EFFECTS OF ABSORPTION AND DESORPTION ON

HYDROGEN PERMEATIONI. THEORETICAL MODELING

AND ROOM TEMPERATURE VERIFICATION
T.-Y. ZHANG{ and Y.-P. ZHENG
Department of Mechanical Engineering, Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon, Hong Kong
(Received 28 October 1997; accepted 27 April 1998)
AbstractA new model for hydrogen permeation is proposed to evaluate hydrogen diusivity, considering
absorption and desorption processes. An analytical solution derived from this model can predict eects of
sample thickness, absorption and desorption processes on the permeation behavior. Drift velocity through
the surface and drift velocity in the bulk are introduced herein and the ratio of drift velocity through the
surface to that in the bulk determines the appropriateness of the time-lag method. The proposed method
can be applied for any value of the ratio of drift velocities, while the time-lag method is appropriate only
as the ratio approaches innity. In order to verify the theoretical predictions, electrochemical permeation
experiments at room temperature were performed on fully-annealed-commercially-pure iron samples that
had dierent thicknesses and were coated by palladium on two sides. Two groups of samples, group I
samples with plasma cleaning and pre-sputtering and group II samples without it, were adopted to vary
the eects of the absorption and desorption processes. The diusivity evaluated from the proposed model
reveals an almost identical value being independent of sample thickness and surface treatment, while the
time-lag method leads to a diusivity two orders smaller in magnitude. The experimental results show that
the ratio of drift velocities for the group I samples is about 100 times higher than that for the group II
samples, conrming that the dierence in diusivity between values obtained by the present model and
the time-lag method decreases by increasing the ratio of drift velocities. # 1998 Acta Metallurgica Inc.
Published by Elsevier Science Ltd. All rights reserved.
1. INTRODUCTION
The permeation experiment is the most commonly
used method in measuring hydrogen diusivity
because it is dicult to measure hydrogen concen-
tration with high spatial accuracy. In 1920
Daynes [1] proposed the time-lag method, which is
derived from Fick's second law and has been widely
used for several decades. The time-lag method
ignores the absorption and desorption processes
and hence adopts concentrations as the entry and
exit boundary conditions. Thus, the permeation ux
and integrated ux can be derived from the solution
to Fick's second law. The integrated ux has an
asymptote that intersects the time axis at L
2
a6D,
where D is the diusivity and L the sample thick-
ness. Daynes called this time the lag [1]. The hydro-
gen diusivity can be evaluated from the time lag,
t
L
, as
D =
L
2
6t
L
X (1)
An alternative method is to measure the half time,
t
1/2
, which is the time required for the permeation
ux to attain a half height of the steady-state
level [2]. There is no essential dierence in nature
between the time-lag method and the half-time
method; hereafter, only the time-lag method will be
used for comparison.
The time-lag method is simple and has been a
very appropriate method, particularly in the past
when computers were not available for data acqui-
sition and tting. However, there are problems in
using the time-lag method to determine diusivity
and to understand the diusion mechanism. One
major problem is the large scatter in measured
hydrogen diusivities determined by the time-lag
method at low temperatures. Vo lkl and Alefeld [3]
summarized 46 sets of data for the hydrogen diu-
sivity in a-iron within the temperature range of 25
14758C. These data exhibited a large degree of
inconsistency at low temperatures, diering by 34
orders of magnitude. In addition to this, the diu-
sion activation energies also revealed a large scatter,
ranging from 4.52 to 69.1 kJ/mol. These inconsis-
tencies indicate that hydrogen diusivities deter-
mined by the time-lag method from the permeation
tests can be aected by spurious surface conditions
and/or the existence of traps [4]. The absorption
and desorption processes may lead to the ``thickness
eect'' in measuring hydrogen diusivity when the
time-lag method is used, wherein permeation tests
on membranes thinner than 1.0 mm (approx.) yield
progressively lower diusivities in pure iron [5, 6].
Acta mater. Vol. 46, No. 14, pp. 50235033, 1998
# 1998 Acta Metallurgica Inc.
Published by Elsevier Science Ltd. All rights reserved
Printed in Great Britain
1359-6454/98 $19.00 +0.00 PII: S1359-6454(98)00176-1
{To whom all correspondence should be addressed.
5023
Wach et al. [7, 8] attributed the thickness eect to
energy barriers at the entry and exit surfaces. They
added an additional layer on the sample surface
and adopted a mean value of 1 mm of the ad-
ditional thickness to correct the apparent diusiv-
ities. The corrected diusivities, however, still
exhibit scatter one order in magnitude [7, 8].
Obviously, the thickness eect is caused by the
absorption and desorption processes in which
hydrogen atoms have to overcome energy barriers
to enter into or exit from the sample. Hence, the
surface eect has attracted great attention and a lot
of eort has been devoted to lowering the surface
energy barrier [712]. The problems of how to
avoid the surface eect in order to measure hydro-
gen diusivities in bulk materials and how to
measure the surface energy barrier using the per-
meation method have not been solved [13]. Another
major problem concerns hydrogen diusion along
grain boundaries and/or dislocations [1419]. Some
experimental results, on the one hand, show that
grain boundaries are fast diusion paths for
hydrogen [1416]. Contradictory results are
reported [1719], on the other hand, showing that
the apparent hydrogen diusivities are lower in
samples with ner grains. A similar contradiction
exists in studies of hydrogen diusion along dislo-
cations. It is clear that only when hydrogen diusiv-
ity in a bulk material is reliably measurable, can the
eects of microstructures such as grain boundaries
and dislocations be studied.
Despite the fact that the time-lag method does
not consider the absorption and desorption pro-
cesses, these processes have been studied for many
years. In 1936, Wang [20] rst presented the disso-
ciative chemisorption permeation model. Wang's
model of the permeation process occurring at the
entry and exit surfaces is schematically shown in
Fig. 1 and described as follows. At the entry sur-
face, there are two forward and two reverse jumps.
(1) The gas molecules strike the material surface
and then split into atoms and adhere there. The
ux of adsorbing atoms J
ads
is second order in
(1 y), giving J
ads
= a(1 y)
2
P, where y is the frac-
tional surface coverage, a is a rate constant for
adsorption and P is the pressure of hydrogen gas.
(2) The reverse jump of the rst forward jump, i.e.
two adsorbed atoms combine to form a molecule
which evaporates into the gas phase. The desorbing
ux J
des
is second order in y since two adjacent
atoms are needed to recombine, giving J
des
= dy
2
,
where d is a rate constant for desorption. (3)
Following the rst forward jump is the passage of
the adsorbed atoms into the bulk of the material
and the associate ux is J
abs
= gy, where g is a pro-
portionality constant. (4) The atoms inside of the
material can jump back into the surface and the
ux is proportional to the hydrogen concentration
just below the surface and the fraction of unoccu-
pied surface sites, J
dsb
= b(1 y)C, where b is
another proportionality constant. The net ux at
the entry surface is then determined by the four
jumps and has the following form:
J
1
= a
1
(1 y
1
)
2
P
1
d
1
y
2
1
, J
1
= g
1
y
1
b
1
(1 y
1
)C
1
(entry surface, x = 0)X (2)
Similarly, the ux at the exit surface is given by
J
2
= b
2
(1 y
2
)C
2
g
2
y
2
, J
2
= d
2
y
2
2
a
2
(1 y
2
)
2
P
2
(exit surface, x = L) (3)
where subscripts 1 and 2 refer to the entry and exit
surfaces, respectively. If the equilibrium case is con-
sidered where the ux nulls and P = P
1
=P
2
,
equation (2) or equation (3) leads to
y
eq
1 y
eq
=

