Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Physical properties of silk fibers treated with ethylene glycol diglycidyl ether by the pad/batch method

This paper deals with the epoxide treatment of silk fabrics by the pad/batch method. The optimum reaction conditions, i.e., NaOH concentration, and reaction temperature were 2.5 g/L and 30°C, respectively. A weight gain of 8.5% was attained at a reaction time of 6 h. This value slightly increased to 10% after 24 h. The reactivity of tyrosine and basic amino acid residues was dependent on the reaction time and did not significantly differ from the results of epoxide-treated silk fiber by the conventional method in tetrachloroethylene. The moisture regain slightly decreased at 4% weight gain and then increased with the epoxide content, exceeding the value of the untreated control. The crease recovery of the epoxide-treated silk fabrics measured in the wet state was significantly improved, whereas that in the dry state was almost unchanged. The rate of photoyellowing of the epoxide-treated silk fabrics by the pad/batch method was reduced significantly compared with that of the untreated control. Among the mechanical properties, elongation at break and tensile modulus remained unchanged, whereas the tensile strength slightly increased following the epoxide reaction. The thermal properties were evaluated by DSC and TGA and on the basis of the dynamic viscoelastic measurements. The DSC curve of the epoxide-treated sample showed a slight increase of the decomposition temperature of silk fibroin. The rate of weight loss determined by TGA remained unchanged regardless of the chemical modification, whereas the peak of loss modulus became broader and shifted to lower temperature. The X-ray diffractograms showed that the crystalline structure of silk fibers was not affected by the reaction with epoxides. © 1993 John Wiley & Sons, Inc.     

Chemical modification of silk with aromatic acid anhydrides

Bombyx mori silk fibers were chemically modified by acylation with aromatic acid anhydrides, such as phthalic and o-sulfobenzoic anhydrides. We examined the reactivity of these modifying agents toward silk fibers, the physical and thermal properties, and the dyeing behavior with acid and cationic dyes. The o-sulfobenzoic anhydride was more reactive toward silk fibroin than phthalic anhydride. The amount of both basic and acidic amino acid residues decreased after modification with aromatic acid anhydrides. The moisture regain of silk treated with phthalic anhydride remained almost unchanged, while that of the samples modified with o-sulfobenzoic anhydride increased linearly as the weight gain increased. Chemically modified silk fabrics showed improved crease recovery behavior, even though phthalic anhydride seemed more effective at comparatively low weight gain. The modification of silk with o-sulfobenzoic anhydride caused a drastic a reduction of acid dye uptake and enhanced the affinity of silk for cationic dye. Silk fibers did not show any significant change in thermal behavior, regardless of the modification with o-sulfobenzoic anhydride. Silk fibers modified with phthalic anhydride showed on differential scanning calorimetry (DSC) curves a minor and broad endothermic peak at around 210°C, attributed probably to the breaking of the crosslinks formed between adjacent fibroin molecules.     

Electrochemical formation of AlN in molten LiCl-KCl-Li3N systems

Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li₃N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li⁺/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure.     

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.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Method for correcting molecular weight from gel-permeation chromatography. I. Skewing and concentration corrections

The purpose of this paper is to present a metod to calculate real molecular weight averages of polymer samples from GPC chromatograms where the instrumental spreading functions are skewed and the concentration effect exists. In this method, it is assumed that (1) the skewed chromatograms of monodisperse polymer samples can be represented as resultant of halves of two different Gaussians, (2) the resolution factors are regarded as constant in the case of low sample loading, and (3) the peak elution volume is independent of the presence of other components in the case of low sample loading. Adequate monodisperse polystyrenes and the mixtures (binary, seven and ten components) were examined for this purpose; and the molecular weight averages calculated by this method were compared with the ones obtained by Rosen and Provder's method. From the results in our study, it is found that this method can be available for correcting molecular weight from GPC chromatograms except for very narrow high molecular weight samples.     

OXIDATION OF SULFUR DIOXIDE IN DIFFERENT TYPES OF THREE PHASE REACTORS

Five different types of three-phase reactors are compared with each other by using oxidation of sulfur dioxide on activated carbon. The kinetic measurements were carried out by changing concentrations of sulfur dioxide from 0.04 to 0.17% (volume) and those of oxygen from 2 to 21%. The reaction rate was 0.2 order with respect to sulfur dioxide and 0.5 order with respect to oxygen. The catalytic effectiveness factor and intraparticle diffusivity were evaluated by changing particle sizes of activated carbon from 0.03 to 1.6 mm. Resistances of gas-liquid, liquid-solid mass transfer and intraparticle diffusion were estimated for individual reactors. The optimum reactor was dependent on operating conditions such as gas flow rates, rotating speeds and particle sizes.     

Ethylene carbonate-based organic electrolytes for electric double layer capacitors

A new electrolytic solution based on a mixed solvent of ethylene carbonate (EC) with sulfolane (SL) or -butyrolactone (-BL) has been examined as an electric double layer capacitor. Fundamental properties, such as electrolytic conductivity, viscosity, and thermal stability, were measured for solutions containing quaternary alkylammonium salts as the supporting electrolyte. Maximum conductivities were obtained for the solutions with mixed solvent of 20–40 mol % EC in the EC+-BL system: 1.2–1.3×10^–2S cm^–1 for EC+-BL dissolving 0.5 M Et₄ NBF₄ (Et=C₂H₅). The electrochemical and the thermal stabilities of the solution were dependent on the electrolytic salt as well as the solvent composition. A stable discharge capacitance and a high coulombic efficiency were obtained in a model capacitor using carbon fibre electrodes and the organic electrolyte of EC+-BL/Et₄NBF₄ (or EC+-BL/Et₄NPF₆).     

Application of the Solvothermal Process in the Synthesis of High-performance Ag/γ-Al_2O_3 Catalysts

1 INTRODUCTION Since Cu-ZSM-5 was reported as an effective catalyst for the selective catalytic reduction (SCR) of NO by hydrocarbons in the presence of excess oxygen, the SCR of NOx has received much attention as a kind of potential technology for cleaning NOx in various oxygen-rich exhausts of diesel engine, lean burning gasoline engine and gas engine. Although a number of catalysts have been tested, to date, it still seems to be difficult to find a catalyst that is completely suit…