Surface & Coatings Technology 194 (2005) 157 – 166

www.elsevier.com/locate/surfcoat

Characterizations of Pd–Ag membrane prepared

by sequential electroless deposition
Wen-Hsiung Lina, Hsin-Fu Changb,*
a
General Education Center, Chien Kuo Institute of Technology, 500 Changhua, Taiwan ROC
b
Department of Chemical Engineering, Feng Chia University, 407 Taichung, Taiwan ROC

Received 4 March 2004; accepted in revised form 8 July 2004

Available online 25 September 2004

Abstract

Palladium alloy membranes were prepared by sequential electroless plating steps on porous stainless steel (PSS). Full characterizations of
Pd–Ag/PSS composite membranes were performed using scanning electron microscopy (SEM), energy dispersive spectroscopic analysis
(EDS), atomic force microscopy (AFM) and X-ray diffractometry (XRD). AFM images show that in the electroless plating process lower
skin layer roughness and lower deposition rate were related. Although electroless plating was conducted in a sequential process, the deposit
over and inside of porous substrate was homogenous as analyzed by EDS analysis. Therefore, the deposited Pd–Ag alloy membrane retained
the same composition over and through the porous substrate. The porous structure of composite membranes was also characterized by the gas
permeability technique. From the experimental results, it can be concluded that a combined mechanism of Knudsen diffusion and viscous
flow was conducted in the porous membrane.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Sequential electroless plating; Pd–Ag/PSS membrane; Energy dispersive spectroscopic analysis; Atomic force microscopy

1. Introduction Silver is added to palladium to prevent hydrogen

Membrane reactors which are processing chemical
reaction and separation in one unit and especially, being
selective to one or more of the product, can be used to
improve the yields of thermodynamically limited reactions.
When conducting dehydrogenation reactions, which are
normally endothermic, palladium-based membrane reactor
technologies appear promising since the selective removal
of hydrogen would inevitably tend to shift the equilibrium
toward increased product yields. Palladium-based mem-
branes are commercially used for hydrogen purification,
and to some extent for improving conversions in dehy-
drogenation reactions by shifting the reaction equilibrium
[1–5].
* Corresponding author. Tel.: +886 4 24517545; fax: +886 4
24510890.
E-mail address: hfchang@fcu.edu.tw (H.-F. Chang).
0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2004.07.089
embrittlement that takes place below near 573 K for pure
palladium and to increase the hydrogen flux. The enhance-
ment of the H2 permeability by alloying the Pd with Ag or
other rare earth elements has been well established [6]. The
optimum silver concentration is in the region of 23 wt.%
silver [7,8].
Electroless plating appears to be quite attractive due to
the possibility of uniform deposition on complex shapes and
large substrate areas, hardness of the deposited film, and
very simple equipment. Electroless plating has been used to
produce Pd and Pd-alloy membranes on a wide variety of
supports, which include porous glass [9–11], alumina [12–
14], and porous stainless steel [15,16]. Yeung and Varma
[17] prepared Pd–alumina composite membrane by using
osmotic pressure for the manipulation of the microstructure,
porosity, and thickness of the deposited metal. The main
advantages of porous stainless steel (PSS) supports over
porous ceramics and Vycor glass are the resistance to crack
and the simplicity of module construction. Additionally, the
158 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166

Fig. 1. A schematic diagram of the experimental apparatus for gas permeability measurement (1). mass flow controller; (2). poston metering pump; (3).
membrane module; (4). pressure gauge; (5). back-pressure regulator; (6). six pore valve; (7); bubble flowmeter; (8) gas chromatograph.

thermal expansion coefficient of stainless steel is almost

identical to that of palladium, insuring good mechanical
properties of the composite membrane during temperature
cycling.
The objective of the present investigation is to prepare
and improve dense defect free palladium and palladium–
silver alloy membranes on porous stainless steel. Research-
ers have not paid much attention to depth information of the
composite and have concentrated mainly on surface analysis
with SEM and XRD. This study used EDS as an additional
analytical technique to analyze the composite film, to
determine intermetal diffusion at the interface layer and
also to investigate diffusion into the support membrane
pores. Also, a promising method for easy, high-resolution
imaging of the skin layer was provided by the atomic force
microscope (AFM), which was used to investigate structures
with submicrometer resolution without having sophisticated
sample preparation [18].

