Journal of Membrane Science 326 (2009) 589–594

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Low temperature diffusion bonding of Pd-based composite membranes

with metallic module for hydrogen separation
Shin-Kun Ryi a,∗ , Jong-Soo Park a,∗∗ , Sung-Hyun Kim b , Dong-Won Kim c , Hyun-Keun Kim c
a
Korea Institute of Energy Research, 71-2 Jang-Dong, Yuseong-Gu, Daejeon 305-343, South Korea
b
Department of Chemical and Biological Engineering, Korea University, 5-Ga Anam-Dong Sungbuk-Gu, Seoul 136-701, South Korea
c
Department of Advanced Materials Engineering, Kyonggi University, Suwon-City, Kyonggi-Do 443-760, South Korea

a r t i c l e i n f o a b s t r a c t

Article history: A diffusion-bonding procedure at a low temperature, i.e. 500 ◦ C, based on the high mobility of silver atoms
Received 24 June 2008 was developed with a newly designed plate-and-frame type hydrogen purification membrane module
Received in revised form 20 October 2008 consisting of a unit cell and a housing. Two membranes made of palladium and copper sputtered on
Accepted 27 October 2008
polished porous nickel supports (PNS) followed by Cu-reflow at 750 ◦ C, respectively, were assembled in
Available online 5 November 2008
a unit cell to verify that the low temperature diffusion-bonding method could be applied to gas-tight
membranes. Ring-shaped silver foils with a thickness of 50 ␮m were placed between the membranes and
Keywords:
the unit cell body made of nickel plate. A pair of membranes, a pair of silver foils and the unit cell body were
Diffusion bonding
Porous nickel support
compressed with a pair of covers and eight screws by a 17 cm long torque wrench at 12 N m. The diffusion-
Pd-based membrane bonded unit cell was welded in a module housing comprised of a feed port and a retentate port by a laser-
Hydrogen separation operated welder. After the module was constructed, gas-tightness tests were carried out using helium and
Membrane module the measured helium leakage was 8 × 10−5 mol m−2 s−1 at 0.7 MPa, which is the same as the value detected
before diffusion bonding with a Viton O-ring. The hydrogen permeation test and durability test consisting
of three cycles of alternately changing the temperature and transmembrane pressure difference were
carried out using a single gas, hydrogen, and it was found that the hydrogen permeation flux remained
constant during the durability test and that the helium leakage did not increase after the durability test.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Recently, the demand for ultra-high purity hydrogen has
increased rapidly in several kinds of industrial processes, such
as chemical synthesis, chemical hydrogenation, semiconductor
manufacturing, fuel cells, etc. Commercially available hydrogen
typically contains impurities including CO, CO2 , O2 , N2 , H2 O, and
CH4 , and these impurities must be separated out for many applica-
tions. Palladium and its alloyed membranes have come to occupy an
important position in hydrogen separation from gaseous mixtures,
because they have high hydrogen permeability, chemical compat-
ibility, and excellent hydrogen selectivity [1–4]. There have been
many attempts to make cost-effective Pd-based membranes.
Before a membrane can be used industrially, methods of
economically and efficiently packaging large areas of the mem-
∗ Corresponding authors. Present address: Chemical and Biological Engineering,
University of British Columbia, 2360 East Mall, Vancouver, BC Canada, V6T 1Z3.
Tel.: +82 42 860 3667; fax: +82 42 860 3309.
∗∗ Korea Institute of Energy Research, 71-2 Jang-Dong, Yuseong-Gu, Daejeon 305-
343, South Korea.
E-mail addresses: pdmembrane@naver.com, h2membrane@gmail.com
(S.-K. Ryi), doedor@kier.re.kr (J.-S. Park).
brane material are required. There are four differently designed
membrane modules: plate-and-frame modules, tubular modules,
spiral-wound modules, and hollow-fiber modules [5]. Among those
kinds of modules, plate-and-frame modules and tubular modules
have been used for Pd-based alloy membranes. As a matter of
fact, hydrogen membrane modules have to withstand both thermal
cycling from ambient temperature to high temperature (generally
773 K) and pressure cycling. In order to obtain ultra-high purity
hydrogen, not only the membranes must be pinhole-free, but also
the assembling technique to join the membranes and modules must
avoid the microstructural degradation of the material.
Various methods of joining metallic membranes with metallic
modules have been tried. Arc welding is generally considered to be
the available method. Tosti et al. developed a gas tungsten arc weld-
ing method to produce membrane tubes consisting of Pd-based
foil and a stainless steel tube [6]. However, the high temperature
required for the arc welding distorts and degrades the strength,
ductility and metallurgical properties of the membrane. Further-
more, the high temperature may cause the membrane surface to
be oxidized. They showed that this welding procedure affected the
welded zones and that, as a consequence of the thermal and hydro-
genation cycling of the membrane, cracks formed after some weeks
of operation of the membrane tube [7]. Electronic beam welding

