Synthesis and modifications of metal oxide nanostructures and their applications

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

A parametric study of imaging subsurface objects using ground penetrating radar

A parametric study was carried out to investigate the effects on reconstructed images from a ground penetrating radar (GPR) due to (a) the centre frequency of the GPR excitation pulse, (b) the height of transmitting and receiving antennas above ground level, and (c) the proximity of the buried objects. An integrated software package was developed to streamline the computer simulation based on synthetic data generated by GPRMax.

System identification and control of an aerobot drive system

Fast thrust changes are important for authoritive control of VTOL micro air vehicles. Fixed-pitch rotors that alter thrust by varying rotor speed require high-bandwidth control systems to provide adequate performace. We develop a feedback compensator for a brushless hobby motor driving a custom rotor suitable for UAVs. The system plant is identified using step excitation experiments. The aerodynamic operating conditions of these rotors are unusual and so experiments are performed to characterise expected load disturbances. The plant and load models lead to a proportional controller design capable of significantly decreasing rise-time and propagation of disturbances, subject to bus voltage constraints.

Analysis of distrubances in large interconnected power systems

World economies increasingly demand reliable and economical power supply and distribution. To achieve this aim the majority of power systems are becoming interconnected, with several power utilities supplying the one large network. One problem that occurs in a large interconnected power system is the regular occurrence of system disturbances which can result in the creation of intra-area oscillating modes. These modes can be regarded as the transient responses of the power system to excitation, which are generally characterised as decaying sinusoids. For a power system operating ideally these transient responses would ideally would have a “ring-down” time of 10-15 seconds. Sometimes equipment failures disturb the ideal operation of power systems and oscillating modes with ring-down times greater than 15 seconds arise. The larger settling times associated with such “poorly damped” modes cause substantial power flows between generation nodes, resulting in significant physical stresses on the power distribution system. If these modes are not just poorly damped but “negatively damped”, catastrophic failures of the system can occur. To ensure system stability and security of large power systems, the potentially dangerous oscillating modes generated from disturbances (such as equipment failure) must be quickly identified. The power utility must then apply appropriate damping control strategies. In power system monitoring there exist two facets of critical interest. The first is the estimation of modal parameters for a power system in normal, stable, operation. The second is the rapid detection of any substantial changes to this normal, stable operation (because of equipment breakdown for example). Most work to date has concentrated on the first of these two facets, i.e. on modal parameter estimation. Numerous modal parameter estimation techniques have been proposed and implemented, but all have limitations [1-13]. One of the key limitations of all existing parameter estimation methods is the fact that they require very long data records to provide accurate parameter estimates. This is a particularly significant problem after a sudden detrimental change in damping. One simply cannot afford to wait long enough to collect the large amounts of data required for existing parameter estimators. Motivated by this gap in the current body of knowledge and practice, the research reported in this thesis focuses heavily on rapid detection of changes (i.e. on the second facet mentioned above). This thesis reports on a number of new algorithms which can rapidly flag whether or not there has been a detrimental change to a stable operating system. It will be seen that the new algorithms enable sudden modal changes to be detected within quite short time frames (typically about 1 minute), using data from power systems in normal operation. The new methods reported in this thesis are summarised below. The Energy Based Detector (EBD): The rationale for this method is that the modal disturbance energy is greater for lightly damped modes than it is for heavily damped modes (because the latter decay more rapidly). Sudden changes in modal energy, then, imply sudden changes in modal damping. Because the method relies on data from power systems in normal operation, the modal disturbances are random. Accordingly, the disturbance energy is modelled as a random process (with the parameters of the model being determined from the power system under consideration). A threshold is then set based on the statistical model. The energy method is very simple to implement and is computationally efficient. It is, however, only able to determine whether or not a sudden modal deterioration has occurred; it cannot identify which mode has deteriorated. For this reason the method is particularly well suited to smaller interconnected power systems that involve only a single mode. Optimal Individual Mode Detector (OIMD): As discussed in the previous paragraph, the energy detector can only determine whether or not a change has occurred; it cannot flag which mode is responsible for the deterioration. The OIMD seeks to address this shortcoming. It uses optimal detection theory to test for sudden changes in individual modes. In practice, one can have an OIMD operating for all modes within a system, so that changes in any of the modes can be detected. Like the energy detector, the OIMD is based on a statistical model and a subsequently derived threshold test. The Kalman Innovation Detector (KID): This detector is an alternative to the OIMD. Unlike the OIMD, however, it does not explicitly monitor individual modes. Rather it relies on a key property of a Kalman filter, namely that the Kalman innovation (the difference between the estimated and observed outputs) is white as long as the Kalman filter model is valid. A Kalman filter model is set to represent a particular power system. If some event in the power system (such as equipment failure) causes a sudden change to the power system, the Kalman model will no longer be valid and the innovation will no longer be white. Furthermore, if there is a detrimental system change, the innovation spectrum will display strong peaks in the spectrum at frequency locations associated with changes. Hence the innovation spectrum can be monitored to both set-off an “alarm” when a change occurs and to identify which modal frequency has given rise to the change. The threshold for alarming is based on the simple Chi-Squared PDF for a normalised white noise spectrum [14, 15]. While the method can identify the mode which has deteriorated, it does not necessarily indicate whether there has been a frequency or damping change. The PPM discussed next can monitor frequency changes and so can provide some discrimination in this regard. The Polynomial Phase Method (PPM): In [16] the cubic phase (CP) function was introduced as a tool for revealing frequency related spectral changes. This thesis extends the cubic phase function to a generalised class of polynomial phase functions which can reveal frequency related spectral changes in power systems. A statistical analysis of the technique is performed. When applied to power system analysis, the PPM can provide knowledge of sudden shifts in frequency through both the new frequency estimate and the polynomial phase coefficient information. This knowledge can be then cross-referenced with other detection methods to provide improved detection benchmarks.

