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Preparation of dense composite membrane with Ba-cerate conducting oxide and rapidly solidied Zr-based alloy
Jin-Ho Kim a,**, Yong-Mook Kang b,*, Byoung-Goan Kim c, Sang-Hoon Lee c, Kwang-Taek Hwang a
a

Icheon Branch, Korea Institute of Ceramic Engineering & Technology (KICET), Icheon-si, Gyeonggi-do, Republic of Korea Division of Advanced Materials Engineering, Kongju National University, 275 Budae-dong, Cheonan, Chungnam 330-717, Republic of Korea c Korea Energy Materials Co.Ltd., 409 Daegu Technopark, 1-11 Hosan-Dong, Dalse-Gu 704-230, Republic of Korea
b

article info
Article history: Received 9 January 2011 Received in revised form 21 February 2011 Accepted 28 February 2011 Available online 6 July 2011 Keywords: Ba cerate perovskite oxide Rapidly solidied Zr-based hydride Hydrogen separation Aerosol deposition Dense BCYO/RSZ alloy composite composite membrane

abstract
Hydrogen separation with dense ceramic membranes is non-galvanic, i.e. it does not require any electrode or an external power supply to drive the separation, and the hydrogen selectivity is almost 100% because the membrane contains no interconnected porosity. In this study, a mixed proton-electron conducting perovskite made from BaCe0.9Y0.1O3-d (BCYO) was prepared using a solidestate reaction, whereas a rapidly solidied Zr-based alloy (RSZ) was obtained via a melt-spinning process at a specied cooling rate. Finally, the BCYO/RSZ composite membrane was successfully fabricated by aerosol deposition (AD) at room temperature. The powders and composite membranes were characterized by high-temperature X-ray diffraction (HTXRD), particle size analysis (PSA), scanning electron microscopy (SEM), and X-ray elemental mapping (XRM). The hydrogen permeability of the dense BCYO/RSZ composite membrane was measured with the change of temperature. Under a pure hydrogen atmosphere at 773 Ke1073 K, the BCYO/RSZ composite membrane exhibited higher permeability compared with the sole BCYO membrane over the entire investigated temperature range. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

In recent years, the development of dense ceramic membranes with mixed protonic and electronic conductivities has received considerable attention due to their possible applications in hydrogen-based energy, petrochemical processes, fuel cells, separating membranes, and other technologies [1,2]. In particular, proton transport in multivalent cation-substituted Ba cerate and Sr cerate (BaCe1-xMxO3-d, SrCe1-xMxO3-d, M: Y, Yb, Tm, Eu) has been widely studied for high temperature hydrogen separation [3e14]. Y-doped Ba cerate materials,

BaCe1-xYxO3-d (BCYO), show the highest proton conductivity among the multivalent cation-substituted cerates. However, despite its fast proton conduction, BCYO has not yet been successfully applied for use in a gas separation membrane due to its long-term chemical instability and poor hydrogen permeability under atmosphere containing carbon dioxide or water content [5e8]. In addition, the abovementioned candidate materials for hydrogen separation membranes require thin metal layers on both sides of the membrane or well-distributed metals throughout the whole membrane [15e17]. These metals can

* Corresponding author. ** Corresponding author. Tel.: 82 31 645 1432; fax: 82 31 645 1488. E-mail addresses: jino.kim@kicet.re.kr (J.-H. Kim), dake1234@kongju.ac.kr (Y.-M. Kang). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.02.145

