234 resultados para classical over barrier model(COBM)

em Queensland University of Technology - ePrints Archive


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The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.

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PURPOSE To study the utility of fractional calculus in modeling gradient-recalled echo MRI signal decay in the normal human brain. METHODS We solved analytically the extended time-fractional Bloch equations resulting in five model parameters, namely, the amplitude, relaxation rate, order of the time-fractional derivative, frequency shift, and constant offset. Voxel-level temporal fitting of the MRI signal was performed using the classical monoexponential model, a previously developed anomalous relaxation model, and using our extended time-fractional relaxation model. Nine brain regions segmented from multiple echo gradient-recalled echo 7 Tesla MRI data acquired from five participants were then used to investigate the characteristics of the extended time-fractional model parameters. RESULTS We found that the extended time-fractional model is able to fit the experimental data with smaller mean squared error than the classical monoexponential relaxation model and the anomalous relaxation model, which do not account for frequency shift. CONCLUSIONS We were able to fit multiple echo time MRI data with high accuracy using the developed model. Parameters of the model likely capture information on microstructural and susceptibility-induced changes in the human brain.

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Ecologically sustainable development has become a major feature of legal systems at the international, national and local levels throughout the world. In Australia, governments have responded to environmental crises by enacting legislation imposing obligations and restrictions over privately-owned land. Whilst these obligations and restrictions may well be necessary to achieve sustainability, the approach to management of information concerning these instruments is problematic. For example, management of information concerning obligations and restrictions in Queensland is fragmented, with some instruments registered or recorded on the land title register, some on external registers, and some information only available in the legislation itself. This approach is used in most Australian jurisdictions. This fragmented approach has led to two separate but interconnected problems. First, the Torrens system is no longer meeting its goal of providing a complete and accurate picture of title. Second, this uncoordinated approach to the management of land titles, and obligations and restrictions on land use, has created a barrier to sustainable management of natural resources. This is because compliance with environmental laws is impaired in the absence of easily accessible and accurate information. These problems demonstrate a clear need for reform in this area. To determine how information concerning these obligations and restrictions may be most effectively managed, this thesis will apply a comparative methodology and consider three case studies, which each utilise different models for management of this information. These jurisdictions will be assessed according to a set of guidelines for comparison to identify which features of their systems provide for effective management of information concerning obligations and restrictions on title and use. Based on this comparison, this thesis will devise a series of recommendations for an effective system for the management of information concerning obligations and restrictions on land title and use, taking into account any potential legal issues and barriers to implementation. This series of recommendations for reform will be supplemented by suggested draft legislative provisions.

