• Journal of Hydrogen and New Energy
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• v.22 no.5
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• pp.649-655
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• 2011

Methane direct cracking can be utilized to produce $CO_x$ and $NO_x$-free hydrogen for PEM fuel cells, oil refineries, ammonia and methanol production. We present the results of a systematic study of methane direct cracking using a mixed conducting oxide, Y-doped $BaZrO_3$ ($BaZr_{0.85}Y_{0.15}O_3$), membrane. In this paper, dense $BaZr_{0.85}Y_{0.15}O_3$ membrane with disk shape was successfully sintered at $1400^{\circ}C$ with a relative density of more 93% via addition of 1 wt% ZnO. The ($BaZr_{0.85}Y_{0.15}O_3$) membrane is covered with Pd as catalyst for methane decomposition with an DC magnetron sputtering method. Reaction temperature was $800^{\circ}C$ and high purity methane as reactant was employed to membrane side with 1.5 bar pressure. The $H_2$ produced by the reaction was transported through mixed conducting oxide membrane to the outer side. In addition, it was observed that the carbon, by-product, after methane direct cracking was deposited on the Pd/ZnO-$BaZr_{0.85}Y_{0.15}O_3$ membrane. The produced carbon has a shape of sphere and nanosheet, and a particle size of 80 to 100 nm.

• Membrane Journal
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• v.25 no.5
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• pp.415-421
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• 2015

$SrCo_{0.8}Fe_{0.1}Nb_{0.1}O_{3-{\delta}}$ oxide was synthesized by solid state reaction method. Dense ceramic membrane was prepared using as-prepared powder by pressing and sintering at $1250^{\circ}C$. XRD result of membrane showed single perovskite structure. The oxygen permeability were measured under 0.21 atm of oxygen partial pressure ($P_{O_2}$) and between 800 and $950^{\circ}C$. The oxygen permeation flux of $SrCo_{0.8}Fe_{0.1}Nb_{0.1}O_{3-{\delta}}$ membrane was increased with the increasing temperature. The maximum oxygen permeation flux was $1.839mL/min{\cdot}cm^2$ at $950^{\circ}C$. Long period permeability experiment was carried out to confirm the phase stability and $CO_2$-tolerance of membrane containing Nb in the condition of air with $CO_2$ (500 ppm) as feed stream at $900^{\circ}C$. The phase stability and $CO_2$-tolerance of $SrCo_{0.8}Fe_{0.1}Nb_{0.1}O_{3-{\delta}}$ were investigated by XRD and TG analysis. The result of $SrCo_{0.8}Fe_{0.1}Nb_{0.1}O_{3-{\delta}}$ which exposed carbon dioxide for 100 hours indicated 8wt% of $SrCO_3$. But it was known that the level of $SrCO_3$ production dose not have a significant effect on oxygen permeability.

• Journal of Surface Science and Engineering
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• v.48 no.1
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• pp.11-22
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• 2015

Pd alloy hydrogen membranes for hydrogen purification and separation need thermal stability at high temperature for commercial applications. Intermetallic diffusion between the Pd alloy film and the porous metal support gives rise to serious problems in long-term stability of Pd alloy membranes. Ceramic barriers are widely used to prevent the intermetallic diffusion from the porous metal support. However, these layers result in poor adhesion at the interface between film and barrier because of the fundamentally poor chemical affinity and a large thermal stress. In this study, we developed Pd alloy membranes having a dense microstructure and saturated composition on modified metal supports by advanced DC magnetron sputtering and heat treatment for enhanced thermal stability. Experimental results showed that Pd-Cu and Pd-Ag alloy membranes had considerably enhanced long-term stability owing to stable, dense alloy film microstructure and saturated composition, effective diffusion barrier, and good adhesive interface layer.

