• Journal of the Korean institute of surface engineering
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• v.39 no.6
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• pp.255-262
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• 2006

Pd-Cu alloy membrane for hydrogen separation was fabricated by sputtering and Cu reflow process. At first, the Pd and Cu was continuously deposited by sputtering method on oxidized Si support, the Cu reflow process was followed. Microstructure of the surface and permeability of the membrane was investigated depending on various reflow temperature, time, Pd/cu composition and supports. With respect to our result, Pd-Cu thin film (90 wt.% Pd/10 wt.% Cu) deposited by sputtering process with thickness of $2{\mu}m$ was heat-treated for Cu reflow The voids of the membrane surface were completely filled and the dense crystal surface was formed by Cu reflow behavior at $700^{\circ}C$ for 1 hour. Cu reflow process, which is adopted for our work, could be applied to fabrication of dense Pd-alloy membrane for hydrogen separation regardless of supports. Ceramic or metal support could be easily used for the membrane fabricated by reflow process. The Cu reflow process must result in void-free surface and dense crystalline of Pd-alloy membrane, which is responsible for improved selectivity oi the membrane.

• Membrane Journal
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• v.34 no.2
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• pp.140-145
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• 2024

In modern times, when a change in the energy paradigm is required, hydrogen is an attractive energy source. Among these hydrogen purification technologies, technology using a membrane is attracted attention as a technology that can purify high purity hydrogen at low cost. However, palladium(Pd), which is mostly used because of its excellent hydrogen separation performance, is very expensive, so a replacement material is needed. In this study, a alloy membrane was manufactured from an alloy of niobium (Nb), which has high hydrogen permeability but is weak to hydrogen embrittlement, and nickel (Ni) and zirconium (Zr), which have low hydrogen permeability but are highly durable. Hydrogen permeation characteristics were confirmed under conditions of 350~450 ℃ at 1 to 4 bar. The maximum hydrogen permeation flux was 0.69 ml/cm²/min for the Ni₄₈Nb₃₂Zr₂₀ alloy membrane without Pd coating, and 13.05 ml/cm²/min for the Pd coated alloy membrane.

• Journal of the Korean institute of surface engineering
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• v.37 no.5
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• pp.289-295
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• 2004

A dense palladium-nikel (Pd-Ni) alloy composite membrane has been fabricated on microporous nickel support mixed with submicron/micron nickel powder instead of mesoporous stainless steel support. Plasma treatment process is introduced as pre-treatment process instead of HCI activation. Pd-Ni alloy composite membrane prepared by electro plating was fairly a uniform and dense surface morphology. The membrane was characterized by permeation experiments with hydrogen and nitrogen gases at temperature 773 K and pressure 2.2 psi. The results showed that hydrogen ($H_2$) permeance was 27 ml/$\textrm{cm}^2$ㆍatmㆍmin and hydrogen/ nitrogen ($_H2$$N_2$) selectivity was 8 at 773 K.

• Journal of the Korean institute of surface engineering
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• v.37 no.5
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• pp.243-248
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• 2004

A palladium-nikel(Pd-Ni) alloy composite membrane has been fabricated on microporous nickel support formed with nickel powder. Plasma surface treatment process is introduced as pre-treatment process instead of HCI activation. Pd coating layer was prepared by dc magnetron sputtering deposition after $H_2$ plasma surface treatment. Palladium-nickel alloy composite layer had a fairly uniform and dense surface morphology. The membrane was characterized by permeation experiments with hydrogen and nitrogen gases at temperature of 773 K and pressure of 2.2psi. The hydrogen permeance was 6 ml/minㆍ$\textrm{cm}^2$ㆍatm and the selectivity was 120 for hydrogen/nitrogen($H_2$/$N_2$) mixing gases at 773 K.

• Journal of the Korean institute of surface engineering
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• v.51 no.5
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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.

• Journal of the Korean institute of surface engineering
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• v.45 no.6
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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.