a
d
P
r
, C
eq
=

a
d
r
g
b

P
_
(4)
where subscript ``eq'' denotes equilibrium. Equation
(4) is well known as Sievert's law.
Wang's model was able to explain quantitatively
how the net ux changes with the external gas
pressure [20]. Later on, Wang's model was further
developed and modied [2126]. Andrew and
Haasz [26] highlighted the similarities and dier-
ences in the modied models and pointed out that
Wang's model is sucient to explain the observed
experimental results at the limiting case of high
pressure. These adsorption, absorption and deso-
rption analyses [2026] are, however, based on per-
meation uxes at steady state. Starting from
Wang's model, the present paper proposes a new
model that is simple and involves both the absorp-
tion and desorption processes at the surfaces and
the diusion process in the bulk. Using uxes rather
than concentrations as the boundary conditions,
Fick's second law is re-solved and an analytical sol-
ution is obtained.
Fig. 1. The course of the entire permeation process includ-
ing adsorption and desorption processes based on Wang's
model.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5024
2. THEORY
In the present work, the permeation process is
considered as a one-dimensional process. Each of
the absorption and desorption processes is simpli-
ed as a forward and a reverse jump without con-
sidering details of the adsorption and absorption
processes. From Wang's model, i.e. equation (2),
the continuity of ux at the entry surface, requires
k

1
P
1
k

1
C = D
dC
dx
, at x = 0 (5)
where k

1
and k

1
are rate parameters, respectively,
for the forward and reverse jumps and are given by
k

