumina was simulated by the molecular dynamics method. The results from the simulation were then compared to results from impedance measurements on single crystalline α-alumina. From the simulation it turned out that diffusion of aluminium ions had lower activation energy than diffusion of oxygen. The activation energy of oxygen was close to the measured activation energy, and the mobility of oxygen was higher than for aluminium. Therefore the dominating charge carrier was suggested to be oxygen ions.</p>

<p>The major part of the present work, deals with the reduction kinetics of Cu₂O powder and a Cu₂O-WO₃ powder mixture by hydrogen gas, studied by ThermoGravimetric Analysis (TGA). The reduction experiments were carried out both isothermally and non-isothermally on thin powder beds over different temperature intervals. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The activation energy for the reactions was evaluated from isothermal as well as non-isothermal reduction experiments.</p><p>In the case of the reduction of Cu₂O, the impact of the stability of the copper oxide on the activation energy for hydrogen reduction under identical experimental conditions is discussed. A closer investigation of additions of Ni or NiO to Cu₂O did not have a perceptible effect on the kinetics of reduction.</p><p>In the case of the reduction of the Cu₂O-WO₃mixture, the reaction mechanism was found to be affected in the temperature range 923-973 K, which is attributed to the reaction/transformation in the starting oxide mixture. At lower temperatures, Cu₂O was found to be preferentially reduced in the early stages, followed by the reduction of the tungsten oxide. At higher temperatures, the reduction kinetics was strongly affected by the formation of a complex oxide from the starting materials. It was found that the Cu₂O-WO₃mixture underwent a reaction/transformation which could explain the observed kinetic behavior.</p><p>The composition and microstructures of both the starting material and the reaction products were analyzed by X-ray diffraction (XRD) as well as by microprobe analysis. vi Kinetic studies of reduction indicated that, the mechanism changes significantly at 923 K and the product formed had unusual properties. The structural studies performed by XRD indicated that, at 923 K, Cu dissolved in W forming a metastable solid solution, in amorphous/nanocrystalline state. The samples produced at higher as well as lower temperatures, on the other hand, showed the presence two phases, pure W and pure Cu. The SEM results were in conformity with the XRD analysis and confirmed the formation of W/Cu alloy. TEM analysis results confirmed the above observations and showed that the particle sizes was about 20 nm.</p><p>The structure of the W/Cu alloy produced in the present work was compared with those for pure copper produced from Cu2O produced by hydrogen reduction under similar conditions. It indicated that the presence of W hinders the coalescence of Cu particles and the alloy retains its nano-grain structure. The present results open up an interesting process route towards the production of intermetallic phases and composite materials under optimized conditions.</p>

<p>Zr-based materials have found their main application in the nuclear field having high corrosion resistance and low neutron absorption cross-section. The oxide layer that is formed on the surface of these alloys is meant to be the barrier between the metal and the corrosive environment. The deterioration of this protective layer limits the lifetime of these alloys. A better understanding of the transport phenomena, which take place in the oxide layer during oxidation, could be beneficial for the development of more resistant alloys.</p><p>In the present study, oxygen and hydrogen transport through the zirconia layer during oxidation of Zr-based materials at temperatures around 400C have been investigated using the isotope-monitoring techniques Gas Phase Analysis and Secondary Ion Mass Spectrometry. The processes, which take place at oxide/gas and oxide/metal interface, in the bulk oxide and metal, have to be considered in the investigation of the mechanism of hydration and oxidation. Inward transport of oxygen and hydrogen species can be influenced by modification of the surface properties. We found that CO molecules adsorbed on Zr surface can block the surface reaction centers for H₂ dissociation, and as a result, hydrogen uptake in Zr is reduced. On the other hand, coating the Zr surface with Pt, resulted in increased oxygen dissociation rate at the oxide/gas interface. This generated enhanced oxygen transport towards the oxide/metal interface and formation of thicker oxides. Our results show that at temperatures relevant for the nuclear industry, oxygen dissociation efficiency decreases in the order: Pt > Zr₂Fe > Zr₂Ni > ZrCr₂ ≥ Zircaloy-2.</p><p>Porosity development in the oxide scales generates easy diffusion pathways for molecules across the oxide layer during oxidation. A novel method for evaluation of the gas diffusion, gas concentration and effective pore size of oxide scales is presented in this study. Effective pore sizes in the nanometer range were found for pretransition oxides on Zircaloy-2.</p><p>A mechanism for densification of oxide scales by obtaining a better balance between inward oxygen and outward metal transport is suggested. Outward Zr transport can be influenced by the presence of hydrogen in the oxide/metal substrate. Inward oxygen transport can be promoted by oxygen dissociating elements such as Fe-containing second phase particles. The results suggest furthermore that a proper choice of the second-phase particle composition and size distribution can lead to the formation of dense oxides, which are characterized by low oxygen and hydrogen uptake rates during oxidation.</p>

