• Title/Summary/Keyword: C - to - T transition

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The α-Effect in SNAr Reaction of Y-Substituted-Phenoxy-2,4-Dinitrobenzenes with Amines: Reaction Mechanism and Origin of the α-Effect

  • Cho, Hyo-Jin;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2448-2452
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    • 2014
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

Fabrication of the Bulk Superconductor by Thermal Diffusion Process (열확산 프로세스에 의한 초전도 벌크 합성)

  • Lee, Sang Heon
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.34 no.6
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    • pp.461-465
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    • 2021
  • A diffusion heat treatment process for YBa2Cu3O7-y bulk superconductor in a Gd2O3 powder was attempted. As a result of measuring the critical temperature of the superconducting bulk, there was no change in the superconducting transition temperature as the Gd particles diffused into the YBa2Cu3O7-y lattice, resulting in dense microstructure. As a result of measuring the critical current, the critical current density (Jc) of the superconducting bulk having treated by the Gd thermal diffusion treatment at 0 T increased to 3×104 A/cm2 at 0 T, which was higher than that of the superconducting bulk without thermal diffusion treatment. The surface magnetic force of the superconducting bulk with Gd thermal diffusion treatment was observed at the center of the superconducting bulk with the maximum trapped magnetic force (Hmax) of 1.51 kG. This result means that the Gd thermal diffusion treatment contributes to improving the critical current density Jc of YBa2Cu3O7-y, and it is believed that Gd particles migrating into the superconducting bulk through thermal diffusion either fill the surface pores of YBa2Cu3O7-y superconductors or act as a flux pinning center.

A Study on Film Boiling Heat Transfer in a Forced Convective Flow System (강제대류계(强制對流系)에 있어서 막비등열전달(膜沸騰熱傳達)에 관한 연구(硏究))

  • Kim, Y.T.;Kwon, S.S.;Jung, D.I.
    • Korean Journal of Air-Conditioning and Refrigeration Engineering
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    • v.3 no.1
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    • pp.51-60
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    • 1991
  • The aim of this study is to investigate the heat transfer characteristics in the transient cooling process of a high temperature wall. The slow transient cooling experiment was carried out with a copper block of high thermal capacity. The results of these experiments are as follows. 1. Temperature histories measured by the thermocouple, which is 0.99, 2.00, 2.99mm from the heat transfer surface showed monotonous during the cooling process. These variation are the curves of typical temperature histories in film-boiling, transition-boiling, and nucleate-boiling regions. 2. The temperature histories were measured by thermocouple installed in the copper block. The variations of the surface heat fluxes and surface temperature were computed from the numerical solution method TDMA from the measured temperature histories for radial position one dimensional heat transfer inverse problem. The boiling curves were found by the computed temperature histories. 3. The rewetting point which starts to change from film boiling to nucleate boiling is not connected with the mass velocity and it were found that the temperature of rewetting point indicated about $100^{\circ}C$. 4. The heat flux of rewetting point was about $10^5Kcal/m^2h$, at that time, the heat transfer coeficient indicated about $1000Kcal/m^2h^{\circ}C$ irrelevent to mass velocity. 5. The wall superheat decreases as the pressure increases. But I found that rewetting point appeared under higher condition in the wall temperature.

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Temperature-Dependent Hydrolysis Reactions of U(VI) Studied by TRLFS

  • Lee, J.Y.;Yun, J.I.
    • Journal of Nuclear Fuel Cycle and Waste Technology
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    • v.1 no.1
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    • pp.65-73
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    • 2013
  • Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

Dependence of Electronic Spectra on the Degree of Conjugation in Organocobalt(Ⅲ) Complexes (공액도에 따른 유기코발트 착화합물의 전자스펙트럼에 관한 연구)

  • Hye Kyung Seo;Chan Ah Bong;Young Ae Hwang Park
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.1047-1052
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    • 1993
  • The electronic spectra of enzyme-model organocobalt(Ⅲ) complexes containing completely or partially conjugated macrocyclic ligands were measured in various solvents to investigate the solvent effect on the charge transfer band for the axial cobalt-carbon bond by the extent of conjugation in the equatorial macrocyclic ring; completely conjugated, $CH_3CoL,\;C_6H_5CoL,\;CNCoL,\;CH_3CoL',\;CNCoL'$, partially conjugated $CH_3(py)Co(DH)_2, CH_3CoL"$, unconjugated dienes, $[CH_3Co(1,4-CT)](ClO_4)_2$, and open ring, $CH_3Co(salen)$. The position of the charge transfer band which corresponds to the cobalt-carbon bond was shifted to a shorter wavelength as the polarity of solvent increased and the transition energy $(E_T)$ had a linear relationship with solvent polarity parameter, Z-value, only in the case of completely conjugated system. However, the linear correlation between $E_T$and Z was not observed for partially conjugated and open ring systems.

