Iodine reaction of vinyl acetate/vinyl propionate copolymers. III. Iodine affinities of the radically polymerized copolymers and the copolymers derived from partially saponified polyvinyl acetate

The minimum sequence lengths (n_c) of vinyl acetate (VAc) units necessary to form a colored iodine complex were determined to be 4 and 17 for radically polymerized VAc/vinyl propionate (VPr) and VAc/isopropenyl acetate (IPAc) copolymers, respectively. The iodine affinities (I/VAc) of VAc/VPr copolymers (SP-series) obtained by propionylation of partially saponified polyvinyl acetate (PVAc) were remarkably affected by the saponification conditions. An increase of the water content in acetone/water mixture as saponification solvent brought about a decrease of the iodine affinities of the SP-series. The dependence of the iodine affinity on the saponification of monomer units in the SP-series was compared with that in the radically polymerized VAc/VPr copolymers by taking the sequence probability as the measure of monomer unit distribution. The results strongly supported an occurence of the slide fastener reaction at high degrees of saponification, which was well-known in the saponification of PVAc. Furthermore, it was found that the saponification mode of PVAc at low degrees of saponification was influenced uniquely by the water content in saponification solvents and the saponification temperature.     

Novel method of preparing Ag–Hg alloy on polyacrylamide films and their structure

A novel method is proposed of preparing thin Ag–Hg alloy on PAAm film surface at room temperature: The film of interest is formed by holding PAAm aqueous solution with AgNO₃ in Hg-saturated atmosphere. Two kinds of films, one of which is a conductor and the other an insulator, can be selectively formed with pH-controlled PAAm solution by ammonia. The conducting surface is assigned to the α phase of Ag–Hg alloy by means of X-ray analysis. Potentiometric titration and IR spectral studies suggest the existence of PAAm–Ag⁺ complexes. On the basis of their structure and the oxidation and reduction potential of Ag⁺ and Hg²⁺, the mechanism of film formation is also discussed.     

Temperature Dependence of KIC for High-Pressure Hot-Pressed Si3N4 Without Additives

Temperature dependence of K_IC values for Si₃N₄ bodies sintered at high pressures without additives was studied from room temperature to 1400°C. Little change in K_K was found in this range.     

Balanced corpus of contemporary written Japanese

The balanced corpus of contemporary written Japanese (BCCWJ) is Japan’s first 100 million words balanced corpus. It consists of three subcorpora (publication subcorpus, library subcorpus, and special-purpose subcorpus) and covers a wide range of text registers including books in general, magazines, newspapers, governmental white papers, best-selling books, an internet bulletin-board, a blog, school textbooks, minutes of the national diet, publicity newsletters of local governments, laws, and poetry verses. A random sampling technique is utilized whenever possible in order to maximize the representativeness of the corpus. The corpus is annotated in terms of dual POS analysis, document structure, and bibliographical information. The BCCWJ is currently accessible in three different ways including Chunagon a web-based interface to the dual POS analysis data. Lastly, results of some pilot evaluation of the corpus with respect to the textual diversity are reported. The analyses include POS distribution, word-class distribution, entropy of orthography, sentence length, and variation of the adjective predicate. High textual diversity is observed in all these analyses.     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.     

A new maritime lifesaving multiple-effect solar still design

This paper presents a new maritime lifesaving multiple-effect solar still design where several extended wicks feed seawater to their evaporating areas by capillary force, and the resulting water vapor diffuses and condenses on facing wicks with the condensate flowing through the wicks into storage bags. A theoretical analysis showed that a temperature drop through diffusion layers between evaporating and condensing wicks slowly increases in the main evaporating areas and rapidly near salt depositions whereas the evaporation rate decreases slowly in the main area and rapidly near salt depositions. These changes are caused by increases in salt concentrations and resulting boiling point elevation. With steady-state transfer analysis, the proposed still is predicted to produce about 15 kg m ⁻²d⁻¹ fresh water on a sunny day of 22 MJm⁻²d⁻¹ solar radiation, showing a potential to be a maritime lifesaving desalinator.     

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.     

Mechanisms of CO2 separation by microporous crystals estimated by computational chemistry

The diffusion and adsorption of CO₂ inside the pores of Li, Na, and K ion-exchanged X-type zeolites were simulated by molecular dynamics and Monte Carlo calculations. Carbon dioxide diffused inside the zeolites pores while it was colliding with pore walls. Then it stayed in a super cage of zeolites. Inside the pore of Li ⁺ ion-exchanged X-type zeolite (Li-X), the electrostatic potential term was −570 kcal/mol, this value was considerably smaller than those of CO₂ inside the pores of Na-X and K-X. On the other hand, from Monte Carlo calculations, CO₂ was found to strongly absorb near the 3B site for Li ⁺ ions. When CO₂ passed through the pores of alkali ion-exchanged X-type zeolites, the interaction between the CO₂ molecule and the 3B site for Li cation was fairly large.     

Morphological study by TEM on uniaxially oriented thin films of PET, PEN and their blends

Uniaxially oriented thin films of poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) and their blends were prepared by applying shear strain to their respective melts, and the resulting morphologies were studied by transmission electron microscopy. Selected-area electron diffraction of each film revealed well-defined uniaxial orientation of polymer chains in the shearing direction. In the uniaxially oriented thin film of PEN, stacked-lamellar structure with the average long period of 27 nm consisting of a crystalline region about 15 nm thick and an amorphous one about 12 nm thick was found here and there in the dark-field image: PEN-type. On the other hand, stacked-lamellar structure was rarely observed in the case of PET: PET-type. In PET/PEN blends, the morphologies changed from the PET-type to the PEN-type with increasing content of PEN.     

Glass transition behavior of emulsion-polymerized polymer films containing a surface-active agent

The glass transition behavior of emulsion-polymerized poly(methyl methacrylate) and polystyrene films containing sodium laurylsulfate as emulsifier was studied by measurements of dynamic mechanical properties and thermal depolarization current. The film specimens of the emulsion-polymerized polymers were prepared by casting from their benzene solutions. The glass transition temperatures of the emulsion-polymerized films are higher than those of the bulk-polymerized films. The higher glass transition temperature of the emulsion-polymerized films is attributed to the colloidal properties of sodium laurylsulfate in the process of the film formation. The restriction of the molecular chains in the emulsion-polymerized films is attributed to the interaction between the hydrophobic groups of sodium laurylsulfate and the polymer molecules.