Coding speech signals at very low rates (below 1 kb/s) with high intelligibility

This thesis presents an original approach to parametric speech coding at rates below 1 kbitsjsec, primarily for speech storage applications. Essential processes considered in this research encompass efficient characterization of evolutionary configuration of vocal tract to follow phonemic features with high fidelity, representation of speech excitation using minimal parameters with minor degradation in naturalness of synthesized speech, and finally, quantization of resulting parameters at the nominated rates. For encoding speech spectral features, a new method relying on Temporal Decomposition (TD) is developed which efficiently compresses spectral information through interpolation between most steady points over time trajectories of spectral parameters using a new basis function. The compression ratio provided by the method is independent of the updating rate of the feature vectors, hence allows high resolution in tracking significant temporal variations of speech formants with no effect on the spectral data rate. Accordingly, regardless of the quantization technique employed, the method yields a high compression ratio without sacrificing speech intelligibility. Several new techniques for improving performance of the interpolation of spectral parameters through phonetically-based analysis are proposed and implemented in this research, comprising event approximated TD, near-optimal shaping event approximating functions, efficient speech parametrization for TD on the basis of an extensive investigation originally reported in this thesis, and a hierarchical error minimization algorithm for decomposition of feature parameters which significantly reduces the complexity of the interpolation process. Speech excitation in this work is characterized based on a novel Multi-Band Excitation paradigm which accurately determines the harmonic structure in the LPC (linear predictive coding) residual spectra, within individual bands, using the concept 11 of Instantaneous Frequency (IF) estimation in frequency domain. The model yields aneffective two-band approximation to excitation and computes pitch and voicing with high accuracy as well. New methods for interpolative coding of pitch and gain contours are also developed in this thesis. For pitch, relying on the correlation between phonetic evolution and pitch variations during voiced speech segments, TD is employed to interpolate the pitch contour between critical points introduced by event centroids. This compresses pitch contour in the ratio of about 1/10 with negligible error. To approximate gain contour, a set of uniformly-distributed Gaussian event-like functions is used which reduces the amount of gain information to about 1/6 with acceptable accuracy. The thesis also addresses a new quantization method applied to spectral features on the basis of statistical properties and spectral sensitivity of spectral parameters extracted from TD-based analysis. The experimental results show that good quality speech, comparable to that of conventional coders at rates over 2 kbits/sec, can be achieved at rates 650-990 bits/sec.