1
=
a
1
g
1
(1 y
1
)
2
g
1
d
1
y
1
, k

1
=
b
1
d
1
y
1
(1 y
1
)
g
1
d
1
y
1
X (6)
At equilibrium, the fractional surface coverage can
be calculated from the gas pressure, using
equation (4) and, consequently, the relationship
between k

1
, k

1
and the gas pressure is determined.
During permeation, however, values of k

1
and k

1
are not the same as the values at equilibrium, even
though the permeation reaches a steady state. At
equilibrium, there is no ux at all, while at the
steady state, the permeation ux reaches its maxi-
mum value. For simplicity, the fractional surface
coverage is assumed to be unchanged with the per-
meation time and then k

1
and k

1
are treated as
constants in the present work. In the same way, the
boundary condition at the exit surface is given by
k

2
C k

2
P
2
= D
dC
dx
, at x = L (7)
where k

2
and k

2
are obtained by exchanging the
subscript 1 to 2. In general, a sample has the same
energy barriers at its two sides, and during per-
meation tests, the entry surface is usually chosen
randomly, unless special treatment is applied to one
surface, e.g. palladium is coated on one surface.
Therefore, it is assumed in the present work that
k

1
= k

2
and k

1
= k

2
.
Both hydrogen pressures P
1
and P
2
in the gas
phase at the entry and exit surfaces can be con-
stantly maintained during permeation tests and,
usually, P
2
=0. Furthermore, the initial concen-
tration inside the material can be maintained as a
constant, which is usually zero also. Thus, the in-
itial and boundary conditions and Fick's second
law can be re-expressed as
dC
dt
= D
d
2
C
dx
2
,
C = 0,for t = 0
(DdCadx kC )
x=0
= k
p
,
(DdCadx kC )
x=L
= 0,for t b 0 (8)
where t is the time, and
k = k

1
= k

2
, k
p
= k

1
P
1
X (9)
The solution to equation (8) is
C =px q

o
m=1
A
m
e
Dl
2
m
t
[Dl
m
cos(l
m
x) k sin(l
m
x)] (10)
where l
m
is the mth positive root of
tan(l
m
L) =
2kDl
m
D
2
l
2
m
k
2
(11)
and
p =
k
p
2DkL
, q =
k
p
(DkL)
2kDk
2
L
,
A
m
=
2k
p
l
m
[(D
2
l
2
m
k
2
)L 2kD]
X (12)
The drift velocities are dened at steady state
through the surfaces and in the bulk, respectively,
as
V
s
= k, V
b
=
D
L
(13)
where subscripts ``s'' and ``b'' denote surface and
bulk, respectively. Then, the steady-state concen-
trations at the entry and exit surfaces are given, re-
spectively, by
C
entry
=
1 V
s
aV
b
2 V
s
aV
b
C
0
, C
exit
=
1
2 V
s
aV
b
C
0
(14)
where
C
0
=
k
p
k
(15)
is termed the permeation concentration. As dis-
cussed above, C
0
does not equal the equilibrium
concentration since the values of k
p
and k at steady
state do not equal the values at equilibrium.
Equation (14) shows that the concentration equals
C
0
at the entry surface and null at the exit surface
when the drift velocity through the surface is much
larger than that in the bulk. In this case, the diu-
sion process in the bulk dominates and hence the
time-lag method is appropriate. On the other hand,
the time-lag method will be inappropriate if the
ratio of the drift velocity through the surface to
that in the bulk is not large enough, which is par-
ticularly true for thin samples with high diusivities.
In such cases, the concentration at the entry surface
will be lower than C
0
and the concentration at the
exit surface will be higher than zero. Another
extreme is the ratio of drift velocities approaching
zero. In this case, the concentration at both surfaces
equals half of C
0
and the diusion ux nulls.
The permeation ux and the integrated ux can
be calculated from equation (10) and are, respect-
ively, given by
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5025
J =
Dk
p
2DkL

o
m=1
Dl
m
A
m
e
Dl
2
m
t
[k cos(l
m
L) Dl
m
sin(l
m
L)] (16)
Q =
Dk
p
2DkL
t

o
m=1
A
m
l
m
[k cos(l
m
L) Dl
m
sin(l
m
L)][1 e
Dl
2
m
t
]X (17)
The integrated ux has also an asymptote
Q =
Dk
p
2DkL
t

o
m=1
A
m
l
m
[k cos(l
m
L) Dl
m
sin(l
m
L)]
(18)
which yields a time lag
t
L
=
2DkL
Dk
p

o
m=1
A
m
l
m
[Dl
m
sin(l
m
L) k cos(l
m
L)]X
(19)
As t approaches innity, the permeation ux will
reach its steady value, J
o
, as
J
o
=
Dk
p
2DkL
=
k
p
2 V
s
aV
b
= C
0
"
V (20)
where a new parameter,
"
V, the mean drift velocity,
is introduced and dened as
1
"
V
=
2
V
s

