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. 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. 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.

The thesis treats roll pass design in wire rod rolling of stainless steel for sequences and series built up by two-symmetrical grooves. It is focused on predicting rolling flexibility, also called working range, as well as product quality. For analysing the flexibility a computer program has been developed. The minimum and maximum roll gap and corresponding bar areas for series of grooves including "oval", "round", "false round", "square" and "diamond" shapes are calculated. Six pass designs used in Swedish mills are analysed. Full-scale rolling is compared with laboratory experiments for the square-oval and false round (round)-oval series. The false round-oval series offers the largest working range and that the flexibility is smaller for pass sequences designed for high reductions. The false round-oval series are also acknowledged as a series for high quality steels and are usually better than the square-oval series having a tendency for defect formation. The thesis also includes high-speed rolling of wire rod in blocks. Here interstand tensions are utilised in order to keep the process stable. For obtaining the required dimensional tolerances of the product they are kept as low as possible. However interstand tensions could be used in order to increase the working range and move the product range towards smaller wire cross sections. For analysing this possibility, a narrow spread technology is utilised. At present time a practical problem is referred to the fixed gearings in the common blocks, which require a certain and given level of interstand tensions and corresponding reductions. This problem can however be solved by means of new block design and modern process control technology. Roll stands can be separately driven and controlled at very high speeds. Thus the eight stand blocks can be subdivided into four plus four passes blocks with a cooling line between enabling also higher productivity without violating the product quality because defect formations caused by a too high rolling temperature. The true working range of a series for a specific steel grade is however not only dependent on the possible spectrum of wire dimensions that can be obtained but might also depend on its ability to decrease or eliminate defects such as surface cracks. Thus, the behaviour of artificial V-shaped cracks in the longitudinal direction has been investigated and compared for the square-oval and false round (round)-oval series mentioned above. In agreement with other research works it was established that efficient rolling conditions for reducing the cracks are obtained when the cracks open up at the same time as their depth is reduced. If the V-shaped crack is closed by contact between its oxidized side surfaces the rolling schedule is not optimal for getting a high quality product. A deeper understanding of the experimental results was obtained by means of an FE-analysis

In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF2single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration technique. The phase compositions and microstructures of the alloys were analysed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). In the Cr-C system, the Gibbs energy of formation of Cr3C2 were obtained from ElectroMotive Force (EMF) measurements conducted in the temperature range 950-1150 K. The values of the enthalpy of formation of Cr3C2 were evaluated by the third-law method. The ground-state energy of the hypothetic end-member compound CrC3, in the bcc structure at 0 K, was calculated by use of the Ab-initio method. Based on the obtained results the Cr-C system was reassessed by use of the CALPHAD approach. In the Fe-Cr-C system, 16 different alloys were quenched at 1223 K and their equilibrium phases identified by XRD. The experimental results show that the substitution of Cr by Fe in the (Cr,Fe)7C3 carbide changes the lattice parameters of the phase. A slight decrease of the lattice parameters with an increase in the Fe content was established. The lattice parameters of the γ-phase in the Fe-Cr solid solution did also show a decrease with an increase of the Fe content. The activities of chromium in Fe-Cr-C alloys were investigated in the temperature range 940-1155 K. The activity of chromium decreases with an increase in the Fe content when the ratio of C/(Cr+C) was constant. It was also established that the activity of chromium decreases with an increase of the carbon content when the iron content was constant. The experimental results obtained were compared with the data calculated by use of the Thermo-Calc software. In the Mn-Ni-C system the phase relationships were investigated at 1073 K as well as at 1223 K. The experimental results obtained showed that the site fraction of Ni in the metallic sublattice of the carbides M23C6, M7C3 and M5C2 (M=Mn and Ni) was quite low (approximately 2~3 percent). The activities of manganese in Mn-Ni-C alloys were investigated in the temperature range 940-1165 K. The three-phase region γ/M7C3/graphite was partly constructed at 1073 K. In the Mn-Ni-C-N system, nitrogen was introduced into Mn-Ni-C alloys by equilibrating with N2 gas. It was established that the solubility of nitrogen in the investigated alloys was effected by the carbon content, and that a (Mn,Ni)4(N,C) compound was formed in the nitrided alloys. EMF measurements were performed on Mn-Ni-C-N alloys in the temperature interval 940-1127 K. The addition of nitrogen to Mn-Ni-C alloys was found to decrease the activity of manganese. The negative effect of nitrogen on the activity of manganese was found to decrease as the carbon content increased. Keywords: Thermodynamic activity; Galvanic cell technique; Transition metal carbides; Transition metal nitrides; Phase equilibrium; Thermodynamics; Differential thermal analysis; Scanning electron microscopy; Transmission electron microscopy; Ab-initio calculations; CALPHAD approach;

