Investigation of RuO2/Ta2O5 thin film evolution by thermogravimetry combined with mass spectrometry

The thermal evolution process of RuO2–Ta2O5/Ti coatings with varying noble metal content has been investigated under in situ conditions by thermogravimetry combined with mass spectrometry. The gel-like films prepared from alcoholic solutions of the precursor salts (RuCl3·3H2O, TaCl5) onto titanium metal support were heated in an atmosphere containing 20% O2 and 80% Ar up to 600 °C. The evolution of the mixed oxide coatings was followed by the mass spectrometric ion intensity curves. The cracking of retained solvent and the combustion of organic surface species formed were also followed by the mass spectrometric curves. The formation of carbonyl- and carboxylate-type surface species connected to the noble metal was identified by Fourier transform infrared emission spectroscopy. These secondary processes–catalyzed by the noble metal–may play an important role in the development of surface morphology and electrochemical properties. The evolution of the two oxide phases does not take place independently, and the effect of the noble metal as a combustion catalyst was proved.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Water uptake of aerosols with a focus on seeded aerosols and instrumentation techniques

This thesis focuses on the volatile and hygroscopic properties of mixed aerosol species. In particular, the influence organic species of varying solubility have upon seed aerosols. Aerosol studies were conducted at the Paul Scherrer Institut Laboratory for Atmospheric Chemistry (PSI-LAC, Villigen, Switzerland) and at the Queensland University of Technology International Laboratory for Air Quality and Health (QUT-ILAQH, Brisbane, Australia). The primary measurement tool employed in this program was the Volatilisation and Hygroscopicity Tandem Differential Mobility Analyser (VHTDMA - Johnson et al. 2004). This system was initially developed at QUT within the ILAQH and was completely re-developed as part of this project (see Section 1.4 for a description of this process). The new VHTDMA was deployed to the PSI-LAC where an analysis of the volatile and hygroscopic properties of ammonium sulphate seeds coated with organic species formed from the photo-oxidation of á-pinene was conducted. This investigation was driven by a desire to understand the influence of atmospherically prevalent organics upon water uptake by material with cloud forming capabilities. Of particular note from this campaign were observed influences of partially soluble organic coatings upon inorganic ammonium sulphate seeds above and below their deliquescence relative humidity (DRH). Above the DRH of the seed increasing the volume fraction of the organic component was shown to reduce the water uptake of the mixed particle. Below the DRH the organic was shown to activate the water uptake of the seed. This was the first time this effect had been observed for á-pinene derived SOA. In contrast with the simulated aerosols generated at the PSI-LAC a case study of the volatile and hygroscopic properties of diesel emissions was undertaken. During this stage of the project ternary nucleation was shown, for the first time, to be one of the processes involved in formation of diesel particulate matter. Furthermore, these particles were shown to be coated with a volatile hydrophobic material which prevented the water uptake of the highly hygroscopic material below. This result was a first and indicated that previous studies into the hygroscopicity of diesel emission had erroneously reported the particles to be hydrophobic. Both of these results contradict the previously upheld Zdanovksii-Stokes-Robinson (ZSR) additive rule for water uptake by mixed species. This is an important contribution as it adds to the weight of evidence that limits the validity of this rule.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.

Kava Anxiety Depression Spectrum Study (KADSS): a mixed methods RCT using an aqueous extract of Piper methysticum

Objectives: To report on the design, significance and potential impacts of the first documented human clinical trial assessing the anxiolytic and thymoleptic efficacy of an aqueous monoextract of Piper methysticum (kava). The significance of the qualitative element of our clinical trial is also explored. The Kava Anxiety Depression Spectrum Study (KADSS) is a 3-week placebocontrolled, double-blind, cross-over trial involving 60 adult participants (18—65) with elevated stable anxiety and varying levels of depressive symptoms. Aims: The aims of KADSS are: (1) to determine whether an aqueous standardised extract of kava is effective for the treatment of anxiety; (2) to assess the effects of kava on differing levels of depression; and (3) to explore participants’ experience of taking kava via qualitative research. The study also provides preliminary assessment of the safety of an aqueous extract of kava in humans. Conclusion: If results reveal that the aqueous kava preparation exerts significant anxiolytic effects and appears safe, potentially beneficial impacts may occur. Data supporting a safe and effective kava extract may encourage a re-introduction of kava to Europe, UK and Canada. This may provide a major socioeconomic benefit to Pacific Island nations, and to sufferers of anxiety disorders.

Raman spectroscopic study of the mixed anion sulphate-arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate, hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm-1 are assigned to the 1 (AsO4)3- symmetric stretching and 3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp band at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite.