The impact of brand and product placements in electronic games

In an environment where it has become increasingly difficult to attract consumer attention, marketers have begun to explore alternative forms of marketing communication. One such form that has emerged is product placement, which has more recently appeared in electronic games. Given changes in media consumption and the growth of the games industry, it is not surprising that games are being exploited as a medium for promotional content. Other market developments are also facilitating and encouraging their use, in terms of both the insertion of brand messages into video games and the creation of brand-centred environments, labelled ‘advergames’. However, while there is much speculation concerning the beneficial outcomes for marketers, there remains a lack of academic work in this area and little empirical evidence of the actual effects of this form of promotion on game players. Only a handful of studies are evident in the literature, which have explored the influence of game placements on consumers. The majority have studied their effect on brand awareness, largely demonstrating that players can recall placed brands. Further, most research conducted to date has focused on computer and online games, but consoles represent the dominant platform for play (Taub, 2004). Finally, advergames have largely been neglected, particularly those in a console format. Widening the gap in the literature is the fact that insufficient academic attention has been given to product placement as a marketing communication strategy overall, and to games in general. The unique nature of the strategy also makes it difficult to apply existing literature to this context. To address a significant need for information in both the academic and business domains, the current research investigates the effects of brand and product placements in video games and advergames on consumer attitude to the brand and corporate image. It was conducted in two stages. Stage one represents a pilot study. It explored the effects of use simulated and peripheral placements in video games on players’ and observers’ attitudinal responses, and whether these are influenced by involvement with a product category or skill level in the game. The ability of gamers to recall placed brands was also examined. A laboratory experiment was employed with a small sample of sixty adult subjects drawn from an Australian east-coast university, some of who were exposed to a console video game on a television set. The major finding of study one is that placements in a video game have no effect on gamers’ attitudes, but they are recalled. For stage two of the research, a field experiment was conducted with a large, random sample of 350 student respondents to investigate the effects on players of brand and product placements in handheld video games and advergames. The constructs of brand attitude and corporate image were again tested, along with several potential confounds. Consistent with the pilot, the results demonstrate that product placement in electronic games has no effect on players’ brand attitudes or corporate image, even when allowing for their involvement with the product category, skill level in the game, or skill level in relation to the medium. Age and gender also have no impact. However, the more interactive a player perceives the game to be, the higher their attitude to the placed brand and corporate image of the brand manufacturer. In other words, when controlling for perceived interactivity, players experienced more favourable attitudes, but the effect was so weak it probably lacks practical significance. It is suggested that this result can be explained by the existence of excitation transfer, rather than any processing of placed brands. The current research provides strong, empirical evidence that brand and product placements in games do not produce strong attitudinal responses. It appears that the nature of the game medium, game playing experience and product placement impose constraints on gamer motivation, opportunity and ability to process these messages, thereby precluding their impact on attitude to the brand and corporate image. Since this is the first study to investigate the ability of video game and advergame placements to facilitate these deeper consumer responses, further research across different contexts is warranted. Nevertheless, the findings have important theoretical and managerial implications. This investigation makes a number of valuable contributions. First, it is relevant to current marketing practice and presents findings that can help guide promotional strategy decisions. It also presents a comprehensive review of the games industry and associated activities in the marketplace, relevant for marketing practitioners. Theoretically, it contributes new knowledge concerning product placement, including how it should be defined, its classification within the existing communications framework, its dimensions and effects. This is extended to include brand-centred entertainment. The thesis also presents the most comprehensive analysis available in the literature of how placements appear in games. In the consumer behaviour discipline, the research builds on theory concerning attitude formation, through application of MacInnis and Jaworski’s (1989) Integrative Attitude Formation Model. With regards to the games literature, the thesis provides a structured framework for the comparison of games with different media types; it advances understanding of the game medium, its characteristics and the game playing experience; and provides insight into console and handheld games specifically, as well as interactive environments generally. This study is the first to test the effects of interactivity in a game environment, and presents a modified scale that can be used as part of future research. Methodologically, it addresses the limitations of prior research through execution of a field experiment and observation with a large sample, making this the largest study of product placement in games available in the literature. Finally, the current thesis offers comprehensive recommendations that will provide structure and direction for future study in this important field.

