• Journal of the Korean Society of Safety
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• v.8 no.4
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• pp.27-40
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• 1993

High temperature tensile tests, steady state creep tests, Internal stress tests and creep rupture tests using A17075 alloy( $T_{6}$ ) were performed over the temperature range of 9$0^{\circ}C$~50$0^{\circ}C$ (0.4 $T_{m}$ ~0.85 $T_{m}$ ) and stress range of 0.64~17.2(kgf/$\textrm{mm}^2$). The main results obtained in this paper were as follows. (1) The activation energies for yielding at the temperature of 0.4 $T_{m}$ ~0.75 $T_{m}$ were calculated to be 25.7~36.5kcal/mol, which were nearly equal to the activation energies for creep. (2) At around the temperature of 9$0^{\circ}C$~12$0^{\circ}C$ and under the stress level of 10~17.2(kgf/$\textrm{mm}^2$), and at around the temperature of 200~41$0^{\circ}C$ and under the stress level of 1.53~9.55(kgf/$\textrm{mm}^2$) and again at around the temperature of 470~50$0^{\circ}C$ and under the stress level of 0.62~l.02(kgf/$\textrm{mm}^2$), the applied stress dependence of steady state creep rate $n_{measu}$ measured were, respectively, 3.15, 6.62 and 1.1, which were in good agreement the calculated stress dependence $n_{ealeu}$ obtained by the difference of the applied stress dependence of the Internal stress and the ratio of the internal stress to the applied stress. (3) At the temperature range of 0.4~0.43 $T_{m}$ , and at the temperature range of 0.52~0.75 $T_{m}$ and again at the temperature range of 0.82~0.85 $T_{m}$ , the activation energies $Q_{measu}$ obtained by steady state creep rate, respective, 26. 16, 34.9, 36.2 and 36.1kcal/mol, which were in good agreement with those obtained with the activation energies under constant effective stress and the temperature dependence of Internal stress. (4) At the temperature range of the 0.52~0.73 $T_{m}$ and under the stress level of 1.53~9.55(kgf/$\textrm{mm}^2$), the stress dependence of rupture life(n’) measured was 6.3~6.6, which was in good agreement with the stress dependence of steady state creep rate(n). And at the same condition the activation energy for rupture( $Q_{f}$ ) measured was 32.0~36.9kca1/mol, which was also in good agreement with the activation energy obtained by steady state creep rate ( $Q_{c}$ ). (5) The rupture life( $t_{f}$ ) might be represented by athermal process attributed to the difference of the applied stress dependence of the internal stress and the ratio of the internal stress to the applied stress, and the thermal activated process attributied to the temperature dependence of the internal stress as $t_{f}$ = A'$\sigma$$_{a}$ ｛n(1-d $\sigma$$_{i}$ /d $\sigma$$_{a}$ )/(1-$\sigma$$_{i}$ / $\sigma$$_{a}$ )｝.exp[｛ $Q_{c}$ $^{*}$-( $n_{o}$ R $T^2$/ $E_{(T)}$) (d $E_{(T)}$/dT) - ( $n_{0}$ R $T^2$/ $\sigma$$_{a}$ - $\sigma$$_{i}$ ) (d $\sigma$$_{i}$ /dT)｝/RT]. (6) The relationship betwween Larson-Miller rupture parameter and logarithmic stress was linearly decreased, so creep rupture life of Al 7075 alloy seemed to be predicted exactly with Larson-Miller parameter.meter.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.1939-1945
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• 2009

Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.174-179
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• 1992

Reaction of aniline and iodine in$CHCl_3,\;CH_2Cl_2 : CHCl_3$(1 : 1), and $CH_2Cl_2$ has been studied kinetically by using conductivity method, Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[aniline]) are dependent on the aniline concentration. Second-order rate constants obtained were increased with increasing aniline concentration. We analysed these results on the basis of formation of charge transfer complex as reaction intermediate. From the construction of react ion scheme and derivation of rate equation, we calculated equilibrium constants and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants were decreased by an increase in the dielectric constant of the solvent and the value is 1.7-3.7$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity. ${\Delta}H^{\neq}$ is about 14.2kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -243J/mol K.

