• Title/Summary/Keyword: 전이온도

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Synthesis of TiO2 Fine Powder by Sol-Gel Process and Reaction Mechanism(II) : Hydrolysis of Titanium n-Propoxide (졸-겔법에 의한 TiO2미분말 합성과 반응메카니즘(II): Titanium n-propoxide의 가수분해)

  • Myung, Jung-Jae;Park, Jin-koo;Chung, Yong-Sun;Kyong, Jin-Bum;Kim, Ho-Kun
    • Applied Chemistry for Engineering
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    • v.8 no.5
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    • pp.777-783
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    • 1997
  • $TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

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Surface Treatment of Al(OH)3 using Dilute Hydrofluoric Acid Aqueous Solution (저농도 HF 수용액을 이용한 Al(OH)3의 표면처리)

  • Kim, Do-Su;Lee, Churl-Kyoung;Yang, Dong-Hyo
    • Journal of the Korean Ceramic Society
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    • v.39 no.3
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    • pp.315-320
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    • 2002
  • Treatment effects of dilute hydrofluoric acid (6 wt% HF) on the surface properties of $Al(OH)_3$ were investigated at the molar ratio of F/Al(fluoride/aluminum)=0.15. Temperature and pH variations in the reaction system were recorded to analyze reaction mechanism between $Al(OH)_3$ and aqueous Hf. The reaction of HF to the surface of $Al(OH)_3$ accompanied with a quantity of heat evolution, resulting in increasing temperature of a reactionsystem. And also the reaction was proceeded as transitional state which metastable ${\alpha}-form\;AlF_3{\cdot}3H_2O$ was transferred to insoluble ${\beta}$-form. The resulting ${\beta}-form\;AlF_3{\cdot}3H_2O$ formed by a surface treatment was identified by FT-IR and X-ray diffractormetry. The formation of ${\beta}$-form aluminum fluoride hydrates with diameter less than $1{\mu}m$ on the surface of $Al(OH)_3$ could be visulaized by SEM imgae, making up a coating layer as precipitate-like. The surface whiteness of $Al(OH)_3$ treated with aqueous HF was furthermore increased approximately 6.6% due to the formation of surface hydrates.

Catalytic Oxidation of Vinyl Chloride on Chromium Oxide Catalysts (크롬 산화물 촉매를 이용한 Vinyl Chloride의 산화 분해반응)

  • Lee, Hae-Wan;Kim, Young Chai;Moon, Sei-Ki
    • Applied Chemistry for Engineering
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    • v.10 no.1
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    • pp.58-66
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    • 1999
  • The catalytic oxidation of vinyl chloride was investigated over $CrO_x$ impregnated on $Al_2O_3$ at temperature between 200 and $400^{\circ}C$. The major carbonaceous products were CO and $CO_2$, and the selectivity of $CO_2$ was gradually increased with increasing reaction temperature, while that of CO was dropped consequently. This suggests that CO is the first product which is further oxidized to $CO_2$ in the oxidation of vinyl chloride over $CrO_x/Al_2O_3$. The addition of HCl in the feed didn't affect the conversion of vinyl chloride, but the selectivity of $CO_2$ decreased by adding HCl. It implies that HCl inhibits, the complete oxidation of vinyl chloride to $CO_2$. When oxidizing vinyl chloride in dry air, significant amounts of $Cl_2$ were observed, while no $Cl_2$ was detected in the humid condition. The activities of several catalysts including various precious metals and other transition metal oxides were measured, it was found that the catalytic activity of 12% $CrO_x/Al_2O_3$ was higher than other catalysts except 1% $Pt/Al_2O_3$. The reaction rate of 12% $CrO_x/Al_2O_3$ was 1.2 times lower than that of 1% Pt/alumina, but it was 3 to 8 times more active than other catalysts for vinyl chloride oxidation at $275^{\circ}C$.

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Structural and optical properties of ZnO epilayers grown on oxygen- and hydrogen-plasma treated sapphire substrates (산소와 수소 플라즈마로 처리한 사파이어 기판 위에 성장된 ZnO 박막의 구조적.광학적 특성)

  • Lee, S.K.;Kim, J.Y.;Kwack, H.S.;Kwon, B.J.;Ko, H.J.;Yao, Takafumi;Cho, Y.H.
    • Journal of the Korean Vacuum Society
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    • v.16 no.6
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    • pp.463-467
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    • 2007
  • Structure and optical properties of ZnO epilayers grown on oxygen- and hydrogen-plasma treated sapphire substrates by plasma-assisted molecular beam epitaxy (denoted as samples A and B, respectively) have been investigated by various techniques. The crystal quality and structural properties of the surface for the ZnO epilayers were investigated by high-resolution X-ray diffraction and atomic force microscope. For investigating the optical properties of excitonic transition of ZnO, we carried out photoluminescence experiments as a function of temperature. The free exciton, bound exciton emission and their phonon replicas were investigated as a function of temperature from 10 to 300 K, and the intensity of excitonic PL peak emission from the sample A is found to be higher than that of sample B. From the results, we found that sample A has better crystal structure quality and optical properties as compared to sample B. The number of oxygen vacancies may be decreased in sample A, resulting in an enhancement of the crystal quality and a higher intensity of excitonic emission band as compared to sample B.

