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.

Grafted fluoropolymers as supports for solid-phase organic chemistry : preparation and characterization

Solid-phase organic chemistry has rapidly expanded in the last decade, and, as a consequence, so has the need for the development of supports that can withstand the extreme conditions required to facilitate some reactions. The authors here prepare a thermally stable, grafted fluoropolymer support (see Figure for an example) in three solvents, and found that the penetration of the graft was greatest in dichloromethane.

An application of near-infrared and mid-infrared spectroscopy to the study of natural halotrichites : halotrichite, apjohnite and wupatkiite

Near-infrared (NIR) and Fourier transform infrared (FTIR) spectroscopy have been used to determine the mineralogical character of isomorphic substitutions for Mg2+ by divalent transition metals Fe, Mn, Co and Ni in natural halotrichite series. The minerals are characterised by d-d transitions in NIR region 12000-7500 cm-1. NIR spectrum of halotrichite reveals broad feature from 12000 to 7500 cm-1 with a splitting of two bands resulting from ferrous ion transition 5T2g ® 5Eg. The presence of overtones of OH- fundamentals near 7000 cm-1 confirms molecular water in the mineral structure of the halotrichite series. The appearance of the most intense peak at around 5132 cm-1 is a common feature in the three minerals and is derived from combination of OH- vibrations of water molecules and 2 water bending modes. The influence of cations like Mg2+, Fe2+, Mn2+, Co2+, Ni2+ shows on the spectra of halotrichites. Especially wupatkiite-OH stretching vibrations in which bands are distorted conspicuously to low wave numbers at 3270, 2904 and 2454 cm-1. The observation of high frequency 2 mode in the infrared spectrum at 1640 cm-1 indicates coordination of water molecules is strongly hydrogen bonded in natural halotrichites. The splittings of bands in 3 and 4 (SO4)2- stretching regions may be attributed to the reduction of symmetry from Td to C2v for sulphate ion. This work has shown the usefulness of NIR spectroscopy for the rapid identification and classification of the halotrichite minerals.

Some aspects of calcium phosphate chemistry in sugarcane clarification

This paper reviews some aspects of calcium phosphate chemistry since phosphate in juice is an important parameter in all sugar juice clarification systems. It uses basic concepts to try and explain the observed differences in clarification performance obtained with various liming techniques. The paper also examines the current colorimetric method used for the determination of phosphate in sugar juice. In this method, a phosphomolybdate blue complex formed due to the addition of a dye is measured at 660 nm. Unfortunately, at this wavelength there is interference of the colour arising from within the juice and results in the underestimation of the amount of soluble inorganic phosphate content of juice. It is suggested that phosphate analysis be conducted at the higher wavelength of 875 nm where the interference of the juice colour is minimised.

Deconstructing neurobiological coordination

Inherent indeterminacy of neurobiological systems has been revealed by research on coordination of multiarticular actions. We consider three important issues that these investigations raise for biomechanical measurement and performance modeling. These issues highlight the role of dynamic systems theory as a platform for integration of motor control and biomechanics in exercise and sports science.

Multitasking, cognitive coordination and cognitive shifts during web searching

As Web searching becomes more prolific for information access worldwide, we need to better understand users’ Web searching behaviour and develop better models of their interaction with Web search systems. Web search modelling is a significant and important area of Web research. Searching on the Web is an integral element of information behaviour and human–computer interaction. Web searching includes multitasking processes, the allocation of cognitive resources among several tasks, and shifts in cognitive, problem and knowledge states. In addition to multitasking, cognitive coordination and cognitive shifts are also important, but are under-explored aspects of Web searching. During the Web searching process, beyond physical actions, users experience various cognitive activities. Interactive Web searching involves many users’ cognitive shifts at different information behaviour levels. Cognitive coordination allows users to trade off the dependences among multiple information tasks and the resources available. Much research has been conducted into Web searching. However, few studies have modelled the nature of and relationship between multitasking, cognitive coordination and cognitive shifts in the Web search context. Modelling how Web users interact with Web search systems is vital for the development of more effective Web IR systems. This study aims to model the relationship between multitasking, cognitive coordination and cognitive shifts during Web searching. A preliminary theoretical model is presented based on previous studies. The research is designed to validate the preliminary model. Forty-two study participants were involved in the empirical study. A combination of data collection instruments, including pre- and post-questionnaires, think-aloud protocols, search logs, observations and interviews were employed to obtain users’ comprehensive data during Web search interactions. Based on the grounded theory approach, qualitative analysis methods including content analysis and verbal protocol analysis were used to analyse the data. The findings were inferred through an analysis of questionnaires, a transcription of think-aloud protocols, the Web search logs, and notes on observations and interviews. Five key findings emerged. (1) Multitasking during Web searching was demonstrated as a two-dimensional behaviour. The first dimension was represented as multiple information problems searching by task switching. Users’ Web searching behaviour was a process of multiple tasks switching, that is, from searching on one information problem to searching another. The second dimension of multitasking behaviour was represented as an information problem searching within multiple Web search sessions. Users usually conducted Web searching on a complex information problem by submitting multiple queries, using several Web search systems and opening multiple windows/tabs. (2) Cognitive shifts were the brain’s internal response to external stimuli. Cognitive shifts were found as an essential element of searching interactions and users’ Web searching behaviour. The study revealed two kinds of cognitive shifts. The first kind, the holistic shift, included users’ perception on the information problem and overall information evaluation before and after Web searching. The second kind, the state shift, reflected users’ changes in focus between the different cognitive states during the course of Web searching. Cognitive states included users’ focus on the states of topic, strategy, evaluation, view and overview. (3) Three levels of cognitive coordination behaviour were identified: the information task coordination level, the coordination mechanism level, and the strategy coordination level. The three levels of cognitive coordination behaviour interplayed to support multiple information tasks switching. (4) An important relationship existed between multitasking, cognitive coordination and cognitive shifts during Web searching. Cognitive coordination as a management mechanism bound together other cognitive processes, including multitasking and cognitive shifts, in order to move through users’ Web searching process. (5) Web search interaction was shown to be a multitasking process which included information problems ordering, task switching and task and mental coordinating; also, at a deeper level, cognitive shifts took place. Cognitive coordination was the hinge behaviour linking multitasking and cognitive shifts. Without cognitive coordination, neither multitasking Web searching behaviour nor the complicated mental process of cognitive shifting could occur. The preliminary model was revisited with these empirical findings. A revised theoretical model (MCC Model) was built to illustrate the relationship between multitasking, cognitive coordination and cognitive shifts during Web searching. Implications and limitations of the study are also discussed, along with future research work.

Scheduling coordination through negotiation between train service providers in an open railway access market

A schedule coordination problem involving two train services provided by different operators is modeled as an optimization of revenue intake. The coordination is achieved through the adjustment of commencement times of the train services by negotiation. The problem is subject to constraints regarding to passenger demands and idle costs of rolling-stocks from both operators. This paper models the operators as software agents having the flexibility to incorporate one of the two (and potentially more) proposed negotiation strategies. Empirical results show that agents employing different combination of strategies have significant impact on the quality of solution and negotiation time.