• Title/Summary/Keyword: $S_N2$ mechanism

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Antioxidation mechanism of Al metal powders on $Al_2O_3-C$ refractory ($Al_2O_3-C$계 내화물에서 알루미늄 금속분말의 산화억제 메카니즘)

  • 류정호;임창성;오근호
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.8 no.1
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    • pp.97-105
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    • 1998
  • Antioxidation mechanism of Al metal powders on $Al_2O_3-C$ refractory was investigated in temperature range from 800 to $1400^{\circ}C$. The addition of 5 wt% Al metal powders suppressed the oxidation of carbon in $Al_2O_3$-C sample. The carbons were distributed uniformly on the surface and the interface of the $Al_2O_3$-C-Al. Reaction products of $Al_4C_3$ and AIN were found with a composition of Al-C at temperatures between 800 and $1200^{\circ}C$ and transformed to $Al_2O_3$ above $1400^{\circ}C$. Cavity structures related to the to the formation of $Al_4C_3$ were observed for the AI-C after heating at $1000^{\circ}C$ ofr 1 hour. Thermodynamic mechanism was considered to discuss the formation $Al_4C_3$, AlN and their transformation to $Al_2O_3$, which leads to the effect of oxidation resistance.

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Low-Temperature Superplastic Deformation Behavior of Fine-Grained Ti-6Al-2Sn-4Zr-2Mo-0.1Si Alloy (미세 결정립 Ti-6Al-2Sn-4Zr-2Mo-0.1Si 합금의 저온 초소성 변형 거동)

  • Park, C.H.;Lee, B.;Lee, C.S.
    • Transactions of Materials Processing
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    • v.18 no.7
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    • pp.544-549
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    • 2009
  • This study aimed to elucidate the deformation mechanism during low-temperature superplasticity of fine-grained Ti-6Al-2Sn-4Zr-2Mo-0.1Si alloy in the context of constitutive equation. For this purpose, initial coarse equiaxed microstructure was refined to $2.2{\mu}m$ via dynamic globularization. Globularized microstructure exhibited large superplastic elongations(434-826%) at temperatures of $650-750^{\circ}C$ and strain rate of $10^{-4}s^{-1}$. It was found that the main deformation mechanism of fine-grained material was grain boundary sliding accommodated by dislocation motion with both stress exponent (n) and grain size exponent (p) values of 2. When the alpha grain size, not sub-grain size, was considered to be an effective grain size, the apparent activation energy for low-temperature superplasticity of the present alloy(169kJ/mol) was closed to that of Ti-6Al-4V alloy(160kJ/mol).

The Research of Fatigue-Crack Initiation and Propagation for S35C Steel (S35C강의 피로균열 발생 및 진전에 관한 연구)

  • 진영준
    • Journal of the Korean Society of Safety
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    • v.16 no.1
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    • pp.31-36
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    • 2001
  • Surface crack growth characteristics and influence of the stress amplitude in rotary bending fatigue test were evaluated for annealed S35C steel, and than fractal dimensions of fatigue crack paths estimated using the box counting method. The following results that will be helpful to understand the fatigue crack growth mechanism were obtained. (1) Crack growth rate ds/dN and db/dN (s : half crack length at the surface crack, b : crack depth) depended on stress amplitude (${\Delta}{\sigma}/2$), stress intensity factor range (${\Delta}K_A, {\Delta}K_C$) and crack length. (2) At the effect area of 0.3 mm hole notch (s<0.5 mm) crack growth rate did not depend on these factors. (3) The fractal dimensions (D) increased with stress amplitude (${\Delta}{\sigma}/2$) but decreased with cyclic number.

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Thermal Stability of Lamellar Eutectic Structure in Fe-Ti Alloy (Fe-Ti합금계에서의 충상공정조직의 열적안정성)

  • Wey, Myeong Yong;Hasebe, Mitsuhiro
    • Journal of the Korean Society for Heat Treatment
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    • v.10 no.2
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    • pp.121-127
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    • 1997
  • In order to elucidate thermal stability of Fe-$Fe_2Ti$ eutectic structure, the initial several structures have been investigated in the changes of coarsening and spheroidization during prolonged annealing under the eutectic temperature. The results are as follows: 1) The rate constant of coarsening and spheroidization was formulated as $S^{-n}-S_0^{-n}=k{\cdot}t$, where S is the total area of the interface between ${\alpha}$ and C($Fe_2Ti$) per unit volume, $S_0$ is initial value and k is the rate constant. 2) The coarsening and spheroidization mechanism was described by Ostwald ripening and controlled by diffusion of Ti-atom in ${\alpha}$-phase. 3) The spheroidization rate constant in eutectic lamellar structures was depended upon annealing temperature and showed the Arrhenius relation. The activation energy for spheroidization of lamellar structure was 365 kJ/mole.

