Diffusion/adsorption model of cellulose dyeing. II. Ordinary cellulose–direct dye system

The diffusion and adsorption of C.I. Direct Yellow 12 and Blue 15 in water-swollen ordinary cellophane sheets were examined at various ionic strengths. The concentration dependence of apparent diffusion coefficients, D_c, for these dyes was obtained from the diffusion profiles in the substrate, which were measured by the use of the cylindrical film roll method. The decrease of apparent porosity with an increase in the amounts of adsorption was observed. To explain the diffusion/adsorption behaviors of these systems, a variable porosity model was proposed and was applied to analyze the concentration dependence of D_c's. The diffusion/adsorption behaviors of these dyes could be quantitatively described by this model at relatively low ionic strengths. At higher ionic strengths and/or lower values of C, i.e., at the large values of C_im/C_m, where the C's are the concentrations of immobilized (suffix im) and mobile (suffix m) species, it needed to introduce the concept of dynamic equilibria which occurred simultaneously with diffusion but deviated from the true equiliblia measured by the adsorption experiments.     

Depolymerization of fluoroalkyl methacrylate polymers as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate) prepared by γ-or UV-ray polymerization were investigated by using thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of fluoroalkyl methacrylate polymers, monomeric units of which were CH₂=C(CH₃)COOCH₂(CF₂CF₂)_nH, n = 1, 2, and 3, proceeded according to the depolymerization mechanism reproducing the pristine monomer exclusively, but the thermogram in inert atmosphere showed the features of a two-step reaction. Two species of polymer differing in the heat stability were supposed to exist in the polymeric substance produced by γ- or UV-ray irradiation, and the fraction of polymer having lower heat stability increased with the increasing length of the fluoroalkyl ester group. In air, however, the thermogram of poly(fluoroalkyl methacrylate) showed no such a stepwise weight decrease as was observed in inert atomsphere with the elevating temperature, and the temperatures at which the depolymerization was introduced shifted to a much higher region. The results were ascribed to the reaction of initiating polymer radicals produced on polymer having lower stability with oxygen to form hydroperoxide, which once stabilized the polymer radicals and obstructed the initiaition of the unzipping reaction till higher temperature.     

A rheo-optical study on the reformation of structure in racemic poly(γ-benzyl glutamate) liquid crystals

Transmitted light intensities were measured by means of the polarized light technique for the nematic liquid crystal phase of racemic poly(γ-benzyl glutamate) (PBG) in m-cresol at 25°C after cessation of steady flow at shear rates ranging from 0.2 to 110 s^?1. Weight-average molecular weights of PBG used were 1.5, 2.1, and 2.6 × 10⁵, while the concentrations varied between 20, 30, and 40 wt percent. Transmitted light intensities with crossed and parallel polarizers, I_x and I_|, show wavy changes with time after cessation of steady flow, indicating the retardation decreases with time. An attempt was made to explain experimental results on the basis of a simple model, in which not only relaxation of molecular orientation but also effects of the wall and disclination were taken into account.     

Photo-induced super-hydrophilic property and photocatalysis on transparent Ti-containing mesoporous silica thin films

The transparent Ti-containing mesoporous silica thin films can be prepared on quartz plate using a spin-coating sol–gel method. The spectroscopic characterization has revealed that the Ti-containing mesoporous silica thin films contain isolated and tetrahedrally-coordinated titanium oxide moieties in the frameworks. Compared with the common mesoporous silica thin films, these Ti-containing mesoporous silica thin films have demonstrated a strong hydrophilic surface property even before UV-irradiation. After UV-light irradiation, the contact angle of water droplet on the Ti-containing mesoporous silica thin films became lower, indicating the appearance of the super-hydrophilic property. Under UV-light irradiation Ti-containing mesoporous silica thin films also exhibited highly selective activity for the photocatalytic oxidation of propylene. The isolated and tetrahedrally-coordinated titanium oxide moieties are responsible for these photo-induced surface reactions.     

