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.

NSW rural land performance : 1990-2008

The annual income return for rural property is based on two major factors being commodity prices and production yields. Commodity prices paid to rural producers can vary depending on the agricultural policies of their respective countries. Free trade countries, such as Australia and New Zealand are subject to the volatility of the world commodity markets to a greater extent than those farmers in protected or subsidised markets. In countries where rural production is protected or subsidised the annual income received by rural producers has been relatively stable. However, the high cost of agricultural protection is now being questioned, particularly in relation to the increasing economic costs of government services such as health, education and housing. When combined with the agricultural production limitations of climate, topography, chemical residues and disease issues, the impact of commodity prices on rural property income is crucial in the ability of rural producers to enter into or expand their holdings in agricultural land. These problems are then reflected in the volatility of the rural land capital returns and the investment performance of this property class. This paper will address the total and capital return performance of a major agricultural area and compare these returns on the basis of both location of land and land use. The comparison will be used to determine if location or actual land use has a greater influence on rural property capital returns. This performance analysis is based on over 35,000 rural sales transactions. These transactions cover all market based rural property transactions in New South Wales, Australia for the period January 1990 to December 2008. Correlation analysis and investment performance analysis has also been carried out to determine the possible relationships between location and land use and subsequent changes in rural land capital values.

Exercise, appetite, and energy balance: The interactions between energy expenditure and intake, and the implications for weight management

This book disseminates current information pertaining to the modulatory effects of foods and other food substances on behavior and neurological pathways and, importantly, vice versa. This ranges from the neuroendocrine control of eating to the effects of life-threatening disease on eating behavior. The importance of this contribution to the scientific literature lies in the fact that food and eating are an essential component of cultural heritage but the effects of perturbations in the food/cognitive axis can be profound. The complex interrelationship between neuropsychological processing, diet, and behavioral outcome is explored within the context of the most contemporary psychobiological research in the area. This comprehensive psychobiology- and pathology-themed text examines the broad spectrum of diet, behavioral, and neuropsychological interactions from normative function to occurrences of severe and enduring psychopathological processes

Governance in the Australian superannuation industry

In the Superannuation/Pension industry ordinary investors entrust their retirement savings to the trustees of the superannuation plan. Investors rely on the trustees to ensure ethical business and risk management practices are implemented to protect their retirement savings. Governance practices ensure the monitoring of ethical risk management (Drennan, 2004). The Australian superannuation industry presents a unique scenario. Legislation requires employers to contribute a minimum of 9% of the employees wage to retirement savings. However, there are no legislated governance standards, although there are standards of recommended governance practices. In this paper, we examine the level of voluntary adoption of governance practices by the trustees of Australian public sector and industry superannuation funds. We also assess whether superannuation governance practices are associated with performance and volatility/riskiness of returns. Survey results show that the majority of superannuation plans adopt recommended governance practices supporting the concept of ethical management of the member’s retirement savings. The examination of governance principles that impact returns and risk show that board size and regular review of conflicts are positively associated with return. Superannuation plans with higher volatility in returns meet more frequently.

Comparing exercise prescribed with exercise completed : effects of gender and mode of exercise

The purpose of this study was to compare the amount of exercise prescribed with the amount completed between two different modes of training intervention and between the sexes. Thirty-two men (mean age = 39.1 years, body mass index = 32.9 kg · m-2) and women (mean age = 39.6 years, body mass index = 32.1 kg · m-2) were prescribed traditional resistance training or light-resistance circuit training for 16 weeks. Lean mass and fat mass were determined by dual-energy X-ray absorptiometry at weeks 1 and 16. A completion index was calculated to provide a measure of the extent to which participants completed exercise training relative to the amount of exercise prescribed. The absolute amount of exercise completed by the circuit training group was significantly greater than the amount prescribed (P < 0.0001). The resistance training group consistently under-completed relative to the amount prescribed, but the difference was not significant. The completion index for the circuit training group (26 ± 21.7%) was significantly different from that of the resistance training group (-7.4 ± 3.0%). The completion index was not significantly different between men and women in either group. These data suggest that overweight and obese individuals participating in light-resistance circuit training complete more exercise than is prescribed. Men and women do not differ in the extent to which they over- or under-complete prescribed exercise.

The role of sulphates and organic vapours in growth of newly formed particles in a eucalypt forest

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photooxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.