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Effect of B2O3 Additives on GaN Powder Synthesis from GaOOH (GaOOH로부터 GaN 분말의 합성에 미치는 B2O3의 첨가효과)

  • Song, Changho;Shin, Dongwhee;Byun, Changsob;Kim, Seontai
    • Korean Journal of Materials Research
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    • v.23 no.2
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    • pp.104-111
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    • 2013
  • In this study, GaN powders were synthesized from gallium oxide-hydroxide (GaOOH) through an ammonification process in an $NH_3$ flow with the variation of $B_2O_3$ additives within a temperature range of $300-1050^{\circ}C$. The additive effect of $B_2O_3$ on the hexagonal phase GaN powder synthesis route was examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transformation infrared transmission (FTIR) spectroscopy. With increasing the mol% of $B_2O_3$ additive in the GaOOH precursor powder, the transition temperature and the activation energy for GaN powder formation increased while the GaN synthesis limit-time ($t_c$) shortened. The XPS results showed that Boron compounds of $B_2O_3$ and BN coexisted in the synthesized GaN powders. From the FTIR spectra, we were able to confirm that the GaN powder consisted of an amorphous or cubic phase $B_2O_3$ due to bond formation between B and O and the amorphous phase BN due to B-N bonds. The GaN powder synthesized from GaOOH and $B_2O_3$ mixed powder by an ammonification route through ${\beta}-Ga_2O_3$ intermediate state. During the ammonification process, boron compounds of $B_2O_3$ and BN coated ${\beta}-Ga_2O_3$ and GaN particles limited further nitridation processes.

Nd1+XBa2-XCu3O7-δ Bulk Superconductor by Zone-melt Process

  • Soh, Dea-Wha;Guo, Fan-Zhan
    • Transactions on Electrical and Electronic Materials
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    • v.3 no.3
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    • pp.21-24
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    • 2002
  • Two kinds of $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$, the sintering samples and zone melting samples, were heat-treated under pure Ar at 950$^{circ}C$. The substitution of Nd ion for Ba ion in the $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ before and after the heat treatment was investigated by XRD. In order to confirm the effects of the heat treatment, the Tc and Jc of samples with/without the heat treatment under Ar were comparatively studied. $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ samples were oxygenated under pure oxygen at $300^{circ}C$. From the XRD pattern it was found that the sample with x<0.4 was transferred from tetragonal phase to orthorhombic phase after the oxygenation, while the sample with x>0.4 did not show the phase transition even after a long time oxygenation. Therefore, the low oxygen partial pressure (Ar+1 % O$_2$) was used for the ambient atmosphere of the zone-melting samples, which could reduce the melting temperature and depress the substitution of Nd for Ba. After the improvement in the zone-melting process, the Jc value was increased to 2 x $10^4$A/$cm^2$ (0 T, 78 K). The particle orientation and the structure of zone-melted NdBaCuO were studied by the XRD and SEM analysis.

The Effects of Physical Aging of PSF/AS4 Laminate on Fatigue (PSF/AS4 복합재료의 가속노화가 피로강도에 미치는 영향)

  • Kim, Hyung-Won
    • Composites Research
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    • v.19 no.4
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    • pp.1-6
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    • 2006
  • The effects of aging on fatigue of PSF/AS4 laminates tvas studied using the new energy release rate analysis. The analysis by the variational mechanics has been useful in providing fracture mechanics interpretation of matrix microcracking in cross-ply laminates. This paper describes the changes of the critical energy release rate ${\Delta}Gmc$(microcracking toughness) about the variation of the aging period during fatigue loading. The master plot by modified Pans-law gives a characterization of a material system's resistance to microcrack formation. PSF/AS4 $[0/902]_s$ laminates were aged at four different temperatures based on the glass transition temperature for 60 days. At all temperatures, the toughness decreased with aging time. The decrease of the toughness at higher temperature was faster than at lower temperature. To assess the effects of aging on fatigue, the unaged laminates were compared with the laminates which were aged for 60 days at $170^{\circ}C$ near $180^{\circ}C\;T_g$. The slope of dD/dN versus A 6u, of the aged laminates was lower than that of the unaged laminates. There was a significant shift of the aged data to formation of microcracks at the lower values of ${\Delta}G_m$.

