• 한국표면공학회지
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• 제49권3호
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• pp.286-300
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• 2016

Pd-Ag alloy membranes have attracted a great deal of attention for their use in hydrogen purification and separation due to their high theoretical permeability, infinite selectivity and chemical compatibility with hydro-carbon containing gas streams. For commercial application, Pd-based membranes for hydrogen purification and separation need not only a high perm-selectivity but also a stable long-term durability. However, it has been difficult to fabricate thin, dense Pd-Ag alloy membranes on a porous stainless steel metal support with surface pores free and a stable diffusion barrier for preventing metallic diffusion from the porous stainless steel support. In this study, thin Pd-Ag alloy membranes were prepared by advanced Pd/Ag/Pd/Ag/Pd multi-layer sputter deposition on the modified porous stainless steel support using rough polishing/$ZrO_2$ powder filling and micro-polishing surface treatment, and following Ag up-filling heat treatment. Because the modified Pd-Ag alloy membranes using rough polishing/$ZrO_2$ powder filling method demonstrate high hydrogen permeability as well as diffusion barrier efficiency, it leads to the performance improvement in hydrogen perm-selectivity. Our membranes, therefore, are expected to be applicable to industrial fields for hydrogen purification and separation owing to enhanced functionality, durability and metal support/Pd alloy film integration.

• 한국표면공학회지
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• 제51권5호
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• pp.277-290
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• 2018

In this study, Pd-Ni-Ag alloy hydrogen separation membranes were fabricated by Pd/Ag/Pd/Ni/Pd multi-layer sputter deposition on the modified MIM(Metal Injection Molding)-PSS(Porous Stainless Steel) support and followed heat treatment. Nickel, used as an alloying element in Pd alloy membranes, is inexpensive and stable material in a hydrogen isotope environment at high temperature up to 1123 K. Hydrogen perm-selectivity of Pd-Ni-Ag alloy membranes is affected not only by composition of membrane films but also by other factors such as surface properties of PSS support, microstructure of membrane films and inter-diffused impurities from PSS support. In order to clarify the effect of surface Ni composition on hydrogen perm-selectivity of Pd-Ni-Ag alloy membranes, the other effects were significantly minimized by the formation of dense and homogeneous Pd-Ni-Ag alloy membranes. Hydrogen permeation test showed that hydrogen permeability decreased from $7.6{\times}10^{-09}$ to $1.02{\times}10^{-09}mol/m{\cdot}s{\cdot}Pa^{0.5}$ as Ni composition increased from 0 to 16 wt% and the selectivity for $H_2/N_2$ was infinite.

• 한국세라믹학회지
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• 제52권4호
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• pp.269-272
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• 2015

$La_2Ce_2O_7$ and $CeO_2$ membranes were fabricated from the corresponding powders derived from sol-gel process with polyvinyl alcohol binder. These powders and membranes were characterized by XRD, BET, and FE-SEM analysis. Hydrogen and CO gas permeation experiments were performed using Sievert's type equipment. Both fluxes on these membranes were found to decrease with increase of the temperature. This phenomenon was followed by the surface and Knudsen diffusion mechanism. The hydrogen permeability of the $La_2Ce_2O_7$ membrane was found to be $7.27{\times}10^{-5}mol/m^2sPa$, with perm-selectivity of 7.24 at 303 K.