The main questions today concerning thermal systems are their economical and environmental impacts. These entities are generally, at present, assessed on the basis of operation performances of newly installed/designed systems, during an assumed lifetime period. While this is the common way of perceiving thermal systems, performance-over-time will change as an effect of degradation, and not solely of different operation scenarios. How and to what extent is the question that needs assessing in order to evaluate if these changes will jeopardise the intended system performance requirement, hence service life (SL). The lack of knowledge/approaches and tools for assessing durability and performance-over-time of thermal systems complicates the task of incorporating these aspects in engineering. In turn, this pro-active assessment and analysis is in line with today’s performance based directives, laws and regulations; of which the working life is an essential part. The durability of materials, components and systems is not a topic that is an end in itself, but becomes a vital part in a comprehensive perspective as sustainability. The lifetime performance assessment of thermal systems, as presented in this thesis, shows that it is a vital part of the R&D in the quest of sustainable energy/thermal systems and energy use. This thesis gives knowledge to the thermal (energy) system/technology R&D and engineering sector, regarding durability and lifetime performance assessment methodologies; but also to the durability of construction works sector, regarding the needs for assessing lifetime performance of materials and components in relation to system performance. It also presents descriptions of requirements on construction works. Specifically, the studies presented in the thesis show how durability and lifetime performance assessment of thermal systems may be sought, with knowledge on: methodologies, exposure test set-ups, modelling and the attainment and use of adequate tools. The main focus is on performance-over-time modelling, tying material/component degradation to altered thermal performance, thereby attaining performance-over-time assessment tools to be used in order to incorporate these aspects when engineering thermal systems; hence enabling the forecasting of SL. The presented work was predominantly done in association to the EU project ENDOHOUSING. The project developed a solar-assisted heat pump system solution, with heat storage, to provide the thermal energy to meet space heating, cooling and hot water requirements for domestic houses in different regions of the EU. The project constituted the platform for the work presented in this thesis, thereby outlining the main context with studies on durability and lifetime performance of: flat plate solar collectors ground heat sources/storages and interaction with a heat pump system evaluation of the ENDOHOUSING solar-assisted heat pump system The thesis also presents a study of SL prediction and estimation of district heating distribution networks (an additional thermal system application). In this particular context, the Factor Method is proposed as a methodology. The main issue of lifetime performance of thermal systems is how and to what extent performance reduction in individual materials or components influence the overall system performance, as the essence of energy/thermal system sustainability is system performance. / QC 20100810

