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.

High resolution imaging of boron carbide microstructures

Two samples of boron carbide have been examined using high resolution transmission electron microscopy (HRTEM). A hot pressed B13C2 sample shows a high density of variable width twins normal to (10-11). Subtle shifts or offsets of lattice fringes along the twin plane and normal to (10 5) were also observed. A B4C powder showed little evidence of stacking disorder in crystalline regions.

Reducing the global burden of depression : population level analysis of intervention cost-effectiveness in 14 world regions

International evidence on the cost and effects of interventions for reducing the global burden of depression remain scarce. Aims: To estimate the population-level cost-effectiveness of evidence-based depression interventions and their contribution towards reducing current burden. Method: Primary-care-based depression interventions were modelled at the level of whole populations in 14 epidemiological subregions of the world. Total population-level costs (in international dollars or I$) and effectiveness (disability adjusted life years (DALYs) averted) were combined to form average and incremental cost-effectiveness ratios. Results: Evaluated interventions have the potential to reduce the current burden of depression by 10–30%. Pharmacotherapy with older antidepressant drugs, with or without proactive collaborative care, are currently more cost-effective strategies than those using newer antidepressants, particularly in lower-income subregions. Conclusions: Even in resource-poor regions, each DALYaverted by efficient depression treatments in primary care costs less than 1 year of average per capita income, making such interventions a cost-effective use of health resources. However, current levels of burden can only be reduced significantlyif there is a substantialincrease substantial increase intreatment coverage.

Urban sustainability and growth management in south-east Asian city-regions : the case of Kuala Lumpur and Hong Kong

Major South-East Asian city-regions have experienced considerable physical, economic and social transformations during the past three decades. The rapid pace of globalisation and economic restructuring has resulted in these city-regions receiving the full impact of urbanisation pressures. In an attempt to ease these pressures, city-regions such as Bangkok, Seoul, Tokyo, Taipei, Hong Kong, Singapore and Kuala Lumpur have advocate growth management approaches giving particular interest to urban sustainability. These approaches promote efforts to achieve the triple bottom line sustainability by balancing economic and social development, and environmental protection, and putting more emphasis on compact and optimum development of urban forms. This paper evaluates the case of two South-East Asian city-regions, Kuala Lumpur and Hong Kong, and assesses their experiences in managing their urban forms whilst promoting sustainable patterns of urban development. The findings show that sustainable urban development initiatives employing a top down approach has yielded encouraging results in these case study city-regions. However the need for a more concerted effort towards the overall sustainability agenda still remains vital.

Promoting sustainable urban development in fast growing city-regions : practices from Kuala Lumpur and Hong Kong

The Asia‐Pacific region is characterised by rapid population growth and urbanisation. These trends often result in an increasing consumption of land, which in turn lead to spatially expansive and discontinuous urban development. As a consequence, local communities and the environment face strong pressures. Many cities in the region have developed policies to tackle the issue of rapid growth and its associated consequences, for example climate change. The broad aim of this paper is to identify the nature, trends and strategies of growth management in major Asia‐Pacific city‐regions, and their implications for natural resource management and infrastructure provision. More specifically, this research seeks to provide insights on sustainable urban development practice, particularly on the promotion of compact urbanisation within the Asia‐Pacific’s fastest growing regions. The methodology of the paper includes a detailed literature review and a comparative analysis of existing strategies and policies. The literature review focuses on the key concepts related to sustainable urban growth management. It also includes existing applications of urban growth management approaches and planning information system in managing growth. Following the literature review, the paper undertakes a comparative analysis of the strategies of major Asia‐Pacific city‐regions of Kuala Lumpur and Hong Kong in terms of their approaches to sustainable urban development. The findings of the paper provide a clear understanding of the necessity of sustainable urban development practices. It contributes to the development of a substantial base for further research. Ultimately, this research aims to shed light on sustainable urban development by providing insights on the management of growth, natural resources and urban infrastructures.

Creative urban regions : harnessing urban technologies to support knowledge city initiatives

In the rapidly growing knowledge economy, the talent and creativity of those around us will be increasingly decisive in shaping economic opportunity. Creativity can be described as the ability to produce new and original ideas and things. In other words, it is any act, idea, or product that changes an existing domain or transforms an existing domain into a new one. From an economic perspective, creativity can be considered as the generation of new ideas that is the major source of innovation and new economic activities. As urban regions have become the localities of key knowledge precincts and knowledge clusters across the globe, the link between a range of new technologies and the development of ‘creative urban regions’ (CURs) has come to the fore. In this sense, creativity has become a buzz concept in knowledge-economy research and policy circles. It has spawned ‘creative milieus,’ ‘creative industries,’ ‘creative cities,’ ‘creative class,’ and ‘creative capital.’ Hence, creativity has become a key concept on the agenda of city managers, development agents, and planners as they search for new forms of urban and economic development. CURs provide vast opportunities for knowledge production and spillover, which lead to the formation of knowledge cities. Urban information and communication technology (ICT) developments support the transformation of cities into knowledge cities. This book, which is a companion volume to Knowledge-Based Urban Development: Planning and Applications in the Information Era (also published by IGI Global) focuses on some of these developments. The Forward and Afterword are written by senior respected academic researchers Robert Stimson of the University of Queensland, Australia, and Zorica Nedovic-Budic of the University of Illinois at Urbana-Champaign, USA. The book is divided into four sections, each one dealing with selected aspects of information and communication technologies and creative urban regions.

Knowledge-based strategic planning: harnessing (in)tangible assets of city-regions

Purpose – The aim of this paper is to investigate the ways of best managing city-regions’ valuable tangible and intangible assets while pursuing a knowledge-based urban development that is sustainable and competitive. Design/methodology/approach – The paper provides a theoretical framework to conceptualise a new strategic planning mechanism, knowledge-based strategic planning, which has been emerged as a planning mechanism for the knowledge-based urban development of post-industrial city-regions. Originality/value – The paper develops a planning framework entitled 6K1C for knowledge-based strategic planning to be used in the analysis of city-regions’ tangible and intangible assets. Practical implications – The paper discusses the importance of asset mapping of cityregions, and explores the ways of successfully managing city-regions’ tangible/intangible assets to achieve an urban development that is sustainable and knowledge-based. Keywords – Knowledge-based urban development, Knowledge-based strategic planning, Tangible assets, Intangible assets, City-regions. Paper type – Academic Research Paper