The Analysis of Structure and Electron Energy State of Potassium-Graphite Fiber Intercalation Compounds (칼륨-흑연 섬유층간화합물의 구조와 전자 에너지 상태의 분석)

  • Oh, Won-Chun;Kim, Myung-Kun;Ko, Young-Shin
    • Analytical Science and Technology
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    • v.6 no.5
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    • pp.479-487
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    • 1993
  • Potassium-Graphite Fiber Intercalation Compounds(K-GFIC) have been prepared from well oriented pitch-based Graphite fiber by the transformed two-bulbs method with variation of reaction temperatures of graphite($T_g$ : $450^{\circ}C$, $400^{\circ}C$, $350^{\circ}C$, $300^{\circ}C$, $250^{\circ}C$). The stage transition process of K-GFICs was studied by X-ray diffraction methods, and we have observed peaks with d-values of (001) diffraction of $5.40{\AA}$ and $8.78({\pm}0.01){\AA}$, which are charecteristic for the stage 1 and stage 2, respectively. The stage stability and energy states of K-GFICs were studied by UV/VIS spectrophotometer. As a results, We found that the minimum values of reflactance of K-GFICs with pure stage was moved to higher energy pristine Graphite fiber's. But because of mixtured stage, we could not observe minimum reflectance in the visible region at high reaction temperatures($400^{\circ}C$, $450^{\circ}C$). From X-ray diffraction and UV/VIS sepctrophotometry data, we can suggest that K-GFICs with lower stage has many charge carriers existed between C atoms of graphite Layers. And then, these results also provides information on the electrical and other physical properties of K-GFICs.

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Osteogenic Differentiation of Bone Marrow Stem Cells Using Thermo-Sensitive Hydrogels (온도감응성 수화젤을 이용한 골수간엽줄기세포의 골분화 유도)

  • Kim, Sun-Kyung;Hyun, Hoon;Kim, Soon-Hee;Yoon, Sun-Jung;Kim, Moon-Suk;Rhee, John-M.;Khang, Gil-Son;Lee, Hai-Bang
    • Polymer(Korea)
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    • v.30 no.3
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    • pp.196-201
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    • 2006
  • Poly (ethylene glycol)-based diblock and triblock thermo- sensitive polyester copolymers were investigated for application on tissue engineering and injectable biomaterials in drug delivery system due to their nontoxicity, biocompatibility and biodegradability. We synthesized the diblock copolymers consisting of methoxy poly (ethylene glycol) (MPEG) (Mn=750 g/mole) and poly $(\varepsilon-caprolactone)$ (PCL) by ring opening polymerization of $\varepsilon-CL$ with MPEG as an initiator in the presence of HCl $Et_2O$. The effect of diblock copolymers on in vivo osteogenic differentiation of rat bone marrow stromal cells (BMSCS) with and without the presence of osteogenic supplements (dexamethasone) was investigated. Thin sections were cut from paraffin embedded tissues and histological sections were stained by H&E, von Kossa, and immunohistochemical staining for osteocalcin. In conclusion, dexamethasone containing thermo- sensitive hydrogel might be improved osteogenic differentiation of BMSCs. We expect the osteoinduction effect to be excellent when it uses stem cell or other osteogenic materials.

Kinetics of the Reaction of Benzyl Chlorides with Pyridine in Methanol Solvent under High Pressure (고압하의 메탄올 용매내에서 염화벤질류와 피리딘과의 반응에 대한 반응속도론적 연구)

  • Oh Cheun Kwon;Young Cheul Kim;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.413-418
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    • 1987
  • Rates of the reaction for p-nitro benzyl chloride, benzyl chloride and p-methyl benzyl chloride with pyridine in methanol solvent have been measured by an electric conductivity method at 40$^{\circ}$C and 50$^{\circ}$C under various pressures (1∼2000bar). Pseudo first-order rate constants and second-order rate constants were determined. Rates of these reactions were increased in the order p-NO$_2$ < p-H < p-CH$_3$ and increased with temperature, pressure and concentration of pyridine. From those rate constants, the activation parameters were evaluated. The activation volume and the activation compressibility coefficient are both negative values, but the activation enthalpy is positive and the activation entropy is large negative value. From the evaluation of the ground state and transition state which was resulted from substituents and pressure, it was found that this reaction proceeds through S$_N$2 reaction, and S$_N$2 fashion is slightly disappeared as pressure increases.

