• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2023-2028
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• 2013

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

• 대한화학회지
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• 제23권6호
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• pp.339-348
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• 1979

물-메탄올, 물-에탄올, 물-아세트니틜, 물-아세톤 및 아세트니트릴-메탄올의 2성분 혼합용매에서 2-염화테노일 및 2-염화퓨로일의 가용매분해 반응을 속도론적으로 연구하였다. 반응 속도는 반양성자성 용매에서 보다 양성자성 용매에서 더 빨랐으며 이것은 양성자성용매의 수소결합능력이 이탈기의 결합의 파괴를 돕기 때문이다. 그러나 아세트니트릴-메탄올 혼합용매에서는 특수용매화가 일어나며, 메탄올 몰분율 0.8부근에서 최대속도를 나타낸다. 또한 이 반응은 염화벤조일보다 느리며 그 속도 순서는 염화벤조일 > 2-염화테노일 > 2-염화퓨로일이며 이 중에서 퓨란고리의 전자흡인성이 제일 강함으로 전이상태에서 결합의 파괴가 어려워져서 반응속도가 늦어지는 것이다. 반응메카니즘은 전이상태에서 결합의 파괴가 결합의 형성보다 많이 진행된 dissociative $S_N2$ 반응이기는 하나 2-염화테노일은 물 함량이 많은 부분에서는 $S_N1$ 성겨기 꽤 크고 $S_N2$ 성격이 약화된다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.139.1-139.1
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• 2016

Multiferroic materials are of great interest because of its potential applications in the design of devices combining magnetic, electronic and optical functionalities. Among various multiferroic materials, $BiFeO_3$(BFO) is known to be one of the intensively focused mainly due to the possibility of multiferroism at device working temperature (> $200^{\circ}C$). However, leakage current and weak polarization resulting from oxygen deficiency and crystalline defect should be resolved. Furthermore the magnetic ordering of pure BFO mainly prefers to have antiferromagnetic coupling. Up to now many attempts have been performed to improve the ferromagnetic and the ferroelectric properties of BFO by doping. In this work, we investigated the effects of Ni substitution on the multiferroism of bulk BFO. Four BFO samples (a pure BFO and three Ni-doped BFO's; $BiFe_{0.99}Ni_{0.01}O_3$, $BiFe_{0.98}Ni_{0.02}O_3$ and $BiFe_{0.97}Ni_{0.03}O_3$) were synthesized by the standard solid-state reaction and rapid sintering technique. The XRD results reveal that Ni atoms are substituted into Fe-sites and give rise to phase transition of cubic to rhombohedal. By using vibrating sample magnetometer and standard ferroelectric tester, the multiferroic properties at room temperature were characterized. We found that the magnetic moment of Ni-doped BFO turned out to be maximized for 3% of Ni dopant.

• 한국재료학회지
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• 제24권12호
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• pp.658-662
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• 2014

$Eu^{2+}/Dy^{3+}$-doped $Sr_2MgSi_2O_7$ powders were synthesized using a solid-state reaction method with flux ($NH_4Cl$). The broad photoluminescence (PL) excitation spectra of $Sr_2MgSi_2O_7:Eu^{2+}$ were assigned to the $4f^7-4f^65d$ transition of the $Eu^{2+}$ ions, showing strong intensities in the range of 375 to 425 nm. A single emission band was observed at 470 nm, which was the result of two overlapping subbands at 468 and 507 nm owing to Eu(I) and Eu(II) sites. The strongest emission intensity of $Sr_2MgSi_2O_7:Eu^{2+}$ was obtained at the Eu concentration of 3 mol%. This concentration quenching mechanism was attributable to dipole-dipole interaction. The $Ba^{2+}$ substitution for $Sr^{2+}$ caused a blue-shift of the emission band; this behavior was discussed by considering the differences in ionic size and covalence between $Ba^{2+}$ and $Sr^{2+}$. The effects of the Eu/Dy ratios on the phosphorescence of $Sr_2MgSi_2O_7:Eu^{2+}/Dy^{3+}$ were investigated by measuring the decay time; the longest afterglow was obtained for $0.01Eu^{2+}/0.03Dy^{3+}$.

• 한국가스학회지
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• 제5권1호
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• pp.29-36
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• 2001

Poylsulfone의 phenyl 고리에 각각 -Br과 $-Si(CH_{3})_{3}$ 기능기를 치환시킨 BPSf와 TMSPSf을 합성하고, BPSf막, TMSPSf막 그리고 BPSf/TMSPSf 블렌드막에 대한 $O_{2}$와 $N_{2}$의 투과특성을 조사 $\cdot$ 비교하였다. BPSf막은 PSf막에 비해 높은 이상분리인자를 보였는데, 이는 유도 쌍극자에 의한 사슬간의 극성 상호작용 때문에 사슬간의 인력이 증가하고 따라서 사슬간의 거리가 감소하기 때문이라고 설명할 수 있다. 반면 TMSPSf막의 경우 부피가 큰 $-Si(CH_{3})_{3}$ 의 치환으로 인해 자유부피가 커져 PSf 보다 높은 투과도 계수를 나타내었다. 이러한 상반된 경향을 보이는 BPSf와 TMSPSf을 블렌드하여 제조한 BPSf/TMSPSf막의 경우 PSf보다 이상분리인자는 약간 감소한 반면 높은 투과도 계수를 나타내었다. 고분자의 구조와 투과 특성과의 상관관계를 밝히기 위해 고분자의 자유부피와 투과도 계수를 플로트한 결과, 투과도 계수가 자유부피에 잘 연관됨을 알 수 있었으며, 특히 specific free volme(SFV)과의 연관성이 보다 우수함을 알 수 있었다.

