Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

How can we exploit mobile data to customise learning based on a student’s environmental surroundings?

User-Based intelligent systems are already commonplace in a student’s online digital life. Each time they browse, search, buy, join, comment, play, travel, upload, download, a system collects, analyses and processes data in an effort to customise content and further improve services. This panel session will explore how intelligent systems, particularly those that gather data from mobile devices, can offer new possibilities to assist in the delivery of customised, personal and engaging learning experiences. The value of intelligent systems for education lies in their ability to formulate authentic and complex learner profiles that bring together and systematically integrate a student’s personal world with a formal curriculum framework. As we well know, a mobile device can collect data relating to a student’s interests (gathered from search history, applications and communications), location, surroundings and proximity to others (GPS, Bluetooth). However, what has been less explored is the opportunity for a mobile device to map the movements and activities of a student from moment to moment and over time. This longitudinal data provides a holistic profile of a student, their state and surroundings. Analysing this data may allow us to identify patterns that reveal a student’s learning processes; when and where they work best and for how long. Through revealing a student’s state and surroundings outside of schools hour, this longitudinal data may also highlight opportunities to transform a student’s everyday world into an inventory for learning, punctuating their surroundings with learning recommendations. This would in turn lead to new ways to acknowledge and validate and foster informal learning, making it legitimate within a formal curriculum.

Vision-based topological mapping and localisation

Competent navigation in an environment is a major requirement for an autonomous mobile robot to accomplish its mission. Nowadays, many successful systems for navigating a mobile robot use an internal map which represents the environment in a detailed geometric manner. However, building, maintaining and using such environment maps for navigation is difficult because of perceptual aliasing and measurement noise. Moreover, geometric maps require the processing of huge amounts of data which is computationally expensive. This thesis addresses the problem of vision-based topological mapping and localisation for mobile robot navigation. Topological maps are concise and graphical representations of environments that are scalable and amenable to symbolic manipulation. Thus, they are well-suited for basic robot navigation applications, and also provide a representational basis for the procedural and semantic information needed for higher-level robotic tasks. In order to make vision-based topological navigation suitable for inexpensive mobile robots for the mass market we propose to characterise key places of the environment based on their visual appearance through colour histograms. The approach for representing places using visual appearance is based on the fact that colour histograms change slowly as the field of vision sweeps the scene when a robot moves through an environment. Hence, a place represents a region of the environment rather than a single position. We demonstrate in experiments using an indoor data set, that a topological map in which places are characterised using visual appearance augmented with metric clues provides sufficient information to perform continuous metric localisation which is robust to the kidnapped robot problem. Many topological mapping methods build a topological map by clustering visual observations to places. However, due to perceptual aliasing observations from different places may be mapped to the same place representative in the topological map. A main contribution of this thesis is a novel approach for dealing with the perceptual aliasing problem in topological mapping. We propose to incorporate neighbourhood relations for disambiguating places which otherwise are indistinguishable. We present a constraint based stochastic local search method which integrates the approach for place disambiguation in order to induce a topological map. Experiments show that the proposed method is capable of mapping environments with a high degree of perceptual aliasing, and that a small map is found quickly. Moreover, the method of using neighbourhood information for place disambiguation is integrated into a framework for topological off-line simultaneous localisation and mapping which does not require an initial categorisation of visual observations. Experiments on an indoor data set demonstrate the suitability of our method to reliably localise the robot while building a topological map.

Correctness ensuring process configuration : an approach based on partner synthesis

A configurable process model describes a family of similar process models in a given domain. Such a model can be configured to obtain a specific process model that is subsequently used to handle individual cases, for instance, to process customer orders. Process configuration is notoriously difficult as there may be all kinds of interdependencies between configuration decisions.} In fact, an incorrect configuration may lead to behavioral issues such as deadlocks and livelocks. To address this problem, we present a novel verification approach inspired by the ``operating guidelines'' used for partner synthesis. We view the configuration process as an external service, and compute a characterization of all such services which meet particular requirements using the notion of configuration guideline. As a result, we can characterize all feasible configurations (i.\,e., configurations without behavioral problems) at design time, instead of repeatedly checking each individual configuration while configuring a process model.