• Korean Journal of Food Science and Technology
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• v.23 no.3
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• pp.355-359
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• 1991

Effects of temperature and pH on thermal degradation of monosodium glutamate(MSG) were investigated during heating of 2% MSG solution at $100{\sim}200^{\circ}C\;and\;pH\;4{\sim}9$. The results showed that the degradation of MSG was very significantly affected by heating temperature and pH. Three hours of heating at $pH\;4\;and\;120^{\circ}C$ resulted appr. 73% MSG degradation while 3 hours at $100^{\circ}C$ decreased only 12%. The comparison study of initial rate of MSG degradation and degradation rate constants showed the highest degradation rate and rate constant and low values in the range of $pH\;6{\sim}8{\sim}$. The values of activation energy calculated from linear relationship of rate constants and 1/T were 18.3 and 9.2 kcal/mole for pH 4 and 5, respectively.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.540-545
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• 1992

Kinetics and mechanism on the solvent extraction of nickel(Ⅱ) with 8-hydroxyquinoline (HOx) was studied spectrophotometrically. Absorbance variation was measured by changing the 8-hydroxyquinoline concentration in the chloroform organic phase and the pH values in the aquous phase. By analyzing absorbance data the reaction rate was found to be the first order for 8-hydroxyquinoline concentration and the inverse first one for [H$^+$]. Therefore the rate determining step of the extraction reaction is the formation of the one-to-one metal chelate NiOx$^+$ and the rate equation is as follows; -d[Ni$^{2+}$]/dt = k[Ni$^{2+}$][Ox$^-$] = k'[Ni$^{2+}$][HOx]$_0$/[H$^+$]. The value of k' was evaluated from the slope of plot of log [Ni$^{2+}$]$_0$/[Ni$^{2+}$]$_t$ versus time and the rate constant k was calculated according to the equation k' = k ${\times}$ K$_{HOx}$ / K$_{D,HOx}$. From the temperature dependence of the extraction rate, the activation energy E$_a$ = 6.26 kcal/mol is calculated, and activation parameters, ${\Delta}$G$^{\neq}_{298}$ = 6.59 kcal/mol, ${\Delta}$H$^{\neq}_{298}$ = 5.68 kcal/mol, ${\Delta}$S$^{\neq}_{298}$ = -3.09 eu/mol are estimated.

• BMB Reports
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• v.32 no.3
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• pp.226-231
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• 1999

In vitro effects of acetone on cytochrome P450 (P450)-dependent benzo(a)pyrene (B(a)P) hydroxylation supported by cumene hydroperoxide (CuOOH) or NADPH/$O_2 $ systems were studied using 3-methylcholanthrene-pretreated rat liver microsomes. The maximal rate of B(a)P hydroxylation at constant concentration ($80\;{\mu}M)$ of the substrate was observed in the presence of $30\;{\mu}M$ CuOOH. However, at concentrations higher than $30\;{\mu}M$ CuOOH the hydroxylation rates were rapidly decreased. In contrast to CuOOH, at a concentration of $200\;{\mu}M$ NADPH, B(a)P hydroxylation rate reached a plateau. At concentrations higher than $200\;{\mu}M$ NADPH, the rates of substrate hydroxylation were maintained at the maximal rate with no inhibition. Acetone at 1% (v/v) enhanced both CuOOH- and NADPH/$O_2$-supported B(a)P hydroxylation at the optimal concentrations of the cofactors. At concentrations higher than 1% (v/v) acetone, substrate hydroxylation was sterero specific under the support of these two cofactors; it was strongly enhanced with $30\;{\mu}M$ CuOOH, but rather inhibited in the $200\;{\mu}M$> NADPH/$0_2 $ system. The lipid peroxidation rate induced during CuOOH-supported P450-dependent B(a)P hydroxylation was increased as CuOOH concentrations were increased. Acetone in the concentration range of 2.5~7.5%(v/v) inhibited lipid peroxidation during CuOOH supported B(a)P hydroxylation. The finding that CuOOH-supported B(a)P hydroxylation is greatly enhanced by acetone suggests that acetone may contribute more to the activation of oxygen (for the insertion of oxygen into the substrate) in the presence of CuOOH than with NADPH/$O_2$. Acetone may also contribute to the partial inhibition of destruction of microsomal membranes by lipid peroxidation.

• Microbiology and Biotechnology Letters
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• v.7 no.3
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• pp.141-147
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• 1979

Naringinase from Atpergillus nidulans was immobillized on DEAE-Sephadex A-25 and its characteristics were studied. The optimal conditions for the preparation of the immobilized enzyme were as follow; optimal pH, incubation time and the suitable amount of enzyme were 6.0, 30 min. and 110 units per gram of the dried ion exchage resin, respectively. The optimal pH of the immobilized enzyme was higher than that of the native enzyme. The optimal temperature increased from 4$0^{\circ}C$ to 5$0^{\circ}C$. The heat and pH stability of the immobillized enzyme were better than those of the native enzyme. No significant difference in the Michaelis constant was detected. Activation energy of the immobilized enzyme was 7.96 Kcal/mole, and the apparent Michaelis rate equation was used to describe the action of this material. The degree of hydrolysis was dependant on the flow rate at low rate of perfusion through the column. As the flow rate increased, the value of the apparent Km decreased.

