Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Random Breath Testing in Australia: Is there an Optimum Level of Intensity?

Background: Random Breath Testing (RBT) is the main drink driving law enforcement tool used throughout Australia. International comparative research considers Australia to have the most successful RBT program compared to other countries in terms of crash reductions (Erke, Goldenbeld, & Vaa, 2009). This success is attributed to the programs high intensity (Erke et al., 2009). Our review of the extant literature suggests that there is no research evidence that indicates an optimal level of alcohol breath testing. That is, we suggest that no research exists to guide policy regarding whether or not there is a point at which alcohol related crashes reach a point of diminishing returns as a result of either saturated or targeted RBT testing. Aims: In this paper we first provide an examination of RBTs and alcohol related crashes across Australian jurisdictions. We then address the question of whether or not an optimal level of random breath testing exists by examining the relationship between the number of RBTs conducted and the occurrence of alcohol-related crashes over time, across all Australian states. Method: To examine the association between RBT rates and alcohol related crashes and to assess whether an optimal ratio of RBT tests per licenced drivers can be determined we draw on three administrative data sources form each jurisdiction. Where possible data collected spans January 1st 2000 to September 30th 2012. The RBT administrative dataset includes the number of Random Breath Tests (RBTs) conducted per month. The traffic crash administrative dataset contains aggregated monthly count of the number of traffic crashes where an individual’s recorded BAC reaches or exceeds 0.05g/ml of alcohol in blood. The licenced driver data were the monthly number of registered licenced drivers spanning January 2000 to December 2011. Results: The data highlights that the Australian story does not reflective of all States and territories. The stable RBT to licenced driver ratio in Queensland (of 1:1) suggests a stable rate of alcohol related crash data of 5.5 per 100,000 licenced drivers. Yet, in South Australia were a relative stable rate of RBT to licenced driver ratio of 1:2 is maintained the rate of alcohol related traffic crashes is substantially less at 3.7 per 100,000. We use joinpoint regression techniques and varying regression models to fit the data and compare the different patterns between jurisdictions. Discussion: The results of this study provide an updated review and evaluation of RBTs conducted in Australia and examines the association between RBTs and alcohol related traffic crashes. We also present an evidence base to guide policy decisions for RBT operations.

Feasibility of ranking articular cartilage conditions with non-destructive near-infrared spectroscopy with extension to the Mankin grading system

Grading osteoarthritic tissue has, until now, been a laboratory process confined to research activities. This thesis establishes a scientific protocol that extends osteoarthritic tissue ranking to surgical practice. The innovative protocol, which now incorporates the structural degeneration of collagen, enhances the traditional Modified Mankin ranking system, enabling its application to real time decision during surgery. Because it is fast and without time consuming laboratory process, it would potentially enable the cataloguing of tissues in osteoarthritic joints in all compartments of diseased joints during surgery for epistemological study and insight into the manifestation of osteoarthritis across age, gender, occupation, physical activities and race.

Exploring the conditions to support assessment for more equitable learning outcomes

NAPLAN RESULTS HAVE gained socio-political prominence and have been used as indicators of educational outcomes for all students, including Indigenous students. Despite the promise of open and in-depth access to NAPLAN data as a vehicle for intervention, we argue that the use of NAPLAN data as a basis for teachers and schools to reduce variance in learning outcomes is insufficient. NAPLAN tests are designed to show statistical variance at the level of the school and the individual, yet do not factor in the sociocultural and cognitive conditions Indigenous students’ experience when taking the tests. We contend that further understanding of these influences may help teachers understand how to develop their classroom practices to secure better numeracy and literacy outcomes for all students. Empirical research findings demonstrate how teachers can develop their classroom practices from an understanding of the extraneous cognitive load imposed by test taking. We have analysed Indigenous students’ experience of solving mathematical test problems to discover evidence of extraneous cognitive load. We have also explored conditions that are more supportive of learning derived from a classroom intervention which provides an alternative way to both assess and build learning for Indigenous students. We conclude that conditions to support assessment for more equitable learning outcomes require a reduction in cognitive load for Indigenous students while maintaining a high level of expectation and participation in problem solving.

