Spelling suggestions: "subject:"matematerials sciences"" "subject:"datenmaterials sciences""
71 |
Probing the effect of oxygen vacancies in strontium titanate single crystalsRahman, Shams ur January 2014 (has links)
This thesis describes investigations into the role of non-stoichiometry in the surface and bulk properties of SrTiO<sub>3</sub> single crystals. A family of (n×n) reconstructions, where n = 2, 3, 4, 5, 6 are produced by argon ion sputtering of the SrTiO<sub>3</sub> (111) single crystals and subsequent annealing in UHV or in an oxygen rich environment. The sputtering process introduces defects or oxygen vacancies in the surface region of the sample, whilst the annealing gives rise to surface reconstructions. The surface preparation conditions such as sputtering time, annealing temperature and environment are optimized to obtain various reconstructions in a controlled and reproducible manner. High resolution STM images of these reconstructions are also obtained and utilized in the investigation of the surface reactivity. Fullerene molecules are deposited on the reconstructed surfaces to elucidate the surface reactivity through template assisted growth. Fullerene molecules are first deposited with substrate surfaces held at room temperature. Being the most highly reduced among the (n×n) family, the 5×5 reconstruction significantly influenced the growth of fullerenes. Both C<sub>60</sub> and C<sub>70</sub> adsorb as individual molecules and produce clusters with magic numbers. The 4×4 and 6×6 reconstructed surfaces encourage the formation of close-packed structures upon the deposition at room temperature. When the surface covered with fullerenes is heated to a temperature of around 200 °C, epitaxial islands are observed. The 6×6 reconstructed surface appeared to be less reactive than the 4×4. Electrical transport, cathodoluminescence (CL) and electron spin resonance (ESR) experiments are also carried out to investigate the effect of oxygen vacancies on the bulk properties of UHV annealed SrTiO<sub>3</sub> single crystals. Thermal reduction leads to carrier doping of the material, which not only gives rise to electrical conduction but also induces room temperature luminescence. Both the electrical conductivity and CL intensity increases with annealing time. The work presented in this thesis provides insight into the defect driven properties in both the surface and bulk of SrTiO<sub>3</sub> single crystals, which could play an important role in the development of oxide-based electronic devices.
|
72 |
Polymer carriers of toll-like receptor-7/8 agonists as vaccine adjuvantsLynn, Geoffrey M. January 2014 (has links)
There is currently a need for vaccine adjuvants that are effective for eliciting Th1-type CD4 and CD8 T cell responses when formulated with protein and peptide-based subunit vaccines. Some of the most promising adjuvants in this regard are combined small molecule Toll-like receptor-7/8 agonists (TLR-7/8a). However, poor pharmacokinetic properties have precluded TLR-7/8a for use in vaccines. In this thesis, polymer carriers were used to control pharmacokinetics and to modulate activity of TLR-7/8a for use as vaccine adjuvants. Combinatorial synthesis and in vivo structure-activity studies were used to evaluate how properties of Polymer-TLR-7/8a conjugates (Poly-7/8a) influence innate immune activation in lymph nodes that drain the site of vaccine administration. The most striking finding was that particle formation by Poly-7/8a strongly enhances the magnitude and duration (>14 days) of innate immune activation in lymph nodes by restricting agonist biodistribution and promoting uptake by dendritic cells. Particle-forming Poly-7/8a optimized for activity were found to induce only local innate immune activation (not systemic) and were effective for eliciting Th1-type CD4 and CD8 T cells that mediated protection against infectious challenge. Based on the importance of particle formation for activity of Poly-7/8a, thermo-responsive Poly-7/8a were developed that exist as single water-soluble macromolecules in solution but undergo temperature-driven particle formation in vivo. In conclusion, polymer carriers of TLR-7/8a represent a versatile and effective platform for modulating innate immune activity and warrant further investigation as a class of adjuvants for vaccines.
