Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)-tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1)

In the title compound, [Al(C8H4F3O2S)3]3[Fe(C8H4F3O2S)3], the metal centre is statistically occupied by AlIII and FeIII cations in a 3:1 ratio. The metal centre is within an octahedral O6 donor set defined by three chelating substituted acetoacetonate anions. The ligands are arranged around the periphery of the molecule with a mer geometry of the S atoms.

Metal oxide nanofibres membranes assembled by spin-coating method

Ceramic membranes are of particular interest in many industrial processes due to their ability to function under extreme conditions while maintaining their chemical and thermal stability. Major structural deficiencies under conventional fabrication approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using larger titanate nanofibres and smaller boehmite nanofibres. This yields a radical change in membrane texture. The differences in the porous supports have no substantial influences on the texture of resulting membranes. The membranes with top layer of nanofibres coated on different porous supports by spin-coating method have similar size of the filtration pores, which is in a range of 10–100 nm. These membranes are able to effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. The retention can attain more than 95%, while maintaining a high flux rate about 900 L m-2 h. The calcination after spin-coating creates solid linkages between the fibres and between fibres and substrate, in addition to convert boehmite into -alumina nanofibres. This reveals a new direction in membrane fabrication.

The paradox of transparency : short-termism and the institutionalisation of Australian capital markets

As the ultimate corporate decision-makers, directors have an impact on the investment time horizons of the corporations they govern. How they make investment decisions has been profoundly influenced by the expansion of the investment chain and the increasing concentration of share ownership in institutional hands. By examining agency in light of legal theory, we highlight that the board is in fact sui generis and not an agent of shareholders. Consequently, transparency can lead to directors being 'captured' by institutional investor objectives and timeframes, potentially to the detriment of the corporation as a whole. The counter-intuitive conclusion is that transparency may, under certain conditions, undermine good corporate governance and lead to excessive short-termism.

Estimating short and long-term residential demand for electricity : new evidence from Sri Lanka

This study investigates the short-run dynamics and long-run equilibrium relationship between residential electricity demand and factors influencing demand - per capita income, price of electricity, price of kerosene oil and price of liquefied petroleum gas - using annual data for Sri Lanka for the period, 1960-2007. The study uses unit root, cointegration and error-correction models. The long-run demand elasticities of income, own price and price of kerosene oil (substitute) were estimated to be 0.78, - 0.62, and 0.14 respectively. The short-run elasticities for the same variables were estimated to be 032, - 0.16 and 0.10 respectively. Liquefied petroleum (LP) gas is a substitute for electricity only in the short-run with an elasticity 0.09. The main findings of the paper support the following (1) increasing the price of electricity is not the most effective tool to reduce electricity consumption (2) existing subsidies on electricity consumption can be removed without reducing government revenue (3) the long-run income elasticity of demand shows that any future increase in household incomes is likely to significantly increase the demand for electricity and(4) any power generation plans which consider only current per capita consumption and population growth should be revised taking into account the potential future income increases in order to avoid power shortages ill the country.

A new multilevel converter configuration for high power and high quality applications

