Synthesis and characterisation of titanium sol-gels in varied gravity environments

Sol-gel synthesis in varied gravity is only a relatively new topic in the literature and further investigation is required to explore its full potential as a method to synthesise novel materials. Although trialled for systems such as silica, the specific application of varied gravity synthesis to other sol-gel systems such as titanium has not previously been undertaken. Current literature methods for the synthesis of sol-gel material in reduced gravity could not be applied to titanium sol-gel processing, thus a new strategy had to be developed in this study. To successfully conduct experiments in varied gravity a refined titanium sol-gel chemical precursor had to be developed which allowed the single solution precursor to remain un-reactive at temperatures up to 50oC and only begin to react when exposed to a pressure decrease from a vacuum. Due to the new nature of this precursor, a thorough characterisation of the reaction precursors was subsequently undertaken with the use of techniques such as Nuclear Magnetic Resonance, Infra-red and UV-Vis spectroscopy in order to achieve sufficient understanding of precursor chemistry and kinetic stability. This understanding was then used to propose gelation reaction mechanisms under varied gravity conditions. Two unique reactor systems were designed and built with the specific purpose to allow the effects of varied gravity (high, normal, reduced) during synthesis of titanium sol-gels to be studied. The first system was a centrifuge capable of providing high gravity environments of up to 70 g’s for extended periods, whilst applying a 100 mbar vacuum and a temperature of 40-50oC to the reaction chambers. The second system to be used in the QUT Microgravity Drop Tower Facility was also required to provide the same thermal and vacuum conditions used in the centrifuge, but had to operate autonomously during free fall. Through the use of post synthesis characterisation techniques such as Raman Spectroscopy, X-Ray diffraction (XRD) and N2 adsorption, it was found that increased gravity levels during synthesis, had the greatest effect on the final products. Samples produced in reduced and normal gravity appeared to form amorphous gels containing very small particles with moderate surface areas. Whereas crystalline anatase (TiO2), was found to form in samples synthesised above 5 g with significant increases in crystallinity, particle size and surface area observed when samples were produced at gravity levels up to 70 g. It is proposed that for samples produced in higher gravity, an increased concentration gradient of water is forms at the bottom of the reacting film due to forced convection. The particles formed in higher gravity diffuse downward towards this excess of water, which favours the condensation reaction of remaining sol gel precursors with the particles promoting increased particle growth. Due to the removal of downward convection in reduced gravity, particle growth due to condensation reaction processes are physically hindered hydrolysis reactions favoured instead. Another significant finding from this work was that anatase could be produced at relatively low temperatures of 40-50oC instead of the conventional method of calcination above 450oC solely through sol-gel synthesis at higher gravity levels. It is hoped that the outcomes of this research will lead to an increased understanding of the effects of gravity on chemical synthesis of titanium sol-gel, potentially leading to the development of improved products suitable for diverse applications such as semiconductor or catalyst materials as well as significantly reducing production and energy costs through manufacturing these materials at significantly lower temperatures.

An exploratory study of the potential of resurfacing articular cartilage with synthetic phospholipids

This thesis is aimed at further understanding the uppermost lipid-filled membranous layer (i.e. surface amorphous layer (SAL)) of articular cartilage and to develop a scientific framework for re-introducing lipids onto the surface of lipid-depleted articular cartilage (i.e. "resurfacing"). The outcome will potentially contribute to knowledge that will facilitate the repair of the articular surface of cartilage where degradation is limited to the loss of the lipids of the SAL only. The surface amorphous layer is of utmost importance to the effective load-spreading, lubrication, and semipermeability (which controls its fluid management, nutrient transport and waste removal) of articular cartilage in the mammalian joints. However, because this uppermost layer of cartilage is often in contact during physiological function, it is prone to wear and tear, and thus, is the site for damage initiation that can lead to the early stages of joint condition like osteoarthritis, and related conditions that cause pain and discomfort leading to low quality of life in patients. It is therefore imperative to conduct a study which offers insight into remedying this problem. It is hypothesized that restoration (resurfacing) of the surface amorphous layer can be achieved by re-introducing synthetic surface-active phospholipids (SAPL) into the joint space. This hypothesis was tested in this thesis by exposing cartilage samples whose surface lipids had been depleted to individual and mixtures of synthetic saturated and unsaturated phospholipids. The surfaces of normal, delipidized, and relipidized samples of cartilage were characterized for their structural integrity and functionality using atomic force microscope (AFM), confocal microscope (COFM), Raman spectroscopy, magnetic resonance imaging (MRI) with image processing in the MATLAB® environment and mechanical loading experiments. The results from AFM imaging, confocal microscopy, and Raman spectroscopy revealed a successful deposition of new surface layer on delipidized cartilage when incubated in synthetic phospholipids. The relipidization resulted in a significant improvement in the surface nanostructure of the artificially degraded cartilage, with the complete SAPL mixture providing better outcomes in comparison to those created with the single SAPL components (palmitoyl-oleoyl-phosphatidylcholine, POPC and dipalmitoyl-phosphatidylcholine, DPPC). MRI analysis revealed that the surface created with the complete mixture of synthetic lipids was capable of providing semipermeability to the surface layer of the treated cartilage samples relative to the normal intact surface. Furthermore, deformation energy analysis revealed that the treated samples were capable of delivering the elastic properties required for load bearing and recovery of the tissue relative to the normal intact samples, with this capability closer between the normal and the samples incubated in the complete lipid mixture. In conclusion, this thesis has established that it is possible to deposit/create a potentially viable layer on the surface of cartilage following degradation/lipid loss through incubation in synthetic lipid solutions. However, further studies will be required to advance the ideas developed in this thesis, for the development of synthetic lipid-based injections/drugs for treatment of osteoarthritis and other related joint conditions.

