Fingerprints of a size-dependent crossover in the dimensionality of electronic conduction in Au-seeded Ge nanowires

We studied the electrical transport properties of Au-seeded germanium nanowires with radii ranging from 11 to 80 nm at ambient conditions. We found a non-trivial dependence of the electrical conductivity, mobility and carrier density on the radius size. In particular, two regimes were identified for large (lightly doped) and small (stronger doped) nanowires in which the charge-carrier drift is dominated by electron-phonon and ionized-impurity scattering, respectively. This goes in hand with the finding that the electrostatic properties for radii below ca. 37 nm have quasi one-dimensional character as reflected by the extracted screening lengths.

In step

In Step was a wearable artwork consisting of a pair of embroidered foot bandages and an actuator ‘cushion’ embedded with 15 electromechanical actuator pistons. The bandage was embedded with woven, soft and flexible fabric sensors - interconnected with metallic connecting threads, fasteners and a wireless interface (in a final form). When wrapped around a foot and lower leg the sensors sat on the ball of the toes and heel. This ‘wearable interface’ was then connected wirelessly to a soft sculptural form, which employed actuators to tap gently in response to the qualities of the walk detected by the soft sensors. In this way the ‘tread qualities’ of the walker could then be felt by someone else holding this device against their stomach – thereby allowing pairs of participants to ‘feel’ the tactile qualities of the other's walk. The work was presented both as a working object and via a short videorecorded performance.----- In Step generated innovative new approaches to interface and sensor embedded clothing/footware whilst also creating an evocative vehicle to comment upon contemporary Post Colonial theories of weight and groundedness – particularly the psycho-geographical ‘separation’ from the landscape that inspired Paul Carter’s “environmentally grounded poetics”. The work’s final form also suggested critical new directions for responsive clothing and footwear for the emerging genre of smart textiles.

Effect of height of bridge above water on salt deposition levels

Maintenance of bridge structures is a major issue for the Queensland Department of Main Roads. In the previous phase of this CRC project an initial approach was made towards the development of a program for lifetime prediction of metallic bridge components. This involved the analysis of five representative bridge structures with respect to salt deposition (a major contributor to metallic corrosion) to determine common elements to be used as “cases” - those defined for buildings are not applicable. The five bridges analysed included the Gladstone Port Access Road Overpass, Stewart Road Overpass, South Johnstone River Bridge, Johnson Creek Bridge and the Ward River Bridge.

Case definition and holistic model modifications required for building elements

This project is an extension of a previous CRC project (220-059-B) which developed a program for life prediction of gutters in Queensland schools. A number of sources of information on service life of metallic building components were formed into databases linked to a Case-Based Reasoning Engine which extracted relevant cases from each source.

Preliminary report on data mining techniques for life prediction

This project is an extension of a previous CRC project (220-059-B) which developed a program for life prediction of gutters in Queensland schools. A number of sources of information on service life of metallic building components were formed into databases linked to a Case-Based Reasoning Engine which extracted relevant cases from each source. In the initial software, no attempt was made to choose between the results offered or construct a case for retention in the casebase. In this phase of the project, alternative data mining techniques will be explored and evaluated. A process for selecting a unique service life prediction for each query will also be investigated. This report summarises the initial evaluation of several data mining techniques.

Report : analysis of maintenance database inputs

In the previous phase of this project, 2002-059-B Case-Based Reasoning in Construction and Infrastructure Projects, demonstration software was developed using a case-base reasoning engine to access a number of sources of information on lifetime of metallic building components. One source of information was data from the Queensland Department of Public Housing relating to maintenance operations over a number of years. Maintenance information is seen as being a particularly useful source of data about service life of building components as it relates to actual performance of materials in the working environment. If a building is constructed in 1984 and the maintenance records indicate that the guttering was replaced in 2006, then the service life of the gutters was 22 years in that environment. This phase of the project aims to look more deeply at the Department of Housing data, as an example of maintenance records, and formulate methods for using this data to inform the knowledge of service lifetimes.

Report : holistic model modifications for selected building elements

This project is an extension of a previous CRC project (220-059-B) which developed a program for life prediction of gutters in Queensland schools. A number of sources of information on service life of metallic building components were formed into databases linked to a Case-Based Reasoning Engine which extracted relevant cases from each source.

Report : effect of natural cleaning on salt deposition on Queensland bridges

Maintenance of bridge structures is a major issue for the Queensland Department of Main Roads. In the previous phase of this CRC project an initial approach was made towards the development of a program for lifetime prediction of metallic bridge components. This involved the analysis of five representative bridge structures with respect to salt deposition (a major contributor to metallic corrosion) to determine common elements to be used as “cases” - those defined for buildings are not applicable. The five bridges analysed included the Gladstone Port Access Road Overpass, Stewart Road Overpass, South Johnstone River Bridge, Johnson Creek Bridge and the Ward River Bridge.

