CVD와 무전해 도금법을 이용하여 TiN 기판상에 구리막을 성장시켰고 그 각각에 대해 증착조건에 따른 성장막의 morphology, 성장기구 및 비저항, 막의 치밀성 등의 물리적 특성을 조사하였다. CVD 증착막의 결정립 크기와 입간의 기공은 막두께에 비례하여 커지는 경향을 나타내었으며 비저항은 4.7μΩcm로 구리의 체적비저항값과 거의 비슷한 것으로 나타났다. 무전해 도금막은 초기에는 layer-by-layer mode로 나중에는 is-land growth mode로 성장하는 경향을 보였다. CVD구리막의 막질은 후열처리 분위기에 따라서도 상당한 차이를 보였다. CVD구리막의 막질은 후열처리 분위기에 따라서도 상당한 차이를 보였으며, 활성화 에너지로부터 350˚C를 기준으로 증착기구가 변하는 것을 확인할 수 있었던 반면, 무전해 도금은 60-80˚C의 온도 구간에서 증착기구는 변하지 않았으나 도금 온도가 높을수록 막표면이 거칠어지는 경향을 나타내었다. 7:1 BHF 에칭 실험의 결과 무전해도금에 의한 구리막에 비해 CVD구리막의 에칭속도가 더 빨랐으며 막질도 덜 치밀한 것으로 나타났다.

The Kinetics velocity for hydrolysis reaction of vanillylidene imine derivatives has been measured by ultra-violet ray spectrophotometer in 20wt% dioxane-H2O at 25℃. It was measured the reaction rate Constant of vanillylidene imine derivatives that can be applied widely following to pH-change at 25℃. Final products that hydrolyzed the vanillylidene imine certified in vanillin and aniline derivative, and the effect of substitution radical that has affected on hydrolysis reaction was largely promoted to reaction rate by electron attrating group in acidity and electron donoring group in basic. From the results of rate constant to hydrolysis reaction, substituent radical effect and final products. It has certified the hydrolysis reaction mechanism of vanillylidene imine derivatives.

Benzoyl styrene derivatives were synthesized by Claisen-Schmidt condensation. It was measured that nucleophilic addition of thiourea for benzoyl styrene made use of ultraviolet spectrophotometery at a wide pH 1.0~13.0 range in 5% dioxane-H2O at 40℃. On the basis of general base catalysis, substitutent effect, and confirmation of addtion reaction product, the nucleophilic addtion kinetics of thiourea for benzoylstyrene derivatives were measured by pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0. It was in propotion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral thiourea molecule. From the results of measurement the reaction rate and there findings, nucleophilic addition of thiourea to benzoylstyrene derivative was proposed a fitting mechanism.

The rate constant of Nucleophilic addition of sodium thiophenoxide to nitrone were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Blow pH 3.0, the reaction was initiated of thiophenol, and in the range of pH 3.0~10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

The rate constant of the nucleophilic addition of 1-propanethiol to α-phenyl-N-iso-propylnitrone derivatives were determined at various pH and a rate equation which can be applied over wide pH range is obtained. Final product of the addition reaction was α-thiopropyl-p-phenylbenzylideneamine. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0, the reaction was initiated by the addition of 1-propanthiol, and in the range of pH 3.0-10.0, proceeded by the competitive addition of 1-propanethiol and propanethiolate. Above the pH 10.0, the reaction proceeded through the addition of propanethiolate.

DGEBA (diglycidyl ether of bisphenol A )/MDA(4,4'-methylene dianiline)/SN(succinonitrile)계와 DGEBA/MDA/SN/HQ(hydroquinone)계의 경화반응 속도론을 Kissinger equation 및 Fractional life 법에 의해 85~150˚C에서 DSC를 이용하여 연구하였다. 경화반응 온도가 높아짐에 따라 반응속도는 증가하는 반면, 반응차수는 거의 일정하였다. 또한 촉매로 HQ를 첨가한 계가 첨가하지 않은 계보다 반응속도는 크게 증가했으며, 활성화 에너지 값은 약 20% 정도 감소하였다 또한, 경화반응 시작온도는 30˚C 정도 낮아졌다.

The Hydrolysis kinetics of Benzoyl Styrene Derivatives[I]~[IV] was investigated by ultraviolet spectrophotometery in 5% dioxane-H2O at 40℃. The structure of these compounds were ascertained by means of ultraviolet, melting point, IR and NMR spectra. The rate equations which were applied over a wide pH range (pH 1.0~13.0) were obtained. The substituent effects on Benzoyl styrene derivatives[I]~[IV] were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation and substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed: At pH 1.0~pH 9.0, not relevant to the hydrogenl ion concentration, neutral H2O molecule competitively attacked on the double bond. By contrary. Above pH 9.0, It was proportional to concentration of hydroxidel ion.

