Thermal analysis and hot stage Raman spectroscopy of the basic copper arsenate mineral : euchroite

The thermal analysis of euchroite shows two mass loss steps in the temperature range 100 to 105°C and 185 to 205°C. These mass loss steps are attributed to dehydration and dehydroxylation of the mineral. Hot stage Raman spectroscopy (HSRS) has been used to study the thermal stability of the mineral euchroite, a mineral involved in a complex set of equilibria between the copper hydroxy arsenates: euchroite Cu2(AsO4)(OH).3H2O → olivenite Cu2(AsO4)(OH) → strashimirite Cu8(AsO4)4(OH)4.5H2O → arhbarite Cu2Mg(AsO4)(OH)3. Hot stage Raman spectroscopy inolves the collection of Raman spectra as a function of the temperature. HSRS shows that the mineral euchroite decomposes between 125 and 175 °C with the loss of water. At 125 °C, Raman bands are observed at 858 cm-1 assigned to the ν1 AsO43- symmetric stretching vibration and 801, 822 and 871 cm-1 assigned to the ν3 AsO43- (A1) antisymmetric stretching vibration. A distinct band shift is observed upon heating to 275 °C. At 275 °C the four Raman bands are resolved at 762, 810, 837 and 862 cm-1. Further heating results in the diminution of the intensity in the Raman spectra and this is attributed to sublimation of the arsenate mineral. Hot stage Raman spectroscopy is most useful technique for studying the thermal stability of minerals especially when only very small amounts of mineral are available.

Addressing issues in sparseness, ecological bias and formulation of the adjacency matrix in Bayesian spatio-temporal analysis of disease counts

The main objective of this PhD was to further develop Bayesian spatio-temporal models (specifically the Conditional Autoregressive (CAR) class of models), for the analysis of sparse disease outcomes such as birth defects. The motivation for the thesis arose from problems encountered when analyzing a large birth defect registry in New South Wales. The specific components and related research objectives of the thesis were developed from gaps in the literature on current formulations of the CAR model, and health service planning requirements. Data from a large probabilistically-linked database from 1990 to 2004, consisting of fields from two separate registries: the Birth Defect Registry (BDR) and Midwives Data Collection (MDC) were used in the analyses in this thesis. The main objective was split into smaller goals. The first goal was to determine how the specification of the neighbourhood weight matrix will affect the smoothing properties of the CAR model, and this is the focus of chapter 6. Secondly, I hoped to evaluate the usefulness of incorporating a zero-inflated Poisson (ZIP) component as well as a shared-component model in terms of modeling a sparse outcome, and this is carried out in chapter 7. The third goal was to identify optimal sampling and sample size schemes designed to select individual level data for a hybrid ecological spatial model, and this is done in chapter 8. Finally, I wanted to put together the earlier improvements to the CAR model, and along with demographic projections, provide forecasts for birth defects at the SLA level. Chapter 9 describes how this is done. For the first objective, I examined a series of neighbourhood weight matrices, and showed how smoothing the relative risk estimates according to similarity by an important covariate (i.e. maternal age) helped improve the model’s ability to recover the underlying risk, as compared to the traditional adjacency (specifically the Queen) method of applying weights. Next, to address the sparseness and excess zeros commonly encountered in the analysis of rare outcomes such as birth defects, I compared a few models, including an extension of the usual Poisson model to encompass excess zeros in the data. This was achieved via a mixture model, which also encompassed the shared component model to improve on the estimation of sparse counts through borrowing strength across a shared component (e.g. latent risk factor/s) with the referent outcome (caesarean section was used in this example). Using the Deviance Information Criteria (DIC), I showed how the proposed model performed better than the usual models, but only when both outcomes shared a strong spatial correlation. The next objective involved identifying the optimal sampling and sample size strategy for incorporating individual-level data with areal covariates in a hybrid study design. I performed extensive simulation studies, evaluating thirteen different sampling schemes along with variations in sample size. This was done in the context of an ecological regression model that incorporated spatial correlation in the outcomes, as well as accommodating both individual and areal measures of covariates. Using the Average Mean Squared Error (AMSE), I showed how a simple random sample of 20% of the SLAs, followed by selecting all cases in the SLAs chosen, along with an equal number of controls, provided the lowest AMSE. The final objective involved combining the improved spatio-temporal CAR model with population (i.e. women) forecasts, to provide 30-year annual estimates of birth defects at the Statistical Local Area (SLA) level in New South Wales, Australia. The projections were illustrated using sixteen different SLAs, representing the various areal measures of socio-economic status and remoteness. A sensitivity analysis of the assumptions used in the projection was also undertaken. By the end of the thesis, I will show how challenges in the spatial analysis of rare diseases such as birth defects can be addressed, by specifically formulating the neighbourhood weight matrix to smooth according to a key covariate (i.e. maternal age), incorporating a ZIP component to model excess zeros in outcomes and borrowing strength from a referent outcome (i.e. caesarean counts). An efficient strategy to sample individual-level data and sample size considerations for rare disease will also be presented. Finally, projections in birth defect categories at the SLA level will be made.

