• Title/Summary/Keyword: Reduction kinetics

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Synthesis and kinetic of ultrafine titanium carbide particles by Mg-thermal reduction of liquid metal chlorides (마그네슘의 금속염 환원에 의한 초미립 탄화티탄 분말 합성거동)

  • 이동원;백진호;김병기
    • Journal of Powder Materials
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    • v.11 no.4
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    • pp.322-327
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    • 2004
  • Ultrafine titanium carbide particles were synthesized by the reaction of liquid-magnesium and vaporized TiCl$_{4}$+C$_{x}$Cl$_{4}$(x = 1 and 2) solution. Fine titanium carbide particles with about 50 nm were successfully produced by combining Ti and C atoms released by chloride reduction of magnesium, and vacuum was then used to remove the residual phases of MgCl$_{2}$ and excess Mg. Small amounts of impurities such as O, Fe, Mg and Cl were detected in the product, but such problem can be solved by more precise process control. The lattice parameter of the product was 0.43267 nm, near the standard value. With respect to the reaction kinetics, the activation energy for the reactions of TiCl$_{4}$+C$_{2}$Cl$_{4}$and Mg was found to 69 kJ/mole, which was about half value against the use of TiCl$_{4}$+CCl$_{4}$, and such higher reactivity of the former contributed to increase the stoichiometry until the level of TiC$_{0.96}$ and decrease the free carbon content below 0.3 wt.%.

A Study on the Effect of Pre-treatment on the Formation of Nitriding Layer by Post Plasma (포스트 플라즈마를 이용한 질화의 질화층 형성에 미치는 전처리의 영향에 대한 연구)

  • Moon, Kyoung Il;Byun, Sang Mo;Cho, Yong Ki;Kim, Sang Gweon;Kim, Sung Wan
    • Journal of the Korean Society for Heat Treatment
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    • v.18 no.1
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    • pp.24-28
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    • 2005
  • New post plasma nitriding can achieve a high uniformity that have been difficult in DC nitriding and have a high productivity comparable to gas nitriding. However, it has not a enough high nitriding potential for a rapid nitriding, because surface activation or ion etching in the general plasma nitriding cannot be expected. Thus, in this study, the effects of pre-treatments with oxidation and reduction gas have been investigated to improve the nitriding kinetics of post plasma nitriding. An effective pre-treatment consisting of oxidation and reduction resulted in the increase of surface energy of STD 11. This induced the surface hardness and the effective nitriding depth of STD 11. It is thought that the increase of the surface energy and the surface area with pre-treatment promote the nucleation of nitriding layer.

Mechanistic Studies on the Hydrogen Evolution and Permeation of Ultra-Strong Automotive Steel in Neutral Chloride Environments (중성의 염화물 환경 내 자동차용 초고강도강의 부식반응에 기인한 수소원자의 발생 및 투과 메커니즘)

  • Hwang, Eun Hye;Ryu, Seung Min;Kim, Sung Jin
    • Korean Journal of Materials Research
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    • v.28 no.7
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    • pp.428-434
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    • 2018
  • Hydrogen evolution on a steel surface and subsequent hydrogen diffusion into the steel matrix are evaluated using an electrochemical permeation test with no applied cathodic current on the hydrogen charging side. In particular, cyclic operation in the permeation test is also conducted to clarify the corrosion-induced hydrogen evolution behavior. In contrast to the conventional perception that the cathodic reduction reaction on the steel in neutral aqueous environments is an oxygen reduction reaction, this study demonstrates that atomic hydrogen may be generated on the steel surface by the corrosion reaction, even in a neutral environment. Although a much lower permeation current density and significant slower diffusion kinetics of hydrogen are observed compared to the results measured in acidic environments, they contribute to the increase in the embrittlement index. This study suggests that the research on hydrogen embrittlement in ultra-strong steels should be approached from the viewpoint of corrosion reactions on the steel surface and subsequent hydrogen evolution/diffusion behavior.

A Study on the Synthesis of Alkoxides and Sialon (알콕사이드와 사이알론 합성에 관한 연구)

  • Ho Ha;Heecheol Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.267-275
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    • 1988
  • Fine powders of amorphous $Al_2O_3,\;SiO_2,\;Al_2O_3-SiO_2$ system were prepared by hydrolysis of solutions containing alkoxides, aluminium tri-isopropoxide and silicon tetra-ethoxide. High purity ultrafine ${\beta}-sialon$ powders were prepared by the carbothermal reduction-nitridation of amorphous $Al_2O_3-SiO_2$ powders mixed with carbon black as a reducing agent. In the hydrolysis step the effect of the factors such as pH, reaction temperature and amount of water on the conversion rate of alkoxides to oxides was investigated. In the carbothermal reduction-nitridation the reaction path was assumed by the analysis of intermediates formed in the process of ${\beta}-sialon$ synthesis and the reaction kinetics of ${\beta}-sialon$ formation was considered.