• 한국표면공학회지
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• 제50권2호
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• pp.98-107
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• 2017

Pd-based membranes have been widely used in hydrogen purification and separation due to their high hydrogen diffusivity and infinite selectivity. However, it has been difficult to fabricate thin and dense Pd-based membranes on a porous stainless steel(PSS) support. In case of a conventional PSS support having the large size of surface pores, it was required to use complex surface treatment and thick Pd coating more than $6{\mu}m$ on the PSS was required in order to form pore free surface. In this study, we could fabricate thin and dense Pd membrane with only $3{\mu}m$ Pd layer on a new PSS support manufactured by metal injection molding(MIM). The PSS support had low surface roughness and mean pore size of $5{\mu}m$. Pd membrane were prepared by advanced Pd sputter deposition on the modified PSS support using fine polishing and YSZ vacuum filling surface treatment. At temperature $400^{\circ}C$ and transmembrane pressure difference of 1 bar, hydrogen flux and selectivity of $H_2/N_2$ were $11.22ml\;cm^{-2}min^{-1}$ and infinity, respectively. Comparing with $6{\mu}m$ Pd membrane, $3{\mu}m$ Pd membrane showed 2.5 times higher hydrogen flux which could be due to the decreased Pd layer thickness from $6{\mu}m$ to $3{\mu}m$ and an increased porosity. It was also found that pressure exponent was changed from 0.5 on $6{\mu}m$ Pd membrane to 0.8 on $3{\mu}m$ Pd membrane.

• 한국표면공학회지
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• 제45권6호
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• pp.248-256
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• 2012

A Pd-based hydrogen membranes for hydrogen purification and separation need high hydrogen perm-selectivity. The surface roughness of the support is important to coat the pinholes free and thin-film membrane over it. Also, The pinholes drastically decreased the hydrogen perm-selectivity of the Pd-based composite membrane. In order to remove the pinholes, we introduced various surface pre-treatment such as alumina powder packing, nickel electro-plating and micro-polishing pre-treatment. Especially, the micro-polishing pretreatment was very effective in roughness leveling off the surface of the porous nickel support, and it almost completely plugged the pores. Fine Ni particles filled surface pinholes with could form open structure at the interface of Pd alloy coating and Ni support by their diffusion to the membrane and resintering. In this study, a $4{\mu}m$ surface pore-free Pd-Cu-Ni ternary alloy membrane on a porous nickel substrate was successfully prepared by micro-polishing, high temperature sputtering and Cu-reflow process. And $H_2$ permeation and $N_2$ leak tests showed that the Pd-Cu-Ni ternary alloy hydrogen membrane achieved both high permeability of $13.2ml{\cdot}cm^{-2}{\cdot}min^{-1}{\cdot}atm^{-1}$ permation flux and infinite selectivity.

• 멤브레인
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• 제28권6호
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• pp.432-443
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• 2018

본 연구에서는 Na형 Faujasite 제올라이트 분리막의 프로필렌/프로페인 분리 거동을 예측하기 위하여 제올라이트 13X 입자의 프로필렌 및 프로페인 단일기체에 대한 중량식흡착 거동을 관찰하고자 하였다. 제올라이트 13X 입자의 프로필렌 및 프로페인에 대한 중량식흡착 거동은 자성부유평형저울(MSB)을 이용하여 323, 343, 363 K의 온도와 0.02-1 bar의 압력 범위에서 0.1 bar씩 증가시키면서 측정되었다. 그 결과, 온도가 증가할수록 프로필렌 및 프로페인의 흡착량은 감소하였으며, 프로필렌/프로페인의 흡착 선택도는 증가하였다. 또한 흡착 온도가 증가함에 따라 프로필렌과 프로페인의 확산계수는 증가하여 아레니우스 식을 따랐고, 프로필렌/프로페인 확산 선택도는 323 K에서 0.9753으로 최대값을 가졌다. 흡착 특성을 통해 분리막의 투과선택도를 계산하였고, Na형 Faujasite 제올라이트 분리막의 단일 기체 투과 특성과 비교하였다. 그 결과 계산된 투과선택도와 측정된 투과선택도가 모두 323 K에서 최대값을 갖는 것을 확인하였다. 따라서 본 연구에서는 중량식 흡착법으로 예측된 분리막의 프로필렌/프로페인 분리거동 예측이 합리적이며 또한 표면확산에 기반한 프로필렌/프로페인 분리용 제올라이트 분리막의 분리성능예측에 적용될 수 있음을 알 수 있었다.

