Synthesis of one-dimensional nanocomposites based on alumina nanofibres and their catalytic applications

Materials with one-dimensional (1D) nanostructure are important for catalysis. They are the preferred building blocks for catalytic nanoarchitecture, and can be used to fabricate designer catalysts. In this thesis, one such material, alumina nanofibre, was used as a precursor to prepare a range of nanocomposite catalysts. Utilising the specific properties of alumina nanofibres, a novel approach was developed to prepare macro-mesoporous nanocomposites, which consist of a stacked, fibrous nanocomposite with a core-shell structure. Two kinds of fibrous ZrO2/Al2O3 and TiO2/Al2O3 nanocomposites were successfully synthesised using boehmite nanofibers as a hard temperate and followed by a simple calcination. The alumina nanofibres provide the resultant nanocomposites with good thermal stability and mechanical stability. A series of one-dimensional (1D) zirconia/alumina nanocomposites were prepared by the deposition of zirconium species onto the 3D framework of boehmite nanofibres formed by dispersing boehmite nanofibres into a butanol solution, followed by calcination at 773 K. The materials were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and Fourier Transform Infrared spectroscopy (FT-IR). The results demonstrated that when the molar percentage, X, X=100*Zr/(Al+Zr), was > 30%, extremely long ZrO2/Al2O3 composite nanorods with evenly distributed ZrO2 nanocrystals formed on their surface. The stacking of such nanorods gave rise to a new kind of macroporous material without the use of any organic space filler\template or other specific drying techniques. The mechanism for the formation of these long ZrO2/Al2O3 composite nanorods is proposed in this work. A series of solid-superacid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid superacid counterparts were characterised by a variety of techniques including 27Al MAS-NMR, SEM, TEM, XPS, Nitrogen adsorption and Infrared Emission Spectroscopy. NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained superacids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia. Preparation of hierarchically macro-mesoporous catalyst by loading nanocrystallites on the framework of alumina bundles can provide an alternative system to design advanced nanocomposite catalyst with enhanced performance. A series of macro-mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesised. The materials were calcined at 723 K and were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and UV-visible spectroscopy (UV-visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100oC), which makes it possible to synthesize such materials on industrial scale. The performances of a series of resultant TiO2/Al2O3 nanocomposites with different morphologies were evaluated as a photocatalyst for the phenol degradation under UV irradiation. The photocatalyst (Ti/Al =2) with fibrous morphology exhibits higher activity than that of the photocatalyst with microspherical morphology which indeed has the highest Ti to Al molar ratio (Ti/Al =3) in the series of as-synthesised hierarchical TiO2/Al2O3 nanocomposites. Furthermore, the photocatalytic performances, for the fibrous nanocomposites with Ti/Al=2, were optimized by calcination at elevated temperatures. The nanocomposite prepared by calcination at 750oC exhibits the highest catalytic activity, and its performance per TiO2 unit is very close to that of the gold standard, Degussa P 25. This work also emphasizes two advantages of the nanocomposites with fibrous morphology: (1) the resistance to sintering, and (2) good catalyst recovery.

Tutorial facilitation in the humanities based on the tenets of Carl Rogers

This article introduces a model for group facilitation in the humanities based on Carl Rogers’s model for group psychotherapy. Certain aspects of Rogers’s reflective learning strategies are re-appraised and principles, specific only to psychotherapy, are introduced. Five of Rogers’s axioms are applied to the tutorial discussion model: a non-directive approach, climate-setting, facilitation, reflective listening and positive regard. The model, which has been trialed in tutorials at The University of Queensland, encourages self-direction, active learning and critical thinking.

