• Bulletin of the Korean Chemical Society
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• v.4 no.1
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• pp.14-17
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• 1983

The effects of trialkylborane on the stereochemistry of ketone reduction with lithium borohydride were studied for the four representative ketones, namely 4-t-butylcyclohexanone, 2-methylcyclohexanone, norcamphor, and camphor. The presence of trialkylborane increased the yields of the less stable alcohols. For example, in the presence of tri-s-butylborane, 42 % yield of cis-4-t-butylcyclohexanol was observed whereas only 8 % yield with lithium borohydride alone in the reduction of 4-t-butylcyclohexanone. The in situ formation of lithium trialkylborohydride, by the hydride transfer from lithium trialkoxyborohydride to trialkylborane, was demonstrated as a possible mechanism for the catalytic effect of trialkylborane.

• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.444-449
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• 1987

Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, $CH_2$ = CHR where R = CN, CHO and $NO_2$, are investigated theoretically using the AM1 method. Results show that the methoxide approaches in-plane in all reactions, but subsequently rotate out-of-plane to form tetrahedral complexes in additon reactions. All reactions of a bare methoxide are found to be exothermic, the exothermicity being the greatest in the ${\beta}$-addition, in which the excess energy is forced to be contained within the ${\beta}$-adduct rendering extreme instability. However a part of the excess energy can be removed by a solvate molecule giving a stable complex prior to the product formation. The hydride transfer processes were found to be unfavorable due to the high activation barriers. The ${\alpha}-H^+$ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.307-309
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• 1990

The stereoselectivity of the reaction between methyl vinyl ketone dimer, which contains two possible sites of chelation, and zinc borohydride or diisobutylaluminum hydride has been studied in order to illuminate the factors involved in the high levels of asymmetric induction obtained in the bicyclic system. The conditions for the formation of the exo-5,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane are DIBAH reduction of MVK dimer in ether at reflux followed by acidic cyclizatioan, and for the endo isomer are $Zn(BH_4)_2$ reduction with $ZnCl_2$ at $0^{\circ}C.$.

• Bulletin of the Korean Chemical Society
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• v.3 no.4
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• pp.157-162
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• 1982

9-Methylenethioxanthene(6) was synthesized and for the first time good mp and spectral data were taken. Reaction of (6) with thioxanthylium ion (1) in acetonitrile led to a carbenium addition adduct (8) which then was either attacked by a variety of nucleophiles subsequently added or underwent deprotonation reaction to give an olefin (13). From these reactions, was obtained bis-9,9'-thioxanthenylmethane (2). These results indicate clearly that (2) can be formed via (8) by accepting hydride. Isolation of (2) and (6) from the reaction of (1) with 9-methylthioxanthylium ion (18) also supports the involvement of (8) in the reaction of (1) with dimethylmercury. However, addition of thioxanthene radical (4) to (6) has not been ruled out.

• Nuclear Engineering and Technology
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• v.56 no.3
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• pp.824-831
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• 2024

In order to investigate the occurring processes during long-term dry storage of spent fuel assemblies, a joined project called SPIZWURZ, between the Karlsruhe Institute of Technology and the Gesellschaft für Anlagen-und Reaktorsicherheit (GRS), was started. Aim of the SPIZWURZ project is the determination and quantification of the influence of texture and elastic strain on diffusion and solubility of hydrogen in three different zirconium alloys used in western Europe during a long-term cooling transient (1 K/d) starting at 400 ℃. The strain in the cladding of an irradiated spent fuel rod shall be measured. Models predicting the formation of radial oriented hydrides will be validated, improved, and implemented in the GRS fuel rod performance code TESPA-ROD. This paper describes the SPIZWURZ project and already obtained first results.