The role of rural land in mixed asset investment portfolios

Rural land has not always been considered as a major long-term investment with both institutional investors and absentee owners in countries such as U.K. and Australia. Although rural land is included in both single asset and mixed asset portfolios in the U.S, it is not at the same levels as either commercial or industrial property. Rural land occupies over 50% of the total area of Australia, and comprises over 115,000 economic farm properties (excludes rural residential, hobby farms and rural lifestyle blocks. However, less than 1.6% of the total economic farm numbers are actually owned by corporate or institutional investors. This low level of corporate involvement in the Australian rural property market has limited both the investment performance research and inclusion of this rural land type in both property and mixed asset investment portfolios. In the U.S. rural land is also the most extensive real estate type based on total area occupied. The United States Department of Agriculture statistics (1998) show that in 1997 there were 2.06 million farms in the U.S., covering 968 million acres, with a total value of $912 billion and generating an annual income of $202 billion. The level of corporate ownership of farms in the U.S. is also higher than the level of corporate farm ownership in Australia. This high level of institutional ownership in rural land in U.S has provided the opportunity for the rural property asset class to be analysed in relation to it’s investment performance and possible role in a mixed asset or mixed property investment portfolio.

Learning in the third space : a sociocultural perspective on learning with analogies

Research on analogies in science education has focussed on student interpretation of teacher and textbook analogies, psychological aspects of learning with analogies and structured approaches for teaching with analogies. Few studies have investigated how analogies might be pivotal in students’ growing participation in chemical discourse. To study analogies in this way requires a sociocultural perspective on learning that focuses on ways in which language, signs, symbols and practices mediate participation in chemical discourse. This study reports research findings from a teacher-research study of two analogy-writing activities in a chemistry class. The study began with a theoretical model, Third Space, which informed analyses and interpretation of data. Third Space was operationalized into two sub-constructs called Dialogical Interactions and Hybrid Discourses. The aims of this study were to investigate sociocultural aspects of learning chemistry with analogies in order to identify classroom activities where students generate Dialogical Interactions and Hybrid Discourses, and to refine the operationalization of Third Space. These aims were addressed through three research questions. The research questions were studied through an instrumental case study design. The study was conducted in my Year 11 chemistry class at City State High School for the duration of one Semester. Data were generated through a range of data collection methods and analysed through discourse analysis using the Dialogical Interactions and Hybrid Discourse sub-constructs as coding categories. Results indicated that student interactions differed between analogical activities and mathematical problem-solving activities. Specifically, students drew on discourses other than school chemical discourse to construct analogies and their growing participation in chemical discourse was tracked using the Third Space model as an interpretive lens. Results of this study led to modification of the theoretical model adopted at the beginning of the study to a new model called Merged Discourse. Merged Discourse represents the mutual relationship that formed during analogical activities between the Analog Discourse and the Target Discourse. This model can be used for interpreting and analysing classroom discourse centred on analogical activities from sociocultural perspectives. That is, it can be used to code classroom discourse to reveal students’ growing participation with chemical (or scientific) discourse consistent with sociocultural perspectives on learning.

An experiment in mixed compilation/interpretation

One of the classic forms of intermediate representation used for communication between compiler front-ends and back-ends are those based on abstract stack machines. It is possible to compile the stack machine instructions into machine code by means of an interpretive code generator, or to simulate the stack machine at runtime using an interpreter. This paper describes an approach intermediate between these two extremes. The front-end for a commercial Modula 2 compiler was ported to the "industry standard PC", and a partially compiling back-end written. The object code runs with the assistance of an interpreter, but may be linked with libraries which are fully compiled. The intent was to provide a programming environment on the PC which is identical to that of the same compilers on 32-bit UNIX machines. This objective has been met, and the compiler is available to educational institutions as free-ware. The design basis of the new compiler is described, and the performance critically evaluated.

Vitamin D and sun protection : the impact of mixed public health messages in Australia

Exposure of the skin to sunlight can cause skin cancer and is also necessary for cutaneous vitamin D production. Media reports have highlighted the purported health benefits of vitamin D. Our aim was to examine attitudes and behaviours related to sun protection and vitamin D. A cross-sectional study of 2,001 residents in Queensland, Australia aged 20-70 years was undertaken. Information collected included: skin cancer risk factors; perceptions about levels of sun exposure required to maintain vitamin D; belief that sun protection increases risk of vitamin D deficiency; intention, and actual change in sun protection practices for adults and children. Multivariate models examined predictors of attitudinal and behavioural change. One-third (32%) believed a fair-skinned adult, and 31% thought a child required at least 30 minutes per day in summer sun to maintain vitamin D levels. Reductions in sun protection were reported by 21% of adults and 14% of children. Factors associated with belief that sun protection may result in not obtaining enough vitamin D included aged ≥ 60 years (OR=1.35, 95% CI 1.09-1.66) and having skin that tanned easily (OR=1.96, 95% CI 1.38-2.78). Participants from low income households, and those who frequently used sun protective clothing were more likely to have reduced sun protection practices (OR=1.33, 95% CI 1.10-1.73 and OR=1.73, 95% CI 1.36-2.20, respectively). This study provides evidence of reductions in sun protection practices in a population living in a high UV environment. There is an urgent need to re-focus messages regarding sun exposure and for continued sun protection practices.

