<p>The solubility of divalent iron oxide in cryolite-based melts was studied. Both electrochemical and chemical techniques were employed. To ensure that only divalent iron was present in solution, the melt was contained in an iron crucible under an atmosphere of argon. The experimental work included investigation of the solubility as a function of alumina concentration, temperature and cryolite ratio (CR = NaF/AlF₃ molar ratio). The solubility at 1020 ºC was found to decrease from 4.17 wt% Fe in cryolite to 0.32 wt% Fe in cryolite saturated with alumina. FeO and FeAl₂O₄were found to coexist as solid phases in equilibrium with the melt at 5.03 wt% Al₂O₃; the former being the stable solid phase below this concentration and the latter at high alumina concentrations. The standard Gibbs energy of formation for FeAl₂O₄from its oxide components at 1020 ºC was determined to be -(17.6 ± 0.5) kJ mol^-1. The solubility of FeAl₂O₄ was found to increase from 0.25 wt% Fe at 981 ºC to 0.36 wt% at 1050 ºC in alumina-saturated melts. By assuming Henrian behaviour, the apparent partial molar enthalpy of dissolution of FeAl₂O₄ was found to be (64.8 2.5) kJ mol^-1. Experiments involving varying cryolite ratio in alumina-saturated melts at 1020 ºC showed a maximum solubility of 0.62 wt% Fe at a cryolite ratio of five. Modelling indicated that divalent iron species were present as NaFeF₃in acidic melts (CR < 3), while Na₃FeF₅and/or Na₄FeF₆ dominated in a basic environment (CR > 3).</p><p>The solubility of TiO_{2 i}n cryolite-alumina melts at 1020 ºC was measured. The analytical data showed that the titanium solubility decreased with increasing total oxide concentration, up to a concentration of ~3.5 wt% O, while it increased at higher concentrations. The solubility was found to be 3.1 wt% Ti and 2.7 wt% Ti, respectively, in cryolite and in alumina-saturated melts. Modelling indicated that the most probable titanium species are TiO²⁺ and TiO₃²-, which coexist in the solution; the former dominating at low alumina concentrations and the latter at high alumina concentrations. Unknown amounts of fluoride may also be associated with the titanium atoms. Determination of the solubility of TiO₂ in alumina-saturated melts as a function of temperature showed that the solubility increased from 1.9 wt% Ti at 975 ºC to 2.8 wt% Ti at 1035 ºC. The apparent partial molar enthalpy of dissolution of TiO₂was found to be (88.3 ± 4.1) kJ mol^-1, provided that Henry’s law holds.</p><p>The electrochemistry of divalent iron in cryolite-based melts was investigated by voltammetry, chronopotentiometry and chronoamperometry. A working electrode of copper was found to be best suited for the study of the reduction of Fe(II), while gold and platinum gave the best results under oxidising conditions. The reduction of Fe(II) ions was found to be diffusion controlled. The number of electrons involved was determined to be two. A discrepancy was observed between the diffusion coefficients obtained by the different techniques. The diffusion coefficient of Fe(II) in alumina-saturated melts at 1020 ºC was found to be D_Fe(II) = 3.0 x10^-5 cm² s^-1 by voltammetry. Experiments performed in an electrolyte with industrial composition at ~970 ºC gave a slightly higher value for the diffusion coefficient. The oxidation of Fe(II) on a gold or a platinum wire electrode showed that the process was diffusion controlled, involving one electron. The reversible potential for the redox couple Fe(III)/Fe(II) was found to be more cathodic than the reversible potential for the oxygen evolution by 350 to 400 mV, depending on the solvent composition and on the temperature.</p><p>The electrochemistry of TiO₂ in cryolite-alumina melts was studied by voltammetry. The deposition of titanium on tungsten was found to be a three-electron diffusion controlled process. The deposition peak increased with increasing titanium concentration. In alumina-saturated melts two waves were observed prior to the titanium deposition. The potential difference between the cathodic wave closest to the deposition peak and its corresponding oxidation peak indicated a diffusion controlled process that involved a one-electron charge transfer. However, in cryolite melts a single wave was observed prior to the titanium deposition. It is suggested that these cathodic waves might have been caused by underpotential deposition of titanium, and subsequent alloying with tungsten. It cannot be ruled out that redox reactions take place between tetravalent titanium and the titanium alloyed with tungsten, thereby forming trivalent titanium prior to the metal deposition.</p><p>In order to determine thermodynamic properties of FeAl₂O₄, a solid electrolyte galvanic cell was used. Cryolite was present in the half-cell containing FeAl₂O₄to ensure that alumina of the alpha modification was in equilibrium with FeAl₂O₄. An oxygen ion conducting yttria-stabilised zirconia tube served as the solid electrolyte. The EMF was measured in the rage 1245 to 1343 K. By using literature data at higher temperatures, thermodynamic properties for the reaction Fe(s) + ½O₂(g) + Al₂O₃(s,α) = FeAl₂O₄(s) could be calculated, i.e. ΔHº_1600K = –(270615 ± 1387) J mol^-1 and ΔSº_1600K= -(56.759 ± 0.856) J K^-1 mol^-1. New thermodynamic data for FeAl₂O₄ were also calculated, and a predominance area diagram for solid iron phases at 1293 K was constructed. The standard potential of the redox couple Fe(III)/Fe(II) as a function of the alumina content was derived from the solubility data of Fe(II) obtained in the present work and literature data for Fe(III). When the standard potentials are put into context of the Hall-Héroult process, the results indicate that neither the CO₂/CO anode gas nor the carbon anode itself can oxidise Fe(II) to Fe(III).