• Bulletin of the Korean Chemical Society
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• v.34 no.7
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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.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.339-348
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• 1979

The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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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.

• Korean Journal of Materials Research
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• v.24 no.12
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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 $0.01Eu^{2+}/0.03Dy^{3+}$.

• Journal of the Korean Institute of Gas
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• v.5 no.1
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• pp.29-36
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• 2001

The permeation properties of $O_2\;and\;N_2$ were measured for bromobisphenol A polysulfone(BPSf), bisphenol A trimethylsilylated polysulfone(TMSPSf) and their blend membrane to investigate the structure-properties relationships. BPSf shows relatively high permselectivity. It can be explained that the strong polarity of bromine in BPSf increases chain packing ability. In this case the distance of polymer chains is reduced by increasing of interchain interaction by induced dipole. TMSPSf shows relatively high permeability. The higher value of permeability coefficients for TMSPSf is due to the substitution of very bulky trimethylsilyl groups. The replacement of phenyl hydrogens of bisphenol A polysulfone(PSf) with trimethylsilyl groups results in higher fractional free volume(FFV). In this work, taking into account the complimentary features of BPSf and TMSPSf, BPSf/TMSPSf blend was prepared and the compatibility in mixing are examined. The BPSf/TMSPSf blend shows higher permeability than commercial PSf, with minimum loss of selectivity. The miscibility of the BPSf/TMSPSf blend is confirmed by the single glass transition temperature.

• Progress in Superconductivity
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• v.9 no.1
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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.

• Proceedings of the Korean Magnestics Society Conference
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• 2009.12a
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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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• v.3 no.1
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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.

• Journal of the Korean Ceramic Society
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• v.48 no.1
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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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• v.32 no.12
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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.