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For the timber industry, the ability to simulate the drying of wood is invaluable for manufacturing high quality wood products. Mathematically, however, modelling the drying of a wet porous material, such as wood, is a diffcult task due to its heterogeneous and anisotropic nature, and the complex geometry of the underlying pore structure. The well{ developed macroscopic modelling approach involves writing down classical conservation equations at a length scale where physical quantities (e.g., porosity) can be interpreted as averaged values over a small volume (typically containing hundreds or thousands of pores). This averaging procedure produces balance equations that resemble those of a continuum with the exception that effective coeffcients appear in their deffnitions. Exponential integrators are numerical schemes for initial value problems involving a system of ordinary differential equations. These methods differ from popular Newton{Krylov implicit methods (i.e., those based on the backward differentiation formulae (BDF)) in that they do not require the solution of a system of nonlinear equations at each time step but rather they require computation of matrix{vector products involving the exponential of the Jacobian matrix. Although originally appearing in the 1960s, exponential integrators have recently experienced a resurgence in interest due to a greater undertaking of research in Krylov subspace methods for matrix function approximation. One of the simplest examples of an exponential integrator is the exponential Euler method (EEM), which requires, at each time step, approximation of φ(A)b, where φ(z) = (ez - 1)/z, A E Rnxn and b E Rn. For drying in porous media, the most comprehensive macroscopic formulation is TransPore [Perre and Turner, Chem. Eng. J., 86: 117-131, 2002], which features three coupled, nonlinear partial differential equations. The focus of the first part of this thesis is the use of the exponential Euler method (EEM) for performing the time integration of the macroscopic set of equations featured in TransPore. In particular, a new variable{ stepsize algorithm for EEM is presented within a Krylov subspace framework, which allows control of the error during the integration process. The performance of the new algorithm highlights the great potential of exponential integrators not only for drying applications but across all disciplines of transport phenomena. For example, when applied to well{ known benchmark problems involving single{phase liquid ow in heterogeneous soils, the proposed algorithm requires half the number of function evaluations than that required for an equivalent (sophisticated) Newton{Krylov BDF implementation. Furthermore for all drying configurations tested, the new algorithm always produces, in less computational time, a solution of higher accuracy than the existing backward Euler module featured in TransPore. Some new results relating to Krylov subspace approximation of '(A)b are also developed in this thesis. Most notably, an alternative derivation of the approximation error estimate of Hochbruck, Lubich and Selhofer [SIAM J. Sci. Comput., 19(5): 1552{1574, 1998] is provided, which reveals why it performs well in the error control procedure. Two of the main drawbacks of the macroscopic approach outlined above include the effective coefficients must be supplied to the model, and it fails for some drying configurations, where typical dual{scale mechanisms occur. In the second part of this thesis, a new dual{scale approach for simulating wood drying is proposed that couples the porous medium (macroscale) with the underlying pore structure (microscale). The proposed model is applied to the convective drying of softwood at low temperatures and is valid in the so{called hygroscopic range, where hygroscopically held liquid water is present in the solid phase and water exits only as vapour in the pores. Coupling between scales is achieved by imposing the macroscopic gradient on the microscopic field using suitably defined periodic boundary conditions, which allows the macroscopic ux to be defined as an average of the microscopic ux over the unit cell. This formulation provides a first step for moving from the macroscopic formulation featured in TransPore to a comprehensive dual{scale formulation capable of addressing any drying configuration. Simulation results reported for a sample of spruce highlight the potential and flexibility of the new dual{scale approach. In particular, for a given unit cell configuration it is not necessary to supply the effective coefficients prior to each simulation.

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There are numerous load estimation methods available, some of which are captured in various online tools. However, most estimators are subject to large biases statistically, and their associated uncertainties are often not reported. This makes interpretation difficult and the estimation of trends or determination of optimal sampling regimes impossible to assess. In this paper, we first propose two indices for measuring the extent of sampling bias, and then provide steps for obtaining reliable load estimates by minimizing the biases and making use of possible predictive variables. The load estimation procedure can be summarized by the following four steps: - (i) output the flow rates at regular time intervals (e.g. 10 minutes) using a time series model that captures all the peak flows; - (ii) output the predicted flow rates as in (i) at the concentration sampling times, if the corresponding flow rates are not collected; - (iii) establish a predictive model for the concentration data, which incorporates all possible predictor variables and output the predicted concentrations at the regular time intervals as in (i), and; - (iv) obtain the sum of all the products of the predicted flow and the predicted concentration over the regular time intervals to represent an estimate of the load. The key step to this approach is in the development of an appropriate predictive model for concentration. This is achieved using a generalized regression (rating-curve) approach with additional predictors that capture unique features in the flow data, namely the concept of the first flush, the location of the event on the hydrograph (e.g. rise or fall) and cumulative discounted flow. The latter may be thought of as a measure of constituent exhaustion occurring during flood events. The model also has the capacity to accommodate autocorrelation in model errors which are the result of intensive sampling during floods. Incorporating this additional information can significantly improve the predictability of concentration, and ultimately the precision with which the pollutant load is estimated. We also provide a measure of the standard error of the load estimate which incorporates model, spatial and/or temporal errors. This method also has the capacity to incorporate measurement error incurred through the sampling of flow. We illustrate this approach using the concentrations of total suspended sediment (TSS) and nitrogen oxide (NOx) and gauged flow data from the Burdekin River, a catchment delivering to the Great Barrier Reef. The sampling biases for NOx concentrations range from 2 to 10 times indicating severe biases. As we expect, the traditional average and extrapolation methods produce much higher estimates than those when bias in sampling is taken into account.

