Gelation of poly(vinyl alcohol)/phenol/water solutions and gel spinning

The light transmittance of the gels of poly(vinyl alcohol) (PVA)/phenol/water solutions was examined for the entire range of phenol/water content. Excellent transparency was found for the gels with phenol contents of 70–95 vol %. In full consideration of the results for the transparency and melting temperature of the gels and the viscosity and gelation ability of solutions, the PVA solutions of 75 vol % phenol content were selected for the gel spinning. The maximum dynamic moduli of drawn filaments at 25°C (room temperature) were 42 GPa (15x) for atactic PVA and 45 GPa (14x) for syndiotacticity-rich PVA. © 1995 John Wiley & Sons, Inc.     

Formation and Properties of Ln-Si-O-N Glasses (Ln = Lanthanides or Y)

Homogeneous Y-Si-O-N glasses containing 15 or 20 eq% nitrogen (N) were prepared from compositions with Y/Si ratios in the vicinity of that of the lowest eutectic point on the Y₂O₃–SiO₂ phase diagram. The liquidus on the phase diagram shifted toward lower temperatures by incorporation of N. The density, the elastic moduli, and the glass transition temperature of the Y-Si-O-N glasses increased with incorporation of N. This is due to the closer packing of atoms in the glasses by the substitution of N, which is in three-fold coordination with Si, for O which is in two-fold coordination, and the stronger covalent nature of the Si–N bond compared with the Si–O bond. The coefficient of thermal expansion of the Y-Si-O-N glasses increased with increasing Y content, because the discontinuity of the glass network developed with increasing nonbridging anions by the introduction of Y. In contrast, the glass transition temperature and the elastic moduli increased with Y content due to the high coordination of Y for O, and the relatively high cationic field strength of Y. Furthermore, the effect of cationic field strength on properties of Ln-Si-O-N glasses (Ln = lanthanides or Y) is discussed.     

Processing Strategy for Producing Highly Anisotropic Silicon Nitride

Silicon nitride with a preferred orientation of large elongated grains was obtained by tape casting of raw powder slurry seeded with rodlike β-Si₃N₄ particles, followed by a gas pressure sintering under 1 MPa nitrogen pressure. The large elongated grains developed from seeds lay in planes parallel to the casting direction in a two-dimensional distribution. Increased fracture toughness (11.1 MPa·m^1/2) and bending strength (1100 MPa) were achieved in the direction perpendicular to the grains alignment compared to specimens with a random distribution of elongated grains. Morover, the specimens exhibited a high Weibull modulus of 46 due to the uniform distribution of large grains.     

Diamond-like carbon thin films by microwave surface-wave plasma CVD aimed for the application of photovoltaic solar cells

The nitrogen doped diamond-like carbon (DLC) thin films were deposited on quartz and silicon substrates by a newly developed microwave surface-wave plasma chemical vapor deposition, aiming the application of the films for photovoltaic solar cells. For film deposition, we used argon as carrier gas, nitrogen as dopant and hydrocarbon source gases, such as camphor (C₁₀H₁₆O) dissolved with ethyl alcohol (C₂H₅OH), methane (CH₄), ethylene (C₂H₄) and acetylene (C₂H₂). The optical and electrical properties of the films were studied using X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, atomic force microscope, electrical conductivity and solar simulator measurements. The optical band gap of the films has been lowered from 3.1 to 2.4 eV by nitrogen doping, and from 2.65 to 1.9 eV by experimenting with different hydrocarbon source gases. The nitrogen doped (flow rate: 5 sccm; atomic fraction: 5.16%) film shows semiconducting properties in dark (i.e. 8.1 × 10^{− 4} Ω^{− 1} cm^{− 1}) and under the light illumination (i.e. 9.9 × 10^{− 4} Ω^{− 1} cm^{− 1}). The surface morphology of the both undoped and nitrogen doped films are found to be very smooth (RMS roughness ≤ 0.5 nm). The preliminary investigation on photovoltaic properties of DLC (nitrogen doped)/p-Si structure show that open-circuit voltage of 223 mV and short-circuit current density of 8.3 × 10^{− 3} mA/cm². The power conversion efficiency and fill factor of this structure were found to be 3.6 × 10^{− 4}% and 17.9%, respectively. The use of DLC in photovoltaic solar cells is still in its infancy due to the complicated microstructure of carbon bondings, high defect density, low photoconductivity and difficulties in controlling conduction type. Our research work is in progress to realize cheap, reasonably high efficiency and environmental friendly DLC-based photovoltaic solar cells in the future.     