1
V
b
X (21)
If V
s
is much larger than V
b
, the mean velocity is
approximately equal to V
b
. In this case, C
entry
= C
0
and equation (20) is reduced to
J
o
=
C
0
D
L
(22)
which is the expression of the steady permeation
ux in the time-lag method. If an additional thick-
ness dened as
DL = 2DaV
s
(23)
is introduced here, equation (20) is re-expressed as
J
o
=
C
0
D
DL L
X (24)
It should be noted that the additional thickness
changes with the temperature and microstructure of
the material. Clearly, the additional thickness intro-
duced in the present work diers from that intro-
duced by Wach et al. [7, 8].
The normalized permeation ux is a direct conse-
quence of equation (16) and has the following form:
J
J
o
=1 2(2DkL)

o
m=1

e
Dl
2
m
t
[k cos(l
m
L) Dl
m
sin(l
m
L)]
[(D
2
l
2
m
k)L 2kD]
X (25)
As expected, the normalized permeation ux is inde-
pendent of k
p
, similar to the fact that the normal-
ized permeation ux is independent of the hydrogen
concentration at the entry surface in the time-lag
method. The diusivity, D, and the desorption rate,
k, will be evaluated from tting the measurednor-
malized permeation ux with equation (25) and
hence the absorption parameter, k
p
, will be calcu-
lated from the steady-state permeation ux. Note
that in the electrochemical permeation experiment,
permeation current density, i, is a product of the
permeation ux, J, and the Faraday constant, F.
The experimental curve tting can be conducted
either on a single curve of a sample or on multi-
curves of a sample or on multi-curves of multi-
samples. If the tting is carried out on multi-curves
of a sample, those curves should be obtained from
the tests performed under the same conditions such
that D, k and k
p
should have the same values for
each of the curves. If the tting is carried out on
multi-curves of multi-samples, a physical justica-
tion is required that D, k and k
p
must have the same
values for each of the samples. The tting process is
described in detail in Appendix A. If the diusivity
is evaluated from the time-lag method, then it can
be expressed in terms of the diusivity and the ratio
of drift velocities, or the normalized diusivity is
determined by the ratio of drift velocities:
D
C
D
=
1