Fuzzy logic power system stabilizer in multimachine stability studies

Power system stabilizers (PSS) work well at the particular network configuration and steady state conditions for which they were designed. Once conditions change, their performance degrades. This can be overcome by an intelligent nonlinear PSS based on fuzzy logic. Such a fuzzy logic power system stabilizer (FLPSS) is developed, using speed and power deviation as inputs, and provides an auxiliary signal for the excitation system of a synchronous motor in a multimachine power system environment. The FLPSS's effect on the system damping is then compared with a conventional power system stabilizer's (CPSS) effect on the system. The results demonstrate an improved system performance with the FLPSS and also that the FLPSS is robust

Rationalizing the SER spectra of bacteria

The SER spectra of riboflavin and FAD are identical and are resonance enhanced at 514 or 532 nm. Signals from FAD/ riboflavin dominated SER spectra whenever these compounds were present with proteins or bacteria. SER spectra of very different bacteria such as Pseudomonas. aeruginosa, Bacillu. subtilis and Geobacillus. stearothermophilus were dominated by signals from FAD, even when these bacteria were added to a preformed colloid. The SERS signal of FAD is greatly reduced at 785 nm, and SER spectra of bacteria excited at 785 nm are quite different than those collected at 514 or 532 nm. This supports the assignment of the peaks in the 514 nm SER spectra of bacteria to FAD rather to amino acids or N-acetylglucosamine. The SER spectra of certain mixes of adenine and FAD showed similar changes to those of bacteria when the excitation was changed from 514/532 nm to 785 nm. The ratio of colloid: bacteria was of critical important for obtaining good SER spectra, and the addition of sodium sulfate was also beneficial. Removal of EPS from bacteria before analysis facilitated interaction with the silver surface, and may be a useful step to include in identification protocols.

Persons with age-related maculopathy risk genotypes and clinically normal eyes have reduced mesopic vision

PURPOSE: To determine if participants with normal visual acuity, no ophthalmoscopically signs of age-related maculopathy (ARM) in both eyes and who are carriers of the CFH, LOC387715 and HRTA1 high-risk genotypes (“gene-positive”) have impaired rod- and cone-mediated mesopic visual function compared to persons who do not carry the risk genotypes (“gene-negative”).---------- METHODS: Fifty-three Caucasian study participants (mean 55.8 ± 6.1) were genotyped for CFH, LOC387715/ARMS2 and HRTA1 polymorphisms. We genotyped single nucleotide polymorphisms (SNPs) in the CFH (rs380390), LOC387715/ARMS2 (rs10490924) and HTRA1 (rs11200638) genes using Applied Biosystems optimised TaqMan assays. We determined the critical fusion frequency (CFF) mediated by cones alone (Long, Middle and Short wavelength sensitive cones; LMS) and by the combined activities of cones and rods (LMSR). The stimuli were generated using a 4-primary photostimulator that provides independent control of the photoreceptor excitation under mesopic light levels. Visual function was further assessed using standard clinical tests, flicker perimetry and microperimetry.---------- RESULTS: The mesopic CFF mediated by rods and cones (LMSR) was significantly reduced in gene-positive compared to gene-negative participants after correction for age (p=0.03). Cone-mediated CFF (LMS) was not significantly different between gene-positive and -negative participants. There were no significant associations between flicker perimetry and microperimetry and genotype.---------- CONCLUSIONS: This is the first study to relate ARM risk genotypes with mesopic visual function in clinically normal persons. These preliminary results could become of clinical importance as mesopic vision may be used to document sub-clinical retinal changes in persons with risk genotypes and to determine whether those persons progress into manifest disease.

The application of a profluorescent nitroxide probe to detect reactive oxygen species derived from combustion-generated particulate matter

