• 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.

• 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.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.

• 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.46 no.6
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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.

• Membrane Journal
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• v.34 no.1
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• pp.50-57
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• 2024

In this experiment, Pd-Ag-Cu membrane was manufactured using electroless plating on an α-Al₂O₃ support. Pd, Ag and Cu were each coated on the surface of the support through electroless plating and heat treatment was performed for 18 h at 500℃ in H₂ in the middle of electroless plating to form Pd alloy. The surface of the Pd-Ag-Cu membrane was observed through Scanning Electron Microscopy (SEM), and the thickness of the Pd membrane was measured to be 7.82 ㎛ and the thickness of the Pd-Ag-Cu membrane was measured to be 3.54 ㎛. Energy dispersive X-ray spectroscopy and X-ray diffraction analysis confirmed the formation of a Pd-Ag-Cu alloy with a composition of Pd-78wt%, Ag-8.81wt% and Cu-13.19wt%. The gas permeation experiment was conducted under the conditions of 350~450℃ and 1~4 bar in H₂ single gas and H₂/N₂ mixed gas. The maximum H₂ flux of the hydrogen separation membrane measured in H₂ single gas is 74.16 ml/cm²·min at 450℃ and 4 bar for the Pd membrane and 113.64 ml/cm²·min at 450℃ and 4 bar for the Pd-Ag-Cu membrane. In the case of the separation factor measured in H₂/N₂ mixed gas, separation factors of 2437 and 11032 were measured at 450℃ and 4 bar.

• Journal of the Korean institute of surface 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.

• Corrosion Science and Technology
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• v.6 no.3
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• pp.133-139
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• 2007

Nickel powder was coated with aluminum nitrate solution to increase the thermal stability of a porous nickel support and control the nickel content in the Pd-Cu-Ni ternary alloyed membrane. Raw nickel powder and alumina coated nickel powder were uniaxialy pressed by home made press with metal cylindrical mold. Though the used nickel powder prepared by pulsed wire evaporation (PWE) method has a good thermal stability, the porous nickel support was too much sintered and the pores of porous nickel support was plugged at high temperature (over $800^{\circ}C$) making it not suitable for the porous support of a palladium based composite membrane. In order to overcome this problem, the nickel powder was coated by alumina and alumina modified porous nickel support resists up to $1000^{\circ}C$ without pore destruction. Furthermore, the compositions of Pd-Cu-Ni ternary alloy membrane prepared by magnetron sputtering and Cu-reflow could be controlled by not only Cu-reflow temperature but also alumina coating amount. SEM analysis and mercury porosimeter analysis evidenced that the alumina coated on the surface of nickel powder interrupted nickel sintering.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.1
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• pp.35-40
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• 2008

Ni-based amorphous alloy ribbon was prepared by a single-roller melt-spinning technique. Palladium coating was found to enhance significantly the absorption/desorption behavior of hydrogen in amorphous alloy. The hydrogen permeability of a Pd-coated $(Ni_{60}Nb_{40}){_{100-X}}$TaX(x=5, 10) amorphous alloy was examined in the temperature range of $623{\sim}773K$, comparable with those of $Pd_{60}-Cu_{40}$ alloys. The permeated hydrogen flux was increased with increasing the temperature and the difference of hydrogen pressure between the feed side and permeates side of the membrane. The Ni-based amorphous alloys were characterized by X-ray diffractometry(XRD) and differential scanning calorimetry(DSC). The morphology of surface and roughness was observed by using scanning electron microscopy(SEM) and atomic force microscopy(AFM).

• Proceedings of the Membrane Society of Korea Conference
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• 1999.07a
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• pp.111-113
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• 1999