The core aim of this research project was to improve understanding of the effects of microstructure and crystallographic texture on the high strain rate plastic deformation behaviour of the industrially important Titanium alloy, Ti-6Al-4V. To facilitate this study, four rolled plates of Ti-6Al-4V, with varying thermo-mechanical processing histories, were provided by TIMET Corp., the world’s largest supplier of Titanium product. To determine the nature of each plate’s microstructure and the crystallographic texture of the dominant α phase, the four Ti-6Al-4V plates were microstructurally characterised using techniques such as optical microscopy and electron backscatter diffraction (EBSD). To determine the effects of the measured microstructures and textures on the strain rate dependent plastic deformation behaviour of the four Ti-6Al-4V plates, uniaxial compression and tension tests were carried out in the three orthogonal material orientations at quasi-static (10^-3 s^-1) and high strain rates (10^3 s^-1) using a standard electro-mechanical test device and split-Hopkinson pressure bars (SHPB), respectively. To provide further understanding of the effects of microstructure and texture on the plastic deformation behaviour of Ti-6Al-4V, this time under complex impact loading conditions, the classic Taylor impact experiment was adapted to include an optical measurement and geometry reconstruction technique. A novel experimental setup was designed that consists of an ultra-high speed camera and mirror arrangement, allowing the Taylor impact specimen to be viewed from multiple angles during the experiment. Using the previously mentioned optical measurement and geometry reconstruction technique, it was then possible to gain valuable, previously unobtainable, data on the deformation history of Taylor impact specimens in-situ, such as the major/minor axes of the anisotropically deforming elliptical specimen cross-sections as a function of time and axial position, true strain as a function of time and axial position, and the true strain rate as a function of axial position. The technique was verified by testing a specimen cut from the in-plane material orientation of a clock-rolled high purity Zirconium plate. The output measurements from a post-deformation image frame were compared with measurements of the recovered specimen made using a coordinate measurement machine (CMM), with analysis showing excellent agreement between the two techniques. The experiment was then carried out on specimens cut from the two orthogonal in-plane material orientations of one of the four Ti-6Al-4V plates. Analysis of the data from these experiments gave significant insight into the plastic deformation behaviour of macroscopically textured Ti-6Al-4V under complex impact loading. Recovered Ti-6Al-4V specimens from the outlined Taylor impact experiments were then sectioned along specific planes and microstructurally characterised using EBSD, with comparisons made between the pre and post-deformation microstructures. From this analysis, and the previously discussed geometry reconstruction technique, insight was gained into the effects of micro-texture on the general anisotropic plastic deformation behaviour of Ti-6Al- 4V plate materials and in particular the role of micro-texture on the formation of deformation twins. Finally, the understanding gained from these experiments, and a detailed review of the literature, was used to inform a novel, physically based material modelling framework, capable of capturing the effects of microstructure and texture on the strain rate and temperature dependent plastic deformation behaviour of Ti-6Al-4V. The model was implemented in the computational software package, MATLAB, and verified by comparison with the mechanical characterisation results from one of the Ti-6Al-4V plates. A number of frameworks are discussed for implementing the new Ti-6Al-4V model within finite element (FE) analysis software packages, such as ABAQUS, LS-DYNA and DEFORM. It is hoped that the new Ti-6Al-4V model can be used to optimise the design of Ti-6Al-4V components and structures for impact loading scenarios.