Although the metallurgical industry has made great strides in the reduction of unwanted emissions to the atmosphere as a result of production processes, significant challenges still exist. From a global perspective, even large reductions in emissions per produced ton become immaterial when considering that the total world production of metals continues to increase. Two such particularly hazardous emissions are sulfur dioxide, primarily from copper ore roasting, and mercury, which has had increasing emissions from the steel industry in recent years. Both pollutants have severe consequences for the environment and also for human health. The primary motivations of this work have hence been: (1). to study sulfate formation on soot from sulfur dioxide emissions reacting with ozone and H2O in the vapor phase and (2). to study factors involving the behavior of mercury adsorption on metal surfaces involved in steelmaking, in order to further the understanding of select emissions from scrap-based steelmaking. Gas phase experiments were conducted to examine the heterogeneous oxidation of sulfur dioxide on soot in the presence of ozone and water vapor. The sulfur dioxide oxidation into sulfate was quantified using a particle-into-liquid sampler coupled with ion chromatography to measure the sulfate formation at atmospheric pressure. Water vapor, ozone and sulfur dioxide concentrations were controlled. Due to the ozone oxidation, multilayer adsorption of sulfur dioxide on soot, as well as sulfate formation and physisorption on secondary surface layer sites were observed. The exposure also caused the soot to become hydrophilic, due to the sulfur dioxide adsorption and also likely the formation of carboxyl groups on the surface. No significant increase in sulfate formation was observed at ozone concentrations above 1000 ppm. The effects of common surface contaminants such as oxygen and chlorine were examined on the metal surfaces, as well as the impact of changes in temperature, with controlled conditions using thermal desorption auger electron spectroscopy. It was established that low temperatures (82 K through 111 K) were conducive to mercury adsorption, wherein physisorption and subsequent lateral mercury interactions in mercury adlayers occurred. Chlorine appeared to favor mercury uptake, as determined by the increased mercury coverage at low temperatures on polycrystalline iron, copper and zinc. Oxygen, however, was found to be an inhibitor of mercury, most notably at room temperature. It was surprising to establish that no mercury adsorbed on zinc surfaces at room temperature and only on polycrystalline samples at low temperature. The mercury signal intensity increased up to the limit of the melting temperature for iron systems, on the oxidized copper surface and the polycrystalline zinc surfaces, prior to desorption from the surfaces. It is suggested that this is due to a rearrangement of mercury atoms on the surface at increasing temperatures, whereas at 85 K, mercury adhered to its initial adsorption position. In other words, mercury wet these surfaces on annealing, transitioning from an islanded surface at low temperature to a smooth layer before desorption. Based on these results, it was concluded that the mercury bond to the oxidized surface was weakened compared to clean copper. Furthermore, it is proposed that a surface phase transition occurred on polycrystalline zinc prior to desorption. No such transition was observed on iron. Activation energies of desorption were calculated for the relevant metal surfaces. It was established that clean iron had the highest activation energy of desorption. The large bond strength between mercury and iron may account for the highest desorption temperature of the iron systems. Zinc and copper had similar activation energies and desorption temperatures, which were respectively lower than that of iron. X-Ray Photoelectron and Auger Electron Spectroscopy were used to ascertain common surface contamination, i.e. chlorine, oxygen and sulfur, which affected mercury adsorption. Laser Ablation Inductively Coupled Plasma Time of Flight Mass Spectrometry was used to determine the depth of mercury adsorption on the samples. The technique also showed that the samples contained mercury in the surface layers. Accompanied by the rising demand for metals is the increase in emissions from metals manufacturing. Moreover, it is critical to minimize sulfur dioxide emissions as particulates from soot continue to be released in the atmosphere. For scrap-based steelmaking, monolayer mercury adsorption on clean iron and copper at room temperature are significant results. With the rising use of electronic devices in vehicles, the sorting of scrap becomes increasingly important. Mercury not adsorbing on zinc at room temperature is also of relevance as it disproves the theory of increased mercury adsorption with the increased use of galvanized scrap in summer conditions. However, the low temperature studies showed multilayer adsorption of mercury on iron, zinc and copper, which has relevance for the reported temporal variations of mercury deposition in arctic regions. Keywords: mercury, iron, zinc, sulfur dioxide, adsorption, pollution, thermal desorption, polycrystalline, surfaces, spectroscopy / QC 20120326

Magnetic properties of selected compounds and superlattices have been experimentally studied using SQUID (superconducting quantum interference device) and VSM (vibrating sample magnetometer) magnetometry, neutron diffraction and Mössbauer spectroscopy measurements combined with theoretical ab initio calculations. The magnetic compounds (Fe1-xMx)3P, M=Co or Mn have been studied extensively. It was found that Co can substitute Fe up to x=0.37. Increasing the Co content leads to a reduction of the Curie temperature and the magnetic moment per metal atom. Mn can substitute Fe up to x=0.25 while Fe can be substituted into Mn3P to 1-x=0.33. On the iron rich side, the drop in Curie temperature and magnetic moment when increasing the Mn content is more rapid than for Co substitution. On the manganese rich side an antiferromagnetic arrangement with small magnetic moments was found. The interlayer exchange coupling and the magnetocrystalline anisotropy energy of Fe/V superlattices were studied. The coupling strength was found to vary with the thickness of the iron layers. To describe the in-plane four-fold anisotropy, the inclusion of surface terms proved necessary. The in-plane four fold anisotropy was also studied in a series of Fe/Co superlattices, where the thickness of the Co layers was kept thin so that the bcc structure could be stabilized. Only for samples with a large amount of iron, the easy axis was found to be [100]. The easy axis of bulk bcc Co was therefor suggested to be [111].