• Journal of the Korean institute of surface engineering
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• v.42 no.5
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• pp.232-239
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• 2009

This study presented the effect of membrane thickness on hydrogen permeability. Microvoids on the surface of the membrane should not exist for the exact values of hydrogen permeability. Pd-Cu-Ni hydrogen alloy membranes were fabricated by Ni powder sintering, substrate plasma pretreatment, sputtering and Cu reflow process. And this leaded to void-free surface and dense film of Pd-Cu-Ni hydrogen alloy membrane. Hydrogen permeation test showed that hydrogen permeability increased from 2.7 to $15.2ml/cm^2{\cdot}min{\cdot}atm^{0.5}$ as membrane thickness decreased from 12 to $4{\mu}m$. This represented the similar trend as a hydrogen permeability of pure palladium membrane based on solution-diffusion mechanism.

• Membrane Journal
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• v.32 no.2
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• pp.116-125
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• 2022

In this experiment, an α-Al₂O₃ ceramic hollow fiber was used as a support, and a hydrogen membrane plated with Pd and Pd-Ag was manufactured through electroless plating. The Pd-Ag membrane was annealed at 500℃ for 10 h to form an alloy of Pd and Ag. It was confirmed that it became a Pd-Ag alloy through EDS (Energy Dispersive X-ray Spectroscopy) analysis. Also, the thickness of the Pd, Pd-Ag plating layer was measured to be about 8.98 and 9.29 ㎛ through SEM (Scanning Electron Microscope) analysis respectively. Hydrogen permeation experiment was performed using the H₂ gas and mixed gas (H₂ and N₂) in the range of 350~450℃ and 1-4 bar using the prepared hydrogen membrane. Under the H₂ gas condition, the Pd and Pd-Ag membrane has a flux of up to 21.85 and 13.76 mL/cm²·min and also separation factors of 1216 and 361 were obtained in the mixed gas at 450℃ and 4 bar conditions respectively.

• Membrane Journal
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• v.21 no.3
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• pp.290-298
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• 2011

The influence of co-existing gases on the hydrogen permeation was studied through a Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane. The hydrogen permeation characteristics of Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane have been investigated in the pressure range 1-3 bar under pure hydrogen and hydrogen mixture gas with carbon dioxide and carbon monoxide at $450^{\circ}C$. Preliminary hydrogen permeation experiments have been confirmed that hydrogen flux was $5.36mL/min/cm^2$ for a Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane (thick: 0.5 mm) using pure hydrogen as the feed gas. In addition, hydrogen fluxes were 4.46, 5.20, $3.91mL /min/cm^2$ for$V_{53}Ti_{26}Ni_{21}$ alloy membrane using $H_2/CO_2$, $H_2/CO$ and $H_2/CO_2/CO$ as the feed gas respectively. Therefore, the hydrogen permeation flux decreased with decrease of hydrogen partial pressure irrespective of temperature and pressure when $H_2/CO_2$, $H_2/CO$ and $H_2/CO_2/CO$ mixture applied as feed gas respectively and permeation fluxes were satisfied with Sievert's law in different feed conditions. It was found from XRD results after permeation test that the Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane had good stability and durability for various mixtures feeding condition.

• Membrane Journal
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• v.32 no.6
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• pp.456-464
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• 2022

Hydrogen permeation performance was analyzed by manufacturing Pd and Pd-Cu membranes through electroless plating. As a support for the Pd and Pd-Cu membranes, α-Al₂O₃ ceramic hollow fiber were used. Pd-Cu membrane was manufactured through sequential electroless plating, and then annealing was performed at 500°C, for 18 h in a hydrogen atmosphere to make Pd and Cu alloy. After annealing, the Pd-Cu membrane confirmed that the alloy was formed through EDS (Energy Dispersive X-ray Spectroscopy) and XRD (X-ray Diffraction) analysis. In addition, the thickness of the Pd and Pd-Cu plating layers were measured to be about 3.21 and 3.72 µm, respectively, through SEM (Scanning Electron Microscope) analysis. Hydrogen permeation performance was tested for hydrogen permeation in the range of 350~450°C and 1~4 bar in hydrogen single gas and mixed gas (H₂, N₂). In a single hydrogen gas, Pd and Pd-Cu membranes have flux of up to 54.42 and 67.17 ml/cm²⋅ min at 450 °C and 4 bar. In the mixed gas, it was confirmed that the separation factors of 1308 and 453 were obtained under the conditions of 450 °C and 4 bar.