0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.10.040
590 S.-K. Ryi et al. / Journal of Membrane Science 326 (2009) 589–594

provides very accurate and localized heat for welding. However,

micro-cracks in and near the welding area are often present that
can cause leakage over time [8]. Brazing is another method that
can be employed to join metallic membranes with metallic mod-
ules, because the brazing filler, usually consisting of Cu–Ag alloy,
has a relatively low melting point. However, the brazing could not
be applied, because the introduction of metal elements in the braz-
ing filler may contaminate the metallic membranes and reduce
the hydrogen permeability [7,8]. In our previous work [9], a plate-
and-frame type hydrogen purification module was designed and
constructed to provide easy assembly using a knife-edge sealing
method. Nevertheless, this knife-edge sealing method required a
flange and this flange occupied a large amount of space.
Diffusion bonding is a solid-state bonding process. Diffusion
bonding does not need a liquid interface, as in the case of brazing,
and does not produce the heat-affected zones created by melting
and re-solidification in the arc welding process. Diffusion-bonding
techniques have been used in the aerospace industry and it was
reported that a silver coated Al-alloy sheet could be bonded at
553–753 K [10,11]. Juda et al. [12] disclosed that a Pd–Cu alloy
membrane could be diffusion-bonded to a copper surfaced (copper
or copper rich alloy coating) metallic frame in the presence of
hydrogen, even when the temperature was in the low range of
473–623 K. Tosti at al. [7] reported that a Pd–Ag membrane tube
Fig. 1. Schematic of the diffusion bonding apparatus.
could be manufactured by diffusion bonding at 1373 K for 1 h and
the tube diffusion-bonded to a silver coated stainless steel tube. Li
[8] disclosed a method of diffusion bonding a metallic membrane
hydrogen permeable metal membranes (2), a pair of porous alu-
with a metallic part involving pressing the metallic membrane
mina plates (4) and a membrane module unit cell body (5). In order
against the metallic part and heating the metallic membrane and
to decrease the diffusion temperature, a pair of ring-shaped silver
metallic part to a temperature above half the melting point of the
foils (3) having high mobility at low temperature is placed between
metallic membrane.
the palladium alloy film of the membranes and the unit cell body.
In this study, we describe a method of accomplishing the low
In this study, the center of the membrane module body was formed
temperature diffusion bonding of Pd–Cu–Ni/porous nickel sup-
with a slot (7) for the collection of the permeated hydrogen, and a
ports (PNS) membranes with a nickel metallic module and silver
metal tube (8) can be welded or brazed onto a radial hole formed
foils using the high mobility of the silver atoms. By means of this
on one side of the unit cell body, which the permeated hydrogen
technique, a defect-free membrane module was developed. The
can flow through. The cover comprises screw holes (6) to compress
hydrogen permeation and helium leak tests confirmed that the
the metallic membranes, silver foils and the unit cell body. Once the
diffusion-bonded membrane module has good performance. The
diffusion-bonding procedure is completed, the covers are removed
temperature and pressure cycling tests showed its physical and
and the unit cell is welded in a module housing. In this way, sev-
mechanical stability.
eral hydrogen permeable metal membranes can be easily coupled
to each other and the size of the hydrogen purification module can
2. Experimental
thus be easily controlled.
2.1. Membrane preparation Fig. 2 shows the constituents and assembling of the diffusion-
bonding apparatus. The unit cell body was made of a nickel plate
Porous nickel supports was made of nickel powder with particle and the covers were made of SS 316L. A smooth metal surface,
sizes ranging from 0.1 to 5.0 ␮m, purchased from Nano Technol- mechanical pressure, the presence of hydrogen and an appropriate
ogy Co. This powder has a smooth spherical shape with a purity temperature are the four requirements of the reduction assisted
of 99.9% of nickel. The nickel powder was compressed without a metallic bonding (RAMB) process [8]. Since the rate of weld-
binder in a cylindrical metal mold having a diameter of 50 mm ing depends on the flatness and roughness of the faying surface,
using a homemade press under high pressure (333 MPa) and then the diffusion-bonding zone was carefully polished. The diffusion-
the compressed supports were treated at 973 K under H2 for 2 h to bonding zone was narrow enough to cover an area of 4.2 cm2 with
improve its mechanical strength. Two hydrogen permeable mem- a width of 6.0 mm in order to provide high pressure to cause plas-
branes, i.e. Pd–Cu–Ni ternary alloy membranes, were prepared by tic deformation at the surface of the materials. A torque wrench
sputtering Pd and Cu on the polishing treated PNS followed by the 17 cm in length provided the eight screws with a similar torque
Cu-reflow method. We can conclude the formation of Pd–Cu–Ni of 12 N m. Before assembling the membrane, the unit cell and the
ternary alloy by XRD analysis. The details of the sputtering, PNS inside of the module housing were cleaned by means of a solvent.
polishing methods and EDS and XRD results are shown in previous The diffusion-bonding process was carried out in a vacuum oven
papers [13–15]. In this study, the thickness of the Pd–Cu–Ni ternary under a reducing atmosphere (pure hydrogen) to avoid membrane
alloy film was expected to be around 7 ␮m. oxidation and provide RAMB conditions. The presence of hydrogen
can allow diffusion bonding to be achieved at a lower tempera-
ture or within a shorter period of time. The heat treatment for the
2.2. Diffusion bonding
diffusion bonding included the following steps:
Fig. 1 shows the exploded perspective view of the diffusion-
bonding apparatus. It comprises a pair of covers (1), a pair of • heating up to a temperature of 500 ◦ C at a ramp rate of 3 ◦ C min−1 ,
 S.-K. Ryi et al. / Journal of Membrane Science 326 (2009) 589–594 591

