Novel semiconductor nanostructures possess a range of notable properties that have the potential to be harnessed in the next generation of optical devices. Electron microscopy is uniquely suited to characterising the complex microstructure, the results of which may be related to the growth conditions and optical properties. This thesis investigates three such novel materials: (1) GaN/InGaN core/shell nanowires, (2) n-GaN/InGaN/p-GaN core/multi-shell microrods and (3) Zn₃N₂ nanoparticles, all of which were grown at Sharp Laboratories of Europe. GaN nanowires were grown by a Ni-catalysed VLS process and were characterised by various techniques before and after InGaN shells were deposited by MOCVD. The majority of the core wires were found to have the expected wurtzite structure and completely defect free – reflected in the strong strain-free photoluminescence peak –with a- and m- axis orientations identified with shadow imaging. A small component, <5%, were found to have the cubic zinc-blende phase and a high density of planar faults running the length of the wires. The deposited shells were highly polycrystalline, partially attributed to a layer of silicon at the core shell interface identified through FIB lift-out of cross section samples, and accordingly the PL was very broad likely due to recombination at defects and grain boundaries. A high throughput method of identifying the core size indirectly via the catalyst particle EDX signal is described which may be used to link the shell microstructure to core size in further studies. An n-GaN/InGaN/p-GaN shell structure was deposited by MOCVD on the side walls of microrods etched from c-axis GaN film on sapphire, which offers the possibility of achieving non-polar junctions without the issues due to non-uniformity found in nanowires. Threading dislocations within the core related to the initial growth on sapphire were shown to be confined to this region, therefore avoiding any harmful effect on the junction microstructure. The shell defect density showed a surprising relationship to core size with the smaller diameter rods having a high density of unusual 'flag' defects in the junction region whereas the larger diameter sample shells appeared largely defect free, suggesting the geometry of the etched core has an impact on the strain in the shell layers. The structure of unusual 'flag' defects in the m-plane junctions was characterised via diffraction contrast TEM, weak beam and atomic resolution ADF STEM and were shown to consist of a basal plane stacking faults meeting a perfect or partial dislocation loop on a pyramidal plane, the latter likely gliding in to resolve residual strain due to the fault formed during growth. Zn₃N₂ has the required bandgap energy to be utilised as a phosphor with the additional advantage over conventional materials of its constituent elements not being toxic or scarce. The first successful synthesis of Zn₃N₂ nanoparticles appropriate to this application was confirmed via SAD, EDX and HRTEM, with software developed to fit experimental polycrystalline diffraction patterns to simulated components suggesting a maximum Zn₃N₂ composition of ~30%. There was an apparent decrease in crystallinity with decreasing particle size evidenced in radial distribution function studies with the smallest particles appearing completely amorphous in 80kV HRTEM images. A rapid change in the particles under the electron beam was observed, characterised by growth of large grains of Zn₃N₂ and ZnO which increased with increasing acceleration voltage suggesting knock-on effects driving the change. PL data was consistent with the bandgap of Zn₃N₂ blue shifted from 1.1eV to around 1.8eV, confirming the potential of the material for application as a phosphor.

This thesis examines the development of a superstructure for a slab-on-girder wood-concrete composite highway bridge. Wood-concrete composite bridges have existed since the 1930's. Historically, they have been limited to spans of less than 10 m. Renewed research interest over the past two decades has shown great potential for longer span capabilities. Through composite action and suitable detailing, improvements in strength, stiffness, and durability can be achieved versus conventional wood bridges. The bridge makes use of a slender ultra-high performance fibre-reinforced concrete (UHPFRC) deck made partially-composite in longitudinal bending with glued-laminated wood girders. Longitudinal external unbonded post-tensioning is utilized to increase span capabilities. Prefabrication using double-T modules minimizes the need for cast-in-place concrete on-site. Durability is realized through the highly impermeable deck slab that protects the girders from moisture. Results show that the system can span up to 30 m while achieving span-to-depth ratios equivalent or better than competing slab-on-girder bridges.