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promote the dissociation and recombination of H2 4 2H 2e as a catalyst in the membrane, resulting in a larger ux of permeated hydrogen through the ceramic membrane. The intrinsic surface activity of the melt-spun Zrbased nanocrystalline alloy is very important for its potential application in areas such as hydrogen storage materials or hydrogenation catalysts [18e20]. In addition, it is well known that rapidly solidied Zr-based alloys are more homogenous in composition and enhanced physical and chemical properties of high strength and low corrosion resistance under toxic atmosphere [21e23]. Adams et al. reported that the melt-spun Zr-based alloys not only exhibit a superior steady-state hydrogen permeation rate but also a high elastic toughness and excellent resistance to hydrogen embrittlement [16]. Hydrogen separation of dense ceramic membranes is signicantly dependent on membrane characteristics such as thickness, particle size, roughness, and adhesion with porous support [24]. Several methods are available for the fabrication of ceramic lms including sol-gel [9,10], sputtering [11], e-beam evaporation [25], metal organic chemical vapor deposition [26], and aerosol deposition [27e33]. Among these methods, the aerosol deposition (AD) method is a novel technique that enables the fabrication of ceramic lms at room temperature with a high deposition rate as well as a strong adhesion to the substrate. It is based on the impact adhesion of sub- or micron particles to a substrate. The oxide particles accelerated by gas up to a subsonic velocity impinge on the substrate, resulting in the formation of a dense ceramic layer. Operation of the aerosol deposition at room temperature enables the fabrication of the ceramic membrane without any phase change. In this study, a cost-effective technique for fabricating BCYO/Rapidly solidied Zr-based alloy (RSZ) composite membranes at room temperature is proposed. A BCYO/Rapidly solidied Zr-based alloy (RSZ) composite membrane with a uniform thickness and composition was successfully fabricated from micron-sized powder using the AD method at room temperature. In order to clarify the membrane performance of the BCYO/RSZ composite, the hydrogen ux measurement was conducted for the BCYO/RSZ composite membrane fabricated by aerosol deposition method.

Fig. 1 e SEM images of (a) VIM-melted ingot and (b) meltspun ribbons of Zr-based alloy.

2.

Experimental

Polycrystalline BCYO, BaCe0.9Y0.1O3-d, powders were prepared using conventional, solidestate reaction methods. Highpurity oxide powders of BaCO3 (99.9%, Aldrich Co.), CeO2 (99.9%, Aldirich Co.), and Y2O3 (99.9%, Aldrich Co.) were mixed, ground in a ball mill with ethanol, and calcined at 1473 K for 2 h in ambient air. The calcined powders were then crushed and sieved into powders below 20 mm. Rapidly soldied Zrbased alloys (RSZ) were fabricated from an ingot of (ZreTi)(VeMneCr)2.0 prepared by vacuum induction melting (VIM). RSZ ribbons with a 300 mm thickness were prepared using the melt-spinning method where its cooling rate was approximately 4 10e5 Ks1. The rapidly solidied Zr-based alloy (RSZ) ribbons were mechanically ground into powders below 50 mm. Then, the calcined BCYO and RSZ powders were mixed with a weight ratio of 80 to 20 by ball milling using ZrO2 balls in ethanol. Fig. 1 shows photographic images of (a) an

ingot of Zr-based alloy prepared by VIM and (b) the melt-spun Zr-based ribbons. Fig. 2(a) shows the schematic diagram of the aerosol deposition apparatus, which consists of three parts: the aerosol generator, the mass-ow controller, and the deposition chamber. The aerosol formed in the aerosol generator was transported with a carrier gas into the deposition chamber, which was evacuated by a rotary pump with a mechanical buster, and accelerated through the nozzle to collide with the substrate. The deposition conditions of the BCYO/RSZ composite lms are given in Table 1. Yttriumstabilized zirconia powders (TZ-8Y, Tosho Co.) were used as a porous substrate, pressed into pellets, and nally sintered at 1533 K for 1 h in ambient air to afford disks with a porosity of 28%. The radius and thickness of the ZrO2 porous substrate are 20 mm and 2 mm, respectively. Rockwell-A indentation tests were conducted to access adhesion of the BCYO/RSZ composite membrane on ZrO2 substrate by a Hoyton indentation instrument. The H2 permeation experiments were performed on labmade high temperature permeation cells as shown in Fig. 2(b).

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online gas chromatography (DS 6200 model). Leakage of neutral gas through pores in the sample or through an incomplete seal was checked by measuring the He tracer content of the permeate stream. No discernible was detected. The particle size distribution of the Ba cerate oxides was measured using a laser diffraction particle size analyzer (HORIBA LA-950V2 model). D50 is dened as the particle size corresponding to 50% accumulation volume in the particle size distribution curve. High temperature X-ray diffraction (HTXRD) was conducted in a q/2q geometry using a Rikaku instrument with Cu Ka radiation at 40 kV and 100 mA in air. The morphology and alloying element distribution of the aerosoldeposited lm were observed via scanning electron microscopy and energy dispersive X-ray spectroscopy including X-ray dot mapping (SEM, HITACHI S-4800 model).

3.