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Volatile organic compounds (VOCs) in the headspace of bubble chambers containing branches of live coral in filtered reef seawater were analysed using gas chromatography with mass spectrometry (GC-MS). When the coral released mucus it was a source of dimethyl sulfide (DMS) and isoprene; however, these VOCs were not emitted to the chamber headspace from mucus-free coral. This finding, which suggests that coral is an intermittent source of DMS and isoprene, was supported by the observation of occasional large pulses of atmospheric DMS (DMSa) over Heron Island reef on the southern Great Barrier Reef (GBR), Australia, in the austral winter. The highest DMSa pulse (320 ppt) was three orders of magnitude less than the DMS mixing ratio (460 ppb) measured in the headspace of a dynamically purged bubble chamber containing a mucus-coated branch of Acropora aspera indicating that coral reefs can be strong point sources of DMSa. Static headspace GC-MS analysis of coral fragments identified mainly DMS and seven other minor reduced sulfur compounds including dimethyl disulfide, methyl mercaptan, and carbon disulfide, while coral reef seawater was an indicated source of methylene chloride, acetone, and methyl ethyl ketone. The VOCs emitted by coral and reef seawater are capable of producing new atmospheric particles < 15 nm diameter as observed at Heron Island reef. DMS and isoprene are known to play a role in low-level cloud formation, so aerosol precursors such as these could influence regional climate through a sea surface temperature regulation mechanism hypothesized to operate over the GBR.

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The issue of ‘rigour vs. relevance’ in IS research has generated an intense, heated debate for over a decade. It is possible to identify, however, only a limited number of contributions on how to increase the relevance of IS research without compromising its rigour. Based on a lifecycle view of IS research, we propose the notion of ‘reality checks’ in order to review IS research outcomes in the light of actual industry demands. We assume that five barriers impact the efficient transfer of IS research outcomes; they are lack of awareness, lack of understandability, lack of relevance, lack of timeliness, and lack of applicability. In seeking to understand the effect of these barriers on the transfer of mature IS research into practice, we used focus groups. We chose DeLone and McLean’s IS success model as our stimulus because it is one of the more widely researched areas of IS.

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A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

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With the advent of Service Oriented Architecture, Web Services have gained tremendous popularity. Due to the availability of a large number of Web services, finding an appropriate Web service according to the requirement of the user is a challenge. This warrants the need to establish an effective and reliable process of Web service discovery. A considerable body of research has emerged to develop methods to improve the accuracy of Web service discovery to match the best service. The process of Web service discovery results in suggesting many individual services that partially fulfil the user’s interest. By considering the semantic relationships of words used in describing the services as well as the use of input and output parameters can lead to accurate Web service discovery. Appropriate linking of individual matched services should fully satisfy the requirements which the user is looking for. This research proposes to integrate a semantic model and a data mining technique to enhance the accuracy of Web service discovery. A novel three-phase Web service discovery methodology has been proposed. The first phase performs match-making to find semantically similar Web services for a user query. In order to perform semantic analysis on the content present in the Web service description language document, the support-based latent semantic kernel is constructed using an innovative concept of binning and merging on the large quantity of text documents covering diverse areas of domain of knowledge. The use of a generic latent semantic kernel constructed with a large number of terms helps to find the hidden meaning of the query terms which otherwise could not be found. Sometimes a single Web service is unable to fully satisfy the requirement of the user. In such cases, a composition of multiple inter-related Web services is presented to the user. The task of checking the possibility of linking multiple Web services is done in the second phase. Once the feasibility of linking Web services is checked, the objective is to provide the user with the best composition of Web services. In the link analysis phase, the Web services are modelled as nodes of a graph and an allpair shortest-path algorithm is applied to find the optimum path at the minimum cost for traversal. The third phase which is the system integration, integrates the results from the preceding two phases by using an original fusion algorithm in the fusion engine. Finally, the recommendation engine which is an integral part of the system integration phase makes the final recommendations including individual and composite Web services to the user. In order to evaluate the performance of the proposed method, extensive experimentation has been performed. Results of the proposed support-based semantic kernel method of Web service discovery are compared with the results of the standard keyword-based information-retrieval method and a clustering-based machine-learning method of Web service discovery. The proposed method outperforms both information-retrieval and machine-learning based methods. Experimental results and statistical analysis also show that the best Web services compositions are obtained by considering 10 to 15 Web services that are found in phase-I for linking. Empirical results also ascertain that the fusion engine boosts the accuracy of Web service discovery by combining the inputs from both the semantic analysis (phase-I) and the link analysis (phase-II) in a systematic fashion. Overall, the accuracy of Web service discovery with the proposed method shows a significant improvement over traditional discovery methods.

