Characterization of thermal diffusion in polymer solutions by thermal field-flow fractionation: Dependence on polymer and solvent parameters

The thermal diffusion coefficient D_T has been obtained for 17 polymer-solvent combinations, each of them spanning a range of polymer molecular weights, using thermal field-flow fractionation. The polymers examined include polystyrene, poly(alpha-methyl)styrene, polymethylmethacrylate, and polysioprene. The solvents include benzene, toluene, ethylbenzene, tetrahydrofuran, methylethylketone, ethylacetate, and cyclohexane. Although D_T was confirmed as essentially independent of polymer molecular weight, it was found to vary substantially with the chemical composition of polymer and solvent. The results were used to evaluate several thermal diffusion theories; the agreement with theory was generally found to be unsatisfactory. Attempts were then made to correlate the measured thermal diffusion coefficients with various physicochemical parameters of the polymers and solvent. A good correlation was found in which D_T increases with the thermal conductivity difference of the polymer and solvent and varies inversely with the activation energy of viscous flow of the solvent.     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

Stability and slightly supercritical oscillatory regimes of natural convection in a 8:1 cavity: solution of the benchmark problem by a global Galerkin method

The global Galerkin method is applied to the benchmark problem that considers an oscillatory regime of convection of air in a tall two‐dimensional rectangular cavity. The three most unstable modes of the linearized system of the Boussinesq equations are studied. The converged values of the critical Rayleigh numbers together with the corresponding oscillation frequencies are calculated for each mode. The oscillatory flow regimes corresponding to each of the three modes are approximated asymptotically. No direct time integration is applied. Good agreement with the previously published results obtained by solution of the time‐dependent Boussinesq equations is reported. Copyright © 2004 John Wiley & Sons, Ltd.     

An improved numerical simulator for multiphase flow in porous media

In basin modelling the thermodynamics of a multicomponent multiphase fluid flux are computationally too expensive when derived from an equation of state and the Gibbs equality constraints. In this article we present a novel implicit molar mass formulation technique using binary mixture thermodynamics. The two proposed solution methods, with and without cross derivative terms between components, are based on a preconditioned Newton‐GMRES scheme for each time‐step with analytical computation of the derivatives. These new algorithms reduce significantly the numerical effort for the computation of the molar masses, and we illustrate the behavior of these methods with numerical computations. Copyright © 2004 John Wiley & Sons Ltd.     

Particle correlations in e + e − → W + W − events

Preliminary results are reported on the two-particle correlation function R(Q) in hadronic Z decays, fully hadronic WW decays, and mixed hadronic-leptonic WW decays using data collected by the DELPHI detector at LEP at energies between 189 and 206 GeV. Evidence for Bose-Einstein correlations was observed in all three cases. The event mixing technique was used to determine correlations between particles arisingfrom different W bosons in fully hadronic WW decays. An excess of like-sign particle pairs with low four-momentum difference in fully hadronic WW events is observed, consistent with the effect expected from correlations between identical particles from different W bosons.     

Pretransition state and structural transition in a deformed crystal

Physics of the Solid State - It is shown theoretically that a deformed crystal exhibiting structural instability can be treated as a quantum system of pseudospins. The quantum behavior of atoms...     

Synthesis and association of poly(N,N‐dimethylacrylamide) copolymers with perfluorocarbon pendent groups connected through polyethylene‐glycol tethers

The synthesis is reported of copolymers of N,N‐dimethylacrylamide (DMA) and methacrylates containing 2,2′‐dihydroperfluorodecanoyl (RF) groups separated from the methacrylate by long polyethylene glycol (PEG) tether groups (between 1000 and 14,000 Da). At concentrations of between 1 and 8 wt % the copolymers with macromonomer contents of 1 mol % or less give gels in organic solvents such as dioxane, THF, or methanol, as well as in water. Given the low molecular weights, this indicates very efficient association of very low numbers of RF groups. Association and gel formation is enormously enhanced in the presence of longer PEG tethers. This is consistent with smaller poly(N,N,‐dimethylacrylamide) (PDMA) intermolecular excluded volume effects that are mediated by the longer PEG tethers and possibly by the incompatibility of PEG and PDMA that may lead to the formation of PEG microdomains. This increases the local concentrations of the RF groups in the PEO domains that are not diluted by the PDMA chains, as would be the case in the absence of PEG tethers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 360–373, 2004     

Living polymerization of styrene initiated by mercaptan/ε‐caprolactam

The bulk polymerization of styrene initiated by ?‐caprolactam (CL) and n‐dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, ¹H NMR, and ¹³C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The results reveal that the initial polymerization starts from thiol via a chain‐transfer reaction, and the propagation proceeds by the insertion of a monomer between the terminal group and the intermediate structure of lactam. Finally, the polymerization kinetics have been examined. The polymerization rate varies linearly with the concentration of CL and RSH, and this confirms the mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4976–4993, 2004