One approach that has demonstrated success in the field of molecular imaging utilizes microparticles of iron oxide (MPIO) conjugated to specific antibodies and/or peptides to provide contrast effects on MRI in relation to the molecular expression of a specified target. The experimental aims of this thesis were 1) to investigate the ability of VCAM-1 and P-selectin targeted MPIO to detect the expression of VCAM-1 and P-selectin on the activated endothelium in-vitro and in-vivo in mouse models of renal and cerebral ischemia reperfusion injury, and 2) develop a novel contrast agent for imaging αvβ3-integrin expression in angiogenesis using RGD peptide conjugated MPIO (RGD-MPIO) in-vitro. MPIO (1.0 µm) were conjugated to monoclonal antibodies against VCAM-1 (VCAM-MPIO) or P-selectin (PSEL-MPIO). In vitro, MPIO bound in a dose-dependent manner to tumor necrosis factor (TNF)-alpha stimulated sEND-1 endothelial cells when conjugated to VCAM-1 (R² = 0.88, P<0.01) and P-selectin antibodies (R² = 0.93, P<0.01), reflecting molecular VCAM-1 and P-selectin mRNA and protein expression. Mice subjected to unilateral, transient (30 minutes) renal ischemia and subsequent reperfusion received intravenous VCAM-MPIO and PSEL-MPIO (4.5 mg iron/kg body weight). In ischemic kidneys, MR related contrast effects of VCAM-MPIO were 4-fold higher than unclamped kidneys (P<0.01) and 1.5-fold higher than clamped kidneys of PSEL-MPIO injected mice (P<0.05). VCAM-MPIO binding was less evident in IRI kidneys pre-treated with VCAM-1 antibody (P<0.001). VCAM-1 mRNA expression and VCAM-MPIO contrast volume were highly correlated (R² = 0.901, P<0.01), indicating that quantification of contrast volume reflected renal VCAM-1 transcription. In mice subjected to cerebral ischemia, contrast volume was 11-fold greater in animals injected with VCAM-MPIO versus control IgG-MPIO (P<0.05). Finally, S-nitroso-N-acetylpenicillamine (SNAP) stimulated HUVEC-C cells, which express αvβ3-integrin, showed 44-fold greater RGD-MPIO binding than unstimulated cells (P<0.001) and 4-fold greater RGD-MPIO binding than SNAP stimulated cells blocked with soluble RGD peptide (P<0.001) in-vitro. This thesis demonstrated that targeted MPIO exhibited contrast effects that defined and quantified the molecular expression of specific targets through the use of high-resolution MRI in in-vitro and in-vivo models of vascular inflammation.

Experimental investigations of the optical properties of GaN nanostructured light emitting diode (LED) arrays are presented. Microphotoluminescence spectroscopy with pulsed and continuous wave lasers was used to probe the carrier dynamics and emission mechanisms of nanorod LED arrays fabricated by a top down etching method. Results show a possible reduction in internal electric field as nanorod diameter decreases. Localisation effects were also observed, affecting the spectral shape of the nanorod emission. Under two-photon excitation, quantum dot-like sharp spectral peaks in the PL spectra are found to exist in abundance amongst all the nanorod samples. The optical properties of these localised states, which are shown to be associated with the nanorod free-surfaces, are characterised using non-linear and time resolved spectroscopy. An investigation into spatially resolved single nanorods was also carried out. Single nanorods were isolated, and characterised using pulsed lasers. The etching is shown to increase the carrier decay life-time at extended intervals over several hundred ns. The temporal evolution and excitation power density dependence of the quantum dot-like states are also presented for the first time. The long lived localised states are thought to arise from surface effects, in particular Fermi-surface pinning, causing localisation and spatial separation of carriers. Additional work on nano-pyramid array LEDs, with quantum wells on semi-polar surfaces is also presented. Optical properties using micro-photoluminescence are compared to cathodoluminescence studies. An uneven distribution of emission wavelengths across the pyramid facet is thought to lead to an emission mechanism involving carriers transferring between multiple spatially localised states. Finally, experimental techniques and fabrication methods for future work are documented in detail.

This thesis is concerned with the chemical modification of polymers in the preparation of a library of materials which exhibit altered surface properties as a result of the surface chemical functionality, with particular emphasis on the development of materials that control biofouling and are antibacterial. Chemical modification of crosslinked polystyrene, in film and microsphere form, was carried out by carbene insertion followed by diazonium coupling. This provided access to a collection of materials with varying surface chemistry, whilst the bulk properties of the polystyrene substrates were maintained. Synthesis of the diaryldiazo and the diazonium salts used to perform the surface modifications is described, as well as the preparation and characterisation of the materials. Analysis of the ability of the materials to adsorb and bind the protein bovine serum albumin (BSA) is presented with data obtained from two methods of observation. Quartz Crystal Microbalance with Dissipation (QCM-D) and a protein assay based on the change in optical density of a BSA/PBS solution are used to demonstrate how the specific surface chemistry of the materials influences the ability to adsorb and bind protein. The behaviour of the materials was time dependent and was rationalised with respect to the surface water contact angle and the calculated parameters polar surface area and % polar surface area of the functional groups added to the surfaces. Finally, penicillin loaded materials were prepared and their antibacterial activity was tested against E. coli and S. aureus, demonstrating that the antibiotic is still active from within the polystyrene scaffold.

