Structural Study on PbO–SiO2 Glasses by X-Ray and Neutron Diffraction and 29Si MAS NMR Measurements

Structure of x PbO–(100− x )SiO₂ ( x =25–89) glasses has been investigated by means of the X-ray and neutron diffraction and ²⁹Si MAS NMR measurements. In the radial distribution functions of all the glasses, the Pb–O correlation was observed at 0.23 nm, indicating that the PbO₃ trigonal pyramids units do exist in the whole glass forming composition range. Furthermore the existence of the first Pb–Pb correlation at ∼0.385 nm in the whole composition range suggests that the basic structural unit is considered to be a Pb₂O₄ unit, which consists of the edge-shared PbO₃ trigonal pyramids. These results strongly imply that the Pb₂O₄ units participate in the glass network constructed by SiO₄ tetrahedra even at low PbO content. Differing from other lead-containing glass systems, these structural characteristics of Pb ions in the PbO–SiO₂ glass system are responsible for the extremely wide glass-forming region.     

Ru-doped nanostructured carbon films

Pure and Ru-doped carbon films are deposited on Si (100) substrates by electron cyclotron resonance chemical vapor deposition. The films are characterized by transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. In both the pure and Ru-doped samples, diamond nanocrystallites are formed in amorphous carbon matrices. The Ru-doped film contains much smaller diamond nanocrystallites (approx. 3 nm) than the pure samples (approx. 11 nm). Lower surface roughnesses are observed in both pure and Ru-doped samples as compared to other reported nanocrystalline diamond films. The conductivity of the Ru-doped film is significantly higher than that of the pure film. The results show that Ru-doped nanocrystalline diamond films have unique structures and properties as compared to pure nanocrystalline diamond films or metal doped diamond-like carbon films, which may offer advantages for electrochemical, optical-window, field emission or tribological applications.     

Thermal shock resistance of flat plastic integrated circuit packages

Flat packages (FPs) were formed from epoxy molding compounds with various physical properties using a transfer molding machine. The compounds were prepared by changing kinds and amounts of additives and addition methods. The thermal shock test was carried out by the following procedures. The plastic package was soaked alternately in liquid nitrogen (?196°) and in liquid solder (200°) in the cycle of 140s. The median life to crack initiation was defined to be the cycles when half of the specimens exhibited crack initiation. According to linear fracture mechanics, the following expression was obtained relating the median life N, thermal stress σ_t, and strength σ_b; N = C/σ·(σ_b/σ_t)^m. We found the linear relation between logarithm of Nσ and logarithm of σ_b/σ_t for various packages, and estimated the values of C and m as 5 × 10⁴ MPa² and 5.5, respectively. The value of m was the same as that obtained for a dual-in-line package.     

Mirror Constant for Tyranno® Silicon-Titanium-Carbon-Oxygen Fibers Measured in Situ in a Three-Dimensional Woven Silicon Carbide/Silicon Carbide Composite

The strength, S , of ceramic and glass fibers often can be estimated from fractographic investigation using the fracture mirror radius, r _m, and the relationship S = A _m/( r _m)^1/2, where A _mis the "mirror constant." The present work estimates the value of A _mfor Tyranno^® Si-Ti-C-O fibers in situ in a three-dimensional woven SiC/SiC-based composite to be 2.50 ± 0.09 MPa·m^1/2. This value is within the range of 2–2.51 MPa·m^1/2 previously obtained for nominally similar Nicalon^® Si-C-O fibers.     

Prostaglandin-like substances formed during autoxidation of methyl linolenate

Prostaglandin-like substances other than 3-(2-ethyl-5-hydroxy-3-oxo)-cyclopentanyl-2-propenal (compound I), which upon reacting with amino acids form reddish pigments, were purified, and their chemical structures were determined. Three red pigment-forming substances (RPS) in autoxidized methyl linolenate were purified successively by gel chromatography on Sephadex LH-20, column chromatography and thin layer chromatography on Silica Gel 60, and by high performance liquid chromatography on μ-Porasil. IR spectra of the RPS showed the absorption of an ester group (νC=O 1730 cm⁻¹ in CHCl₃) and of a longer branched chain (νC-H 2800–3100 cm⁻¹), in addition to the absorption bands observed in compound I. Electron impact mass spectra of the trimethylsilyl ethers obtained after reduction with NaBH₄ and NaBD₄ were analyzed in detail and compared with those of compound I. The structures of the RPS were identified as stereoisomeric methyl 8-[2-(2-formylvinyl)-3-hydroxy-5-oxo-cyclopentanyl]-octanoates derived from methyl 12-hydroperoxy-linolenate. Presented at the general meeting of the Japanese Society of Scientific Fisheries, held at Tohoku University, Sendai, Japan, October 1984.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Template synthesis of novel porous carbons using various types of zeolites

As previously reported, high surface area microporous carbons with long-range order can be synthesized by using zeolite Y as a template. In this work, an attempt is made to synthesize porous carbon using several other types of zeolites (zeolite β, ZSM-5, mordenite and zeolite L). Special attention is paid to whether the structural regularity of each zeolite can be transferred to the carbon structure as well as with the case of zeolite Y. The carbon filling method was then examined to see which gives the highest regularity to the carbon structure. It has been found that the optimum carbon filling method for zeolite Y is not an optimum one for the other zeolites and the degree of the regularity of long-range ordering in the carbons strongly depends on zeolite type. The order of the regularity in the resultant carbons is zeolite β>>zeolite L>mordenite>ZSM-5. The effect of zeolite type on the regularity is discussed in relation to the size and the shape of the zeolite channels.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. I. Comparison of the inhibitory effects

The effects of chlorophyll and pheophytin on the autoxidation of oils in the dark were investigated by oven tests. The results indicated that both chlorophyll and pheophytin show antioxidant activity when methyl linoleate is used as substrate. Furthermore, chlorophyll retarded the oxidative deterioration of triglycerides in rapeseed and soybean oils at 30 C. Among the four chlorophyll derivatives (chlorophylls a and b and pheophytins a and b), chlorophyll a showed the strongest antioxidant activity. The antioxidant effects of chlorophyll and pheophytin depended on the storage temperature and the kinds of oil used as substrate.     

Effect of MgO Addition on the Bondability and Interfacial Reaction between Dielectric and Glass-Ceramics for the Fabrication of Multi-Component Ceramic Substrates

Bondability and interfacial reaction between dielectric and insulator layers have been examined to obtain a basic understanding of bonding mechanisms. Lead-containing complex perovskite was used as a dielectric material. Two kinds of glass-ceramics were used as insulator material; lead borosilicate glass containing Al_2O3 (insulator A) and the same containing Al₂O₃ and M_gO (insulator B). Dielectric and insulator layers did not bond when insulator A was used. When insulator B was used, however, strong bonding was achieved between the two layers by firing the powder compacts at temperatures between 800° and 1000°C. Addition of M_gO to lead borosilicate glass increased the thermal expansion coefficient to that of the dielectric and enhanced the formation of reaction layers, resulting in good bonding. Two reaction layers were identified. The main reaction products were enstatite and bredigite for one layer contacting the dielectric, and enstatite and a compound with the same diffraction pattern as that of faujasite for the other layers contacting insulator B.