2. Experimental

2.1. Preparation of Pd-based/PSS composite membranes

Pd and Pd–Ag/PSS membranes were prepared using the

conventional electroless plating process. Prior to the
membrane preparation, dirt and grease in the porous
(average pore size>4 Am from pore size distribution) SS-
316L tube support (effect area>20 cm2; Mott Metallurgical)
were removed by cleaning successively with dilute sodium
hydroxide solution, dilute phosphate acid solution and
deionised water. The activation procedure consisted of the
two-step immersion sequence, which was in acidic SnCl2 Fig. 2. Membrane tube module.
 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166
Fig. 3. Film growth as a function of plating time.
solution (1 g/L) followed by acidic PdCl2 solution (1 g/L).
After surface activation, palladium deposition was per-
formed first in a 4 g Pd(NH3)4Cl2/L plating bath which
lasted 1 h at 333 K, with moderate N2H4 being added. Silver
deposition in a 0.5 g AgNO3/L plating bath was then
performed for 1 h under similar conditions. The plating step
was repeated until the expected thickness of the membrane
Fig. 4. SEM images of (A) M2, (B) M4, (C) M3 and (D) M6 membrane after annealing.
159
was reached. After each deposition, the membrane was
rinsed with deionised water, then dried in an oven at 393 K
for 2 h. Finally, the membrane was sintered and annealed in
hydrogen at atmospheric pressure for more than 18 h [19].
2.2. Membrane characterization analysis
The surface morphology of deposited layer was observed
with a Scanning Electron Microscopy (SEM, S3000N,
Hitachi) equipped with an Energy dispersive Spectrometer
(EDS, Horiba), and with an atomic force microscope (AFM,
ThermoMicroscopes) in which no coating was necessary. X-
ray diffraction patterns (XRD, XRD-6000, Shimadzu) with
a copper target (Cu Ka radiation, k=1.5405 2) and a nickel
filter was used to determine the crystal structure of the alloy
films. The voltage was set at 40 kV and the current at 30
mA. The crystallite sizes of Pd and Ag were estimated using
the simplified Scherrer relation:
kk
D hkl ¼
bcosh hkl
where hkl denotes the diffraction plane; k is the so-called
Scherrer constant, taken as 0.9; k is the wavelength of the
X-rays (1.5405 2 for Cu Ka radiation); b is the true width
(FWHM in radians) of a diffracted line caused by restricted
crystallite dimension.
160 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166

Table 1 catalyst packed), a gas chromatograph, a back-pressure

The properties of Pd-based/PSS membranes regulator, and pressure gauges. The upstream pressure
Membrane Composition Thickness Roughnessa Permselectivity was controlled by the back-pressure regulator, whereas the
(wt.%) (Am) (nm) ( J H2/J N2) downstream of gas vented to air. Prior to the hydrogen
Pd Ag permeation measurement, the flow system was preheated
M1 0 100 5.88 11.39 – to the setting temperature in the nitrogen atmosphere. The
M2 100 0 10.00 36.47 2–5 permeation rates of individual gases (hydrogen and
M3 100 0 30.00 27.64 300
nitrogen) were measured by a soap-bubble flowmeter at
M4 18 82 15.77 14.65 –
M5 75 25 22.00 – – atmospheric pressure and ambient temperature.
M6 78 22 29.00 25.63 N2000
a
Atomic Force Microscope (AFM, ThermoMicroscopes) images with
Nanoscope II software were used to analyze the surface roughness. 3. Results and discussion

2.3. Gas permeation measurement 3.1. Deposition rate of palladium and silver

Permeation measurements were conducted on the Pd
and Pd–Ag/PSS membranes at elevated temperature (623
to 873 K) and pressures (differences up to 1 MPa). The
schematic diagram of gas permeation apparatus was
shown in Fig. 1. The assembly of permeability testing
consisted of gas cylinders, a membrane reactor (Fig. 2, no
After surface activation, palladium nucleates have been
doped in substrate surface. The reduction agent (N2H4)
engaged in the redox reaction then N2 would be released in
the electroless plating process. The Ag or Pd content of Pd–
Ag alloy membrane was determined based on the weight
gains, which was the difference in weight before and after