• Progress in Superconductivity
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• 제9권1호
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• pp.80-84
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• 2007

Charcoal was used as a carbon source for improving the critical current density of $MgB_2$ and the effect of annealing temperature on the $J_c$ of $MgB_2$ was investigated. The charcoal powder used in this study was $1{\sim}2$ microns in size and was prepared by wet attrition milling. $MgB_2$ bulk samples with a nominal composition of $Mg(B_{0.95}C_{0.05})_2$ were prepared by in situ process of Mg and B powders. The powder mixture was uniaxially compacted into pellets and heat treated at temperatures of $650^{\circ}C\;-\;1000^{\circ}C$ for 30 minutes in flowing Ar gas. It was found that superconducting transition temperature of $Mg(B_{0.95}C_{0.05})_2$ decreased by charcoal additions which indicates the carbon substitution for boron site. $J_c$ of $Mg(B_{0.95}C_{0.05})_2$ was lower than that of the undoped $MgB_2$ at the magnetic fields smaller than 4 Tesla, while it was higher than that of the undoped sample especially at the magnetic field higher than 4 T. High temperature annealing seems to be effective in increasing $J_c$ due to the enhanced carbon diffusion into boron sites.

• 한국자기학회:학술대회 개요집
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• 한국자기학회 2009년도 정기총회 및 동계학술연구발표회
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• pp.192-192
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• 2009

Magnetic and magnetotransport properties of (1-x) $La_{0.7}Sr_{0.3}MnO_3-xRE_2O_3$ (RE=La, Nd) (x = 0.025, 0.05, 0.075, 0.1, 0.2, 0.3) composite polycrystalline samples were systematically studied. Samples were prepared using conventional solid-state reaction. LSMO and $RE_2O_3$ react at high temperature and become chemically compatible. The ferromagnetic-paramagnetic transition temperatures ($T_c$) of the LSMO-$Nd_2O_3$ composite samples were decreased 313K~349K with increasing x, while the $T_c$ values of the LSMO-$La_2O_3$ composite samples were almost unaltered in the range of 355K~358K, representing that the ferromagnetism of LSMO might be more seriously degraded by Nd substitution on the ($La_{0.7}Sr_{0.3}$) site. However, LSMO-$RE_2O_3$ composite samples exhibit greatly enhanced low field magnetoresistance (LFMR) and dMR/dH value without an appreciable increase in its resistivity. Remarkably improved LFMR properties are attributed to LSMO grain boundaries acting as effective spin-dependent scattering centers. The relationship among the $RE_2O_3$ addition, microstructure, magnetic and magnetotransport properties will be discussed in this paper.

• Journal of Information Display
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• 제3권1호
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• pp.6-10
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• 2002

We have synthesized a new green Ir(III) complex fac-tris-(3-methyl-2-phenyl pyridine)iridium(III) $Ir(mpp)_3$ and fabricated phosphorescent polymer light-emitting device using it as a triplet emissive dopant in PVK. $Ir(mpp)_3$ showed absorption centered at 388 nm corresponding to the $^1MLCT$ transition as .evidenced by its extinction coefficient of the order of $10^3{\cdot}$ From the PL and EL spectra of the $Ir(mpp)_3$ doped PVK film, the emission maximum was observed at 523 nm, due to the radiative decay from the $^3MLCT$ state to the ground state, confirming a complete energy transfer from PVK to $Ir(mpp)_3$. The methyl substitution has probably caused a red shift in the absorption and emission spectrum compared to $Ir(mpp)_3$. The device consisting of a 2 % doped PVK furnished 4.5 % external quantum efficiency at 72 $cd/m^2$ (current density of 0.45 $mA/cm^2$ and drive voltage of 13.9 V) and a peak luminance of 25,000 $cd/m^2$ at 23.4 V (494 $mA/cm^2$). This work demonstrates the impact of the presence of a methyl substituent at the 3-position of the pyridyl ring of 2-phenylpyridine on the photophysical and electroluminescence properties.

• 한국세라믹학회지
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• 제48권1호
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• pp.63-68
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• 2011

The investigation is directed to lead free (Pb-free) frits that can be used for organic light emitting diode, plasma display screen devices and other sealing materials. $P_2O_5$-SnO system glasses have been prepared for Pb-free low temperature glass frit. Structure and properties of the glasses with the composition SnO-$xB_2O_3-(60-x)P_2O_5$ (x=0, 5, 10, 15, 20, 25, 30, 35, 40 mol%) were characterized by infrared spectra (IR), X-ray diffraction(XRD), Density, Molar volume, Thermo mechanical analysis(TMA) and weight loss after immersion test. Glass transition temperature($T_g$), dilatometric softening temperature($T_d$) and chemical durability increased, and coefficient of thermal expansion($\alpha$) decrease with the substitution of $B_2O_3$ for $P_2O_5$ in the range of 0~25 mol%.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4185-4190
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.