• 자원환경지질
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• 제54권2호
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• pp.233-245
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• 2021

암석의 미세구조에 대한 많은 연구는 실제 암석 관찰 뿐만 아니라 다양한 실험 장비를 이용하여 미구조의 발달 과정과 그 메커니즘을 이해하기 위해 수행되어 왔다. 변성이나 변형 작용 중에 입자 성장이나 입도의 변화를 일으킬 수 있는 광물 군집 내 입자 경계 이동 작용은 주요한 재결정작용 메커니즘 중 하나이다. 특히, 변형 과정 중 나타날 수 있는 입자 경계 이동의 연속적 관찰은 암석 유사 실험을 이용하여 수행될 수 있었다. 이번 연구에서는 다양한 실험 방법 중 유사 물질을 이용한 입자 성장 및 변형 실험 방법에 대해 기존 방법을 개량할 수 있는 실험 장비의 개발과 이를 통한 효과적인 미구조 분석 방법을 제시하였다. 개발된 실험 장비는 유사 물질 실험이 가능한 변형 장치와 실체 현미경에 회전 조작이 가능한 편광판들을 장착하여 광학적 조작이 가능하도록 구성되었다. 이들 장치들은 마이크로 컨트롤러를 통해 온도 및 변형 속도 제어 및 실험 동안 관찰되는 미구조 변화를 연속적으로 촬영할 수 있도록 자동화하여 구성되었다. 또한 편광판 회전 조작을 통해 취득되고 합성된 디지털 이미지들은 보다 정확한 입자 경계를 구분하고 분석할 수 있게 해주었다. 실험 결과의 입도 및 형태와 같은 미구조 분석을 위해 선분 교점 측정 방법과 입자 경계 트레이싱 방식을 비교하여 적용하였다. 유사물질로써는 석영과 유사한 광학적 성질을 가지는 노캠퍼(Norcamphor, C7H10O)라는 물질을 사용하였다. 개발된 장비의 실효성을 검증하고자 노캠퍼를 이용한 정적 입자 성장 실험과 단순 전단 변형 실험 및 이에 대한 미구조 분석을 수행하였다. 정적 입자 성장 실험은 시간이 지남에 따라 입자 수의 감소와 입도가 증가하는 전형적인 입자 성장 작용의 특징과 온도에 따른 성장 곡선들의 명확한 차이를 보여주었다. 중온-저변형율 조건의 단순 전단 변형 실험 결과는 평균 입도의 큰 변화는 없었으나, 입자 형태에 대해 전단 변형이 증가함에 따라 전단력 방향에 수직한 방향에 대해 약 53°의 방향으로 신장률이 증가하는 변화를 보여주었다. 이러한 미구조의 발달과정은 주어진 실험 조건에서 변형에 의해 입자 내부의 소성 변형과 내부 회복 작용이 균형을 이루면서 진행된 것으로 해석된다. 개량화 및 자동화된 실험장치를 이용한 이들 입자 성장 작용 실험 및 변형 실험의 예는 유사물질 실험에서 목적하는 바와 같이 실험 과정 동안의 입자의 미구조 변화과정을 순차적으로 관찰할 수 있고, 전체 수행 과정동안 수동적 조작없이 효율적으로 실험을 진행할 수 있다는 장점을 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제4권1호
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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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• 제10권4호
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• pp.382-388
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• 1989

