This thesis aims to measure the mechanical properties of ceramics on the microscale using microcantilever beams. Focussed Ion Beam milled triangular cross-sectional beams (approximately 3 x 5 x 20µm) were fractured using a nanoindenter to measure the Young’s modulus, fracture strength, and fracture toughness. By developing the technique with a sapphire bicrystal, it was found that the mechanical properties could be successfully ascertained if correction factors were used. Experiments and theoretical work showed that sapphire and polycrystalline alumina beams undergo moisture assisted sub-critical crack growth when tested in air. Whilst corrections for the Young’s modulus have been previously reported, this is the first reported attempt to correct for the notch tip residual stress and the first to consider sub-critical crack growth. Once these factors were characterised using the sapphire bicrystal, the technique was applied to a range of different ceramics, such as polycrystalline α-alumina and silicon nitride. These are the first reported direct measurements the grain boundary toughness of these ceramics using microcantilever beams. The grain boundary toughness was correlated with the macroscopic fracture properties and the characteristics of the ceramic (grain boundary composition, impurities, and fracture mode). Two grades of α-alumina were used and the macro- and micro-scale properties extensively compared. The damage evolution during uniaxial compression of alumina was investigated in depth, and compared to a previous reported microcrack evolution model using the measured grain boundary toughness. Investigation of whether deformation twins formed during loading was undertaken and the phenomenon was shown to not occur.

This thesis studies lead suphide (PbS) colloidal quantum dots and their photovoltaic applications. Different sizes of PbS QDs were synthesised and characterised using absorption spectroscopy and transmission electron microscopes. PbS QD Schottky junction devices were fabricated with AM1.5 power conversion efficiency up to 1.8 %. The Schottky junction geometry limits the device performance. A semiconductor heterojunction using ZnO as an electron acceptor was built and the device efficiency increased to 3%. By studying the light absorption and charge extraction profile of the bilayer device, the absorber layer has a charge extraction dead zone which is beyond the reach of the built-in electric field. Therefore, strategies to create a QD bulk heterojunction were considered to address this issue by distributing the junction interface throughout the absorber layer. However, the charge separation mechanism of the QD heterojunction is not clearly understood: whether it operates as an excitonic or a depleted p-n junction, as the junction operating mechanism determines the scale of phase separation in the bulk morphology. This study shows a transitional behaviour of the PbS/ZnO heterojunction from excitonic to depletion by increasing the doping density of ZnO. To utilise the excitonic mechanism, a PbS/ZnO nanocrystal bulk heterojunction was created by blending the two nanocrystals in solution such that a large interface between the two materials could facilitate fast exciton dissociation. However, the devices show poor performance due to a coarse morphology and formation of germinate pairs. To create a bulk heterojunction where a built-in electric field could assist the charge separation, a TiO₂ porous structure with the pore size matching with the depletion width was fabricated and successfully in-filled by PbS QDs. The porous device produces 5.7% power conversion efficiency, among one of the highest in literature. The enhancement comes from increased light absorption and suppression of charge recombination.

This thesis presents information on the subcellular localisation of two important trace elements, selenium and arsenic, in wheat, rice and rice roots for what is believed to be the first time. The general aim of this work was to illustrate the potential of using physical science techniques to solve biological problems. High resolution secondary ion mass spectrometry was undertaken using the CAMECA NanoSIMS50 with a sensitivity down to ppm concentrations and a lateral resolution of less than 100 nm. Selenium in wheat grain was found to be distributed across both the bran layer and the endosperm region with Se-rich hotspots found in the aleurone cells and a higher intensity of Se in the subaleurone region. Arsenic in rice grain was found in two key regions. In grains with high As and high dimethylarsinic acid (DMA) content, As was predominantly localised to the subaleurone region yet in lower concentration, hydroponically grown As(III)-treated grains the As was only localised to the aleurone layer near the ovular vascular trace (OVT). A combined NanoSIMS and S-XRF experiment revealed As hotspots near the OVT. A combination of high pressure freezing, high resolution secondary ion mass spectrometry and TEM was used to localise As in the roots of rice plants revealing a contrasting subcellular distribution of As and Si in the roots even though arsenite and silicic acid are transported across the plasma membranes by the same transporters. Fe plaque forms only on the root epidermis and was shown to be a strong sink for As. Colocalisation of S with As in the vacuoles of the endodermis, pericycle and xylem parenchyma supports the notion that As is stored as arsenite-phytochelatin complexes in the roots while Si is localised in the endodermis cell walls and is not strongly affected by the Lsi2 mutation.