Integrating collaborative filtering and search-based techniques for personalized online product recommendation

The existing Collaborative Filtering (CF) technique that has been widely applied by e-commerce sites requires a large amount of ratings data to make meaningful recommendations. It is not directly applicable for recommending products that are not frequently purchased by users, such as cars and houses, as it is difficult to collect rating data for such products from the users. Many of the e-commerce sites for infrequently purchased products are still using basic search-based techniques whereby the products that match with the attributes given in the target user's query are retrieved and recommended to the user. However, search-based recommenders cannot provide personalized recommendations. For different users, the recommendations will be the same if they provide the same query regardless of any difference in their online navigation behaviour. This paper proposes to integrate collaborative filtering and search-based techniques to provide personalized recommendations for infrequently purchased products. Two different techniques are proposed, namely CFRRobin and CFAg Query. Instead of using the target user's query to search for products as normal search based systems do, the CFRRobin technique uses the products in which the target user's neighbours have shown interest as queries to retrieve relevant products, and then recommends to the target user a list of products by merging and ranking the returned products using the Round Robin method. The CFAg Query technique uses the products that the user's neighbours have shown interest in to derive an aggregated query, which is then used to retrieve products to recommend to the target user. Experiments conducted on a real e-commerce dataset show that both the proposed techniques CFRRobin and CFAg Query perform better than the standard Collaborative Filtering (CF) and the Basic Search (BS) approaches, which are widely applied by the current e-commerce applications. The CFRRobin and CFAg Query approaches also outperform the e- isting query expansion (QE) technique that was proposed for recommending infrequently purchased products.

Towards semantic search and inference in electronic medical records : an approach using concept-based information retrieval

For more than a decade research in the field of context aware computing has aimed to find ways to exploit situational information that can be detected by mobile computing and sensor technologies. The goal is to provide people with new and improved applications, enhanced functionality and better use experience (Dey, 2001). Early applications focused on representing or computing on physical parameters, such as showing your location and the location of people or things around you. Such applications might show where the next bus is, which of your friends is in the vicinity and so on. With the advent of social networking software and microblogging sites such as Facebook and Twitter, recommender systems and so on context-aware computing is moving towards mining the social web in order to provide better representations and understanding of context, including social context. In this paper we begin by recapping different theoretical framings of context. We then discuss the problem of context- aware computing from a design perspective.

Rule-based approach for identifying assertions in clinical free-text data

A rule-based approach for classifying previously identified medical concepts in the clinical free text into an assertion category is presented. There are six different categories of assertions for the task: Present, Absent, Possible, Conditional, Hypothetical and Not associated with the patient. The assertion classification algorithms were largely based on extending the popular NegEx and Context algorithms. In addition, a health based clinical terminology called SNOMED CT and other publicly available dictionaries were used to classify assertions, which did not fit the NegEx/Context model. The data for this task includes discharge summaries from Partners HealthCare and from Beth Israel Deaconess Medical Centre, as well as discharge summaries and progress notes from University of Pittsburgh Medical Centre. The set consists of 349 discharge reports, each with pairs of ground truth concept and assertion files for system development, and 477 reports for evaluation. The system’s performance on the evaluation data set was 0.83, 0.83 and 0.83 for recall, precision and F1-measure, respectively. Although the rule-based system shows promise, further improvements can be made by incorporating machine learning approaches.

A phenomenological model for the structure-composition relationship of the high Tc cuprates based on simple chemical principles

A simple phenomenological model for the relationship between structure and composition of the high Tc cuprates is presented. The model is based on two simple crystal chemistry principles: unit cell doping and charge balance within unit cells. These principles are inspired by key experimental observations of how the materials accommodate large deviations from stoichiometry. Consistent explanations for significant HTSC properties can be explained without any additional assumptions while retaining valuable insight for geometric interpretation. Combining these two chemical principles with a review of Crystal Field Theory (CFT) or Ligand Field Theory (LFT), it becomes clear that the two oxidation states in the conduction planes (typically d8 and d9) belong to the most strongly divergent d-levels as a function of deformation from regular octahedral coordination. This observation offers a link to a range of coupling effects relating vibrations and spin waves through application of Hund’s rules. An indication of this model’s capacity to predict physical properties for HTSC is provided and will be elaborated in subsequent publications. Simple criteria for the relationship between structure and composition in HTSC systems may guide chemical syntheses within new material systems.