Energy-based motion control of marine vehicles using interconnection and damping assignment passivity-based control : a survey

This paper reviews some recent results in motion control of marine vehicles using a technique called Interconnection and Damping Assignment Passivity-based Control (IDA-PBC). This approach to motion control exploits the fact that vehicle dynamics can be described in terms of energy storage, distribution, and dissipation, and that the stable equilibrium points of mechanical systems are those at which the potential energy attains a minima. The control forces are used to transform the closed-loop dynamics into a port-controlled Hamiltonian system with dissipation. This is achieved by shaping the energy-storing characteristics of the system, modifying its interconnection structure (how the energy is distributed), and injecting damping. The end result is that the closed-loop system presents a stable equilibrium (hopefully global) at the desired operating point. By forcing the closed-loop dynamics into a Hamiltonian form, the resulting total energy function of the system serves as a Lyapunov function that can be used to demonstrate stability. We consider the tracking and regulation of fully actuated unmanned underwater vehicles, its extension to under-actuated slender vehicles, and also manifold regulation of under-actuated surface vessels. The paper is concluded with an outlook on future research.

Total energy shaping of a class of underactuated Port-Hamiltonian Systems using a new set of closed-loop potential shape variables

This paper proposes a method for designing set-point regulation controllers for a class of underactuated mechanical systems in Port-Hamiltonian System (PHS) form. A new set of potential shape variables in closed loop is proposed, which can replace the set of open loop shape variables-the configuration variables that appear in the kinetic energy. With this choice, the closed-loop potential energy contains free functions of the new variables. By expressing the regulation objective in terms of these new potential shape variables, the desired equilibrium can be assigned and there is freedom to reshape the potential energy to achieve performance whilst maintaining the PHS form in closed loop. This complements contemporary results in the literature, which preserve the open-loop shape variables. As a case study, we consider a robotic manipulator mounted on a flexible base and compensate for the motion of the base while positioning the end effector with respect to the ground reference. We compare the proposed control strategy with special cases that correspond to other energy shaping strategies previously proposed in the literature.

Manoeuvring control of underactuated surface vessels using manifold regulation for Port-Hamiltonian systems

This paper considers the manoeuvring of underactuated surface vessels. The control objective is to steer the vessel to reach a manifold which encloses a waypoint. A transformation of configuration variables and a potential field are used in a Port-Hamiltonian framework to design an energy-based controller. With the proposed controller, the geometric task associated with the manoeuvring problem depends on the desired potential energy (closed-loop) and the dynamic task depends on the total energy and damping. Therefore, guidance and motion control are addressed jointly, leading to model-energy-based trajectory generation.

Control of energy and matter at nanoscales : challenges and opportunities for plasma nanoscience in a sustainability age

Plasma nanoscience is an emerging multidisciplinary research field at the cutting edge of a large number of disciplines including but not limited to physics and chemistry of plasmas and gas discharges, materials science, surface science, nanoscience and nanotechnology, solid-state physics, space physics and astrophysics, photonics, optics, plasmonics, spintronics, quantum information, physical chemistry, biomedical sciences and related engineering subjects. This paper examines the origin, progress and future perspectives of this research field driven by the global scientific and societal challenges. The future potential of plasma nanoscience to remain a highly topical area in the global research and technological agenda in the age of fundamental-level control for a sustainable future is assessed using a framework of the five Grand Challenges for Basic Energy Sciences recently mapped by the US Department of Energy. It is concluded that the ongoing research is very relevant and is expected to substantially expand to competitively contribute to the solution of all of these Grand Challenges. The approach to controlling energy and matter at nano- and subnanoscales is based on identifying the prevailing carriers and transfer mechanisms of the energy and matter at the spatial and temporal scales that are most relevant to any particular nanofabrication process. Strong accent is made on the competitive edge of the plasma-based nanotechnology in applications related to the major socio-economic issues (energy, food, water, health and environment) that are crucial for a sustainable development of humankind. Several important emerging topics, opportunities and multidisciplinary synergies for plasma nanoscience are highlighted. The main nanosafety issues are also discussed and the environment- and human health-friendly features of plasma-based nanotech are emphasized.