The Queensland University of Technology (QUT) allows the presentation of theses for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of ten published /submitted papers and book chapters of which nine have been published and one is under review. This project is financially supported by an Australian Research Council (ARC) Discovery Grant with the aim of investigating multilevel topologies for high quality and high power applications, with specific emphasis on renewable energy systems. The rapid evolution of renewable energy within the last several years has resulted in the design of efficient power converters suitable for medium and high-power applications such as wind turbine and photovoltaic (PV) systems. Today, the industrial trend is moving away from heavy and bulky passive components to power converter systems that use more and more semiconductor elements controlled by powerful processor systems. However, it is hard to connect the traditional converters to the high and medium voltage grids, as a single power switch cannot stand at high voltage. For these reasons, a new family of multilevel inverters has appeared as a solution for working with higher voltage levels. Besides this important feature, multilevel converters have the capability to generate stepped waveforms. Consequently, in comparison with conventional two-level inverters, they present lower switching losses, lower voltage stress across loads, lower electromagnetic interference (EMI) and higher quality output waveforms. These properties enable the connection of renewable energy sources directly to the grid without using expensive, bulky, heavy line transformers. Additionally, they minimize the size of the passive filter and increase the durability of electrical devices. However, multilevel converters have only been utilised in very particular applications, mainly due to the structural limitations, high cost and complexity of the multilevel converter system and control. New developments in the fields of power semiconductor switches and processors will favor the multilevel converters for many other fields of application. The main application for the multilevel converter presented in this work is the front-end power converter in renewable energy systems. Diode-clamped and cascade converters are the most common type of multilevel converters widely used in different renewable energy system applications. However, some drawbacks – such as capacitor voltage imbalance, number of components, and complexity of the control system – still exist, and these are investigated in the framework of this thesis. Various simulations using software simulation tools are undertaken and are used to study different cases. The feasibility of the developments is underlined with a series of experimental results. This thesis is divided into two main sections. The first section focuses on solving the capacitor voltage imbalance for a wide range of applications, and on decreasing the complexity of the control strategy on the inverter side. The idea of using sharing switches at the output structure of the DC-DC front-end converters is proposed to balance the series DC link capacitors. A new family of multioutput DC-DC converters is proposed for renewable energy systems connected to the DC link voltage of diode-clamped converters. The main objective of this type of converter is the sharing of the total output voltage into several series voltage levels using sharing switches. This solves the problems associated with capacitor voltage imbalance in diode-clamped multilevel converters. These converters adjust the variable and unregulated DC voltage generated by renewable energy systems (such as PV) to the desirable series multiple voltage levels at the inverter DC side. A multi-output boost (MOB) converter, with one inductor and series output voltage, is presented. This converter is suitable for renewable energy systems based on diode-clamped converters because it boosts the low output voltage and provides the series capacitor at the output side. A simple control strategy using cross voltage control with internal current loop is presented to obtain the desired voltage levels at the output voltage. The proposed topology and control strategy are validated by simulation and hardware results. Using the idea of voltage sharing switches, the circuit structure of different topologies of multi-output DC-DC converters – or multi-output voltage sharing (MOVS) converters – have been proposed. In order to verify the feasibility of this topology and its application, steady state and dynamic analyses have been carried out. Simulation and experiments using the proposed control strategy have verified the mathematical analysis. The second part of this thesis addresses the second problem of multilevel converters: the need to improve their quality with minimum cost and complexity. This is related to utilising asymmetrical multilevel topologies instead of conventional multilevel converters; this can increase the quality of output waveforms with a minimum number of components. It also allows for a reduction in the cost and complexity of systems while maintaining the same output quality, or for an increase in the quality while maintaining the same cost and complexity. Therefore, the asymmetrical configuration for two common types of multilevel converters – diode-clamped and cascade converters – is investigated. Also, as well as addressing the maximisation of the output voltage resolution, some technical issues – such as adjacent switching vectors – should be taken into account in asymmetrical multilevel configurations to keep the total harmonic distortion (THD) and switching losses to a minimum. Thus, the asymmetrical diode-clamped converter is proposed. An appropriate asymmetrical DC link arrangement is presented for four-level diode-clamped converters by keeping adjacent switching vectors. In this way, five-level inverter performance is achieved for the same level of complexity of the four-level inverter. Dealing with the capacitor voltage imbalance problem in asymmetrical diodeclamped converters has inspired the proposal for two different DC-DC topologies with a suitable control strategy. A Triple-Output Boost (TOB) converter and a Boost 3-Output Voltage Sharing (Boost-3OVS) converter connected to the four-level diode-clamped converter are proposed to arrange the proposed asymmetrical DC link for the high modulation indices and unity power factor. Cascade converters have shown their abilities and strengths in medium and high power applications. Using asymmetrical H-bridge inverters, more voltage levels can be generated in output voltage with the same number of components as the symmetrical converters. The concept of cascading multilevel H-bridge cells is used to propose a fifteen-level cascade inverter using a four-level H-bridge symmetrical diode-clamped converter, cascaded with classical two-level Hbridge inverters. A DC voltage ratio of cells is presented to obtain maximum voltage levels on output voltage, with adjacent switching vectors between all possible voltage levels; this can minimize the switching losses. This structure can save five isolated DC sources and twelve switches in comparison to conventional cascade converters with series two-level H bridge inverters. To increase the quality in presented hybrid topology with minimum number of components, a new cascade inverter is verified by cascading an asymmetrical four-level H-bridge diode-clamped inverter. An inverter with nineteen-level performance was achieved. This synthesizes more voltage levels with lower voltage and current THD, rather than using a symmetrical diode-clamped inverter with the same configuration and equivalent number of power components. Two different predictive current control methods for the switching states selection are proposed to minimise either losses or THD of voltage in hybrid converters. High voltage spikes at switching time in experimental results and investigation of a diode-clamped inverter structure raised another problem associated with high-level high voltage multilevel converters. Power switching components with fast switching, combined with hard switched-converters, produce high di/dt during turn off time. Thus, stray inductance of interconnections becomes an important issue and raises overvoltage and EMI issues correlated to the number of components. Planar busbar is a good candidate to reduce interconnection inductance in high power inverters compared with cables. The effect of different transient current loops on busbar physical structure of the high-voltage highlevel diode-clamped converters is highlighted. Design considerations of proper planar busbar are also presented to optimise the overall design of diode-clamped converters.