Poly(3-hexyl-thiophene) coil-wrapped single wall carbon nanotube investigated by scanning tunneling spectroscopy

Scanning Tunneling Spectroscopy was performed on a (15,0) single wall carbon nanotube partially wrapped by Poly(3-hexyl-thiophene). On the bare nanotube section, the local density of states is in good agreement with the theoretical model based on local density approximation and remarkably is not perturbed by the polymer wrapping. On the coiled section, a rectifying current-voltage characteristic has been observed along with the charge transfer from the polymer to the nanotube. The electron transfer from Poly(3-hexyl-thiophene) to metallic nanotube was previously theoretically proposed and contributes to the presence of the Schottky barrier at the interface responsible for the rectifying behavior.

Characterization of electron trapping in dye-sensitized solar cells by near-IR transmittance measurements

In situ near-IR transmittance measurements have been used to characterize the density of trapped electrons in dye-sensitized solar cells (DSCs). Measurements have been made under a range experimental conditions including during open circuit photovoltage decay and during recording of the IV characteristic. The optical cross section of electrons at 940 nm was determined by relating the IR absorbance to the density of trapped electrons measured by charge extraction. The value, σn = 5.4 × 10-18 cm2, was used to compare the trapped electron densities in illuminated DSCs under open and short circuit conditions in order to quantify the difference in the quasi Fermi level, nEF. It was found that nEF for the cells studied was 250 meV over wide range of illuminat on intensities. IR transmittance measurements have also been used to quantify shifts in conduction band energy associated with dye adsorption.

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.

The rate-limiting mechanism for the heterogeneous burning of cylindrical iron rods

This paper presents the findings of an investigation into the rate-limiting mechanism for the heterogeneous burning in oxygen under normal gravity and microgravity of cylindrical iron rods. The original objective of the work was to determine why the observed melting rate for burning 3.2-mm diameter iron rods is significantly higher in microgravity than in normal gravity. This work, however, also provided fundamental insight into the rate-limiting mechanism for heterogeneous burning. The paper includes a summary of normal-gravity and microgravity experimental results, heat transfer analysis and post-test microanalysis of quenched samples. These results are then used to show that heat transfer across the solid/liquid interface is the rate-limiting mechanism for melting and burning, limited by the interfacial surface area between the molten drop and solid rod. In normal gravity, the work improves the understanding of trends reported during standard flammability testing for metallic materials, such as variations in melting rates between test specimens with the same cross-sectional area but different crosssectional shape. The work also provides insight into the effects of configuration and orientation, leading to an improved application of standard test results in the design of oxygen system components. For microgravity applications, the work enables the development of improved methods for lower cost metallic material flammability testing programs. In these ways, the work provides fundamental insight into the heterogeneous burning process and contributes to improved fire safety for oxygen systems in applications involving both normal-gravity and microgravity environments.

Determination of burn criterion for promoted combustion testing

Promoted ignition testing [1–3] is used to determine the relative flammability of metal rods in oxygen-enriched atmospheres. In these tests, a promoter is used to ignite each metal rod to start the sample burning. Experiments were performed to better understand the promoted ignition test by obtaining insight into the effect a burning promoter has on the preheating of a test sample. Test samples of several metallic materials were prepared and coupled to fast-responding thermocouples along their length. Various ignition promoters were used to ignite the test samples. The thermocouple measurements and test video were synchronized to determine temperature increase with respect to time and length along each test sample. A recommended length of test sample that must be consumed to be considered a flammable material was determined based on the preheated zone measured from these tests. This length was determined to be 30 mm (1.18 in.). Validation of this length and its rationale are presented.

Porous polyurethane coatings bonded onto surface-modified titanium substrates for the growth of an endothelial cell layer

Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.

Design and evaluation of an MRI compatible axial compression device for 3D assessment of spinal deformity and flexibility

Magnetic Resonance Imaging (MRI) offers a valuable research tool for the assessment of 3D spinal deformity in AIS, however the horizontal patient position imposed by conventional scanners removes the axial compressive loading on the spine which is an important determinant of deformity shape and magnitude in standing scoliosis patients. The objective of this study was to design, construct and test an MRI compatible compression device for research into the effect of axial loading on spinal deformity using supine MRI scans. The compression device was designed and constructed, consisting of a vest worn by the patient, which was attached via straps to a pneumatically actuated footplate. An applied load of 0.5 x bodyweight was remotely controlled by a unit in the scanner operator’s console. The entire device was constructed using non-metallic components for MRI compatibility. The device was evaluated by performing unloaded and loaded supine MRI scans on a series of 10 AIS patients. The study concluded that an MRI compatible compression device had been successfully designed and constructed, providing a research tool for studies into the effect of axial loading on 3D spinal deformity in scoliosis. The 3D axially loaded MR imaging capability developed in this study will allow future research investigations of the effect of axial loading on spinal rotation, and for imaging the response of scoliotic spinal tissues to axial loading.