This Thesis explores the role of structural defects and disorder and their relationship to experimental data, with a particular emphasis on molecular framework materials. The question of how we can build atomistic models of amorphous materials from experimental data without needing to make system-specific assumptions is addressed. The role of 'structural invariance', <i>i.e.</i> the limited range of distinct local atomic environments within a material, as a restraint within reverse Monte Carlo refinement (RMC) is investigated. The operation of these invariance restraints operate is shown to be system-dependent and the challenges associated with effective refinement, <i>e.g.</i> configurational 'jamming', are also investigated. A generalisation to the 'structural simplicity', <i>i.e.</i> the simplest model, holding all else constant, is most likely to be correct. Three new metrics of structural simplicity are proposed: two intrinsically three-dimensional measures of local geometric invariance and one measure of local symmetry. These metrics are shown to robustly quantify the configurational quality. The ability of these metrics to act as effective restraints for the RMC refinement of amorphous materials is demonstrated by the construction of the first data-driven tetrahedral models of amorphous silicon. The role of defects and disorder within metal–organic frameworks (MOFs) is investigated through the canonical MOF UiO-66(Hf). Through a combination of techniques, including X-ray diffuse scattering, anomalous diffraction, total scattering and electron diffraction measurements, the existence of correlated metal-cluster absences in UiO-66(Hf) is demonstrated. Furthermore the ability to synthetically tune both the interactions and concentration of defects is shown. The thermomechanical properties of defective UiO-66(Hf) are also examined. UiO-66(Hf) is shown to rapidly densify by up to 5% (ΔV/V ) on ligand elimination. The resultant densified phase exhibits colossal (≥100MK^-1) volumetric negative thermal expansion (NTE); the largest reported value for any MOF. Finally, the capability to tune the physical properties of MOFs through defect incorporation is demonstrated through the defect-dependence of both the densification and the NTE.

Compressive residual stresses (CRS) are beneficial for enhancing the fatigue life of metal components. Shot Peening (SP) is an industrial cold working process that is applied to induce a field of CRS and modify the mechanical properties of the metal component. The SP process involves impacting a surface with tiny shots with forces sufficient to create plastic deformation. The process is governed by a number of important parameters such as the shot size, angle of attack, initial velocity, mass flow rate and the distance from the shot nozzle to the surface being peened. The relationship between the optimal peening outcome, particularly the residual stress distribution of the treated surface, and the peening parameters is still unknown and needs to be investigated further. Manufacturers are interested in producing a uniform peening process for complex geometries which optimises the SP parameters. Modelling the process is complex as it involves the interaction of a metallic surface with a large number of shots of very small diameter. Conventionally, such problems are solved using finite element software to predict stresses and strains of a single shot impact then applying superposition. At the moment there are no Finite Element Method (FEM) modelling solutions involving more than tens of shots. The number of shots and elements required for such a modelling process made the approach unfeasible prior to the work described herein. The objective of this work is to develop an appropriate numerical modelling approach that can better simulate the real SP process. The model will be provided by combining Discrete Element Method (DEM) with FEM. The DEM is employed to get a distribution of impact velocities over space and time which are then implemented into a FEM analysis. A discrete element model with randomly distributed steel shots bombarding a steel component at various velocities has been developed as benchmark example. With this model the SP shot - shot interaction, the shot - target interaction, the surface coverage, angle of impingement, shot size, impact velocity and the overall shot flow can be parametrically studied in details and with little computational effort. The novel approach also proposes a new method to dynamically change the coefficient of restitution for repeated impacts during the simulation and predicts the CRS more effectively. The effects of SP on different materials of relevance to gas turbine engine components will be investigated in order to improve the understanding of the interaction between the shots and the targeted material. Initially, an uncoupled analysis was peforned, in order to assess the capabilities of the two modelling systems, DEM and FEM, to delivery an improved solutuion when combining two commercially available codes. This parametric analysis is performed using the state-of-the-art Discrete Element (DE) application EDEM. In the subsequent part of this work, a dynamic Finite Element (FE) application Abaqus will be used to investigate single shot impacts and to obtain the residual stress distribution. This gives us a prescribed residual stress distribution and peening coverage. A Combined DEM/FEM tool (DEST) is proposed that eliminates any manual pre-processing required for linking/coupling, eliminating the use of two different applications and provide an integrated solution for the simulation of the Shot Peening process. In the subsequent chapter, the implementation of essential tools for the enchanced modelling of Shot Peening process functionalities, such as the nozzle, bounding box, coverage and intensity is described. A number of computational improvements are also implemented to reduce the computation time. The existing binary search is enhanced to self-balancing search tree and further improved to allow insertion and deletion of elements. A bounding box feature which removes shots that move out of the domain during the course of the simulation is also implemented. Experiments featuring single shot impacts are performed to gain better understanding the deformation process in the target material subjected to impact conditions to those occurring in the production peening. The single shot impacts are experimentally examined using SEM and EBSD. During final chapter, case studies are performed to compare the results of the simulations with large-scale experimental work. The coverage of peening of single and multiple nozzles with different angle of impingements are assessed. Finally, possible directions for further research concerning the accurate quantification of material responses to SP are identified in the report.

