• Title/Summary/Keyword: Accelerated oxidation

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Intermittent Operation Induced Deactivation Mechanism for HER of Ni-Zn-Fe Electrode for Alkaline Electrolysis (수소발생용 Ni-Zn-Fe 합금 전극의 간헐적 작동에 따른 비활성화 특성)

  • HAN, JIMIN;KIM, JONGWON;BAE, KIKWANG;PARK, CHUSIK;JEONG, SEONGUK;JUNG, KWANGJIN;KANG, KYOUNGSOO;KIM, YOUNGHO
    • Journal of Hydrogen and New Energy
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    • v.31 no.1
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    • pp.8-22
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    • 2020
  • In this study, we investigated the deactivation characteristics of Ni-Zn-Fe electrodes due to intermittent operation in alkaline water electrolysis. To find suitable method to accelerate deactivation of electrode, the accelerated stress-test (AST) which repeated on/off step was performed with constant current/voltage control. The AST under constant voltage control is suitable to deactivate electrode so it were selected to investigate deactivation of electrode. The AST which repeated on/off step in range of -1.3 V and 0 V was performed and the relationship between oxidation current and electrode deactivation in the off step was investigate. As results, it was confirmed that the nickel and zinc on electrode surface were oxidized due to anodic current which occurred at off step.

Solubility and Physicochemical Stability of Caroverine Hydrochloride in Aqueous Solution (수용액중 염산카로베린의 용해성 및 안정성)

  • Gwak, Hye-Sun;Lee, Dong-Soo;Chun, In-Koo
    • Journal of Pharmaceutical Investigation
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    • v.28 no.2
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    • pp.121-126
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    • 1998
  • The solubility and physicochemical stability of caroverine hydrochloride (CRV), an antispasmodic, in buffered aqueous solutions were studied using a reverse phase high performance liquid chromatography. The solubilty of the drug at pH 2.76-5.40 was similar at the range 31.9-36.2 mg/ml $(34^{circ}C)$, but, at the pH higher than 6.0, markedly decreased. The use of polyethylene glycol 400 as a cosolvent did not increase the solubility at any compositions examined. Moreover. increasing molar concentration of aqueous phosphate buffer from 0 to 0.5 M remarkably decreased the solubility. The degradation of CRY followed the apparent first-order kinetics. The degradation was accelerated with decreasing pH and increasing storage temperature. The half-lives for the degradation of CRY (1.0 mg/ml) at pH 1.28. 4.01 and 5.93 $(45^{\circ}C)$ were 2.8, 31.4 and 124 hr. respectively. The pHs of incubated solutions were to some extent lowered perhaps due to the formation of acidic degradation products. The addition of disodium edetate (0.01%) to the CRY solution (pH 4.95) retarded 2.5 times the degradation rate at $45^{\circ}C$, but the use of sodium bisulfite (0.1%) accelerated 2.9 times the rate. The activation energy for the CRY solution (20 mg/ml. pH 5.4) containing 0.01% EDTA was calculated to be 5.98 kcal/mole. When the solution was stored under nitrogen displacement in ampoule, there was no significant degradation even after 3 months at $40^{\circ}C$, indicating that protection from oxidation by air (oxygen) is essential for the complete stabilization of CRY solution.

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Investigation of Pitting Corrosion of Copper Heat-Return Pipe in District Heating (지역난방 구리난방환수관의 공식 원인 분석)

  • Keun Hyung Lee;Min Ji Song;Tae Uk Kang;Woo Cheol Kim;Heesan Kim;Soo Yeol Lee
    • Corrosion Science and Technology
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    • v.23 no.4
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    • pp.315-323
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    • 2024
  • This work examined pitting corrosion failure of a copper heat-return pipe used in a district heating system. The copper pipe was corroded with a 48% reduction in thickness due to localized corrosion on the inner surface exposed to heating water of 20 ~ 40 ℃. Fe and Si elements as corrosion products were found around pits. Cl element was also observed, which accelerated oxidation of copper inside pits. Cu2O deposits on the pit's bottom surface decreased the pH inside the pit. X-ray diffraction analysis revealed hematite, cuprite, malachite and brochantite as corrosion products. Chemical analysis demonstrated that Fe and Si elements did not exist in the copper, supply water, or heating water, indicating that Fe and Si species might have entered into the pipe from the exterior. These results indicated that pits were initiated due to ion concentration gradient near Fe and Si species. Moreover, the interior of pits had lower pH due to Cl- concentration and Cu2O reactions, which accelerated the pit's growth and led to formation of pinholes. Additionally, we confirmed that the type of pitting corrosion was a complex combination of types I and II based on the HCO3-/SO42- ratio, pH, temperature, and corrosion products.

