For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason for using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is useful to support material designers. In this thesis some aspects of the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. amount and composition of phases, oxygen activity, heat capacity etc, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy as a function of composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. The elements included in the databse are: C, Fe, Cr, Nb, Ni, Mo, O, Si, Sn, and Zr + H, and the assessment performed under this thesis are: Cr-Sn, Mo-Zr, Sn-Zr, Fe-Nb-Zr and Nb-O-Zr. All the calculations have been made using Thermo-Calc software and the representation of the Gibbs energy obtained by applying Calphad technique with some use of ab initio calculations. / QC 20100902

A new NOx sensor for high-temperature applications has been developed and thouroghly characterised. The sensor layers are a mixed oxide of CoO, MgO and MgO2 deposited by thermal evaporation with a porous platinum gate on top, deposited by thermal evaporation or sputtering. The sensitivity and selectivity of the sensor is promising and is shown to depend upon the ratio between Co and Mg in the film and a number of competing mechanisms are shown to take place on the sensor surface. Response and recovery of the device is still slow and there are some drift, which are suggested to be due to a restructuring sensor surface during operation that was found by SEM-studies. Finally,the oxide surface has been characterized by XPS and a novel process for deposition of the sensor layers by lift-off technique has been developed.

<p>In the first part of this thesis, the FE program MSC.Marc is applied for coupled thermomechanical simulations of wire-rod rolling. In order to predict material behaviour of an AISI 302 stainless steel at high strain rates generated during wire-rod rolling, a material model based on dislocation density is applied. Then, the evolution of temperature, strain rate and flow stress is predicted in the first four rolling passes of a wire block.</p><p>In the second part of the thesis, an alternative approach to simulation of shape rolling is evaluated. The approach is applied in order to save the computational time in cases where many shape-rolling passes are to be simulated. The approach is a combination of the slab method and a 2D FEM with a generalized plane-strain formulation. A number of various isothermal shape-rolling passes are simulated applying the simplified approach. The simulations are carried out using an in-house 2D FE code implemented in Matlab. The results are compared to fully 3D FE analyses. The comparison shows that the simplified approach can predict roll forces and roll torques with a fair accuracy, but the predicted area reductions are a bit underestimated. The reasons for the deviations between the simplified approach and the 3D FEM are discussed.</p>

<p>This licentiate study was initiated by copper, zinc and galvanized steel producers in Europe, who felt a need to assess runoff rates of copper and zinc from the pure metals and commercial products at marine exposure conditions. Their motive was the increasing concern in various European countries and the on-going risk assessments of copper and zinc within the European commission. Also the circumstance that available runoff rates so far, had been reported for mainly urban exposure conditions, rather than marine. A collaboration was therefore established with the French Corrosion Institute, which runs a marine test site in Brest, and a set of vital questions were formulated. Their answers are the essence of this licentiate study.</p><p>Based on the ISO corrosivity classification and one-year exposures, the marine atmosphere of Brest is fairly corrosive for zinc (class C3) and highly corrosive for copper (C4). Despite higher corrosivity classifications for both metals in Brest compared to the urban site of Stockholm, used as a reference site, nearly all runoff rates assessed for copper, zinc and their commercial products were lower in Brest compared to Stockholm. This was attributed to a higher surface wetting in Brest and concomitant higher removal rate of deposited chloride and sulphate species from the marine-exposed surfaces. The comparison shows that measured corrosion rates cannot be used to predict runoff rates, since different physicochemical processes govern corrosion and runoff respectively.</p><p>For copper, the runoff rate in Brest was approximately 1.1 g m^-2 yr^-1 with cuprite (Cu2O) as main patina constituent. During periods of very high chloride and sulphate deposition, paratacamite (Cu₂Cl(OH)₃) formed which increased the runoff rate to 1.5 g m^-2 yr^-1. For zinc, with hydrozincite (Zn₅(CO₃)2(OH)₆) as the main patina constituent, the runoff rate was relatively stable at 2.6 g m^-2 yr^-1 throughout the year, despite episodes of heavy chloride and sulphate deposition.</p><p>The application of organic coatings of varying thickness on artificially patinated copper or on different zinc-based products resulted in improved barrier properties and reduced runoff rates that seem highly dependent on thickness. The thickest organic coating (150 µm thick), applied on hot dipped galvanized steel, reduced the runoff rate by a factor of 100. No deterioration of organic coatings was observed during the one-year exposures. Alloying zinc-based products with aluminium resulted in surface areas enriched in aluminium and concomitant reduced zinc runoff rates.</p><p>The release rate and bioavailability of copper from different anti-fouling paints into artificial seawater was also investigated. It turned out that the release rate not only depends on the copper concentration in the paint, but also on paint matrix properties and other released metal constituents detected. Far from all copper was bioavailabe at the immediate release situation. In all, the results suggest the importance of assessing the ecotoxic response of anti-fouling paints not only by regarding the copper release, but rather through an integrated effect of all matrix constituents.</p>