Improving the PLDA based speaker verification in limited microphone data conditions

A significant amount of speech data is required to develop a robust speaker verification system, but it is difficult to find enough development speech to match all expected conditions. In this paper we introduce a new approach to Gaussian probabilistic linear discriminant analysis (GPLDA) to estimate reliable model parameters as a linearly weighted model taking more input from the large volume of available telephone data and smaller proportional input from limited microphone data. In comparison to a traditional pooled training approach, where the GPLDA model is trained over both telephone and microphone speech, this linear-weighted GPLDA approach is shown to provide better EER and DCF performance in microphone and mixed conditions in both the NIST 2008 and NIST 2010 evaluation corpora. Based upon these results, we believe that linear-weighted GPLDA will provide a better approach than pooled GPLDA, allowing for the further improvement of GPLDA speaker verification in conditions with limited development data.

Pre-crash traffic flow trend analysis on motorways

Crashes on motorway contribute to a significant proportion (40-50%) of non-recurrent motorway congestions. Hence reduce crashes will help address congestion issues (Meyer, 2008). Crash likelihood estimation studies commonly focus on traffic conditions in a Short time window around the time of crash while longer-term pre-crash traffic flow trends are neglected. In this paper we will show, through data mining techniques, that a relationship between pre-crash traffic flow patterns and crash occurrence on motorways exists, and that this knowledge has the potential to improve the accuracy of existing models and opens the path for new development approaches. The data for the analysis was extracted from records collected between 2007 and 2009 on the Shibuya and Shinjuku lines of the Tokyo Metropolitan Expressway in Japan. The dataset includes a total of 824 rear-end and sideswipe crashes that have been matched with traffic flow data of one hour prior to the crash using an incident detection algorithm. Traffic flow trends (traffic speed/occupancy time series) revealed that crashes could be clustered with regards of the dominant traffic flow pattern prior to the crash. Using the k-means clustering method allowed the crashes to be clustered based on their flow trends rather than their distance. Four major trends have been found in the clustering results. Based on these findings, crash likelihood estimation algorithms can be fine-tuned based on the monitored traffic flow conditions with a sliding window of 60 minutes to increase accuracy of the results and minimize false alarms.

Measurement, modelling and capacity analysis for novel, fixed multi-user single-antenna MIMO-OFDM system, in rural environments

High-speed broadband internet access is widely recognised as a catalyst to social and economic development. However, the provision of broadband Internet services with the existing solutions to rural population, scattered over an extensive geographical area, remains both an economic and technical challenge. As a feasible solution, the Commonwealth Scientific and Industrial Research Organization (CSIRO) proposed a highly spectrally efficient, innovative and cost-effective fixed wireless broadband access technology, which uses analogue TV frequency spectrum and Multi-User MIMO (MUMIMO) technology with Orthogonal-Frequency-Division-Multiplexing (OFDM). MIMO systems have emerged as a promising solution for the increasing demand of higher data rates, better quality of service, and higher network capacity. However, the performance of MIMO systems can be significantly affected by different types of propagation environments e.g., indoor, outdoor urban, or outdoor rural and operating frequencies. For instance, large spectral efficiencies associated with MIMO systems, which assume a rich scattering environment in urban environments, may not be valid for all propagation environments, such as outdoor rural environments, due to the presence of less scatterer densities. Since this is the first time a MU-MIMO-OFDM fixed broadband wireless access solution is deployed in a rural environment, questions from both theoretical and practical standpoints arise; For example, what capacity gains are available for the proposed solution under realistic rural propagation conditions?. Currently, no comprehensive channel measurement and capacity analysis results are available for MU-MIMO-OFDM fixed broadband wireless access systems which employ large scale multiple antennas at the Access Point (AP) and analogue TV frequency spectrum in rural environments. Moreover, according to the literature, no deterministic MU-MIMO channel models exist that define rural wireless channels by accounting for terrain effects. This thesis fills the aforementioned knowledge gaps with channel measurements, channel modeling and comprehensive capacity analysis for MU-MIMO-OFDM fixed wireless broadband access systems in rural environments. For the first time, channel measurements were conducted in a rural farmland near Smithton, Tasmania using CSIRO's broadband wireless access solution. A novel deterministic MU-MIMO-OFDM channel model, which can be used for accurate performance prediction of rural MUMIMO channels with dominant Line-of-Sight (LoS) paths, was developed under this research. Results show that the proposed solution can achieve 43.7 bits/s/Hz at a Signal-to- Noise Ratio (SNR) of 20 dB in rural environments. Based on channel measurement results, this thesis verifies that the deterministic channel model accurately predicts channel capacity in rural environments with a Root Mean Square (RMS) error of 0.18 bits/s/Hz. Moreover, this study presents a comprehensive capacity analysis of rural MU-MIMOOFDM channels using experimental, simulated and theoretical models. Based on the validated deterministic model, further investigations on channel capacity and the eects of capacity variation, with different user distribution angles (θ) around the AP, were analysed. For instance, when SNR = 20dB, the capacity increases from 15.5 bits/s/Hz to 43.7 bits/s/Hz as θ increases from 10° to 360°. Strategies to mitigate these capacity degradation effects are also presented by employing a suitable user grouping method. Outcomes of this thesis have already been used by CSIRO scientists to determine optimum user distribution angles around the AP, and are of great significance for researchers and MU-MUMO-OFDM system developers to understand the advantages and potential capacity gains of MU-MIMO systems in rural environments. Also, results of this study are useful to further improve the performance of MU-MIMO-OFDM systems in rural environments. Ultimately, this knowledge contribution will be useful in delivering efficient, cost-effective high-speed wireless broadband systems that are tailor-made for rural environments, thus, improving the quality of life and economic prosperity of rural populations.