Results and discussion

Fig. 3 shows the (a) X-ray diffraction (XRD) spectra and the (b) particle size distribution (PSD) of the BaCe0.9Y0.1O3-d (BCYO) powders calcined at 1473 K for 2 h. As shown in Fig. 3(a)), the XRD spectrum conrms a single-phase perovskite with an orthorhombic structure. To further analyze the size

Fig. 2 e Schematic illustration of (a) aerosol deposition apparatus and (b) set-up used to measure hydrogen ux through dense ceramic membrane.

In order to measure the H2 permeation rate (i.e. H2 ux), an alumina tube was inserted into the furnace with a sealed membrane and the associated gas ow tubes. A mixture of 10% H2: 90% N2 was used as the feed gas, while 0.5 ml$min1 inner standard Ar was used as the sweep gas on the permeation side. The efuent on the permeation side was analyzed using an

Table 1 e Deposition conditions of hydrogen separation membrane by AD method.

Raw powder Substrate Carrier gas Size of nozzle orice Working pressure Consumption of carrier gas Deposition area BCYO& Melt-spun Zr-based powders ZrO2 Porous disc (dia. 20 mm, th. 22 mm) He 20 0.4 mm2 <10 Torr 8e10 L/min 10 10 mm2

Fig. 3 e (a) XRD pattern and (b) Particle size distribution of BCYO.

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distribution of the calcined BCYO powders, a laser diffraction particle size analysis was used and it has a high accuracy of 0.6% over discrete size ranges, as shown in Fig. 3(b). Based on this method, the geometric mean diameter, D50, of the BCYO particles had an average value of 6.5 mm, with the values ranging from 2 mm to 11 mm. Fig. 4 shows the XRD patterns of the (a) as-cast and (b) meltspun Zr-based alloys. Herein, it is clear that the as-cast alloy is composed of C14 and C15 Laves phases. The peak intensity of the melt-spun alloy is much weaker than that in the as-cast alloy. However, it is not amorphous and all diffraction peaks can be reasonably attributed to the C14 Laves phase. As is well known, the microstructure of the melt-spun alloy is determined by its composition, melting temperature, and cooling rate. Lu et al. reported that the rapidly solidied Zr-based alloys are mostly composed of micro-crystalline C14 and C15 Laves phases, and the increase of the cooling rate tends to exclude the C15 Laves phase [20]. Due to its ne grain and lamellar structure of the thin plates, there are many interfaces in the C14 Laves phase, which may cause a large anisotropic stress and strain in the melt spun alloy [19]. Many interfaces, including the grain boundaries and the interfaces between the thin plates, in the C14 Laves phase provide local stress relaxation to delay the pulverizing of the C14 phase powders. In this study, the hydrogen permeation of the aerosoldeposited BCYO/RSZ composite membrane was measured at a high temperature conclusively showing that the RSZ alloy is more likely to be crystallized. To predict this occurrence, in-situ HTXRD measurements of the melt-spun Zr-based alloy were conducted from 373 K to 1073 K in ambient air as shown in Fig. 5. The XRD proles of the RSZ alloy at different temperatures with 100 K intervals shows that there is no marked change in both phase and peak intensity, indicating that the microstructure of the C14 Laves single phase is retained up to 1073 K. Fig. 6 shows SEM images of the aerosol-deposited BCYO/RSZ composite lm (membrane) on ZrO2 porous support. In Fig. 6(a), a dense lm without micro cracks or pores was observed, which maintained good adhesion with the ZrO2 porous support with an adhesive strength of up to 30 MPa. The high-resolution SEM image of the aerosol-deposited lm in Fig. 6(b) shows that

Fig. 5 e The multiple plots of powder XRD patterns of the melt-spun Zr-based alloy scanned in air at various temperatures from 373 K to 1073 K at 100 K intervals (Scan rate:10 K/min, Holding time:1 h).

Fig. 4 e XRD patterns of (a) VIM-melted and (b) melt-spun ribbon of melt-spun Zr-based alloy.

Fig. 6 e SEM images of top view of the aerosol-deposited BCYO/RSZ composite lm (a) low magnitude and (b) high magnitude.