Fig. 5. AFM images of the skin layer surface of (a) M1, (b) M3, (c) M4 and (d) M6 membrane.
 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166 161

the deposition. The average thickness of the Pd–Ag film
was calculated by dividing the total weight gain by the
plated surface area and the density of the alloy (ca.11.7 g/
cm3 for 23% Ag/Pd alloy). Fig. 3 shows the plating rates of
palladium and silver as a function of time. Silver has a
relatively low activity compared to palladium for the
electroless plating process. It is well known that the
electroless deposition of silver needs to be initiated by Pd
nuclei. This is the reason that the silver was deposited after
the deposition of the Pd film on the supports was completed.
The amount of hydrazine could enhance both of Pd and Ag
deposition rates. However, Ag deposition rate was more
efficiently increased than Pd when the amount of N2H4 was
double.
3.2. Surface morphology
Fig. 4 shows the SEM images of Pd and Pd–Ag
composite membranes subjected to annealing (t=18 h) in
flowing hydrogen at 723 K. The holes of metal surface were

Fig. 6. EDS analysis of cross-sectional distribution of deposits in M6 membrane.

162 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166

the positions of low carbon alkane, proved by energy
dispersive spectroscopic analysis. The EDS pictures of
membrane cross section showed that the amount of carbon
distribution decreased after calcination [20]. Apparently, the
morphology in M4 surface was coarser than M3 and M6.
The permeability test results of H2 and N2 fluxes through
membranes proved this and are listed in Table 1.
The AFM capability to reconstruct the three-dimen-
sional image of the membrane surface can be exploited to
obtain quantitative information about the surface roughness
that is useful for explaining the ultrafiltration process
[21,22]. Fig. 5 shows AFM images of the skin layer
surface of Ag (M1), Pd (M3) and Pd–Ag (M4, M6)
membranes. Nanoscope II software was used to perform a

Fig. 7. Deposition distribution of Pd and Ag with EDS and analysis in (A) M5 and (B) M6 membrane.
 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166
Fig. 8. The distribution of Pd and Ag inside PSS substrate determined by
EDS.
quantitative analysis of the surface roughness. The analysis
results were listed in Table 1. The roughness of M2 was
larger than that of M3, while the latter had a much larger
thickness than the former one. The skin surface layer of
pure silver film M1 is more smother than that of pure
palladium film. Since silver has a relatively low deposition
rate compared to palladium, it has more time, during the
electroless plating, to diffuse horizontally along the
epitaxial plane and to fill the irregular pores possessed
Fig. 9. XRD patterns of M1, M3 and M6 membranes before and after annealing.
163
by the substrate. Likewise, among the composite mem-
branes, M4 and M6, the roughness increased with
increasing Pd loading. Evidently, lower skin layer rough-
ness and lower deposition rate were correlated.
To examine the in-depth distribution component, the
EDS analysis was performed for the Pd–Ag (M6) alloy
composite membrane. The elements of Pd, Ag, Fe, Cr and
Ni were inspected. Fig. 6 shows the cross-section distribu-
tion of impurities (Fe, Cr, Ni) and deposited materials (Pd,
Ag). Since the deposition rates of Pd and Ag were different
in electroless plating process, co-deposition could not yield
exact thickness of Pd or Ag [23]. We fabricated membranes
with sequential deposition process that could certainly
control the compositions of Pd and Ag. Although deposition
proceeded with the sequential process, a homogenous
deposition layer shown by EDS analysis was over the
surface or inside the pores of the substrate.
Fig. 7 shows the profile of Pd and Ag, indicating that the
amounts of Pd and Ag components have diffused into the
substrate. The membrane composition along the depth was
not uniform, because the last process of sequential
deposition was Ag deposited, so the surface region was
rich in Ag. Evidently, Fig. 7B shows the profiles of Pd and
Ag in which both Pd and Ag have diffused into the
substrate.
164 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166

