Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

Service employee behaviour : the role of compliance and risk taking

This paper looks at the decision-making process that determines the amount of effort frontline service employees will expend in delivering a service in a business-to-business context. Using theories in behavioural economics and interactional and social psychology, the paper develops and presents a model of employee decision-making. Managerial implications, which have the potential to enhance the marketing of business-to-business services and directions for future research in this area, are indicated.

Sourcing business and software services

With the advancement of Service-Oriented Architecture in the technical and business domain, the management & engineering of services requires a thorough and systematic understanding of the service lifecycle for both business and software services. However, while service-oriented approaches acknowledge the importance of the service ecosystem, service lifecycle models are typically internally focused, paying limited attention to processes related to offering services to or using services from other actors. In this paper, we address this need by discussing the relations between a comprehensive service lifecycle approach for service management & engineering and the sourcing & purchasing of services. In particular we pay attention to the similarities and differences between sourcing business and software services, the alignment between service management & engineering and sourcing & purchasing, the role of sourcing in the transformation of an organization towards a service-oriented paradigm, the role of architectural approaches to sourcing in this transformation, and the sourcing of specific services at different levels of granularity.

Identification and specification of relationships as the foundation for service bundling

Service bundling can be regarded as an option for service providers to strengthen their competitive advantages, cope with dynamic market conditions and heterogeneous consumer demand. Despite these positive effects, actual guidance for the identification of service bundles and the act of bundling itself can be regarded as a gap. Previous research has resulted in a conceptualization of a service bundling method relying on a structured service description in order to fill this gap. This method addresses the reasoning about the suitability of services to be part of a bundle based on analyzing existing relationships between services captured by a description language. This paper extends the aforementioned research by presenting an initial set of empirically derived relationships between services in existing bundles that can subsequently be utilized to identify potential new bundles. Additionally, a gap analysis points out to what extent prominent ontologies and service description languages accommodate for the identified relationships.

Regulating IVF and pre-implantation tissue-typing for the creation of "saviour siblings" : a harm analysis

Scientific discoveries, developments in medicine and health issues are the constant focus of media attention and the principles surrounding the creation of so called ‘saviour siblings’ are of no exception. The development in the field of reproductive techniques has provided the ability to genetically analyse embryos created in the laboratory to enable parents to implant selected embryos to create a tissue-matched child who may be able to cure an existing sick child. The research undertaken in this thesis examines the regulatory frameworks overseeing the delivery of assisted reproductive technologies (ART) in Australia and the United Kingdom and considers how those frameworks impact on the accessibility of in vitro fertilisation (IVF) procedures for the creation of ‘saviour siblings’. In some jurisdictions, the accessibility of such techniques is limited by statutory requirements. The limitations and restrictions imposed by the state in relation to the technology are analysed in order to establish whether such restrictions are justified. The analysis is conducted on the basis of a harm framework. The framework seeks to establish whether those affected by the use of the technology (including the child who will be created) are harmed. In order to undertake such evaluation, the concept of harm is considered under the scope of John Stuart Mill’s liberal theory and the Harm Principle is used as a normative tool to judge whether the level of harm that may result, justifies state intervention or restriction with the reproductive decision-making of parents in this context. The harm analysis conducted in this thesis seeks to determine an appropriate regulatory response in relation to the use of pre-implantation tissue-typing for the creation of ‘saviour siblings’. The proposals outlined in the last part of this thesis seek to address the concern that harm may result from the practice of pre-implantation tissue-typing. The current regulatory frameworks in place are also analysed on the basis of the harm framework established in this thesis. The material referred to in this thesis reflects the law and policy in place in Australia and the UK at the time the thesis was submitted for examination (December 2009).

Review of railway research in China

Railways in Hong Kong have been one of the few successful stories in the major metropolitan cities around the world, not only for their profit-making operation but also the efficiency in dealing with the astonishingly high traffic demands every day. While railway operations require a chain of delicate systems working in harmony all the time, there are numerous engineering problems arising and jeopardising the quality of services. Research in various railway engineering problems is therefore a must to tackle these problems. This paper highlights the railway research works in Hong Kong and discusses their relevance to Mainland China.