<b>En metod för dispersiv analys av försök med delad hopkinsonstång tillämpad på provning av granved vid hög töjningshastighet</b> Syftet var att etablera en metod för att studera sambandet mellan spänning och töjning för granved vid hög töjningshastighet. Detta åstadkoms genom att anpassa och något vidareutveckla tekniken med delad hopkinsonstång ("Split Hopkinson Pressure Bar", SHPB). Vanligtvis har hopkinsonstavar cirkulärt tvärsnitt och en diameter som är mycket mindre än de verksamma våglängderna. Under sådana förhållanden är vågutbredningen i stängerna approximativt ickedispersiv, och en endimensionell (1D) vågutbredningsmodell kan användas. När det, som är fallet i denna studie, däremot inte kan säkerställas att stängernas tvärdimensioner är små i förhållande till våglängderna, är en helt igenom 1D vågutbredningsmodell otillräcklig, och tvärsnittets geometri, vilken var kvadratisk i denna studie, måste beaktas. Därför utvecklades med hjälp av Hamiltons princip en approximativ 3D vågutbredningsmodell för stänger med godtyckligt tvärsnitt. Modellen ger ett dispersionssamband (vågtal som funktion av vinkelfrekvens) samt medelvärden för förskjutningar och spänningar över gränsytorna mellan stänger och provstav. En kalibreringsprocedur utvecklades också. Provning av granved genomfördes vid hög töjningshastighet (omkring 103 s-1) med den anpassade SHPB-tekniken, samt för jämförelse vid låg (8×10-3 s-1) och måttlig (17 s-1) töjningshastighet med en servohydraulisk provningsmaskin. Fukthalterna i veden motsvarade ugnstorr, fibermättnad och fullständig mättnad, och proven utfördes i radiell, tangentiell och axiell riktning i förhållande till trädets stam. För vart fall utfördes fem försök vid rumstemperatur. Resultaten visar töjningshastighetsberoendet för sambandet mellan spänning och töjning för granved under alla studerade förhållanden. / The aim was to establish a method for studying the relation between stress and strain in spruce wood at high strain rate. This was achieved by adapting and somewhat further developing the split Hopkinson pressure bar (SHPB) technique. Hopkinson bars usually have a circular cross-section and a diameter much smaller than the operative wavelengths. The wave propagation in the bar is then approximately non-dispersive and a one-dimensional (1D) wave propagation model can be used. When, as in this study, it is not certain that the transverse dimensions of the bars are small in relation to the wavelengths, a solely 1D wave propagation model is insufficient and the geometry of the cross-section, which was square in this study, must be taken into account. Therefore, an approximate 3D wave propagation model for bars with arbitrary cross-section was developed using Hamilton's principle. The model provides a dispersion relation (wavenumber vs. angular frequency) and average values for displacements and stresses over the bar/specimen interfaces. A calibration procedure was also developed. Tests on spruce wood specimens were carried out at a high strain rate (about 103 s-1) using the adapted SHPB technique, and for comparison at low (8×10-3 s-1) and medium (17 s-1) strain rates using a servohydraulic testing machine. The moisture contents of the wood specimens corresponded to oven dry, fibre saturated and fully saturated, and the testing was performed in the radial, tangential and axial directions relative to the stem of the tree. In each case, five tests were run at room temperature. The results show the strain rate dependence of the relation between stress and strain for spruce wood under all conditions studied.