</p><p>The mass transfer of the impurities Fe, Si and Ti between bath and aluminium in industrial Hall-Héroult cells was investigated. The experiments were performed in several types of cells with prebaked anodes. The impurities were added to the bath in the form of Fe₂O₃, SiO₂ and TiO₂. Bath and metal samples were collected periodically before and after the addition was made. With the criterion that the mass transport was diffusion controlled, a model involving first order reaction kinetics was used to calculate the mass transfer coefficients for transfer into the metal phase. Large scatter were observed in the obtained mass transfer coefficients, but the general trend seemed to be k_Fe > k_Si > k_Ti. By averaging the data obtained, it was found: k_Fe = (10 ± 3) x 10^-6 m s^-1, k_Si = (7 ± 3) x 10^-6m s^-1, and k_Ti = (5 ± 2) x 10-⁶ m s^-1.</p>

<p>Pitches are used on a large scale in the manufacture of carbon anodes for the production of primary aluminium. The role of the pitch is to act as a binder between the petroleum coke grains. The structure of the carbonized pitch binder (pitch coke) has an important impact on the overall performance of the anode. Even though the binder pitch is the minor constituent in an anode, it is impossible to make a good quality anode without a good quality binder pitch.</p><p>Pitch is an extremely complex mixture of numerous, essentially aromatic and heterocyclic compounds derived from pyrolysis of organic material or tar distillation. Upon heat treatment pitches form cokes in relatively high yields. Physical and chemical properties of the anode such as mechanical strength, electrical resistivity, thermal conductivity and resistance towards oxidation by air and CO2 are dependent on the structure of the aggregate material as well as the carbonized binder pitch. The properties of the pitch coke is in turn mainly dependent on the chemical characteristics of the parent pitch.</p><p>Coal-tar pitch is the preferred choice of binder material in anode manufacture today. However, the availability of high quality coal-tar is in decline and at least partial replacement by alternative binder sources will become increasingly important in the future. Due to environmental regulations, petroleum pitches are interesting as they generally have lower PAH emissions than coal-tar pitches during baking. Blends of coal-tar pitches and petroleum pitches are in use today on an industrial scale. The aluminium industry must be prepared to meet the challenges involved in adapting binder pitches from new sources which may be of inferior quality to the pitches available on the market today. An increased understanding of the processes involved in the transformation of a pitch into a coke and the link between raw material composition and properties and the final artifact is thus highly relevant.</p><p>Traditionally, the suitability of a binder pitch for use in anodes, has been defined from parameters like softening point, insolubility in toluene (TI) and quinoline (QI), coke yield, H/C atomic ratio, ash content and density. Although these parameters, which are mostly empirical in nature, give an indication of the pitch quality, more information on the chemical characteristics and carbonization behavior of pitches is certainly valuable. The present work aims to describe and explain the link between “classical” pitch properties, hydrogen transfer properties, information derived from NMR spectroscopy and the structure of the carbonized binder pitch.</p><p>Coal-tar and petroleum pitches pass through a fluid stage during carbonization. In the early stages of carbonization, free radicals are formed due to thermal rupture of C-C and C-H bonds in reactive components. Polymerization occurs mainly via a free radical mechanism leading to molecular size enlargement (aromatic growth)and the formation of oligomeric systems (mesogens). If the intermolecular reactivity of the pitch constituents is too high, extensive cross-linking and a rapid transformation of pitch molecules through polymerization will occur at a relatively low temperature. In this case, either mesophase will not be formed or the growth and coalescence of mesophase will take place under low fluidity/high viscosity conditions leading to a premature solidification of the pyrolysis system. An isotropic coke or a pitch coke of small optical domains will then be formed. On the other hand, if the pitch has a low thermal reactivity, aromatic growth is constrained and the mesogens will have sufficient mobility to stack parallel to each other and establish a liquid crystal system (mesophase). The growth and coalescence of mesophase take place at a higher temperature where the viscosity of the pyrolysis system is at a low level. Eventually, the system will solidify and an anisotropic coke of large well-developed optical domains is formed.</p><p>In particular, the presence of alkyl side chains and oxygenated functional groups are considered to lead to an increased thermal reactivity. If free radicals formed by thermal rupture of bonds in reactive pitch species can be stabilized by hydrogen transfer from within the system, extensive cross-linking at a too early stage is prevented. The initiation, growth and coalescence of mesophase are facilitated and consequently a coke of large well-developed optical domains is formed. Hydroaromatic rings and naphthenic rings in hydroaromatic species are considered to be principal hydrogen donor groups. Oxygen acceptor sites are believed to deplete the supply of donatable hydrogen and leave radicals free to recombine. The thermal reactivity of a pitch is thus dependent on both the amount of reactive species and the ability of the pitch to stabilize free radicals by hydrogen transfer.