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Conduction Band Model of the System ${\alpha}-Fe_2O_3$-CdO at Extrinsic Region (외성영역에서 ${\alpha}-Fe_2O_3$-CdO 계의 전도띠 모델)

  • Keu Hong Kim;Seok Ho Yun;Young Sik Kwon;Jae Shi Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.406-412
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    • 1987
  • The electrical conductivities of ${\alpha}-Fe_2O_3$ containing 2.5 and 5.0mol% of cadmium were measured from 300 to $900^{\circ}C$ under oxygen pressures of 10$^{-7}$ to 10$^{-1}$ atmosphere. Plots of log ${\sigma}$ vs. 10$^3$/T show the extrinsic conductivity at oxygen pressure higher than $5{\times}10$^{-2}$atm. The transition points appear at about 550$^{\circ}$C and the activation energies are 1.34 eV for the intrinsic region and 0.50 eV for the extrinsic region on 5mol% Cd-doped ${\alpha}-Fe_2O_3$. The extrinsic conductivity disappears at oxygen partial pressures lower than $5{\times}10$^{-2}$ atm, and the intrinsic conductivity predominates. The electrical conductivities decrease with increasing mol% of cadmium doped. The predominant defect of ${\alpha}-Fe_2O_3$ doped with Cd is believed to be Fe${2+}$ interstitial for the intrinsic, however, oxygen vacancy predominates for the extrinsic region. The electrical conduction mechanisms are proposed and the conduction band model is suggested for the extrinsic region.

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The Adsorption of COS with a Modified-Activated Carbon for Ultra-Cleanup of Coal Gas (석탄가스의 초정밀 정제를 위한 변형된 활성탄의 흡착특성 연구)

  • Lee, You-Jin;Park, No-Kuk;Lee, Tae-Jin
    • Clean Technology
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    • v.13 no.4
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    • pp.266-273
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    • 2007
  • The adsorption properties of the activated carbon-based adsorbents were studied to remove COS emitted from $SO_2$ catalytic reduction process on the integrated gasification combined cycle (IGCC) system in this work. Transition metal supported catalysts and mixed metal oxide catalysts were used for the $SO_2$ catalytic reduction. The mechanism of COS produced from the $SO_2$ reduction and the COS concentration s according to the reaction temperature were investigated. In this study, an activated carbon and a modified activated carbon doped with KOH were used to remove the very low concentration of COS effectively. The adsorption rate and the breakthrough time of COS were measured by a thermo gravity analyzer (TGA, Cahn Balance) and a fixed bed flow reactor equipped with GC-pulsed flammable photometric detector (PFPD), respectively. It was confirmed that the COS breakthrough time of the activated carbon doped with KOH was longer than that of an activated carbon. In conclusion, the modified-activated carbon having a high surface area showed a high adsorption rate of COS produced from the $SO_2$ reduction.

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Gas Separation Properties of Microporous Carbon Membranes Containing Mesopores (중간기공을 갖는 미세다공성 탄소 분리막의 기체 투과 특성)

  • Shin, Jae Eun;Park, Ho Bum
    • Membrane Journal
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    • v.28 no.4
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    • pp.221-232
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    • 2018
  • The silica containing carbon ($C-SiO_2$) membranes were fabricated using poly(imide siloxane)(Si-PI) and polyvinylpyrrolidone (PVP) blended polymer. The characteristics of porous carbon structures prepared by the pyrolysis of polymer blends were related with the micro-phase separation behaviors of the two polymers. The glass transition temperatures ($T_g$) of the mixed polymer blends of Si-PI and PVP were observed with a single $T_g$ using differential scanning calorimetry. Furthermore, the nitrogen adsorption isotherms of the $C-SiO_2$ membranes were investigated to define the characteristics of porous carbon structures. The $C-SiO_2$ membranes derived from Si-PI/PVP showed the type IV isotherm and possessed the hysteresis loop, which was associated with the mesoporous carbon structures. For the molecular sieving probe, the $C-SiO_2$ membranes were prepared with the ratio of Si-PI/PVP and the pyrolysis conditions, such as the pyrolysis temperature and the isothermal times. Consequently, the $C-SiO_2$ membranes prepared by the pyrolysis of Si-PI/PVP at $550^{\circ}C$ with the isothermal time of 120 min showed the $O_2$ permeability of 820 Barrer ($1{\times}10^{-10}cm^3(STP)cm/cm^2{\cdot}s{\cdot}cmHg$) and $O_2/N_2$ selectivity of 14.