Graft polymerization of triethoxyvinylsilane–styrene and triethoxyvinylsilane–methyl methacrylate binary monomers onto various silicates

Triethoxyvinylsilane–styrene and triethoxyvinylsilane–methyl methacrylate binary monomers were polymerized by chemical initiation or by γ-ray irradiation in the presence of silica gel, fire brick, quartz wool, and glass beads. The amount and composition of the polymers grafted to silicates were analyzed by using pyrolysis gas chromatography. When triethoxyvinylsilane alone was subjected to the reaction with silicates, condensation occurred irrespective of the initiating means, and the extent of the reaction was almost proportional to the specific surface area of the silicate. When binary monomer mixture was applied, incorporation of styrene or methyl methacrylate into the grafted polymer was observed whenever a monomer mixture of high styrene or methyl methacrylate content was submitted to the reaction. On each silicate, the relationship between the composition of polymer grafted on it and that of monomer showed a similar pattern in spite of the great difference of the specific surface area. Almost no participation of styrene or methyl methacrylate was observed when the silicate preirradiated in air or under vacuum was heated with the binary monomer mixture. It was concluded that triethoxyvinylsilane reacts with silicates by condensation and that some of the pendent vinyl groups on the silicates are incorporated into the copolymer with styrene or methyl methacrylate.     

Diffusion/adsorption model of cellulose dyeing. I. The diffusion through never-dry cellulose

The diffusion coefficients D₀, of C.I. Direct Yellow 12, Red 2, Blue 1, and Blue 15 in aqueous NaCl solution were measured at 90°C by the diaphagm cell method. The values of D₀ for Yellow 12 and Red 2 showed a salt concentration dependence and those for Blue 1 and Blue 15 were constant over the ionic strength range from 0.01 to 0.10. In the adsorption/diffusion models proposed so far for the direct dye–cellulose system, the Standing–Warwicker–Willis model was shown to be similar in principle to the Weisz–Zollinger model. The adsorption/diffusion behaviors in never-dry cellophane sheet for C.I. Direct Yellow 12 and Blue 15 were examined by the method of cylindrical film roll at 90°C. The concentration dependence of the apparent diffusion coefficient for these dyes showed an incomplete validity of both the models.     

Cold Spraying of TiO<Subscript>2</Subscript> Photocatalyst Coating With Nitrogen Process Gas

Titanium dioxide (TiO₂) is a promising material for photocatalyst coatings. However, it is difficult to fabricate a TiO₂ coating with anatase phase by conventional thermal spray processes due to a thermal transformation to rutile phase. In this paper, anatase TiO₂ coatings were fabricated by the cold spray process. To understand the influence of process gas conditions on the fabrication of the coatings, the gas nature (helium or nitrogen) and the gas temperature are investigated. It was possible to fabricate TiO₂ coatings with an anatase phase in all spraying conditions. The process gas used is not an important factor to fabricate TiO₂ coatings. The thickness of the coatings increased with the process gas temperature increasing. It indicates that the deposition efficiency of the sprayed particles can be enhanced by controlling the spray conditions. The photocatalytic activity of the coatings is similar or better than the feedstock powder due to the formation of a large reaction area. Concludingly, cold spraying is an ideal process for the fabrication of a TiO₂ photocatalyst coating.     

Effects of sintering additives on dispersion properties of Al2O3 slurry containing polyacrylic acid dispersant

The effects of sintering aid adsorption on the dispersion properties of aluminum oxide slurries were investigated. We considered Al₂O₃ slurry without additives and Al₂O₃ slurry with a Mg additive with 0.1 mass% in oxide equivalent as a sintering aid. In this study, we evaluated the adsorption isotherm of polyacrylic acid (PAA) onto Al₂O₃ and the dispersion degree of Al₂O₃ slurries in sedimentation tests under gravity. The adsorption isotherm featured a characteristic adsorption isothermal line with a maximum value when Mg additive was present in Al₂O₃. In addition, the packing fractions did not correspond to the apparent viscosity. However, in slurry that was allowed to settle for several days, both of them agreed.Therefore, the disagreement between the packing fraction and the apparent viscosity immediately after preparation arose from changes of the dispersion state, such as the decrease of the distance between particles with time.