Basin analysis and economic geology of the Northern Mount Isa Basin

The Mount Isa Basin is a new concept used to describe the area of Palaeo- to Mesoproterozoic rocks south of the Murphy Inlier and inappropriately described presently as the Mount Isa Inlier. The new basin concept presented in this thesis allows for the characterisation of basin-wide structural deformation, correlation of mineralisation with particular lithostratigraphic and seismic stratigraphic packages, and the recognition of areas with petroleum exploration potential. The northern depositional margin of the Mount Isa Basin is the metamorphic, intrusive and volcanic complex here referred to as the Murphy Inlier (not the "Murphy Tectonic Ridge"). The eastern, southern and western boundaries of the basin are obscured by younger basins (Carpentaria, Eromanga and Georgina Basins). The Murphy Inlier rocks comprise the seismic basement to the Mount Isa Basin sequence. Evidence for the continuity of the Mount Isa Basin with the McArthur Basin to the northwest and the Willyama Block (Basin) at Broken Hill to the south is presented. These areas combined with several other areas of similar age are believed to have comprised the Carpentarian Superbasin (new term). The application of seismic exploration within Authority to Prospect (ATP) 423P at the northern margin of the basin was critical to the recognition and definition of the Mount Isa Basin. The Mount Isa Basin is structurally analogous to the Palaeozoic Arkoma Basin of Illinois and Arkansas in southern USA but, as with all basins it contains unique characteristics, a function of its individual development history. The Mount Isa Basin evolved in a manner similar to many well described, Phanerozoic plate tectonic driven basins. A full Wilson Cycle is recognised and a plate tectonic model proposed. The northern Mount Isa Basin is defined as the Proterozoic basin area northwest of the Mount Gordon Fault. Deposition in the northern Mount Isa Basin began with a rift sequence of volcaniclastic sediments followed by a passive margin drift phase comprising mostly carbonate rocks. Following the rift and drift phases, major north-south compression produced east-west thrusting in the south of the basin inverting the older sequences. This compression produced an asymmetric epi- or intra-cratonic clastic dominated peripheral foreland basin provenanced in the south and thinning markedly to a stable platform area (the Murphy Inlier) in the north. The fmal major deformation comprised east-west compression producing north-south aligned faults that are particularly prominent at Mount Isa. Potential field studies of the northern Mount Isa Basin, principally using magnetic data (and to a lesser extent gravity data, satellite images and aerial photographs) exhibit remarkable correlation with the reflection seismic data. The potential field data contributed significantly to the unravelling of the northern Mount Isa Basin architecture and deformation. Structurally, the Mount Isa Basin consists of three distinct regions. From the north to the south they are the Bowthorn Block, the Riversleigh Fold Zone and the Cloncurry Orogen (new names). The Bowthom Block, which is located between the Elizabeth Creek Thrust Zone and the Murphy Inlier, consists of an asymmetric wedge of volcanic, carbonate and clastic rocks. It ranges from over 10 000 m stratigraphic thickness in the south to less than 2000 min the north. The Bowthorn Block is relatively undeformed: however, it contains a series of reverse faults trending east-west that are interpreted from seismic data to be down-to-the-north normal faults that have been reactivated as thrusts. The Riversleigh Fold Zone is a folded and faulted region south of the Bowthorn Block, comprising much of the area formerly referred to as the Lawn Hill Platform. The Cloncurry Orogen consists of the area and sequences equivalent to the former Mount Isa Orogen. The name Cloncurry Orogen clearly distinguishes this area from the wider concept of the Mount Isa Basin. The South Nicholson Group and its probable correlatives, the Pilpah Sandstone and Quamby Conglomerate, comprise a later phase of now largely eroded deposits within the Mount Isa Basin. The name South Nicholson Basin is now outmoded as this terminology only applied to the South Nicholson Group unlike the original broader definition in Brown et al. (1968). Cored slimhole stratigraphic and mineral wells drilled by Amoco, Esso, Elf Aquitaine and Carpentaria Exploration prior to 1986, penetrated much of the stratigraphy and intersected both minor oil and gas shows plus excellent potential source rocks. The raw data were reinterpreted and augmented with seismic stratigraphy and source rock data from resampled mineral and petroleum stratigraphic exploration wells for this study. Since 1986, Comalco Aluminium Limited, as operator of a joint venture with Monument Resources Australia Limited and Bridge Oil Limited, recorded approximately 1000 km of reflection seismic data within the basin and drilled one conventional stratigraphic petroleum well, Beamesbrook-1. This work was the first reflection seismic and first conventional petroleum test of the northern Mount Isa Basin. When incorporated into the newly developed foreland basin and maturity models, a grass roots petroleum exploration play was recognised and this led to the present thesis. The Mount Isa Basin was seen to contain excellent source rocks coupled with potential reservoirs and all of the other essential aspects of a conventional petroleum exploration play. This play, although high risk, was commensurate with the enormous and totally untested petroleum potential of the basin. The basin was assessed for hydrocarbons in 1992 with three conventional exploration wells, Desert Creek-1, Argyle Creek-1 and Egilabria-1. These wells also tested and confrrmed the proposed basin model. No commercially viable oil or gas was encountered although evidence of its former existence was found. In addition to the petroleum exploration, indeed as a consequence of it, the association of the extensive base metal and other mineralisation in the Mount Isa Basin with hydrocarbons could not be overlooked. A comprehensive analysis of the available data suggests a link between the migration and possible generation or destruction of hydrocarbons and metal bearing fluids. Consequently, base metal exploration based on hydrocarbon exploration concepts is probably. the most effective technique in such basins. The metal-hydrocarbon-sedimentary basin-plate tectonic association (analogous to Phanerozoic models) is a compelling outcome of this work on the Palaeo- to Mesoproterozoic Mount lsa Basin. Petroleum within the Bowthom Block was apparently destroyed by hot brines that produced many ore deposits elsewhere in the basin.