Disentangling fluxes of energy and matter in plasma-surface interactions : effect of process parameters

The possibility to discriminate between the relative importance of the fluxes of energy and matter in plasma-surface interaction is demonstrated by the energy flux measurements in low-temperature plasmas ignited by the radio frequency discharge (power and pressure ranges 50-250 W and 8-11.5 Pa) in Ar, Ar+ H2, and Ar+ H2 + CH4 gas mixtures typically used in nanoscale synthesis and processing of silicon- and carbon-based nanostructures. It is shown that by varying the gas composition and pressure, the discharge power, and the surface bias one can effectively control the surface temperature and the matter supply rates. The experimental findings are explained in terms of the plasma-specific reactions in the plasma bulk and on the surface.

Internal oscillating current-sustained RF plasmas : Parameters, stability, and potential for surface engineering

A new source of low-frequency (0.46 MHz) inductively coupled plasmas sustained by the internal planar "unidirectional" RF current driven through a specially designed internal antenna configuration has been developed. The experimental results of the investigation of the optical and global argon plasma parameters by the optical and Langmuir probes are presented. It is shown that the spatial profiles of the electron density, the effective electron temperature and plasma potential feature a great deal of the radial and axial uniformity compared with conventional sources of inductively coupled plasmas with external at coil configurations. The measurements also reveal a weak azimuthal dependence of the global plasma parameters at low values of the input RF power, which was earlier predicted theoretically. The azimuthal dependence of the global plasma parameters vanishes at high input RF powers. Moreover, under certain conditions, the plasma becomes unstable due to spontaneous transitions between low-density (electrostatic, E) and high-density (electromagnetic, H) operating modes. Excellent uniformity of high-density plasmas makes the plasma reactor promising for various plasma processing applications and surface engineering.

Hybrid polymer/metal nanoparticles with surface enhanced raman tracking for potential use in nanomedicine

This project was a preliminary step towards the development of novel methods for early stage cancer diagnosis and treatment. Diagnostic imaging agents with high Raman signal enhancement were developed based on tailored assemblies of gold nanoparticles, which demonstrated potential for non-invasive detection from deep under the skin surface. Specifically designed polymers were employed to assemble gold nanoparticles into controlled morphologies including dimers, nanochains, nanoplates, globular and core-satellite nanostructures. Our findings suggest that the Raman enhancement is strongly dependent on assembly morphology and can be tuned to adapt to the requirements of the diagnostic agent.

Examining the potential for design and renewable energy to contribute to zero energy housing in Queensland

This was a comparative study of the possibility of a net zero energy house in Queensland, Australia. It examines the actual energy use and thermal comfort conditions of an occupied Brisbane home and compares performance with the 10 star scale rating scheme for Australian residential buildings. An adaptive comfort psychometric chart was developed for this analysis. The house's capacity for the use of the natural ventilation was studied by CFD modelling. This study showed that the house succeeded in achieving the definition of net zero energy on an annual and monthly basis for lighting, cooking and space heating / cooling and for 70% of days for lighting, hot water and cooking services.

Potential-dependent surface-enhanced resonance raman spectroscopy at nanostructured TiO2 : A case study on cytochrome b5

Abstract: Nanostructured titanium dioxide (TiO2) electrodes, prepared by anodization of titanium, are employed to probe the electron-transfer process of cytochrome b5 (cyt b5) by surface-enhanced resonance Raman (SERR) spectroscopy. Concomitant with the increased nanoscopic surface roughness of TiO2, achieved by raising the anodization voltage from 10 to 20 V, the enhancement factor increases from 2.4 to 8.6, which is rationalized by calculations of the electric field enhancement. Cyt b 5 is immobilized on TiO2 under preservation of its native structure but it displays a non-ideal redox behavior due to the limited conductivity of the electrode material. The electron-transfer efficiency which depends on the crystalline phase of TiO2 has to be improved by appropriate doping for applications in bioelectrochemistry. Nanostructured TiO2 electrodes are employed to probe the electron-transfer process of cytochrome b5 by surface-enhanced resonance Raman spectroscopy. Concomitant with the increased nanoscopic surface roughness of TiO2, the enhancement factor increases, which can be attributed to the electric field enhancement. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transitioning to energy efficient vehicles: An analysis of the potential rebound effects and subsequent impact upon emissions