In recent years, surface engineering techniques have been developed in order to improve the tribological performance in many industrial applications. In sheet metal forming processes, the usage of liquid lubricants can be decreased by using self lubricated tribo surfaces which will result in more environmentally friendly workshops. In the present work two different concepts, i.e. the deposition of thin organic coatings on the steel sheet and PVD coatings on the tool, have been evaluated. The sheet materials investigated include Zn and 55%Al-Zn metal coated steel sheet, which in general are difficult materials to form under dry conditions since they are sticky and thus have a high tendency to adhere to the tool surface. The PVD coatings include CrN, TiN and various DLC coatings. The work comprises tribo testing and post test characterisation using surface analytical techniques in order to evaluate the tribological properties of the tribo surfaces. The tribological tests of different tribo couples were conducted by using modified scratch testing and ball-on-disc testing. From these test results different friction and wear mechanisms have been identified. The deposition of thin organic coatings on the steel sheet metal has been found to be promising in order to control the friction and to avoid metal-metal contact resulting in galling. However, it has been found that the tribological characteristics of organic coated steel sheet are strongly influenced by coating chemical composition, the substrate surface topography and the coating thickness distribution. The performance of the PVD coatings depends mainly on the chemical composition and topography of the coated surface. By choosing PVD coatings such as diamond like carbon (DLC) low and stable friction coefficients can be obtained in sliding contact against Zn. Surface irregularities such as droplet-like asperities may cause an initial high friction coefficient. However, after a running in process or by polishing the PVD coating low friction coefficients can be obtained resulting in a stable sliding contact. The combination of imaging (optical profilometry, LOM, SEM) and chemical analytical techniques (EDS, AES, ToF-SIMS) gave valuable information concerning the friction and wear properties of the tribo surfaces investigated.

The concept of photonic crystals was born in the late 1980's when two important letters were published that showed the possibility to control light propagation by a periodic structure. A photonic crystals consists of two or more materials with different dielectric functions periodically arranged on the length scale of light. If the conditions are favorable, a gap will open in the dispersion relation, often called photonic band structure, and electromagnetic waves with frequency in the gap range cannot propagate through the photonic crystal. In this thesis, mainly two types of structures and their properties have been numerically investigated: two-dimensional structures that are either square or triangular. In the calculations, both dielectric and polaritonic materials have been used. Polaritonic materials have an interval of high reflectance in the IR range, due to strong lattice resonances. Within such an interval, the real part of the dielectric function is negative, which causes a metal-like behavior. A polaritonic material, BeO has been introduced in photonic crystals to study the coexistence of structure and polaritonic gaps. Band structures and for some cases transmission spectra have been calculated to study the existence of complete gaps, i.e. energy intervals in which an incoming electromagnetic wave is totally reflected regardless of polarization and angle of incidence. A brief discussion on signature management and thermal emission, and calculations for low-emittance coatings is included. It is shown that a 50-60µm layer of a 3D photonic crystal can be sufficient to achieve a thermal emittance of 20%.

Solar thermal collectors at high latitudes have been studied, with emphasis on concentrating collectors. A novel design of concentrating collector, the Maximum Reflector Collector (MaReCo), especially designed for high latitudes, has been investigated optically and thermally. The MaReCo is an asymmetrical compound parabolic concentrator with a bi-facial absorber. The collector can be adapted to various installation conditions, for example stand-alone, roof- or wall mounted. MaReCo prototypes have been built and outdoor-tested. The evaluation showed that all types work as expected and that the highest annually delivered energy output, 340 kWh/m2, is found for the roof MaReCo. A study of the heat-losses from the stand-alone MaReCo lead to the conclusion that teflon transparent insulation should be placed around the absorber, which decreases the U-value by about 30%. A method was developed to theoretically study the projected radiation distribution incident on the MaReCo bi-facial absorber. The study showed that the geometry of the collectors could be improved by slight changes in the acceptance intervals. It also indicated that the MaReCo design concept could be used also at mid-European latitudes if the geometry is changed. A novel method was used to perform outdoor measurements of the distribution of concentrated light on the absorber and then to calculate the annually collected zero-loss energy, Ea,corr, together with the annual optical efficiency factor. A study using this method indicated that the absorber should be mounted along the 20º optical axis instead of along the 65º optical axis, which leads to an increase of about 20% in Ea,corr. The same absorber mounting is suggested from heat loss measurements. The Ea,corr at 20º absorber mounting angle can be increased by 5% if the absorber fin thickness is changed from 0.5 to 1 mm and by 13% if two 71.5 mm wide fins are used instead of one that is 143 mm wide. If the Ea,corr for the standard stand-alone MaReCo with 143 mm wide absorber mounted at 65º is compared to that of a collector with a 71.5 mm wide absorber mounted at 20º, the theoretical increase is 38%.