• Journal of the Korean Ceramic Society
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• v.51 no.5
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• pp.466-471
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• 2014

Hydrous zirconia particles were prepared from $ZrOCl_2$ aqueous solution using an electro-dialysis [ED] process. For the preparation of $(Zr,Y)(OH)_4$ precipitates, 3 mol% $YCl_3$ was added into $ZrOCl_2$ aqueous solution. During the hydrolysis of 0.5 mol/L $(Zr,Y)OCl_2$ solution at $90^{\circ}C$ a slurry solution was obtained. The ED process was used for the removal of chlorine from the slurry solution. Two kinds of slurry solution were sampled at the beginning and end of the ED process. The morphology of hydrous zirconia particles in the solution was observed using an inverted optical microscope and an FE-SEM. The hydrous zirconia particles were nano-crystalline, and easily coagulated with drying. Yttrium stabilized zirconia [YSZ] powder could be obtained by the calcination of $(Zr,Y)(OH)_4$ precipitates prepared from a $(Zr,Y)OCl_2$ solution by the ED process. The coagulated dry powders were shaped and sintered at $1500^{\circ}C$ for 2 h. The sintered body showed a dense microstructure with uniform grain morphology.

• Journal of the Korean Ceramic Society
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• v.43 no.5 s.288
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• pp.309-314
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• 2006

We synthesized lithium zirconate using solid-state reaction and analyzed thermal properties (TG/DTA) of starting materials and the synthesized one. When $Li_2ZrO_3$ powder was exposed to $CO_2$ environment at $500^{\circ}C$, 93% of the theoretical absorption weight was gained within 280 min with fairly high sorption rate. Almost all the absorbed $CO_2$ was generated by heating the sample to $800^{\circ}C$. We also investigated densification behavior of $Li_2ZrO_3$ under $CO_2$ environment. By sintering $Li_2ZrO_3$ at $760^{\circ}C$ using 2-step process, we obtained dense product, composed mainly of $Li_2ZrO_3\;and\;ZrO_2$, with relative density of 92%.

• Membrane Journal
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• v.22 no.2
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• pp.113-119
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• 2012

$YBaCo_2O_{5+{\delta}}$ oxide was synthesized by solid state reaction and a typical dense membrane has been prepared using as-prepared powder by unilateral pressing and sintering at $1,180^{\circ}C$. The $YBaCo_2O_{5+{\delta}}$ membraneswas analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). XRD analysis showed the double layered perovskite structure was observed over $1,150^{\circ}C$ without impurities. Oxygen permeation was measured in the temperature range from 750 to $950^{\circ}C$ according to oxygen partial pressure difference between feed and permeation side. The oxygen permeation flux increased with increasing temperature and oxygen partial pressure and the maximum oxygen flux of $YBaCo_2O_{5+{\delta}}$ membrane with 1.0 mm thickness was about 0.15 mL/$cm^2{\cdot}min$ at $950^{\circ}C$ and $PO_2$ = 0.42 atm. The activation energy for oxygen permeation decreased with decreasing oxygen partial pressure to be 76.0 kJ/mol at the condition of $PO_2$ = 0.21 atm.

• Applied Chemistry for Engineering
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• v.8 no.3
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• pp.374-381
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• 1997

Ceramic membranes are prepared by using molding method of the glass materials, ceramic-silicone composite membranes are synthesized with immersing silicone compound of sodiumate, $S_3$-Al, S3and we investigated the properties of gas permeation. Ceramic membranes and ceramic-sodiumate membranes that has been prepared were identified as porous structure and ceramic-$S_3$-Al membranes and ceramic-$S_3$ membranes were showed with dense structure by immersion of silicone compounds. Gas permeation properties through the ceramic membranes and ceramic-sodiumate membranes decreased with increasing temperature and linearly increased with increasing pressure, ceramic-$S_3$-Al membranes and ceramic-$S_3$ membranes increased with increasing temperature and pressure effect was low. Permeation rate was found out high value with ceramic membranes and in order of ceramic-sodiumate membranes, ceramic-$S_3$-Al membranes and ceramic-$S_3$ membranes, but selectivity reversed in the order. Gas permeation mechanism through the ceramic membranes and ceramics-sodiumate composite membrane decreased with increasing temperature, suggesting an Knudsen diffusion mechanism, but ceramic-$S_3$-Al composite membranes and ceramic-$S_3$ composite membranes showed an activated diffusion by which gas permeation rates through the membranes increased with an increase in temperature.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.310-315
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• 2009