o
m=1
12(2 V
s
aV
b
)V
s
aV
b
[(l
m
L)
2
(V
s
aV
b
)
2
]cos(l
m
L)
(l
m
L)
2
[(l
m
L)
2
(V
s
aV
b
)
2
2V
s
aV
b
][(l
m
L)
2
(V
s
aV
b
)
2
]
X (26)
equation (26) shows that the normalized diusivity
approaches unity as the ratio of drift velocities
approaches innity.
3. EXPERIMENTAL PROCEDURE
In order to verify the theoretical predictions and
clarify the confusing situation in hydrogen diusion
in a-iron, a hydrogen permeation experiment on a-
iron was carried out. Fully-annealed- commercially-
pure iron (99.7 wt%) was used in the present study.
The composition of the material is listed in Table 1.
The permeation samples have a circular shape with
a radius of 1.0 cm, and hence a large permeation
area of 3.14 cm
2
to avoid the edge eect and ensure
the appropriateness of the one-dimensional model.
Optical microscopy reveals an average grain size of
the fully-annealed iron sample of about 0.082 mm,
as shown in Fig. 2.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5026
Two kinds of surface treatments were adopted to
prepare samples in order to vary the eects of
absorption and desorption processes. First, all
samples were ground using grinding papers down to
No. 800 grit. Then electrochemical polishing was
carried out on both sides of the samples at room
temperature in a solution of 90% acetic
acid + 10% perchloride at a potential of 12.0 V for
30 min in order to remove surface or subsurface
damage caused by the mechanical preparation.
After the electrochemical polish, the samples were
divided into two groups for two dierent surface
treatments. Before coating palladium on two sides,
surfaces of the group I samples were further treated
by plasma cleaning for 15 min and pre-sputtering
for 5 min, while there was no pretreatment for
samples of group II. Finally, double sides of all
samples were coated with 0.1 mm palladium using
sputter-deposition in an ultra-high vacuum. The
sputter-deposition and pre-sputtering were all con-
ducted in a thin lm sputtering system (DVI SJ/24
LL, Denton) at room temperature.
The double cell electrochemical permeation set-up
is shown in Fig. 3. A 0.2 N NaOH solution lled
both cells and the whole system was controlled by a
computerized potentiostat (EG&G273A). The
anodic current density was stable for 24 h under
0.3 V SCE anodic polarization. A low charging cur-
rent density of 2 mA/cm
2
was used in the per-
meation tests to reduce the Joule heating eect [27].
The sensitivity of the complete experimental system
was about 0.1% of the measuring range, which
could be automatically adjusted. All the electroche-
mical permeation tests were carried out at room
temperature.
4. RESULTS
The repeatability of the experimental system has
been veried by running the permeation tests ve
times on a sample in group I with a thickness of
0.608 mm. From each of the ve permeation curves,
the diusivity, D, and the desorption rate, k, and
the absorption parameter, k
p
, were evaluated. The
results are listed in Table 2. As can be seen in
Table 2, the diusivity D varies from 3.47 10
5
to
4.68 10
5
cm
2
/s, having a mean value of
4.07 10
5
cm
2
/s with a standard deviation of
0.53 10
5
cm
2
/s. It is clearly shown in Table 2 that
the rst test yields the lowest hydrogen diusivity.
This phenomenon may be caused by the existence
of hydrogen traps in the sample [4]. If the result of
the rst test is not taken into account, the mean
value of the diusivity D will be 4.22 10
5
cm
2
/s
with a standard deviation of 0.3310
5
cm
2
/s.
Although the mean value increases just slightly, the
standard deviation drops by almost half. Therefore,
results of the second test for every sample will be
used in the following in order to demonstrate dier-
ences between the present model and the time-lag
method.
Table 2 also indicates the repeatability in
measuring the desorption rate k and absorption
parameter k
p
. Similar to the diusivity, the rst
Table 1. The ingredients of the material
Element C Si Mn P S
Ingredient (wt%) 0.046 0.140 0.103 0.0065 0.012
Fig. 2. Metallography of fully-annealed-commercially-pure
iron samples.
Fig. 3. Double-cell electrochemical permeation set-up.
Table 2. Repeatability of permeation experiments on the sample with thickness of 0.608 mm in
group I
nth test 1st 2nd 3rd 4th 5th mean
k (10
3
cm/s) 1.065 1.043 0.993 0.950 0.986 1.007
D (10
5
cm
2
/s) 3.47 4.14 3.88 4.68 4.18 4.07
k
p
(10
13
mol/cm
2
s) 6.41 6.10 6.23 5.64 5.85 6.05
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5027
time test yields the largest deviation for both k
and k
p
. The mean values of k are 1.0120.05 10
3
and 0.9920.04 10
3
cm/s, and k
p
are
6.0520.31 10
13
and 5.9620.2610
13
mol/
cm
2
s, respectively, for those tests both including
and excluding the rst one. Obviously, the standard
deviation is small when the rst time test is not
taken into account. The repetitive tests provide a
guideline to estimate the errors for the diusivity
and the desorption rate and the absorption par-
ameter.
Figure 4 shows the permeation curve for a
sample from group I with a thickness of 0.108 mm.
A diusivity D = 4.32 10
5
cm
2
/s and a deso-
rption rate k = 1.01 10
3
cm/s are obtained from
tting the normalized permeation curve with
equation (25). For comparison, diusivity was also
evaluated using the time-lag method and it turned
out to be D
C
=3.2610
6
cm
2
/s, which is about
one order of magnitude smaller than that evaluated
by the present method. After that, the value of D
C
was used to plot the normalized permeation curve
based on the time-lag method. As can be seen in
Fig. 4, the curve plotted by the present model ts
the experimental data much better than the time-lag
one. Kiuchi and McLellan [10] analyzed 62 sets of
hydrogen diusivity data and believed that data
obtained by electrochemical methods using Pd-
coated membranes were reliable. The hydrogen
diusivity in pure iron is between 7 10
5
and
8 10
5
cm
2
/s [10] at room temperature, which is
about twice as high as the present result. This
inconsistency may be caused by various purities of
iron used in dierent research groups. Figure 5
shows the diusivities for the group I samples,
where the solid circles denote the values resulting
from tting each of the permeation curves with
either the present model or the time-lag model, and
the solid lines are the predications of the present
model. As expected, the diusivity evaluated by the
present model remains almost unchanged and has
a mean value of 4.11 10
5
cm
2
/s with a standard
deviation of 0.1310
5
cm
2
/s, while the diusivity
calculated by the time-lag method increases from
0.326 10
5
to 1.94 10
5
cm
2
/s as the sample
thickness increases from 0.108 to 1.330 mm, which
demonstrates the ``thickness eect'' [7, 8, 28]. When
the ve permeation curves are put together
to t the diusivity, the value turns out to be
4.03 10
5
cm
2
/s, having a relative error of 2% to
the mean value. Table 3 also lists the tting value
of the desorption rate k for each permeation curve.
As expected, k is independent of the sample thick-
ness and its mean value is 9.8620.76 10
4
cm/s,
while the value obtained by tting all ve curves is
9.87 10
4
cm/s, almost identical to the mean
value.
Figure 5 indicates that the dierence in diusivity
from the two methods decreases as the sample
thickness increases. However, even for a 1.330 mm
thick sample, the value of the diusivity calculated
Fig. 5. Hydrogen diusivity as a function of the sample
thickness for the group I samples, where the solid circles
denote the experimental results and the lines represent the
theoretical predictions of the present model.
Table 3. Results of curve tting for samples in group I
L (mm) 0.108 0.267 0.608 0.995 1.330 mean
k (10
3
cm/s) 1.011 0.994 1.043 0.910 0.970 0.986
D (10
5
cm
2
/s) 4.32 3.99 4.14 4.01 4.11 4.11
