• 제목/요약/키워드: R.O.K

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Anilinolysis of Diphenyl Thiophosphinic Chloride and Theoretical Studies on Various R1R2P(O or S)Cl

  • Dey, Nilay Kumar;Han, In-Suk;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제28권11호
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    • pp.2003-2008
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    • 2007
  • The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

Solvent Effect on the Nature of the Metallamacrocycles Formed: Formation of Octanuclear and Dodecanuclear Manganese Metalladiazamacrocycles

  • John, Rohith P.;Lee, Kyung-Jin;Lee, Kyung-Jae;Park, Mi-Ra;Lah, Myoung-Soo
    • Bulletin of the Korean Chemical Society
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    • 제28권11호
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    • pp.2009-2014
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    • 2007
  • The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

Study of MgSrO and MgCaO thin films as protective layers for PDPs

  • Matulevich, Y.T;Moon, Sung-Hwan;Choi, Jong-Seo;Zang, Dong-Sik
    • 한국정보디스플레이학회:학술대회논문집
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    • 한국정보디스플레이학회 2009년도 9th International Meeting on Information Display
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    • pp.181-183
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    • 2009
  • Comparative study of the dependence of the firing voltage of MgSrO and MgCaO protective layers on chemical composition was carried out. It was observed that the firing voltage increases when CaO/MgO or SrO/MgO ratio increases.

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Flux 용융법에 의한 2차원 및 3 차원 구조의 티탄산칼륨 섬유의 합성 (Flux Melting Route to 2-and 3-dimensional Fibrous Potassium Titanates, K$_2Ti_{2n}O_{4n+1}$ (n = 2 and 3))

  • 최진호;한양수;송승완
    • 대한화학회지
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    • 제37권8호
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    • pp.765-772
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    • 1993
  • Flux인 $K_2MoO_4$와 섬유원료물질인 $K_2CO_3,\;TiO_2$를 혼합하고 1150$^{\circ}C$에서 용융시킨 다음 950$^{\circ}C$까지 서냉하여(서냉속도=5$^{\circ}C$/h) 층상구조를 갖는 사티탄산칼륨($K_2Ti_4O_9$)과 육티탄산칼륨($K_2Ti_6O_{13}$) 섬유를 합성하였다. Flux(F)와 출발원료물질(R)의 혼합비에 따른 최적 섬유성장 조건을 조사하기 위하여 F:R을 변화시키면서 반응시킨 결과 섬유의 결정상 및 성장속도가 F:R의 비에 크게 의존함을 알 수 있었으며 본 실험조건에서는 사티탄산칼륨과 육티탄산칼륨 모두 F:R=7:3 일 때 섬유의 성장이 가장 양호하였다. F:R = 7:3이고, 출발조성이 $K_2O{\cdot}4TiO_2$인 경우 생성물은 $K_2Ti_4O_9$과 약간의 $K_2Ti_6O_{13}$의 혼합상이 얻어졌으며 평균 섬유 길이는 ${\thickapprox}$ 4 mm 정도의 비교적 장섬유를 얻을 수 있었다. $K_2O{\cdot}6TiO_2$ 조성인 경우도 $K_2Ti_4O_9$의 혼합상이 형성되었고 섬유의 평균길이는 ${\thickapprox}$ 2 mm 정도임을 관찰할 수 있었다.

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고온/저가습 PEMFC 운전을 위한 Nafion$^{(R)}$/$ZrO_2-TiO_2$ 복합 전해질 막의 특성 연구 (A Characterization Study on Nafion$^{(R)}$/$ZrO_2-TiO_2$ Composite Membranes for PEMFC Operation at High Temperature and Low Humidity)

  • 박기태;전정환;최동웅;김성현
    • 한국수소및신에너지학회논문집
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    • 제22권1호
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    • pp.60-68
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    • 2011
  • [ $ZrO_2-TiO_2$ ]binary oxides with various Zr:Ti molar ratios were prepared by sol-gel method and Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were fabricated for proton exchange membrane fuel cells (PEMFCs) at high temperature and low humidity. Water uptake, Ion exchange capacity (IEC), and proton conductivity of Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were characterized and these composite membranes were tested in a single cell at $120^{\circ}C$ with various relative humidity (R.H.) conditions. The obtained results were compared with the unmodified membranes (Nafion$^{(R)}$ 112 and Recast Nafion$^{(R)}$). A Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membrane with 1:3 of Zr:Ti molar ratio showed the highest performance. The performance showed 500 mW/$cm^2$ (0.499V) at $120^{\circ}C$, 50% R. H., and 2 atm.

