Viscoelasticity of some engineering plastics analyzed with the modified stress-optical rule

The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, E(ω) and E(ω); the modified stress-optical coefficient, C_R and C_G, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, C_R, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, C_G, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, E(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, E(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers.     

Anisotropic crack propagation behavior for the silicon-bond coat layer in a multilayer coated system

This study sought to examine the relationship between the degradation mechanism, thermal stress, and crack propagation behavior in environmental barrier coating (EBC) systems. An EBC system composed of a mullite topcoat (TC), Si-bond coat (BC), and SiC substrate was prepared by atmospheric plasma spraying. Heat exposure tests were conducted to evaluate the microstructure of the EBC system at 1300°C for 1, 10, 50, and 100 h. The fracture resistance of the Si BC for the in-plane (direction parallel to each layer, 0.4–0.6 MP) and through-thickness directions (direction from the TC to substrate, 1.7–2.1 MP) differed because a thermal compressive stress was induced for the in-plane direction owing to the mismatch of the thermal expansion coefficients for each layer, which acted as a barrier for crack propagation. However, cracks tended to propagate in the in-plane direction because they were not affected by the in-plane compressive stress. These results clearly showed that Si BC exhibited in-plane anisotropy and crack propagation after heat exposure, which were the major sources of delamination of the EBC system.     

Biosynthesis of sterols and ecdysteroids in Ajuga hairy roots

Hairy roots of Ajuga reptans var. atropurpurea produce clerosterol, 22-dehydroclerosterol, and cholesterol as sterol constituents, and 20-hydroxyecdysone, cyasterone, isocyasterone, and 29-norcyasterone as ecdysteroid constituents. To better understand the biosynthesis of these steroidal compounds, we carried out feeding studies of variously ²H- and ¹³C-labeled sterol substrates with Ajuga hairy roots. In this article, we review our studies in this field. Feeding of labeled desmosterols, 24-methylenecholesterol, and ¹³C₂-acetate established the mechanism of the biosynthesis of the two C₂₉-sterols and a newly accumulated codisterol, including the metabolic correlation of C-26 and C-27 methyl groups. In Ajuga hairy roots, 3α-, 4α-, and 4β-hydrogens of cholesterol were all retained at their original positions after conversion into 20-hydroxyecdysone, in contrast to the observations in a fern and an insect. Furthermore, the origin of 5β-H of 20-hydroxyecdysone was found to be C-6 hydrogen of cholesterol exclusively, which is inconsistent with the results in the fern and the insect. These data strongly support the intermediacy of 7-dehydrocholesterol 5α,6α-epoxide. Moreover, 7-dehydrocholesterol, 3β-hydroxy-5β-cholest-7-en-6-one (5β-ketol), and 3β,14α-dihydroxy-5β-cholest-7-en-6-one (5β-ketodiol) were converted into 20-hydroxyecdysone. Thus, the pathway cholesterol→7-dehydrocholesterol→7-dehydrocholesterol 5α,6α-epoxide→5β-ketol→5β-ketodiol is proposed for the early stages of 20-hydroxyecdysone biosynthesis. 3β-Hydroxy-5β-cholestan-6-one was also incorporated into 20-hydroxyecdysone, suggesting that the introduction of a 7-ene function is not necessarily next to cholesterol. C-25 Hydroxylation during 20-hydroxyecdysone biosynthesis was found to proceed with ca. 70% retention and 30% inversion. Finally, clerosterol was shown to be a precursor of cyasterone and isocyasterone.     

Preparation and Thermal Behavior of Magnesium-Germanium Hydroxide

Poorly crystallized Mg₃Ge₂O₅(OH)₄ powder was prepared by simultaneous hydrolysis of magnesium and germanium alkoxides, followed by washing and drying. When this material is heated, spinel-type Mg₂GeO₄ and MgGeO₃ crystallize at 580° to 850°C and 860° to 1070°C, respectively. The spinel subsequently transforms to the olivine-type structure at 940° to 1050°C. Both Mg₂GeO₄ and MgGeO₃ crystallize directly from an amorphous phase .     

Rejection of phenolic derivatives in aqueous solution by an interpolymer anionic composite reverse osmosis membrane

Reverse osmosis separation for 23 phenollic derivatives was examined by an anionic charged composite membrane. The solute permeation was carried out in single-solute aqueous solution (200 mg/L) under applied pressure of 3.92–7.85 MPa at 25°C. The correlation between the solute rejection and polar parameters for phenolic derivatives has been investigated. For p-alkylphenols, the solute rejection increased with molecular weight and/or molecular branching. In undissociated state, the rejection of phenolic derivatives was closely related with the Taft's number and the Hammett's number of substituents. Also rejections of phenolic derivatives depended upon the pH value of feed soultion and the polar effect of substituted groups. For example, rejections of aminophenols showed the minimum value at a certain pH value and on either side of the minimum point, the rejection of aminophenol increased. From these facts, the main factors in reverse osmosis serparation by an anionic composite membrane were discussed.     

Optical and Mechanical Properties of α/β Composite Sialons

Two-phase α/β composites have been produced with a combination of high hardness, fracture toughness, and strength. Compared with a single-phase α-sialon, the composite showed around a twofold increase in both fracture toughness and bending strength, with only minimal reduction in hardness. Despite being a two-phase material, the optical properties of the composite were very good, showing transparency in sections of around 0.5 mm thickness. The optical properties were in fact better for the composite than for the single-phase α-sialon. Work to date on transparent sialons has focused on single-phase α-materials, which have inherently low fracture toughness unless elongated microstructures are developed. However, this microstructural development appears to adversely affect optical transparency. In this work it has been shown that good combination of mechanical properties can be achieved while maintaining optical transparency in two-phase composite sialons. The development of such materials should widen their range of application.     

