• 한국염색가공학회지
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• 제6권2호
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• pp.10-16
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• 1994

Neutral salts have negative or positive effects on the rates of many chemical reactions and also on the rates of acidic and alkaline hydrolysis of carboxylic esters. The direction of neutral salt effects on the hydrolysis of ester depends on the charge of esters. Neutral salts accelerate alkaline hydrolysis of esters with negative charge, but decelerate alkaline hydrolysis of esters with positive charge, and have little effect on the alkaline hydrolysis of neutral esters. It is expected that the rate of the alkaline hydrolysis of Poly(ethylene terephthalte) (PET), polymeric solid carboxylic polyester with carboxyl end group at the polymer end, is also influenced positively by neutral salts. In the present work, to clarify the mechanism of the neutral salt effect on the alkaline hydrolysis of PET, many salts with different anions like NaF, NACl, NaBr, NaI were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous solutions of many salts in alkali metal hydroxides under various conditions. Some conclusions obtained from the experimental results were summarized as follows. The reaction rate of the alkaline hydrolysis of PET was increased by the addition of neutral salts and In k was increased nearly linearly with the square root of ionic strength of reaction medium. This fact suggested that the ionic strength effect by Debye-Huckel and Bronsted theory was exerted on the reaction. The specific salt effect was also observed. The reaction rate was increased with the decrease in the nucleophilicity of anions of neutral salts, i.e., in the order of $F^-$ <$Cl^-$<$Br^-$<$I^-$. It was thought that the reaction rate was increased in the order of $F^-$ <$Cl^-$<$Br^-$<$I^-$. because the completion of anions with $OH^-$ for carbonyl carbon became weaker with the decrease in the nucleophilicity and with the increase in the size of anions.

• 한국염색가공학회지
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• 제6권1호
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• pp.33-43
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• 1994

In the present work, to clarify the mechanism of the neutral salt effect on the alkaline hydrolysis of PET, many salts with different cations like LiCl, NaCl, KCl, CsCl were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous solutions of many salts in alkali metal hydroxides under various conditions. Some conclusions obtained from the experimental results were summarized as follows. The reaction rate of the alkaline hydrolysis of PET was increased by the addition of neutral salts and In k was increased nearly linearly with the square root of ionic strength of reaction medium. This fact suggested that the ionic strength effect by Debye-Huckel and Bronsted theory was exerted on the reaction. The specific salt effect was also observed. The reaction rate was increased with the increase in the electrophilicity of cations of neutral salts, i. e., in the order of $Cs^+$/ < $K^+$/ $a^+$/ $i^$^+$. It was considered that the reaction rate was increased in the order of C $s^+$. < $K^+$. $a^+$. $i^+$. because the lowering effect of the cations on the negative charge of PET surface was increased with the electrophilicity of cations. It was thought that $E_{a}$ was increased because the cations of neutral salts decreased the negative charge of PET surface. It, however, was inferred from the increase in ${\Delta}$S＊ and the decrease in the ${\Delta}$G＊ that the cations of neutral salts associated with PET increased the collision frequency between carbonyl carbon and OH- ion and then accelerated the reaction rate.te.

• 공업화학
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• 제22권5호
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• pp.526-531
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• 2011

본 연구는 이산화탄소 흡수성능을 향상시키기 위하여 아미노산에 알칼리금속을 함침시키는 것이다. 사용된 아미노산은 글리신이었으며, 알칼리성분 추가에 따라 pH가 11까지 증가하였다. 시험제조한 아미노산 염은 회분식과 연속식 흡수공정에서 이산화탄소의 포집능을 평가하였다. 치환된 금속종류에 따른 이산화탄소 흡수량은 Sodium Glycinate (Na-Gly) ${\geq}$ Lithium Glycinate (Li-Gly) > Potassium Glycinate (K-Gly) 순으로 나타났다. 흡수반응온도에 따른 $CO_2$ 흡수량 시험결과, $20^{\circ}C$에서는 알칼리금속을 함침시킨 아미노산 염이 1차 아민보다 약간 낮은 흡수능을 보였으나, 연속식 흡수반응기에서는 10% $CO_2$ 흐름에 대하여 반응기 내부온도가 상승하면서($40^{\circ}C$, $60^{\circ}C$) 아미노산 염의 흡수량 증가폭이 아민에 비하여 상대적으로 크게 나타났다.