Surface Analysis Study on ZIRLO Cladding Hulls Oxidized at Low Temperatures (저온 산화된 ZIRLO 피복관의 표면분석 연구)

  • Jeon, Min Ku;Choi, Yong Taek;Lee, Chang Hwa;Kang, Kweon Ho;Park, Geun Il
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.12 no.3
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    • pp.235-243
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    • 2014
  • Surface oxidation behavior of ZIRLO (ZIRconium Low Oxidation) hulls was investigated using an X-ray photoelectron spectroscopy (XPS) technique. The effects of oxidation time (10-336 h at $500^{\circ}C$) and temperature ($400-700^{\circ}C$ for 10 h) were studied. Deconvolution results of the hulls oxidized at $500^{\circ}C$ revealed that a $ZrO_2$ phase appeared after 24 h (11.86%), and an increase in the $ZrO_2$ ratio was observed when the hulls were oxidized for 336 h (17.93%). On the other hand, the ZrO phase which employed 5.68% in the 10 h oxidized sample disappeared when the oxidation time increased to 24 h. The XPS results also showed that an increase in the oxidation temperature resulted in an increase in the ratio of ZrO, which increased from 0 to 5.68, 8.31, and 9.16% when the oxidation temperature increased from 400 to 500, 600, and $700^{\circ}C$, respectively. $ZrO_2$ phase was observed only in the sample that was oxidized at $700^{\circ}C$. The mechanism of ZrO formation was not conclusive, but it was suggested that a formation of hydroxide might have been accelerated at elevated temperatures leading to a formation of a $Zr(OH)_4$ phase. The relationship between the surface oxidation status of the hulls oxidized at $500^{\circ}C$ and their chlorination reaction feasibility was discussed, and it was suggested that the thickness of the oxide layer is an important parameter that determines the chlorination reaction feasibility.

Effect of Final Annealing Temperature on Precipitate and Oxidation of Zr- Nb Alloys (Zr-Nb계 합금의 석출물 특성과 산화 특성에 미치는 마지막 열처리 온도의 영향)

  • Yun, Yeong-Gyun;Jeong, Yong-Hwan;Park, Sang-Yun;Wi, Myeong-Yong
    • Korean Journal of Materials Research
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    • v.11 no.8
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    • pp.647-654
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    • 2001
  • Effects of final annealing temperature on the precipitate and oxidation were investigated for the Zr-lNb and Zr-lNb-lSn-0.3Fe alloys. The microstructure and oxidation of both alloys were evaluated for the optimization of final annealing process of these alloys in the annealing temperature regime of 450 to $800^{\circ}C$. The corrosion test was performed under steam at $400^{\circ}C$ for 270 days in a static autoclave. The oxide formed was identified by low angle X-ray diffraction method. The $\beta$-Zr was observed at annealing temperature above $600^{\circ}C$. Above $600^{\circ}C$, the precipitate area volume fraction of Zr-lNb and Zr-1Nb-lSn-0.3Fe alloys appeared to be increased with increasing the final annealing temperature. The corrosion resistance of Zr-lNb was higher than that of Zr- lNb-lSn-0.3Fe alloy. The corrosion rate of both alloys were accelerated due to the formation and growth of $\beta$-Zr with increasing the annealing temperature.

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Effects of High Dose Gamma Irradiation on Shelf Stability and Lipid Oxidation of Marinated and Precooked Pork Rib Steak (고선량 감마선 조사가 즉석 취식용 양념 돼지 갈비 구이의 저장성 및 지질 산화에 미치는 영향)