Adaptive dual control of topic-based information retrieval

Information Retrieval is an important albeit imperfect component of information technologies. A problem of insufficient diversity of retrieved documents is one of the primary issues studied in this research. This study shows that this problem leads to a decrease of precision and recall, traditional measures of information retrieval effectiveness. This thesis presents an adaptive IR system based on the theory of adaptive dual control. The aim of the approach is the optimization of retrieval precision after all feedback has been issued. This is done by increasing the diversity of retrieved documents. This study shows that the value of recall reflects this diversity. The Probability Ranking Principle is viewed in the literature as the “bedrock” of current probabilistic Information Retrieval theory. Neither the proposed approach nor other methods of diversification of retrieved documents from the literature conform to this principle. This study shows by counterexample that the Probability Ranking Principle does not in general lead to optimal precision in a search session with feedback (for which it may not have been designed but is actively used). Retrieval precision of the search session should be optimized with a multistage stochastic programming model to accomplish the aim. However, such models are computationally intractable. Therefore, approximate linear multistage stochastic programming models are derived in this study, where the multistage improvement of the probability distribution is modelled using the proposed feedback correctness method. The proposed optimization models are based on several assumptions, starting with the assumption that Information Retrieval is conducted in units of topics. The use of clusters is the primary reasons why a new method of probability estimation is proposed. The adaptive dual control of topic-based IR system was evaluated in a series of experiments conducted on the Reuters, Wikipedia and TREC collections of documents. The Wikipedia experiment revealed that the dual control feedback mechanism improves precision and S-recall when all the underlying assumptions are satisfied. In the TREC experiment, this feedback mechanism was compared to a state-of-the-art adaptive IR system based on BM-25 term weighting and the Rocchio relevance feedback algorithm. The baseline system exhibited better effectiveness than the cluster-based optimization model of ADTIR. The main reason for this was insufficient quality of the generated clusters in the TREC collection that violated the underlying assumption.

Predicate-based key exchange

We provide the first description of and security model for authenticated key exchange protocols with predicate-based authentication. In addition to the standard goal of session key security, our security model also provides for credential privacy: a participating party learns nothing more about the other party's credentials than whether they satisfy the given predicate. Our model also encompasses attribute-based key exchange since it is a special case of predicate-based key exchange.---------- We demonstrate how to realize a secure predicate-based key exchange protocol by combining any secure predicate-based signature scheme with the basic Diffie-Hellman key exchange protocol, providing an efficient and simple solution.

Location-based games : transforming everyday environments into dynamic learning spaces

Location based games (LBGs) provide an opportunity to look at how new technologies can support a reciprocal relationship between formal classroom learning and learning that can potentially occur in other everyday environments. Fundamentally many games are intensely engaging due to the resulting social interactions and technical challenges they provide to individual and group players. By introducing the use of mobile devices we can transport these characteristics of games into everyday spaces. LBGs are understood as a broad genre incorporating ideas and tools that provide many unique opportunities for us to to reveal, create and even subvert various social, cultural, technical, and scientific interpretations of place, in particular places where learning is sometimes problematic.--------- A team of Queensland game developers have learnt a great deal through designing a range of LBGs such as SCOOT for various user groups and places. While these LBGs were primarily designed as social events, we found that the players recognised and valued the game as an opportunity to learn about their environment, it's history, cultural significance, inhabitants, services etc. Since identifying the strong pedagogical outcomes of LBGs, the team has created a set of authoring tools for people to design and host their own LBGs. A particular version of this is known as MiLK the mobile learning kit for schools.---------- This presentation will include examples of how LBGs have been used to improve the teaching and learning outcomes in various contexts. Participants will be introduced to MiLK and invited to trial it in their own classrooms with students.

Developing a culture of enquiry to sustain evidence-based practice

Evidence-based practice (EBP) is having a significant effect on the health service environment. It constructs a language that bridges the healthcare disciplines and the clinical and managerial components of health services. Most experienced clinicians in nursing, medicine and allied health now recognise that the contemporary healthcare environment calls for our practice to be justified by sound, credible evidence. There is pressure on all clinicians to accommodate innovation, while at the same time ensuring their practice is effective, safe and efficient (Forbes & Griffiths 2002). Consequently, EBP in healthcare is having a profound effect on nursing and the way we think about nursing. There are many available models for research utilisation that are dependent on organisational strategies for change. This chapter describes the relationship between organisation and culture, and explores the notion of cultural change; that is, developing a culture of inquiry that can sustain evidence-based practice. We begin this chapter with a clear conception of what we mean by EBP and what we mean by ‘culture’.

Effectiveness of community-based nonpharmacological interventions for early-stage dementia : conclusions and recommendations

In 2007, a comprehensive review of the extant research on nonpharmacological interventions for persons with early-stage dementia was conducted. More than 150 research reports, centered on six major domains, were included: early-stage support groups, cognitive training and enhancement programs, exercise programs, exemplar programs, health promotion programs, and “other” programs not fitting into previous categories. Theories of neural regeneration and plasticity were most often used to support the tested interventions. Recommendations for practice, research, and health policy are outlined, including evidence-based, nonpharmacological treatment protocols for persons with mild cognitive impairment and early-stage dementia. A tested, community-based, multimodal treatment program is also described. Overall, findings identify well-supported nonpharmacological treatments for persons with early-stage dementia and implications for a national health care agenda to optimize outcomes for this growing population of older adults.