Irradiation damage structures induced in pure Fe and Fe-Cr (up to 14%Cr) alloys by 2 MeV Fe+ ion irradiations in the temperature range 300-460°C were investigated by transmission electron microscopy. Specimens were irradiated in bulk to doses of 1.5 x 1019 Fe+/m2 (about 2.5 displacements per atom: dpa) and 4.5 x 1019 Fe+/m2 (about 7 dpa). In most cases, damage took the form of dislocation loops with diameters from 2-100nm; the loops were distributed uniformly within all the samples. At higher irradiation temperatures (400°C, 460°C), complex microstructures such as finger loops (50nm in width and 1 micron in length) and perpendicular <100> loop clusters, were observed in both pure Fe and Fe-Cr samples. Loop sizes and densities were seen to change as a function of irradiation temperature and dose. Loop sizes were seen to increase as the increase of irradiation temperatures and doses, while loop densities only increased with increasing doses and decreased as increasing temperatures. Loops with both types of Burgers vectors (<100> and ½<111>) were observed in all the samples. The proportion of <100> loops was higher in Fe than that in Fe-Cr alloys at the same irradiation condition, which has can be attributed to the high mobility of ½<111> loops in Fe, so that a large proportion of them will escape to the (001) foil surface. A transition in loop Burgers vectors as a consequence of increasing temperature was observed. In Fe, the proportion of <100> loops increased with increasing irradiation temperature from 40% at 300°C to 60% at 460°C. A similar trend was found in the Fe-Cr alloys, but due to the higher proportion of ½<111> loops in these alloys, the increase of <100> loops was not that obvious, being from 30% at 300°C to 45% at 460°C(Fe-11Cr). The effects of irradiation dose rate on the formation of dislocation loops by 2 MeV Fe+ ions were also investigated. These irradiations were carried out at 300°C with two different implantation dose rates: 6 x 10-4 dpa/s and 3 x 10-5 dpa/s. The implantation dose for both implantations was 0.38 x 1019 Fe+/m2 (0.5 dpa). Both the average loop size and loop densities for the Fe-Cr specimens subjected to the high dose rate irradiation were higher than that in the low dose rate irradiations. Take Fe-14Cr as an example, that the loop densities in high dose rate irradiation increased about 90% compared to that in low dose rate, and the average loop size in high dose rate irradiation was 30% larger than that in low dose rate irradiation. The ‘inside-outside contrast’ method was applied to determine the loop nature in all the samples. It was found that all the large loops (>5nm) are of interstitial type. Any vacancies are believed to exist in the form of small dislocation loops (<5nm) or sub-microscopic voids.

Organic photovoltaics have attracted considerable research and commercial interest due to their lightness, mechanical flexibility and low production costs. There are two main approaches for the fabrication of organic solar cells – solution and vacuum processing. The former relies on morphology control in polymer-fullerene blends resulting from natural phase separation in these systems. The latter takes advantage of solvent-free processing allowing highly complex multi-junction architectures similar to inorganic solar cells. This work aims to combine the benefits of both by depositing conjugated polymers using vacuum thermal evaporation. By employing this unconventional approach it aims to enhance the efficiency of organic photovoltaics through increased complexity of the thin-film architecture while improving the nanoscale morphology control of the individual active layers. The thesis explores the vacuum thermal deposition of polythiophenes, mainly poly(3-hexylthiophene) (P3HT) and side-group free poly(thiophene) (PTh). A variety of chemical techniques, such as NMR, FT-IR, GPC, DSC and TGA, are used to examine the effect of heating on chemical structure of the polymers. Optimal processing parameters are identified and related to the resulting thin-film morphology and charge transport properties. Efficient photovoltaic devices based on polythiophene donors and fullerene acceptors are fabricated. Materials science techniques AFM, XRD, SEM, TEM and MicroXAM are used to characterize topography and morphology of the thin films, and UV-Vis, EQE, I-V and C-V measurements relate these to the optical and electronic properties. The results of the study show that polymer side groups have a strong influence on molecular packing and charge extraction in vacuum-deposited polymer thin films. Unlike P3HT, evaporated PTh forms highly crystalline films. This leads to enhanced charge transport properties with hole mobility two orders of magnitude higher than that in P3HT. The effect of molecular order is demonstrated on polymer/fullerene planar heterojunction solar cells. PTh-based devices have significantly better current and recombination characteristics, resulting in improved overall power conversion efficiency (PCE) by 70% as compared to P3HT. This confirms that the chemical structure of the molecule is a crucial parameter in deposition of large organic semiconductors. It is also the first-ever example of vacuum-deposited polymer photovoltaic cell. Next, vacuum co-deposited PTh:C60 bulk heterojunctions with different donor-acceptor compositions are fabricated, and the effect of post-production thermal annealing on their photovoltaic performance and morphology is studied. Co-deposition of blended mixtures leads to 60% higher photocurrents than in thickness-optimized PTh/C60 planar heterojunction counterparts. Furthermore, by annealing the devices post-situ the PCE is improved by as much as 80%, achieving performance comparable to previously reported polythiophene and oligothiophene equivalents processed in solution and vacuum, respectively. The enhanced photo-response is a result of favourable morphological development of PTh upon annealing. In contrast to standard vacuum-processed molecular blends, annealing-induced phase separation in PTh:C60 does not lead to the formation of coarse morphology but rather to an incremental improvement of the already established interpenetrated nanoscale network. The morphological response of the evaporated PTh within the blend is further verified to positively differ from that of its small-molecule counterpart sexithiophene. This illustrates the morphological advantage of polymer-fullerene combination over all other vacuum-processable material systems. In conclusion, this processing approach outlines the conceptual path towards the most beneficial combination of solution/polymer- and vacuum-based photovoltaics. It opens up a fabrication method with considerable potential to enhance the efficiency of large-scale organic solar cells production.