Fig. 2. Constituents (a) and assembling (b) of the diffusion bonding apparatus.

• holding at 500 ◦ C for 5 h,
• cooling down to room temperature in about 5 h.
Once all of the heat treatment steps were finished, the diffusion-
bonding apparatus was disjointed and the two covers were
removed.
2.3. Permeation measurements
The permeation tests were conducted using hydrogen at tem-
peratures in the range of 623–723 K and transmembrane pressure
difference of 0.14–0.70 MPa. The helium leak test was carried out at
a transmembrane pressure difference of 0.7 MPa and room temper-
ature. The selectivities between hydrogen and helium were defined
by the permeation fluxes of the hydrogen and helium leakages at
the same pressure differences.
The permeation apparatus consists of a membrane module, fur-
nace, temperature controller, pressure gauge/controller and mass
flow controller, as shown in detail in Fig. 3. The gases were intro-
duced by a mass flow controller (MCF, Brooks 5850 E series) and
the feed side pressure was regulated by a pressure controller (Ali-
cat PC-100PSIG-D). In order to prevent damage to the membrane
film caused by its contact with the air, both the feed and perme-
ate sides of the membrane module were evacuated to a pressure
of 1.0 × 10−3 Torr by means of a vacuum pump and then filled with
helium after closing the needle valve (11). The temperature was
increased to 623 K at a rate of 3 K min−1 while introducing helium
into both the feed and permeate sides of the membrane module.

Fig. 3. Schematic diagram of the permeation test apparatus.

592 S.-K. Ryi et al. / Journal of Membrane Science 326 (2009) 589–594
Table 1
Melting points of various metals [16].
Element Melting point (◦ C)
Ag 960.8
Cu 1083.4
Ni 1453
Pd 1552
Once the temperature reached 623 K, hydrogen instead of helium
was introduced and then the 3-way valve on the permeate side
(9) and 3-way valve on the retentate side (10) were connected to
the digital soap-bubble flow meter and digital pressure controller,
respectively. The permeation rate of hydrogen was measured by the
digital soap-bubble flow meter.
3. Results and discussion
3.1. Configuration of membrane module
Fig. 4 shows the diffusion-bonded unit cell and the membrane
module equipped with the unit cell. The diffusion-bonded unit cell
was welded in the module housing with a laser-operated welder.
The module housing consists of a feed port and a retentate port.
The external view of the constructed membrane module shows the
feed port, retentate port and permeate port. After the module was
constructed, the gas-tightness test was carried out using helium
and the helium leakage was found to be 8 × 10−5 mol m−2 s−1 at
0.7 MPa, which was the same as the value detected using a Viton
O-ring before diffusion bonding. Although diffusion bonding gen-
erally occurs at a temperature of 0.5–0.8 of the melting point in
Kelvin of the materials to be welded at a high pressure of 5–15 MPa
[8,16], we were able to decrease the diffusion-bonding temperature
to below 0.5 of the melting point of nickel and palladium by intro-
ducing silver layers between the palladium alloy film and the nickel
unit cell, because 0.5 of the melting point of silver is relatively low,
as shown in Table 1.
3.2. Performance of the membrane module
The diffusion of hydrogen through a palladium-based alloy
membrane occurs via a solution and diffusion mechanism. This
Fig. 4. The diffusion-bonded unit cell and the membrane module equipped with
the unit cell by means of a laser-operated welder.
Fig. 5. Hydrogen permeation flux as a function of the transmembrane pressure
difference with a pressure exponent of 0.558.
phenomenon frequently has been described by Eq. (1):
Q  n n