The health information practices of people living with chronic health conditions: Implications for health literacy

The reduction of the health literacy concept to a functional relationship with text, does not acknowledge the range of information sources that people draw from in order to make informed decision about their health and treatment. Drawing from two studies that explored how people with two different but complex and life-threatening chronic health conditions, chronic kidney disease and HIV, a socio-cultural understanding of the practise of health literacy is described. Health information is experienced by patients as a chronic health condition landscape, and develops from three information sources; namely epistemic, social and corporeal sources. Participants in both studies used activities that involved orienting, sharing and creating information to map this landscape which was used to inform their decision-making. These findings challenge the traditional conceptions of health literacy and suggest an approach that views the landscape of chronic illness as being socially, physically and contextually constructed. This approach necessitates a recasting of health literacy away from a sole interest in skills and towards understanding how information practices facilitate people becoming health literate.

Mapping the conditions of penal hope

This article examines the conditions of penal hope behind suggestions that the penal expansionism of the last three decades may be at a ‘turning point’. The article proceeds by outlining David Green’s (2013b) suggested catalysts of penal reform and considers how applicable they are in the Australian context. Green’s suggested catalysts are: the cycles and saturation thesis; shifts in the dominant conception of the offender; the global financial crisis (GFC) and budgetary constraints; the drop in crime; the emergence of the prisoner re‐entry movement; apparent shifts in public opinion; the influence of evangelical Christian ideas; and the Right on Crime initiative. The article then considers a number of other possible catalysts or forces: the role of trade unions; the role of courts; the emergence of recidivism as a political issue; the influence of ‘evidence based’/‘what works’ discourse; and the emergence of justice reinvestment (JR). The article concludes with some comments about the capacity of criminology and criminologists to contribute to penal reductionism, offering an optimistic assessment for the prospects of a reflexive criminology that engages in and engenders a wider politics around criminal justice issues.

Electropolishing of polycrystalline YBa2Cu3O7-δ to meet the need for sharp needle geometry

An electropolishing method has been developed for preparing sharp needles from polycrystalline YBa2Cu3O7-δ by modifying a recipe for TEM specimen preparation. The method is characterized by a polishing temperature of below 0°C, a non-acidic electrolyt and an even removal of the constituent phases. An approach was employed of combining I-V measurements for polishing process and microscopical observation of surface morphology in finding optimum polishing conditions. TEM evidenced that no preferential attack appeared to grain boundaries. X-ray diffractometry and electron diffraction implied that no change in oxygen content occurred during electropolishing. The sharpness of the tip was examined by field-ion microscopy.

Investigation of mediated oxidation of ascorbic acid by ferrocenemethanol using large-amplitude fourier transformed ac voltammetry under quasi-reversible electron-transfer conditions at an indium tin oxide electrode

The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.