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Kinetics and Mechanism of the Anilinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl -5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.1037-1041
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    • 2012
  • The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) 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 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

A Study on the Determination of$N(NO_2^-),\;N(NO_3^-)$and$N(NH_4^+)$in Environmental Samples by Flow Injection Analysis (흐름주입분석법에 의한 환경시료 중$N(NO_2^-),\;N(NO_3^-)$$N(NH_4^+)$의 정량분석에 관한 연구)

  • Rhee, Jae Seong;Kim, Young Sang;Jung, Yun Hee;Rhee, Hee Jung
    • Journal of the Korean Chemical Society
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    • v.41 no.5
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    • pp.256-265
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    • 1997
  • A rapid and sequential method was studied, which can determine nitrite, nitrate and ammonium ion in soil or water samples with flow injection analysis. Geometric factors including injection volume, length of the reaction coil and flow rate of carrier solution were investigated prior to sample measurement. Nitrite was determined at 540 nm by Griess reaction producing azo dye between N-(1-naphthylethylenediamine dihydrochloride) and sulfanilamide. Nitrate was also measured under the help of reduction mechanism toward nitrite with hydrazine. Ammonium was analyzed at 440 nm with Nessler's reagent. At the optimum condition, the detection limit(S/N=3) has been shown 0.1 ㎍/mL N(NO2-), 0.4 ㎍/mL N(NO3-) and 0.3 ㎍/mL N(NH4+) respectively. The results measured by colorimetry, ion chromatography and FIA were compared showing 80%-125% reasonable match each other. Injection throughput rate could be performed better than 30 times per hour.

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Kinetic Study on Aminolysis of Phenyl 2-Pyridyl Carbonate in Acetonitrile: Effect of Intramolecular H-bonding Interaction on Reactivity and Reaction Mechanism

  • Song, Ji-Hyun;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2081-2085
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    • 2014
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

Novel Synthesis of Sulfated Chitosan Derivatives and its Anti-HIV-1 Activity (황산화 키토산 유도체의 합성과 항에이즈활성)

  • Han Sang-Mun
    • Journal of environmental and Sanitary engineering
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    • v.21 no.1 s.59
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    • pp.21-34
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    • 2006
  • To investigate anti-HIV-1 activity of water soluble chitosans, sulfated chitosan derivatives were prepared in mild condition. Various sulfated chitosan derivatives (N-3,6-O-S-chitosan, N-desulfated 3,6-O-S-chitosan, 3,6-O-S-chitin, and 3,6-O-sulfated-N-(o-carboxybenzoyl) chitosan) were synthesized with sulfurtrioxidepyridene complex in pyridine solvent. Characterization of the sulfated chitosan derivatives was carried out by $^{13}C$ NMR and IR spectroscopies. To observe ionic reaction properties, pKas of the sulfated chitosan derivatives and chitosan of low molecular weight were estimated by potentiometric titration. The sulfated chitosan derivatives had high water solubility, pKas (pKa : 7.7) of N-3,6-O-S-chitosan and N-desulfated 3,6-O-S-chitosan were increased than pKa of water insoluble chitosan (pKa : 6.2), These results suggest the participation of electrostatic interaction of amino and sulfate groups on the sulfated chitosans. Anti-HIV-1 drugs, such as AZT, ddC, and ddI for anti-HIV activity had higher selective index compared with SCB-chitosan but N-3,6-O-S-chitosan has shown higher selective index compared with ddC and ddI as HIV drugs.. These results suggest that sulfated chitosan derivatives were expected as an anti-HIV drug with differential driving force mechanism against some nucleoside analogs drug in the future.

Evaluation on Odor Removal Performance of Bacteria-Based Odor Reduction Kit for Revetment Blocks (호안블록용 박테리아 기반 악취저감 키트의 악취제거 성능평가)

  • Keun-Hyoek Yang;Ju-Hyun Mun;Ki-Tae Jeong;Hyun-Sub Yoon;Jae-Il Sim
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.12 no.2
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    • pp.229-238
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    • 2024
  • This study evaluated the odor removal performance of a bacteria-based odor reduction kit. The bacteria used were Rhodobacter capsulatus, Paracoccus limosus, and Brevibacterium hankyongi, which can remove ammonia (NH3), hydrogen sulfide (H2S), total nitrogen (T-P), and total phosphorus (T-N), which are odor pollutants. The materials used were bacteria and porous aggregates (expanded vermiculite, zeolite beads, activated carbon), and the combination of the materials varied depending on the removal mechanism. Materials with a physical adsorption mechanism (zeolite beads and activated carbon) gradually slowed down the concentration reduction rate of odor pollutants (NH3, H2S, T-P, and T-N), and had no further effect on reducing the concentration of odor pollutants after 60 hours. Expanded vermiculite, in which bacteria that remove odors through a bio-adsorption mechanism were immobilized, had a continuous decrease in concentration, and the concentration of odor pollutants reached 0 ppm after 108 hours. As a result, the odor removal performance of materials with physical adsorption mechanisms in actual river water did not meet the odor emission standard required by the Ministry of Environment, while the expanded vermiculite immobilized with bacteria satisfied the odor emission permissible standard and achieved water quality grade 1.

Kinetics and Mechanism of the Pyridinolysis of Aryl Cyclopropanecarboxylates in Acetonitrile

  • Koh, Han-Joong;Kang, Suk-Jin;Kim, Cheol-Ju;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.7
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    • pp.925-930
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    • 2003
  • Kinetic studies of the reaction of Z-aryl cyclopropanecarboxylates with X-pyridines in acetonitrile at 55.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$. These mechanistic conclusions are drawn base on (i) the large magnitude of ρx and ρz, (ii) the positive sign of ρxz and the larger magnitude of ρxz than normal $S_N2$ processes, (iii) a small positive enthalpy of activation, Δ$H^≠$, and a large negative, Δ$S^≠$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.