Validation of the impact of Health Information Technology (I-HIT) scale : an international collaborative

In 2005, the Healthcare Information Management Systems Society (HIMSS) Nursing Informatics Community developed a survey to measure the impact of health information technology (HIT), the IHIT Scale, on the role of nurses and interdisciplinary communication in hospital settings. In 2007, nursing informatics colleagues from Australia, England, Finland, Ireland, New Zealand, Scotland and the United States formed a research collaborative to validate the IHIT across countries. All teams have completed construct and face validation in their countries. Five out of six teams have initiated reliability testing by practicing nurses. This paper reports the international collaborative’s validation of the IHIT Scale completed to date.

Bulk compressive properties of the heel fat pad during walking: a pilot investigation in plantar heel pain

Background: Altered mechanical properties of the heel pad have been implicated in the development of plantar heel pain. However, the in vivo properties of the heel pad during gait remain largely unexplored in this cohort. The aim of the current study was to characterise the bulk compressive properties of the heel pad in individuals with and without plantar heel pain while walking. ---------- Methods: The sagittal thickness and axial compressive strain of the heel pad were estimated in vivo from dynamic lateral foot radiographs acquired from nine subjects with unilateral plantar heel pain and an equivalent number of matched controls, while walking at their preferred speed. Compressive stress was derived from simultaneously acquired plantar pressure data. Principal viscoelastic parameters of the heel pad, including peak strain, secant modulus and energy dissipation (hysteresis), were estimated from subsequent stress–strain curves.---------- Findings: There was no significant difference in loaded and unloaded heel pad thickness, peak stress, peak strain, or secant and tangent modulus in subjects with and without heel pain. However, the fat pad of symptomatic feet had a significantly lower energy dissipation ratio (0.55 ± 0.17 vs. 0.69 ± 0.08) when compared to asymptomatic feet (P < .05).---------- Interpretation: Plantar heel pain is characterised by reduced energy dissipation ratio of the heel pad when measured in vivo and under physiologically relevant strain rates.

Incidental walking activity is sufficient to induce time-dependent conditioning of the Achilles tendon

The Achilles tendon has been seen to exhibit time-dependent conditioning when isometric muscle actions were of a prolonged duration, compared to those involved in dynamic activities, such as walking. Since, the effect of short duration muscle activation associated with dynamic activities is yet to be established, the present study aimed to investigate the effect of incidental walking activity on Achilles tendon diametral strain. Eleven healthy male participants refrained from physical activity in excess of the walking required to carry out necessary daily tasks and wore an activity monitor during the 24 h study period. Achilles tendon diametral strain, 2 cm proximal to the calcaneal insertion, was determined from sagittal sonograms. Baseline sonographic examinations were conducted at ∼08:00 h followed by replicate examinations at 12 and 24 h. Walking activity was measured as either present (1) or absent (0) and a linear weighting function was applied to account for the proximity of walking activity to tendon examination time. Over the course of the day the median (min, max) Achilles tendon diametral strain was −11.4 (4.5, −25.4)%. A statistically significant relationship was evident between walking activity and diametral strain (P < 0.01) and this relationship improved when walking activity was temporally weighted (AIC 131 to 126). The results demonstrate that the short yet repetitive loads generated during activities of daily living, such as walking, are sufficient to induce appreciable time-dependant conditioning of the Achilles tendon. Implications arise for the in vivo measurement of Achilles tendon properties and the rehabilitation of tendinopathy.