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submicron particles were uniformly deposited on the ZrO2 support, indicating that the fragmentation of the BCYO/RSZ composite powders occurred during aerosol deposition method. The SEM image and X-ray mapping for the polished cross section of the aerosol deposition composite lm on ZrO2 porous support are given in Fig. 7. The lm thickness was approximately 10 mm and it appears to be rmly deposited on the support. In addition, the X-ray mapping in Fig. 7(b) shows that various elements such as Ba, Ce, Y, O, Zr, Ti, Cr, V and Mn, which originated from the Ba cerate oxides and rapidly solidied Zr-based alloy, were uniformly dispersed without any elemental segregation. This means that the mixture composed of BaCe0.9Y0.1O3-d and RSZ can be well deposited on ZrO2 porous supports using the aerosol deposition method, satisfying the thickness and uniformity for the H2 separation membrane. The H2 uxes through the aerosol-deposited BCYO and BCYO/RSZ composite membranes were measured as a function of the temperature under dry hydrogen ambient, as shown in Fig. 8. At 1073 K, the H2 uxes of the BCYO and BZYO/RSZ composite membranes reached the 0.113 and 0.170 ml$min1 $cm-2, respectively. In Fig. 8, the hydrogen uxes increase with the temperature for both systems, and the BCYO/RSZ composite

membrane exhibited higher permeability when compared with the BCYO membrane over the investigated temperature range under dry conditions. The superiority of the BCYO/RSZ composite to BCYO in the hydrogen ux can be explained by the excellent catalytic activity of the melt-spun Zr-based alloy upon hydrogen dissociation. Generally, the hydrogen permeation through the dense membrane includes the following stages: (1) absorption of H2 molecules, (2) dissociation of H2 molecules, (3) dissolution and diffusion of proton and electron, and (4) recombination and desorption of H2 molecules [15,24]. The larger ux permeated hydrogen through the dense membrane could be resulted in improvement of the dissociation and recombination of H2 4 2H. According to previous literatures, amorphous or nanocrystalline Zr-based alloy formed by melt-spinning method showed an enhanced electrocatalytic activity and hydrogen permeability [34e37]. The rapidly solidied Zr-based nanocrystalline alloy tends to show good hydrogenation properties due to its ne grain size and uniformly distributed composition [19,20]. However, it was difcult to investigate the hydrogen permeability of amorphous alloys having high Zr content due to severe hydrogen embrittlement during the measurement. Therefore, it appears that the enhanced hydrogen permeability

Fig. 7 e X-ray mapping of elemental constituents within the cross section of BCYO/Rapidly solidied Zr-based alloy (RSZ) composite membrane.

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research was performed for the Hydrogen Energy R&D Center, one of the 21st Century Frontier R&D Program, funded by the Ministry of Education, Science and Technology of Korea.

references

Fig. 8 e H2 permeation ux of aerosol-deposited BCYO/ Rapidly solidied Zr-based alloy (RSZ) composite membrane as a function of temperature under dry H2 condition. to the BCYO/RSZ composite membrane can be attributed to not only better electrocatalytic activity by the addition melt-spun Zr based alloy but also suppression of the embrittlement by the existence of Ba-cerate oxide alloy.

4.

Conclusion

A mixed proton-electron conducting perovskite fabricated from BaCe0.9Y0.1O3-d (BCYO) and rapidly solidied Zr-based alloy (RSZ) were prepared using solidestate reaction and melt-spinning processing, respectively. A nano-sized, dense BCYO/RSZ composite membrane was successfully fabricated from micronsized raw powders via aerosol deposition at room temperature. An extremely rough and dense composite membrane with a 10 mm thickness was obtained without heat treatment. The Xray mapping indicates that various elements such as Ba, Ce, Y, O, Zr, Ti, Cr, V and Mn, were uniformly dispersed without elemental segregation. This indicates that the mixture composed of BaCe0.9Y0.1O3-d and RSZ powders can be deposited well on ZrO2 porous support using the AD method, satisfying the thickness and uniformity for H2 separation membranes. Its hydrogen permeability was studied by measuring the gas permeation as a function of the temperature. The H2 uxes increased with the temperature for both systems, and the BCYO/RSZ composite membrane exhibited higher permeability when compared with the BCYO membrane over the entire investigated temperature range under dry conditions. The enhanced hydrogen permeability to the BCYO/RSZ composite membrane can be attributed to not only better electrocatalytic activity by the addition meltspun Zr based alloy but also suppression of the embrittlement by the existence of Ba-cerate oxide alloy.

Acknowledgement
This work was supported by Energy & Resource Technology Development Program (2008-C-CD11-P-10-0-0000) under the Ministry of Knowledge Economy, Republic of Korea. This

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