Syntheses and conformational studies of poly(S-menthyloxycarbonylmethyl l- and d-cysteines)

S-menthyloxycarbonylmethyl l- and d-cysteines were prepared by the reaction of l- or d-cysteine and (?)-menthyl chloroacetate in liquid ammonia and were then polymerized to poly(S-menthyloxycarbonylmethyll- and d-cysteines) by the N-carboxyanhydride (NCA) method. From the results obtained by means of infra-red spectra, X-ray diffractions, optical rotatory dispersions (o.r.d.), and circular dichroisms (c.d.), $\text{poly}\text{(S-}\text{menthyloxycarbonylmethyl-}\text{l}\text{-cysteine}\text{)}$ was found to be a right-handed α-helix in the solid state and in ethyl ether/chloroform and chloroform solutions. Similarly, $\text{poly}\text{(S-}\text{menthyloxycarbonylmethyl-}\text{d}\text{-cysteine}\text{)}$ was a left-handed α-helix. The helix-coil transition of these polymers was observed in the vicinity of 3–4% trifluoroacetic acid (TFA) in chloroform/TFA mixtures.     

Microstructure and Thermal Shock Resistance of Molten Glass-Coated Carbon Materials Fabricated by Interfacial Control

Carbon substrates were coated completely with a molten silicate glass, where the wettability of carbon to glass was improved by infiltration and pyrolysis of perhydropolysilazane. Microstructures of the carbon–glass interface were dependent on P n ₂ during coating. Coating at lower P n ₂ induced the formation of cristobalite at the carbon–glass interface. When the coating was performed at higher P n ₂, the glass and carbon were strongly adhered, without the formation of cristobalite. Coating at higher P n ₂ improved the thermal shock resistance of the glass layer, because crack initiation was not induced by the phase transformation of cristobalite during the cooling process. In the case of coating at higher P n ₂, an oxynitride glass layer was formed at the glass subsurface by dissolution of N₂. A porous glass subsurface layer with uniform spherical micro-pores could be produced by soaking near the glass transition temperature in a steam environment. The porous layer with fine and homogeneous microstructure acts as a thermal shock absorbing layer, so that glass-coated carbon with a porous glass layer has excellent thermal shock resistance in addition to steam oxidation resistance.     

Spherical Aluminum Nitride Fillers for Heat-Conducting Plastic Packages

It is necessary for encapsulants to have not only a suitable coefficient of thermal expansion (CTE) compatible to IC devices and a low dielectric constant to reduce the device propagation delay, but also a high thermal conductivity to dissipate large amounts of heat from power-hungry, high-speed IC and high-density packages. Fillers such as silica have been mixed with polymers to improve their properties. Aluminum nitride (AlN) is considered as an alternative one, because it has a higher theoretical thermal conductivity of ∼320 W/mK¹, a compatible CTE with silicon chips and a low dielectric constant. Commercial AlN fillers are angular in shape, because they are prepared via grinding coarse AlN powders synthesized by direct nitridation of aluminum metal and classification. The angular AlN are not expected to have high fluidity when mixed with polymers and hence low packing density. Recently, we successfully obtained single-crystalline spherical AlN fillers. Furthermore, polymer composites filled with the spherical AlN showed excellent thermal conductivity (>8 W/mK) as encapsulants for dissipating the heat generated in electronic devices.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

An improved prediction result of entropic‐FV model for vapor–liquid equilibria of solvent–polymer systems

In this work, entropic expressions of UNIFAC‐FV and Entropic‐FV models were evaluated by using an extensive database of infinite dilution vapor–liquid equilibrium (VLE) data of athermal systems containing polypropylene, polyethylene, and polyisobutylene. For the infinite dilution athermal systems, performance of the Entropic‐FV model was better than that of the UNIFAC‐FV model. Then, finite concentration VLE data of non‐athermal systems that consisted of 16 polymers and 36 solvents containing a large variety of solvent–polymer systems ranging from nonpolar to polar substances were considered to optimized 46 pairs of group interaction parameters of the Entropic‐FV model. For systems containing polar solvents of three types of solvents studied, revised group interaction parameters gave significant improvements from 17.9 to 13.0% average absolute deviation (AAD) of solvent activities. For overall results, improvements were achieved from 15.1 to 12.4% AAD. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1145–1153, 2005     

Preparation and morphology of electrically conductive and transparent poly(vinylchloride)-polypyrrole composite films

Summary The chemical process of preparing poly(vinylchloride)-polypyrrole composite films with high electrical conductivity and transparency has been studied. Pyrrole has been diffused into the poly(vinylchloride) matrix in the swelling medium of n-hexane and acetone mixture. The oxidative polymerization of the diffused pyrrole in the binary solvent system of acetonitrile and methanol gives high conductivity of the polypyrrole as well as the good penetration of the oxidant into the PVC polymer matrix. The analytical testing of the composite film shows the formation of homogeneous mixture of polypyrrole and poly(vinylchloride) conductive layer within the 1.0m of thickness on the film surface. The transparency of the composite film showed about 50–60% at 500 nm. The electrical conductivity of the composite was about 20 s/cm.     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

A facile antistatic modification of polyester fiber based on ion-exchange reaction of sulfonate-modified polyester and various cationic surfactants

A new technique for imparting antistatic properties to poly(ethylene terephthalate) (PET) fiber has been developed. In this technique, blend polyester fibers containing poly(ethylene terephthalate/5-sulfoisophthalate) (SIP-PET) were prepared by blend spinning and then treated with various cationic surfactants in the process of dyeing. The surfactants could effectively be immobilized on the fiber as the counter cations of the sulfonate groups of the 5-sulfoisophthalate (SIP) units and aid the release of static electrons formed in the fiber. Thus, the half-life time (t_1/2) of leakage of static charge and the surface resistivity (Rs) of the blend PET fibers became much lower after treating. The best result was obtained with a methylated quaternary ammonium salt of a stearylamine-ethylene oxide (EO) adduct or hydrochloride of a laurylamine-EO adduct as the surfactant of which the number of EO units was around ten. Even after five washing cycles the t_1/2 value of the fibers treated with these surfactants was kept lower than 30 s with the Rs value maintained in the order of 10¹³ Ω cm^-2. Therefore, the present technique could be useful for practical production of polyester fibers with “semi-permanent” antistatic properties which can be recovered by re-treatment even if they were lost.     

Viscoelastic characterization of moderately concentrated polystyrene solutions by dynamic light scattering

The dynamic light scattering measurements were performed for moderately concentrated entangled solutions of atactic polystyrene in benzene (BZ) at 25.0 °C, in cyclohexane (CH) at 34.5 °C (Θ), and in diethyl malonate (DEM) at 35.0 °C (Θ) to characterize their viscoelastic properties. The results have shown that while the mutual diffusion coefficient D increases in the BZ solutions and decreases in the CH and DEM solutions with increasing polymer mass concentration c, the friction coefficient ζ for the three solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for the CH and DEM solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but the L₀ values for these solutions are somewhat smaller than the values predicted from the relation. The terminal relaxation time τ_m for the two Θ solvent systems has been found to follow the power-law τ_m∝c^2.7, showing good correspondence to the relation established by rheological measurements.