• 공업화학
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• 제23권3호
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• pp.284-288
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• 2012

본 연구는 이산화탄소에 대한 화학적 흡수공정의 새로운 흡수제로서 글리신 수용액의 화학적 특성과 흡수성능을 고찰하였다. 이산화탄소 흡수에 관여하는 작용기인 아미노기를 활성화시키기 위해 세 종류의 알칼리원소(Na, Li, K)를 선택하여 글리신에 함침시켰다. 제조한 흡수제에 대한 IR 분석결과, 글리신 수용액의 암모늄이온(${-NH_{3}}^+,\;1600cm^{-1}$,single )형태로 존재하던 작용기가 아미노기($-NH_2,\;1550{\sim}1650\;cm^{-1}$, scissoring)형태로 전환된 것을 확인할 수 있었다. 또한, $^{1}H-NMR$과 $^{13}C-NMR$ 분석결과, 금속 양이온의 치환에 의한 염화현상(salting)으로 기존 글리신에서의 수소와 탄소원자의 화학적 이동의 차이를 확인할 수 있었다. 즉, 치환된 금속의 전기 음성도에 따라 리튬염, 나트륨염 그리고 칼륨염 순으로 화학적 이동이 나타났다. 한편 상온에서의 이산화탄소 흡수량은 비교대상인 1차 아민이 가장 높았으며, 나트륨 글리신염, 리튬 글리신염, 칼륨 글리신염 순으로 나타났다. 그러나 연소공정 배출가스 내 이산화탄소 포집을 가정하여 온도상승($40,\;60,\;80^{\circ}C$)에 따른 실험결과, 나트륨 글리신염이 MEA보다 높은 흡수량을 보였다.

• Nuclear Engineering and Technology
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• 제51권7호
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• pp.1866-1870
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• 2019

Residual salt separation is an essential step in pyroprocessing because its reaction products, as prepared by electrochemical unit processes, contain frozen residual electrolyte species, which are generally composed of alkali-metal chloride salts (e.g., LiCl, KCl). In this study, a simple technique that utilizes high-temperature gas flux as a driving force to melt and push out the residual salt in the reaction products was developed. This technique is simple as it only requires the use of a heating gun in combination with a gas injection system. Consequently, $LiNO_3-ZrO_2$ and $LiCl-ZrO_2$ mixtures were successfully separated by the high-temperature gas injection (separation efficiency > 93%), thereby demonstrating the viability of this simple technique for residual salt separation.

• 분석과학
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• 제8권4호
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• pp.675-682
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• 1995

Thin films of buckminsterfullerene($C_{60}$) formed by solution drop casting on Pt foil electrode surfaces were studied by cyclic voltammetry(CV) in acetonitrile(MeCN) containing quaternary ammonium or alkali-metal salts as supporting electrolyte. The electrochemical behaviors of $C_{60}$ films are found to be strongly dependent on the nature of the supporting electrolytes, especially with tetrabutyl ammonium perchlorate (TBAP, $NBu_4ClO_4$), and tetrabutyl ammonium tetrafluoroborate ($TBABF_4$, $NBu_4BF_4$). Reasonably stable films are formed into which electrons can be injected. The interaction of $C_{60}$ film with the quaternary ammonium cation may produce the fulleride salts $(TBA^+)(C{_{60}}^-)$ and $(TBA^+)_2(C{_{60}}^{2-})$. The bulk electroreduction with a controlled potential to generate the soluble $C{_{60}}^{3-}$ anions(dark red-brown color) is followed by electrooxidative deposition to produce a neutral $C_{60}$ film on the surface. The peak currents($I_{pc}$ and $I_{pa}$) of these thin film were dramatically decreased with repetitive potential scanning. These results could be explained by the adsorption-desorption phenomena and ion pairing interaction of reduced species($C{_{60}}^-$, and $C{_{60}}^{2-}$) onto the electrode surface. The peak current changes and peak potential shifts of the thin $C_{60}$ film in cyclic voltammograms formed from solution were observed by varying scan rates.