</p><p>In the present work, the subject of study was five coal-tar pitches and four petroleum pitches. In addition, a QI-free coal-tar pitch supplied by GrafTech International was studied. The pitches were characterized by 1H NMR and 13C NMR spectroscopy, hydrogen transfer properties, elemental analysis and the release of volatiles during carbonization. In addition, the pitches were characterized by more “traditional” pitch parameters like insolubility in quinoline (QI), insolubility in toluene (TI), softening point and coking value. The structure of the carbonized pitches was examined by optical microscopy and X-ray diffraction.</p><p>The hydrogen transfer properties of the pitches were evaluated from their ability to donate hydrogen to an acceptor compound, anthracene, or abstract hydrogen from a donor compound, 1,2,3,4-tetrahydronaphthalene (tetralin). A mixture of pitch and anthracene or tetralin was heat treated in sealed glass tubes filled with argon gas at 400 ºC. Two different heat treatment procedures were tested. In the first, the sample was kept at 400 ºC for 8 hours while in the second, the sample was heated at a rate of 5 ºC/min to 400 ºC with no soaking time. The major hydrogenated products from the reaction between anthracene and pitch were 9,10-dihydroanthracene (DHA) and 1,2,3,4-tetrahydroanthracene (THA). After the reaction, the semi-coke residue was dissolved in carbon disulphide and analyzed by gas chromatography. The hydrogen donor ability (HDa) was calculated from the amounts of DHA and THA formed and expressed as milligrams of hydrogen transferred to anthracene per gram of pitch. For the hydrogen donor ability test, the less severe heat treatment (5ºC/min to 400 ºC, no soaking time) was found to be the most appropriate. The reaction between tetralin and pitch gave one major dehydrogenated product, naphthalene. The hydrogen acceptor ability (HAa) was calculated from the ratio of naphthalene to tetralin as determined by gas chromatography and expressed as milligrams of hydrogen transferred per gram of pitch. For the acceptor ability test, the heat treatment at 400 ºC with 8 hours soaking time was found to be the most appropriate.</p><p>The release of volatiles during carbonization was studied by thermogravimetric analysis. The amount of volatiles released between 300 and 500 ºC (VM300-500)relative to the total amount of volatiles released at 1000 ºC was selected as a parameter reflecting the thermal behavior of pitches during the critical stages of carbonization.</p><p>Carbonization of pitches was performed under inert gas pressure (15 bar) and the green cokes obtained at 550 ºC were studied by optical microscopy. Computerized image analysis was performed to quantify the optical texture. The output parameters from the image analysis were the mosaic index, which is a measure of the optical domain size, and the fiber index, which is a measure of the parallel alignment of optical domains. The green cokes were further heat treated to 1150 ºC and the microstructure of the resulting calcined pitch cokes was characterized by X-ray diffraction.</p><p>The carbon disulphide soluble part of the pitches was investigated by 1H NMR and 13C NMR spectroscopy. Results from elemental analysis of the pitches were used in conjunction with the results obtained from the NMR spectroscopy. The main objective of the NMR analysis was to identify and quantify structures in the pitch which are considered either to increase or decrease the thermal reactivity. The coal-tar pitches were as expected found to be more aromatic than the pitches of petroleum origin. A relationship was found between the aromaticity of the pitches and the H/C atomic ratio as determined from elemental analysis. Elemental analysis is a rapid and convenient method to estimate the aromaticity of pitches. Due to a more hydroaromatic structure, the petroleum pitches were in general found to have a higher estimated concentration of donatable hydrogen which will suppress intermolecular reactivity. However, the petroleum pitches also had a high concentration of alkyl side chains which are generally believed to give increased thermal reactivity. Carbon connected to oxygen could not be distinguished in the NMR spectra. Pitch constituents containing heteroatoms are generally concentrated in the heavier pitch fractions which may not be soluble in carbon disulphide. This could be an explanation for the failure in the detection of aromatic carbon connected to heteroatoms. However,the oxygen content was determined by elemental analysis.</p><p>The pitches could be distinguished due to their ability to donate hydrogen to anthracene or abstract hydrogen from tetralin. The hydrogen donor ability was not found to correlate with the concentration of donatable hydrogen (NMR) which might have been expected. A likely explanation for this apparent inconsistency is that potential donatable hydrogen in reactive pitches will be preferentially consumed by free radicals and oxygenated acceptor sites instead of being transferred to anthracene.</p><p>A correlation between the hydrogen donor (HDa) and acceptor ability (HAa) was not found. This indicates that the two parameters represent two separate properties where both are linked to the thermal reactivity of the pitch. The ratio between the hydrogen donor and acceptor ability, HDa/HAa, was used as a parameter reflecting the thermal reactivity of pitches. Pitches which exhibit a high HDa/HAa ratio (low thermal reactivity) are expected to form an anisotropic coke of large optical domains. On the other hand, pitches with a relatively low HDa/HAa ratio are expected to have a high thermal reactivity and form a more isotropic (small optical domains) coke. Despite the higher concentration of donatable hydrogen, the petroleum pitches were not generally considered to have a lower thermal reactivity than the coal-tar pitches expressed by the HDa/HAa ratio.