Particulate pollution has been widely recognised as an important risk factor to human health. In addition to increases in respiratory and cardiovascular morbidity associated with exposure to particulate matter (PM), WHO estimates that urban PM causes 0.8 million premature deaths globally and that 1.5 million people die prematurely from exposure to indoor smoke generated from the combustion of solid fuels. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. Oxidative stress caused by generation of free radicals and related reactive oxygen species (ROS) at the sites of deposition has been proposed as a mechanism for many of the adverse health outcomes associated with exposure to PM. In addition to particle-induced generation of ROS in lung tissue cells, several recent studies have shown that particles may also contain ROS. As such, they present a direct cause of oxidative stress and related adverse health effects. Cellular responses to oxidative stress have been widely investigated using various cell exposure assays. However, for a rapid screening of the oxidative potential of PM, less time-consuming and less expensive, cell-free assays are needed. The main aim of this research project was to investigate the application of a novel profluorescent nitroxide probe, synthesised at QUT, as a rapid screening assay in assessing the oxidative potential of PM. Considering that this was the first time that a profluorescent nitroxide probe was applied in investigating the oxidative stress potential of PM, the proof of concept regarding the detection of PM–derived ROS by using such probes needed to be demonstrated and a sampling methodology needed to be developed. Sampling through an impinger containing profluorescent nitroxide solution was chosen as a means of particle collection as it allowed particles to react with the profluorescent nitroxide probe during sampling, avoiding in that way any possible chemical changes resulting from delays between the sampling and the analysis of the PM. Among several profluorescent nitroxide probes available at QUT, bis(phenylethynyl)anthracene-nitroxide (BPEAnit) was found to be the most suitable probe, mainly due to relatively long excitation and emission wavelengths (λex= 430 nm; λem= 485 and 513 nm). These wavelengths are long enough to avoid overlap with the background fluorescence coming from light absorbing compounds which may be present in PM (e.g. polycyclic aromatic hydrocarbons and their derivatives). Given that combustion, in general, is one of the major sources of ambient PM, this project aimed at getting an insight into the oxidative stress potential of combustion-generated PM, namely cigarette smoke, diesel exhaust and wood smoke PM. During the course of this research project, it was demonstrated that the BPEAnit probe based assay is sufficiently sensitive and robust enough to be applied as a rapid screening test for PM-derived ROS detection. Considering that for all three aerosol sources (i.e. cigarette smoke, diesel exhaust and wood smoke) the same assay was applied, the results presented in this thesis allow direct comparison of the oxidative potential measured for all three sources of PM. In summary, it was found that there was a substantial difference between the amounts of ROS per unit of PM mass (ROS concentration) for particles emitted by different combustion sources. For example, particles from cigarette smoke were found to have up to 80 times less ROS per unit of mass than particles produced during logwood combustion. For both diesel and wood combustion it has been demonstrated that the type of fuel significantly affects the oxidative potential of the particles emitted. Similarly, the operating conditions of the combustion source were also found to affect the oxidative potential of particulate emissions. Moreover, this project has demonstrated a strong link between semivolatile (i.e. organic) species and ROS and therefore, clearly highlights the importance of semivolatile species in particle-induced toxicity.

Reduction of nitroaromatic compounds on supported gold nanoparticles by visible and ultraviolet light

Shedding light: Nitroaromatic compounds on gold nanoparticles (3 wt %) supported on ZrO2 can be reduced directly to the corresponding azo compounds when illuminated with visible light or ultraviolet light at 40 °C (see picture). The process occurs with high selectivity and at ambient temperature and pressure, and enables the selection of intermediates that are unstable in thermal reactions.

Vibration characteristics of slender structures under human induced loads

This paper presents the outcome of investigations and studies of the vibratioon characteristics and response of low frequency structural systems for a composite concrete steel floor plate and a reverse profiled cable tensioned foot bridge. These highly dynamic and slender structure are the engineering response to planning, aesthetic and environmental influences, but are prone to excessive and complex vibration. A number of design codes and practice guides provided information to engineers for vibration mitigation However, they are limited to very simple load function applied to a few uncoupled translational modes of excitation. Motivated by the need to address the knowledge gaps in this area, the investigations described in this paper focused on synchronous multi-modal and coupled excitation of the floor plate and footbridge with considerations for torsinal effects. The results showed the potential for adverse dynamic response from multi-modal and coupled excitation influenced by patterned loading, structure geometry, stiffness distribution, directional effects, forcing functions based on activity frequency and duration of foot contact, and modal participation. It was also shown that higher harmonics of the load frequency can excite higher modes in the composite floor structure. Such responsive behaviour is prevalent mainly in slender and lightweight construction and not in stiffer and heavier structural systems. The analytical techniques and methods used in these investigations can supplement the current limited code and best practice provisions for mitigating the impact of human induced vibrations in slender structural systems.