Reduced-activation ferritic steels are considered as the primary candidate materials for structural applications within nuclear fusion power plants. It is known that by mechanically alloying ferritic steel powder with Y (usually in the form of Y₂O₃) then consolidating the material by hot isostatic pressing, a nanoscale dispersion of oxygen rich nanoclusters as small as ~2nm is introduced into the microstructure. This vastly improves high temperature strength and creep resistance, and the nanoclusters also act as trapping sites for helium and point defects produced under irradiation. In this thesis, the evolution of the oxide nanoclusters in a Fe-14Cr-2W-0.3Ti & 0.3Y₂O₃ ODS alloy was investigated primarily using atom probe tomography. The microstructure was characterised at various points during processing to give an insight into the factors influencing the formation of the nanoclusters. It was found that the nanoclusters nucleated during the mechanical alloying stage, then followed near classical nucleation and growth mechanisms keeping the same composition of ~8%Y, ~12%Ti,~25%O and ~45%Cr throughout. The formation and evolution of 5-15nm grain boundary oxides was also observed, and these were shown to form first as Cr₂O₃ particles that subsequently transform into a Y-Ti-O based oxide on further processing. The influence of mechanical alloying with 0.5wt.%Fe₂Y rather than 0.3wt.%Y₂O₃ was also investigated, and this showed that there was no difference in the final microstructure produced provided the level of Ti in the starting powder was tightly controlled. Without sufficient Ti, the nanoclusters were Y-O based and ~6nm diameter. Both the Y-O and Y-Ti-O nanoclusters were moderately stable on annealing at 1200°C for up to 100 hours, with only minimal coarsening observed. Ti was found not to influence the coarsening rate of the nanoclusters significantly. The stability of the oxide nanoclusters under irradiation was investigated by using Fe²⁺ ion irradiation to simulate displacement cascade damage in the ODS-Eurofer material (the official European candidate material for testing in the ITER fusion test reactor). Doses up to ~6 dpa at 400°C were used, and there was no significant change to the nanocluster distribution. However segregation of Mn to dislocations was observed after irradiation. These results indicate that ODS steels are good candidate structural materials, as the microstructure is stable at high temperature and under irradiation. The starting powders, and processing parameters need to be tightly controlled in order to produce the optimal material for use in service.

