• Korean Journal of Metals and Materials
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• v.49 no.4
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• pp.334-341
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• 2011

The mechanism behind super-filling of high-aspect-ratio features with Cu by catalyst-enhanced chemical vapor deposition (CECVD) coupled with plasma treatment is described and the metrology required to predict the filling feasibility is identified and quantified. The reaction probability of a Cu precursor was determined as a function of substrate temperature. Iodine adatoms are deactivated by the bombardment of energetic particles and also by the overdeposition of sputtered Cu atoms during the plasma treatment. The degree of deactivation of adsorbed iodine was experimentally quantified. The quantified factors, reaction probability and degree of deactivation of iodine were introduced to the simulation for the prediction of the trench filling aspect by CECVD coupled with plasma treatment. Simulated results show excellent agreement with the experimental filling aspects.

• Clean Technology
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• v.21 no.3
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• pp.200-206
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• 2015

In order to investigate the effect of cerium oxide addition, Cu-ZnO-CeO₂ catalysts were prepared using co-precipitation method for water gas shift (WGS) reaction. A series of Cu-ZnO-CeO₂ catalyst with fixed Cu Content (50 wt%, calculated as CuO) and a given ceria content (e.g., 0, 5, 10, 20, 30, 40 wt%, calculated as CeO₂) were tested for catalytic activity at a GHSV of 95,541 h^-1, and a temperature range of 200 to 400 ℃. Cu-ZnO-CeO₂ catalysts were characterized by using BET, SEM, XRD, H₂-TPR, and XPS analysis. Varying composition of Cu-ZnO-CeO₂ catlysts led the difference characteristics such as Cu dispersion, and binding energy. The optimum 10 wt% doping of cerium facilitated catalyst reduction at lower temperature and improved the catalyst performance greatly in terms of CO conversion. Cerium oxide added catalyst showed enhanced activities at higher temperature when it compared with the catalyst without cerium oxide. Consequently, ceria addition of optimal composition leads to enhanced catalytic activity which is attributed to enhanced Cu dispersion, lower binding energy, and hindered Cu metal agglomeration.

• Transactions of the Korean hydrogen and new energy society
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• v.26 no.5
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• pp.423-430
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• 2015

$Cu/ZnO/Al_2O_3$ catalysts for water gas shift (WGS) reaction were synthesized by co-precipitation method with the fixed molar ratio of Cu/Zn/Al precursors as 45/45/10. Copper and zinc precursor were added into sodium carbonate solution for precipitation and aged for 24h. During the aging period, aluminum precursor was added into the aging solution with different time gap from the precipitation starting point: 6h, 12h, and 18h. The resulting catalysts were characterized with SEM, XRD, BET surface measurement, $N_2O$ chemisorption, TPR, and $NH_3$-TPD analysis. The catalytic activity tests were carried out at a GHSV of $27,986h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The catalyst morphology and crystalline structures were not affected by aluminum precursor addition time. The Cu dispersion degree, surface area, and pore diameter depended on the aging time of Cu-Zn precipitate without the presence of $Al_2O_3$ precursor. Also, the interaction between the active substance and $Al_2O_3$ became more stronger as aging duration, with Al precursor presented in the solution, increased. Therefore, it was confirmed that aluminum precursor addition time affected the catalytic characteristics and their catalytic activities.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.3
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• pp.214-223
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• 2002

Kinetic and effectiveness factors for methanol steam reforming using commercial copper-containing catalysts in a plug flow reactor were investigated over the temperature ranges of $180-250^{\circ}C$ at atmospheric pressure. The selectivity of $CO_2$/$H_2$ was almost 100%, and CO products were not observed under reaction conditions employed in this work. It was indicated that $CO_2$ was directly produced and CO was formed via the reverse water gas shift reaction after methanol steam reforming. The intrinsic kinetics for such reactions were well described by the Langmuir-Hinshelwood model based on the dual-site mechanism. The six parameters in this model, including the activation energy of 103kJ/mol, were estimated from diffusion-free data. The significant effect of internal diffusion was observed for temperature higher than $230^{\circ}C$ or particle sizes larger than 0.36mm. In the diflusion-limited case, this model combined with internal effectiveness factors was also found to be good agreement with experimental data.

• Korean Journal of Materials Research
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• v.23 no.1
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• pp.1-6
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• 2013

A simple thermal oxidation of Cu thin films deposited on planar substrates established a growth of vertically aligned copper oxide (CuO) nanorods. DC sputter-deposited Cu thin films with various thicknesses were oxidized in environments of various oxygen partial pressures to control the kinetics of oxidation. This is a method to synthesize vertically aligned CuO nanorods in a relatively shorter time and at a lower cost than those of other methods such as the popular hydrothermal synthesis. Also, this is a method that does not require a catalyst to synthesize CuO nanorods. The grown CuO nanorods had diameters of ~100 nm and lengths of $1{\sim}25{\mu}m$. We examined the morphology of the synthesized CuO nanorods as a function of the thickness of the Cu films, the gas environment, the oxidation time, the oxidation temperature, the oxygen gas flow rate, etc. The parameters all influence the kinetics of the oxidation, and consequently, the volume expansion in the films. Patterned growth was also carried out to confirm the hypothesis of the CuO nanorod protrusion and growth mechanism. It was found that the compressive stress built up in the Cu film while oxygen molecules incorporated into the film drove CuO nanorods out of the film.