The organic fraction of bubble-generated, accumulation mode Sea Spray Aerosol (SSA)

Recent studies have detected a dominant accumulation mode (~100 nm) in the Sea Spray Aerosol (SSA) number distribution. There is evidence to suggest that particles in this mode are composed primarily of organics. To investigate this hypothesis we conducted experiments on NaCl, artificial SSA and natural SSA particles with a Volatility-Hygroscopicity-Tandem-Differential-Mobility-Analyser (VH-TDMA). NaCl particles were atomiser generated and a bubble generator was constructed to produce artificial and natural SSA particles. Natural seawater samples for use in the bubble generator were collected from biologically active, terrestrially-affected coastal water in Moreton Bay, Australia. Differences in the VH-TDMA-measured volatility curves of artificial and natural SSA particles were used to investigate and quantify the organic fraction of natural SSA particles. Hygroscopic Growth Factor (HGF) data, also obtained by the VH-TDMA, were used to confirm the conclusions drawn from the volatility data. Both datasets indicated that the organic fraction of our natural SSA particles evaporated in the VH-TDMA over the temperature range 170–200°C. The organic volume fraction for 71–77 nm natural SSA particles was 8±6%. Organic volume fraction did not vary significantly with varying water residence time (40 secs to 24 hrs) in the bubble generator or SSA particle diameter in the range 38–173 nm. At room temperature we measured shape- and Kelvin-corrected HGF at 90% RH of 2.46±0.02 for NaCl, 2.35±0.02 for artifical SSA and 2.26±0.02 for natural SSA particles. Overall, these results suggest that the natural accumulation mode SSA particles produced in these experiments contained only a minor organic fraction, which had little effect on hygroscopic growth. Our measurement of 8±6% is an order of magnitude below two previous measurements of the organic fraction in SSA particles of comparable sizes. We stress that our results were obtained using coastal seawater and they can’t necessarily be applied on a regional or global ocean scale. Nevertheless, considering the order of magnitude discrepancy between this and previous studies, further research with independent measurement techniques and a variety of different seawaters is required to better quantify how much organic material is present in accumulation mode SSA.

Observation of the suppression of water uptake by marine particles

A 4 week intensive measurement campaign was conducted in March–April 2007 at Agnes Water, a remote coastal site on the east coast of Australia. A Volatility-Hygroscopicity-Tandem Differential Mobility Analyser (VH-TDMA) was used to investigate changes in the hygroscopic properties of ambient particles as volatile components were progressively evaporated. Nine out of 18 VH-TDMA volatility scans detected internally mixed multi-component particles in the nucleation and Aitken modes in clean marine air. Evaporation of a volatile, organic-like component in the VH-TDMA caused significant increases in particle hygroscopicity. In 3 scans the increase in hygroscopicity was so large it was explained by an increase in the absolute volume of water uptake by the particle residuals, and not merely an increase in their relative hygroscopicity. This indicates the presence of organic components that were suppressing the hygroscopic growth of mixed particles on the timescale of humidification in the VH-TDMA (6.5 secs). This observation was supported by ZSR calculations for one scan, which showed that the measured growth factors of mixed particles were up to 18% below those predicted assuming independent water uptake of the individual particle components. The observed suppression of water uptake could be due to a reduced rate of hygroscopic growth caused by the presence of organic films or organic-inorganic interactions in solution droplets that had a negative effect on hygroscopicity.

Freeway traffic estimation in Beijing based on particle filter

Short-term traffic flow data is characterized by rapid and dramatic fluctuations. It reflects the nature of the frequent congestion in the lane, which shows a strong nonlinear feature. Traffic state estimation based on the data gained by electronic sensors is critical for much intelligent traffic management and the traffic control. In this paper, a solution to freeway traffic estimation in Beijing is proposed using a particle filter, based on macroscopic traffic flow model, which estimates both traffic density and speed.Particle filter is a nonlinear prediction method, which has obvious advantages for traffic flows prediction. However, with the increase of sampling period, the volatility of the traffic state curve will be much dramatic. Therefore, the prediction accuracy will be affected and difficulty of forecasting is raised. In this paper, particle filter model is applied to estimate the short-term traffic flow. Numerical study is conducted based on the Beijing freeway data with the sampling period of 2 min. The relatively high accuracy of the results indicates the superiority of the proposed model.

