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.     

Graft polymerization of some vinyl monomers onto acrylic rubber. II. Mechanical properties of graft polymers

Some mechanical properties of styrene and acrylonitrile copolymers grafted onto acrylic rubber are investigated. The impact strength of graft polymers depended upon the nature and the concentration of the catalyst, the composition and the intrinsic viscosity of the rubber, and the acrylonitrile content in the rigid matrix. The most desirable result was obtained when benzoyl peroxide as the catalyst, n-butyl acrylate–acrylonitrile copolymer of 7–10% acrylonitrile content, and about 0–5% acrylonitrile in the rigid matrix were used. Dynamic mechanical tests show the increase in efficiency of rubber modification by the grafted chains. The better weathering resistance of these graft polymers, as compared with commercial ABS plastics, was confirmed.     

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.     

Depolymerization of poly(fluoroalkyl methacrylate-co-methyl methacrylate) as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate-co-methyl methacrylate) prepared by γ-ray copolymerization were investigated by using thermogravimetric measurements together with the intermittent analysis of the gaseous products. The thermal degradation of copolymers composed of one of fluoroalkyl methacrylates of the following structures: CH₂?C(CH₃)COOCH₂(CF₂CF₂)_nH, where n = 1,2, and 3, and methyl methacrylate proceeded according to the depolymerization mechanism reproducing the pristine component comonomers exclusively, but their thermograms in inert atmosphere showed the feature of a two-step reaction. In air, however, thermograms of copolymers did not show such a stepwise decrease in weight with the elevating temperature, and temperatures at which depolymerization was introduced shifted to a much higher region. The overall aspects of depolymerization of copolymers seemed to be much similar to that of fluoroalkyl methacrylate homopolymer previously reported, and the retardation of depolymerization by air was considered to be due mainly to the stabilization of once-formed polymer radicals by oxygen.     

Carbonization and liquid-crystal (mesophase) development. 7. Optical textures of cokes from acenaphthylene and decacyclene

Optical textures of cokes prepared by carbonizing acenaphthylene, decacyclene and mixtures thereof at selected values of heat-treatment temperatures and soak time have been compared. Optical textures are assessed using polished surfaces and reflected-polarized-light microscopy in conjunction with a half-wave plate. The acenaphthylene is chemically more reactive than the decacyclene which is itself formed during the carbonization of acenaphthylene. Products of carbonization of acenaphthylene can influence rates of carbonization of the decacyclene. Similar optical textures in cokes cannot be formed by compensating low heat-treatment temperatures with long soak periods. In addition to chemical rate-controlling processes, the physical properties of the system must be acknowledged, in particular the viscosity. Very large non-coalesced growth units of mesophase (800 μm diameter) have been observed. Pre-alignment of growth units of mesophase may occur prior to coalescence.     

High-temperature oxidation of pure titanium in CO2 and Ar-10%CO2 atmospheres

The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO₂ or Ar-10%CO₂. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO₂) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.     

Analysis of electro‐optical properties of polymer‐stabilized OCB and the application to TFT‐LCDs

Abstract— A 9‐in. full‐color polymer‐stabilized OCB TFT‐LCD with stable bend alignment in the absence of an electric field was developed. The condition of the polymer stabilization, the characteristics of UV‐curable monomers, and their influence on the configurations of the polymer network in the cell were studied. Possible models of the configuration were proposed and their relationship to the electro‐optical properties was analyzed using a novel simulation method considering the distribution of anchoring effects from both alignment surfaces and the polymer network. It was suggested that a good performance such as high contrast ratio and fast response could be expected in the polymer network originating from newly developed monomers composed of multifunctional LC acrylates due to a relatively weak‐anchoring effect and presumably its localization near the alignment surfaces. By using the newly developed monomers under the optimized polymer‐stabilizing process, a high contrast ratio of 250:1 and fast response nearly equal to that of a conventional OCB cell were achieved.     

Production of monodisperse water-in-oil emulsions consisting of highly uniform droplets using asymmetric straight-through microchannel arrays

This paper reports the production of monodisperse water-in-oil (W/O) emulsions using new microchannel emulsification (MCE) devices, asymmetric straight-through MC arrays that were hydrophobically modified. The silicon asymmetric straight-through MC arrays consisted of numerous pairs of microslots and circular microholes whose cross-sectional sizes were 10 μm. This paper primarily focused on investigating the effect of the osmotic pressure of a dispersed phase (Π_d) on MCE. This paper also investigated the effects of the type of continuous-phase oils and the dispersed-phase flux (J _d) on MCE. The dispersed phases were Milli-Q water and Milli-Q water solutions containing sodium chloride. The continuous phases were decane (as control), hexane, medium chain triacylglyceride (MCT), and refined soybean oil (RSO) solutions containing tetraglycerin monolaurate condensed ricinoleic acid ester (TGCR) as a surfactant. At Π_d of exceeding threshold, highly uniform aqueous droplets with coefficients of variation of less than 3% were stably generated via hydrophobic asymmetric straight-through MCs. Monodisperse W/O emulsions with average droplet diameters between 32 and 45 μm were produced using the alkane–oil and triglyceride–oil solutions as the continuous phase. This work also demonstrated that the hydrophobic asymmetric straight-through MC array had remarkable ability to produce highly uniform aqueous droplets at very high J _d of up to 1,200 L m⁻² h⁻¹.     

Magnetic order and evolution of the electronic state aroundx=0.12 in La2?xBaxCuO4 and La2?xSrxCuO4

Muon spin rotation ( ⁺SR) measurement provides clear evidence of the antiferromagnetic order of Cu moments below 35 K for La_2–x Ba _x CuO₄ and below 15 K for La_2–x Sr _x CuO₄ in the narrow range ofx where the high-T _c superconductivity (SC) is suppressed remarkably. The results suggest that the change of the electronic state coupled with the lattice instability is relevant to the local suppression of SC and freezing of spin fluctuations of the Cu moment.