|
73 |
Elemental growth of oxide thin filmsWu, Chen January 2010 (has links)
This thesis reports on the elemental growth of oxide thin films including TiO<sub>x</sub>, BaO<sub>x</sub> and Ba<sub>x</sub>Ti<sub>y</sub>O<sub>z</sub> by Ti/Ba deposition and oxidation. The films were grown on two different substrates, Au(111) and SrTiO₃(001), and studied using a variety of surface characterisation techniques. On the reconstructed Au(111) surface, three different TiO<sub>x</sub> structures were obtained with increasing Ti amounts deposited: a (2 × 2) Ti₂O₃ honeycomb structure, a pinwheel structure that is the result of a Moiré pattern, and a triangular island TiO<sub>1.30</sub> structure. The structures arise from raised Ti coverages and have increased Ti densities. Although Ba deposited on the reconstructed Au(111) has a weak interaction with the substrate, the BaO<sub>x</sub> thin films can grow epitaxially and lift the Au(111) reconstruction. Two well-ordered phases, a (6 × 6) and a (2√3 × 2√3) BaO<sub>x</sub> structure, were obtained which may have octopolar-based surface structures. For Ba & Ti deposition on Au(111), a locally ordered (5 × 5) BaxTiyOz structure was observed in the sub-monolayer regime. What is more interesting is the possible formation of a BaO-TiO surface alloy with short-range ordering achieved by Ba deposition on the (2 × 2) Ti₂O₃-templated Au(111) surface. This is the first time that surface-alloying has been observed for oxides. When Ti is deposited onto the SrTiO₃(001) surface, it is incorporated into the substrate by forming a variety of Ti-rich SrTiO₃ surface reconstructions, such as c(4 × 2), (6 × 2), (9 × 2) and (√5 ×√5)-R26.6°. Ti deposition provides a completely different route to obtaining these reconstructions at much lower anneal temperatures than the previously reported preparation procedures involving sputtering and annealing the SrTiO₃ sample. Anatase islands with (1 × 3) and (1 × 5) periodicities were also formed by increasing the Ti deposition amount and post-annealing. Reconstructed SrTiO₃ substrate surface has a lattice that differs from the bulk crystal and affects the epitaxial growth of BaO, however, a locally ordered BaO<sub>x</sub> structure was observed on the sputtered substrate with a growth temperature of 300 °C. Depositing Ba & Ti on SrTiO₃(001) results in the formation of BaO<sub>x</sub> clusters and the Ti incorporation into the substrate, forming the familiar Ti-rich SrTiO₃ surface reconstructions.
|
74 |
Powder processing of oxide dispersion strengthened steels for nuclear applicationsGorley, Michael January 2014 (has links)
Ferritic ODS steels show improved high temperature strength and irradiation tolerance compared with conventional ferritic steels, and are one of the key potential materials for fusion blanket structural applications. The processing of ODS steels is critical to their subsequent performance; however knowledge of the optimum processing approaches for these alloys is not complete. The microstructural evolution of ODS steels containing Y<sub>2</sub>O<sub>3</sub> and other additions during manufacture has been investigated and the processing conditions optimised based on microstructural and mechanical investigations. Ferritic powders with Y<sub>2</sub>O<sub>3</sub> and other additions were investigated, primarily using analysis on the micro- and nano-scale, with an emphasis on identifying the requirements for homogenization of the Y within the steel matrix. The Y<sub>2</sub>O<sub>3</sub> dispersion and subsequent development of the nano-precipitates during thermal treatment was investigated using in-situ neutron diffraction. The nano-precipitates were resolved at approximately 900◦C after 1hr, with coarsening and/or re-precipitation progressively increasing at higher temperatures. A significantly increased number density of nano-precipitates (∼2x10<sup>23</sup>m−3 to ∼7x10<sup>23</sup>m−3) was established by hot isostatically pressing an Fe-14Cr-3W-0.2Ti0.25Y<sub>2</sub>O<sub>3</sub> alloy at 950◦C compared with more traditional temperatures at 1150◦C, attributed to the increased coarsening and/or re-precipitation of the nano-precipitates at the higher temperatures. The influence of the mechanical alloy (MA)ing conditions on bulk mechanical properties was investigated using four point bend. The highest fracture toughness of ∼55MN/m<sup>3/2</sup> and ultimate strength of ∼1450MPa was achieved under conditions that minimised the mechanical alloying time and increased the average final size of the powders. An Fe-14Cr-3W-0.2Ti-0.25Y<sub>2</sub>O<sub>3</sub> (wt%) ODS alloy manufactured under optimised conditions showed a bi-modal grain structure size distribution and had a comparatively high yield strength of >1200MPa at 20◦C and >330MPa at 700◦C. The grain structure and high yield strength were attributed to the random distribution of 25nm radius of gyration (R<sub>g</sub>) Y, Ti and O rich nano-precipitates randomly dispersed throughout the alloy. Long term thermal ageing (750hr at 1000◦C) reduced the room temperature yield strength and increased the proportion of larger grains in the bi-modal distribution, but high temperature yield strength was remarkably stable.