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

<p>At present the automotive industry is due to an EU directive, replacing hexavalent chrome on vehicles. This is an extensive job as hexavalent chrome is used all over the vehicle and to large extent on fasteners (screws, nuts, rivets etc.). Chrome (VI) is used as a passivating layer on mainly zinc-iron. When replacing the hexavalent chrome with a chrome (VI) free product, the passivating properties are reduced. One of the alternatives is to replace the zinc-iron coating with a zinc-nickel coating. This coating shows great promise from the corrosion resistance point of view. Zinc-nickel is a cathodically protecting coating, and will in principle dissolve to protect the substrate from corrosion. It is therefore important to understand how, and at what rates nickel is released from zinc-nickel coatings when exposed to a chloride-rich automotive environment. The potential environmental impact of nickel needs to be evaluated before Scania can introduce this alternative as corrosion protection. Tests by Scania have previously shown that contact allergy is not an issue for zinc-nickel coatings with Cr (III) passivation.</p><p>Nickel release rates corresponding to 0,12 mg m^-2yr^-1 for zinc-15 % nickel coatings at a pH of 4,2 were determined from an accelerated corrosion test. Based on these values, less than 1 kg of nickel per year would be released from the Scania rolling stock if Scania were to introduce zinc-nickel coatings preferably on fasteners. This value is low compared to other sources of nickel release. In order to evaluate the toxicity of the released nickel, information about the chemical speciation, i.e. chemical forms, is needed.</p><p>Total or dissolved metal are not good predictors of ecotoxicity of metals. Chemical speciation and bioavailability must be incorporated in toxicity testing. Total or dissolved metal may be used as a worst case approximation.</p>

<p>Humans are exposed to metals and metal-containing materials daily, either conscious, e.g. using metal tools or objects, or unconscious, e.g. during exposure to airborne metal-, and metal-containing particles. The diffuse dispersion of metals from different sources in the society, and the concern related to its potential risk for adverse effects on humans have gained an increased public and governmental attention both on a national and international level. In this context, the knowledge on metal release from metallic objects or metal-containing particles is essential for health risk assessment.</p><p>This thesis focuses on the study of metal release from powder particles of stainless steel and Cu-based materials exposed to synthetic body fluids mainly for simulating lung-like environments. The study comprises: i) development of a suitable experimental method for metal release studies of micron sized particles, ii) metal release data of individual alloy constituents from stainless steel powder particles of different particle sizes, and iii) Cu release from different Cu-based powder particles. In addition, the influence of chemical and physical properties of metallic particles and the test media are investigated. Selected results from Ni powder particles exposed to artificial sweat are presented for comparison. The outcome of this research is summarized through ten questions that are formulated to improve the general understanding of corrosion-induced metal release from metallic particles from a health risk perspective.</p><p>A robust, reproducible, fairly simple, and straightforward experimental procedure was elaborated for metal release studies on particles of micron or submicron size. Results in terms of metal release rates show, for stainless steel powder particles, generally very low metal release rates due to a protective surface oxide film, and Fe preferentially released compared to Cr and Ni. Metal release rates are time-dependent for both stainless steel powder particles and the different Cu-containing powders investigated. The release of Cu from the Cu-containing particles depends on the chemical and compositional properties of the Cu-based material, being either corrosion-induced or chemically dissolved. Moreover, the test medium also influences the metal release process. The metal release rate increases generally with decreasing pH of the test media. However, even at a comparable pH, the release rate may be different due to differences in the interaction between the particle surface and specific media.</p><p>The nature of particles is essentially different compared to massive sheet in terms of physical shape, surface composition and morphology. The surface area, and even the surface composition of metallic particles, depend on the particle size. The specific surface area of particles, area per mass, is intimately related to the particle size and has a large effect on the metal release process. Release rates increase with decreasing particle size due to a larger active surface area that takes part in the corrosion/dissolution process. The surface area that actually is active in the corrosion and metal release process (the effective area) governs the metal release process for both particles and massive sheet of metals or alloys. For particles, the effective surface area depends also on agglomeration conditions of particles during exposure.</p>