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In architecture courses, instilling a wider understanding of the industry specific representations practiced in the Building Industry is normally done under the auspices of Technology and Science subjects. Traditionally, building industry professionals communicated their design intentions using industry specific representations. Originally these mainly two dimensional representations such as plans, sections, elevations, schedules, etc. were produced manually, using a drawing board. Currently, this manual process has been digitised in the form of Computer Aided Design and Drafting (CADD) or ubiquitously simply CAD. While CAD has significant productivity and accuracy advantages over the earlier manual method, it still only produces industry specific representations of the design intent. Essentially, CAD is a digital version of the drawing board. The tool used for the production of these representations in industry is still mainly CAD. This is also the approach taken in most traditional university courses and mirrors the reality of the situation in the building industry. A successor to CAD, in the form of Building Information Modelling (BIM), is presently evolving in the Construction Industry. CAD is mostly a technical tool that conforms to existing industry practices. BIM on the other hand is revolutionary both as a technical tool and as an industry practice. Rather than producing representations of design intent, BIM produces an exact Virtual Prototype of any building that in an ideal situation is centrally stored and freely exchanged between the project team. Essentially, BIM builds any building twice: once in the virtual world, where any faults are resolved, and finally, in the real world. There is, however, no established model for learning through the use of this technology in Architecture courses. Queensland University of Technology (QUT), a tertiary institution that maintains close links with industry, recognises the importance of equipping their graduates with skills that are relevant to industry. BIM skills are currently in increasing demand throughout the construction industry through the evolution of construction industry practices. As such, during the second half of 2008, QUT 4th year architectural students were formally introduced for the first time to BIM, as both a technology and as an industry practice. This paper will outline the teaching team’s experiences and methodologies in offering a BIM unit (Architectural Technology and Science IV) at QUT for the first time and provide a description of the learning model. The paper will present the results of a survey on the learners’ perspectives of both BIM and their learning experiences as they learn about and through this technology.

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Recent decisions of the Family Court of Australian reflect concerns over the adversarial nature of the legal process. The processes and procedures of the judicial system militate against a detailed examination of the issues and rights of the parties in dispute. The limitations of the family law framework are particularly demonstrated in disputes over the custody of children where the Court has tended to neglect the rights and interests of the primary carer. An alternative "unified family court" framework will be examined in which the Court pursues a more active and interventionist approach in the determination of family law disputes.