• Journal of the Korean institute of surface engineering
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• v.46 no.1
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• pp.29-35
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• 2013

The effect of DC bias on the growth of nanocrystalline diamond films on silicon substrate by microwave plasma chemical vapor deposition has been studied varying the substrate temperature (400, 500, 600, and $700^{\circ}C$), deposition time (0.5, 1, and 2h), and bias voltage (-50, -100, -150, and -200 V) at the microwave power of 1.2 kW, working pressure of 110 torr, and gas ratio of Ar/1%$CH_4$. In the case of low negative bias voltages (-50 and -100 V), the diamond particles were observed to grow to thin film slower than the case without bias. Applying the moderate DC bias is believed to induce the bombardment of energetic carbon and argon ions on the substrate to result in etching the surfaces of growing diamond particles or film. In the case of higher negative voltages (-150 and -200 V), the growth rate of diamond film increased with the increasing DC bias. Applying the higher DC bias increased the number of nucleation sites, and, subsequently, enhanced the film growth rate. Under the -150 V bias, the height (h) of diamond films exhibited an $h=k{\sqrt{t}}$ relationship with deposition time (t), where the growth rate constant (k) showed an Arrhenius relationship with the activation energy of 7.19 kcal/mol. The rate determining step is believed to be the surface diffusion of activated carbon species, but the more subtle theoretical treatment is required for the more precise interpretation.

• The Korean Journal of Pesticide Science
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• v.2 no.2
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• pp.10-15
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• 1998

The bimolecular inhibition rate constants of carbofuran and N-dimethylphosphinothioyl carbofuran(PSC) to acetylcholinesterase(AChE) were $7.7{\times}10^{5}\;M^{-1}{\cdot}min^{-1}$ and $1.2{\times}10^{3}\;M^{-1}{\cdot}min^{-1}$, respectively. These results showed that PSC required a bioactivation process for its toxic action because it didn't inhibit the target enzyme effectively. The potency of PSC as an inhibitor of AChE increased when PSC and AChE were incubated with microsomes fortified with NADPH compared with microsome alone. Piperonyl butoxide(PBO) addition to these coupled systems greatly reduced the inhibition of the target enzyme by blocking the bioactivation process. In vivo inhibition study of mouse brain AChE, $I_{50}$ value for AChE was 28 mg/kg for PSC and the value increased to 57 mg/kg when PBO was pretreated. This result showed that cytochrome $P_{450}$ would also play a role in the bioactivation process of PSC in vivo. And conversioin of carbofuran from PSC was 55 % in a chemical oxidation system using meta-chloroperoxybenzoic acid. The oxidative activation of PSC to carbofuran was shown to be essential for showing its toxicological action and cytochrome $P_{450}$ was identified as an important enzyme which participated in this process.

• Transactions of the Korean hydrogen and new energy society
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• v.8 no.3
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• pp.121-129
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• 1997

$ZrV_{0.1}Mn_{0.7}Ni_{1.2}$ alloy ingot (bulk alloy) made by the arc melting was found to be consisting of mostly of $ZrV_{0.2}Mn_{0.98}Ni_{1.04}$ matrix alloy and $ZrV_{0.01}Mn_{0.13}Ni_{1.2}$ 2nd phase alloy. The former alloy had the form of the C15 type Laves alloy structure and the latter one had the intermetallic compound structure of $Zr_9Ni_{11}$. In order to investigate the effect of these two phases on the electrochemical charge-discharge characteristics of bulk $ZrV_[0.1}Mn_0.7}Ni_{1.2}$ alloy, the matrix and the 2nd phase alloys were fabricated separately by arc melting method and their electrochemical characteristics were studied and compared with the bulk alloy. It was found that the discharge capacity was the lowest of 160 mAh/g in the 2nd phase alloy. The matrix alloy exhibited 200 mAh/g. Both were lower than that of the bulk alloy of 250 mAh/g. The matrix and the bulk alloys showed a similar properties in the activation stage, the high rate dischargeability and the self discharge characteristics. Also a signigicant capacity decrease was observed after activation in both alloys. Whereas the 2nd phase alloy showed the very different characteristics. This alloy was found to be difficult to activate. However the capacity was remained constant after the activation. Also the self discharge rate was seen to be better than those of the matrix and the bulk alloys.