</p><p>The processes taking place during thermal treatment of pitches are reflected in the release of volatiles. A correlation was observed between the HDa/HAa ratio and the relative amount of volatiles released between 300 and 500 ºC (VM300-500). Thermally reactive pitches exhibiting a low HDa/HAa ratio will have a high activity at low temperatures and release low boiling point molecules and fragmentation species. If on the other hand the pitch has a low thermal reactivity, fragmentation species will be stabilized by hydrogen transfer and retained in the pyrolysis system.</p><p>The resulting thermally stable molecules of relatively low molecular weight may then act as solvating vehicles maintaining a low viscosity in the system and may also be important as hydrogen shuttling agents. When the system has reached a critical stage for mesophase growth and coalescence, these smaller thermally stable molecules (non-mesogens) are eventually released at higher temperatures.</p><p>The petroleum pitches developed cokes of relatively large optical domains (coarse mosaic). A correlation was observed between the HDa/HAa ratio and the mosaic index (size of optical texture) for the petroleum pitches. As expected, a high thermal reactivity (low HDa/HAa ratio) resulted in a pitch coke of small optical domains (high mosaic index). The HDa/HAa ratio was, however, not successful in predicting the size of optical texture in the cokes obtained from the coal-tar pitches. This was mainly due to the influence of QI material on the pitch coke structure. It is recognized that particulate matter (primary QI material) hinders the growth and coalescence of mesophase. This was found for the coal-tar pitches. Scanning electron (SEM) and polarized light microscopy images taken at a high magnification revealed how the QI particles were arranged and clustered around smaller anisotropic domains. The detrimental effect of QI material on the development of anisotropic texture in the resulting coke was demonstrated by comparing the structure of the coke obtained from a QI-free coal-tar pitch and a coal-tar pitch containing QI. The QI-free pitch developed a coke of large optical domains whereas the coke obtained from the pitch containing QI material had mainly a fine mosaic texture (small optical domains).</p><p>However, some large anisotropic domains were present in between the QI clusters. It is also not to be excluded that the QI fraction not only acts physically by obstructing the growth and coalescence of mesophase but may also be chemically active. Findings indicate that the oxygen is concentrated in the QI fraction. Solid QI particles with oxygenated functional groups or heteroatomic structures containing oxygen, which due to their large size are insoluble in quinoline, may act as acceptor sites for hydrogen thus increasing the thermal reactivity.</p><p>The average coherent stacks of the calcined (1150 ºC) pitch cokes was found to consist of between 7 and 8 graphene layers (Lc divided by d002). The average crystallite size (Lc) was fairly similar for all the calcined pitch cokes but significant differences were found. The coal-tar pitches generally developed cokes of slightly higher average crystallite sizes than the pitches of petroleum origin. The microstructure of the coal-tar pitch cokes is probably influenced by the amount and nature of the QI fraction. For the petroleum pitches there was a tendency that a high average crystallite size was connected to a more well-developed structure (larger domains) at the green coke stage.</p><p>The evaluation of hydrogen donor and acceptor abilities provides a rapid and relatively simple method to differentiate pitches which can be linked to the development of structure during carbonization. These properties thus reflect the thermal reactivity of pitches and can be connected to the release of volatiles during pyrolysis. However, for coal-tar pitches the QI content was found to be the most influential factor on the development of optical texture and must be considered in addition to the hydrogen transfer properties. Considerations on thermal reactivity from NMR spectroscopy and elemental analysis were found to generally support the results from the hydrogen donor and acceptor ability tests.</p>

<p>The main objectives of the thesis work were: (1), to study the oxidation of methanol and formic acid on platinum electrodes by employing conventional and advanced electrochemical methods, and (2), to develop membrane electrode assemblies based on polybenzimidazole membranes that can be used in fuel cells up to 200 °C.</p><p>D.c. voltammetry and a.c. voltammetry studies of methanol and formic acid on polycrystalline platinum in sulphuric acid electrolyte were performed to determine the mechanism and kinetics of the oxidation reactions.</p><p>A combined potential step and fast cyclic voltammetry experiment was employed to investigate the time dependence primarily of methanol oxidation on platinum. Charge measurements clearly demonstrated the existence of a parallel path at low potentials and short times without formation of adsorbed CO. Furthermore, experimental results showed that only the serial path, via adsorbed CO, exists during continuous cycling, with the first step being diffusion controlled dissociative adsorption of methanol directly from the bulk electrolyte. The saturation charge of adsorbed CO derived from methanol was found to be significantly lower than CO derived from formic acid or dissolved CO. This was attributed to the site requirements of the dehydrogenation steps, and possibly different compositions of linear, bridged or multiply bonded CO. The coverage of adsorbed CO from formic acid decreased significantly at potentials just outside of the hydrogen region (0.35 V vs. RHE), while it did not start to decrease significantly until about 0.6 V vs. RHE for methanol. Adsorbed CO from dissolved CO rapidly oxidized at potentials above about 0.75 V due to formation of platinum oxide.