Effect of the addition of NH4F on anodic behaviors of DSA-type electrodes in H2SO4-(NH4)2SO4 solutions

The effect of NH₄F addition on the high-anodic behaviors of various DSA-type electrodes was investigated in a mixture of sulfuric acid and ammonium sulfate. The pronounced effect of NH₄ addition was observed on DSA-type Ti/RuO₂, Ti/IrO₂?TiO₂ electrodes, but not observed on the other electrodes studied. The close relationship was found between the increment of the electrode potential caused by the NH₄ addition and the quantity of F^? adsorbed on the electrode surface. The effect of NH₄F addition was considered to be resulted from the adsorption of F^? on the electrode surface, and the presence of adsorbed F^? was directly proved.     

Creep rupture properties of homopolymer,copolymer, and terpolymer based on poly(oxymethylene)

Polyacetal copolymers were prepared by cationic ring‐opening copolymerizations of 1,3,5‐trioxane (TOX) with 1,3‐dioxolane (DOX), and polyacetal terpolymers were prepared by terpolymerizations of TOX, DOX, and 2‐ethylhexyl glycidyl ether (EHGE). Polyacetal polymers with three different structures such as polyacetal homopolymers, polyacetal copolymers, and polyacetal terpolymers were compared in the mechanical properties and the creep characteristics, and discussed from the view point of the polymer structure. The polyacetal copolymers and the polyacetal terpolymers were determined by ¹H‐MNR measurement. About 80 mol % of DOX and EHGE amounts in feed were incorporated randomly into the each polymer. From the plots of the degree of crystallinity (X_c) versus the tensile strength, the tensile strength and crystallintiy of the polyacetal homopoymers are higher than those of the polyacetal copolymers and the polyacetal terpolymers. However, the tensile strength does not decrease linearly with a decrease in the crystallinity among the polyacetal polymers with three different structures, the polyacetal homopolymer, the polyacetal copolymers, and the polyacetal terpolymers. Creep rupture was characterized by the activation volume, υ_c, value in Zhurkov's equation, which can be estimated from the slope in the plots of load versus log (rupture time) at 80°C. The polyacetal polymers with higher molecular weight have larger values of the activation volume than those with lower molecular weight. When the activation volume values are compared among the polyacetal polymers with the same molecular weights, they increase in the following order: the polyacetal homopolymers < the polyacetal copolymers < polyacetal terpolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Heterogeneous nucleation of organic vapours on a cold substrate

The heterogeneous phase transition of the organic vapours, cyclohexane and p-xylene, on a cold substrate was observed by cooling the substrate at a slow rate under reduced pressure conditions. Either organic vapour at a vapour pressure lower than 130 Pa formed directly solid crystals but p-xylene vapour at a higher vapour pressure formed liquid condensates with subsequent formation of solid crystals. The dependence of the critical supersaturation ratios on the critical temperatures and the physical properties of the organic vapours has been clarified by the equation derived on the basis of classical nucleation theory.     

Positive-temperature-coefficient effect of electrical resistivity below melting point of poly(vinylidene fluoride) (PVDF) in Ni particle-dispersed PVDF composites

This paper discusses the positive-temperature-coefficient effects of resistivity in Ni particle-dispersed poly(vinylidene fluoride) (PVDF) composites based on experiment results from SEM, DSC, and pressure-volume-temperature (PVT) measurements. The melting points of composites with Ni content of 20, 30, 40, and 50vol.% were equal to that of pure PVDF. The PTC effects in composites with Ni content of 40 and 50vol.% occurred at temperatures near the melting point of the PVDF matrix, whereas those in composites with Ni content of 20 and 30vol.% occurred at temperatures below the melting point of the PVDF matrix. We found that the PTC effect occurs even without melting of the matrix polymer. Moreover, we determined that a slight increase in specific volume at temperatures below the melting point of the matrix polymer acts fully as a driving force for forming a gap between fillers. This suggestion was backed up by theoretical analyses using percolation theory and a thermal-fluctuation-induced tunneling model.     

Preparation of TiO2 thin films using octadecylamine Langmuir-Blodgett films and evaluation of their photocatalytic activity

A study was conducted to demonstrate that nanometer-thick titanium dioxide (TiO(2)) thin films could be prepared by the hydrolysis of titanium potassium oxalate using octadecylamine (ODA) Langmuir-Blodgett (LB) films as templates. The amount of TiO(2) generated in the LB film was found to be proportional to the number of deposited ODA layers, which enables precise control of the TiO(2) film thickness. After heat treatment of the LB films at 300-600°C, the photocatalytic activities of the resulting TiO(2) films were determined from the decomposition of stearic acid cast films when irradiated with UV light for different time periods. Higher photocatalytic activity was observed in TiO(2) films heat treated at lower temperatures.     

Fabrication and characterization of poly‐γ‐glutamic acid nanofiber

Poly‐γ‐glutamic acid (γ‐PGA) is a natural polymer that is widely recognized as a component in the viscous filaments of fermented soybean (natto). γ‐PGA is known for its superior biodegradability, biocompatibility and water retention characteristics. Crosslinked γ‐PGA is commonly used as a hydrogel, but it is not used in the fiber form because it is soluble in water. In this study, we demonstrate the use of γ‐PGA‐Na for production of water insoluble γ‐PGA nanofibers by electrospinning. This result was accomplished using an aqueous solvent containing 10 wt % of an oxazoline component polymer as the crosslinking agent and by heat treatment. The crosslinking reaction was evaluated by solid‐state NMR. The nanofiber webs showed a high level of moisture absorption capability while retaining their fibrous shape. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improving the gas recovery and separation efficiency of a hydrate-based gas separation

Efficient gas recovery and separation in a hydrate-based system was investigated for a model gaseous mixture of R22 and nitrogen. The formed hydrate settled in the recovery vessel; excess water was recycled and the hydrate was subsequently decomposed by releasing pressure from the vessel. The gas uptake rate of R22 gas from the vapor phase and the gas recovery rate from the hydrate were determined from hydrate formation and decomposition, respectively. The gas recovery rate of R22 gas gradually increased with time. On the contrary, the nitrogen gas recovery rate was a maximum in the initial stage of hydrate decomposition. A high separation factor (S.F.) was achieved by first separating the N₂-rich gas generated during initial hydrate decomposition. An efficient hydrate-based gas separation and recovery process is proposed.     

Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Anisotropic structure of alkali metaphosphate glasses

Orientation anisotropy, which is well known in organic polymers with appropriate network structures, is less common in oxide glasses. We present the intermediate-range order in anisotropic alkali metaphosphate glass which consists of oriented PO₄ tetrahedral chains and intervening alkali cations along the elongation direction. The X-ray total structure factor S(Q) indicates that the inter-chain spacing depends on the size of alkali cations and varies from 5.03 to 6.28 Å. The mixed alkali effect is primarily related to an increase of the separation. The total correlation function T(r) provides the first definite evidence that the anisotropic structure is composed of phosphorus-bridging oxygen bonds (P–O_B) lying along the elongation direction and phosphorus-non-bridging oxygen bonds (P–O_T) oriented perpendicular to the elongation direction. The present result unveils fundamental aspects of the anisotropic structure of an oxide glass and provides essential information for the development of oxide glasses to control structural anisotropy.