The psychosocial factors influencing aggressive driving behaviour

Many drivers in highly motorised countries believe that aggressive driving is increasing. While the prevalence of the behaviour is difficult to reliably identify, the consequences of on-road aggression can be severe, with extreme cases resulting in property damage, injury and even death. This research program was undertaken to explore the nature of aggressive driving from within the framework of relevant psychological theory in order to enhance our understanding of the behaviour and to inform the development of relevant interventions. To guide the research a provisional ‘working’ definition of aggressive driving was proposed encapsulating the recurrent characteristics of the behaviour cited in the literature. The definition was: “aggressive driving is any on-road behaviour adopted by a driver that is intended to cause physical or psychological harm to another road user and is associated with feelings of frustration, anger or threat”. Two main theoretical perspectives informed the program of research. The first was Shinar’s (1998) frustration-aggression model, which identifies both the person-related and situational characteristics that contribute to aggressive driving, as well as proposing that aggressive behaviours can serve either an ‘instrumental’ or ‘hostile’ function. The second main perspective was Anderson and Bushman’s (2002) General Aggression Model. In contrast to Shinar’s model, the General Aggression Model reflects a broader perspective on human aggression that facilitates a more comprehensive examination of the emotional and cognitive aspects of aggressive behaviour. Study One (n = 48) examined aggressive driving behaviour from the perspective of young drivers as an at-risk group and involved conducting six focus groups, with eight participants in each. Qualitative analyses identified multiple situational and person-related factors that contribute to on-road aggression. Consistent with human aggression theory, examination of self-reported experiences of aggressive driving identified key psychological elements and processes that are experienced during on-road aggression. Participants cited several emotions experienced during an on-road incident: annoyance, frustration, anger, threat and excitement. Findings also suggest that off-road generated stress may transfer to the on-road environment, at times having severe consequences including crash involvement. Young drivers also appeared quick to experience negative attributions about the other driver, some having additional thoughts of taking action. Additionally, the results showed little difference between males and females in the severity of behavioural responses they were prepared to adopt, although females appeared more likely to displace their negative emotions. Following the self-reported on-road incident, evidence was also found of a post-event influence, with females being more likely to experience ongoing emotional effects after the event. This finding was evidenced by ruminating thoughts or distraction from tasks. However, the impact of such a post-event influence on later behaviours or interpersonal interactions appears to be minimal. Study Two involved the quantitative analysis of n = 926 surveys completed by a wide age range of drivers from across Queensland. The study aimed to explore the relationships between the theoretical components of aggressive driving that were identified in the literature review, and refined based on the findings of Study One. Regression analyses were used to examine participant emotional, cognitive and behavioural responses to two differing on-road scenarios whilst exploring the proposed theoretical framework. A number of socio-demographic, state and trait person-related variables such as age, pre-study emotions, trait aggression and problem-solving style were found to predict the likelihood of a negative emotional response such as frustration, anger, perceived threat, negative attributions and the likelihood of adopting either an instrumental or hostile behaviour in response to Scenarios One and Two. Complex relationships were found to exist between the variables, however, they were interpretable based on the literature review findings. Factor analysis revealed evidence supporting Shinar’s (1998) dichotomous description of on-road aggressive behaviours as being instrumental or hostile. The second stage of Study Two used logistic regression to examine the factors that predicted the potentially hostile aggressive drivers (n = 88) within the sample. These drivers were those who indicated a preparedness to engage in direct acts of interpersonal aggression on the road. Young, male drivers 17–24 years of age were more likely to be classified as potentially hostile aggressive drivers. Young drivers (17–24 years) also scored significantly higher than other drivers on all subscales of the Aggression Questionnaire (Buss & Perry, 1992) and on the ‘negative problem orientation’ and ‘impulsive careless style’ subscales of the Social Problem Solving Inventory – Revised (D’Zurilla, Nezu & Maydeu-Olivares, 2002). The potentially hostile aggressive drivers were also significantly more likely to engage in speeding and drink/drug driving behaviour. With regard to the emotional, cognitive and behavioural variables examined, the potentially hostile aggressive driver group also scored significantly higher than the ‘other driver’ group on most variables examined in the proposed theoretical framework. The variables contained in the framework of aggressive