• 한국세라믹학회지
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• 제52권4호
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• pp.234-236
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• 2015

$Y_2O_3$-SiC composite membrane was dip-coated using $Y_2O_3$ sol solution; this membrane was compared with a non- coated one. Each membrane was characterized by XRD, FE-SEM and BET techniques. Hydrogen and CO permeation were tested with self-manufactured Sievert's type equipment. $Y_2O_3$ coating was enhanced for the selectivity of the membrane ($H_2$ versus CO). The hydrogen permeation was measured at 1 bar with increasing temperatures. In case of the coated membrane, hydrogen permeation was found to be $1.24{\times}10^{-7}mol/m^2sPa$ with perm-selectivity of 4.26 at 323 K.

• 한국막학회:학술대회논문집
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• 한국막학회 2003년도 The 4th Korea-Italy Workshop
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• pp.25-28
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• 2003

Low cost composite metallic membranes for the hydrogen separation and production have been prepared by using thin Pd-Ag foils reinforced by metallic (stainless steel and nickel) structures. Especially, “supported membranes” have been obtained by a diffusion welding procedure in which Pd-Ag thin foils have been joined with perforated metals (nickel) and expanded metals (stainless steel): in these membranes the thin palladium foil assures both the high hydrogen permeability and the perm-selectivity while the metallic support provides the mechanical strength. A second studied method of producing "laminated membranes" consists of coating non-noble metal sheets with very thin palladium layers by diffusion welding and cold-rolling. Palladium thin coatings over these metals reduce the activation energy of the hydrogen adsorption process and make them permeable to the hydrogen. In this case, the dense non-noble metal has been used as a support structure of the thin Pd-Ag layers coated over its surfaces: a proper thickness of the metal assures the mechanical strength, the absence of defects (cracks, micro-holes) and the complete hydrogen selectivity of the membrane. membrane.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2014년도 추계학술대회 논문집
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• pp.207-208
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• 2014

고순도의 수소를 정제 및 분리하기 위한 팔라듐계 합금 수소분리막은 높은 수소 투과-선택 특성이 요구된다. 그러나 종래의 스퍼터 공정 조건으로 팔라듐계 분리막을 제조하면 주상정 구조에 기인하여 표면에 기공이 형성되게 된다. 본 연구에서는 개선된 스퍼터 시스템에서 고진공, 고온 및 높은 직류 전원 공정조건 하에 치밀하고 균일한 팔라듐/금 수소분리층을 제조하였다. 이와 같은 공정 조건에 의해 종래의 제조 공정 조건 보다 얇은 분리막을 제조하여 공정의 경제성을 향상 시켰으며, 기공이 포함되지 않은 수소분리층을 형성하여 수소 선택 특성이 무한대의 값을 가지는 것으로 관찰되었다.

• 한국표면공학회지
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• 제46권6호
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• pp.248-257
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• 2013

It is generally recognized that thin Pd-Cu alloy films fabricated by sputtering show a wide range of microstructures and properties, both of which are highly dependent on the sputtering conditions. In view of this, the present study aims to investigate the relationship between the performance of hydrogen separation membranes and the microstructure of Pd alloy films depending on sputtering deposition conditions such as substrate temperature, working pressure, and DC power. We fabricated thin and dense Pd-Cu alloy membranes by the micro-polishing of porous Ni support, an advanced Pd-Cu sputtered multi-deposition under the conditions of high substrate temperature / low working pressure / high DC power, and a followed by Cu-reflow heat-treatment. The result of a hydrogen permeation test indicated that the selectivity for $H_2/N_2$ was infinite because of the void-free and dense surface of the Pd alloy membranes, and the hydrogen permeability was 10.5 $ml{\cdot}cm^{-2}{\cdot}min^{-1}{\cdot}atm^{-1}$ for a 6 ${\mu}m$ membrane thickness.