The approximate rates and stoichiometry of the reaction of excess potassium tri-sec-butylborohydride ($K_s-Bu_3BH$) with selected organic compounds containing representative functional groups were determined under the standard conditions (0$^{\circ}C$, THF) in order to define the characteristics of the reagent for selective reductions. Primary alcohols evolve hydrogen in 1 h, but secondary and tertiary alcohols and amines are inert to this reagent. On the other hand, phenols and thiols evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to the corresponding alcohols. Reduction of norcamphor gives 99.3% endo- and 0.7% exo-isomer of norboneols. The reagent rapidly reduces cinnamaldehyde to the cinamyl alcohol stage and shows no further uptake of hydride. p-Benzoquinone takes up one hydride rapidly with 0.32 equiv hydrogen evolution and anthraquinone is cleanly reduced to the 9,10-dihydoxyanthracene stage. Carboxylic acids liberate hydrogen rapidly and quantitatively, however further reduction does not occur. Anhydrides utilize 2 equiv of hydride and acyl chlorides are reduced to the corresponding alcohols rapidly. Lactones are reduced to the diol stage rapidly, whereas esters are reduced moderately (3-6 h). Terminal epoxides are rapidly reduced to the more substituted alcohols, but internal epoxides are reduced slowly. Primary and tertiary amides are inert to this reagent and nitriles are reduced very slowly. 1-Nitropropane evolves hydrogen rapidly without reduction and nitrobenzene is reduced to the azoxybenzene stage, whereas azobenzene and azoxybenzene are inert. Cyclohexanone oxime evolves hydrogen without reduction. Phenyl isocyanate utilizes 1 equiv of hydride to proceed to formanilide stage. Pyridine and quinoline are reduced slowly, however pyridine N-oxide takes up 1.5 equiv of hydride in 1 hr. Disulfides are rapidly reduced to the thiol stage, whereas sulfide, sulfoxide, sulfonic acid and sulfone are practically inert to this reagent. Primary alkyl bromide and iodide are reduced rapidly, but primary alkyl chloride, cyclohexyl bromide and cyclohexyl tosylate are reduced slowly.

• Bulletin of the Korean Chemical Society
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• 제13권2호
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• pp.199-207
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• 1992

The approximate rates and stoichiometry of the reaction of excess sodium diethyldihydroaluminate (SDDA) with 68 selected organic compounds containing representative functional groups were examined under standard conditions (THF-toluene, $0^{\circ}C$ in order to compare its reducing characteristics with lithium aluminum hydride (LAH), aluminum hydride, and diisobutylaluminum hydride (DIBAH) previously examined, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, thiols and amines evolve hydrogen rapidly and quantitatively. Aldehydes and ketones of diverse structure are reduced rapidly to the corresponding alcohols. Reduction of norcamphor gives 11% exo-and 89% endo-norborneol. Conjugated aldehydes such as cinnamaldehyde are rapidly and cleanly reduced to the corresponding allylic alcohols. p-Benzoquinone is mainly reduced to hydroquinone. Hexanoic acid and benzoic acid liberate hydrogen rapidly and quantitatively, however reduction proceeds very slowly. Acid chlorides and esters tested are all reduced rapidly to the corresponding alcohols. However cyclic acid anhydrides such as succinic anhydride are reduced to the lactone stage rapidly, but very slowly thereafter. Although alkyl chlorides are reduced very slowly alkyl bromides, alkyl iodides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced very slowly; however, tertiary amides take up 1 equiv of hydride rapidly. Tertiary amides could be reduced to the corresponding aldehydes in very good yield ( > 90%) by reacting with equimolar SDDA at room temperature. Hexanenitrile is reduced moderately accompanying 0.6 equiv of hydrogen evolution, however the reduction of benzonitrile proceeds rapidly to the imine stage and very slowly thereafter. Benzonitrile was reduced to give 90% yield of benzaldehyde by reaction with 1.1 equiv of hydride. Nitro compounds, azobenzene and azoxybenzene are reduced moderately at $0^{\circ}C$, but nitrobenzene is rapidly reduced to hydrazobenzene stage at room temperature. Cyclohexanone oxime is reduced to the hydroxylamine stage in 12 h and no further reaction is apparent. Pyridine is reduced sluggishly at $0^{\circ}C$, but moderately at room temperature to 1,2-dihydropyridine stage in 6 h; however further reaction is very slow. Disulfides and sulfoxides are reduced rapidly, whereas sulfide, sulfone, sulfonic acid and sulfonate are inert under these reaction conditions.