Sorption of water vapor into polyelectrolyte complex of poly(styrenesulfonic acid)/poly(4-vinyl-N-ethylpyridinium bromide)

Successive differential and integral sorptions of water vapor into the polyelectrolyte complex of poly (sty renesulfonic acid) / poly(4-vinyl-N-ethylpyridinum bromide) have been measured; films of stoichiometric (1/1 molar ratio) and nonstoichiometric (2/1 molar ratio) complex were employed in the experiments. Sorption isotherms have been also determined by using the values obtained from integral sorption experiments. The sorption data have suggested the following. (i) The rearrangement of polymer chains plays a relatively unimportant role in sorption of water. (ii) The relaxation motion of network chains is suppressed. (iii) The change of morphological structure caused by vapor sorption is obscure. (iv) The ionic character of the 1/1 complex is higher than that of 2/1 complex. (v) A small amount of water can be dispersed on specific polymer sites, but the sorption of a large amount of water is accompanied by an expansion of network structure. Points (i)-(v) have been consistently interpreted on the basis of the network structure and ionic character of this complex.     

Contraction of swollen coil of flexible polymer chain below theta temperature

In our previous study on thermodynamic equilibrium at infinite dilution, chain segments at the periphery of a polymer coil were shown to be more extended than the average expansion of the coil. This is because such segments are in contact with pure solvent, whereas inside the coil there is a concentration of the segments. In a subsequent work examining the low concentration range, this excess extension of the segments was shown to diminish as the concentration was increased. Having more and more neighboring coils, the chain segments at the periphery of the coil have less and less excess extension, because the concentration difference between the inside and the outside of the coil decreases. In the present work the range below the theta temperature is examined; for polymers of finite molecular weights there are soluble ranges including partial and critical miscibility. When the limits of miscibility are approached either by lowering the temperature at a constant concentration or by increasing concentration at a constant temperature, the excess extension of the chain segments at the periphery of the coil disappears. The calculation makes use of a modified Maron theory. The required input data are intrinsic viscosity and polymer-solvent interaction parameter as a function of polymer concentration. These parameters must be known as functions of temperature and molecular weight. The example used in this work is the polystyrene-cyclohexane system.     

Dynamic Light Scattering Studies on Crystallization of Isotactic Polystyrene from Dilute Solutions at High Supercoolings

Crystallization of isotactic polystyrene (it‐PS) from dilute solution at high supercooling has been investigated by dynamic light scattering (DLS). We successfully obtained simultaneously, in situ in solutions, the time developments of both random coils of it‐PS molecules and the growing crystals. The size of coils remains constant during growth, while the crystals pass through two stages, that is, an induction period at the early stage with very slow growth rates and a subsequent linear growth stage. It is confirmed that the temperature dependence of the linear growth rates, determined by DLS, agree well with that determined by electron microscopy. The temperature dependences of the growth rate and the inverse of induction time are dependent on the viscosity of solvent, which indicates that all dynamics are dominated by the segmental motion of polymer chains in solution at high supercoolings (low temperatures). Two possibilities are proposed for the induction period.     

Microstructure of Milled Mesophase Pitch-Based Carbon Fibers as an Anode Material for Li-ion Batteries

Abstract

The microstructure of milled mesophase pitch-based carbon fibers (mMPCFs) that have been developed as an anode material for Li ion batteries have been studied as a function of heat treatment temperature (HTT), by SEM, X-ray diffraction, and Raman spectroscopy. And the results obtained are compared with those by X-ray diffraction (XRD) and SEM observations, for the characterization of specific structural features of mMPCFs as a promising anode material.     

High spatial and angular resolution diffusion-weighted imaging reveals forniceal damage related to memory impairment

Introduction

Diffusion tensor imaging (DTI) measures in patients with multiple sclerosis (MS), particularly those measures associated with a specific white matter pathway, have consistently shown correlations with function. This study sought to investigate correlations between DTI measures in the fornix and common cognitive deficits in MS patients, including episodic memory, working memory and attention.

Materials and Methods

Patients with MS and group age- and sex-matched controls underwent high-resolution diffusion scanning (1-mm isotropic voxels) and cognitive testing. Manually drawn forniceal regions of interest were applied to individual maps of tensor-derived measures, and mean values of transverse diffusivity (TD), mean diffusivity (MD), longitudinal diffusivity (LD) and fractional anisotropy (FA) were calculated.

Results

In 40 patients with MS [mean age±S.D.= 42.55±9.1 years; Expanded Disability Status Scale (EDSS)=2.0±1.2; Multiple Sclerosis Functional Composite (MSFC) score=0.38±0.46] and 20 healthy controls (mean age±S.D.= 41.35±9.7 years; EDSS=0.0±0; MSFC score=0.74±0.24), we found that FA, MD and TD values in the fornix were significantly different between groups (P< .03), and patient performance on the Brief Visuospatial Memory Test-Revised (BVMT-R) was correlated with DTI measures (P< .03).

Discussion

These results are consistent with findings of axonal degeneration in MS and support the use of DTI as an indicator of disease progression.     