<p>Recrystallization kinetics, during and after hot deformation, has been investigated for decades. From these investigations several equations have been derived for describing it. The equations are often empirical or semi-empirical, i.e. they are derived for certain steel grades and are consequently only applicable to steel grades similar to these. To be able to describe the recrystallization kinetics for a variety of steel grades, more physically based models are necessary.</p><p>During rolling in hot strip mills, recrystallization enables the material to be deformed more easily and knowledge of the recrystallization kinetics is important in order to predict the required roll forces. SSAB Tunnplåt in Borlänge is a producer of low-carbon steel strips. In SSAB’s hot strip mill, rolling is conducted in a reversing roughing mill followed by a continuous finishing mill. In the reversing roughing mill the temperature is high and the inter-pass times are long. This allows for full recrystallization to occur during the inter-pass times. Due to the high temperature, the rather low strain rates and the large strains there is also a possibility for dynamic recrystallization to occur during deformation, which in turn leads to metadynamic recrystallization after deformation. In the finishing mill the temperature is lower and the inter-pass times are shorter. The lower temperature means slower recrystallization kinetics and the shorter inter-pass times could mean that there is not enough time for full recrystallization to occur. Hence, partial or no recrystallization occurs in the finishing mill, but the accumulated strain from pass to pass could lead to dynamic recrystallization and subsequently to metadynamic recrystallization.</p><p>In this work a newly developed physically based model has been used to describe the microstructural evolution of austenite. The model is based on dislocation theory where the generated dislocations during deformation provide the driving force for recrystallization. The model is built up by several submodels where the recrystallization model is one of them. The recrystallization model is based on the unified theory of continuous and discontinuous recovery, recrystallization and grain growth by Humphreys.</p><p>To verify and validate the model, rolling in the hot strip mill was modeled using process data from SSAB’s hot strip mill. In addition axisymmetric compression tests combined with relaxation was modeled using experimental results from tests conducted on a Gleeble 1500 thermomechanical simulator at Oulu University, Finland. The results show good agreement with measured data.</p>

<p>The role of intrinsic hydrodynamic instability of the premixed flame (known as Landau-Darrieus instability) in various flame phenomena is studied by means of direct numerical simulations of the complete system of hydrodynamic equations. Rigorous study of flame dynamics and effect of Landau-Darrieus instability is essential for all premixed combustion problems where multidimensional effects cannot be disregarded.</p><p>The present thesis consists of three parts. The first part deals with the fundamental problem of curved stationary flames propagation in tubes of different widths. It is shown that only simple "single-hump" slanted stationary flames are possible in wide tubes, and "multi-hump" flames in a laminar flow are possible in wide tubes only as a non-stationary mode of flame propagation. The stability limits of curved stationary flames in wider tubes are obtained, together with the dependence of the velocity of the stationary flame on the tube width. The flame dynamics in wider tubes is shown to be governed by a large-scale stability mechanism resulting in a highly slanted flame front.</p><p>The second part of the thesis is dedicated to studies of acceleration and fractal structure of outward freely propagating flames. It is shown that in direct numerical simulation the development of Landau-Darrieus instability results in the formation of fractal-like flame front structure. The fractal excess for radially expanding flames in cylindrical geometry is evaluated. Two-dimensional simulation of radially expanding flames in cylindrical geometry displays a radial growth with 1.25 power law temporal behavior after some transient time. It is shown that the fractal excess for 2D geometry obtained in the numerical simulation is in good agreement with theoretical predictions. The difference in fractal dimension between 2D cylidrical and three-dimensional spherical radially expanding flames is outlined. Extrapolation of the obtained results for the case of spherical expanding flames gives a radial growth power law that is consistent with temporal behavior obtained in the survey of experimental data.</p><p>The last part of the thesis concerns the role of Landau-Darrieus instability in the transition from deflagration to detonation. It is found that in sufficiently wide channels Landau-Darrieus instability may invoke nucleation of hot spots within the folds of the developing wrinkled flame, triggering an abrupt transition from deflagrative to detonative combustion. It is found that the mechanism of the transition is the temperature increase due to the influx of heat from the folded reaction zone, followed by autoignition. The transition occurs when the pressure elevation at the accelerating reaction front becomes high enough to produce a shock capable of supporting detonation.</p>

<p>The Vickers residual stress field (VRSF) in soda-lime glass results from the elastic-plastic contact event that takes place when a Vickers diamond pyramid is loaded onto the surface of the material in an indentation cycle. The importance of elastic-plastic indentation lies in the contact damage that it gives rise to in the surface of the glass. Since such surface flaws can be characterised, with respect to shape and size, they offer the opportunity to study naturally occurring flaws in glass and brittle materials in general. The residual stress field is not passive; rather it exerts a crack opening force on the associated crack system during subsequent strength testing of a Vickers-indented sample through a residual stress field coefficient, c. Besides the strength-controlling properties, the elastic-plastic contact residual stress field is also important as a region where the influence of mechanical excitation on material properties such as hardness, H, and elastic modulus, E, can be studied.</p><p>This thesis concerns studies that were made to characterise the Vickers residual stress field by first measuring the magnitude and distribution of stresses around it, using nanoindentation with a cube corner tip. With a Berkovich tip in nanoindentation, experiments were conducted in the VRSF to study the dependence of hardness, H and elastic modulus, E, on stresses in soda-lime glass: a strong E dependence on stress was observed, while H was not affected unless the stresses were high. In the process, a method was developed to determine the true contact area during elastic-plastic nanoindentation when the Oliver-Pharr method is used for the data analysis.</p><p>The observed elastic modulus dependence on stress was then utilised in a study where it was shown that the VRSF responds differently to relaxation annealing on either side of the glass transition temperature. This result was then used to explain strength recovery trends in annealed Vickers-indented glass specimens.</p>