</p><p>Data from a.c. voltammograms from 0.5 Hz up to 30 kHz were assembled into electrochemical impedance spectra (EIS) and analyzed using equivalent circuits. The main advantages of collecting EIS spectra from a.c. voltammetry experiments are the ability to directly correlate the impedance spectra with features in the corresponding d.c. voltammograms, and the ability to investigate conditions with partially covered surfaces that are inaccessible in steady-state measurements.</p><p>A variety of spectral types were observed, and for methanol these showed only a single adsorption relaxation aside from the double-layer/charge-transfer relaxation, though some structure in the phase of the latter relaxation hints at another process. The charge-transfer resistance showed Tafel behaviour for potentials in the rising part of the oxidation peak consistent with a one-electron process in the rate-determining step. The rate limiting step was proposed to be the electrochemical reaction between adsorbed CO and OH at the edge of islands of OH, with competition between OH and CO adsorption for the released reaction sites. Only a single adsorption relaxation in methanol oxidation was observed, implying that only one single coverage is required to describe the state of the surface and the kinetics. It was assumed that this single coverage is that of OH, and all the surface not covered with OH is covered with CO so that the coverage of CO is not an independent variable. Inductive behaviour and negative relaxation times in the methanol oxidation were attributed to nucleation and growth behaviour. Linear voltammetry reversal and sweep-hold experiments also indicated nucleation-growth-collision behaviour in distinct potential regions, both in the forward and reverse potential scan for methanol oxidation on platinum.</p><p>In both methanol oxidation and formic acid oxidation, a negative differential resistance (NDR) was observed in the potential regions that possess a negative d.c. polarization slope, and was attributed to the formation of surface oxide which inhibited the oxidation of methanol or formic acid.</p><p>EIS spectra for formic acid clearly showed the presence of an additional low frequency relaxation at potentials where we expect adsorbed dissociated water or platinum oxide to be present, implying that more than one single coverage is required to describe the state of the surface and the kinetics. Two potential regions with hidden negative differential resistance (HNDR) behaviour were identified in the positive-going sweep, one prior to platinum oxide formation, assumed to involve adsorbed dissociated water, and one just negative of the main oxidation peak, assumed to involve platinum oxide. Oscillatory behaviour was found in the formic acid oxidation on platinum by adding a large external resistance to the working electrode circuit, which means that there is no longer true potentiostatic control at the interface. By revealing the system time constants, impedance measurements can be used to assist in explaining the origin of the oscillations. In the case of formic acid, these measurements showed that the oscillations do not arise from the chemical mechanism alone, but that the potential plays an essential role.</p><p>Preparation and optimization of gas-diffusion electrodes for high temperature polymer electrolyte fuel cells based on phosphoric acid doped polybenzimidazole (PBI) membranes was performed. This fuel cell allows for operating temperatures up to 200 °C with increased tolerance towards catalytic poisons, typical carbon monoxide. In this work we employed pure hydrogen and oxygen as the fuel cell feeds, and determined the optimum morphology of the support layer, and subsequently optimized the catalytic layer with respect to platinum content in the Pt/C catalyst and PBI loading. A smooth and compact support layer with small crevices and large islands was found to be beneficial with our spraying technique in respect to adhesion to the carbon backing and to the catalyst layer. We found that a high platinum content catalyst gave a significantly thinner catalyst layer (decreased porosity) on both anode and cathode with superior performance. The PBI loading was found to be crucial for the performance of the electrodes, and a relatively high loading gave the best performing electrodes.</p>