A Missense Mutation in Exon 5 of the Bovine Growth Hormone Gene (소 성장호르몬 유전자의 Exon 5번에서의 새로운 다형성 연구)

  • Yoon, D. H.;Kim, T. H.;Lee, K. H.;Park, E. W.;Lee, H. K.;Cheong, I. C.;Hong, K. C.
    • Journal of Animal Science and Technology
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    • v.45 no.1
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    • pp.13-22
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    • 2003
  • Growth Hormone (GH) gene is a member of gene family through the evolutionary process from a small common ancestral gene by a series of gene duplications. The role of the GH in growth and performance controls has been extensively studied in human, mice and livestock. Many researchers have considered GH as a strong candidate gene for evaluation of genetic polymorphisms that could be associated with economic traits in cattle. We report here a novel missense mutation within the exon 5 of the bovine Growth Hormone (bGH) gene. We could amplified 522 bp fragments from eight unrelated Hanwoo cattle by PCR, then, subsequently cloned and sequenced. An Msp I RFLP corresponding to a C to T transition was observed at position 2258 nt. From this result, we could predict a missense mutation (Arg to Trp) at codon 166 in a highly conserved region among many mammals. Codominant Mendelian segregation of the two alleles, Msp I (+) and Msp I (-), was observed in two full-sib F2 families (n = 32, African taurine Bos taurus ${\times}$ African zebu Bos indicus) and eight half-sib Hanwoo families. For the availability of genetic marker, we have performed PCR-RFLP with a large number of individual animals from 15 different cattle breeds (European and Asian taurines, and African indicines). Consideration of breed frequencies of Msp I (-) allele in relation to breed type and their geographic origins, shows higher frequencies in humped breeds or Asian cattle breeds than in humpless or European breeds. This result indicates that the missense mutation can be contributed the functional significance such as the signal transduction through the receptor binding, also may be used as a marker for selection of the economic traits in Hanwoo.

Optical Properties of Cdlnsub 2Ssub 4 and Cdlnsub 2Ssub 4 : $CdIn_2S_4$$CdIn_2S_4 : Co^{2+}$Single Crystals ($CdIn_2S_4$$CdIn_2S_4 : Co^{2+}$ 단결정의 광학적 특성)

  • Choe, Seong-Hyu;Bang, Tae-Hwan;Kim, Hyeong-Gon
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.48 no.5
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    • pp.296-302
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    • 1999
  • $CdIn_2S_4 and CdIn_2S_4 : Co^{2+}$ singlecrystals of thenormal spinel structure were grown by the C.T.R. method. The optical energy band structure of these compounds had a indirect band gap at the fundamental optical absorption band edge. The direct and the indirect energy gaps are found to be 2.325 and2.179eV for $Cdln_2S_4$ , and 2.303 and 2.169eV for $CdIn_2S_4 and CdIn_2S_4 : Co^{2+}$ at 5K, respectivly. The fundamental absorption band edge of these single crystals shift to a shorter wavelength region with decreasing temperature, and the temperature dependence of the optical energy gaps in these compounds satisfy Varshni equation. The Varshni constants$\alpha and \beta$ of the direct energy gap are given by $13.39{\times}10_{-4}eV/K$ and 509 K for $Cdln_2S_4$ and $29.73{\times}10_{-4} eV/K$ and 1398K for $CdIn_2S_4 and CdIn_2S_4 : Co^{2+}$. The Varshni constants ${\alpha}and {\beta}$ of the indirect energy gap are given by 9.68${\times}10^{-4}$ eV/K 308K for $Cdln_2S_4$ and $13.33{\times}10_{-4}eV/K$ and 440K for $CdIn_2S_4 : Co^{2+}$ respectivly. The impurity optical absorption peaks due to cobalt dopant are observed in $CdIn_2S_4 : Co^{2+}$ single crystal. These impurity optical absorption peaks can be attributed to the electronic transitions between the split energy levels of $Co_{2+}$ ions located at $T_d$ symmetry site of $Cdln_2S_4$ host lattece.

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