Properties of Va metal-B films prepared by r.f.-sputtering

Ta_100-x B _x alloy films were prepared by r.f.-sputtering in the chemical composition range 45 x 77. Ta_100-x B _x (45 x 58) films consist of the amorphous phase, while the TaB₂ crystal phase was observed in Ta_100-x B _x (66 x 77) films. A remarkable preferred orientation with the (001) plane of TaB₂ parallel to the film surface was observed in Ta₃₄B₆₆. The d.c. electrical conductivity of Ta_100-x B _x (45 x 77) films decreases with increasing boron content in the range 6.7 × 10³ to 1.3 × 10^3–1 cm^–1. The micro-Vickers hardness of Ta_100-x B _x (45 x 77) films was in the range 2200 to 2600 kg mm^–2.     

Co-crosslinking blend of incompatible polymers VI: Poly(vinyl chloride) toughened with polyethylene via a co-crosslinking technique

A binary blend which consists of two incompatible polymers such as poly(vinyl chloride) and polyethylene has been performed through a partial co-crosslinking reaction with peroxide to give a co-crosslinked blend with a uniform dispersion of small polyethylene particles and with an improved mechanical property. The results are obtained through the formation of a co-crosslinked product which acts as a potential solid phase dispersant as well as a well-bonded reinforcing interlayer on polyethylene particles uniformly dispersed in poly(vinyl chloride) matrix. The resulting blends (PVC/PE=10/90 wt) give carbon spherules of 0.5 to 1m diameter through pressure-carbonization at 650° C for 1 h.     

Chemical Modification of Phage-Displayed Helix-Loop-Helix Peptides to Construct Kinase-Focused Libraries

Conformationally constrained peptides hold promise as molecular tools in chemical biology and as a new modality in drug discovery. The construction and screening of a target-focused library could be a promising approach for the generation of de novo ligands or inhibitors against target proteins. Here, we have prepared a protein kinase-focused library by chemically modifying helix-loop-helix (HLH) peptides displayed on phage and subsequently tethered to adenosine. The library was screened against aurora kinase A (AurA). The selected HLH peptide Bip - 3 retained the α-helical structure and bound to AurA with a K_D value of 13.7 μM. Bip - 3 and the adenosine-tethered peptide Bip - 3 - Adc provided IC₅₀ values of 103 μM and 7.7 μM, respectively, suggesting that Bip - 3 - Adc bivalently inhibited AurA. In addition, the selectivity of Bip - 3 - Adc to several protein kinases was tested, and was highest against AurA. These results demonstrate that chemical modification can enable the construction of a kinase-focused library of phage-displayed HLH peptides.     

Study on triazine thiols. IV. Action of triazine thiols and their metal salts to peroxide

Decomposition of t-butylhydroperoxide was retarded by triazine thiols and their zinc salts, but accelerated by the copper salts of triazine thiols as well as sulfur compounds such as dithiocarbamates and mercaptobenzothiazolates. Triazine thiols and their zine salts are effective antioxidants for polyethylene crosslinked with peroxide and containing copper, and for protecting epichlorohydrin vulcanizates against attack by “sour” or hydroperoxide-containing gasoline.     

Molecular aggregation of PEEK with PES blends and the block copolymers composed of PEEK and PES components

Polymer blends of PEEK with PES were prepared by the solution blending method. Copolymers composed of PEEK and PES components were synthesized from these oligomers. The formation conditions exerted an influence over the molecular aggregation and the crystallization behaviors of the blend films and block copolymers which were examined by X-ray diffractometry and DSC analysis. As a result, phase-separation in the blend films was found when the formation temperature was high. The blend films formed at 340°C, quenched and annealed at 180°C, exhibited the same crystallization behavior as those of PEEK. In the case of the blend films formed at 300°C, the annealing of the films at 250°C was required to crystallize the blend films. The T_g of a copolymer with a PEEK component content of more than 50% tends to shift toward a higher temperature than the T_g of PEEK itself, and the T_m of the copolymer toward a lower temperature than that of PEEK ist.     

Residual Stress in Siliceous Glass Between Mullite Crystals

A birefringence of siliceous glass, which is coexisting with mullite crystals, was studied by an optical polarizing microscope. The cause of the birefringence was assumed to be the residual stress induced by a large contraction difference between the mullite and glass on cooling. The stress has been evaluated to be as high as—0.3 GPa, and to correspond to the elastic one which began to develop at the glass transition point.     