This thesis examines the development of a superstructure for a slab-on-girder wood-concrete composite highway bridge. Wood-concrete composite bridges have existed since the 1930's. Historically, they have been limited to spans of less than 10 m. Renewed research interest over the past two decades has shown great potential for longer span capabilities. Through composite action and suitable detailing, improvements in strength, stiffness, and durability can be achieved versus conventional wood bridges. The bridge makes use of a slender ultra-high performance fibre-reinforced concrete (UHPFRC) deck made partially-composite in longitudinal bending with glued-laminated wood girders. Longitudinal external unbonded post-tensioning is utilized to increase span capabilities. Prefabrication using double-T modules minimizes the need for cast-in-place concrete on-site. Durability is realized through the highly impermeable deck slab that protects the girders from moisture. Results show that the system can span up to 30 m while achieving span-to-depth ratios equivalent or better than competing slab-on-girder bridges.

The ability to predict fatigue crack growth rates is essential in safety critical systems. The discovery of fatigue crack closure in 1970 caused a flourish of research in attempts to simulate this behaviour, which crucially affects crack growth rates. Historically, crack tip plasticity models have been based on one-dimensional rays of plasticity emanating from the crack tip, either co-linear with the crack (for the case of plane stress), or at a chosen angle in the plane of analysis (for plane strain). In this thesis, one such model for plane stress, developed to predict fatigue crack closure, has been refined. It is applied to a study of the relationship between the apparent stress intensity range (easily calculated using linear elastic fracture mechanics), and the true stress intensity range, which includes the effects of plasticity induced fatigue crack closure. Results are presented for all load cases for a finite crack in an infinite plane, and a method is demonstrated which allows the calculation of the true stress intensity range for a growing crack, based only on the apparent stress intensity range for a static crack. Although the yield criterion is satisfied along the plastic ray, these one-dimensional plasticity models violate the yield criterion in the area immediately surrounding the plasticity ray. An area plasticity model is therefore required in order to model the plasticity more accurately. This thesis develops such a model by distributing dislocations over an area. Use of the model reveals that current methods for incremental plasticity algorithms using distributed dislocations produce an over-constrained system, due to misleading assumptions concerning the normality condition. A method is presented which allows the system an extra degree of freedom; this requires the introduction of a parameter, derived using the Prandtl-Reuss flow rule, which relates the magnitude of slip on complementary shear planes. The method is applied to two problems, confirming its validity.

This thesis describes the design, manufacture and characterisation of thick vacuum plasma sprayed tungsten (W) coatings on steel substrates. Fusion is a potentially clean, sustainable, energy source in which nuclear energy is generated via the release of internal energy from nuclei. In order to fuse nuclei the Coulomb barrier must be breached - requiring extreme temperatures or pressures – akin to creating a ‘star in a box’. Tungsten is a promising candidate material for future fusion reactors due to a high sputtering threshold and melting temperature. However, the large coefficient of thermal expansion mismatch with reactor structural steels such as the low activation steel Eurofer’97 is a major manufacturing and in-service problem. A vacuum plasma spraying approach for the manufacture of tungsten and tungsten/steel graded coatings has been developed successfully. The use of graded coatings and highly textured 3D interface surfi-sculpt substrates has been investigated to allow the deposition of thick plasma sprayed tungsten coatings on steel substrates. Finite element models have been developed to understand the residual stresses that develop in W/steel systems and made use of experimental measurements of coating thermal history during manufacture and elastic moduli measured by nano-indentation. For both the graded and surfi-sculpt coating, the models have been used to understand the mechanism of residual stress redistribution and relief in comparison with simple W on steel coatings, particularly by consideration of stored strain energy. In the case of surfi-sculpt W coatings, the patterned substrate gave rise to regular stress concentrating features, and allowed 2mm thick W coatings to be produced reproducibly without delamination. Preliminary through thickness residual stress measurements were compared to model predictions and provided tentative evidence of significant W coating stress relief by regulated coating segmentation.