Influence of drying conditions on the moisture diffusion and fluidization quality during multi-stage fluidized bed drying of bovine intestine for pet food

In order to establish the influence of the drying air characteristics on the drying performance and fluidization quality of bovine intestine for pet food, several drying tests have been carried out in a laboratory scale heat pump assisted fluid bed dryer. Bovine intestine samples were heat pump fluidized bed dried at atmospheric pressure and at temperatures below and above the materials freezing points, equipped with a continuous monitoring system. The investigation of the drying characteristics have been conducted in the temperature range −10 to 25 ◦C and the airflow in the range 1.5–2.5 m/s. Some experiments were conducted as single temperature drying experiments and others as two stage drying experiments employing two temperatures. An Arrhenius-type equation was used to interpret the influence of the drying air temperature on the effective diffusivity, calculated with the method of slopes in terms of energy activation, and this was found to be sensitive to the temperature. The effective diffusion coefficient of moisture transfer was determined by the Fickian method using uni-dimensional moisture movement in both moisture, removal by evaporation and combined sublimation and evaporation. Correlations expressing the effective moisture diffusivity and drying temperature are reported. Bovine particles were characterized according to the Geldart classification and the minimum fluidization velocity was calculated using the Ergun Equation and generalized equation for all drying conditions at the beginning and end of the trials. Walli’s model was used to categorize stability of the fluidization at the beginning and end of the dryingv for each trial. The determined Walli’s values were positive at the beginning and end of all trials indicating stable fluidization at the beginning and end for each drying condition.

Visual performance with lenses correcting peripheral refractive errors

Purpose To design and manufacture lenses to correct peripheral refraction along the horizontal meridian and to determine whether these resulted in noticeable improvements in visual performance. Method Subjective refraction of a low myope was determined on the basis of best peripheral detection acuity along the horizontal visual field out to ±30° for both horizontal and vertical gratings. Subjective refraction was compared to objective refractions using a COAS-HD aberrometer. Special lenses were made to correct peripheral refraction, based on designs optimized with and without smoothing across a 3 mm diameter square aperture. Grating detection was retested with these lenses. Contrast thresholds of 1.25’ spots were determined across the field for the conditions of best correction, on-axis correction, and the special lenses. Results The participant had high relative peripheral hyperopia, particularly in the temporal visual field (maximum 2.9 D). There were differences > 0.5D between subjective and objective refractions at a few field angles. On-axis correction reduced peripheral detection acuity and increased peripheral contrast threshold in the peripheral visual field, relative to the best correction, by up to 0.4 and 0.5 log units, respectively. The special lenses restored most of the peripheral vision, although not all at angles to ±10°, and with the lens optimized with aperture-smoothing possibly giving better vision than the lens optimized without aperture-smoothing at some angles. Conclusion It is possible to design and manufacture lenses to give near optimum peripheral visual performance to at least ±30° along one visual field meridian. The benefit of such lenses is likely to be manifest only if a subject has a considerable relative peripheral refraction, for example of the order of 2 D.

Rebuilding in Ranongga : reflecting on practice based research

Two hundred million people are displaced annually due to natural disasters with a further one billion living in inadequate conditions in urban areas. Architects have a responsibility to respond to this statistic as the effects of natural and social disasters become more visibly catastrophic when paired with population rise. The research discussed in this paper initially questions and considers how digital tools can be employed to enhance rebuilding processes, but still achieve sensitive, culturally appropriate and accepted built solutions. Secondly the paper reflects on the impact ‘real-world’ projects have on architectural education. Research aspirations encouraged an atypical ‘research by design’ methodology involving a focused case study in the recently devastated village Keigold, Ranongga, Solomon Islands. Through this qualitative approach specific place data and the accounts of those affected were documented through naturalistic and archival methods of observation and participation. Findings reveal a number of unanticipated results which would have been otherwise undetected if field research within the design and rebuilding process was not undertaken, reflecting the importance of place specific research in the design process. Ultimately, the study proves that it is critical for issues of disaster to be addressed on a local rather than global scale; decisions cannot be speculative, or solved at a distance, but require intensive collaborative work with communities to achieve optimum solutions. Architectural education and design studios would continue to benefit from focused community engagement and field research within the design process.