A genealogy of the problematic of homelessness and the homeless in Australia

The homeless have been subject to considerable scrutiny, historically and within current social, political and public discourse. The aetiology of homelessness has been the focus of a large body of economic, sociological, historical and political investigation. Importantly, efforts to conceptualise, explain and measure, the phenomenon of homelessness and homeless people has occurred largely within the context of defining “the problem of the homeless” and the generation of solutions to the ‘problem’. There has been little consideration of how and why homelessness has come to be seen, or understood, as a problem, or how this can change across time and/or place. This alternative stream of research has focused on tracing and analysing the relationship between how people experiencing homeless have become a matter of government concern and the manner in which homelessness itself has been problematised. With this in mind this study has analysed the discourses - political, social and economic rationalities and knowledges - which have provided the conditions of possibility for the identification of the homeless and homelessness as a problem needing to be governed and the means for translating these discourses into the applied domain. The aim of this thesis has been to contribute to current knowledge by developing a genealogy of the conditions and rationalities that have underpinned the problematisation of homelessness and the homeless. The outcome of this analysis has been to open up the opportunity to consider alternative governmental possibilities arising from the exposure of the way in which contemporary problematisation and responses have been influenced by the past. An understanding of this process creates an ability to appreciate the intended and unintended consequences for the future direction of public policy and contemporary research.

Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Poverty in perception : a study of the twentieth-century prime ministers of Australia and New Zealand

Australia and New Zealand, as English-speaking nations with dominant white populations, present an ethnic anomaly not only in South East Asia, but also in the Southern Hemisphere. Colonised by predominantly workingclass British immigrants from the late eighteenth century, an ethnic and cultural connection grew between these two countries even though their indigenous populations and ecological environments were otherwise very different. Building a new life in Australia and New Zealand, the colonists shared similar historic perceptions of poverty – perceptions from their homelands that they did not want to see replicated in their new adopted countries. Dreams of a better life shaped their aspirations, self-identity and nationalistic outlook. By the twentieth century, national independence and self-government had replaced British colonial rule. The inveterate occurrence of poverty in Australia and New Zealand had created new local perspectives and different perceptions of, and about, poverty. This study analyses what relationship existed between the political directions adopted by the twentieth-century prime ministers of Australia and New Zealand and their perceptions of poverty. Using the existential phenomenological theory and methodology of Maurice Merleau-Ponty, the study adds to the body of knowledge about poverty in Australia and New Zealand by revealing the structure and origin of the poverty perceptions of the twentieth-century prime ministers.

A psychometric comparison of the Toronto Alexithymia Scale (TAS-20) and the Observer Alexithymia Scale (OAS) in an alcohol-dependent sample

Alexithymia is characterised by deficits in emotional insight and self reflection, that impact on the efficacy of psychological treatments. Given the high prevalence of alexithymia in Alcohol Use Disorders, valid assessment tools are critical. The majority of research on the relationship between alexithymia and alcohol-dependence has employed the self-administered Toronto Alexithymia Scale (TAS-20). The Observer Alexithymia Scale (OAS) has also been recommended. The aim of the present study was to assess the validity and reliability of the OAS and the TAS-20 in an alcohol-dependent sample. Two hundred and ten alcohol-dependent participants in an outpatient Cognitive Behavioral Treatment program were administered the TAS-20 at assessment and upon treatment completion at 12 weeks. Clinical psychologists provided observer assessment data for a subsample of 159 patients. The findings confirmed acceptable internal consistency, test-retest reliability and scale homogeneity for both the OAS and TAS-20, except for the low internal consistency of the TAS-20 EOT scale. The TAS-20 was more strongly associated with alcohol problems than the OAS.

Skydweller and representations of the adolescent crisis : group identity versus alienation

This document contains a creative work – the text of a young adult novel, Skydweller – and an exegesis discussing the ways in which identity and the adolescent crisis of group identity versus alienation are represented in young adult science fiction/fantasy novels.

Do board contacts matter? : an analysis of the relationship between boards of directors’ ties and the performance of Australia’s largest companies.