|
75 |
Characterisation of engineered nanoparticles and their interaction with natural biological and non-biological materialTaylor, Cameron S. January 2014 (has links)
Form, mobility, toxicity and the eventual fate of engineered nanomaterials in environmental ecosystems are currently not well defined and are needed to improve risk assessment and legislation. The present study subjected uncoated zinc oxide (ZnO) nanoparticles (30nm and 200nm) and coated silver (Ag) nanoparticles (Paraffin: 3-8nm and citrate/PVP: 50nm) to different ionic strength media and different types of algal/bacterial extracellular-polymeric species (EPS) at long (6 months) and short (2 weeks) timescales. Changes in particle size distribution and stability were examined using a multi-method approach. Sample concentration and sample polydispersity are important factors when selecting techniques. Uncoated ZnO nanoparticles aggregated heavily in water at high concentrations (1000mg/L). However silver nanoparticles (1-10mg/L) remained stable at all ionic strengths and EPS in this study due to the steric component of their coatings. Nano-toxicological experiments involving cyanobacteria S.leopoliensis and green algae C.reinhardtii showed size-dependent toxicity from coated nanosilver particles. Smaller nanoparticles (3-8nm) showed greater dissolution over 72h and greater toxicity to both species than 50nm particles indicating silver ions are an important toxicity mechanism. Nanoparticle coatings were likely important in controlling dissolution levels. Cell viability and production of reactive oxygen species (ROS) were shown to be important mechanisms of toxicity to phycological species. Species specific effects were noted for both silver nanoparticles. EPS from S.leopoliensis were noted to remove ionic silver from suspension and different types of C.reinhardtii EPS were produced when particles underwent different levels of toxic stress indicating that EPS could both affect particle toxicity and be affected by it. This work has demonstrated that coated nanoparticles could remain stable under various ionic strengths and with exposure to algal organic matter for timescales up to 6 months. This could result in adverse effects to aquatic organisms were they to reach environmental systems and is of concern to nanomaterial risk assessors.
|
76 |
Heart valve tissue engineeringTseng, Yuan-Tsan January 2011 (has links)
Since current prosthetic heart valve replacements are costly, cause medical complications, and lack the ability to regenerate, tissue-engineered heart valves are an attractive alternative. These could provide an unlimited supply of immunological-tolerated biological substitutes, which respond to patients' physiological condition and grow with them. Since collagen is a major extra cellular matrix component of the heart valve, it is ideal material for constructing scaffolds. Collagen sources have been shown to influence the manufacturing of collagen scaffolds, and two commercial sources of collagen were obtained from Sigma Aldrich and Devro PLC for comparison. Consistencies between the collagens were shown in the primary and secondary structures of the collagen, while inconsistencies were shown at the tertiary level, when a higher level of natural crosslinking in the Sigma collagen and longer polymer chains in the Devro collagen were observed. These variations were reduced and the consistency increased by introducing crosslinking via dehydrothermal treatment (DHT). Collagen scaffolds produced via freeze-drying (FD) and critical point-drying with cross-linking via DHT or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide /N-hydroxysuccinimide (EDC/NHS) were investigated. All the scaffolds were compatible with mesenchymal stem cells (MSCs) according to the proliferation of the cells and their ability to produce ECM, without differentiating between osteogenic, chondrogenic or endothelial lineages. The FD EDC/NHS scaffold demonstrated the most suitable physical property of all. This result illustrates that FD EDC/NHS crosslinking is the most suitable scaffold investigated as a start for heart valve tissue engineering. To prepare a scaffold with a controlled local, spatial and temporal delivery of growth factor, a composite scaffold comprising poly (lactic-co-glycolic acid) (PLGA) microspheres was developed. This composite scaffold demonstrated the same compatibility to the MSCs as untreated scaffold. However, the PLGA microspheres showed an increase in the deterioration rate of Young's modulus because of the detachment of the microspheres from the scaffold via cellular degradation.
|
77 |
p-block hydrogen storage materialsSmith, Christopher January 2010 (has links)
The development of a clean hydrogen economy will aid a smooth transition from fossil fuels which is required to stem the environmental impact and economic instability caused by oil dependency. For vehicular application, in addition to being cheap and safe, a commercial hydrogen store must contain a certain weight percentage of hydrogen to provide a reasonable range (~300 miles). It must also be able to release hydrogen under near-ambient conditions (80-120°C) and have a reasonable cycling capacity (~1000 cycles). The primary motivation of this thesis is to gain a fundamental understanding into the sorption processes of hydrogen on carbon- and aluminium-based materials to improve their hydrogen storage capacity. The sorption processes of hydrogen on mechanically milled graphite have been investigated, primarily using Electron Spin Resonance Spectroscopy and Inelastic Neutron Scattering. An investigation into the storage properties of tetrahydroaluminates, primarily NaAlH<sub>4</sub> and LiAlH<sub>4</sub>, is performed in the presence and absence of a catalyst, and a new phase of NaAlH<sub>4</sub> is observed prior to its decomposition. Variable temperature neutron and synchrotron diffraction, in conjunction with gravimetric and mass spectroscopy data were obtained for several mixtures of tetrahydroaluminates and alkali amides and the hydrogen desorption processes are shown to be quite different from the constituent materials. The structure of Ca(AlH<sub>4</sub>)<sub>2</sub> has been experimentally determined for the first time and a complete set of equations describing its decomposition pathway is given.