• Korean Journal of Materials Research
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• v.24 no.7
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• pp.388-392
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• 2014

$Cu_2O$ nanowires were synthesized at large scale on copper plate by thermal oxidation in air. The effect of oxidation time and temperature on the morphology of the nanowires was examined. The oxidation time had no effect on the diameter of the nanowires, while it had a great effect on the density and the length of the nanowires. The density and the length of the nanowires increased, and then decreased, with increasing oxidation time. The oxidation temperature had a tremendous effect on the size-distribution as well as the density of the nanowires. When the oxidation temperature was $700^{\circ}C$, uniform size-distribution and high density of the nanowires was achieved. At lower and higher temperatures, the density of the nanowires was lower, and they displayed a broader size-distribution. It is suggested that the $Cu_2O$ nanowires were grown via a vapor-solid mechanism because no catalyst particles were observed at the tips of the nanowires.

• Applied Chemistry for Engineering
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• v.26 no.5
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• pp.593-597
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• 2015

Tricyclopentadiene (TCPD) as a next generation high density fuel was synthesized by Diels-Alder oligomerization reaction of DCPD. TCPD was prepared by ionic liquid (IL) catalysts with combination of cationic and anionic precursors. Two kinds of anionic precursors such as copper(I) chloride (CuCl) and iron(III) chloride ($FeCl_3$) and cationic precursors such as triethylamine hydrochloride (TEAC) and 1-butyl-3-methylimidazolium chloride (BMIC) were used. The preparation of TCPD using IL catalyst was superior to that using Diels-Alder reaction in terms of DCPD conversion and TCPD yield. In addition, TCPD yield was correlated with Lewis acidity by changing the ratio of anionic and cationic precursors. The TCPD yield was higher when using CuCl as anionic precursor than that of using $FeCl_3$. Control of Lewis acidity by changing the molar ratio of anionic and cationic precursors could further improve TCPD yield as well.

• Clean Technology
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• v.20 no.3
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• pp.256-262
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• 2014

Catalytic oxidation characteristics of benzene as a VOC was investigated in a fixed bed flow reactor using $Cu/{\gamma}-Al_2O_3$ catalyst. The parametric tests were conducted at the reaction temperature range of $200{\sim}500^{\circ}C$, benzene concentration of 400~650 ppm, gas flow rate of 50~100 cc/min, and space velocity range of $7,500{\sim}22,500hr^{-1}$. The property analyses by using the BET, SEM, TGA and the conversion of catalytic oxidation of benzene were examined. The experimental results showed that the conversion was increased with decreasing benzene concentration, gas flow rate and space velocity. Benzene oxidation reaction over $Cu/{\gamma}-Al_2O_3$ catalyst could be expressed as the first order homogeneous reaction of which the activation energy was 17.2 kcal/mol and frequency factor was $1.33{\times}10^6sec^{-1}$.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.4
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• pp.444-451
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• 2007

Catalytic oxidation characteristics of benzene as a VOC was investigated using a fixed bed reactor system over transition $metals/\gamma-Al_2O_3$ catalysts. As transition metals, eight metals including copper, nickel, manganese, iron etc. were adopted. The parametric tests were conducted at the reaction temperature range of $200\sim500^{\circ}C$, benzene concentration of $1,000\sim3,000$ ppm, and space velocity range of $5,000\sim60,000\;hr^{-l}$. The property analyses such as BET, SEM, XRD and the conversions of catalytic oxidation of VOC were examined. The experimental results showed that the conversion was increased with decreasing VOC concentration and space velocity. It was also found that $Cu/\gamma-Al_2O_3$ catalyst calcinated at $500^{\circ}C$ showed the highest activity for the oxidation of benzene and 15% metal loading was the optimum impregnation level.

• Polymer(Korea)
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• v.35 no.3
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• pp.244-248
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• 2011

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) was synthesized by oxidative polymerization using various Cu(I)-amine catalyst system. The effects of catalyst/monomer ratio, different amine ligand, and the content of 2,4,6-trimethylphenol (TMP) additive on the polymer yield and molecular weight were investigated by using gel permeation chromatography. The catalytic activity of various Cu-amine systems on the 2,S-dimethylphenol (DMP) polymerization was monitored and compared each other through oxygen-uptake experiment. In addition, the effect of catalyst removal using aqueous EDTA on the thermal stability of the prepared polymer was elucidated by thermogravimetric analysis.