Metal Contaminants in Leachate from Sanitary Landfills

The uncontrolled disposal of solid wastes poses an immediate threat to public health and a long term threat to the environmental well being of future generations. Solid waste is waste resulting from human activities that is solid and unwanted (Peavy et al., 1985). If unmanaged, dumped solid wastes generate liquid and gaseous emissions that are detrimental to the environment. This can lead to a serious form of contamination known as metal contamination, which poses a risk to human health and ecosystems. For example, some heavy metals (cadmium, chromium compounds, and nickel tetracarbonyl) are known to be highly toxic, and are aggressive at elevated concentrations. Iron, copper, and manganese can cause staining, and aluminium causes depositions and discolorations. In addition, calcium and magnesium cause hardness in water causing scale deposition and scum formation. Though not a metal but a metalloid, arsenic is poisonous at relatively high concentrations and when diluted at low concentrations causes skin cancer. Normally, metal contaminants are found in a dissolved form in the liquid percolating through landfills. Because average metal concentrations from full-scale landfills, test cells, and laboratory studies have tended to be generally low, metal contamination originating from landfills is not generally considered a major concern (Kjeldsen et al., 2002; Christensen et al., 1999). However, a number of factors make it necessary to take a closer look at metal contaminants from landfills. One of these factors relates to variability. Landfill leachate can have different qualities depending on the weather and operating conditions. Therefore, at one moment in time, metal contaminant concentrations may be quite low, but at a later time these concentrations could be quite high. Also, these conditions relate to the amount of leachate that is being generated. Another factor is biodiversity. It cannot be assumed that a particular metal contaminant is harmless to flora and fauna (including micro organisms) just because it is harmless to human health. This has significant implications for ecosystems and the environment. Finally, there is the moral factor. Because uncertainty surrounds the potential effects of metal contamination, it is appropriate to take precautions to prevent it from taking place. Consequently, it is necessary to have good scientific knowledge (empirically supported) to adequately understand the extent of the problem and improve the way waste is being disposed of

Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.

