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Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-4,4'-Bipyridine Complex (크롬(VI)-4,4'-Bipyridine 착물에 의한 치환 벤질 알코올류의 산화반응 속도론과 메카니즘)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.13 no.1
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    • pp.462-469
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    • 2012
  • Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

High Strength SA508 Gr.4N Ni-Cr-Mo Low Alloy Steels for Larger Pressure Vessels of the Advanced Nuclear Power Plant (차세대 원전 대형 압력용기용 고강도 SA508 Gr.4N Ni-Cr-Mo계 저합금강 개발)

  • Kim, Min-Chul;Park, Sang-Gyu;Lee, Ki-Hyoung;Lee, Bong-Sang
    • Transactions of the Korean Society of Pressure Vessels and Piping
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    • v.10 no.1
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    • pp.100-106
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    • 2014
  • There is a growing need to introduce advanced pressure vessel steels with higher strength and toughness for the optimizatiooCn of the design and construction of longer life and larger capacity nuclear power plants. SA508 Gr.4N Ni-Cr-Mo low alloy steels have superior strength and fracture toughness, compared to SA508 Gr.3 Mn-Mo-Ni low alloy steel. Therefore, the application of SA508 Gr.4N low alloy steel could be considered to satisfy the strength and toughness required in advanced nuclear power plants. The purpose of this study is to characterize the microstructure and mechanical properties of SA508 Gr.4N low alloy steels. 1 ton ingot of SA508 Gr.4N model alloy was fabricated by vacuum induction melting followed by forging, quenching, and tempering. The predominant microstructure of the SA508 Gr.4N model alloy is tempered martensite having small packet and fine Cr-rich carbides. The yield strength at room temperature was 540MPa, and it was decreased with an increase of test temperature while DSA phenomenon occurred at around $288^{\circ}C$. Overall transition property of SA508 Gr.4N model alloy was much better than SA508 Gr.3 low alloy steel. The index temperature, $T_{41J}$, of SA508 Gr.4N model alloy was $-132^{\circ}C$ in Charpy impact tests, and reference nil-ductility transition temperature, $RT_{NDT}$ of $-105^{\circ}C$ was obtained from drop weight tests. From the fracture toughness tests performed in accordance with the ASTM standard E1921 Master curve method, the reference temperature, $T_0$ was $-147^{\circ}C$, which was improved more than $60^{\circ}C$ compared to SA508 Gr.3 low alloy steels.

Mechanization of Pine Cone Harvest(III) -Power Requirements to Cut Shoots of Korean Pine Trees by Circular Saw- (잣 수확의 기계화 연구(III) -원형톱에 의한 잣나무 가지의 절단에 소요되는 동력-)

  • 강화석;강위수;이재선
    • Journal of Biosystems Engineering
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    • v.20 no.3
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    • pp.245-249
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    • 1995
  • In this study power requirements to saw shoots with circular saw were determined by measuring and analyzing the required maximum torque to provide the information for the mechanization of Korean pine cone harvest. Two levels of feed rate of shoots, 10.4mm/s and 20.8mm/s, three levels of sawing speed 5.8㎧, 11.6㎧, and 17.4㎧, and 14 levels of shoot diameter from 7.7 to 18.1mm were used as variables. 1) The maximum torques were significantly affected by all three variables. The average maximum torque, 18.2 N-cm for feed rate of 20.Bmm/s was greater as much as 80% of 10.1 N-cm for feed rate of 10.4mm/s. 2) As the sawing speed was increased from 5.8㎧ to 11.6㎧ and 17.4㎧, the maximum torques were decreased to 14.8N-cm, 8.5N-cm, and 7.IN-cm, respectively when the feed rate was 10.4mm/s. The maximum torque ranged from 4.5 to 19.3N-cm as shoot diameter increased from 7.7 to 18.1mm. The minimum power requirements to saw shoots of 18.1mm with circular saw was 30W for the feed rate of 10.4mm/s. 3) The maximum torques were 28.6N-cm, 14.6N-cm, and 11.4N-cm when sawing speeds were 5.8㎧, 11.6㎧, and 17.4㎧, respectively when the feed rate was 20.8mm/s and these torques were increased as much as 93%, 36%, and 61% of those for the feed rate of 10.4mm/s. The maximum torque increased from 9.7N-cm to 30.7N-cm as shoot diameter increased from 7.7 to 18.1mm. The minimum power requirements to saw shoots of 18.1mm was 54W which was 1.8 times of 30W for the feed rate of 10.4mm/s.

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One-Pot Reaction Involving Two Different Amines and Formaldehyde Leading to the Formation of Poly(Macrocyclic) Cu(II) Complexes

  • Lee, Yun-Taek;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2517-2522
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    • 2012
  • New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

Refinement of the Structure of p-Dimethylaminobenzaldehyde 4-(p-Ethoxyphenyl) Thiosemicarbazone (p-Dimethylaminobenzaldehyde 4-(p-Ethoxyphenyl) Thiosemicarbazone구조의 정밀화)