Pressure-induced weak moment in the two-dimensional antiferromagnet (C2H5NH3)2CuCl4

Abstract

The two-dimensional Heisenberg antiferromagnet (C₂H₅NH₃)₂CuCl₄ has the ferromagnetic intralayer exchange interaction, while the extremely weak interlayer exchange interaction is antiferromagnetic. Neutron scattering experiments under high pressures have been performed on this compound. We confirm that the spin structure changes around 1～2 GPa from the collinear alignment along the a-axis to a spin-canting one. The weak moment due to the canting is parallel to the c-axis. The results indicate that the ferromagnetic intralayer and the antiferromagnetic interlayer exchange interactions are maintained up to 1～2 GPa. Why the weak ferromagnetic moment along the c-axis occurs is due to a lowering of crystal symmetry by pressure.     

Design of New Reaction Fields for Spherical Polypyrrole Particle Synthesis

Summary: Polypyrrole conducting polymers have been investigated widely for various applications because of their thermal and environmental stability and good electrical conductivity. Using chemical oxidative polymerization for the synthesis of polypyrrole particles, the reaction rate is very fast. In this study, we designed two new reaction fields for the synthesis of spherical polypyrrole nanoparticles. In the first system, oxidative polymerization of monomer droplets infused in a water/oil (W/O) emulsion reaction field was investigated. The second system employed dispersed monomer in an aqueous solution with a low concentration of oxidant in which polymerization was augmented by ultrasonic irradiation. Effective control of the reaction rate was important for enabling the synthesis of fine spherical polypyrrole particles.     

DE-Sinc methods have almost the same convergence property as SE-Sinc methods even for a family of functions fitting the SE-Sinc methods

In this paper, the theoretical convergence rate of the trapezoidal rule combined with the double-exponential (DE) transformation is given for a class of functions for which the single-exponential (SE) transformation is suitable. It is well known that the DE transformation enables the rule to achieve a much higher rate of convergence than the SE transformation, and the convergence rate has been analyzed and justified theoretically under a proper assumption. Here, it should be emphasized that the assumption is more severe than the one for the SE transformation, and there actually exist some examples such that the trapezoidal rule with the SE transformation achieves its usual rate, whereas the rule with DE does not. Such cases have been observed numerically, but no theoretical analysis has been given thus far. This paper reveals the theoretical rate of convergence in such cases, and it turns out that the DE’s rate is almost the same as, but slightly lower than that of the SE. By using the analysis technique developed here, the theoretical convergence rate of the Sinc approximation with the DE transformation is also given for a class of functions for which the SE transformation is suitable. The result is quite similar to above; the convergence rate in the DE case is slightly lower than in the SE case. Numerical examples which support those two theoretical results are also given.     

Mechanistic study of photocatalytic CO2 reduction using a Ru(ii)–Re(i) supramolecular photocatalyst

Supramolecular photocatalysts comprising [Ru(diimine)₃]²⁺ photosensitiser and fac-[Re(diimine)(CO)₃{OC(O)OC₂H₄NR₂}] catalyst units can be used to reduce CO₂ to CO with high selectivity, durability and efficiency. In the presence of triethanolamine, the Re catalyst unit efficiently takes up CO₂ to form a carbonate ester complex, and then direct photocatalytic reduction of a low concentration of CO₂, e.g., 10% CO₂, can be achieved using this type of supramolecular photocatalyst. In this work, the mechanism of the photocatalytic reduction of CO₂ was investigated applying such a supramolecular photocatalyst, RuC2Re with a carbonate ester ligand, using time-resolved visible and infrared spectroscopies and electrochemical methods. Using time-resolved spectroscopic measurements, the kinetics of the photochemical formation processes of the one-electron-reduced species RuC2(Re)−, which is an essential intermediate in the photocatalytic reaction, were clarified in detail and its electronic structure was elucidated. These studies also showed that RuC2(Re)− is stable for 10 ms in the reaction solution. Cyclic voltammograms measured at various scan rates besides temperature and kinetic analyses of RuC2(Re)− produced by steady-state irradiation indicated that the subsequent reaction of RuC2(Re)− proceeds with an observed first-order rate constant of approximately 1.8 s⁻¹ at 298 K and is a unimolecular reaction, independent of the concentrations of both CO₂ and RuC2(Re)−.

Formation processes and reactivity of an important intermediate of photocatalytic CO₂ reduction, one-electron reduced species of a Ru(ii)–Re(i) supramolecular photocatalyst with a carbonate ester ligand, were investigated in detail.     

Oxidation behaviour of Ni nanoparticles and formation process of hollow NiO

The oxidation behaviour of Ni nanoparticles at temperatures from 573 to 673 K and the formation process of hollow oxide particles were studied by transmission electron microscopy. In the course of oxidation, a single large void was observed at one site of the interface between inner Ni and outer NiO layer due to vacancy clustering, which occurs during the oxidation process resulting from the rapid outward diffusion of Ni ions through the NiO layer. This suggests that supersaturated vacancies generated at the interface migrate to the site over a long-range distance and aggregate at the site. Ni nanoparticles were fully oxidized to become hollow NiO, in which nano-holes in the form of vacancy clusters were located at the off-centred positions. The de-centring of the voids in hollow NiO is probably due to the large mobility of vacancies inside Ni during oxidation.