<p>This dissertation deals with the unintended sideeffects of utilizing resources and causing environmental load.</p><p>The intention of this report is to contribute to a leap improvement in enviornmental performance of industrial products. The results of the dissertation are directed towards companies that want to eliminate, or at best reduce the unintended side effects of their activities and industrial products.</p><p>The results are directed to the research community as a contribution to research on the effect of a shift from product-based to function-based economic system, and the potential improvement in environmental performance this may imply.</p><p>The main contribution of this dissertation is a strategy for developing product service combinations and thereby closing material loops of industrial products. The result is based upon product development models, creative tools and performance measurement combined with the resolution of the basic physical contradiction into a four step strategy for a long term shift of a business model based on product service combinations instead of products only. The fourstep strategy involves traditional product development models with focus on holistic lifespan thinking. Furthermore, emphasize is made to the need to include the creative tools to conquer psychological inertia and barriers for leap improvements in environmental performance.</p><p>The strategy is mainly based upon logical resoning and thought experiments and combined with observations in industry. It is difficult to give a final proof of the usefulness of the strategy, due to the time needed to perform such a strategic shift in the core activities of a business.This research has furthermore contributed to</p><p>• a clarification of the source of environmental load during the meetings between product and product life system where any action to reduce the original load will result in load of its own which means that the fundamental cause of load is still not resolved. Any attempt to remove the fundamental cause of side-effect is a true physical contradiction which violates the second law of thermodynamics.</p><p>• a clearer understanding of the need not only to integrate the different disciplines across a company’s operations, but also integrate along the value chain to capture the valuable information which arise during meetings between product and product life systems.</p><p>• a deeper understanding of the need to include creative techniques into the early phases of product development proejcts where dispositions for subsequent project phases and subsequent product life phases are disposed and locked against subsequent major modifications. Creative techniques contribute to the break out of existing mind patterns and contribute to the creation of solutions which reduce the business-as-usual pattern which acts as a barrier to leap improvement in environmental performance</p><p>• a clarification of the need to identify and develop the company’s environmental perspective. The need to develop strategies for improvingenvironmental performance of company internal processes, product systems and systemic networks of actors along the value chain is vital to achieve leap improvements in environemntal performance.</p><p>• a deeper understanding of the barriers to overcome to transform products-based business to service-based business.</p>

<p>Welding is the main joining method used in shipbuilding. A multi-electrode submerged arc welding is usually applied to long joints of massive components since the early 1950s.</p><p>The problem of welding stresses and deformations arose almost simultaneously with the introduction of welding as a joining method. In 1892 Slavianov, in his works, mentioned about "harmful stresses in metal" appearing during welding. Despite tremendous development in welding technology since that time, this problem is still present.</p><p>This dissertation presents the development of an experimental, numerical and analytical approach to the analysis of weldability. Focus is placed on the investigation of transient and residual welding stresses and distortions in thick-walled ship hull structures. The investigation mostly relies on the finite element analysis. Some recommendations about mitigation techniques for reducing their negative influence on welded structure efficiency are given.</p><p>A number of simulation systems for the sequentially coupled thermo-mechanical analysis of welding process, taking into account the welding conditions during the butt welding of thick-walled steel panels, are developed. Two welding techniques are investigated. The three-electrode one-pass welding process and the one-electrode multipass process are compared in terms of the joint characteristics and transient stresses and deformations.</p><p>The accuracy of each finite element models is evaluated based on experimental results and the results of the analytical solution.</p><p>Several techniques allowing to reduce residual stresses and deformations are investigated. Both, obtained results and governing phenomena, are studied and explained based on physical principles.</p><p>The first part of the thesis is a significant part of the work. Its purpose is a deep analysis of the thermo-mechanics of welding allowing better understanding of the complicated phenomena.</p>

<p>The main part of this work has been a literature survey, reviewing scientifical reports forinformation on how steel cleanness is evaluated today, and also how the steel cleanness is related tothe fatigue performance of clean steels.</p>

<p>The general trend in the car body manufacturing industry is towards low-series production and reduction of press lubricants and car weight. The limited use of press lubricants, in combination with the introduction of high and ultra-high strength sheet materials, continuously increases the demands of the forming tools. To provide the means of forming new generations of sheet material, development of new tool materials with improved galling resistance is required, which may include tailored microstructures, introducing of specific(MC, M(C,N))carbides and nitrides, coatings and improved surface finish. In the present work, the wear mechanisms in real forming operations have been studied and emulated on a laboratory scale by developing a test equipment. The wear mechanisms identified in the real forming process, were distinguished into a sequence of events consisting of initial local adhesive wear of the sheets resulting in transfer of sheet material to the tool surfaces. Successive forming operations led to growth of the transfer layer and initiation of scratching of the sheets. Finally, scratching changed into severe adhesive wear, associated with gross macroscopic damage. The wear process was repeated in the laboratory test-equipment in sliding between several tool materials, ranging from cast iron to conventional ingot cast tool steels to advanced powder metallurgy tool steel, against dual-phase carbon steel sheets. By use of the test-equipment, selected tool materials were ranked regarding wear resistance in sliding against ferritic-martensitic steel sheets at different contact pressures.