Synthesis of nitrogen incorporated diamond-like carbon thin films using microwave surface-wave plasma CVD

Nitrogenated diamond-like (DLC:N) carbon thin films have been deposited by microwave surface wave plasma chemical vapor deposition on silicon and quartz substrates, using argon gas, camphor dissolved in ethyl alcohol composition and nitrogen as plasma source. The deposited DLC:N films were characterized for their chemical, optical, structural and electrical properties through X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Raman spectroscopy, atomic force microscope and current–voltage characteristics. Optical band gap decreased (2.7 to 2.4 eV) with increasing Ar gas flow rate. The photovoltaic measurements of DLC:N / p-Si structure show that the open-circuit voltage (V_oc) of 168.8 mV and a short-circuit current density (J_sc) of 8.4 μA/cm² under light illumination (AM 1.5 100 mW/cm²). The energy conversion efficiency and fill factor were found to be 3.4 × 10^{− 4}% and 0.238 respectively.     

High oleic acid oil suppresses lung tumorigenesis in mice through the modulation of extracellular signal-regulated kinase cascade

This study was undertaken to estimate the effect of dietary high oleic acid oil (OA) on 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)-induced lung tumorigenesis in mice. Diet containing 10% oil was fed to mice through experimental periods. On day 30 after NNK injection (100 mg/kg body weight, i.p.), the treatment increased the level of prostaglandin E₂ (PGE₂) as well as proliferating cell nuclear antigen, a marker of cell proliferation in a high linoleic acid oil (LA)-fed group but not in an OA-fed group. The NNK treatment also induced the activation of an extracellular signal-regulated kinase (Erk) cascade (Erk, Mek and Raf-1) in an LA-fed group. On the other hand, OA feeding abolished the NNK-induced activation of the Erk cascade. In conjugation with these events, OA feeding reduced lung tumor incidence and tumor multiplicity (percentage of mice with tumors) in mice compared with LA feeding at the 20th experimental week. These results suggest that OA suppresses lung tumorigenesis and that this suppression is correlated with the inhibition of PGE₂ production and inactivation of the Erk cascade.     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

Spherical Aluminum Nitride Fillers for Heat-Conducting Plastic Packages

It is necessary for encapsulants to have not only a suitable coefficient of thermal expansion (CTE) compatible to IC devices and a low dielectric constant to reduce the device propagation delay, but also a high thermal conductivity to dissipate large amounts of heat from power-hungry, high-speed IC and high-density packages. Fillers such as silica have been mixed with polymers to improve their properties. Aluminum nitride (AlN) is considered as an alternative one, because it has a higher theoretical thermal conductivity of ∼320 W/mK¹, a compatible CTE with silicon chips and a low dielectric constant. Commercial AlN fillers are angular in shape, because they are prepared via grinding coarse AlN powders synthesized by direct nitridation of aluminum metal and classification. The angular AlN are not expected to have high fluidity when mixed with polymers and hence low packing density. Recently, we successfully obtained single-crystalline spherical AlN fillers. Furthermore, polymer composites filled with the spherical AlN showed excellent thermal conductivity (>8 W/mK) as encapsulants for dissipating the heat generated in electronic devices.     

Dehydrogenative Cracking of n-Butane over Modified HZSM-5 Catalysts

Dehydrogenative cracking reaction of n-butane was studied using HZSM-5 catalyst modified with various metal oxides. Alkaline earth (magnesium), transition metal (cobalt) and rare earth (lanthanum) elements are used for the modification. The selectivity of the products was studied at low conversion (20%). Methane, ethane, ethylene, propylene, butenes and butadiene were the main products. With the use of the cobalt- or magnesium-containing HZSM-5, dehydrogenative cracking was observed and the selectivity of ethylene was much larger than that of ethane. On the other hand, the selectivity of ethylene and ethane were almost the same in the reaction using the lanthanum-containing HZSM-5. It is considered that the cobalt- and magnesium-loaded sites on HZSM-5 played an important role in the dehydrogenative cracking.     

Microstructure and properties of (Sr, Ca)CuO2/(Sr, Ca)RuO3 multilayers

Epitaxial multilayer thin films of infinite-layer (Sr, Ca)CuO₂ and perovskite (Sr, Ca)RuO₃ have been prepared on (100) SrTiO₃ substrates by multitarget rf magnetron sputtering. X-ray diffraction analyses revealed that the multilayer structure of (Sr, Ca)CuO₃/(Sr, Ca)RuO₃ was successfully fabricated with a minimum layer thickness of 20 Å. Transmission electron microscopy measurements of the multilayers indicated that there was no dislocation which normally exists in single-layer films with an infinite-layer structure. Resistivities of multilayer films at room temperature ranged from 1 to 10 m cm and showed semiconductor-like dependence against the temperature.