• Title/Summary/Keyword: Transition substitution

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Electrical Characteristics of Cathode Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$ Substituted by Transition Metals in Li-Ion Secondary Batteries (전이금속 치환 리튬이온 이차전지 정극 Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$의 전기적 특성)

  • 박재홍;김정식;유광수
    • Journal of the Korean Ceramic Society
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    • v.37 no.5
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    • pp.466-472
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    • 2000
  • As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

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Theoretical Studies on the Nucleophilic Substitution Reaction of Methyl Thiocyanate (티오시안산 메틸의 친핵성치환 반응에 관한 이론적 연구)

  • Ikchoon Lee;Chang Hyun Song
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.123-132
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    • 1987
  • Nucleophilic substitution reactions of methylthiocyanate(MTC) with anion nucleophiles,$SH^-,\;CN^-$ and $OH^-$, have been investigated using MNDO method. For the three reaction centers of MTC, gas-phase and solution-phase selectivities are discussed for each nucleophile by considering potential energy profiles calculated(intrinsic term) and magnitudes of negative charge on the nucleophile at the transition state(solvation term). It was found that both components of the selectivity for $SH^-$agreed with the experimental results obtained for 4-methylbenzylthiocyanate (4-MBTC), but the selectivity order for TEX>$CN^-$ was found to agree only with that of the intrinsic term and that of $OH^-$disagreed with any theoretical selectivity order. The MNDO optimized geometries for all species at the stationary points are reported.

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Test for substitution in telecommunication market system (통화시장체계의 대체성 검정)

  • Kim, Tae-Ho
    • Journal of the Korean Data and Information Science Society
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    • v.22 no.1
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    • pp.9-18
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    • 2011
  • After the launch of PCS in 1997, the mobile telephone industry has achieved a remarkable growth in market share and sales, and substituted for long-distance wire communication market. This study investigates the interrelationships between the two markets in transition and attempts to perform the statistical tests if the diffusion of mobile telephone was the direct factor for the reduction in sales of long-distance communication industry. The evidence of the direct substitution effect between the two markets is not likely to be found. Unlike the general expectations, the test result seems to prove the sustained initial complementary relation for awhile.

Effects of Calcination Process and $ZrO_2$ Addition on the Electrical Properties of $BaTiO_3$ Ceramics (하소공정과 $ZrO_2$ 첨가량이 $BaTiO_3$의 전기적 특성에 미치는 영향)

  • 차진이;박재관;오태성;김윤호
    • Journal of the Korean Ceramic Society
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    • v.28 no.11
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    • pp.935-941
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    • 1991
  • Effects of calcination process and ZrO2 addition on the electrical properties of [(Ba0.82Sr0.08Ca0.1)O]m(Ti1-$\chi$Zr$\chi$)O2 ceramics have been investigated. With the variation of A/B-site ratio m of the dielectric formulations, sintering behavior and the resistivity after sintering in a reducing atmosphere have been affected by the calcination process. When the dielectric formulations of m=1.01 were sintered in a reducing atmosphere, the room-temperature resitivity of 109 {{{{ OMEGA }}.cm was obtained for samples processed with two-step calcination, which was much lower than 1012 {{{{ OMEGA }}.cm of samples calcined once. It was confirmed that high resistivity of Ca-doped BaTiO3 ceramics, after sintering in a reducing atmosphere, is maintained by acceptor-like behavior of CaTi" which is formed by Ca substitution to Ti-site. It was also found out that the critical amount of B-site Ca substitution for reduction inhibition of BaTiO3 is around 0.005 mol. With the increasing amount of ZrO2 addition to dielectric formulations, Curie peak was depressed and Curie temperature was lowered due to the enhanced diffuse phase transition.tion.

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A Study on the Capacity Fading and the Replacement of Surface Film at the Surface of $LiMn_2O_4$ Thin Film Electrode

  • Chung Kyung Yoon;Shu Dong;Kim Kwang-Bum
    • 한국전기화학회:학술대회논문집
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    • 2002.11a
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    • pp.57-65
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    • 2002
  • The presence of tetragonal phase at the surface of $LiMn_2O_4$ pinicle due to a Jahn-Teller offset was previously reported to be one of the causes for capacity fading observed during cycling of $Li//Li_xMn_2O_4$ in 4V range. Further, it is reported that a Jahn-Teller effect in 4V range may be suppressed by substitution of Mn ions with Li ions or other transition metal ions. However, the direct evidence of the suppression of a Jahn-Teller effect in 4V range by substitution of Mn ions with other metal ions has not been reported. The dissolution and formation of surface film at the surface of $LiMn_2O_4$ electrodes also reportedly affect the capacity fading or rate capability. This study reports on the evidence of the onset and suppression of a Jahn-Teller effect in 4V range and the dissolution and formation of surface film at the surface of $LiMn_2O_4$ thin film electrodes using in situ bending beam method (BBM) in situ electrochemical quartz crystal microbalance (EQCM).