  • Seo, Il-Hwan;Seo, Chu-Myeong;Park, Yeong-Ja
    • Korean Journal of Crystallography
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    • v.2 no.1
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    • pp.12-16
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    • 1991
  • C18H22N4OS, Mr=342.47, monoclinic, P2₁/c,a=11.802(2), b=31.962(2), c=9.829(2)A, β=100.12(1)˚, V=3694.8A3,F(000)=1472, Z=8, Dx=1.246 Mg m-3, Dm=1.17Mg m-3,λ=0.71073 A, μ=0.15mm-1, T=294 K. final R=0.0856 for 3718 observed reflection (Fo>3σ(Fo)) There are two molecules in an asymmetric unit and a major difference between these molecules is in the C(9)-N(1)-C(6)-C(7) torsion angles [58.8(8)˚and 1(1)˚]. Both molecules have intramolecular N(1)-H(10)'N(3) hydrogen bonds [ 2.613(7) and 2.566(7) A] and assume V-shaped conformation with N(2) atoms at the verices. The two independent molecules are linked by the two N(2)-H(11)'S' hydrogen bonds[3.367(5) A and 3.421(4)A] and the dimergen are held together by van der Waals forces.

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Soft Magnetic Properties of FeTaNC Nanocrystalline Thin Films (FeTaNC 초미세결정박막의 반응가스 분압에 따른 자기특성 변화)

  • 고태혁;신동훈;김형준;남승의;안동훈
    • Journal of the Korean Magnetics Society
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    • v.6 no.3
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    • pp.151-157
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    • 1996
  • Magnetic properties and microstructures of FeTaNC thin films, which were deposited by magnetron reactive sputtering rrethod, were investigated as a function of $CH_{4}$ and $N_{2}$ gas partial pressures. Magnetic properties of FeTaNC films depended on total reactive gas pressure as well as $CH_{4}/N_{2}$ pressure ratios. For reactive gas partial pressures of 5~10 %, optimum magnetic properties were observed in the FeTaNC films with proper $CH_{4}/N_{2}$ ratio. On the other hand, at 15% of gas partial pressure, FeTaN and FeTaC films showed superior properties to FeTaNC films. Above 15%, the magnetic properties of films rapidly degraded due to an excess incorporation of C and/or N atoms. Excellent soft magnetic properties of 17 kG of Bs, 0.3 Oe of He, and 4000 of $\mu'$(at 5 MHz) were obtained in the FeTaNC films. High permeabilities of FeTaNC films could be explained by the Fe lattice distortion caused by N atoms, hence reduction of magnetic anisotopy. While precipitated TaN and TaC particles effectively supress the growth of $\alpha-Fe$ grains leading to a good soft magentic properties, FeN and FeC phases such as $Fe_3N$, $Fe_4N$, FexC have detrimental effects.

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Kinetics for the Transformation of Outer Charge Transfer Complex to Inner Complex (Outer Charge Transfer Complex가 Inner Complex로의 변환에 따른 속도론적 연구)

  • Kwon Oh-Yun;Paek U-Hyon;Kim Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.343-349
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    • 1991
  • Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

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Effect of electron-beam irradiation on leakage current of AlGaN/GaN HEMTs on sapphire

  • Oh, Seung Kyu;Song, Chi Gyun;Jang, Taehoon;Kwak, Joon Seop
    • JSTS:Journal of Semiconductor Technology and Science
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    • v.13 no.6
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    • pp.617-621
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    • 2013
  • This study examined the effect of electron-beam (E-beam) irradiation on the electrical properties of n-GaN, AlGaN and AlGN/GaN structures on sapphire substrates. E-beam irradiation resulted in a significant decrease in the gate leakage current of the n-GaN, AlGaN and HEMT structure from $4.0{\times}10^{-4}A$, $6.5{\times}10^{-5}A$, $2.7{\times}10^{-8}A$ to $7.7{\times}10^{-5}A$, $7.7{\times}10^{-6}A$, $4.7{\times}10^{-9}A$, respectively, at a drain voltage of -10V. Furthermore, we also investigated the effect of E-beam irradiation on the AlGaN surface in AlGaN/GaN heterostructure high electron mobility transistors(HEMTs). The results showed that the maximum drain current density of the AlGaN/GaN HEMTs with E-beam irradiation was greatly improved, when compared to that of the AlGaN/GaN HEMTs without E-beam irradiation. These results strongly suggest that E-beam irradiation is a promising method to reduce leakage current of AlGaN/GaN HEMTs on sapphire through the neutralization the trap.

Synthesis of Anticoagulant 3-(N-Aryalmino)-1,4-Naphthoquinones(III) (항응고성의 3-(N-Arylamino)-1,4-Naphthoquinone 유도체 합성(III))

  • Ryu, Chung-Kyu
    • YAKHAK HOEJI
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    • v.34 no.6
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    • pp.422-428
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    • 1990
  • 2,3-Dibromo-1,4-naphthoquinone was reacted with p-aminobenzoic acid, 2-aminopyridine, 2-amino-4-metylpyridine, m-nitroaniline, sulfathiazol, p-chloroaniline, phenetidine and 2-bromo-3-(N-arylamino)-1,4-naphthoquinones($1{\sim}8$). 2,3-Epoxy-2,3-dihydro-1,4-naphthoquinone was also reacted with p-amonobenzoic acid, p-toluidine, p-chloroaniline, m-chloroaniline, m-nitroaniline, p-phenetidine, N,N-dimethyl-1,4-pheylenediamine as a ring opening and dehydogenation to form 2-hydroxy-3-(N-arylamino)-naphthoquinones ($9{\sim}16$) in good yield. These new compounds($1{\sim}16$) are expected to have a biological activities such as anticoagulant and cytotoxic.

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