driving reliably distinguished potentially hostile aggressive drivers from other drivers (Nagalkerke R2 = .39). Study Three used a case study approach to conduct an in-depth examination of the psychosocial characteristics of n = 10 (9 males and 1 female) self-confessed hostile aggressive drivers. The self-confessed hostile aggressive drivers were aged 24–55 years of age. A large proportion of these drivers reported a Year 10 education or better and average–above average incomes. As a group, the drivers reported committing a number of speeding and unlicensed driving offences in the past three years and extensive histories of violations outside of this period. Considerable evidence was also found of exposure to a range of developmental risk factors for aggression that may have contributed to the driver’s on-road expression of aggression. These drivers scored significantly higher on the Aggression Questionnaire subscales and Social Problem Solving Inventory Revised subscales, ‘negative problem orientation’ and ‘impulsive/careless style’, than the general sample of drivers included in Study Two. The hostile aggressive driver also scored significantly higher on the Barrett Impulsivity Scale – 11 (Patton, Stanford & Barratt, 1995) measure of impulsivity than a male ‘inmate’, or female ‘general psychiatric’ comparison group. Using the Carlson Psychological Survey (Carlson, 1982), the self-confessed hostile aggressive drivers scored equal or higher scores than the comparison group of incarcerated individuals on the subscale measures of chemical abuse, thought disturbance, anti-social tendencies and self-depreciation. Using the Carlson Psychological Survey personality profiles, seven participants were profiled ‘markedly anti-social’, two were profiled ‘negative-explosive’ and one was profiled as ‘self-centred’. Qualitative analysis of the ten case study self-reports of on-road hostile aggression revealed a similar range of on-road situational factors to those identified in the literature review and Study One. Six of the case studies reported off-road generated stress that they believed contributed to the episodes of aggressive driving they recalled. Intense ‘anger’ or ‘rage’ were most frequently used to describe the emotions experienced in response to the perceived provocation. Less frequently ‘excitement’ and ‘fear’ were cited as relevant emotions. Notably, five of the case studies experienced difficulty articulating their emotions, suggesting emotional difficulties. Consistent with Study Two, these drivers reported negative attributions and most had thoughts of aggressive actions they would like to take. Similarly, these drivers adopted both instrumental and hostile aggressive behaviours during the self-reported incident. Nine participants showed little or no remorse for their behaviour and these drivers also appeared to exhibit low levels of personal insight. Interestingly, few incidents were brought to the attention of the authorities. Further, examination of the person-related characteristics of these drivers indicated that they may be more likely to have come from difficult or dysfunctional backgrounds and to have a history of anti-social behaviours on and off the road. The research program has several key theoretical implications. While many of the findings supported Shinar’s (1998) frustration-aggression model, two key areas of difference emerged. Firstly, aggressive driving behaviour does not always appear to be frustration driven, but can also be driven by feelings of excitation (consistent with the tenets of the General Aggression Model). Secondly, while the findings supported a distinction being made between instrumental and hostile aggressive behaviours, the characteristics of these two types of behaviours require more examination. For example, Shinar (1998) proposes that a driver will adopt an instrumental aggressive behaviour when their progress is impeded if it allows them to achieve their immediate goals (e.g. reaching their destination as quickly as possible); whereas they will engage in hostile aggressive behaviour if their path to their goal is blocked. However, the current results question this assertion, since many of the hostile aggressive drivers studied appeared prepared to engage in hostile acts irrespective of whether their goal was blocked or not. In fact, their behaviour appeared to be characterised by a preparedness to abandon their immediate goals (even if for a short period of time) in order to express their aggression. The use of the General Aggression Model enabled an examination of the three components of the ‘present internal state’ comprising emotions, cognitions and arousal and how these influence the likelihood of a person responding aggressively to an on-road situation. This provided a detailed insight into both the cognitive and emotional aspects of aggressive driving that have important implications for the design of relevant countermeasures. For example, the findings highlighted the potential value of utilising Cognitive Behavioural Therapy with aggressive drivers, particularly the more hostile offenders. Similarly, educational efforts need to be mindful of the way that person-related factors appear to influence one’s perception of another driver’s behaviour as aggressive or benign. Those drivers with a predisposition for aggression were more likely to perceive aggression or ‘wrong doing’ in an ambiguous on-road situation and respond with instrumental and/or hostile behaviour, highlighting the importance of perceptual processes in aggressive driving behaviour.