Boards of directors are thought to provide access to a wealth of knowledge and resources for the companies they serve, and are considered important to corporate governance. Under the Resource Based View (RBV) of the firm (Wernerfelt, 1984) boards are viewed as a strategic resource available to firms. As a consequence there has been a significant research effort aimed at establishing a link between board attributes and company performance. In this thesis I explore and extend the study of interlocking directorships (Mizruchi, 1996; Scott 1991a) by examining the links between directors’ opportunity networks and firm performance. Specifically, I use resource dependence theory (Pfeffer & Salancik, 1978) and social capital theory (Burt, 1980b; Coleman, 1988) as the basis for a new measure of a board’s opportunity network. I contend that both directors’ formal company ties and their social ties determine a director’s opportunity network through which they are able to access and mobilise resources for their firms. This approach is based on recent studies that suggest the measurement of interlocks at the director level, rather than at the firm level, may be a more reliable indicator of this phenomenon. This research uses publicly available data drawn from Australia’s top-105 listed companies and their directors in 1999. I employ Social Network Analysis (SNA) (Scott, 1991b) using the UCINET software to analyse the individual director’s formal and social networks. SNA is used to measure a the number of ties a director has to other directors in the top-105 company director network at both one and two degrees of separation, that is, direct ties and indirect (or ‘friend of a friend’) ties. These individual measures of director connectedness are aggregated to produce a board-level network metric for comparison with measures of a firm’s performance using multiple regression analysis. Performance is measured with accounting-based and market-based measures. Findings indicate that better-connected boards are associated with higher market-based company performance (measured by Tobin’s q). However, weaker and mostly unreliable associations were found for accounting-based performance measure ROA. Furthermore, formal (or corporate) network ties are a stronger predictor of market performance than total network ties (comprising social and corporate ties). Similarly, strong ties (connectedness at degree-1) are better predictors of performance than weak ties (connectedness at degree-2). My research makes four contributions to the literature on director interlocks. First, it extends a new way of measuring a board’s opportunity network based on the director rather than the company as the unit of interlock. Second, it establishes evidence of a relationship between market-based measures of firm performance and the connectedness of that firm’s board. Third, it establishes that director’s formal corporate ties matter more to market-based firm performance than their social ties. Fourth, it establishes that director’s strong direct ties are more important to market-based performance than weak ties. The thesis concludes with implications for research and practice, including a more speculative interpretation of these results. In particular, I raise the possibility of reverse causality – that is networked directors seek to join high-performing companies. Thus, the relationship may be a result of symbolic action by companies seeking to increase the legitimacy of their firms rather than a reflection of the social capital available to the companies. This is an important consideration worthy of future investigation.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

Student perceptions of the impact of online discussion forum participation on learning outcomes

Choosing the “right” type of technology, either synchronous or asynchronous, to facilitate learning outcomes is a new challenge as the pace of emerging technologies increases and diversifies. Teachers are encouraged to design courses that require collaboration in online learning communities to facilitate the development of higher order thinking skills for life long learning. It is therefore important to gather evidence of the kinds of opportunities afforded to students and whether the students themselves endorse collaborative online tools as a legitimate method of assisting in their learning. This paper outlines the way in which one secondary school has used an online discussion forum to support students in the International Baccalaureate (IB) Diploma Program in enhancing research skills and skills for lifelong learning. The paper considers whether online collaborative tools are perceived by students as a positive way to improve learning outcomes.

Election campaigns, and television news coverage : the case of the 2001 Australian election

This paper examines the patterns of television news coverage of the political parties, their leaders and the issues they raised during the 2001 Australian federal election campaign. By focusing on some issues, parties and leaders, television has long been argued to constrain voters' evaluations. We find that television news coverage in the 2001 Australian election campaign focused primarily on international issues, especially terrorism and asylum seekers, and on the two major parties - virtually to the exclusion of coverage of the minor parties and their leaders. Within the major party 'two-horse race', television gave substantially more coverage to the leaders than to the parties themselves, thereby sustaining what some have called a 'presidential'-style political contest. John Howard emerged as the winner in the leaders' stakes, garnering more coverage than Labor's Kim Beazley.

Corporate governance in China : the role of the state and ideology in shaping reforms

Examines the political and ideological influences on China's economic reforms since the early 1980s. Discusses the influence of the Chinese Communist Party and Confucianism on economic progress and assesses the effect of reforms. Outlines the requirement for new corporate governance laws to meet the needs of expanding private businesses and considers China's use and adaptation of some Western models of corporate governance. Comments on whether these fit easily with China's business culture. Criticises the shortcomings of China's corporate laws. Looks in particular at the telecommunications industry and at the Company Law 2006.