Regulating greenhouse gas emissions from coal mining activities in the context of climate change

Current approaches to the regulation of coal mining activities in Australia have facilitated the extraction of substantial amounts of coal and coal seam gas. The regulation of coal mining activities must now achieve the reduction or mitigation of greenhouse gas emissions in order to address the challenge of climate change and achieve ecologically sustainable development. Several legislative mechanisms currently exist which appear to offer the means to bring about the reduction or mitigation of greenhouse gas emissions from coal mining activities, yet Australia’s emissions from coal mining continue to rise. This article critiques these existing legislative mechanisms and presents recommendations for reform.

Volatile properties of particles emitted by compressed natural gas and diesel buses during steady state and transient driving modes

Volatile properties of particle emissions from four compressed natural gas (CNG) and four diesel buses were investigated under steady state and transient driving modes on a chassis dynamometer. The exhaust was diluted utilising a full-flow continuous volume sampling system and passed through a thermodenuder at controlled temperature. Particle number concentration and size distribution were measured with a condensation particle counter and a scanning mobility particle sizer, respectively. We show that, while almost all the particles emitted by the CNG buses were in the nanoparticle size range, at least 85% and 98% were removed at 100ºC and 250ºC, respectively. Closer analysis of the volatility of particles emitted during transient cycles showed that volatilisation began at around 40°C with the majority occurring by 80°C. Particles produced during hard acceleration from rest exhibited lower volatility than that produced during other times of the cycle. Based on our results and the observation of ash deposits on the walls of the tailpipes, we suggest that these non-volatile particles were composed mostly of ash from lubricating oil. Heating the diesel bus emissions to 100ºC removed ultrafine particle numbers by 69% to 82% when a nucleation mode was present and just 18% when it was not.

Nanostructures for sensors, electronics, energy and environment

Nanoscale science is growing evermore important on a global scale and is widely seen as playing an integral part in the growth of future world economies. The daunting energy crisis we are facing could be solved not only by new and improved ways of getting energy directly from the sun, but also by saving power thanks to advancements in electronics and sensors. New, cheap dye-sensitized and polymer solar cells hold the promise of environmentally friendly and simple production methods, along with mechanical flexibility and low weight, matching the conditions for a widespread deployment of this technology. Cheap sensors based on nanomaterials can make a fundamental contribution to the reduction of greenhouse gas emissions, allowing the creation of large sensor networks to monitor countries and cities, improving our quality of life. Nanowires and nano-platelets of metal oxides are at the forefront of the research to improve sensitivity and reduce the power consumption in gas sensors. Nanoelectronics is the next step in the electronic roadmap, with many devices currently in production already containing components smaller than 100 nm. Molecules and conducting polymers are at the forefront of this research with the goal of reducing component size through the use of cheap and environmentally friendly production methods. This, and the coming steps that will eventually bring the individual circuit element close to the ultimate limit of the atomic level, are expected to deliver better devices with reduced power consumption.

Regulating coal seam gas in Queensland : lessons in an adaptive environmental management approach?

The current regulatory approach to coal seam gas projects in Queensland is based on the philosophy of adaptive environmental management. This method of “learning by doing” is implemented in Queensland primarily through the imposition of layered monitoring and reporting duties on the coal seam gas operator alongside obligations to compensate and “make good” harm caused. The purpose of this article is to provide a critical review of the Queensland regulatory approach to the approval and minimisation of adverse impacts from coal seam gas activities. Following an overview of the hallmarks of an effective adaptive management approach, this article begins by addressing the mosaic of approval processes and impact assessment regimes that may apply to coal seam gas projects. This includes recent Strategic Cropping Land reforms. This article then turns to consider the preconditions for land access in Queensland and the emerging issues for landholders relating to the negotiation of access and compensation agreements. This article then undertakes a critical review of the environmental duties imposed on coal seam gas operators relating to hydraulic fracturing, well head leaks, groundwater management and the disposal and beneficial use of produced water. Finally, conclusions are drawn regarding the overall effectiveness of the Queensland framework and the lessons that may be drawn from Queensland’s adaptive environmental management approach.