Processing and Thermal Conductivity of Sintered Reaction-Bonded Silicon Nitride: (II) Effects of Magnesium Compound and Yttria Additives

The effects of the magnesium compound and yttria additives on the processing, microstructure, and thermal conductivity of sintered reaction-bonded silicon (Si) nitride (SRBSN) were investigated using two additive compositions of Y₂O₃–MgO and Y₂O₃–MgSiN₂, and a high-purity coarse Si powder as the starting powder. The replacement of MgO by MgSiN₂ leads to the different characteristics in RBSN after complete nitridation at 1400°C for 8 h, such as a higher β-Si₃N₄ content but finer β-Si₃N₄ grains with a rod-like shape, different crystalline secondary phases, lower nitrided density, and coarser porous structure. The densification, α→β phase transformation, crystalline secondary phase, and microstructure during the post-sintering were investigated in detail. For both cases, the similar microstructure observed suggests that the β-Si₃N₄ nuclei in RBSN may play a dominant role in the microstructural evolution of SRBSN rather than the intergranular glassy chemistry during post-sintering. It is found that the SRBSN materials exhibit an increase in the thermal conductivity from ∼110 to ∼133 (Wm·K)⁻¹ for both cases with the increased time from 6 to 24 h at 1900°C, but there is almost no difference in the thermal conductivity between them, which can be explained by the similar microstructure. The present investigation reveals that as second additives, the MgO is as effective as the MgSiN₂ for enhancing the thermal conductivity of SRBSN.     

Chemical modification of nylon 6 and polyester fabrics by ozone‐gas treatment

In a previous article, we reported on the ozone‐gas treatment of wool and silk fabrics in relation to the gas‐phase processing of textile fabrics. The treatment incorporated an oxygen element into the fiber surface and contributed to an increase in water penetration into the fabric. In this study, nylon 6 and polyester fabrics were treated with ozone gas in the same way as that of the wool and silk fabrics. The treatment incorporated much more oxygen into the fiber surface in the form of ? COH and ? COOH, as shown by electron spectroscopy for chemical analysis. Water penetration increased considerably with treatment, and the apparent dyeing rate and equilibrium dye uptake were also improved, especially for the polyester fabric, despite an increase in the crystallinity. Therefore, it seemed that the treatment brought about a change not only in the fiber surface but also in the internal structure of the fibers (the crystalline and amorphous regions) with regard to the dyeing behavior. Further, the mechanical characteristics of the ozone‐gas‐treated polyester and nylon 6 fabrics were measured with a Kawabata evaluation system apparatus. The shearing modulus and hysteresis widths increased with treatment, especially for the polyester fabric. Therefore, it was clear that the treatment caused a change in the fabric hand to crisp. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1344–1348, 2006     

Graft polymerization of triethoxyvinylsilane–styrene and triethoxyvinylsilane–methyl methacrylate binary monomers onto various silicates

Triethoxyvinylsilane–styrene and triethoxyvinylsilane–methyl methacrylate binary monomers were polymerized by chemical initiation or by γ-ray irradiation in the presence of silica gel, fire brick, quartz wool, and glass beads. The amount and composition of the polymers grafted to silicates were analyzed by using pyrolysis gas chromatography. When triethoxyvinylsilane alone was subjected to the reaction with silicates, condensation occurred irrespective of the initiating means, and the extent of the reaction was almost proportional to the specific surface area of the silicate. When binary monomer mixture was applied, incorporation of styrene or methyl methacrylate into the grafted polymer was observed whenever a monomer mixture of high styrene or methyl methacrylate content was submitted to the reaction. On each silicate, the relationship between the composition of polymer grafted on it and that of monomer showed a similar pattern in spite of the great difference of the specific surface area. Almost no participation of styrene or methyl methacrylate was observed when the silicate preirradiated in air or under vacuum was heated with the binary monomer mixture. It was concluded that triethoxyvinylsilane reacts with silicates by condensation and that some of the pendent vinyl groups on the silicates are incorporated into the copolymer with styrene or methyl methacrylate.     

Site-directed mutagenesis study on the roles of evolutionally conserved aspartic acid residues in human glutathione S-transferase P1-1

The evolutionally conserved aspartyl residues (Asp57, Asp98and Asp152) in human glutathione S-transferase P1-1 were replacedwith alanine by site-directed mutagenesis to obtain the mutants(D57A, D98A and D152A). The replacement of Asp98 with alanineresulted in a decrease of the affinity for S-hexyl-GSH-agarose,a 5.5-fold increase of the K_m^GHS and a 2.9-fold increase ofthe I₅₀ of S-hexyl-GSH for GSH–CDNB conjugation. Asp98seems to participate in the binding of GSH through hydrogenbonding with the -carboxylate of the -glutamyl residue of GSH.The k_cat of D98A was 2.6-fold smaller than that of the wild-type,and the pK_a of the thiol group of GSH bound in D98A was {smalltilde}0.8 pK units higher than those in the wild-type. Asp98also seems to contribute to the activation of GSH to some extent.On the other hand, most of the kinetic parameters of D57A andD152A were similar to those of the wild-type. However, the thermostabilitiesof D57A and D152A were significantly lower than that of thewild-type. Asp57 and Asp152 seem to be important for maintainingthe proper conformation of the enzyme.