Single-crystal micro/nanostructures and thin films of lamellar molybdenum oxide by solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene

The solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene is demonstrated to be a new, simple and versatile solid-state templating method for obtaining single-crystal micro- and nanocrystals of transition and valve metal oxides. The technique, when applied to Mo-containing organometallics N3P3[OC6H4CH2CN·Mo(CO)5]6 and N3P3[OC6H4CH2CN·Mo(CO)4 py]6, results in stand-alone and surface-deposited lamellar MoO3 single crystals, as determined by electron and atomic force microscopies and X-ray diffraction. The size and morphology of the resulting crystals can be tuned by the composition of the precursor. X-ray photoelectron and infrared spectroscopies indicate that the deposition of highly lamellar MoO3 directly on an oxidized (400 nm SiO2) surface or (100) single-crystal silicon surfaces yields a layered uniphasic single-crystal film formed by cluster diffusion on the surface during pyrolysis of the metal-carbonyl derivatives. For MoO3 in its layered form, this provides a new route to an important intercalation material for high energy density battery materials.

The influence of neoliberal thought on contemporary politics: an examination of the interrelationships between ideological hegemony, neoliberal thought and contemporary politics

This thesis critically assesses the impact of neoliberal ideology on liberal thought and contemporary politics specifically examining the question, To what extent has neoliberalism, as elucidated originally by Hayek affected change in contemporary politics? This question is crucial to understanding the nature, role, influence and impact of neoliberal ideas. This investigation required a broad engagement with the literature, identifying and discussing the relationships within neoliberalism allowing a clearer understanding of the role of ideas in neoliberalism’s continuing hegemony. The methodological approach adopted a social constructivist character that encompassed an individual centric emphasis, acknowledging the breadth and complexity of Neoliberalization through the use of interpretive repertoires. The initial chapters examine the ideational process and the role of particular understanding in motivating political conduct. In this context of the transfer of ideas through their everyday resonance eventually becoming ‘stubborn social facts’ (Habermas 2006:413) is highlighted. Later chapters discuss the historical and economic context of Neoliberalization focussing on the role of the hegemon and its influence, outlining and evaluating the contribution of Hayek to liberal thought. The penultimate chapter deals with the contemporary situation and the irony associated with Hayek’s original ideas. Concluding, several findings emerged contributing by combining available knowledge in a uniquely fresh way and generating originality by linking old ideas, new ideas and new facts. The results are grouped as, - Pragmatic, recognising that political pragmatism trumps ideological aspiration where liberal democratic processes require politicians are held to account. - Realistic, recognising the contrast and irony between political action and ideological insight reflected in the operationalization of neoliberalism. - General, recognising Hayek’s on-going but increasingly indirect influence. The thesis finishes with a short aside on ideational change within the context of the current crisis and advocates an introspective approach that includes entrepreneurial spirit, good conscience and duty as part of future deliberations.

The quality of diabetes care in the community: practice, policy and culture

Aim: Diabetes is an important barometer of health system performance. This chronic condition is a source of significant morbidity, premature mortality and a major contributor to health care costs. There is an increasing focus internationally, and more recently nationally, on system, practice and professional-level initiatives to promote the quality of care. The aim of this thesis was to investigate the ‘quality chasm’ around the organisation and delivery of diabetes care in general practice, to explore GPs’ attitudes to engaging in quality improvement activities and to examine efforts to improve the quality of diabetes care in Ireland from practice to policy. Methods: Quantitative and qualitative methods were used. As part of a mixed methods sequential design, a postal survey of 600 GPs was conducted to assess the organization of care. This was followed by an in-depth qualitative study using semi-structured interviews with a purposive sample of 31 GPs from urban and rural areas. The qualitative methodology was also used to examine GPs’ attitudes to engaging in quality improvement. Data were analysed using a Framework approach. A 2nd observation study was used to assess the quality of care in 63 practices with a special interest in diabetes. Data on 3010 adults with Type 2 diabetes from 3 primary care initiatives were analysed and the results were benchmarked against national guidelines and standards of care in the UK. The final study was an instrumental case study of policy formulation. Semi-structured interviews were conducted with 15 members of the Expert Advisory Group (EAG) for Diabetes. Thematic analysis was applied to the data using 3 theories of the policy process as analytical tools. Results: The survey response rate was 44% (n=262). Results suggested care delivery was largely unstructured; 45% of GPs had a diabetes register (n=157), 53% reported using guidelines (n=140), 30% had formal call recall system (n=78) and 24% had none of these organizational features (n=62). Only 10% of GPs had a formal shared protocol with the local hospital specialist diabetes team (n=26). The lack of coordination between settings was identified as a major barrier to providing optimal care leading to waiting times, overburdened hospitals and avoidable duplication. The lack of remuneration for chronic disease management had a ripple effect also creating costs for patients and apathy among GPs. There was also a sense of inertia around quality improvement activities particularly at a national level. This attitude was strongly influenced by previous experiences of change in the health system. In contrast GP’s spoke positively about change at a local level which was facilitated by a practice ethos, leadership and special interest in diabetes. The 2nd quantitative study found that practices with a special interest in diabetes achieved a standard of care comparable to the UK in terms of the recording of clinical processes of care and the achievement of clinical targets; 35% of patients reached the HbA1c target of <6.5% compared to 26% in England and Wales. With regard to diabetes policy formulation, the evolving process of action and inaction was best described by the Multiple Streams Theory. Within the EAG, the formulation of recommendations was facilitated by overarching agreement on the “obvious” priorities while the details of proposals were influenced by personal preferences and local capacity. In contrast the national decision-making process was protracted and ambiguous. The lack of impetus from senior management coupled with the lack of power conferred on the EAG impeded progress. Conclusions: The findings highlight the inconsistency of diabetes care in Ireland. The main barriers to optimal diabetes management center on the organization and coordination of care at the systems level with consequences for practice, providers and patients. Quality improvement initiatives need to stimulate a sense of ownership and interest among frontline service providers to address the local sense of inertia to national change. To date quality improvement in diabetes care has been largely dependent the “special interest” of professionals. The challenge for the Irish health system is to embed this activity as part of routine practice, professional responsibility and the underlying health care culture.