Graphene has unrivalled properties and is heralded as a revolutionary material for the 21^st century. Chemical vapour deposition (CVD) on metals is a promising method to produce large-area graphene. Controlling the properties of CVD graphene is vital for its integration in a wide-range of future applications. Many factors can influence the CVD growth of graphene and its properties, therefore further investigations will be beneficial to fully understand and control this technique. In this thesis I expand the knowledge about the growth of pure and heteroatom-doped graphene by low pressure chemical vapour deposition (LPCVD) and atmospheric pressure chemical vapour deposition (APCVD) on commercially available Cu and Pt foils. Using a range of characterisation techniques, I investigate the influence of the substrate’s properties and the synthesis conditions on the growth of graphene, in pursuit of improved, controlled or optimised production, which can promote high quality, large-area, single-layer graphene, or other as desired. By characterising the topography, surface roughness, crystallographic orientations, and chemical composition of six Cu foils, I find that their properties vary greatly and this influences the growth of CVD graphene. I elucidate that the commonly used 99.8 % Alfa Aesar Cu foil has a surface coating composed of calcium, chromium, and phosphorus, which detrimentally influences graphene growth. Cleaning Cu foils with CH₃COOH is shown to reduce the concentration of surface contaminants, consequently reducing the nucleation density and increasing the growth rate of CVD graphene. I also demonstrate that the shape, orientation, edge-geometry and thickness of CVD graphene domains can be controlled by the Cu crystallographic orientations. Single layer LPCVD graphene domains align with zigzag edges parallel to a single <101> direction on Cu{111} and Cu{101}, while bilayer domains align to two directions on Cu{001}. Hexagonal APCVD domains also preferentially align with edges parallel to the <101> direction(s). This discovery resolves a key challenge of controlling the orientation of individual graphene domains and opens a new avenue for tailored production of large-area CVD graphene with improved properties. By controlling the synthesis conditions of APCVD graphene on Pt foils I optimise production of ~0.5 mm single layer graphene domains with reduced nucleation density and increased growth rate of ~100 &mu;m/min by synthesis at 1150°C, a higher temperature than previously reported. The absence of large, hexagonal, single-crystal domains on pristine Pt foil, and observation of a reaction between quartz and Pt that promotes hexagonal domains, suggests that a silicon or platinum silicide surface layer may be advantageous for improved growth of graphene. Finally, I demonstrate that the dopant concentration of nitrogen-doped graphene is increased at lower synthesis temperatures and higher NH₃ concentration, up to 1.3 %, but with an associated decrease in the growth rate. Direct visualisation, elemental confirmation, and electronic characterisation of individual nitrogen atoms is shown for the first time using aberration corrected scanning transmission electron microscopy and electron energy loss spectroscopy. Boron-doped graphene is also synthesised. The implications of these findings, and many additional minor contributions, are wide-ranging and of considerable importance for the future understanding of CVD growth of graphene on metals, and more generally for the advancement of scientific knowledge for manufacturing large-area graphene. Collectively, these discoveries represent a significant body of work that can improve the efficiency of production and assist with controlling the properties of large-area CVD graphene.