|
78 |
Transferable reduced TB models for elemental Si and N and binary Si-N systemsGehrmann, Jan January 2013 (has links)
Silicon nitride is a bulk and a coating material exhibiting excellent mechanical properties. The understanding of the complex processes at the nanometre scale gained through experimental research will be enhanced by the existence of a computationally efficient and accurate model that is able to describe the mechanical properties of silicon nitride. Such a model has yet to be proposed. In this thesis we present a transferable reduced tight-binding (TB) model for the silicon nitride system. More precisely, this model consists of a reduced TB model for elemental silicon, a reduced TB model for elemental nitrogen, and a reduced TB model for silicon nitride. These models are developed within the framework of coarse-graining the electronic structure from density functional theory (DFT) to tight binding (TB) to bond-order potentials (BOPs), and can therefore be used in the future as the stepping stone to develop BOPs for the application in large scale simulations. The bond integrals employed in the reduced TB models are obtained directly from mixed-basis DFT projections of wave functions onto a minimal basis of atom-centred orbitals. This approach reduces the number of overall parameters to be fitted and provides models which are transferable through the different coarse-graining levels. We provide an example by using the same bond integrals in the reduced TB model for silicon and the preliminary bond-based BOP for silicon. DFT binding energies of ground state and metastable crystal structures are used as the benchmark to which the TB and BOP repulsive parameters are fitted. In addition to model development, we present an improved methodology when going from TB to reduced TB. By weighting all four σ TB bond integrals equally, we provide a new parameterisation (Eqs. (2.73) and (2.74)) and show that the quality of the silicon reduced TB model can be increased by choosing one of the reduced TB parameters to be distance invariant. The ingredients, the development methodology, and the quality of each of the four models are discussed in a separate chapter. The quality of the reduced TB models and BOP is demonstrated by comparing their predictions for the binding energies, heats of formation, elastic constants, and defect energies with DFT and experimental values.
|
79 |
Structural and electronic investigations of In₂O₃ nanostructures and thin films grown by molecular beam epitaxyZhang, Kelvin Hongliang January 2011 (has links)
Transparent conducting oxides (TCOs) combine optical transparency in the visible region with a high electrical conductivity. In2O3 doped with Sn (widely, but somewhat misleadingly, known as indium tin oxide or ITO) is at present the most important TCO, with applications in liquid crystal displays, touch screen displays, organic photovoltaics and other optoelectronic devices. Surprisingly, many of its fundamental properties have been the subject of controversy or have until recently remained unknown, including even the nature and magnitude of the bandgap. The technological importance of the material and the renewed interest in its basic physics prompted the research described in this thesis. This thesis aims (i) to establish conditions for the growth of high-quality In2O3 nanostructures and thin films by oxygen plasma assisted molecular beam epitaxy and (ii) to conduct comprehensive investigations on both the surface physics of this material and its structural and electronic properties. It was demonstrated that highly ordered In2O3 nanoislands, nanorods and thin films can be grown epitaxially on (100), (110) and (111) oriented Y-stabilized ZrO2 substrates respectively. The mismatch with this substrate is -1.7%, with the epilayer under tensile strain. On the basis of ab initio density functional theory calculations, it was concluded that the striking influence of substrate orientation on the distinctive growth modes was linked to the fact that the surface energy for the (111) surface is much lower than for either polar (100) or non-polar (110) surfaces. The growth of In2O3(111) thin films was further explored on Y-ZrO2(111) substrates by optimizing the growth temperature and film thickness. Very thin In2O3 epilayers (35 nm) grew pseudomorphically under high tensile strain, caused by the 1.7% lattice mismatch with the substrate. The strain was gradually relaxed with increasing film thickness. High-quality films with a low carrier concentration (5.0 1017 cm-3) and high mobility (73 cm2V-1s-1) were obtained in the thickest films (420 nm) after strain relaxation. The bandgap of the thinnest In2O3 films was around 0.1 eV smaller than that of the bulk material, due to reduction of bonding-antibonding interactions associated with lattice expansion. The high-quality surfaces of the (111) films allowed us to investigate various aspects of the surface structural and electronic properties. The atomic structure of In2O3 (111) surface was determined