J= Pup − Pdown (1)
l
where J, Q and l denote the hydrogen flux (mol m−2 s−1 ), permeabil-
ity (mol m m−2 s−1 Pa−n ) and thickness (m) of the palladium alloy
membrane (film), respectively. In addition, Pup and Pdown stand for
the hydrogen partial pressure of the feed side and permeate side,
respectively. If the diffusion of hydrogen atoms through the dense
metal layer is rate-limiting, then the hydrogen flux is directly pro-
portional to the n-value of 0.5 derived from Sieverts’ law. The Q-
and n-value were calculated from the overall hydrogen flux rather
than the hydrogen flux through the alloy layer, because the mem-
brane that was used was a composite membrane which consists of a
dense film and a porous support. Fig. 5 shows the dependency of the
hydrogen flux on the feed side pressure for the prepared composite
membrane at various temperatures. As shown in Fig. 5, the pressure
exponents deviated from 0.5. The n-values were almost constant
for three cycles of the transmembrane pressure differences. So, it
can be said that the experimental errors could not be considered
and the precision for n-value is very high. Generally, it appears that
the pressure exponent is affected by the membrane thickness, sur-
face activity, defects and mass transfer on hydrogen permeation
[17–20]. The gas-tightness test showed that the helium leakage
was 8 × 10−5 mol m−2 s−1 at a transmembrane pressure difference
of 0.7 MPa. From the results of the permeation test, we can see that
the hydrogen permeation flux increased to 0.25 mol m−2 s−1 at a
temperature of 723 K and transmembrane pressure difference of
0.7 MPa. At that time, the selectivity (H2 /He) was as high as 3125.
We cannot attribute the deviation from Sieverts’ law to the defects
of the membranes because the flow of hydrogen through defects
will be very small compared to the flow through the dense layer
because of the high selectivity. The present membranes are com-
posed of palladium alloy layers and porous supports. In previous
study, we can see that the PNS has Knudsen diffusion and viscous
(laminar) flow [15]. It means that the support resistance could be
attributed to the deviation from Sieverts’ law.
Thin palladium membranes easily suffer from hydrogen
embrittlement, particularly due to the ␣–␤ phase transition at tem-
peratures below the critical points of the Pd–H system, i.e. 565 K,
1.97 MPa [21,22]. The difference in the specific volumes of the lat-
tices of the ␣ and ␤ phases is up to 10% [23], so that the phase
transitions are accompanied by the generation of defects, causing
 S.-K. Ryi et al. / Journal of Membrane Science 326 (2009) 589–594
Fig. 6. Hydrogen permeance of Pd–Cu–Ni ternary alloy membranes as a function of
inverse temperature: the transmembrane pressure difference was 0.14 MPa.
the fatal fracture of the thin palladium membranes [24]. Palladium
alloys such as Pdx Ag1−x and Pdx Cu1−x can withstand repeated tem-
perature cycling with less distortion than pure palladium. However,
there is still a small difference in the lattice parameters between the
␣ and ␤ phases, so that the phase transitions are accompanied by
the generation of defects after several temperature cycles [24,25].
We carried out ␣–␤ phase transition tests in the temperature
range from 323 to 683 K. Fig. 6 shows the hydrogen permeabil-
ity of the Pd–Cu–Ni ternary alloy membranes as a function of the
inverse temperature measured at a transmembrane pressure dif-
ference of 0.14 MPa. Okazaki et al. [24] observed peaks and changes
in the slope in the range of 443–473 K for Pdx Ag1−x membranes,
which indicated the ␣–␤ phase transition points. However, unlike
in these previous reports, there was no slope change in the case of
the present membranes [26]. From the results, it can be concluded
that no ␣–␤ phase transition occurred in these Pd–Cu–Ni ternary
alloy membranes at temperatures below the critical point of the
Pd–H system.
The hydrogen transport through a dense Pd-based alloy mem-
brane is an activated process. Under the assumption that the
Fig. 7. Variation of the hydrogen permeation flux with the number of temperature and transmembrane pressure difference cycles.
593
hydrogen pressure exponent does not depend on the temperature,
the relationship between the hydrogen permeability and tempera-
ture can be described by Arrhenius’ law as follows:
 E 
a
Q = Q0 exp − (2)
RT
or
Q Q0 Ea
 