D
C
(10
5
cm
2
/s) 0.326 0.687 1.24 1.67 1.94
Fig. 4. Experimental permeation curve and the curves
tted by the present model and the time-lag model for the
sample in group I with a thickness of 0.108 mm and the
sample in group II with a thickness of 0.429 mm.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5028
by the time-lag method is still half as small as that
evaluated by the present model. The appropriate-
ness of the time-lag method can be gauged by the
ratio of the drift velocity through the surface to
that in the bulk. Figure 6 shows the normalized dif-
fusivity, D
C
aD, for all samples in groups I and II as
a function of the ratio of drift velocities, V
s
aV
b
which is directly proportional to the sample thick-
ness for samples in each group. For the samples in
group I, the normalized diusivity increases from
0.08 to 0.47 as the ratio of drift velocities increases
from 0.25 to 3.14. The theoretical prediction of the
thickness eect is also shown in Fig. 6. For the nor-
malized diusivity larger than 0.85, the ratio of
drift velocities should be higher than 20.0, which
requires a sample thickness larger than 8.0 mm for
group I. The critical sample thickness of 1.0 mm
suggested by previous work [7, 8, 28] may be under-
estimated such that the eects of the absorption
and desorption processes could not be eliminated.
Since the samples in group II lacked pre-treat-
ment before coating with palladium, the surface
energy barrier would be higher than that in the
group I samples. Experimental results conrmed
this intuition. Figure 4 also shows a permeation
curve for a sample in group II with a thickness
of 0.429 mm and its tting curves from the two
models. Table 4 lists the evaluated results of the dif-
fusivity and the desorption rate k for the group II
samples. Comparing the results in Table 4 with
those in Table 3 shows that the scatter for the
group II samples is larger than that for the group I
samples and this may be caused by the unclean sur-
faces. The mean value of parameter k for the group
II samples turns out to be 8.6322.0610
6
cm/s
(the value obtained by tting all ve curves is
9.16 10
6
cm/s), two orders of magnitude smaller
than that for the group I samples. The desorption
rate k represents the rate of desorption and depends
on the surface condition. A small k means there is a
high energy barrier for hydrogen atoms to over-
come so that the absorption and desorption pro-
cesses will play an important role during
permeation. The unclean surfaces in the group II
samples lead to a smaller k and, consequently, a
smaller ratio of drift velocities. In this case, the
time-lag method is not appropriate for the group II
samples at all. Figure 7 shows the diusivity as a
function of the sample thickness, wherein the lines
denote the theoretical predictions and circles stand
for the values resulting from tting each of the per-
meation curves with either the present model or the
time-lag model. For the group II samples, neverthe-
less, the diusivity evaluated by the present model
has a mean value of 4.2720.7310
5
cm
2
/s, while
the diusivity obtained by tting all ve curves is
4.26 10
5
cm
2
/s, almost the same as the mean
value. Furthermore, the relative dierence in
mean value of diusivity between the two groups
Fig. 6. Normalized diusivity, D
C
aD, vs the ratio of the
drift velocities, V
s
aV
b
, for both group I and II samples,
where the circles and solid circles denote the experimental
results, respectively, for group I and II samples, and the
line represents the theoretical prediction of the present
model.
Fig. 7. Hydrogen diusivity as a function of sample thick-
ness for the group II samples, where the circles denote the
experimental results and the lines represent the theoretical
predictions of the present model.
Table 4. Results of curve tting for samples in group II
L (mm) 0.429 0.864 1.184 1.474 mean
k (10
5
cm/s) 0.942 0.556 1.000 0.953 0.863
D (10
5
cm
2
/s) 4.28 3.27 5.00 4.54 4.27
D
C
(10
7
cm
2
/s) 1.41 1.54 3.92 5.68
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5029
is just 4%. However, the time-lag model results
in the diusivities ranging from 1.4110
7
to
5.68 10
7
cm
2
/s when the sample thickness
changes from 0.429 to 1.474 mm, being two orders
of magnitude smaller than that evaluated from the
present model. The normalized diusivity vs the
ratio of drift velocities is also shown in Fig. 6, indi-
cating that the experimental results are well pre-
dicted by the present model. The results re-conrm
that one reason for a large scatter in measuring
hydrogen diusivity in iron using the time-lag
method lies on the eects of the absorption and
desorption processes on the permeation behavior.
Since the normalized diusivity depends only on
the ratio of drift velocities, a smaller value of k
requires a larger sample thickness to maintain an
unchanged ratio of drift velocities. Thus, the critical
thickness for the group II samples should be
1000 mm if 8 mm is the critical thickness for the
group I samples. There is no doubt that increasing
thickness will increase the size of the sample and
the time to reach a steady state. From a practical
point of view, the permeation experiment for a
sample with a thickness of 1000 mm would be im-
possible. In this case, therefore, the time-lag method
would not be appropriate at all.
Using equation (20), the absorption parameter k
p
is evaluated from the permeation rate at a steady
state. Figure 8 shows the permeation rate at a
steady state as a function of the reciprocal of
(2 V
s
aV
b
) for the group I and II samples, where
the circles denote the data evaluated from tting
each permeation curve with equation (20) and the
solid line represents the theoretical prediction. The
mean values of the absorption parameter k
p
are
5.9620.2210
13
and 1.1220.06 10
11
mol/
cm
2
s, respectively, for the group I and II samples.
Since the ratios of drift velocities for the group II
samples are all much smaller than 2, ranging from
0.0094 to 0.031, the steady-state rate is almost inde-
pendent of the sample thickness, as shown by
equation (20) and Fig. 8.
Using the mean values of k and k
p
for the two-
group samples, the permeation concentrations are
calculated to be C
0
=6.04 10
10
and
1.30 10
6
mol/cm
3
, respectively, for the group I
and II samples. Under the same charging current
density, the permeation concentration for the group
II samples is about 34 orders of magnitude higher
than that for the group I samples. This fact
conrms the argument that the permeation concen-
tration does not equal the equilibrium concen-
tration because the values of k and k
p
during
permeation dier from those at equilibrium.
The additional thickness DL, representing the
eects of absorption and desorption processes, is
evaluated using equation (23) to be 0.83 mm for the
group I samples and 98.95 mm for the group II
samples, 100 times larger than that for the group I
samples.
Fig. 8. The permeation current density at a steady state as a function of 1a(2 V
s
aV
b
), where the solid
circles and circles denote the experimental results and the line represents the theoretical predictions of
the present model.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5030
5. DISCUSSION
In the present experiment, both sides of the
samples were coated with 0.1 mm palladium in an
ultra-high vacuum. The real diusion system is a
three-layer medium, as shown in Fig. 9. The ux
at the entry surface could be divided into the
following steps. Hydrogen ions are reduced to
hydrogen atoms on the entry surface of the palla-
dium lm. Part of the reduced hydrogen atoms are
adsorbed and absorbed and the others are recom-
bined into hydrogen molecules. The continuity of
net ux at the entry surface of palladium lm
requires
k
Pd
p
C
s
k

