Gelation of poly(vinyl alcohol) solutions at low temperatures (20 to −78°C) and properties of gels

The flow points of atactic poly(vinyl alcohol) (a-PVA) gels with H₂O/dimethyl sulfoxide (DMSO) = 90/10 (v/v) chilled at 20 to ?78°C for 24 h depended on the chilling temperature and were 0–30°C for gels with the initial polymer concentrations (C_i) of 2–5 g/dL, whereas those for H₂O/DMSO = 50/50 chilled at 0 to ?78°C were independent of the chilling temperature and were 70–75°C. Syneresis occurred after eight cycles of freezing (?24°C) and thawing (20°C) for a-PVA hydrogels at concentrations above C_i = 4 g/dL and two such cycles for syndiotacticity-rich PVA (s-PVA) hydrogels at concentrations above C_i = 1 g/dL. The extent of syneresis per one cycle for s-PVA hydrogels was higher than that for a-PVA hydrogels at the initial cycles. In the a-PVA hydrogels with an initial polymer concentration of ca. 30 g/dL, syneresis was expected not to occur even after 20 cycles. If all the free water in the gels is assumed to have transuded by syneresis after 20 cycles, the residual water is bound water and is estimated to be six water molecules per one vinyl alcohol monomer unit. © 1994 John Wiley & Sons, Inc.     

Molecular association complex of urea with polyethylene: 3. Structural studies of the complex

The crystal structure of urea-polyethylene complex in the hexagonal form, obtained by one of our preparation methods, is analysed by X-ray power diffractometry. In this analysis, the fixed molecular parameters of urea are used, and three models with respect to rotational disorder of the guest polyethylene molecule are assumed. It is shown that the host lattice structure constructed by urea molecules is essentially the same as that of urea-n-paraffin complex. Effects of the disorder structure of the guest on X-ray scattering of the complex are presented. However, there is a difficulty in identifying the disorder structure by X-ray analysis. With the aid of a potential energy calculation between the hexagonal urea tunnel and the guest molecule, a rotational disorder model is preferred.     

Effect of Silicon Dioxide on the Thermal Diffusivity of Aluminum Nitride Ceramics

The thermal diffusivity of AlN ceramics was significantly decreased by the addition of SiO₂. The AlN ceramics with 4 wt% SiO₂ could not be densified by pressureless sintering in the temperature range 1400° to 1800°C. The thermal diffusivity of these samples was very low because of their porous structure. The AlN ceramics containing 2, 4, and 8 wt% SiO₂ were densified by hot-pressing and also had low thermal diffusivity. In these samples, the grains of the 27R polytype that resulted from the reaction between AlN and SiO₂ were dispersed, obstructing the conduction of heat. The relation between the amount of 27R polytype and the thermal diffusivity of the AlN ceramics was determined.     

Hydrolysis of human horny cells by alkaline protease: Morphological observation of the process

The interaction of highly purified alkaline protease fromBacillus sp. KSM-K16 with the horny cells of human skin contained in skin grime was directly visualized by electron microscopy. It became clear that the protease first penetrates the horny cells and then adsorbs, mainly onto the internal structure of the cells at the initial stage of hydrolysis, and directly hydrolyzes the keratin filaments, though the marginal band surrounding them retains its original shape. Then, hydrolysate produced from the keratin filaments flows out of the cell, and early in the hydrolysis process keratin filaments decrease and then disappear, leaving a marginal band, i.e., the cell turns to a hollow state. As a result, the remaining marginal band loses support from inside the cell, thus promoting cleavage and dispersion. Until this stage in the protease reaction, the remarkable liberation of hydrolysis products as water-soluble protein does not occur.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

In-situ monitoring of the stabilization with hydrogen of free radicals thermally induced from coal using high pressure e.s.r., d.t.a. and p.d.a. equipment

High temperature, high pressure e.s.r. measurements of the hydrogenation reaction of Taiheiyo coal in the presence of catalysts were carried out to understand the stabilization of thermally and/or catalytically induced free radicals. A decrease in free radical concentration with increasing temperature was observed for ZnCl₂ and SnCl₂ · 2H₂O catalysts at 10MPa under hydrogen gas. High pressure modified single-cell d.t.a. and p.d.a. equipment augmented the uniquely designed high temperature, high pressure e.s.r. cell. The hydrogenation reaction was monitored under the same experimental conditions as for e.s.r. From the results of the combination of high temperature, high pressure e.s.r. with high pressure d.t.a. and p.d.a., it was established that H₂ molecules can react efficiently with free radicals from coal molecules created by the presence of ZnCl₂ and SnCl₂ · 2H₂O catalysts.     

Gelation of poly(vinyl alcohol)/phenol/water solutions and gel spinning

The light transmittance of the gels of poly(vinyl alcohol) (PVA)/phenol/water solutions was examined for the entire range of phenol/water content. Excellent transparency was found for the gels with phenol contents of 70–95 vol %. In full consideration of the results for the transparency and melting temperature of the gels and the viscosity and gelation ability of solutions, the PVA solutions of 75 vol % phenol content were selected for the gel spinning. The maximum dynamic moduli of drawn filaments at 25°C (room temperature) were 42 GPa (15x) for atactic PVA and 45 GPa (14x) for syndiotacticity-rich PVA. © 1995 John Wiley & Sons, Inc.     

Effect of perchloric acid on the molecular weight and yield of poly-THF

Polytetramethylene glycol (molecular weight range 1000–8000) was prepared by the polymerization of tetrahydrofuran (THF) using a binary catalyst system of fuming sulfuric acid and perchloric acid. When 28% fuming sulfuric acid alone was used as the catalyst, the average molecular weight of polymer was low, the maximum value being 1000–1100. By the combination of fuming sulfuric acid with a small amount of perchloric acid, the average molecular weight of the polymer was increased to about 8000. Furthermore, the molecular weight was readily controlled in the range of 1000 to 8000 by varying the amount of the binary catalyst.     

Synthesis of High-Purity Zirconium Fluoride for Fluoride Glass Fibers by Chemical Vapor Deposition

A technique for synthesizing ultra-high-purity ZrF₄ using chemical vapor deposition in a ZrBr₄–HF system is developed and a purification mechanism is clarified. The Fe concentration in ZrF₄ is evaluated at less than 10 ppb based on analysis of the transmission loss spectrum of a fiber prepared using synthesized ZrF₄. Purification is achieved mainly in a sublimation process of ZrBr₄, and purification efficiency is determined by sublimation temperature and activity of impurities in ZrBr₄. The concentration of transition-metal impurities in ZrF₄, synthesized by chemical vapor deposition in the ZrBr₄–HF system, is expected to be less than 1 ppb.     

In Situ Synthesis and Microstructures of Tungsten Carbide-Nanoparticle-Reinforced Silicon Nitride-Matrix Composites

A W₂C-nanoparticle-reinforced Si₃N₄-matrix composite was fabricated by sintering porous Si₃N₄ that had been infiltrated with a tungsten solution. During the sintering procedure, nanometer-sized W₂C particles grew in situ from the reaction between the tungsten and carbon sources considered to originate mainly from residual binder. The W₂C particles resided in the grain-boundary junctions of the Si₃N₄, had an average diameter of ∼60 nm, and were polyhedral in shape. Because the residual carbon, which normally would obstruct sintering, reacted with the tungsten to form W₂C particles in the composite, the sinterability of the Si₃N₄ was improved, and a W₂C–Si₃N₄ composite with almost full density was obtained. The flexural strength of the W₂C–Si₃N₄ composite was 1212 MPa, ∼34% higher than that of standard sintered Si₃N₄.