= exp − (3)
l l RT
where Ea is the activation energy (kJ mol−1 ), R is the universal gas
constant (8.314 J mol−1 K−1 ) and T is the temperature in Kelvin.
The activation energy of Pd-based membranes has been reported
to range from 5.4 to 38 kJ mol−1 [15,27]. There is little data on
the factors which might have an effect on the activation energy.
The activation energy may depend on the fabrication method
which apparently influences the permeation in ultra thin Pd-based
membranes, probably due to differences in the microstructure or
impurities which could be present on the surface, in the bulk, or
in the grain boundaries [28]. In this study, the activation energy of
the membranes evaluated from the Arrhenius plot of the hydro-
gen permeability against the reciprocal temperature in Fig. 6 was
25.8 kJ mol−1 . This value is in good agreement with those reported
by other research groups for similar palladium-based alloy com-
posite [29,30].
3.3. Durability of the membranes and membrane module
In order to verify the durability of the present membranes and
membrane module, temperature cycling from room temperature to
723 K was carried out with a transmembrane pressure difference
ranging from 0.14 to 0.70 MPa for a week. The hydrogen perme-
ation fluxes were obtained at temperatures of 623–723 K. Since the
membranes have no ␣–␤ phase changes below the critical point of
the Pd–H system, hydrogen was fed during the cooling and heating
periods. As shown in Fig. 7, the hydrogen permeation flux remained
constant for three cycles of alternating temperature and the trans-
membrane pressure differences and the helium leakages were not
increased at the end of the durability test. The present membranes
and membrane module is to be applied to the hydrogen purifier
which is designed by our group. And the results of the durability
test of the hydrogen purifier will be reported. The good durability
of the membranes and membrane module can be attributed to the
594 S.-K. Ryi et al. / Journal of Membrane Science 326 (2009) 589–594
high mobility of the silver atoms, which provides good adhesion
between the palladium alloy film, silver layer and nickel unit cell
body.
4. Conclusions
A hydrogen membrane module was developed by diffusion
bonding at 500 ◦ C for 5 h. To bring about the high mobility of the
metal atoms at low temperature, ring-shaped silver foils were intro-
duced. The performance of the developed membrane module was
measured using single gases, viz. hydrogen and helium. The helium
leakage was below 8 × 10−5 mol m−2 s−1 at 0.7 MPa and room tem-
perature, which was the same as the value detected using the Viton
O-ring before diffusion bonding. The hydrogen flux increased with
increasing temperature and transmembrane pressure difference.
The hydrogen flux reached a maximum value of 0.25 mol m−2 s−1
at a temperature of 723 K and transmembrane pressure difference
of 0.7 MPa with a selectivity of H2 /He of 3125. The hydrogen per-
meation and helium leak tests showed that the membrane module
developed based on the high mobility of silver atoms functioned
perfectly.
The ␣–␤ phase transition test in the temperature range from 323
to 683 K showed that no ␣–␤ phase transition occurred in these
Pd–Cu–Ni ternary alloy membranes. Since there was no ␣–␤ phase
transition below the critical point of the Pd–H system, the mem-
brane module durability test was carried out using hydrogen with
temperature cycling from room temperature to 723 K and trans-
membrane pressure difference cycling from 0.14 to 0.70 MPa for a
week. The durability test showed that the hydrogen permeation
flux and the helium leakage remained constant after three cycles
of alternate temperature and transmembrane pressure differences.
We conclude that the durability of the membrane module can be
attributed to the high mobility of the silver atoms, which provides
good adhesion between the palladium alloy film, silver layer and
nickel unit cell body.
Acknowledgement
The research was performed for the Future Generation Technol-
ogy Project of KIER.
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