In the absence of a fusion neutron source, research on the structural integrity of materials in the fusion environment relies on current fission data and simulation methods. Through investigation of the Fe-Cr system, this detailed study explores the challenges and limitations in the use of currently available radiation sources for fusion materials research. An investigation of ion-irradiated Fe12%Cr using nanoindentation with a cube corner, Berkovich and spherical tip, and micro-cantilever testing with two different geometries, highlighted that the measurement of irradiation hardening was largely dependent on the type of test used. Selected methods were used for the comparison of Fe6%Cr irradiated by ions and neutrons to a dose of 1.7dpa at a temperature of 288&deg;C. Micro-cantilever tests of the Fe6%Cr alloy with beam depths of 400 to 7000nm, identified that size effects may significantly obscure irradiation hardening and that these effects are dependent on radiation conditions. Irradiation hardening in the neutron-irradiated alloy was approximately double that of the ion-irradiated alloy and exhibited increased work hardening. Similar differences in hardening were observed in an Fe5%Cr alloy after ion-irradiation to a dose of 0.6dpa at 400&deg;C and doses rates of 6 x 10^-4dpa/s and 3 x 10^-5dpa/s. Identified by APT, it was shown that increased irradiation hardening was likely to be caused by the enhanced segregation of Cr observed in the alloy irradiated with the lower dose rate. These observations have significant implications for future fusion materials research in terms of the simulation of fusion relevant radiation conditions and micro-mechanical testing.

In this work the electronic and magnetic structure of the crystals Sr2FeMoO6, Fe0.5Cu0.5Cr2S4, LuFe2O4 and the molecules FeStar, Mo72Fe30, W72Fe30 are investigated by means of X-ray spectroscopic techniques. These advanced materials exhibit very interesting properties like magnetoresistance or multiferroic behaviour. In case of the molecules they also could be used as spin model systems. A long standing issue concerning the investigation of these materials are contradicting results found for the magnetic and electronic state of the iron (Fe) ions present in these compounds. Therefore this work focuses on the Fe state of these materials in order to elucidate reasons for these problems. Thereby the experimental results are compared to multiplet simulations.

Traditional fabrication methods used to manufacture biosensors for physiological, therapeutics, or health monitoring purposes are complex and rely on costly materials, which has hindered their adoption as single-use medical devices. The development of a new kind of wearable and implantable electronics relying on inexpensive materials for their manufacturing will pave the way towards the ubiquitous adoption of sticker-like health tracking devices.<div>One of growing and most promising applications for biosensors is the continuous health monitoring using mechanically soft, stretchable sensors. While these healthcare devices showed an excellent compatibility with human tissues, they still need highly trained personnel to perform multi-step, prolonged fabrication for several functioning layers of the device. In this dissertation, I propose low-cost, scalable, simple, and rapid manufacturing techniques to fabricate multifunctional epidermal and implantable sensors to monitor a range of biosignals including heart, muscle, or eye activity to characterizing of biofuids such as sweat. I have also used these devices as an implant to provide heat therapy for muscle regeneration and optical stimulation of neurons using optogenetics. These devices have also combined with those of triboelectric<br>nanogenerators to realize self-powered sensors for monitoring imperceptible mechanical biosignals such as respiratory and pulse rate.</div><div>Food health and safety has also emerged as another important frontier to develop biosensors and improve the human health and quality of life. The recent progresses on detecting microbial activity inside foods or their packages rely on development of highly functional materials. The existing materials for fabrication of food sensors, however,<br>are often costly and toxic for human health or the environment. In this dissertation, I proposed biocompatible food sensors using protein/PCL microfibers to reinforce the protein microfibrous structure in humid conditions and exploit their excellent hygroscopic properties to sense biogenic gas, as an indicator for early detection of food spoilage. Finally, my battery-free food sensors are capable of monitoring food safety with no need of extra measurement devices. Collectively, this dissertation proposes cost-effective solutions to solve human health issues, enabled by developing low-cost, functional materials and exploiting simple fabrication techniques.<br></div>