An ESR study of the film formation steps of vapor deposition polymerization of polyamic acid

A film of polyamic acid is formed by vapor deposition polymerization of pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA). We have taken ESR spectrum during the polymerization process and compared it with the ESR spectrum of films obtained from solution polymerization. In the intermediate polymers during vapor deposition polymerization, the amide bond (? CONH? ) is coplanar with the benzene ring and two protons in the PMDA molecule. This intermediate polymer has one unpaired electron that interacts with the two nitrogen nuclei equally. On the other hand, in the polymer obtained by solution polymerization, the amide bond and the benzene ring of PMDA are not coplanar. In this polymer, too, some of the molecules have an unpaired electron that seems to have almost no coupling with NH groups. These results imply that the polymer formation via vapor deposition proceeds through different intermediates and different molecular configurations from that via the solution process.     

MASS TRANSFER IN GAS-SPARGED POROUS ELECTRODES

The electrochemical limiting current method was used to measure mass transfer coefficients with cocurrent upward gas-liquid flow in packed bed electrodes. Liquid-solid and overall gas-solid coefficients were determined from limiting current data in the presence of inert or reactive gas flows with the use of a plug flow model. The presence of inert gas flow increased mass transfer coefficients over those in single-phase flow by a factor of up to 1.7. As a result of boundary layer penetration by gas bubbles, sparging with reactive gas increased mass transfer rates by a factor of up to 3.5.     

Hydroliquefaction of low-sulfur coals using iron carbonyl complexes—Sulfur as catalysts

Hydroliquefaction of low-sulfur Australian coals (Wandoan and Yallourn) was studied using iron carbonyl complexes as catalyst. The addition of Fe(CO)₅ (2.8 wt% Fe of coal) increased coal conversion from 48.6 to 85.2% for Wandoan coal, and from 36.7 to 69.7% for Yallourn coal in 1-methylnaphthalene at 425°C under an initial hydrogen pressure of 50 kg cm^?2. When molecular sulfur was added to iron carbonyls (Fe(CO)₅, Fe₂(CO)₉ and Fe₃(CO)₁₂), higher coal converions ( > 92%) and higher oil yields (>46%) were obtained, along with an increase in the amount of hydrogen transferred to coal from the gas phase (0.2 to 2.8%, d.a.f. coal basis). In the liquefaction studies using a hydrogen donor solvent, tetralin, Fe(CO)₅S catalyst increased the amount of hydrogen absorbed from the gaseous phase and decreased the amount of naphthalene dehydrogenated from tetralin. The direct hydrogen transfer reaction from molecular hydrogen to coal fragment radicals seems to be a major reaction pathway. Organic sulfur compounds, dimethyldisulfide and benzothiophene, and inorganic FeS₂ and NiS were found to be good sulfur sources to Fe(CO)₅. From X-ray diffraction analyses of liquefaction residues, it is concluded that Fe(CO)₅ was converted into pyrrhotite (Fe_1?xS) when sulfur was present, but into Fe₃O₄ in the absence of sulfur.     

Fracture behaviour of unmodified and rubber-modified epoxies under hydrostatic pressure

The fracture toughness and uniaxial tensile yield strengths of unmodified and CTBN-rubber-modified epoxies were measured under hydrostatic pressure. The purpose of these experiments was to learn how suppressing cavitation in rubber particles affects the deformation mechanisms and the fracture toughness of rubber-modified epoxy. It was found that the cavitation of CTBN-rubber could be suppressed at a relatively low pressure (between 30 and 38 M Pa). With cavitation suppressed, the rubber particles are unable to induce massive shearyielding in the epoxy matrix, and the fracture toughness of the rubber-modified epoxy is no higher than that of the unmodified epoxy in the pressure range studied. Unmodified epoxy shows a brittle-to-ductile transition in fracture toughness test. The reason for this transition is the postponement of the cracking process by applied pressure.Work performed while on a sabbatical leave at the University of Michigan.     

