Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

A proposed qualitative framework for heterogeneous burning of metallic materials : the 'melting rate triangle'

This paper presents a proposed qualitative framework to discuss the heterogeneous burning of metallic materials, through parameters and factors that influence the melting rate of the solid metallic fuel (either in a standard test or in service). During burning, the melting rate is related to the burning rate and is therefore an important parameter for describing and understanding the burning process, especially since the melting rate is commonly recorded during standard flammability testing for metallic materials and is incorporated into many relative flammability ranking schemes. However, whilst the factors that influence melting rate (such as oxygen pressure or specimen diameter) have been well characterized, there is a need for an improved understanding of how these parameters interact as part of the overall melting and burning of the system. Proposed here is the ‘Melting Rate Triangle’, which aims to provide this focus through a conceptual framework for understanding how the melting rate (of solid fuel) is determined and regulated during heterogeneous burning. In the paper, the proposed conceptual model is shown to be both (a) consistent with known trends and previously observed results, and (b)capable of being expanded to incorporate new data. Also shown are examples of how the Melting Rate Triangle can improve the interpretation of flammability test results. Slusser and Miller previously published an ‘Extended Fire Triangle’ as a useful conceptual model of ignition and the factors affecting ignition, providing industry with a framework for discussion. In this paper it is shown that a ‘Melting Rate Triangle’ provides a similar qualitative framework for burning, leading to an improved understanding of the factors affecting fire propagation and extinguishment.

Experimental tests on structural members fabricated from high strength steel materials

Typical high strength steels (HSS) have exceptional high strengths with improved weldability making the material attractive in modern steel constructions. However, due to lack of understanding, most of the current steel design standards are limited to conventional low strength steels (LSS, i.e. fy ≤ 450 MPa). This paper presents the details of full-scale experimental tests on short beams fabricated from BISPLATE80 HSS materials (nominal fy = 690 MPa). The various slenderness ratios of the plate elements in the test specimens were chosen in the range near the current yield limit (AS4100-1998, etc.). The experimental studies presented in this paper have produced a better understanding of the structural behaviour of HSS members subjected to local instabilities. Comparisons have also presented in the paper regarding to the design predictions from the current steel standards (AS4100-1998). This study has enabled to provide a series of proposals for proper assessment of plate slenderness limits for structural members made of representative HSS materials. This research work also enables the inclusion of further versions in the steel design specifications for typical HSS materials to be used in buildings and bridges. This paper also presents a distribution model of residual stresses in the longitudinal direction for typical HSS I-sections.

Bioactive inorganic materials/alginate composite microspheres with controllable drug-delivery ability

Alginate microspheres are considered a promising material as a drug carrier in bone repair due to excellent biocompatibility, but their main disadvantage is low drug entrapment efficiency and non-controllable release. The aim of this study was to investigate the effect of incorporating mesoporous bioglass (MBG), non-mesoporous bioglass (BG) or hydroxyapatite (HAp) into alginate microspheres on their drug-loading and release properties. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and atomic emission spectroscopy (AES) were used to analyse the composition, structure and dissolution of bioactive inorganic materials and their microspheres. Dexamethasone (DEX)-loading and release ability of four microspheres were tested in phosphate buffered saline with varying pHs. Results showed that the drug-loading capacity was enhanced with the incorporation of bioactive inorganic materials into alginate microspheres. The MBG/Alginate microspheres had the highest drug loading ability. DEX release from alginate microspheres correlated to the dissolution of MBG, BG and HAp in PBS, and that the pH was an efficient factor in controlling the DEX release; a high pH resulted in greater DEX release, whereas a low pH delayed DEX release. In addition, MBG/alginate, BG/alginate and HAp/alginate microspheres had varying apatite-formation and dissolution abilities, which indicate that the composites would behave differently with respect to bioactivity. The study suggests that microspheres made of a composite of bioactive inorganic materials and alginate have a bioactivity and degradation profile which greatly improves their drug delivery capacity, thus enhancing their potential applications as bioactive filler materials for bone tissue regeneration.