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Photoelectrochemical Water Oxidation and $CO_2$ Conversion for Artificial Photosynthesis

  • Park, Hyunwoong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.70-70
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    • 2013
  • As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

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Enhance degradation of insecticide chlorpyrifos by iron salts and potassium persulfate during zerovalent iron treatment in aqueous solution

  • Rahman, M. Mokhlesur;Hwang, Jung-In;Kwak, Se-Yeon;Kim, Jang-Eok
    • Journal of Applied Biological Chemistry
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    • v.61 no.4
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    • pp.383-389
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    • 2018
  • Degradation of the insecticide O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifos) in aqueous solution was investigated using iron salts and potassium persulfate during ZVI treatment through a series of batch experiments. The degradation rate of chlorpyrifos increased with increases in the concentrations of iron salts and potassium persulfate in the aqueous system. Ferric chloride was found to be the most effective iron salt for the ZVI-mediated degradation of chlorpyrifos in aqueous solution. Further, the iron salts tested could be arranged in the following order in terms of their effectiveness: $FeCl_3$> $Fe_2(SO_4)_3$> $Fe(NO_3)_3$. The persulfate-ZVI system could significantly degrade chlorpyrifos present in the aqueous medium. This revealed that chlorpyrifos degradation by treatment with $Fe^0$ was promoted on adding ferric chloride and potassium persulfate. The kinetics of the degradation of chlorpyrifos by persulfate-amended $Fe^0$ was higher than that for iron-salt-amended $Fe^0$. This suggests that using a sequential $Fe^0$ reduction-ferric chloride or $Fe^0$ reduction-persulfate process may be an effective strategy to enhance the removal of chlorpyrifos in contaminated water.

Kinetic Investigation on the Reaction between Cu(II) and Excess D-penicillamine in Aqueous Media

  • Lee, Yong-Hwan;Choi, Sung-Nak;Cho, Mi-Ae;Kim, Yong-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.281-286
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    • 1990
  • The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.

Synthesis and Magnetic Property of Nanocrystalline Fe-Ni-Co Alloys during Hydrogen Reduction of Ni0.5Co0.5Fe2O4 (Ni0.5Co0.5Fe2O4의 수소환원에 의한 나노구조 Fe-Ni-Co 합금의 제조 및 자성특성)

  • Paek, Min Kyu;Do, Kyung Hyo;Bahgat, Mohamed;Pak, Jong Jin
    • Korean Journal of Metals and Materials
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    • v.49 no.2
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    • pp.167-173
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    • 2011
  • Nickel cobalt ferrite($Ni_{0.5}Co_{0.5}Fe_2O_4$) powder was prepared through the ceramic route by the calcination of a stoichiometric mixture of NiO, CoO and $Fe_2O_3$ at $1100^{\circ}C$. The pressed pellets of $Ni_{0.5}Co_{0.5}Fe_2O_4$ were isothermally reduced in pure hydrogen at $800{\sim}1100^{\circ}C$. Based on the thermogravimetric analysis, the reduction behavior and the kinetic reaction mechanisms of the synthesized ferrite were studied. The initial ferrite powder and the various reduction products were characterized by X-ray diffraction, scanning electron microscopy, reflected light microscope and vibrating sample magnetometer to reveal the effect of hydrogen reduction on the composition, microstructure and magnetic properties of the produced Fe-Ni-Co alloy. The arrhenius equation with the approved mathematical formulations for the gas solid reaction was applied to calculate the activation energy($E_a$) and detect the controlling reaction mechanisms. In the initial stage of hydrogen reduction, the reduction rate was controlled by the gas diffusion and the interfacial chemical reaction. However, in later stages, the rate was controlled by the interfacial chemical reaction. The nature of the hydrogen reduction and the magnetic property changes for nickel cobalt ferrite were compared with the previous result for nickel ferrite. The microstructural development of the synthesized Fe-Ni-Co alloy with an increase in the reduction temperature improved its soft magnetic properties by increasing the saturation magnetization($M_s$) and by decreasing the coercivity($H_c$). The Fe-Ni-Co alloy showed higher saturation magnetization compared to Fe-Ni alloy.

Ammonium Ion Effects and Its In Situ Removal by Using Immobilized Adsorbent in Hybridoma Cell Culture (하이브리도마 세포배양에서 암모늄 이온의 영향 및 고정화 흡착제에 의한 암모늄 이온의 동시제거)

  • 정연호;이해익
    • KSBB Journal
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    • v.11 no.3
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    • pp.329-339
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    • 1996
  • The effects of ammonium ion on cell growth kinetics, monoclonal antibody productivity, and cell metabolism of hybridoma cells were investigated. The mouse-mouse hybridoma cell line VlIIH-8 producing mouse IgG2a was used as a model system. Ammonium ion showed an inhibitory effect on cell growth and monoclonal antibody production. New immobilized adsorbents were developed for the reduction of the inhibitory effect of ammonium ion. The ammonium ion selective zeolite, Phillipsite-Gismondine was entrapped in calcium alginate bead or in dialysis membrane and applied to the hybridoma cell culture system for the in situ removal of ammonium ion from culture media. The effects of ammonium the both serum supplemented and serum free media on the cell growth were studied by applying immobilized adsorbents of calcium alginate bead type. The results demonstrated a substantial enhancement in cell growth. Applying immobilized adsorbents of dialysis membrane type to serum supplemented media also resulted in the stimulation of cell growth, cell viability and monoclonal antibody production.

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Shock Tube and Modeling Study of the Formation and the Reduction of Nitrogen Oxides; Ammonia Oxidation (질소산화물의 생성과 제어반응에 관한 충격관 실험 및 모델 연구 ; 암모니아 연소)

  • Shin, Kuan-Soo;Cho, Hye-Yun;Shim, Seung-Bo;Jee, Sung-Bae
    • Journal of the Korean Society of Combustion
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    • v.4 no.1
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    • pp.59-65
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    • 1999
  • Ignition of $NH_3-O_2-Ar$ mixtures have been studied behind reflected shock waves over the temperature range of 1600-2300 K and the pressures in the range of 1.1-1.6 atm. The pressure profile and the radiation emitted behind the shock waves have been monitored to give empirical correlations between ignition delay times and the mixture concentrations with the experimental conditions. On the basis of this data, several kinetic mechanisms proposed for ammonia oxidation at high temperatures have been tested. The ignition delay times obtained from the mechanism proposed by Miller and Smook were in good agreement with our experimental results.

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