using a combination of scanning tunnelling microscopy, analysis of intensity/voltage curves in low energy electron diffraction and first-principles ab initio calculations. The (111) termination has an essentially bulk terminated (1 × 1) surface structure, with minor relaxations normal to the surface. Good agreement was found between the experimental surface structure and that derived from ab initio density functional theory calculations. This work emphasises the benefits of a multi-technique approach to determination of surface structure. The electronic properties of In2O3(111) surfaces were probed by synchrotron-based photoemission spectroscopy using photons with energies ranging from the ultraviolet (6 eV) to the hard X-ray regime (6000 eV) to excite the spectra. It has been shown that In2O3 is a highly covalent material, with significant hybridization between O and In orbitals in both the valence and the conduction bands. A pronounced electron accumulation layer presents itself at the surfaces of undoped In2O3 films with very low carrier concentrations, which results from the fact the charge neutrality level of In2O3 lies well above the conduction band minimum. The pronounced electron accumulation associated with a downward band bending in the near surface region creates a confining potential well, which causes the electrons in the conduction band become quantized into two subband states, as observed by angle resolved photoemission spectra (ARPES) Fermi surface mapping. The accumulation of high density of electrons near to the surface region was found to shrink the surface band gap through many body interactions. Finally epitaxial growth of In2O3 thin films on α-Al2O3(0001) substrates was investigated. Both the stable body centred cubic phase and the metastable hexagonal corundum In2O3 phase can be stabilized as epitaxial thin films, despite large mismatches with the substrate. The growth mode involves matching small but different integral multiples of lattice planes of the In2O3 and the substrate in a domain matching epitaxial growth mode.
|
80 |
The rational design of photocatalytic semiconductor nanocrystalsEley, Clive William January 2014 (has links)
This thesis reports the successful rational design of three highly active photocatalytic semiconductor nanocrystal (SNC) systems by exploiting morphology effects and the electronic properties of type II semiconductor heterojunctions. Novel architectures of colloidal SNCs are produced with the aim of suppressing exciton recombination and improving charge extraction for the successful initiation of desirable redox chemistry. Rod-shaped niobium pentoxide Nb<sub>2</sub>O<sub>5</sub> nanocrystals (NCs) are shown to exhibit significantly enhanced activity (10-fold increase in rate constant) relative to spherical-shaped NCs of the same material. The increase is attributed to Nb5<sup>+</sup> Lewis acid site rich (001) surfaces, present in higher proportions in the rod morphology, which bind organic substrates from solution resulting in direct interaction with photogenerated charges on the surface of the NC. Building on the insights into morphology-activity dependence, type II semiconductor heterojunctions are exploited for their ability to increase exciton lifetimes and spatially separate charges. Two novel II-VI heterostructured semiconductor nanocrystals (HSNCs) systems are investigated: a series of CdX/ZnO (X = S, Se, Te) HSNCs and ZnS/ZnO HSNCs capped with two different surface ligands. In the first case, substantial photocatalytic activity improvement is observed for HSNCs (relative to pure ZnO analogues) according to the following trend: CdTe/ZnO > CdS/ZnO > CdSe/ZnO. The observed trend is explained in terms of heterojunction structure and fundamental chalcogenide chemistry. In the second case, both ZnS/ZnO HSNCs exhibit activity enhancement over analogous pure ZnO, but the degree of enhancement is found to be a function of surface ligand chemistry. Photocatalytic activity testing of all the materials investigated in this work is performed via the photodecomposition of methylene blue dye in aerated aqueous conditions under UVA (350 nm) irradiation. The synthetic techniques employed for the synthesis of colloidal SNCs investigated in this thesis range from chemical precipitation and solvothermal techniques to several different organometallic approaches. A wide variety of analytical techniques are employed for the chemical, structural and optical characterisation of SNC photocatalysts including: XRD, XPS, TEM, UV-vis absorption, PL spectroscopy and FTIR. Atom Probe Tomography (APT) is employed for the first time in the structural characterisation of II-VI heterojunctions in colloidal HSNCs. Overall, this thesis provides a useful contribution to the growing body of knowledge pertaining to the enhancement of photocatalytic SNCs for useful applications including: solar energy conversion to chemical fuels, the photodecomposition of pollutants and light-driven synthetic chemistry.
|
Page generated in 0.06 seconds