Chemical vapour deposition of complex ferroic oxide thin films

Herein is presented a novel chemical vapour deposition (CVD) route for the fabrication of oxide ferroelectrics. A versatile layer-by-layer growth mode was developed to prepare naturally super-latticed bismuth based materials belonging to the Aurivillius phase family, with which good control over composition and crystal structure was achieved. In chapter 3, the effect of epitaxial strain on one of the very simple oxide materials TiO2 was studied. It has been found that the ultra-thin TiO2 films demonstrate ferroelectric behaviour when grown on NdGaO3 substrates. TiO2 exists in various crystal phases, but none of them show ferroelectric behaviour. The epitaxial strain due to the substrate, changes the crystal structure from tetragonal to orthorhombic which in turn leads to ferroelectric behaviour. In chapter 4, a unique growth method for multiferroic BiFeO3 (BFO) thin films is shown, where a phase pure BFO thin films can be prepared even in the presence of excess bismuth precursor during the growth process. This type of growth is usually called adsorption controlled growth and can be used for growing various bismuth containing compounds, where the volatility of bismuth can create various types of defects. Chapter 5 describes the growth of Bi4Ti3O12 thin films in a layer-by-layer growth mode. In this section, the effect of Bi and Ti precursor flows on the growth of thin films is discussed and it is shown that how change in precursor flows leads to out-ofphase boundary defects during the layer-by-layer growth mode. In chapter 6, the growth of a compound Bi5Ti3FeO15, which is a 1:1 mixture of BiFeO3 and Bi4Ti3O12, is presented. The growth mechanism of Bi5Ti3FeO15 thin films is presented, where the Fe precursor flow was controlled from zero to the insertion of one full BiFeO3 perovskite unit cell into the Bi4Ti3O12 structure in addition, the effect of iron precursor flow on crystalline properties is demonstrated. The methods presented in this thesis can be adopted to grow ferroelectric and multiferroic films for industrial applications.

Challengers to provisional republicanism: the official republican movement, people’s democracy and the Irish republican socialist party, 1968–98

The Provisional IRA and its political wing Sinn Féin have attracted by far the greatest scholarly interest of all the players in the Northern Irish conflict. This emphasis is perfectly legitimate, given the centrality of the Provos to so many turning-points in the conflict, from the collapse of Stormont in the early 1970s to the hunger strikes of the following decade and the ceasefires which were followed by the Belfast Agreement. My project, however, looks at political groups that at one time or another challenged the Provos for leadership of the militant, anti-state constituency in Northern Ireland (chiefly based in the Catholic working class). Although never as large or influential as the Provisional republicans, groups such as the Official IRA and the Irish Republican Socialist Party sometimes had a discernible impact on the course of events which is overlooked by most studies, and often pioneered ideas and tactics that were later adopted by the Provos themselves. The idea that republicans should embrace political action and work in broad campaigning alliances was promoted by the IRSP and socialist groups such as People’s Democracy before it was taken up by Gerry Adams and his allies, while the Official IRA supported the principle of a settlement based on democratization of the Northern Irish state, which was later accepted by Sinn Féin in the form of the Belfast Agreement. The goal of my research is to provide a novel perspective on the conflict in Northern Ireland, while engaging with theoretical debates about its character.