• 폴리머
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• 제24권6호
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• pp.802-809
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• 2000

Poly(L-glutamic acid) (PLGA)와 PVA 블렌드막을 제조한 후, ethanol 수용액중에서 막증의 polypeptide 사슬의 2차구조 전이거동에 미치는 용매조성 및 대이온종의 영향과 알칼리 금속 이온 (Li, na, K, Cs)에 대한 투과특성을 조사하였다. 막중 PLG 알칼리 금속염의 helix 형성거동에 있어 대이온 선택성은 Li>Na>K>Cs의 순으로 관찰되었고, 이와 같은 특이성은 탈용매화 에너지와 정전에너지의 감소에 따른 고분자 하전기와 대이온과의 contact ion-pair 형성에 의한 것으로 설명하였다. 또한 PLGA/PVA 블렌드막의 ethanol 수용액 중에서의 알칼리 금속이온의 투과거동을 살펴보면, ethanol 농도가 점차 증가함에 따라 K, Cs의 경우는 투고도가 증가한, Li, Na의 경우에는 감소하였다. K, Cs 이온의 경우 대이온과 염소이온간의 ion-pair (M$^{+}{\cdot}$Cl$^{-}$)형성에 의한 Donnan배제효과의 감소와 중성염 형태로의 분배량 증가때문인 것으로, Li, Na 이온의 경우 막중의 coil-helix 구조전이에 따른 자유체적의 감소와 고분자 하전기와의 상호작용이 증가하여 확산성이 크게 감소하였기 때문인 것으로 생각된다.

• 공업화학
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• 제9권2호
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• pp.286-293
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• 1998

연소배가스로부터 $CO_2$를 선택적으로 분리하기 위한 활성탄 흡착공정 사용시 흡착능 향상을 위하여 $CO_2$와 친화력이 있는 화합물을 함침시키는 방법과 KOH를 함침시킨 후 고온에서 열처리하므로서 활성화시키는 방법이 사용되었다. 알칼리금속, 알칼리토금속, 또는 전이금속의 염화물을 함침시킨 활성탄에 대한 $CO_2$의 흡착량을 측정한 결과 함침 전의 활성탄의 흡착량보다 적었다. 이것은 함침되는 물질이 $CO_2$에 대한 친화력이 없이 단지 활성탄의 미세기공만 막는 결과임을 알 수 있었다. 알칼리금속수산화물 중 KOH를 함침시킨 활성탄에 대한 $CO_2$의 파과실험 결과 유입되는 기체에 수분이 있을 경우 흡착량이 증가했는데 이것은 KOH가 $CO_2$를 흡수하는 성질 때문이었다. 그러나 이 흡착제에 함친된 KOH가 $CO_2$와 반응하여 $K_2CO_3$로 변함에 따라 재현성이 없음을 알 수 있었다. KOH를 함침시킨 후 $800^{\circ}C$에서 열처리하여 활성화시킨 활성탄의 경우 함침된 KOH의 양이 증가할수록 $CO_2$의 흡착량이 증가했으며, KOH와 활성탄의 무게비(KOH/Activated-Carbon)가 4일 때 최대였다. 이 흡착제에 대해 온도별로 측정된 $CO_2$의 흡착량으로부터 Clausius-Clapeyron식을 이용하여 등량흡착열을 구했다. 그리고 고정층 파과실험을 통해 $CO_2$농도와 유속에 따른 파과특성을 살펴보았다.

• 한국세라믹학회지
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• 제47권3호
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• pp.256-261
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• 2010

Physical properties of Plasma electrolytic oxidized 8 different types of Al alloys, A-1100, A-2024, A-5052, A-6061, A-6063, A-7075, ACD-7B and ACD-12 were investigated. The electrolyte for PEO was $Na_2SiO_3$ solutions with NaOH and some alkali earthen metal salts. Porous layer near the surface of PEO coating was not found, and surface roughness Ra50 was below 2.5 ${\mu}m$. Surface roughness was affected by growth rate of plasma electrolytic oxidized layer, not by Si content in Al alloy.

• 한국세라믹학회지
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• 제47권4호
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• pp.283-289
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• 2010

Physical properties of Plasma electrolytic oxidized 8 different kinds of Al alloys, A-1100, A-2024, A-5052, A-6061, A-6063, A-7075, ACD-7B and ACD-12 were investigated. The electrolyte for PEO was $Na_2SiO_3$ and NaOH and some alkali earthen metal salts system solution. $\eta$-alumina, as well as $\gamma$-alumina, was main crystal phase, which were ever reported. Also, $Al_{4.95}Si_{1.05}O_{9.52}$ was found only in this research. So we can conclude that the process conditions of PEO apparatus and composition and concentration of its electrolyte affects crystal structure and physical properties of PEO layers much more than the compositions of Al alloy.