Patterns-based evaluation of open source BPM systems: The cases of jBPM, OpenWFE, and Enhydra Shark

In keeping with the proliferation of free software development initiatives and the increased interest in the business process management domain, many open source workflow and business process management systems have appeared during the last few years and are now under active development. This upsurge gives rise to two important questions: What are the capabilities of these systems? and How do they compare to each other and to their closed source counterparts? In other words: What is the state-of-the-art in the area?. To gain an insight into these questions, we have conducted an in-depth analysis of three of the major open source workflow management systems – jBPM, OpenWFE, and Enhydra Shark, the results of which are reported here. This analysis is based on the workflow patterns framework and provides a continuation of the series of evaluations performed using the same framework on closed source systems, business process modelling languages, and web-service composition standards. The results from evaluations of the three open source systems are compared with each other and also with the results from evaluations of three representative closed source systems: Staffware, WebSphere MQ, and Oracle BPEL PM. The overall conclusion is that open source systems are targeted more toward developers rather than business analysts. They generally provide less support for the patterns than closed source systems, particularly with respect to the resource perspective, i.e. the various ways in which work is distributed amongst business users and managed through to completion.

A capabilities-based approach to obtaining a deeper understanding of information technology governance effectiveness : evidence from IT steering committees

Given the substantial investment in information technology (IT), and the significant impact IT has on organizational success, organizations consume considerable resources to manage acquisition and use of their IT resources. While various arguments proposed suggest which IT governance arrangements may work best, our understanding of the effectiveness of such initiatives is limited. We examine the relationship between the effectiveness of IT steering committee driven IT governance initiatives and firm's IT management and IT infrastructure related capabilities. We further propose that firm's ITrelated capabilities generated through IT governance initiatives should improve its business processes and firm-level performance. We test these relationships empirically by a field survey. Results suggest that firms' effectiveness of IT steering committee driven IT governance initiatives positively relates to the level of their IT-related capabilities. We also found positive relationships between IT-related capabilities and internal process-level performance. Our results also support that improvement in internal process-level performance positively relates to improvement in customer service and firm-level performance.

On IT and business value in developing countries : A complementarities-based approach

Developing economies accommodate more than three quarters of the world's population. This means understanding their growth and well-being is of critical importance. Information technology (IT) is one resource that has had a profound effect in shaping the global economy. IT is also an important resource for driving growth and development in developing economies. Investments in developing economies, however, have focused on the exploitation of labor and natural resources. Unlike in developed economies, focus on IT investment to improve efficiency and effectiveness of business process in developing economies has been sparse, and mechanisms for deriving better IT-related business value is not well understood. This study develops a complementarities-based business value model for developing economies, and tests the relationship between IT investments, IT-related complementarities, and business process performance. It also considers the relationship between business processes performance and firm-level performance. The results suggest that a coordinated investment in IT and IT-related complementarities related favorably to business process performance. Improvements in process-level performance lead to improvements in firm-level performance. The results also suggest that the IT-related complementarities are not only a source of business value on their own, but also enhance the IT resources' ability to contribute to business process performance. This study demonstrates that a coordinated investment approach is required in developing economies. With this approach, their IT resources and IT-related complementaries would help them significantly in improving their business processes, and eventually their firm-level performances.

A process evaluation of a comprehensive school based injury prevention program

A process evaluation enables understanding of critical issues that can inform the improved, ongoing implementation of an intervention program. This study describes the process evaluation of a comprehensive, multi-level injury prevention program for adolescents. The program targets change in injury associated with violence, transport and alcohol risks and incorporates two primary elements: an 8-week, teacher delivered attitude and behaviour change curriculum for Grade 8 students; and a professional development program for teachers on school level methods of protection, focusing on strategies to increase students’ connectedness to school.

Project-based organization as adaptation to risk and opportunity in small firms

Recent years have seen a rapid increase in SMEs working collaboratively in inter-organizational projects. But what drives the emergence of such projects, and what types of industries breed them the most? To address these questions, this paper extends the long running literature on the firm and industry antecedents of new venturing and alliance formation to the domain of project-based organization by SMEs. Based on survey data collected among 1,725 small and medium sized organizations and longitudinal industry data, we find an overall pattern that indicates that IOPV participation is primarily determined by a focal SME’s scope of innovative activities, and the munificence, dynamism and complexity of its environment. Unexpectedly, these variables have different effects on whether SMEs are likely to engage in IOPVs, compared to with how many there are in their portfolio at a time. Implications for theory development are discussed.