An evaluation methodology for the tangible and intangible assets of city-regions : the 6K1C framework

Together with hard and soft networks tangible and intangible regional assets play an important role in the knowledge-based development of competing city-regions. The aim of this paper, therefore, is to investigate the best ways of managing invaluable tangible and intangible assets of city-regions. The paper explores the importance of asset management of city-regions by giving special emphasis on their knowledge asset base. This paper develops and introduces a theoretical framework to conceptualise a new approach to articulate the strategic planning mechanism, so called the 6K1C framework. The 6K1C framework is part of the strategic planning process of continuous improvement of overall public sector performance. The framework provides a proactive check-list approach integrated for managing and harnessing tangible and intangible assets of the post-industrial city-regions.

Self-service technology and the moderating effects of consumer characteristics

The incidence of self-service technology, where the consumer delivers the service themselves using technology, is increasing in the service encounter. One area that is under-explored is the potential impact of self-service technology on consumer satisfaction and affective commitment. Accordingly, this paper presents an empirical study that investigates the relative impact of self-service technology on consumer satisfaction (both overall and transaction-specific) and affective commitment, accounting for the moderating effects of consumer characteristics. The results highlight the importance of personal service for evaluations of satisfaction and commitment, and the importance of social competency as a moderator in this relationship. An understanding of these consumer perceptions will allow organisations to develop strategies to deliver the services expected by their consumers, improving consumer satisfaction and commitment.

Stereotypes of Taiwanese salespeople at the service interface

Stereotypes of salespeople are common currency in US media outlets and research suggests that these stereotypes are uniformly negative. However, there is no reason to expect that stereotypes will be consistent across cultures. The present paper provides the first empirical examination of salesperson stereotypes in an Asian country, specifically Taiwan. Using accepted psychological methods, Taiwanese salesperson stereotypes are found to be twofold, with a negative stereotype being quite congruent with existing US stereotypes, but also a positive stereotype, which may be related to the specific culture of Taiwan.

The Australian Palliative Care Outcomes Collaboration (PCOC) : measuring the quality and outcomes of palliative care on a routine basis

Australia is leading the way in establishing a national system (the Palliative Care Outcomes Collaboration – PCOC) to measure the outcomes and quality of specialist palliative care services and to benchmark services across the country. This article reports on analysis of data collected routinely at point-of-care on 5939 patients treated by the first fifty one services that voluntarily joined PCOC. By March 2009, 111 services have agreed to join PCOC, representing more than 70% of services and more than 80% of specialist palliative care patients nationally. All states and territories are involved in this unique process that has involved extensive consultation and infrastructure and close collaboration between health services and researchers. The challenges of dealing with wide variation in outcomes and practice and the progress achieved to date are described. PCOC is aiming to improve understanding of the reasons for variations in clinical outcomes between specialist palliative care patients and differences in service outcomes as a critical step in an ongoing process to improve both service quality and patient outcomes. What is known about the topic? Governments internationally are grappling with how best to provide care for people with life limiting illnesses and how best to measure the outcomes and quality of that care. There is little international evidence on how to measure the quality and outcomes of palliative care on a routine basis. What does this paper add? The Palliative Care Outcomes Collaboration (PCOC) is the first effort internationally to measure the outcomes and quality of specialist palliative care services and to benchmark services on a national basis through an independent third party. What are the implications for practitioners? If outcomes and quality are to be measured on a consistent national basis, standard clinical assessment tools that are used as part of everyday clinical practice are necessary.

QUT Digital Repository: Integrating the University’s IR with other digital collections

Queensland University of Technology’s Institutional Repository, QUT ePrints (http://eprints.qut.edu.au/), was established in 2003. With the help of an institutional mandate (endorsed in 2004) the repository now holds over 11,000 open access publications. The repository’s success is celebrated within the University and acknowledged nationally and internationally. QUT ePrints was built on GNU EPrints open source repository software (currently running v.3.1.3) and was originally configured to accommodate open access versions of the traditional range of research publications (journal articles, conference papers, books, book chapters and working papers). However, in 2009, the repository’s scope, content and systems were broadened and the ‘QUT Digital repository’ is now a service encompassing a range of digital collections, services and systems. For a work to be accepted in to the institutional repository, at least one of the authors/creators must have a current affiliation with QUT. However, the success of QUT ePrints in terms of its capacity to increase the visibility and accessibility of our researchers' scholarly works resulted in requests to accept digital collections of works which were out of scope. To address this need, a number of parallel digital collections have been developed. These collections include, OZcase, a collection of legal research materials and ‘The Sugar Industry Collection’; a digitsed collection of books and articles on sugar cane production and processing. Additionally, the Library has responded to requests from academics for a service to support the publication of new, and existing, peer reviewed open access journals. A project is currently underway to help a group of senior QUT academics publish a new international peer reviewed journal. The QUT Digital Repository website will be a portal for access to a range of resources to support copyright management. It is likely that it will provide an access point for the institution’s data repository. The data repository, provisionally named the ‘QUT Data Commons’, is currently a work-in-progress. The metadata for some QUT datasets will also be harvested by and discoverable via ‘Research Data Australia’, the dataset discovery service managed by the Australian National Data Service (ANDS). QUT Digital repository will integrate a range of technologies and services related to scholarly communication. This paper will discuss the development of the QUT Digital Repository, its strategic functions, the stakeholders involved and lessons learned.