<p>Over one million hip prostheses are implanted in patients worldwide each year and the need is increasing as the patient group of younger and more active patients is increasing. Many parameters affect the longevity of the implant, where aseptic loosening caused by wear debris is the most common reason for revision. To be able to monitor wear in vivo and also to predict the longevity of new materials for hip prostheses are therefore important issues in this interdisciplinary research area. This thesis comprise a true non-invasive 3D method for determination of acetabular cup wear using Computed Tomography (CT) intended for clinical routine use in order to plan for a revision. It also comprises investigations of the influence of surface roughness and sterilization method in wear testing of materials for hip prostheses. Mainly wear of ultra high molecular weight polyethylene (UHMWPE) was investigated since it is the most common soft bearing in hip prostheses. The 3D-CT method was found to be easy to use and showed an accuracy and repeatability at a clinical relevant level for acetabular cup wear. It should lend itself well to semi-automation. The influence of surface roughness was investigated with both a multidirectional pin-on-disk machine and with a hip simulator. A new low friction coating, Micronite, was also evaluated with the pin-on-disk machine. This coating showed potential for use in artificial joints, but further investigations are needed. In the hip simulator test, it was found that not only a rougher counter surface increased wear, but also sterilization by γ-irradiation increased wear of UHMWPE cups.</p>

<p>Very often defects are present in rolled products. For wire rods, defects are very deleterious since the wire rods are generally used directly in various applications. For this reason, the market nowadays requires wire rods to be completely defect-free. Any wire with defects must be rejected as scrap which is very costly for the production mill. Thus, it is very important to study the formation and evolution of defects during wire rod rolling in order to better understand and minimize the problem, at the same time improving quality of the wire rods and reducing production costs.</p><p>The present work is focused on the evolution of artificial defects during rolling. Longitudinal surface defects are studied during shape rolling of an AISI M2 high speed steel and a longitudinal central inner defect is studied in an AISI 304L austenitic stainless steel during ultra-high-speed wire rod rolling. Experimental studies are carried out by rolling short rods prepared with arteficial defects. The evolution of the defects is characterised and compared to numerical analyses. The comparison shows that surface defects generally reduce quicker in the experiments than predicted by the simulations whereas a good agreement is generally obtained for the central defect.</p>

NiTiHf shape memory alloys have been receiving considerable attention for high temperature and high strength applications since they could have transformation temperatures above 100 °C, shape memory effect under high stress (above 500 MPa) and superelasticity at high temperatures. Moreover, their shape memory properties can be tailored by microstructural engineering. However, NiTiHf alloys have some drawbacks such as low ductility and high work hardening in stress induced martensite transformation region. In order to overcome these limitations, studies have been focused on microstructural engineering by aging, alloying and processing. Shape memory properties and microstructure of four Ni-rich NiTiHf alloys (Ni50.3Ti29.7Hf20, Ni50.7Ti29.3Hf20, Ni51.2Ti28.8Hf20, and Ni52Ti28Hf20 (at. %)) were systematically characterized in the furnace cooled condition. H-phase precipitates were formed during furnace cooling in compositions with greater than 50.3Ni and the driving force for nucleation increased with Ni content. Alloy strength increased while recoverable strain decreased with increasing Ni content due to changes in precipitate characteristics. The effects of the heat treatments on the transformation characteristics and microstructure of the Ni-rich NiTiHf shape memory alloys have been investigated. Transformation temperatures are found to be highly annealing temperature dependent. Generation of nanosize precipitates (~20 nm in size) after three hours aging at 450 °C and 550 °C improved the strength of the material, resulting in a near perfect dimensional stability under high stress levels (> 1500 MPa) with a work output of 20–30 J cm– 3. Superelastic behavior with 4% recoverable strain was demonstrated at low and high temperatures where stress could reach to a maximum value of more than 2 GPa after three hours aging at 450 and 550 °C for alloys with Ni great than 50.3 at. %. Shape memory properties of polycrystalline Ni50.3Ti29.7Hf20 alloys were studied via thermal cycling under stress and isothermal stress cycling experiments in tension. Recoverable strain of ~5% was observed for the as-extruded samples while it was decreased to ~4% after aging due to the formation of precipitates. The aged alloys demonstrated near perfect shape memory effect under high tensile stress level of 700 MPa and perfect superelasticity at high temperatures up to 230 °C. Finally, the tensioncompression asymmetry observed in NiTiHf where recoverable tensile strain was higher than compressive strain. The shape memory properties of solutionized and aged Ni-rich Ni50.3Ti29.7Hf20 single crystals were investigated along the [001], [011], and [111] orientations in compression. [001]-oriented single crystals showed high dimensional stability under stress levels as high as 1500 MPa in both the solutionized and aged conditions, but with transformation strains of less than 2%. Perfect superelasticity with recoverable strain of more than 4% was observed for solutionized and 550 °C-3h aged single crystals along the [011] and [111] orientations, and general superelastic behavior was observed over a wide temperature range. The calculated transformation strains were higher than the experimentally observed strains since the calculated strains could not capture the formation of martensite plates with (001) compound twins.