• Transactions of the Korean hydrogen and new energy society
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• v.2 no.1
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• pp.29-37
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• 1990

The effect of pressure cycling of $Zr_{0.9}Ti_{0.1}Cr_{0.7}Fe_{1.3}$ on the hydrogenation properties was investigated using the P-C-Isotherm curves and hydrogen absorption rate curves in the isotherm condition. The reversible hydrogen absorption capacity was decreased about 45 % after 3300 cycles. In the case of activated sample, the rate controlling steps of hydriding reaction changed from the surface reaction to the hydrogen diffusion process through hydride phase sequentially as reaction proceeded. After 3300 cycles, the sequential change of rate controlling step was same as activated one. However, the hydrogen absorption rate significantly decreased. It is suggested that the degradation of $Zr_{0.9}Ti_{0.1}Cr_{0.7}Fe_{1.3}$ can be interpreted with the formation of $ZrFe_3$ phase at the particle surface.

• Journal of the Korean Ceramic Society
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• v.33 no.10
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• pp.1170-1176
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• 1996

Porous silicon was prepared by anodic reaction. The process was controlled by current density and etching time an the thickness change and the room temperature PL was measured. The thickness of porous silicon was increased with etching time and was decreased after critical time. It was the same as increasing current density. It needed only 15 sec to electropolish the surface of porous silicon above current density 70 mA/cm2. We can understand that increasing etching time leads narrow size of Si column by porous silicon formation mechanism. And the sample with narrow Si column revealed PL blue shift. The specimens were heated in the range of 300-1000$^{\circ}C$ in order to see PL changes. The heat treatment was proceeded in H2 atmosphere vacuum system to avoid oxidation. The PL was disappeared above 600$^{\circ}C$. In high temperature some sintered Si columns were observed in SEM photography. There was no difference of -Hx bonds which was suggested as evidence of hydride compounds luminescence between 500$^{\circ}C$ and 600$^{\circ}C$. Thus it is concluded that quantum confinement is major factor of PL of porous silicon.

• Transactions of the Korean hydrogen and new energy society
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• v.1 no.1
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• pp.1-8
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• 1989

The hydriding kinetic mechanism and the change of the hydriding reaction rate of $MmNi_{4.5}Al_{0.5}$ during the thermally induced hydrogen absorption-desorption cycling are investigated. Comparison of the reaction rate data which are obtained by the pressure sweep method with the theoretical rate equations suggests that the hydriding rate controlling step has changed from the dissociative chemisorption of hydrogen molecules at the surface to the hydrogen diffusion through the hydride phase with the increase of the hydriding fraction. These hydriding kinetic mechanism is not changed during the cycling. However, the intrinsic hydriding reaction rate of $MmNi_{4.5}Al_{0.5}$ after 5500 cycles increases significantly comparing with the activated one. It is suggested that the change of the hydriding kinetic behavior due to intrinsic degradation of $MmNi_{4.5}Al_{0.5}$ can be interpreted as follows ; the formation of nickel cluster at the surface of the sample and the host metal atom exchange in bulk by thermal cycling.

• Proceedings of the KSME Conference
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• 2003.11a
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• pp.1133-1138
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• 2003

The pressure tubes, which contain high temperature heavy water and fuel, are within the core of a CANDU nuclear reactor, and are thus subjected to high stresses, temperature gradient, and neutron flux. Further, it is well known that pressure tubes of cold-worked Zr-2.5Nb materials result in hydrogen diffusion, which create fully-hydrided regions (frequently called Blister). Thus a proper investigation of hydrogen diffusion within zirconium-alloy nuclear components, such as CANDU pressure tube and fuel channels is essential to predict the structural integrity of these components. In this respect, this paper presents numerical investigation of hydrogen diffusion to quantify the hydrogen concentration for blister growth of CANDU pressure tube. For this purpose, coupled temperature-hydrogen diffusion analyses are performed by means of two-dimensional finite element analysis. Comparison of predicted temperature field and blister with published test data shows good agreement.

• Bulletin of the Korean Chemical Society
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• v.23 no.4
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• pp.563-566
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• 2002

Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.