본연구는 DSC (dynamic run)의 Barrett method Integral mdthod DGEBA/MDA/MN(malononitrile) DSC DSC pre exponential factor, kinetic parameter 들을 구할 수 있었다.

The rate constants of hydrolysis of α-phenly-N-iso-propylnitrone and its derivatives have been determined by UV spectrophotometry at 25℃ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and general base and substituent effects, plausible mechanism of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to α-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. In the range of 4.5~10.0, the addition of water to nitrone was rate controlling step.

The hydrolysis reaction kinetics of 2-thienyl chalcone derivatives [II]~[V] was investigated by ultraviolet spectrophotometery in 20% dioxane-H2O at 25℃ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH 1.0~13.0) were obtained. The substituent effects on 2-thienyl chalcone derivatives[II]~[V] were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation, substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed : At pH 1.0~9.0, not relevant to the hydrogen ion concentration, neutral H2O molecule competitvely attacked on the double bond. By contraries, above pH 9.0, it was proportional to concentration of hydroxide ion.

The kinetics of the addition of thiourea to cinnamenylisophorone derivatives(X : H, p-Br, p-CH3 m-CH3, p-OCH3) was investigated using ultraviolet spectrophotometry in 20%(v/v) dioxane-H2O at 25℃. A rate equation which can be applied over wide pH range(pH 1.0~13.0) was obtained. In order to investigate the substituent effects of cinnamenylisophorone derivatives. Hammett constant was plotted. As the result, the rate of uncleophilic addition of thiourea to cinnamenylisophorone derivatives was facilitated by electron donating group. It was found that addition of neutral thiourea which was not dissociated at the pH 1.0~9.0 was proceeded, the reaction was proceeded by addition of dissociated anion of thiourea above the pH 10.0. On the basis of this kinetic study, the reaction mechanism of nucleophilic addition of thiourea was investigated.

3원계 U-Ce-O산화물의 소결거동을 연구하기 위하여 UO2 및 CeO2분말을 ball-mill 방법으로 혼합한 (U, Ce)O2의 영향이고, 나중에 나타나는 극대점은 CeO2의 영향 때문이다. 또한 Ceo2함량이 증가할수록 소결이 지연됨을 알수 있었다. 동일한 10wt. % CeO2함량에서, 4시간동안 ball-milling을 하였을때가 소결속도는 가장 빨랐다.

The hydrolysis kinetics of 2-furyl chalcone derivatives [I]~[V] was investigated by ultraviolet spectrophotometery in 30% dioxane-H2O at 25℃ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH 1.0~12.0) were obtained. The substituent effects on 2-furyl chalcone derivatives [I]~[V] were studied, and the hydrolysis were facilitated by the electron attrecting groups. On the basis of the rate equation, substituent effect, general base effect and final product. the plausible hydrolysis mechaism was proposed: Below pH 4.0, it was only proportional to concentration of hydronium ion, at pH 4.0~9.0, neutral H2O molecule competitively attacked on the double bond. By contrast, above pH 9.0, it was proportional to concentration of hydroxide ion.

1, 2-Isopropylidene glycerol produced by ketalyzation of glycerol with aceton was esterified with long chain fatty acids in the presence of a Mucor miehei lipase to obtain 1, 2-isopropylidene 3-long chain acyl glycerol. To determine optimal conditions for the esterification reaction, esterification was proceeded as a reversible second-order reaction in various parameters that are enzyme<SUB>strate ratio 0.096g</SUB>g at reaction temperatures ranged from 25℃ to 70℃. The order of reaction rate of fatty acids were lauric acid, myristic acid, oleic acid, and stearic acid. The range of their activation energies were from 7.8 to 11.4 (kcal/mol) and that of entropies of activation which have negative values were from 42.8 to 52.5(e.u.).

The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-H2O at 25℃ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0~9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

Diglycidyl ether of bisphenol A (DGEBA)와 경화제로서 4, 4'-methylene dianiline(MDA) 에 반응성 첨가제 succinonitrile(SN)을 첨가한 새로운 계를 Differential Scanning Calorimetry (DSC)로 이용하여 30˚C부터 350˚C의 온도 범위에서 승온적 진행 방범(dynamic run method)으로 얻은 값을 가지고 최대 반응속도에서의 온도에 승온속도가 미치는 영향을 해석 할 수 있는 kissinger식을 적용하여 경화반응 속도론을 연구하였다. SN을 첨가한 DGEBA/MDA계의 활성화에너지 (Ea)와 pre-exponential factor(A) 그리고, SN이 첨가될 때 에폭시와 아민과의 반응속도 상수 k를 구하였다.

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -H2O at 25℃. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0~14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.