The present work extends the Parametric Formulation of the Finite-Volume Theory to the case of heterogeneous materials with time-dependent behavior. Such a theory has already proved to be an efficient alternative to the Finite Element Method in the modeling of linear elastic heterogeneous materials. Firstly, general expressions for linear viscoelasticity are considered, determining deferred strains with a State Variables formulation. Expressions for the basic rheological models are given, extended to 3D situations and set in an adequate matrix form. Temperature dependence is modeled using the time-temperature equivalence principle. Then, the Parametric Formulation of the Finite-Volume Theory is reviewed and extended including the consideration of viscoelastic deformations. Detailed matrix expressions for the incremental solution of linear thermoviscoelastic problems are given. The numerical results are verified with several examples using analytical solutions found in the literature or determined by using the Correspondence Principle. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente trabalho tem por objetivo expandir a formulação numérica denominada Formulação Paramétrica da Teoria de Volumes Finitos para o caso de materiais com comportamento dependente do tempo. Tal teoria tem demonstrado ser uma eficiente alternativa ao Método dos Elementos Finitos para a modelagem de materiais heterogêneos elásticos lineares. Primeiramente, expressões gerais da viscoelasticidade linear são apresentadas, empregando-se uma formulação baseada em Variáveis de Estado para determinação das deformações dependentes do tempo. Expressões para os modelos reológicos básicos são dadas, estendidas para situações tridimensionais e estabelecidas em adequada forma matricial. A influência da temperatura sobre as propriedades viscoelásticas é modelada através de um princípio de equivalência tempo-temperatura. Em seguida, a Formulação Paramétrica da Teoria de Volumes Finitos é revisada e estendida para incluir a consideração de deformações viscoelásticas. Expressões detalhadas para a solução incremental de problemas termoviscoelásticos lineares são apresentadas. Os resultados numéricos são verificados através de vários exemplos usando soluções analíticas disponíveis na literatura ou determinadas pelo uso do Princípio da Correspondência.

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.

The aim of this thesis is to develop a deeper understanding and the technology in the nascent field of solid-state organic-inorganic perovskite solar cells. In recent years, perovskite materials have emerged as a low-cost, thin-film technology with efficiencies exceeding 16% challenging the quasi-paradigm that high efficiency photovoltaics must come at high costs. This thesis investigates perovskite solar cells in more detail with a focus on incorporating plasmonic nanostructures and perovskite film formation. Chapter 1 motivates the present work further followed by Chapter 2 which offers a brief background for solar cell fabrication and characterisation, perovskites in general, perovskite solar cells in specific, and plasmonics. Chapter 3 presents the field of plasmonics including simulation methods for various core-shell nanostructures such as gold-silica and silver-titania nanoparticles. The following Chapters 4 and 5 analyze plasmonic core-shell metal-dielectric nanoparticles embedded in perovskite solar cells. It is shown that using gold@silica or silver@titania NPs results in enhanced photocurrent and thus increased efficiency. After photoluminescence studies, this effect was attributed to an unexpected phenomenon in solar cells in which a lowered exciton binding energy generates a higher fraction of free charge. Embedding thermally unstable silver NPs required a low-temperature fabrication method which would not melt the Ag NPs. This work offers a new general direction for temperature sensitive elements. In Chapters 6 and 7, perovskite film formation is studied. Chapter 6 shows the existence of a previously unknown crystalline precursor state and an improved surface coverage by introducing a ramped annealing procedure. Based on this, Chapter 7 investigates different perovskite annealing protocols. The main finding was that an additional 130°C flash annealing step changed the film crystallinity dramatically and yielded a higher orientation of the perovskite crystals. The according solar cells showed an increased photocurrent attributed to a decrease in charge carrier recombination at the grain boundaries. Chapter 8 presents on-going work showing noteworthy first results for silica scaffolds, and layered, 2D perovskite structures for application in solar cells.