Consumer-based brand equity for Australia as a long haul tourism destination in an emerging market

Purpose: Although the branding literature emerged during the 1940s, research relating to tourism destination branding has only gained momentum since the late 1990s. There remains a lack of theory in particular that addresses the measurement of the effectiveness of destination branding over time. The purpose of the research was to test the effectiveness of a model of consumer-based brand equity (CBBE) for a country destination.---------- Design/methodology: A model of consumer-based brand equity was adapted from the marketing literature and applied to a nation context. The model was tested by using structural equation modelling with data from a large Chilean sample (n=845), comprising a mix of previous visitors and non-visitors. The model fits the data well. Findings: This paper reports the results of an investigation into brand equity for Australia as a long haul destination in an emerging market. The research took place just before the launch of the nation’s fourth new brand campaign in six years. The results indicate Australia is a well known but not compelling destination brand for tourists in Chile, which reflects the lower priority the South American market has been given by the national tourism office (NTO).---------- Practical implications: It is suggested that CBBE measures could be analysed at various points in time to track any strengthening or weakening of market perceptions in relation to brand objectives. A standard CBBE instrument could provide long-term effectiveness performance measures regardless of changes in destination marketing organisation (DMO) staff, advertising agency, other stakeholders, and budget.---------- Originality/value: This study contributes to the nation-branding literature by being one of the first to test the efficacy of a model of consumer-based brand equity for a tourism destination brand.

Data-driven background dataset selection for SVM-based speaker verification

The recently proposed data-driven background dataset refinement technique provides a means of selecting an informative background for support vector machine (SVM)-based speaker verification systems. This paper investigates the characteristics of the impostor examples in such highly-informative background datasets. Data-driven dataset refinement individually evaluates the suitability of candidate impostor examples for the SVM background prior to selecting the highest-ranking examples as a refined background dataset. Further, the characteristics of the refined dataset were analysed to investigate the desired traits of an informative SVM background. The most informative examples of the refined dataset were found to consist of large amounts of active speech and distinctive language characteristics. The data-driven refinement technique was shown to filter the set of candidate impostor examples to produce a more disperse representation of the impostor population in the SVM kernel space, thereby reducing the number of redundant and less-informative examples in the background dataset. Furthermore, data-driven refinement was shown to provide performance gains when applied to the difficult task of refining a small candidate dataset that was mis-matched to the evaluation conditions.

Carbodiimide-mediated synthesis of poly(L-lactide)-based networks

Poly(L-lactide-co-succinic anhydride) networks were synthesised via the carbodiimide-mediated coupling of poly(L-lactide) (PLLA) star polymers. When 4-(dimethylamino)pyridine (DMAP) alone was used as the catalyst gelation did not occur. However, when 4-(dimethylamino)pyridinium p-toluenesulfonate (DPTS), the salt of DMAP and p-toluenesulfonic acid (PTSA), was the catalyst, the networks obtained had gel fractions comparable to those which were reported for networks synthesised by conventional methods. Greater gel fractions and conversion of the prepolymer terminal hydroxyl groups were observed when the hydroxyl-terminated star prepolymers reacted with succinic anhydride in a one-pot procedure than when the hydroxyl-terminated star prepolymers reacted with presynthesised succinic-terminated star prepolymers. The thermal properties of the networks, glass transition temperature (Tg), melting temperature (Tm) and crystallinity (Xc) were all strongly influenced by the average molecular weights between the crosslinks ((M_c). The network with the smallest (M_c )(1400 g/mol) was amorphous and had a Tg of 59 °C while the network with the largest (M_c ) (7800 g/mol) was 15 % crystalline and had a Tg of 56 °C.

Evaluation of community participation for the development of culture-based fisheries in village reservoirs of Sri Lanka

In this paper an attempt is made to identify the socioeconomic characteristics of a community that influences the development and management of culture-based fisheries in village reservoirs of Sri Lanka. Socioeconomic data were collected from 46 agricultural farming communities associated with 47 village reservoirs in Sri Lanka. Principal component analysis indicated that scores of the first principal component were positively influenced by socioeconomic characteristics that are favorable for making collective decisions. These included leadership of the officers, age of the group, percentage of active members of the group, percentage of kinship of the group, percentage of common interest of the group, and percentage of participation of the group. The size of the group had negative effect on the first principal component. The principal component scores of communication were positively related to willingness to pay (P< 0.001). The communities with socioeconomic characteristics favouring collective decision making were in favor of culture-based fisheries. Homogeneity of group characteristics facilitated successful development of culture-based fisheries.