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Dielectirc Properties of $(Ba_{0.5}Sr_{0.5}){TiO_3}$ Thick Films Doped with MgO (MgO의 첨가량에 따른 $(Ba_{0.5}Sr_{0.5}){TiO_3}$ 후막의 유전 특성)

  • Kang, Won-Seok;Nam, Song-Min;Koh, Jung-Hyuk;Lee, Young-Hie
    • Proceedings of the KIEE Conference
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    • 2006.10a
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    • pp.5-6
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    • 2006
  • Using the $(Ba_{0.5}Sr_{0.5}){TiO_3}$(BST) powders prepared by the Sol-Gel method, the EST thick films were fabricated on the ${Al_2}{O_3}$ substrates coated with Pt by the screen printing method. Compared with pure EST thick films, the structural and dielectric properties of the EST thick films doped with 1${\sim}$10 wt % MgO were investigated. It was observed that the Mg substitution into EST causes a shift in the cubic-tetragonal EST phase transition peak to a lower temperature. The microstructure of the EST substituted with Mg was homogeneous and dense. Mg substitution into EST had a significant effect on the grain size reduction. Dielectric constant was decreased with increasing the MgO content and temperature. In the case of EST thick films doped with 1 wt% MgO, the relative permittivity and dielectric loss were 158] and 1.4 % at 1 MHz.

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Structural and Dielectirc Properties of $Ba_{0.5}Sr_{0.5}TiO_3$ Thick Films Doped with MgO (MgO가 첨가된 $Ba_{0.5}Sr_{0.5}TiO_3$ 후막의 구조 및 유전 특성)

  • Kang, Won-Seok;Nam, Sung-Pil;Koh, Jung-Hyuk;Lee, Sung-Gap;Lee, Young-Hie
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.55 no.12
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    • pp.555-559
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    • 2006
  • Using the $Ba_{0.5}Sr_{0.5}TiO_3$(BST) powders prepared by the Sol-Gel method, the BST thick films were fabricated on the $Al_2O_3 $substrates coated with Pt by the screen printing method. Compared with pure BST thick films, the structural and dielectric properties of the BST thick films doped with $1{\sim}10$ wt % MgO were investigated. It was observed that the Mg substitution into BST causes a shift in the cubic-tetragonal BST phase transition peak to a lower temperature. The microstructure of the BST substituted with Mg was homogeneous and dense. Mg substitution into BST had a significant effect on the grain size reduction. Dielectric constant was decreased with increasing the MgO content and temperature. In the case of BST thick films doped with 1 wt% MgO, the relative permittivity and dielectric loss were 1581 and 1.4 % at 1 MHz.

A Mechanistic Study on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates with Anionic Nucleophiles

  • Um Ik-Hwan;Lee Seok-Joo;Kim Jung-Joo;Kwon Dong-Sook
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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    • pp.473-477
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    • 1994
  • Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates

  • Ik-Hwan Um;Seok-Joo Lee;Hee-Sun Park;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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    • pp.161-167
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    • 1994
  • Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

Self-assembly of Retinoic Acid-conjugated Poly(Amino Acid)'s Derivative (레티노익산이 접목된 폴리아미노산 유도체의 자기조립 현상)

  • Han, Sa Ra;Lee, Hyeongyeong;Kim, Hee-Jin;Cho, Yoon Na;Lee, Seung-Jun;Zhoh, Choon-Koo;Jeong, Jae Hyun
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.42 no.4
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    • pp.433-440
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    • 2016
  • In this study, a poly (amino acid)s derivative grafted with retinoic acids, which could form self-assemblies in an aqueous solution, was successfully synthesized. The synthesized amphiphilic poly (amino acid)s were controlled with 5, 10, 30 mol% substitution of retinoic acid. Then, the amphiphilic poly (amino acid)s were self-assembled by inter/intra molecular stacking of retinoic acids in an aqueous solution. Also, the increasing the degree of substitution (DS) of retinoic acids decreased the size of self-assembled nanoparticles and induced structural transition to bilayer structure from spherical structure. The retinol was stably encapsulated into a core of self-assembled nanoparticle with 10 mol% of DS. This strategy to prepare the self-assemblies of amphiphilic polyaspartamide will serve to improve the efficiency of targeted delivery for a functional cosmetic with various biological modalities.