Ocular surface changes with short-term contact lens wear

Contact lenses are a common method for the correction of refractive errors of the eye. While there have been significant advancements in contact lens designs and materials over the past few decades, the lenses still represent a foreign object in the ocular environment and may lead to physiological as well as mechanical effects on the eye. When contact lenses are placed in the eye, the ocular anatomical structures behind and in front of the lenses are directly affected. This thesis presents a series of experiments that investigate the mechanical and physiological effects of the short-term use of contact lenses on anterior and posterior corneal topography, corneal thickness, the eyelids, tarsal conjunctiva and tear film surface quality. The experimental paradigm used in these studies was a repeated measures, cross-over study design where subjects wore various types of contact lenses on different days and the lenses were varied in one or more key parameters (e.g. material or design). Both, old and newer lens materials were investigated, soft and rigid lenses were used, high and low oxygen permeability materials were tested, toric and spherical lens designs were examined, high and low powers and small and large diameter lenses were used in the studies. To establish the natural variability in the ocular measurements used in the studies, each experiment also contained at least one “baseline” day where an identical measurement protocol was followed, with no contact lenses worn. In this way, changes associated with contact lens wear were considered in relation to those changes that occurred naturally during the 8 hour period of the experiment. In the first study, the regional distribution and magnitude of change in corneal thickness and topography was investigated in the anterior and posterior cornea after short-term use of soft contact lenses in 12 young adults using the Pentacam. Four different types of contact lenses (Silicone hydrogel/ Spherical/–3D, Silicone Hydrogel/Spherical/–7D, Silicone Hydrogel/Toric/–3D and HEMA/Toric/–3D) of different materials, designs and powers were worn for 8 hours each, on 4 different days. The natural diurnal changes in corneal thickness and curvature were measured on two separate days before any contact lens wear. Significant diurnal changes in corneal thickness and curvature within the duration of the study were observed and these were taken into consideration for calculating the contact lens induced corneal changes. Corneal thickness changed significantly with lens wear and the greatest corneal swelling was seen with the hydrogel (HEMA) toric lens with a noticeable regional swelling of the cornea beneath the stabilization zones, the thickest regions of the lenses. The anterior corneal surface generally showed a slight flattening with lens wear. All contact lenses resulted in central posterior corneal steepening, which correlated with the relative degree of corneal swelling. The corneal swelling induced by the silicone hydrogel contact lenses was typically less than the natural diurnal thinning of the cornea over this same period (i.e. net thinning). This highlights why it is important to consider the natural diurnal variations in corneal thickness observed from morning to afternoon to accurately interpret contact lens induced corneal swelling. In the second experiment, the relative influence of lenses of different rigidity (polymethyl methacrylate – PMMA, rigid gas permeable – RGP and silicone hydrogel – SiHy) and diameters (9.5, 10.5 and 14.0) on corneal thickness, topography, refractive power and wavefront error were investigated. Four different types of contact lenses (PMMA/9.5, RGP/9.5, RGP/10.5, SiHy/14.0), were worn by 14 young healthy adults for a period of 8 hours on 4 different days. There was a clear association between fluorescein fitting pattern characteristics (i.e. regions of minimum clearance in the fluorescein pattern) and the resulting corneal shape changes. PMMA lenses resulted in significant corneal swelling (more in the centre than periphery) along with anterior corneal steepening and posterior flattening. RGP lenses, on the other hand, caused less corneal swelling (more in the periphery than centre) along with opposite effects on corneal curvature, anterior corneal flattening and posterior steepening. RGP lenses also resulted in a clinically and statistically significant decrease in corneal refractive power (ranging from 0.99 to 0.01 D), large enough to affect vision and require adjustment in the lens power. Wavefront analysis also showed a significant increase in higher order aberrations after PMMA lens wear, which may partly explain previous reports of "spectacle blur" following PMMA lens wear. We further explored corneal curvature, thickness and refractive changes with back surface toric and spherical RGP lenses in a group of 6 subjects with toric corneas. The lenses were worn for 8 hours and measurements were taken before and after