Degenerative disorders of the rotator cuff tendons account for nearly 75% of all shoulder pain, causing considerable pain and morbidity. Given the strong correlation between age and tendinopathy, and unprecedented population aging, these disorders will become increasingly prevalent. Improved understanding of tendon degeneration will guide the development of future diagnostic and treatments, and is therefore urgently needed. However, the aetiology and pathology of rotator cuff tendinopathy remain unclear. The complicated mechanical environment of the rotator cuff is hypothesised to influence the susceptibility of the tendons to degeneration and tearing. Studies have reported biological adaptations in torn cuff tendons indicative of increased compressive loading within the tendon. The material adaptations of healthy and degenerative cuff tendons are largely unreported but will provide further insight into the role of the mechanical environment in rotator cuff aetiology and pathology. This thesis examined the material adaptations of healthy and diseased tendons to explore the role of mechanical loading in rotator cuff pathology. The material adaptations of healthy animal tendons, and healthy and delaminated human cadaveric rotator cuff tendons, in response to different loading environments were characterised. The effects of age, tears, steroid injection and subacromial decompression surgery on the structural adaptations of human cuff tendons were also studied, as was the effect of tendon cell proliferation on the mechanical properties and degradation behaviour of collagen scaffolds. Loading environment significantly affected the structural adaptations of healthy tendons. Regions exposed to compressive and shear strains exhibited thinner fibres, shorter crimp lengths and thinner, less aligned fibrils compared with regions exposed to tensile strains alone. In healthy rotator cuff tendons, the inhomogeneous loading environment produced topographically inhomogeneous structural adaptations. The tendons of a delaminated rotator cuff exhibited less topographical variation in properties and thinner, less aligned fibrils compared with healthy cuff tendons. Torn cuff tendons exhibited thinner fibrils and shorter crimp lengths compared with control samples. These adaptations were identifiable early in the disease progression, and neither steroid injection nor subacromial decompression surgery significantly influenced these adaptations at seven weeks post‐treatment. Significant correlations between decreasing dimensions and increasing tear size were found when age was included as a confounding factor, reflecting the importance of age and tear size in determining the material properties of tendons. Tendon cell proliferation influenced the mechanical properties and degradation behaviour of the collagen scaffolds, emphasising the integral role of cells in the functional adaptation of biological materials. These results demonstrate the effect of mechanical environment on the material adaptations of tendons. They also indicate the importance of the complicated mechanical environment experienced by the rotator cuff tendons in predisposing the tendons to degeneration and tearing. The observed material adaptations of degenerative and torn tendons suggest that rotator cuff pathology is associated with increased levels of compressive and/or shear strains within the tendon. These changes begin early in the disease progression and neither steroid injection nor sub‐acromial decompression surgery are capable of reversing the changes in the timeframe investigated. These findings highlight the urgent clinical need for pre‐rupture diagnostic techniques for the detection of early pathological changes in the rotator cuff. They also emphasize the requirement for new intervention strategies that restore the healthy mechanical environment and reverse early pathological adaptations in order to prevent catastrophic failure of the tendons.

Austenitic stainless steels are frequently used in the cooling circuits of nuclear reactors. It has been found that cold-worked 304 stainless steels can be particularly susceptible to stress corrosion cracking at the operating conditions of such reactors. Despite more than 130 years of research underlying mechanisms are still not properly understood. For this reason, the effects of cold-work and applied stress on the oxidation behaviour of 304SS have been studied in this thesis. A set of samples with/without prior cold-work, and with/without stress applied during oxidation, were oxidized in autoclaves under simulated pressurised water reactor primary circuit conditions. Atom-probe tomography and analytical transmission electron microscopy were used to investigate the local chemistry and microstructure in the different samples tested. Regions containing grain boundaries, deformation bands, and matrix material in contact with the environment, were extracted from the coupon specimens with a focused ion beam machine. Cross-sections of crack tips were studied with secondary ion mass spectrometry and electron backscatter diffraction. The compositions of oxides grown along the surface and the different microstructural features were analysed. Fe-rich spinels were found at the surface and Cr-rich spinels were observed along fast diffusion paths. Ni-enrichment was found at the metal/oxide interfaces and a Ni-rich phase was detected in precipitates ahead of grain boundary oxides. Li was observed in all oxidised regions and B segregation, originating from impurities in the alloy, was observed in grain boundaries and crack tip oxides. Cavities and hydrogen associated with Ni-rich regions were found ahead of the bulk Cr-rich oxide in some of the samples. The implications of these findings for the understanding of SCC mechanisms are discussed. It is suggested that Ni precipitation as well as the presence of deformation bands may play an important role in controlling SCC susceptibility in 304 stainless steel. A modification of the film-rupture model including internal oxidation and fast diffusion along H-stabilised vacancies in strain fields at the crack front is proposed.