  • Lee, Ju-Woon;Park, Jae-Nam;Kim, Jae-Hun;Park, Jin-Gyu;Kim, Cheon-Jei;Kim, Kwan-Soo;Byun, Myung-Woo
    • Food Science of Animal Resources
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    • v.26 no.4
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    • pp.471-477
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    • 2006
  • This study was conducted to evaluate the application of high dose irradiation for ensuring shelf stability of marinated and precooked pork rib steak in the severe environments such as desert or space, etc. Marinated and precooked pork rib steak was manufactured, vacuum-packaged and gamma-irradiated with the absorbed doses of 10, 20, 30, 40 and 50 kGy, and used for the tests of the growth of microorganisms and lipid oxidation during storage at 35t of acceleration condition. Any growth of microorganisms was not observed in irradiated samples after irradiation immediately. However, the growths were observed in 10, 20 and 30 kGy samples at 4, 7 and 14 day storage, respectively. High dose (40 and 50 kGy) gamma irradiation retarded the growth of aerobic microorganisms by the analysis of kinetic parameter. The content of malondialdehyde increased in all samples during storage periods, and gamma irradiation accelerated the increase of lipid oxidation. Therefore, the application of combination of the various food processing technology should be considered for the sterilization of marinated and precooked pork rib steak without any deterioration of the quality occurred by high dose irradiation.

Physicochemical Assessment of Quality Characteristics of Extruded Barley under Varied Storage Conditions (상이한 조건하에서 저장한 압출보리의 품질특성에 관한 이화학적 평가 -제 1 보 : 지방질 산화-)

  • Shin, Hyo-Sun;Gray, J. Ian
    • Korean Journal of Food Science and Technology
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    • v.15 no.2
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    • pp.189-194
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    • 1983
  • Raw and extruded barleys prepared by three different conditions were powdered and stored for four months at ambient $(25^{\circ}C)$ and accelerated temperatures $(40^{\circ}C)$ with $A_w$ of 0.31 and 0.71, respectively. The stability of the these samples with respect to lipid oxidation was studied. The lipid oxidation of all samples, as measured by the lipid diene conjugation of the extracted oil, increased with increased $A_w$ and temperature and with the storage time elapsed. The ratio of unsaturated to saturated fatty acids (U/S ratio) tended to decreased as the $A_w$ and temperature were increased. The raw sample had a greater increase in lipid conjugation diene but a decrease in U/S ratio than the extruded samples. The extruded sample containing the added sucrose had greater lipid stability than the other extruded samples. Lipid free-amino group content in all samples decreased with increased $A_w$ and temperature.

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using Cr(VI)-6-Methylquinoline (Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구)

  • Park, Young Cho;Kim, Young Sik
    • Applied Chemistry for Engineering
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    • v.26 no.3
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    • pp.372-376
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    • 2015
  • 6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid ($H_2SO_4$), 6-MQCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

Mechanism for the Oxidation Reaction of Alcohols Using Cr(VI)-Pyrazine Complex (크롬(VI)-피라진 착물을 이용한 알코올류의 산화반응과 메카니즘)

  • Park, Young Cho;Kim, Young Sik
    • Applied Chemistry for Engineering
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    • v.27 no.1
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    • pp.110-114
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    • 2016
  • Cr(VI)-pyrazine complex (PZCC) was synthesized by the reaction of pyrazine with chromium (VI) trioxide in 6 M HCl. The structure was characterized using IR spectroscopy and inductively coupled plasma (ICP). The oxidation of benzyl alcohol using PZCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: N,N'-dimethylform-amide > acetone > chloroform > cyclohexene. In the presence of N,N'-dimethylformamide solvent with an acidic catalyst such as sulfuric acid ($H_2SO_4$ solution), PZCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate-determining step.

Degradation Characteristics of Perfluoropolyether Lubricant for Computer Hard Disk (컴퓨터 하드디스크 윤활제로 사용되는 Perfluoropolyether의 분해거동)

  • Lee, Ji-Hye;Chun, Sang-Wook;Kang, Ho-Jong
    • Polymer(Korea)
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    • v.31 no.4
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    • pp.278-282
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    • 2007
  • The degradation characteristics of perfluoropolyether (PFPE) for computer hard disk drive have been investigated. Thermal degradation in PFPE started at $170\;^{\circ}C$ and it was completed at $450\;^{\circ}C$. If PFPE was contacted with wear fragment from slider made by $Al_2O_3{\cdot}TiC$, the thermal degradation was accelerated by the catalytic Lewis acid degradation. The Lewis acid degradation mainly took placed in methylene oride(fluoride) chain scission as well as methylene(fluoride) and hydroxy end chain. As a result, the degradation reaction accomplished as early as at $300\;^{\circ}C$. The photo oxidation due to UV exposure on PFPE caused the chain scission in methylene(fluoride), and end chain in PFPE without chain scission in methylene oxide(fluoride) and then the molecular weight of PFPE increased by expected secondary reactions between formed radicals in the photo oxidation.