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The weaknesses of ‗traditional‘ modes of instruction in accounting education have been widely discussed. Many contend that the traditional approach limits the ability to provide opportunities for students to raise their competency level and allow them to apply knowledge and skills in professional problem solving situations. However, the recent body of literature suggests that accounting educators are indeed actively experimenting with ‗non-traditional‘ and ‗innovative‘ instructional approaches, where some authors clearly favour one approach over another. But can one instructional approach alone meet the necessary conditions for different learning objectives? Taking into account the ever changing landscape of not only business environments, but also the higher education sector, the premise guiding the collaborators in this research is that it is perhaps counter productive to promote competing dichotomous views of ‗traditional‘ and ‗non-traditional‘ instructional approaches to accounting education, and that the notion of ‗blended learning‘ might provide a useful framework to enhance the learning and teaching of accounting. This paper reports on the first cycle of a longitudinal study, which explores the possibility of using blended learning in first year accounting at one campus of a large regional university. The critical elements of blended learning which emerged in the study are discussed and, consistent with the design-based research framework, the paper also identifies key design modifications for successive cycles of the research.

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Principal Topic Small and micro-enterprises are believed to play a significant part in economic growth and poverty allevition in developing countries. However, there are a range of issues that arise when looking at the support required for local enterprise development, the role of micro finance and sustainability. This paper explores the issues associated with the establishment and resourcing of micro-enterprise develoment and proposes a model of sustainable support of enterprise development in very poor developing economies, particularly in Africa. The purpose of this paper is to identify and address the range of issues raised by the literature and empirical research in Africa, regarding micro-finance and small business support, and to develop a model for sustainable support for enterprise development within a particular cultural and economic context. Micro-finance has become big business with a range of models - from those that operate on a strictly business basis to those that come from a philanthropic base. The models used grow from a range of philosophical and cultural perspectives. Entrepreneurship training is provided around the world. Success is often measured by the number involved and the repayment rates - which are very high, largely because of the lending models used. This paper will explore the range of options available and propose a model that can be implemented and evaluated in rapidly changing developing economies. Methodology/Key Propositions The research draws on entrepreneurial and micro-finance literature and empirical research undertaken in Mozambique, which lies along the Indian ocean sea border of Southern Africa. As a result of war and natural disasters over a prolonged period, there is little industry, primary industries are primitive and there is virtually no infrastructure. Mozambique is ranked as one of the poorest countries in the world. The conditions in Mozambique, though not identical, reflect conditions in many other parts of Africa. A numebr of key elements in the development of enterprises in poor countries are explored including: Impact of micro-finance Sustainable models of micro-finance Education and training Capacity building Support mechanisms Impact on poverty, families and the local economy Survival entrepreneurship versus growth entrepreneurship Transitions to the formal sector. Results and Implications The result of this study is the development of a model for providing intellectual and financial resources to micro-entrepreneurs in poor developing countries in a sustainable way. The model provides a base for ongoing research into the process of entrepreneurial growth in African developing economies. The research raises a numeber of issues regarding sustainability including the nature of the donor/recipient relationship, access to affordable resources, the impact of individual entrepreneurial activity on the local economny and the need for ongoing research to understand the whole process and its impact, intended and unintended.

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Capital works procurement and its regulatory policy environment within a country can be complex entities. For example, by virtue of Australia’s governmental division between the Commonwealth, states and local jurisdictions and the associated procurement networks and responsibilities at each level, the tendering process is often convoluted. There are four inter-related key themes identified in the literature in relation to procurement disharmony, including decentralisation, risk & risk mitigation, free trade & competition, and tendering costs. This paper defines and discusses these key areas of conflict that adversely impact upon the business environments of industry through a literature review, policy analysis and consultation with capital works procurement stakeholders. The aim of this national study is to identify policy differences between jurisdictions in Australia, and ascertain whether those differences are a barrier to productivity and innovation. This research forms an element of a broader investigation with an aim of developing efficient, effective and nationally harmonised procurement systems. Keywords: capital works, procurement policy reform Acknowledgement: The research described in this paper carried out by the Australian Cooperative Research Centre for Construction Innovation.