s
= D
Pd
dC
dx

Pd1
(27)
where subscript ``s'' denotes the entry surface of
the palladium lm, D
Pd
the hydrogen diusivity
in the palladium thin lm, k
Pd
p
the forward jump
ux at the palladium surface, and k

s
the reverse
jump rate constant. Since the palladium lm is
so thin, the concentration gradient can be assumed
to be a constant. Thus, equation (27) is rearranged
as
k
Pd
p
C
s
k

s
= D
Pd
C
s
C
i
D
(28)
where C
i
is the concentration inside the lm adja-
cent to the interface between the lm and the sub-
strate and D the thickness of the coated palladium
lm. A similar equation to equation (27) is used to
present the ux continuity at the interface:
C
i
k

i
Ck

i
= D
dC
dx
at x = 0 (29)
where subscript ``i'' means the interface between the
palladium lm and the iron substrate. Combining
equations (28) and (29) results in
K

CK

= D
dC
dx
, at x = 0 (30)
where
K

=
k
Pd
p
k

i
k

s
k

i
k

s
k

i
DaD
Pd
,
K

=
k

s
k

i
k

s
k

i
k

s
k

i
DaD
Pd
X (31)
In the same way, if the hydrogen concentration
at the exit surface is assumed to be zero, the bound-
ary condition at the exit surface should be modied
for the palladium-coated samples as
CK