The nature of pedagogic teacher-student interactions : a phenomenographic study

Globally, teaching has become more complex and more challenging over recent years, with new and increased demands being placed on teachers by students, their families, governments and wider society. Teachers work with more diverse communities in times characterised by volatility, uncertainty and moral ambiguity. Societal, political, economic and cultural shifts have transformed the contexts in which teachers work and have redefined the ways in which teachers interact with students. This qualitative study uses phenomenographic methods to explore the nature of pedagogic teacherstudent interactions. The data analysis reveals five qualitatively different ways in which teachers experience pedagogic engagements with students. The resultant categories of description ranged from information providing, with teachers viewed as transmitters of a body of knowledge through to mentoring in which teachers were perceived as significant others in the lives of students with their influence extending beyond the walls of the classroom and beyond the years of schooling. The paper concludes by arguing that if teachers are to prepare students for the challenges and opportunities in changing times, teacher education programs need to consider ways to facilitate the development of mentoring capacities in new teachers.

Colonising Shakespeare? : agency and authority in Gregory Rogers's Shakespearean picture books

“You need to be able to tell stories. Illustration is a literature, not a pure fine art. It’s the fine art of writing with pictures.” – Gregory Rogers. This paper reads two recent wordless picture books by Australian illustrator Gregory Rogers in order to consider how “Shakespeare” is produced as a complex object of consumption for the implied child reader: The Boy, The Bear, The Baron, The Bard (2004) and Midsummer Knight (2006). In these books other worlds are constructed via time-travel and travel to a fantasy world, and clearly presume reader competence in narrative temporality and structure, and cultural literacy (particularly in reference to Elizabethan London and William Shakespeare), even as they challenge normative concepts via use of the fantastic. Exploring both narrative sequences and individual images reveals a tension in the books between past and present, and real and imagined. Where children’s texts tend to privilege Shakespeare, the man and his works, as inherently valuable, Rogers’s work complicates any sense of cultural value. Even as these picture books depend on a lexicon of Shakespearean images for meaning and coherence, they represent William Shakespeare as both an enemy to children (The Boy), and a national traitor (Midsummer). The protagonists, a boy in the first book and the bear he rescues in the second, effect political change by defeating Shakespeare. However, where these texts might seem to be activating a postcolonial cultural critique, this is complicated both by presumed readerly competence in authorized cultural discourses and by repeated affirmation of monarchies as ideal political systems. Power, then, in these picture books is at once rewarded and withheld, in a dialectic of (possibly postcolonial) agency, and (arguably colonial) subjection, even as they challenge dominant valuations of “Shakespeare” they do not challenge understandings of the “Child”.

Government : charity boundaries

The Preamble1 was the initial legislative statement of matters construed by government to constitute charitable purposes in a common law context. It provided an outline of what was to become the core agenda for government’s relationship with charity. The resulting implied partnership, as viewed by government, endured for four centuries and in many different cultural contexts across the common law world. During that period, judicial mediation on the balance to be struck between government interest in acquiring value for granting tax exempt privileges and the right of individuals to freely dispose of property in accordance with their particular altruistic wishes steadily broadened the range of purposes deemed to be charitable, the vagaries of donor choice often prevailing over government interest in acquiring value for tax exemption.

Intelligent physical modelling systems - Why?

“What did you think you were doing?” Was the question posed by the conference organizers to me as the inventor and constructor of the first working Tangible Interfaces over 40 years ago. I think the question was intended to encourage me to talk about the underlying ideas and intentionality rather than describe an endless sequence of electronic bricks and that is what I shall do in this presentation. In the sixties the prevalent idea for a graphics interface was an analogue with sketching which was to somehow be understood by the computer as three dimensional form. I rebelled against this notion for reasons which I will explain in the presentation and instead came up with tangible physical three dimensional intelligent objects. I called these first prototypes “Intelligent Physical Modelling Systems” which is a really dumb name for an obvious concept. I am eternally grateful to Hiroshi Ishii for coining the term “Tangible User Interfaces” - the same idea but with a much smarter name. Another motivator was user involvement in the design process, and that led to the Generator (1979) project with Cedric Price for the world’s first intelligent building capable of organizing itself in response to the appetites of the users. The working model of that project is in MoMA. And the same motivation led to a self builders design kit (1980) for Walter Segal which facilitated self-builders to design their own houses. And indeed as the organizer’s question implied, the motivation and intentionality of these projects developed over the years in step with advancing technology. The speaker will attempt to articulate these changes with medical, psychological and educational examples. Much of this later work indeed stemming from the Media Lab where we are talking. Related topics such as “tangible thinking” and “intelligent teacups” will be introduced and the presentation will end with some speculations for the future. The presentation will be given against a background of images of early prototypes many of which have never been previously published.