This thesis describes the fabrication and characterization of ex situ magnesium diboride (MgB<sub>2<) bulk material to study its sintering behaviour. Since the discovery of superconductivity in magnesium diboride in 2001, many research studies have identified the attractive properties of this easy-to-fabricate, low cost superconductor which can attain high critical current density even without heat-treatment. However there is little consensus in the literature on the processing requirements to produce high quality MgB<sub>2< material with low impurity content and high density. In this work, the key parameters in the production of dense ex situ MgB<sub>2< produced from Alfa Aesar MgB<sub>2< powder are established by examining the effect of modifying the characteristics of the starting material and the processing parameters during pressureless and pressure assisted heat-treatment. The particle size distribution, impurity content and particle morphology of Alfa Aesar MgB<sub>2< powder were determined using laser dffraction, X-ray diffraction, X-ray photoelectron spectroscopy, electron dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. This powder was also modified by separation (sieving and sedimentation) and milling (ball milling and attrition milling), with changes made to the powder determined by the same techniques. A pressureless heat-treatment method using a magnesium diboride powder bed was developed. This minimised MgO formation in samples produced from as-purchased MgB<sub>2< powder to less than 8 wt.% for heat-treatment at 1100°C. MgO content was determined by X-ray diffraction using calibrated standards. MgB<sub>2< bulk material was produced from as-purchased and modified powders by pressureless heat-treatment under Ar gas, and characterized using Archimedes' density method, X-ray diffraction, Vickers hardness testing, scanning electron microscopy, and magnetization measurements. Very limited densification was observed for all samples prepared by pressureless heat-treatment, with only limited increases in connectivity observed for some samples heat-treated at 1100°C. Pressure-assisted bulk samples were prepared from as-purchased MgB<sub>2< and selected modified powders using resistive sintering, spark plasma sintering, and hot pressing. These were characterized using the same techniques, which indicated much more extensive densification with similar levels of impurity formation as for pressureless heat-treatment at 1100°C. The results indicate that densification and applied pressure are strongly correlated, while the effect of temperature is less significant. The optimum processing environment (inert gas or vacuum) was dependent on the technique used. These results indicate that pressure-assisted heat-treatment is required in order to produce dense bulk MgB<sub>2<.

The primary aim of this research was to develop and improve the experimental method and data interpretation for strain measurements using diffraction methods to gain a better understanding of micromechanical deformation and anisotropy of lattice strain response. Substantial part of the research was devoted to the development of the laboratory high energy X-ray diffractometer (HEXameter) for bulk residual strain evaluation. White beam energy dispersive X-ray diffraction was chosen as the principal diffraction mode due to its extreme efficiency in utilising X-ray flux and its ability to capture large segments of diffraction patterns. The specimens that have been examined were real engineering components, mechanically deformed specimens and thermally treated specimens, ranging from dynamic in-situ measurements to ex-situ materials engineering. For the real engineering components, a wedge coupon from the trailing edge of a Ti64 wide fan blade and a turbine combustion casing were examined. Among the mechanically deformed specimens that have been measured were shot-peened steel plates, elasto-plastically bent bars of Mg alloy and cold expanded Al disks. Amongst the thermally deformed specimens, laser-formed steel plates, thermal spray coatings, a manual inert gas weld of Al plates, a friction stir weld of Al plates and Ni tubes and a quenched Ni superalloy cylinder used for strain tomography were studied. In-situ loading experiments have also been carried out, such as experiments on pointwise mapping of grain orientation and strain using the 3DXRD microscope at the ESRF and in-situ loading experiments on titanium alloy, rheo-diecast and high pressure diecast Mg alloy, IN718 Ni-base superalloy and Al2024 aluminium alloy. Experimental results from X-Ray diffraction and strain tomography were used to achieve a better understanding of the material properties. Some results were compared with polycrystal Finite Element model predictions. Amongst the most prominent research achievements are the development on the HEXameter laboratory instrument, including: (i) the development of special collimation systems for the detectors and the source tube; (ii) the development of a twin-detector setup (that allows for simultaneous determination of strain in two mutually orthogonal directions); (iii) improved alignment procedures for better performance; and (iv) the adaptation of instrumentation for efficient scanning of both large and small components, that included choosing and adapting translation devices, programming of the translation system and designing sample mounting procedures. In this research several approaches to data treatment were investigated. Quantitative phase analysis, single peak fitting (using custom Matlab routines and GSAS) and full pattern fitting (with individual pattern data refined by GSAS and batch refinement done by invoking GSAS via a Matlab routine) were applied. Different Matlab routines were written for specific experimental setups; and various analysis methods were selected and used for refinement depending on the requirements of the measurement results interpretation. 16 papers were published, ensuring that the results of this thesis are readily available to other researchers in the field.