Optical Energy Gap and Below Gap Optical Absorption of Fullerene Films Measured by the Constant Photocurrent Method and Photothermal Deflection Spectroscopy

The CPM spectra of fullerene films was measured to obtain the below gap absorption. The optical energy gap E_o was obtained by using the Tauc's plots. E_o did not change greatly with intercalated impurities. The absorption due to intercalated impurities was found below 1.6eV.     

Study on modified phenolic resin. I. Modification with homopolymer prepared from p-hydroxyphenylmaleimide

We studied the improvement of heat resistance and mechanical properties of phenolic resin modified with polymers prepared from p-hydroxyphenylmaleimide (HPMI). Homopolymers of HPMI and copolymers of HPMI with some vinyl monomers were synthesized and M_n T_g and thermal decomposition temperature of them were measured by GPC, DSC, and TG, respectively. The miscibility of homopolymer with novolac was examined by DSC. It was found that the homopolymer had good heat resistance and good miscibility with novolac. Molding compounds were prepared by hot roll-kneading the mixtures of novolac, the homopolymer, hexamethylenetetramine, and glass fiber. It was found that molded test pieces had good heat resistance.     

Examination of acetolysis products of phosphatidylcholine by gas chromatography-mass spectrometry

A comparison of monoacetyldiglycerides obtained from authentic phosphatidylcholines by acetolysis with those obtained by phospholipase C-acetylation was made to examine the intermolecular acyl migration, the intramolecular acyl migration between C-1 and C-2, and the formation of 1,3-isomer in the acetolysis reaction. Egg yolk phosphatidylcholine also was used. It was revealed that is acetolysis, the intermolecular acyl migration and selective degradation of polyunsaturated fatty acids did not take place at all. The intramolecular acyl migration, including the formation of 1,3-isomer, occurred to a small extent. Appreciable difference was not found in comparison of molecular species compositions of monoacetyldiglycerides derived by both methods from egg yolk phosphatidylcholine, except small differences found in the contents of two kinds of molecular species.     

Network formation and swelling behavior of photosensitive poly(vinyl alcohol) gels prepared by photogenerated crosslinking

Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained. The proportion of the free water to the bound water in PVA-SbQ gels was 3.3?2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27?0.58. The water uptake after swelling of the gels in water increased 6–27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2?5.8) × 10^?5 cm² S^?1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.     

Stepwise increase of hardness in the curing process of one-step phenolic folding compounds

The curing behavior of one-step phenolic molding compounds was studied using results of Rockwell hardness measurements at elevated temperatures with a cone indenter. The curing process was found to advance in a stepwise manner to the final stage of cure at a specific temperature. An explanation for this phenomenon has been attempted by suggesting the alternating occurrence of two types of curing reactions—propagation and crosslinking. After proceeding to some extent of cure, only the propagation reaction can occur through the migration of low molecular resin to the reactive sites of polymer chains. The propagation facilitates the subsequent crosslinking which drastically enhances the hardness of the resin. The results of electrical resistivity measurements and acetone extraction tests were also found to support the occurrence of above phenomenon.     

Characterization of Silicon Carbide–Silicon Nitride Composite Ultrafine Particles Synthesized Using a CO2 Laser by Silicon-29 Magic Angle Spinning NMR and ESR

The structure of silicon carbide–silicon nitride (SiC–Si₃N₄) composite particles synthesized using a CO₂ laser was studied by magic angle spinning nuclear magnetic resonance (MAS-NMR) and electron spin resonance (ESR). The structure around Si atoms changed by introducing N. C atoms around Si were substituted by N atoms, and N-rich configurations around Si atoms increased stepwise as the N content increased. The low N content composite particles consisted of mainly SiC phase containing dissolved N. N atoms were partly present in β-SiC microcrystal and partly in the grain boundary layer in the particle. N atoms were tetrahedrally surrounded by four Si atoms in β-SiC microcrystal and were trivalent state bonded to three Si atoms in the grain boundary layer. The high N content particles consisted of SiC, Si₃N₄, and amorphous phases, whose amount depended on N content.     

Chemospecific ring-opening polymerization of α-methylenemacrolides

α-Methylenemacrolides having various groups, such as aromatic, ether, and amine, were enzymatically, anionically, and radically polymerized. The polymerization with the lipase catalyst successfully afforded polymers only through the ring-opening process, whereas the vinyl polymerizations selectively proceeded by using anionic and radical initiators. The polyesters obtained by the enzymatic polymerization have a polymerizable methacrylic methylene group in the main-chain, in addition to the aromatic and polar groups, and were further radically polymerized to quantitatively produce a cross-linked polymer gel.     

Preparation of Titanium Nitride Films from Amide Precursors Synthesized by Electrolysis

A TiN precursor solution was synthesized by galvanostatic electrolysis of Ti metal and isopropylamine at a current density of 50 mA·cm⁻² at room temperature. TiN films were prepared by dip-coating of the precursor solution on a Si wafer, followed by two-stage heat treatment at 400°C and a fixed temperature of 800–1200°C in flowing N₂, N₂/NH₃, or NH₃ gas. The TiN films were characterized by XRD, chemical analysis, XPS, and electrical resistivity measurements. The TiN films were composed of uniform grains 20 to 200 nm in size with thicknesses ranging from 300 to 400 nm at temperatures of 800–1200°C. The effect of the heat treatment atmosphere (N₂ and NH₃) on the impurity content, crystallinity, particle size, and electrical resistivity is discussed.     

Study on modified phenolic resin. II. Modification with p-hydroxyphenylmaleimide/styrene copolymer

The improvement of heat resistance and mechanical properties of phenolic resin was examined with the blend of novolac and copolymers prepared from p-hydroxyphenylmaleimide (HPMI) and styrene. Copolymers of HPMI and styrene with various molecular weights were synthesized. Glass transition (T_g) and thermal decomposition temperatures of the copolymers were measured by differential scanning calorimetry (DSC) and thermogravimetry (TG), respectively. The miscibility of the copolymers with novolac was examined by DSC. It was found that the copolymers had a good heat resistance and a good miscibility with novolac. Molding compounds were prepared by hot roll-kneading of mixtures that involved novolac, copolymer, hexamethylenetetramine (hexamine), and glass fiber. It was found that the test pieces prepared by transfer molding from the molding compounds showed a good heat resistance and better mechanical properties than phenolic resin modified with HPMI homopolymer.     

Evaluation for the curing characteristics of phenolic molding compounds by rockwell hardness test at an elevated temperature

Rockwell hardness measurement at an elevated temperature has been proposed as an evaluation method for the curing characteristics of thermosetting molding compounds. This method is convenient and has a high accuracy over a wide range of curing, Using a cone indenter, the following advantages are brought about: a good correspondence with acetone extraction test, in showing the degree of cure of the internal part of a molding rather than that of the skin layer, and a higher sensitivity in measuring higher degrees of cure. On examining curing behavior of commercial phenolic molding compounds by this method, an inflection point was observed on a plot of the hardness vs log curing time. This critical point has been called “the minimum cure time”, beyond which the molding exhibits good physical properties.