lens wear, as in previous experiments. Both lens types caused anterior corneal flattening and a decrease in corneal refractive power but the changes were greater with the spherical lens. The spherical lens also caused a significant decrease in WTR astigmatism (WRT astigmatism defined as major axis within 30 degrees of horizontal). Both the lenses caused slight posterior corneal steepening and corneal swelling, with a greater effect in the periphery compared to the central cornea. Eyelid position, lid-wiper and tarsal conjunctival staining were also measured in Experiment 2 after short-term use of the rigid and SiHy contact lenses. Digital photos of the external eyes were captured for lid position analysis. The lid-wiper region of the marginal conjunctiva was stained using fluorescein and lissamine green dyes and digital photos were graded by an independent masked observer. A grading scale was developed in order to describe the tarsal conjunctival staining. A significant decrease in the palpebral aperture height (blepharoptosis) was found after wearing of PMMA/9.5 and RGP/10.5 lenses. All three rigid contact lenses caused a significant increase in lid-wiper and tarsal staining after 8 hours of lens wear. There was also a significant diurnal increase in tarsal staining, even without contact lens wear. These findings highlight the need for better contact lens edge design to minimise the interactions between the lid and contact lens edge during blinking and more lubricious contact lens surfaces to reduce ocular surface micro-trauma due to friction and for. Tear film surface quality (TFSQ) was measured using a high-speed videokeratoscopy technique in Experiment 2. TFSQ was worse with all the lenses compared to baseline (PMMA/9.5, RGP/9.5, RGP/10.5, and SiHy/14) in the afternoon (after 8 hours) during normal and suppressed blinking conditions. The reduction in TFSQ was similar with all the contact lenses used, irrespective of their material and diameter. An unusual pattern of change in TFSQ in suppressed blinking conditions was also found. The TFSQ with contact lens was found to decrease until a certain time after which it improved to a value even better than the bare eye. This is likely to be due to the tear film drying completely over the surface of the contact lenses. The findings of this study also show that there is still a scope for improvement in contact lens materials in terms of better wettability and hydrophilicity in order to improve TFSQ and patient comfort. These experiments showed that a variety of changes can occur in the anterior eye as a result of the short-term use of a range of commonly used contact lens types. The greatest corneal changes occurred with lenses manufactured from older HEMA and PMMA lens materials, whereas modern SiHy and rigid gas permeable materials caused more subtle changes in corneal shape and thickness. All lenses caused signs of micro-trauma to the eyelid wiper and palpebral conjunctiva, although rigid lenses appeared to cause more significant changes. Tear film surface quality was also significantly reduced with all types of contact lenses. These short-term changes in the anterior eye are potential markers for further long term changes and the relative differences between lens types that we have identified provide an indication of areas of contact lens design and manufacture that warrant further development.

Functionalised zinc oxide nanowire gas sensors : enhanced NO2 gas sensor response by chemical modification of nanowire surfaces

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Zinc aluminium layered double hydroxides for the removal of iodine and iodide from aqueous solutions

129I is a radioactive isotope of iodine that is readily absorbed by the body. In this paper we investigated the potential of a 3:1 Zn/Al layered double hydroxide (LDH) as a sorbent for the removal of iodine and iodide from water. Synthetic Zn6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation before thermal activation. The LDH was treated with solutions containing iodide and iodine. It was found that iodine could be more easily removed from solution than iodide. Powder X-ray diffraction revealed the destruction of the LDH structure during thermal activation and the successful reformation of a similar LDH material after treatment with the iodide or iodine solution. Thermal decomposition of all samples studied by thermogravimetry appeared to be similar. A new decomposition mechanism similar to one previously described in the literature was proposed for the Zn/Al LDH. The total mass loss of samples treated with iodide and iodine was significantly lower than that of the original LDH indicating that iodine species may form non-removable anions when intercalated into the LDH structure. Evolved gas mass spectrometry failed to detect any iodine species lost as gases during the decomposition of iodide treated LDH however, small quantities of iodine species were observed during decomposition of samples treated with iodine solution.