Re-thinking physics teaching with web-based learning

There is extensive uptake of ICT in the teaching of science but more evidence is needed on how ICT impacts on the learning practice and the learning outcomes at the classroom level. In this study, a physics website (Getsmart) was developed using the cognitive apprenticeship framework for students at a high school in Australia. This website was designed to enhance students’ knowledge of concepts in physics. Reflexive pedagogies were used in the delivery learning materials in a blended learning environment. The students in the treatment group accessed the website over a 10 week period. Pre and post-test results of the treatment (N= 48) and comparison group (N=32) were compared. The MANCOVA analysis showed that the web-based learning experience benefited the students in the treatment group. It not only impacted on the learning outcomes, but qualitative data from the students suggested that it had a positive impact on their attitudes towards studying physics in a blended environment.

Measuring bitrate and quality trade-off in a fast region-of-interest based video coding

Prevailing video adaptation solutions change the quality of the video uniformly throughout the whole frame in the bitrate adjustment process; while region-of-interest (ROI)-based solutions selectively retains the quality in the areas of the frame where the viewers are more likely to pay more attention to. ROI-based coding can improve perceptual quality and viewer satisfaction while trading off some bandwidth. However, there has been no comprehensive study to measure the bitrate vs. perceptual quality trade-off so far. The paper proposes an ROI detection scheme for videos, which is characterized with low computational complexity and robustness, and measures the bitrate vs. quality trade-off for ROI-based encoding using a state-of-the-art H.264/AVC encoder to justify the viability of this type of encoding method. The results from the subjective quality test reveal that ROI-based encoding achieves a significant perceptual quality improvement over the encoding with uniform quality at the cost of slightly more bits. Based on the bitrate measurements and subjective quality assessments, the bitrate and the perceptual quality estimation models for non-scalable ROI-based video coding (AVC) are developed, which are found to be similar to the models for scalable video coding (SVC).

Performance and scalability assessment for non-certificate-based public key management in VANETS

Current research in secure messaging for Vehicular Ad hoc Networks (VANETs) appears to focus on employing a digital certificate-based Public Key Cryptosystem (PKC) to support security. The security overhead of such a scheme, however, creates a transmission delay and introduces a time-consuming verification process to VANET communications. This paper proposes a non-certificate-based public key management for VANETs. A comprehensive evaluation of performance and scalability of the proposed public key management regime is presented, which is compared to a certificate-based PKC by employing a number of quantified analyses and simulations. Not only does this paper demonstrate that the proposal can maintain security, but it also asserts that it can improve overall performance and scalability at a lower cost, compared to the certificate-based PKC. It is believed that the proposed scheme will add a new dimension to the key management and verification services for VANETs.

New perspectives on context-based chemistry education : using a dialectical sociocultural approach to view teaching and learning

Context-based chemistry education aims to improve student interest and motivation in chemistry by connecting canonical chemistry concepts with real-world contexts. Implementation of context-based chemistry programmes began 20 years ago in an attempt to make the learning of chemistry meaningful for students. This paper reviews such programmes through empirical studies on six international courses, ChemCom (USA), Salters (UK), Industrial Science (Israel), Chemie im Kontext (Germany), Chemistry in Practice (The Netherlands) and PLON (The Netherlands). These studies are categorised through emergent characteristics of: relevance, interest/attitudes motivation and deeper understanding. These characteristics can be found to an extent in a number of other curricular initiatives, such as science-technology-society approaches and problem-based learning or project based science, the latter of which often incorporates an inquiry-based approach to science education. These initiatives in science education are also considered with a focus on the characteristics of these approaches that are emphasised in context-based education. While such curricular studies provide a starting point for discussing context-based approaches in chemistry, to advance our understanding of how students connect canonical science concepts with the real-world context, a new theoretical framework is required. A dialectical sociocultural framework originating in the work of Vygotsky is used as a referent for analysing the complex human interactions that occur in context-based classrooms, providing teachers with recent information about the pedagogical structures and resources that afford students the agency to learn.