Surface of the substrate was marked with white dot line.
The penetration depth was about 5 Am from the surface,
after that the amount of diffusion was too small to be
measured. The amounts of Pd and Ag diffused into the
substrate were depicted in Fig. 8. The composition of Pd–
Ag alloy was nearly identical to that on the outer surface and
remained the same no matter how deep the alloy penetrated
into the pore. This proved that the electroless plating process
appears to be quite promising due to the possibility of
uniform deposition on complex shapes.
3.3. Effect of calcinations
Fig. 9 shows the XRD patterns of Pd, Ag and Pd–Ag
membranes before and after annealing. The reflection
peaks of (111), (200) and (220) planes of Pd appeared at
2h=41.228, 47.758 and 69.088, and those of Ag appeared
at 2h=39.158, 45.328 and 65.378. After annealing (723 K
under H2 atmosphere for 18 h), the reflection peaks of Pd
or Ag membrane remained the same. However, the peaks
of Pd–Ag membranes after annealing appeared at
2h=40.118, 46.668 and 68.088 [24]. All of these peaks
are smooth and located right between the reflection peaks
of Pd (111) and Ag (111), Pd (200) and Ag (200), Pd
(220) and Ag (220), respectively, which infers that
palladium and silver have formed a homogeneous alloy
after annealing.
sity, s the tortuosity factor of pores, and L the media
thickness.
The permeation of hydrogen through the dense mem-
brane usually involves several steps in series [27]:
(a) dissociated adsorption of molecular hydrogen on the
membrane surface,
(b) reversible dissolution of surface atomic hydrogen in
bulk layer of palladium,
(c) diffusion of atomic hydrogen in the bulk palladium
layer, and
(d) association of atomic hydrogen into molecular hydro-
gen and desorption on the other surface of palladium
layer.
Consequently, the hydrogen fluxes in the Pd layer via
solution-diffusion mechanism can be expressed in terms of
Fick’s first law as follows


J ¼ Fpl P1n  P2n ð3Þ
where F pl is permeation and n is a constant.
Fig. 10 shows the dependences of hydrogen and nitrogen
fluxes, respectively, on temperature at various transmem-
brane pressure differences for M2 composite membrane.

3.4. Permselectivity

Inorganic membranes will be classified into two broad

categories: dense and porous membranes. The difference
between the two categories is not so much a matter of
the absolute size of the bporesQ in the membrane
structures, but rather more a distinction of the generally
accepted transport mechanisms for the permeate. For
dense membranes, the general solution-diffusion type
mechanisms, similar to that prevailing in reverse osmosis
membranes, are believed to be responsible for the
transport and separation of species. With detectable
pores throughout their structures, the porous membranes
operate in various pore-related transport mechanisms
[25].
When a gas permeates through porous membrane that is
fabricated to contain both micropores and mesopores, the
flux is mainly attributed to Knudsen diffusion and viscous
flow combined, as can be expressed by Eq. (1)
J ¼ Fp DP ð1Þ
where DP is the transmembrane pressure, and F p the
permeance. The permeance can be correlated as

Fp ¼ Fpv Pave þ Fpk ð2Þ

where F pk=(ed/3sLRT)(8RT/pM)0.5, P ave the mean pres- Fig. 10. The effect of temperature on fluxes of (A) N2 and (B) H2 in M2
sure and F pv=ed 2/32slLRT [26], e is the medium poro- membrane.
 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166 165

Fig. 12. Comparison of experimental and calculated data on H2 and N2

fluxes.

