Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers     

Cover Image,Volume 69, Issue 3

The cover image is based on the Mini‐Review Well‐defined, environment‐friendly synthesis of polypeptides based on phosgene‐free transformation of amino acids into urethane derivatives and their applications by Takeshi Endo et al., https://doi.org/10.1002/pi.5952 . Cover image © Takeshi Endo Images.

     

Novel hepatitis C virus protease inhibitors: thiazolidine derivatives

This study evaluated the inhibitory effects of thiazolidine derivatives on hepatitis C virus (HCV) protease and other human serine proteases. The inhibition efficacy was tested with a reversed-phase high-performance liquid chromatography (HPLC) assay system using a NS3-NS4A fusion protein as the HCV protease and a synthetic peptide substrate that mimics the NS5A-5B junction. Nine thiazolidine derivatives showed more than 50% inhibition at 50 microg/ml. The most potent derivative was RD4-6250, with 50% inhibition at a concentration of 2.3 microg/ml; this concentration was lower than those of other protease inhibitors reported previously. The most selective derivative was RD4-6205, with 50% inhibition at a concentration of 6.4 microg/ml, a lower concentration than those on other serine proteases (chymotrypsin, trypsin, plasmin, and elastase). These results suggest that the RD4-6205 skeleton is an important structure for inhibitory activity on the HCV protease NS3-NS4A.     

Prediction of spectral reflectance factor distribution of automotive paint finishes

It is necessary to determine the accurate reflectance of painted surfaces for the review of paint finishes by computer graphics (CG) before actual painting of the exterior color of automobiles, and for quality control during production and inspection processes. We have optimized a method for measuring reflectance by using a statistical technique. We have found that the reflectance of a painted surface is best measured at an incident angle of 60° and at five aspecular angles of 10°, 18°, 28°, 40°, and 90°. Our method makes it possible to accurately reproduce reflection characteristics of paint finishes containing special flake pigments, such as pearl mica. Also it was proved that our method can apply not only to solid and metallic coatings but to all painted surfaces. © 2005 Wiley Periodicals, Inc. Col Res Appl, 30, 275–282, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.20125     

New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

Phenol novolac/poly(4- hydroxyphenylmaleimide) blend hardeners for DGEBA-type epoxy resin

Phenol novolac/poly (4-hydroxyphenylmaleimide) (PHPMI) blends were used as an epoxy resin hardener. The curing behavior of the above system and the thermal and mechanical properties of the cured epoxy resin were studied. It was not necessary to use a curing accelerator for this system, because PHPMI caused acceleration of the curing reaction. The curing mechanism of this system was investigated by using model compounds. Test pieces from the neat resins and the glass fiber reinforced resins were evaluated in terms of thermal and mechanical properties, respectively. It was found that heat resistance and mechanical properties were improved by increasing the amount of PHPMI in the hardener.     

Preparation and photoconduction of rapidly quenched films in the Bi2O31bM2O5 system (M=V,Nb and Ta)

The Bi₂O₃1bM₂O₅ films (M=V, Nb and Ta) were prepared by a rapid quenching technique using a twin-roller type equipment. Quenched film of pure Bi₂O₃ partially precipitated a tetragonal phase which differs from well-known β-Bi₂O₃ in structure. In every (Bi₂O₃)_0.975 (M₂O₅)_0.025 composition (2.5% M₂O₅), the tetragonal phase was obtained as single phase, and the tetragonality became greater than that of the pure Bi₂O₃. Beyond this composition, the tetragonality decreased to form δ-phase with a fcc structure with increasing the M₂O₅ content. The lowest V₂O₅ content forming a δ-phase was 5%, while a slight tetragonality still remained in the samples containing 10% Nb₂O₅ and 10% Ta₂O₅, respectively. From the measurement of the photoconductivities of the quenched films, it was proved that a photoconduction appeared in the tetragonal phase while no photoconductivity was observed in the cubic phase. The characteristic of the photoconduction was that a remarkable decrease in the resistivity was observed when a light of ca. 500 nm in wave length was irradiated on the films.     

The oxidation properties of fourth generation single-crystal nickel-based superalloys

The fourth-generation nickel-based single-crystal superalloys, which contain large amounts of refractory metals for strengthening and platinum group metals for topologically close-packed phase prevention, show excellent high-temperature strength. However, these alloying elements seem to decrease high-temperature oxidation resistance. In this study, nickel-based superalloys with various amounts of tantalum, rhenium, and ruthenium were examined in isothermal and cyclic exposures at 1,100°C to investigate the effect on the oxide growth rate and resistance to scale spallation. Ruthenium and rhenium were found to degrade the oxidation resistance by the vaporization of their oxide. Tantalum-rich oxide in the spinel layer acts to stabilize ruthenium and rhenium oxide in the scale. The addition of hafnium and yttrium is effective in improving the oxidation resistance of ruthenium-containing nickel-based superalloys.