</p><p>Wear in sheet metal forming is mainly determined by adhesion; initially between the tool and sheet surface interaction and subsequently, after initiation of material transfer, between a sheet to sheet contact. Atomic force microscopy force curves showed that adhesion is sensitive to both chemical composition and temperature. By alloying of iron with 18wt.% Cr and 8wt.% Ni, alloying in itself, or changes in crystal structure, led to an increase of 3 times in adhesion at room temperature. Hence, alloying may be assumed a promising way for control of adhesive properties. Additionally, frictional heating should be controlled to avoid high adhesion as, generally, adhesion was found to increase with increasing temperature for all investigated materials.</p>

<p>Syftet med examensarbetet var att undersöka manganhaltens inverkan på skärbarheten och de mekaniska egenskaperna i varmarbetsstål Dievar samt kontrollera och undersöka hypotesen<em> </em>att material med låga Ac1 temperaturer maskinbearbetas svårare än material med högre temperaturer. </p><p>Skärbarhet hos Dievar med olika Mn-halt från 0,084 till 1,59 vikts% studerades i härdat tillstånd med ett pinnfräsningstest. Skärbarheten karakteriserades genom mätning av verktygslivslängd och skärkrafter. Verktygslivslängd bestämdes av fasförslitningsutvecklingen på verktyget. Förslitningsmekanismer studerades på verktygets spån- och släppningssidor med hjälp av svepelektronmikroskop (SEM). Dragprov vid rums- och förhöjd temperatur genomfördes för att studera mangans inverkan på hållfasthetsegenskaper hos Dievar. Mikrostrukturen av stålen i härdat och anlöpt tillstånd undersöktes i SEM. Ac1 temperatur i stålen uppmättes med dilatometer.</p><p>Mangan visade sig ha en positiv inverkan på skärbarheten i Dievar. Verktygets livslängd var två gånger längre vid pinnfräsning av Dievar 1,59 vikts% Mn i jämförelse med Dievar 0,084 och 0,27 vikts% Mn. Mer påkletningsbenägna stål med lägre Mn-halt orsakade mer adhesiv nötning och urflisning av fräsens skäregg. Detta ledde till att förslitningen utvecklades hastigare under bearbetningen av Dievar med lägre Mn-halt.</p><p>De uppmätta skärkrafterna under bearbetning förklarade inte skillnaden i skärbarheten mellan Dievar med olika Mn-halt; skärkrafter var lika i alla material.</p><p>Dievar med högre Mn-halt innehöll mindre primära molybdenrika karbider än Dievar med lägre Mn-halt. Detta berodde på att manganet minskade Ac1 temperaturen i Dievar.</p><p>Mn-halten i Dievar påverkade inte hållfasthetsegenskaperna vid rumstemperatur men visade en tendens att minska stålets hållfasthet vid hög temperatur.</p><p>De genomförda undersökningarna bekräftade inte hypotesen att material med lägre Ac1 temperaturer har sämre maskinbearbetbarhet än material med högre temperaturer. Dievar 1,59 vikts% Mn hade betydligt lägre Ac1 temperatur än andra Dievar-material samt modifierat Orvar men visade sig vara lättare att bearbeta.</p> / <p>The aim of the study was to investigate influence of manganese content on the machinability and mechanical properties of a hot-work tool steel Dievar and verify a hypothesis that materials with low Ac1 temperatures are more difficult to machine than steels with higher Ac1 temperatures.</p><p>Machinability of Dievar with varying manganese content from 0,084 to 1,59 wt% was investigated in the hardened condition in the milling operation. The machinability of the steels was characterized by measuring tool life and cutting forces during machining. The tool life was estimated by measuring flank wear on the tools. Wear mechanisms were investigated on the clearance and rake faces of the tools by SEM. Tensile tests at room and elevated temperatures were carried out to examine the manganese influence on the mechanical properties of Dievar. Microstructure of the steels in hardened and tempered condition was investigated by SEM. Dilatometer tests were done to determine the Ac1 temperature for the steels.</p><p>Manganese content showed to have a positive effect on the machinability of Dievar. Two times longer tool life was reached when end milling Dievar 1,59 wt% Mn comparing to end milling Dievar 0,084 and 0,27 wt% Mn. More adhesive wear and chipping were observed on the tools after end milling the lower manganese containing steels. This resulted in more progressive wear and shorter tool life during machining of these steels.</p><p>The measured cutting forces could not be related to the difference in machinability of the steels with different manganese content. The generated cutting forces were similar for all the tested steels.</p><p>Dievar with higher manganese content contained less primary molybdenum-rich carbides in the microstructure. It was related to the lower Ac1 temperature of Dievar 1,59 wt% Mn comparing to the lower manganese containing steels.</p><p>The manganese content showed no influence on the tensile properties of Dievar at room temperature and a tendency to a slight decrease in yield and ultimate strength at the elevated temperature.</p><p>The machinability tests carried out in the present study did not confirm the hypothesis that materials with low Ac1 temperatures have poor machinability.  Dievar 1,59 wt% Mn had much lower Ac1 temperatures than the other Dievar steels and the modified Orvar steel but showed to have an improved machinability compared to the others.</p>