According to Eq. (2), the dependences of F p on P ave are

Fig. 11. The effect of P ave on fluxes of (A) N2 and (B) H2 in M2 membrane.
Apparently, hydrogen permeated at a greater rate than
nitrogen. The H2/N2 permselectivity, which is defined as
h H2/N2=( J H2/J N2), was about 3 at 623 K and 1 atm. As also
can be seen from Fig. 10, both of H2 and N2 fluxes were
decreasing with temperature; these tendencies were in
accordance with viscous flow. In Fig. 11, the H2 fluxes
were independent of P ave when P ave was over 5 atm, and
both H2 and N2 fluxes decrease with increasing temper-
atures; these tendencies are in accordance with Knudsen
flow. The aforementioned results indicate that there exists a
combined Knudsen flow and viscous flow behavior.
Conclusively, M2 composite membrane can be inferred as
a porous membrane.
linear with a slope F pv and an intercept F pk, where F pv is
directly proportional to 1/(lT) and F pk to 1/(MT)0.5.
Therefore, the flux can be expressed as
h i
J ¼ ða=T ÞPave þ b=ðT Þ0:5 DP ð4Þ
where a and b are obtained as slopes from linear regressions
of F pv with respect to 1/T and F pk to T 0.5, respectively.
After calculations, the following parameters are obtained for
membrane M1:a H2=108.3, b H2=23.9, a N2=55.7, b N2=6.0.
Values a and b are different for N2 and H2 since they have
different viscosities and molecular weights. If we incorpo-
rate the factors for viscosity and molecular weight, an
unified equation can be obtained as
h
i
J ¼ 5:84  109 =lT Pave þ 3:17  105 =ð M T Þ0:5 DP
ð5Þ
Calculations of fluxes were ascertained and listed in
Table 2. The calculated fluxes for N2 and H2 at various
temperatures and transmembrane pressures are compared
with experimental data, shown in Fig. 12, with a deviation
within 10%.

Table 2
The flux through porous membrane M2
Temperature (K) J=F pDP=( F ppP ave+F pk)DP J=F pDP=[(a/T)P ave+b/(T)0.5]DP
F pp(H2) F pk(H2) F pp(N2) F pk(N2) a (H2) b (H2) a (N2) b (N2)
623 0.197 0.968 0.089 0.317 108.3 23.9 55.7 6.0
673 0.161 0.864 0.079 0.208  
Pave 1
723 0.124 0.930 0.090 0.185 J ¼ 5:84  109  þ 3:17  105  pffiffiffiffiffiffiffiffi DP
lT MT
773 0.107 0.909 0.060 0.197
873 0.116 0.756 0.047 0.134
J: mol/s cm2, l: g/s cm, T: K, P ave: atm, M: g/mol.
166 W.-H. Lin, H.-F. Chang / Surface & Coatings Technology 194 (2005) 157–166
4. Conclusions
Silver has a negligible initial activity in the electroless
plating process. Therefore, electroless deposition of silver
needs to be triggered by Pd nuclei. This was the reason that
silver was deposited after the deposition of the Pd film on
the supports was completed at each plating cycle. AFM
images show that in the electroless plating process lower
skin layer roughness and lower deposition rate was related.
Although electroless plating was conducted in a sequential
process, the deposit over and inside of porous substrate was
homogenous as analyzed by EDS analysis. Therefore, The
deposited Pd–Ag alloy membrane retained the same
composition over and through the substrate.
Nomenclature
A0 Pre-exponential, mol/m2 s Pan
d Mean pore diameter, m
Ea Activation energy of permeability coefficient, kJ/mol
Fp Gas permeance, mol/m2 s Pa
F pk Gas permeance due to Knudsen diffusion, mol/m2 s
Pa
F pl Pre-multiplication factor, mol/m2 s Pan
F pvP ave Gas permeance due to viscous flow, mol/m2 s Pa
J Gas flux, mol/m2 s
L Thickness of membrane, m
M Molecular weight of gas, g/mol
P 1, P 2 Partial pressure of gas in the high pressure side and
low pressure side of membrane, respectively, Pa
P ave Mean pressure, Pa
R Gas constant, 8.314 J/mol K
r Mean pore size, m
T Temperature, K
Greek symbols
a Constant defined in Eq. (4)
b Constant defined in Eq. (4)
l Viscosity of gas, g/s cm
e Porosity of a porous medium, –
s Tortuosity factor of a porous medium, –
k Mean free path, m
h Permselectivity ( J H2/J N2), –
Acknowledgements
The authors like to thank of the National Science Council
of the Republic of China, for the financial support under
Contract Number NSC92-2214-E-035-003.
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