Al2O3-ZrO2-SiO2-R2O와 Al2O3-ZrO2-SiO2-La2O3-R2O계 유리와 부분안정화 지르코니아간의 접합거동 (Joining Behavior of YSZ Ceramics to Al2O3-ZrO2-SiO2-R2O and Al2O2-ZrO2-SiO2-La2O3-R2O Glass Systems)

  • 최진삼;배원태
    • 한국세라믹학회지
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    • 제52권1호
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    • pp.19-22
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    • 2015
  • The joining behavior of YSZ ceramics to the glasses used in the $9Al_2O_3-24ZrO_2-51SiO_2-16R_2O$ and $9Al_2O_3-24ZrO_2-51SiO_2-7La_2O_3-9R_2O$ (wt%) glass systems was investigated. The glass transition and softening temperatures were determined to be $430^{\circ}C$ and $760^{\circ}C$, respectively. The behavior of the contact angle was inversely proportional to an increase in the temperature. The Zr element in YSZ acted as a nucleation agent and contributed to the bonding behavior at the interface.

GC-OTC/FID에서 Dead Time 결정을 위한 새로운 방법 개발에 대한 연구 (A Study on the New Development for Determination of Dead Time in GC-OTC/FID)

  • 오도석;김성화;고은아;전형우
    • 대한화학회지
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    • 제63권4호
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    • pp.246-252
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    • 2019
  • GC-OTC/FID(Gas chromatography-Open Tubular Column/Flame Ionization Detector) 계에서 극성 용매(Alcohols)를 분리 하기 위하여 DMSO(Dimethyl sulfoxide)를 사용하였다. 이 계에서는 극성 용매들 보다 DMSO가 늦게 용출이 된다. 이런 계에서 크로마토그래픽 인자인 조정된 머무름 시간($t_R^{\prime}=t_R-t_O$)과 용량 인자{$k^{\prime}=(t_R-t_O)/t_O$} 및 분리 인자{${\alpha}=(t_{R2}-t_O)/(t_{R1}-t_O)$}를 구하기 위하여 불감시간($t_O$)이 필요하다. 그러나 이런 계에서 $t_O$ 를 구하기 위한 보고가 현재까지 된 바가 없기 때문에, 본 연구에서는 $t_O$ 를 구하는 방법을 개발하고자 하였다. $t_O$ 를 계산하기 위하여 DMSO의 머무름 시간($DMSO\;t_R$)을 상용로그로 전환하였다($f(x)={\log}\;t_{R(DMSO)}{\rightarrow}t_O$, $t_O={\log}$ 9.551=0.980). 개발된 방법의 적합 여부를 확인하기 위하여 $CH_4$$t_R$${\ln}\;t_{R(DMSO)}$${\log}\;t_{R(DMSO)}$와 비교하였다. 세 가지 방법 중 $CH_4\;t_R$${\ln}\;t_{R(DMSO)}$는 k' 과 ${\alpha}$를 계산하는데 적합하지 않았다. 본 연구에서 개발한 방법인 ${\log}\;t_{R(DMSO)}$는 일반적인 기준인 k'(1${\alpha}(1<{\alpha}<2)$를 만족하였다. 본 연구에서 개발한 계산방법은 쉽고 편리하기 때문에, 이와 유사한 계에서도 활용될 것으로 기대된다.

$Al_2O_3-ZrO_2-SiC$ Whisker 복합재료에서의 R-curve 거동에 관한 연구 (Study on the R-curve Behaviour in $Al_2O_3-ZrO_2-SiC$ Whisker Comosite)

  • 김현하;박현;최성철
    • 한국세라믹학회지
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    • 제30권9호
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    • pp.731-739
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    • 1993
  • R-curve measurements were performed on Al2O3(matrix)-ZrO2-SiC whisker composite and Al2O3-ZrO2, Al2O3-SiC whisker composites in the favor of comparing the effect of ZrO2 and SiC whisker, as a second phase, to Al2O3 matrix. Al2O3-SiC whisker and Al2O3-ZrO2-SiC whisker were fabricated by hot pressing at 1$700^{\circ}C$, 15MPa and Al2O3-ZrO2 by pressureless sintering at 1$600^{\circ}C$. A controlled flaw/strength technique was utilized to determine fracture resistance as a function of crack extension and R-curve behaviour was determined from the relationship which is KR=K0(Δa)m. R-curveresults were KR=6.173$\times$Δa0.031 for Al2O3-ZrO2, KR=18.796$\times$Δa0.172 for Al2O3-SiC whisker and KR=11.96$\times$Δa0.110 for Al2O3-ZrO2-SiC whisker composite. From the analysis of R-curve and expeirmental data above three composites, it is found that R-curve behaviour of Al2O3-ZrO2-SiC whisker composite was dominated initially by the strengthening effect of ZrO2 and after, some extended crack were influenced by the effect of SiC whisker. Analysis of SEM and X-ray data revealed that whisker bridging in the crack wake and whisker pull-out mechanisms were the main mechanism for the R-curve behaviour.

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