Perovskite-type ceramic powder, $La_{0.7}Sr_{0.3}Co_{0.3}Fe_{0.7}O_{3-{\delta}}$, have been synthesized successfully by the citrate method. As a result of TGA for precursor, metal-citrate complex in precursor was decomposed in the temperature range of $150{\sim}650^{\circ}C$. XRD analysis showed the single perovskite structure was observed over $1,000^{\circ}C$ without impurities. Typical dense membrane with 1.6 mm thickness has been prepared using as-prepared powder by pressing unilaterally and sintering at $1,300^{\circ}C$. The electrical conductivity of $La_{0.7}Sr_{0.3}Co_{0.3}Fe_{0.7}O_{3-{\delta}}$ membrane increased with increasing temperature at atmosphere of air and then decreased over $600^{\circ}C$ due to oxygen loss from the crystal lattice. The oxygen flux of $La_{0.7}Sr_{0.3}Co_{0.3}Fe_{0.7}O_{3-{\delta}}$ membrane in the range of 700 to $950^{\circ}C$ increased with the increasing temperature from 0.045 to $0.415ml/cm^2{\cdot}min$. The activation energy for oxygen permeation was calculated to be 89.17 kJ/mol.

• Journal of Hydrogen and New Energy
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• v.24 no.1
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• pp.29-35
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• 2013

A dense mixed ionic and electronic conducting ceramic membrane is one of the most promising materials because it can be used for separation of oxygen from the mixture gas. The $ABO_3$ perovskite structure shows high chemical stability at high temperatures under reduction and oxidation atmospheres. $BaCo_{1-x-y}Fe_xZr_yO_{3-{\delta}}$ (BCFZ) was well-known material as high mechanical strength, low thermal conductivity and stability in the high valence state. Glycine Nitrate Process (GNP) is rapid and effective method for powder synthesis using glycine as a fuel and show higher product crystallinity compared to solid state reaction and citrate-EDTA method. BCFZ was fabricated by modified glycine nitrate process. In order to control the burn-up reaction, $NH_4NO_3$ was used as extra nitrate. According to X-Ray Diffraction (XRD) results, BCFZ was single phase regardless of Zr dopants from y=0.1 to 0.3 on B sites. The green compacts were sintered at $1200^{\circ}C$ for 2 hours. Oxygen permeability, methane partial oxidation rate and hydrogen production ability of the membranes were characterized by using Micro Gas Chromatography (Micro GC) under various condition. The high oxygen permeation flux of BCFZ 1-451 was about $1ml{\cdot}cm^{-2}s^{-1}$. Using the humidified Argon gas, BCFZ 1-433 produced hydrogen about $1ml{\cdot}cm^{-2}s^{-1}$.

• Membrane Journal
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• v.11 no.4
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• pp.143-151
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• 2001

We have fabricated mixed-ionic conducting membranes, L $a_{0.6}$S $r_{0.4}$ $Co_{0.2}$F $e_{0.8}$ $O_{3-}$$\delta$/ and L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ by the solid state method. Ceramic membranes consisted of perovskite-type structures and exhibited high relative density, >95%. Especially, dense L $a_{0.6}$S $r_{0.4}$Co $O_{3-}$$\delta$/ layer was coated on the L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membranes by using screen printing technique in order to improve oxygen ion flux. We measured oxygen ion flux on uncoated L $a_{0.6}$S $r_{0.4}$ $Co_{0.2}$F $e_{0.8}$ $O_{3-}$$\delta$/, uncoated L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/, and coated L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membranes. The L $a_{0.6}$S $r_{0.4}$ $Co_{0.2}$F $e_{0.8}$ $O_{3-}$$\delta$/ membranes showed the highest flux, 0.26 mL/min.$\textrm{cm}^2$ at 90$0^{\circ}C$, after steady state had been reached. The oxygen flux of coated L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membranes showed higher value, 0.19 mL/min.$\textrm{cm}^2$ at 95$0^{\circ}C$. This flux was as much as 2 or 3 times higher than those of uncoated L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membranes. 3-$\delta$/ membranes.X> 3-$\delta$/ membranes.membranes.