In-session processes in online counselling with young people : an exploratory approach

Aims : The aim of this study was to conduct an exploratory investigation into the in-session processes and behaviours that occur between therapists and young people in online counseling. Method: The Consensual Qualitative Research method was employed to identify in-session behaviours and a coding instrument was developed to determine their frequency of use and assess whether nuances carried in the meaning of text messages have an influential effect during sessions. Eighty-five single-session transcripts were examined in total by two independent coders. Results: Sample statistics revealed that, on average, rapport-building processes were used more consistently across cases with both types of processes having a moderately strong positive effect on young people. However, closer examination of these processes revealed weaker positive effects for in-session behaviours that rely more heavily on verbal and non-verbal cues to be accurately interpreted. Implications for Practice and Future Research: These findings imply that therapists may focus more on building rapport than accomplishing tasks with young people during online counselling sessions due to the absence of verbal and non-verbal information when communicating via text messages.

Social support and fires in the workplace : a preliminary investigation

Workers who experience fire in the workplace are faced with disruption to their work routine, as well as the emotional strain of the fire. In the broader occupational stress literature, researchers have suggested that social support will be most effective at reducing the negative effects of stressors on strain when the type of support matches the type of stressor being experienced (either instrumental or emotional). This study was a preliminary investigation into employee responses to less routine stressors, such as workplace fires, and the role of different sources of social support in predicting coping effectiveness. This study also was a first attempt at considering the influence of the social context (in terms of group identification) on the effectiveness of social support as a predictor of coping effectiveness. Specifically, it was predicted that social support would be more effective when it came from multiple sources within the organization, that it would be especially effective when provided from a group that workers identified more strongly with, and that simply feeling part of a group would improve adjustment. Both quantitative and qualitative data were collected from 33 employees who had recently experienced a significant fire in their workplace. Results suggested that the type of stressors experienced and the type of support were mismatched, but despite this, coping effectiveness was generally moderate to high. There was mixed support for predictions about the effects of social support–no moderating effect of group identification on coping effectiveness was observed for measures of workplace support, although it did moderate the effects of family support on this adjustment indicator.

Implementing change within a school science department: progressive and dissonant voices

The purpose of this study was to describe the teaching and leadership experiences of a science teacher who, as head of department, was preparing to introduce changes in the science department of an independent school in response to the requirements of the new junior science syllabus in Queensland, Australia. This teacher consented to classroom observations and interviews with the researchers where his beliefs about teaching practice and change were explored. Other science teachers at the school also were interviewed about their reactions to the planned changes. Interpretive analysis of the data provides an account of the complex interactions, negotiations, compromises, concessions, and trade-offs faced by the teacher during a period of education reform. Perceived barriers existing within the school that impeded proposed change are identified

Sustainability of a multimodal intervention to promote lifestyle factors associated with the prevention of cardiovascular disease in midlife Australian women : a 5-year follow-up

We evaluated sustainability of an intervention to reduce women’s cardiovascular risk factors, determined the influence of self-efficacy, and described women’s current health. We used a mixed method approach that utilized forced choice and open-ended questionnaire items about health status, habits, and self-efficacy. Sixty women, average age 61, returned questionnaires. Women in the original intervention group continued health behaviors intended to reduce cardiovascular disease (CVD) at a higher rate than the control group, supporting the feasibility of a targeted intervention built around women’s individual goals. The role of self-efficacy in behavior change is unclear. The original intervention group reported higher self-reported health.

Two voices : the marginalised body as a voice & Imperfect Offerings a novel

This thesis investigates the phenomenon of self-harm as a form of political protest using two different, but complementary, methods of inquiry: a theoretical research project and a novel. Through these two approaches, to the same research problem, I examine how we can re-position the body that self-harms in political protest from weapon to voice; and in doing so find a path towards ethical and equitable dialogue between marginalised and mainstream communities. The theoretical, or academic, portion of the thesis examines self-harm as protest, positing these acts as a form of tactical selfharm, and acknowledge its emergence as a voice for the otherwise silenced in the public sphere. Through the use of phenomenology and feminist theory I examine the body as site for political agency, the circumstances which surround the use of the body for protest, and the reaction to tactical self-harm by the individual and the state. Using Bakhtin’s concept of dialogism, and the dialogic space I propose that by ‘hearing’ the body engaged in tactical selfharm we come closer to entering into an ethical dialogue with the otherwise silenced in our communities (locally, nationally and globally). The novel, Imperfect Offerings, explores these ideas in a fictional world, and allows me to put faces, names and lives to those who are compelled to harm their bodies to be heard. Also using Bakhtin’s framework I encourage a dialogue between the critical and creative parts of the thesis, challenging the traditional paradigm of creative PhD projects as creative work and exegesis.