Ferritic superalloys strengthened by coherent ordered NiAl B2-type precipitates are promising candidates for ultra-supercritical steam-turbine applications, due to their superior resistance to creep, coarsening, oxidation, and steam corrosion as compared to Cr ferritic steels at high temperatures. Combined computational and experimental tools have been employed to investigate the interrelationships among the composition, microstructure, and mechanical behavior, and provide insight into deformation micromechanisms at elevated temperatures. Self and impurity diffusivities in a body-centered-cubic (bcc) iron are calculated using first-principles methods. Calculated self and impurity diffusivities compare favorably with experimental measurements in both ferromagnetic and paramagnetic states of bcc Fe. The calculated impurity diffusivities of W and Mo are larger than the self diffusivity of Fe, mainly owing to the lower activation energies. The microstructural attributes of NiAl-type B2 precipitates are investigated in several designed ferritic superalloys. Ultra-small-angle X-ray scattering in conjunction with transmission electron microscopy is employed to quantify the average size, size distribution, inter-particle spacing, and volume fraction of the primary precipitates. It is observed that as the Al amount increases from 4 to 10 mass%, there is a decrease in the average inter-particle spacing and average particle diameter. An alloy with 6.5 weight percent Al exhibits the optimal creep resistance and an associated maximum Orowan stress at 973 K. The dislocations-particle interaction mode during the secondary creep regime is identified as a combination of Orowan looping and dislocation climb. In-situ neutron diffraction experiments during tensile and creep deformations reveal the intergranular and interphase load-sharing mechanisms during plastic deformation at elevated temperatures. The change of deformation mechanisms from dislocation slip below 773 K to power-law creep above 873 K is well captured by the evolution of the different lattice strains. High-temperature deformation above 873 K is possibly assisted by the relaxation processes, e.g., grain-boundary sliding and/or diffusional flow along grain boundaries and matrixparticle interfaces. The evolution of lattice strains during high-temperature deformation is further verified by crystal-plasticity finite-element simulations. The significant findings in the present work provide the crucial baseline information for further alloy optimization and improvement in high-temperature creep resistance of ferritic superalloys.

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes exhibited an unusual phenomenon of capacity increase upon cycling which was ascribed to the decreased cell resistance and enhanced interfacial charge storage. In summary, this dissertation provides investigation of sulfur based electrode materials with sulfur/N-doped graphene composites and MnS nanocrystals. Their electrochemical performances have been evaluated and discussed. The understanding of their reaction mechanisms and electrochemical enhancement could make progress on development of secondary batteries.

Multifunctional materials both with damping properties and strain sensing properties are very important. They promise to be more weight-efficient, and provide volume-efficient performance, flexibility and potentially, less maintenance than traditional multi-component brass-board systems. The goal of this dissertation work was to design, synthesize, investigate and apply polyaniline/Multiwall carbon nanotube (PANI/MWCNT) and polyurethane (PU) /MWCNT composites films for structural vibration control and strain sensors using free layer damping methods and static and dynamic strain sensing test methods. The PANI/MWCNT was made by in situ polymerization of PANI in the presence of MWCNT, then frit compression was used to make circular and rectangular PANI/MWCNT composite films. PU/MWCNT composites were made by the layer-by-layer method. Free end vibration test results showed both of PANI/MWCNT and PU/MWCNT have better damping ratios than each of their components. Static sensing test indicated that though there appears to be residual strain in both composite sensors after the load is removed, both the sensor and the foil strain gage react linearly when re-engaged. A drift test of the sensor showed that it is stable. The dynamic sensing test results showed that over the range of 10-1000 Hz, the PANI/MWCNT composite sensor was consistently superior to foil strain gage for sensing purposes since the highest peak consistently corresponded to the input frequency and was much higher, for example, at 20 Hz, 820 times higher than those of the strain gage. Using the same criterion, the PU/Buckypaper composite sensor was comparable to or superior to the foil strain gage for sensing purposes over the range of 10 Hz to 200 Hz. The relationship of loss factor, η, and beam coverage length, L1/L, is discussed for single sided and double sided attachment. For both PANI/MWCNT and PU/MWCNT, the loss factor, η, was found to increase as coverage length, L1/L, increases. The loss factor, η, was found to have a maximum as with coverage length, L1/L, as the coverage length continues to increase. The trend for double sided attachment was found to follow the trends discussed by Rao (2004) and Levy and Chen (1994) for viscoelastic material constrained damping.