The increased flammability of metallic materials burning in reduced gravity

Data generated in a normal gravity environment is often used in design and risk assessment for reduced gravity applications. It has been clearly demonstrated that this is a conservative approach for non-metallic materials which have been repeatedly shown to be less flammable in a reduced gravity environment. However, recent work has demonstrated this is not true for metallic materials. This work, conducted in a newly completed drop tower observed a significant increase in both lowest burn pressure and burn rate in reduced gravity. Hence the normal gravity qualification of a metallic materials’ lowest burn pressure or burn rate for reduced-gravity or space-based systems is clearly not conservative. This paper presents a summary of this work and the results obtained for several metallic materials showing an increased flammability and burn rate for a range of oxygen pressures, and discusses the implications of this work on the fire-safety of space-based systems.

Research training and national innovation systems in Australia, Finland and the United States : a policy and systems study supported by 30 case studies of research students in the fields of geospatial science, wireless communication, biosciences, and materials science and engineering

Reforms to the national research and research training system by the Commonwealth Government of Australia sought to effectively connect research conducted in universities to Australia's national innovation system. Research training has a key role in ensuring an adequate supply of highly skilled people for the national innovation system. During their studies, research students produce and disseminate a massive amount of new knowledge. Prior to this study, there was no research that examined the contribution of research training to Australia's national innovation system despite the existence of policy initiatives aiming to enhance this contribution. Given Australia's below average (but improving) innovation performance compared to other OECD countries, the inclusion of Finland and the United States provided further insights into the key research question. This study examined three obvious ways that research training contributes to the national innovation systems in the three countries: the international mobility and migration of research students and graduates, knowledge production and distribution by research students, and the impact of research training as advanced human capital formation on economic growth. Findings have informed the concept of a research training culture of innovation that aims to enhance the contribution of research training to Australia's national innovation system. Key features include internationally competitive research and research training environments; research training programs that equip students with economically-relevant knowledge and the capabilities required by employers operating in knowledge-based economies; attractive research careers in different sectors; a national commitment to R&D as indicated by high levels of gross and business R&D expenditure; high private and social rates of return from research training; and the horizontal coordination of key organisations that create policy for, and/or invest in research training.

CC & Government Guide : Using Creative Commons 2.5 Australia Licences on Government Copyright Materials

This guide explains how copyright law applies to Australian government material, how copyright can be managed to facilitate beneficial open access practices by government, how CC licences can be used to achieve open access to government material, and provides practical step-by-step guidance for agencies and their officers on licensing and use of government copyright materials under CC 2.5 Australia licences.

Piezoelectric PVDF materials performance and operation limits in space environments

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films are achieved via charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to suffer due to strong vacuum UV, gamma, X-ray, energetic particles and atomic oxygen under low earth orbit exposure conditions. The degradation of PVDF and its copolymers under various stress environments has been investigated. Initial radiation aging studies using gamma- and e-beam irradiation have shown complex material changes with significant crosslinking, lowered melting and Curie points (where observable), effects on crystallinity, but little influence on overall piezoelectric properties. Surprisingly, complex aging processes have also been observed in elevated temperature environments with annealing phenomena and cyclic stresses resulting in thermal depoling of domains. Overall materials performance appears to be governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and AO exposure is evident as depoling and surface erosion. Major differences between individual copolymers have been observed providing feedback on material selection strategies.

Fouling of tubular ceramic membranes during processing of cane sugar juice

This paper examines the fouling characteristics of four tubular ceramic membranes with pore sizes 300 kDa, 0.1 μm and 0.45 μm installed in a pilot plant at a sugar factory for processing clarified cane sugar juices. All the membranes, except the one with a pore size of 0.45 μm, generally gave reproducible results through the trials, were easy to clean and could handle operation at high volumetric concentration factors. Analysis of fouled and cleaned ceramic membranes revealed that polysaccharides, lipids and to a lesser extent, polyphenols, as well as other colloidal particles cause fouling of the membranes. Electrostatic and hydrophobic forces cause strong aggregation of the polymeric components with one another and with colloidal particles. To combat irreversible fouling of the membranes, treatment options that result in the removal of particles having a size range of 0.2–0.5 μm and in addition remove polymeric impurities, need to be identified. Chemical and microscopic evaluations of the juices and the structural characterisation of individual particles and aggregates identified options to mitigate the fouling of membranes. These include conditioning the feed prior to membrane filtration to break up the network structure formed between the polymers and particles in the feed and the use of surfactants to prevent the aggregation of polymers and particles.