Magnetorheological (MR) rubber materials are the solid analogue of magnetorheological fluids; i.e. their rheological properties can be controlled continously, rapidly, and reversibly by an applied magnetic field. They consist of magnetically polarisable particles in an elastomer matrix and they can be made to respond to changes in their environment; hence, they are considered as "smart" materials. Examples of potential applications for these materials are adaptive tuned vibration absorbers, stiffness-tuneable mounts and suspensions, and automotive bushings. The purpose of this work was to increase the knowledge relating to magnetorheological materials for damping applications. The materials should exhibit a large response to an applied magnetic field, and have good mechanical and long-term properties. MR rubber materials were made from nitrile, natural and silicone rubber, with irregularly shaped iron particles several micrometres in size. The particles were not aligned by a magnetic field prior to the vulcanisation; hence, the materials can be considered to be isotropic. These materials show a large MR effect, i.e. an increase in the shear modulus when a magnetic field is applied, although the particles are not aligned within the material. This is explained by the low critical particle volume concentration (CPVC) of such particles. Similar behaviour can be obtained with materials containing carbonyl iron, if the particles are aggregated so that they behave like large irregular particles. The iron particle concentration must be very close to the CPVC in order to obtain a large MR effect without alignment of the particles. The absolute MR effect (MPa) in an isotropic MR rubber material with large irregular iron particles is independent of the matrix material, and the relative MR effect (%) can thus be increased by the addition of plasticisers. However, the obtainable effect is limited by the reinforcement of the particles and by friction between the particles. Therefore, it is very difficult, if not impossible, to achieve an MR effect larger than 60%. Other ways of increasing the MR effect are to increase the strength of the magnetic field, although the materials saturate magnetically at high field strengths, or to use small strain amplitudes. The strong strain amplitude dependence of the MR effect suggests that MR rubber materials are most suitable for low amplitude applications, such as sound and vibration insulation. Measurements at frequencies within the audible frequency range show that this is a promising application for MR rubber materials. The incorporation of large amounts of iron into the rubber matrix decreases the oxidative stability dramatically. This is probably due to iron oxides on the surface of the particles, and to the fact that the oxidation rate is enhanced by iron ions, which are able to diffuse into the matrix. Standard antioxidants do not provide sufficient stabilisation for MR rubbers. Thus, proper stabilisation systems have to be found in order for these materials to be successful in applications.

The general trend in the car body manufacturing industry is towards low-series production and reduction of press lubricants and car weight. The limited use of press lubricants, in combination with the introduction of high and ultra-high strength sheet materials, continuously increases the demands of the forming tools. To provide the means of forming new generations of sheet material, development of new tool materials with improved galling resistance is required, which may include tailored microstructures, introducing of specific(MC, M(C,N))carbides and nitrides, coatings and improved surface finish. In the present work, the wear mechanisms in real forming operations have been studied and emulated on a laboratory scale by developing a test equipment. The wear mechanisms identified in the real forming process, were distinguished into a sequence of events consisting of initial local adhesive wear of the sheets resulting in transfer of sheet material to the tool surfaces. Successive forming operations led to growth of the transfer layer and initiation of scratching of the sheets. Finally, scratching changed into severe adhesive wear, associated with gross macroscopic damage. The wear process was repeated in the laboratory test-equipment in sliding between several tool materials, ranging from cast iron to conventional ingot cast tool steels to advanced powder metallurgy tool steel, against dual-phase carbon steel sheets. By use of the test-equipment, selected tool materials were ranked regarding wear resistance in sliding against ferritic-martensitic steel sheets at different contact pressures. Wear in sheet metal forming is mainly determined by adhesion; initially between the tool and sheet surface interaction and subsequently, after initiation of material transfer, between a sheet to sheet contact. Atomic force microscopy force curves showed that adhesion is sensitive to both chemical composition and temperature. By alloying of iron with 18wt.% Cr and 8wt.% Ni, alloying in itself, or changes in crystal structure, led to an increase of 3 times in adhesion at room temperature. Hence, alloying may be assumed a promising way for control of adhesive properties. Additionally, frictional heating should be controlled to avoid high adhesion as, generally, adhesion was found to increase with increasing temperature for all investigated materials.