Customers behaving badly : a state of the art review, research agenda and implications for practitioners

The purpose of this paper is to highlight important issues in the study of dysfunctional customer behavior and to provide a research agenda to inspire, guide, and enthuse. Through a critical evaluation of existing research, the aim is to highlight key issues and to present potentially worthy avenues for future study.

Design of a model-generated repository as a service for USDL

SAP and its research partners have been developing a lan- guage for describing details of Services from various view- points called the Unified Service Description Language (USDL). At the time of writing, version 3.0 describes technical implementation aspects of services, as well as stakeholders, pricing, lifecycle, and availability. Work is also underway to address other business and legal aspects of services. This language is designed to be used in service portfolio management, with a repository of service descriptions being available to various stakeholders in an organisation to allow for service prioritisation, development, deployment and lifecycle management. The structure of the USDL metadata is specified using an object-oriented metamodel that conforms to UML, MOF and EMF Ecore. As such it is amenable to code gener-ation for implementations of repositories that store service description instances. Although Web services toolkits can be used to make these programming language objects available as a set of Web services, the practicalities of writing dis- tributed clients against over one hundred class definitions, containing several hundred attributes, will make for very large WSDL interfaces and highly inefficient “chatty” implementations. This paper gives the high-level design for a completely model-generated repository for any version of USDL (or any other data-only metamodel), which uses the Eclipse Modelling Framework’s Java code generation, along with several open source plugins to create a robust, transactional repository running in a Java application with a relational datastore. However, the repository exposes a generated WSDL interface at a coarse granularity, suitable for distributed client code and user-interface creation. It uses heuristics to drive code generation to bridge between the Web service and EMF granularities.

Communicating friendships : a case study of women in an Australian 'seachange' town

This thesis proposes =friendworks‘ as an important sub-group of social networks, comprised of networks of friends. It investigates friendworks of a particular group of adult Australian women as a way of understanding neglected aspects of social networking practices. Friendworks are contextualised to highlight two main themes of interest: population mobility and communication practices. The impact of relocation on individuals, local communities and the wider society is explored through a case study of female friendworks in a seachange community. Research findings point to the importance of friendworks in building and cohering social and emotional support, well-being, belonging and senses of place and community. Different types of communication methods were used by research participants for mediating different kinds of social ties within the friendworks considered here. Communication patterns were influenced by geographical proximity to friends, and the type of social support required of them (emotional, instrumental or companionship). Most findings were consistent with broader social patterns of communication. For example, face-to-face interactions were the dominant and most favoured communication method between local friends, regardless of whether they were weak or strong ties. The fixed-telephone and the internet were commonly in use to maintain old and geographically distant social ties, while mobile phones were used the least among friends in comparison with other communication methods. The key finding of this thesis is that friendworks are an extremely important solid network in contemporary society, providing mooring relations in a mobile world. Paradoxically, however, for women in this study, the mobile phone, which is popularly perceived as a flexible, multi-purpose communication technology for people on the move, was the least versatile of all technologies for maintaining friendworks. The cost of services was the main inhibitor here. The internet was found to be the most versatile communication technology and was used to support various types of social ties: strong, weak, local and distant. This thesis also highlights the value of the concept of friendworks as well as networks for communication research and policy investigating individuals‘ motivations and practices.

Biomashups: the new world of exploratory bioinformatics?

Bioinformatics is dominated by online databases and sophisticated web-accessible tools. As such, it is ideally placed to benefit from the rapid, purpose specific combination of services achievable via web mashups. The recent introduction of a number of sophisticated frameworks has greatly simplified the mashup creation process, making them accessible to scientists with limited programming expertise. In this paper we investigate the feasibility of mashups as a new approach to bioinformatic experimentation, focusing on an exploratory niche between interactive web usage and robust workflows, and attempting to identify the range of computations for which mashups may be employed. While we treat each of the major frameworks, we illustrate the ideas with a series of examples developed under the Popfly framework