Occurrence of heterogeneity of N-linked oligosaccharides attached to sycamore (Acer pseudoplatanus L.) laccase after excretion

The N-linked oligosaccharide moieties of sycamore (Acer pseudoplatanus L.) laccase are known to be highly heterogeneous. We confirmed that this oligosaccharide heterogeneity was caused not only during the oligosaccharide biosynthesis in Golgi apparatus, but also after the excretion of laccase protein into a culture medium. The culture medium for the sycamore cells (Acer pseudoplatanus L.) contained beta-galactosidase, alpha-L-fucosidase, beta-N-acetylglucosaminidase, alpha-mannosidase and beta-xylosidase activities. We showed that the largest sugar chain in laccase, oligosaccharide F, [formula: see text] was degraded to [formula: see text] by a crude exoglycosidase mixture in the culture medium.     

Mode I interlaminar fracture toughness of commingled carbon fibre/PEEK composites

Carbon fibre/poly (ether-ether-ketone) (PEEK) composites were fabricated from plain weave cloth using the commingled yarn of carbon fibres with PEEK filaments. The undirectional specimen was made from the warp of commingled yarn and the weft of PEEK yarn, while the two-dimensional specimen was made from commingled yarns both of the warp and the weft. During the hot-pressing process, PEEK filaments melt to form the matrix of the composite. The interlaminar fracture toughness of the commingled composite was measured and compared with that of the prepreg composite. The critical strain energy release rates,/'G _Ics, obtained for the commingled composites were higher than the prepreg composite. In particular, the two-dimensional composite exhibited higherG _Ic than the unidirectional commingled composite. Factors increasing the fracture toughness of commingled composites have also been investigated by SEM observation of the fractured surface.     

Photoelectrochemical properties of sol–gel-derived Ti1−xVxO2 solid solution film photoelectrodes

Ti_1−xV_xO₂ solid solution film photoelectrodes were prepared by the dip-coating sol–gel method. X-ray diffraction and X-ray photoelectron spectroscopy were employed to ensure the formation of the solid solution and their composition. Obvious photoresponses were observed in the visible region for the solid solution film electrodes with x0.05 and the red shift of the photoresponse was enhanced with increasing x. Moreover, the solid solution film electrodes were found to be photoelectrochemically stable. However, the onset potential of photocurrent shifted positively with increasing x. Band model of the solid solution was suggested to explain the effects of the vanadium incorporation on the photoelectrochemical properties.     

0.25 μm gate length CMOS devices for cryogenic operation

Under cryogenic operation, a low V_th realizes a high speed performance at a greatly reduced power-supply voltage, which is the most attractive feature of Cryo-CMOS. It is very important in sub-0.25 μm Cryo-CMOS devices to reconcile the miniaturization and the low V_th. Double implanted MOSFET's technology was employed to achieve the low V_th while maintaining the short channel effects immunity. We have investigated both the DC characteristics and the speed performance of 0.25 μm gate length CMOS devices for cryogenic operation. The measured transconductances in the saturation region were 600 mS/mm for 0.2 μm gate length n-MOSFET's and 310 mS/mm for 0.25 μm gate length p-MOSFET's at 80 K. The propagation delay time in the fastest CMOS ring oscillator was 22.8 ps at V_dd=1 V at 80 K. The high speed performance at extremely low power-supply voltages has been experimentally demonstrated. The speed analysis suggests that the sub-l0 ps switching of Cryo-CMOS devices will be realized by reducing the parasitic capacitances and through further miniaturization down to 0.1 μm gate length or below     

Fat-soluble vitamin therapy in senile dementia and Parkinson's disease

In the pathogenesis of Parkinson's disease and senile dementia of the Alzheimer type, free radicals might play a role. Fat-soluble vitamins are a kind of anti-oxidative substance. Therefore, fat-soluble vitamins, such as vitamin E, may be useful in treatment of Parkinson's disease and senile dementia of the Alzheimer type. However, it is still unclear whether the concentration of vitamin E in the blood or in the brain tissue, in patients with Parkinson's disease or with of the senile dementia Alzheimer type, is higher than or the same as that in normal subjects. Furthermore, although the effectiveness of vitamin E in the treatment of Parkinson's disease has been reported, the usefulness of vitamin E is still obscure. Further study will be necessary, in order to clarify the role of fat-soluble vitamins in the treatment of Parkinson's disease and senile dementia of the Alzheimer type.