Given the shift toward energy efficient vehicles (EEVs) in recent years, it is important that the effects of this transition are properly examined. This paper investigates some of these effects by analyzing annual kilometers traveled (AKT) of private vehicle owners in Stockholm in 2008. The difference in emissions associated with EEV adoption is estimated, along with the effect of a congestion-pricing exemption for EEVs on vehicle usage. Propensity score matching is used to compare AKT rates of different vehicle owner groups based on the treatments of: EEV ownership and commuting across the cordon, controlling for confounding factors such as demographics. Through this procedure, rebound effects are identified, with some EEV owners found to have driven up to 12.2% further than non-EEV owners. Although some of these differences could be attributed to the congestion-pricing exemption, the results were not statistically significant. Overall, taking into account lifecycle emissions of each fuel type, average EEV emissions were 50.5% less than average non-EEV emissions, with this reduction in emissions offset by 2.0% due to rebound effects. Although it is important for policy-makers to consider the potential for unexpected negative effects in similar transitions, the overall benefit of greatly reduced emissions appears to outweigh any rebound effects present in this case study.

On the measurement of the surface energy budget over a land surface during the summer monsoon

The measurement of surface energy balance over a land surface in an open area in Bangalore is reported. Measurements of all variables needed to calculate the surface energy balance on time scales longer than a week are made. Components of radiative fluxes are measured while sensible and latent heat fluxes are based on the bulk method using measurements made at two levels on a micrometeorological tower of 10 m height. The bulk flux formulation is verified by comparing its fluxes with direct fluxes using sonic anemometer data sampled at 10 Hz. Soil temperature is measured at 4 depths. Data have been continuously collected for over 6 months covering pre-monsoon and monsoon periods during the year 2006. The study first addresses the issue of getting the fluxes accurately. It is shown that water vapour measurements are the most crucial. A bias of 0.25% in relative humidity, which is well above the normal accuracy assumed the manufacturers but achievable in the field using a combination of laboratory calibration and field intercomparisons, results in about 20 W m(-2) change in the latent heat flux on the seasonal time scale. When seen on the seasonal time scale, the net longwave radiation is the largest energy loss term at the experimental site. The seasonal variation in the energy sink term is small compared to that in the energy source term.

The potential role of a late gene expression factor, lef2, from Bombyx mori nuclear polyhedrosis virus in very late gene transcription and DNA replication

Several late gene expression factors (Lefs) have been implicated in fostering high levels of transcription from the very late gene promoters of polyhedrin and p10 from baculoviruses. We cloned and characterized from Bombyx mori nuclear polyhedrosis virus a late gene expression factor (Bmlef2) that encodes a 209-amino-acid protein harboring a Cys-rich C-terminal domain. The temporal transcription profiles of lef2 revealed a 1.2-kb transcript in both delayed early and late periods after virus infection. Transcription start site mapping identified the presence of an aphidicolin-sensitive late transcript arising from a TAAG motif located at -352 nucleotides and an aphidicolin-insensitive early transcript originating from a TTGT motif located 35 nucleotides downstream to a TATA box at -312 nucleotides, with respect to the +1 ATG of lef2. BmLef2 trans-activated very late gene expression from both polyhedrin and p10 promoters in transient expression assays. Internal deletion of the Cys-rich domain from the C-terminal region abolished the transcriptional activation. Inactivation of Lef2 synthesis by antisense lef2 transcripts drastically reduced the very late gene transcription but showed little effect on the expression from immediate early promoter. Decrease in viral DNA synthesis and a reduction in virus titer were observed only when antisense lef2 was expressed under the immediate early (ie-1) promoter. Furthermore, the antisense experiments suggested that lef2 plays a direct role in very late gene transcription.

Oxygen transfer and energy dissipation rate in surface aerator

The dissipation rate of turbulent kinetic energy (epsilon) is a key parameter for mixing in surface aerators. In particular, determination epsilon across the impeller stream, where the most intensive mixing takes place, is essential to ascertain that an appropriate degree of mixing is achieved. Present work by using commercial software VisiMix (R) calculates the energy dissipation rate in geometrically similar unbaffled surface aeration systems in order to scale-up the oxygen transfer process. It is found that in geometrically similar system, oxygen transfer rate is uniquely correlated with dissipation rate of energy. Simulation or scale-up equation governing oxygen transfer rate and dissipation rate of energy has been developed in the present work.