Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides

The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H₂, Ar, and CO₂, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H₂ atmosphere was white, whereas that obtained from the CO₂ atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO₂ atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H₂ atmosphere increasingly approached near‐stoichiometric SiO₂–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO₂ atmosphere approached a composition of SiO₂–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO₂–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO₂. Estimating from the signal intensity, the residual spin concentrations were in the range 10¹⁸–10¹⁹ g^?1. Meanwhile, the spectra from the samples obtained in H₂ showed weak and sharp signals with estimated spin concentrations ranging from 10¹⁶–10¹⁷ g^?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis.     

混合制冷工质核态沸腾的传热研究

Heat transfer coefficients in nucleate pool boiling were measured on a horizontal copper surface for refrigerants, HFC-134a, HFC-32, and HFC-125, their binary and ternary mixtures under saturated conditions at 0.9MPa. Compared to pure components, both binary and ternary mixtures showed lower heat transfer coefficients.This deterioration was more pronounced as heat flux was increased. Experimental data were compared with some empirical and semi-empirical correlations available in literature. For binary mixture, the accuracy of the correlations varied considerably with mixtures and the heat flux. Experimental data for HFC-32/134a/125 were also compared with available correlated equation obtained by Thome. For ternary mixture, the boiling range of binary mixture composed by the pure fluids with the lowest and the medium boiling points, and their concentration difference had important effects on boiling heat transfer coefficients.     

Development on a coaxial heat integrated distillation column (HIDiC)

Various configurations of a column for performing the principle of HIDiC can be proposed, but a coaxial column which is installed a packing in an inside tube and outer side may be one of the simplest columns for HIDiC. In order to examine whether or not the configuration of the packed column mentioned above is appropriate to HIDiC, an experimental apparatus has been set up and heat and mass transfer rates have been measured by using benzene-toluene system. This paper was presented at The 5th International Symposium on Separation Technology-Korea and Japan held at Seoul between August 19 and 21, 1999.     

Chemical dehydrofluorination and electrical conductivity of poly(vinylidene fluoride) films

The dehydrofluorination of poly(vinylidene fluoride) (PVDF) powder and films was studied using several kinds of base solution. Especially the reactivity of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in ethanol, KOH in 2-propanol and aqueous NaOH solution with tetrabutylammonium bromide was investigated by the change in infrared (IR) and ultraviolet-visible (UV-VI) absorptions of PVDF films. The elimination reactions by DBU or KOH were considered to be accompanied by substitution reaction. The electrical conductivity of dehydrofluorinated PVDF films increased markedly by doping with iodine, and the activation energies of conduction were found to be between 0.4 and 0.5 eV. When a drawn PVDF film was dehydrofluorinated and doped with iodine, anisotropy in conductivity was observed.     

Formation Mechanism of Porous Alumina With Oriented Cylindrical Pores Fabricated by Unidirectional Solidification

Porous alumina whose pores were aligned in one direction was fabricated by the unidirectional solidification method under a pressurized hydrogen atmosphere. The porous structure is formed at the solid–liquid interface during solidification due to a hydrogen solubility gap at the melting point. The hydrogen gas is dissolved into molten alumina according to Sieverts' law and insoluble gas that corresponds to the amount of solubility gap evolves from the solid phase at the solid–liquid interface during the unidirectional solidification to form the pores. The porosity and pore size of the solidified samples decreased with increasing total pressure where the environmental gas consisted of pure hydrogen or hydrogen–argon mixed gases. There is a reverse proportion relation between the pore diameter and the total pressure according to Boyle's law.     

Diamond-like carbon thin film with controlled zeta potential for medical material application

With the purpose of applying diamond-like carbon (DLC) thin films as a biocompatible material, we experimented with introducing functional groups such as amino and carboxyl groups to the surface of DLC thin films by plasma surface treatment. From the results, it was found that the contact angle values of the DLC thin films surface were decreased with increasing in the OCO bonded network on the surface. Measurement of the zeta potential when the amounts of the functional groups were varied showed that this successfully varied the zeta potential over the wide range of − 48 mV to + 12 mV. It was found that when carboxyl groups are introduced by O₂ plasma modification of the DLC thin films surface, the zeta potential was lower than that of untreated DLC thin films sample. It was also found that amino groups can be introduced to the DLC thin films surface by NH₃ plasma treatment, the zeta potential was higher than that of untreated DLC thin films sample. This means that zeta potential of the DLC thin films can also be controlled by controlling these two functional groups. Therefore, we have succeeded in developing a multifunctional DLC thin films that does not use polymers and is suitable as a biocompatible material.     

Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase

Biodiesel derived from vegetable oils has drawn considerable attention with increasing environmental consciousness. We attempted continuous methanolysis of vegetable oil by an enzymatic process. Immobilized Candida antarctica lipase was found to be the most effective for the methanolysis among lipases tested. The enzyme was inactivated by shaking in a mixture containing more than 1.5 molar equivalents of methanol against the oil. To fully convert the oil to its corresponding methyl esters, at least 3 molar equivalents of methanol are needed. Thus, the reaction was conducted by adding methanol stepwise to avoid lipase inactivation. The first step of the reaction was conducted at 30°C for 10 h in a mixture of oil/methanol (1:1, mol/mol) and 4% immobilized lipase with shaking at 130 oscillations/min. After more than 95% methanol was consumed in ester formation, a second molar equivalent of methanol was added and the reaction continued for 14 h. The third molar equivalent of methanol was finally added and the reaction continued for 24 h (total reaction time, 48 h). This three-step process converted 98.4% of the oil to its corresponding methyl esters. To investigate the stability of the lipase, the three-step methanolysis process was repeated by transferring the immobilized lipase to a fresh substrate mixture. As a result, more than 95% of the ester conversion was maintained even after 50 cycles of the reaction (100 d).     

Origin of the Red Color of Satsuma Copper-Ruby Glass as Determined by EXAFS and Optical Absorption Spectroscopy

The origin of the ruby color of Satsuma glass, a famous copper-ruby glass produced in Japan in the mid-19th century, has been examined by electron microprobe analysis (EPMA), X-ray absorption fine structure (XAFS), and optical absorption spectroscopy analyses. Cu K XAFS analysis reveals that the major component of copper in the ruby glass consists of Cu(I) ions in the glass structure. This species is distinct from Cu₂O (cuprite), which we conclude is not responsible for the ruby color. Optical absorption spectra measured at 300 and 77 K clearly distinguishes the absorptions due to the colloidal particles of metallic copper and Cu₂O. It is concluded that the trace amount of copper in the ruby glass, which is below the detection limit of the EPMA and XAFS techniques, exists as metallic copper particles of nanometer size and is responsible for the ruby-red appearance of the Satsuma glass.     

Extraction of lanthanide ions from aqueous solution by bis(2-ethylhexyl)phosphoric acid with room-temperature ionic liquids

Extractions of five kinds of lanthanide metal ions by bis(2-ethylhexyl)phosphoric acid (DEHPA) with [1-Cn-3-methylimidazolium][PF₆](Cn = C₂, C₄) or [1-butyl-4-methylpyridinium][PF₆] were carried out under various DEHPA and HNO₃ concentrations from 0 to 1 M and under different temperature conditions from 298 to 333 K. These results were compared with those using the conventional organic solvent, hexane, in terms of their distribution coefficient values. Under all of the conditions in this study, the ionic liquid system shows more than three times greater extractability for lanthanide compared to when hexane was used. The distribution coefficient of lanthanide ions decreased as the length of the alkyl chain increased from the ethyl to the butyl. In addition, the imidazolium cation generally shows a higher distribution coefficient compared to the pyridinium cation in an ionic liquid. The concentration ratio of lanthanides and DEHPA resulted in an extraction affinity transition for lanthanides. Also evaluated in this study were issues related to the selectivity associated with the lanthanide mixture and the dependency of the ionic radius during lanthanide extraction.     

Relative reactivity of phenylboronic acid to phenylboronate ion toward L-lactate and mandelate at physiological pH

Kinetic studies were performed on the reactions of phenylboronic acid with L-lactic acid and mandelic acid in acidic aqueous and alkaline solutions in order to specify reactive species in these reactions. It was confirmed that the diprotonated ligand (H₂L: L-lactic acid or mandelic acid) is less reactive than the monoprotonated ligand (HL^?: L-lactate ion or mandelate ion), which made possible direct determination of the rate constants of phenylboronic acid (PhB(OH)₂) and its conjugate base, phenylboronate ion (PhB(OH)₃^?). It was found that PhB(OH)₂ is more reactive than PhB(OH)₃^?. On the basis of kinetic results, it was concluded that the most reactive species are PhB(OH)₂ and HL^? at physiological pH 7.4, so the reaction in the boronic acid-based sensor for L-lactate mainly would occur between these species.