Adhesive properties of cured epoxide resin containing the intermolecular compound of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid

The intermolecular compound of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid was synthesized, and the glass transition temperature and the adhesive properties of the cured epoxide resin containing the above compound were studied. Epoxide reacted with amino groups of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid at the curing conditions of 150 to 180°C for 60 min and formed the cured compounds. The infrared spectra showed that epoxide reacted with isocyanuric acid in the presence of imidazole compounds and converted to 2-oxazolidinone compound on the curing process. The glass transition temperatures of the cured compounds having isocyanurate and 2-oxazolidinone rings in their structures were higher than that of the epoxide resin cured with imidazole and rise as the curing temperature rises, but fall as 2-oxazolidinone ring content increases in their cured compounds. The tensile shear and peel strengths of the steel and steel bonded with the cured compounds and the cured epoxide resin were measured at 25 and 150°C. The adhesive strengths were improved due to isocyanurate and 2-oxazolidinone rings formed in their cured compounds.     

Fat splitting by the twitchell process at low temperature

Summary A study was made of the degree of splitting of coconut and soybean oils by the Twitchell process at 35±0.1°C. with no shaking or stirring, using an agent consisting mainly of tetrabutyl naphthalene sulfonic acid with water or dilute sulfuric acid. The degree of splitting was greater with sulfuric acid than with water. In general, the degree of splitting of soybean oil was greater when the sulfonic acid was dissolved in the oil layer than when it was in water. The reverse was true with coconut oil. Although addition of glycerol had no effect on the degree of splitting, addition of glacial acetic acid to the coconut oil system decreased fat splitting to a considerable extent. Addition of coconut fatty acids to the coconut oil system had little effect, but soybean fatty acids added to the soybean oil system markedly increased the degree of splitting. For the first time it has been demonstrated that, at 35±0.1°C., splitting of a fat by the Twitchell process occurs in a stepwise way. Coconut oil in contact with 1N sulfuric acid containing the sulfonic acid, corresponding to 1% by the weight of the oil, was about 90% split in 15 to 30 days, depending on the area of contact of the two layers. The diglyceride concentration reached a maximum during the early days of the reaction and then decreased somewhat. Monoglyceride concentration appeared to reach a maximum more slowly and then continued at that level as the concentrations of free fatty acids and glycerol steadily increased. Presented at the symposia on fat of the Chemical Society of Japan, Nov. 10, 1954, and Nov. 8, 1955, Nagoya, Japan; and the 8th annual meeting of the Chemical Society of Japan, Apr. 2, 1955, Tokyo, Japan.     

A Practical Model for the Interactions Between Hydrating Portland Cements and Poly-β-Naphthalene Sulfonate Condensate Superplasticizers

The performance of poly-β-naphthalene sulfonate condensate superplasticizer (BNS) as a dispersant for cement in concrete is affected severely by slight differences in the characteristics of the cement. In order to be able to predict these effects, a model for estimating the fluidity of cement paste containing BNS is proposed. This model is based on an assumption that the fluidity of cement paste is proportional to the BNS adsorption amount per surface area of hydrated cement (Ad/Hy). BNS is known to show two types of sorption on hydrated cement: one is the bulk absorption into initial hydrates and the other one is the superficial adsorption onto hydrates. Only the superficially adsorbed BNS is expected to work as a dispersant. By assuming a competitive Langmuir-type adsorption on hydrates between BNS and SO₄²⁻, a simple method to estimate Ad/Hy is developed, with the concentrations of BNS and SO₄²⁻ as the only two independent parameters. The resulting estimates of Ad/Hy show a good correlation with paste flow and its change with elapsed time for a broad range of cements. The SO₄²⁻ concentration in the aqueous phase of the cement paste just after the beginning of the mixing is known to affect the performance of BNS as a dispersant. By using the proposed model to discriminate between the superficial adsorption and bulk absorption of BNS, this phenomenon is explained quantitatively.     

Gelation of poly(vinyl alcohol) solutions at low temperatures (20 to −78°C) and properties of gels

The flow points of atactic poly(vinyl alcohol) (a-PVA) gels with H₂O/dimethyl sulfoxide (DMSO) = 90/10 (v/v) chilled at 20 to ?78°C for 24 h depended on the chilling temperature and were 0–30°C for gels with the initial polymer concentrations (C_i) of 2–5 g/dL, whereas those for H₂O/DMSO = 50/50 chilled at 0 to ?78°C were independent of the chilling temperature and were 70–75°C. Syneresis occurred after eight cycles of freezing (?24°C) and thawing (20°C) for a-PVA hydrogels at concentrations above C_i = 4 g/dL and two such cycles for syndiotacticity-rich PVA (s-PVA) hydrogels at concentrations above C_i = 1 g/dL. The extent of syneresis per one cycle for s-PVA hydrogels was higher than that for a-PVA hydrogels at the initial cycles. In the a-PVA hydrogels with an initial polymer concentration of ca. 30 g/dL, syneresis was expected not to occur even after 20 cycles. If all the free water in the gels is assumed to have transuded by syneresis after 20 cycles, the residual water is bound water and is estimated to be six water molecules per one vinyl alcohol monomer unit. © 1994 John Wiley & Sons, Inc.