= D
dC
dx
, at x = LX (32)
Comparing equations (30) and (32), respectively,
with equations (5) and (7) shows both correspond-
ing equations have the same form, which means the
boundary conditions at the entry and exit surfaces
can be described by equation (8) if the two par-
ameters of k and k
p
are interpreted as
k = K

, k
p
= K

X (33)
It should be noted that a linear concentration distri-
bution in the palladium thin lm is used here to
ensure the concentration gradient is a constant.
This simplication is appropriate when the palla-
dium lm is very thin. Since the experimental
results can be well interpreted by the proposed
model, it is believed that 0.1 mm of the double-sided
coating is a suitable thickness. In this case, the
absorption and desorption processes include the dif-
fusion process in the palladium thin lms.
Equation (14) shows that the ratio of drift vel-
ocities also determines the hydrogen concentration
distribution at steady state. The concentration at the
entry surface ranges from 0.5C
0
to C
0
as the ratio of
drift velocities varies from zero to innity, and the
concentration at the exit surface changes from 0.5C
0
to zero. For the group I samples, C
0
=6.04
10
10
mol/cm
3
, the ratio of drift velocities rises
from 0.26 to 3.20 when the thickness increases
from 0.108 to 1.330 mm. The corresponding concen-
tration ranges are from 0.56C
0
to 0.81C
0
for the
entry surface and 0.44C
0
to 0.19C
0
for the exit
surface, respectively. For the group II samples,
C
0
=1.30 10
6
mol/cm
3
, the ratio of drift velocities
has values much smaller than unity, from 0.0094 to
0.0310, as the thickness increases from 0.429 to
1.474 mm. The small ratio of drift velocities leads to
the concentration at the entry surface being slightly
higher than 0.5C
0
and the concentration at the exit
surface slightly lower than 0.5C
0
. Taking the highest
ratio of drift velocities, 0.0310, as an example, the
concentrations at the entry and exit surface are
0.51C
0
and 0.49C
0
, respectively. As discussed above,
the hydrogen content at a steady state in the group II
samples is much higher than that in the group I
samples. This assumes charging concentrations are
the same, however, electrochemical charging is notor-
Fig. 9. Schematic illustration of a three-layer permeation
system.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5031
ious for variability. Under the same charging current
density, it must take a much longer time for hydrogen
to reach such a high content in the group II samples.
This phenomenon was also observed during per-
meation tests. Comparing permeation curves between
the two groups, e.g. Fig. 4, indicates the time to reach
steady state is about 14 000 s for the group II
samples, while it is around 40 s, or three orders of
magnitude smaller, for the group I samples.
The absorption and desorption processes occur
not only at surfaces but also at interfaces. The
eects of absorption and desorption could be sig-
nicant in permeation through a multilayer system
with each layer having a small thickness. Takano et
al. reported that the measured diusivity of a multi-
layer system with each layer having a thickness of
micrometers is much lower than the true
diusivity [29]. The reason for this is that the
model [30] used by them ignored the eects of
absorption and desorption processes, i.e. concen-
tration boundary conditions rather than ux
boundary conditions were used at interfaces and
surfaces. In principle, the methodology developed in
the present work can be used to attack the per-
meation problem in the multilayer system.
6. CONCLUSIONS
1. A new model on hydrogen permeation is pro-
posed to evaluate hydrogen diusivity, consider-
ing absorption and desorption processes. An
analytical solution to Fick's second law and
satisfying the ux continuity rather than the con-
centration boundary conditions is derived from
this model. Drift velocity through the surface
and drift velocity in the bulk are introduced and
their ratio determines the validity of the time-lag
method.
2. The diusivity, evaluated from the proposed
model, for hydrogen diusion in fully-annealed-
commercially-pure iron at room temperature is
4 10
5
cm
2
/s and independent of sample thick-
ness and surface conditions.
3. At room temperature and a charging current
density of 2 mA/cm
2
, the mean values of the
parameter k
p
for the group I and II samples are,
respectively, 5.9620.22 10
13
and 1.1220.06
10
11
mol/cm
2
s, and the mean value of the deso-
rption rate k is 9.86 10
4
cm/s for the group I
samples and 8.63 10
6
cm/s for the group II
samples. This means a well cleaned surface yields
a larger k parameter and consequently a higher
drift velocity through the surface, but a lower k
p
.
4. At room temperature and a charging current
density of 2 mA/cm
2
, the permeation concen-
trations are C
0
=6.04 10
10
and 1.3010
6
mol/cm
3
, respectively, for the group I and II
samples.
AcknowledgementsThis project was nancially supported
by the Hong Kong Research Grants Council under RGC
grant HKUST805/96E. The experimental tests were con-
ducted at the Advanced Engineering Materials Facility,
HKUST.
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APPENDIX A
Curve tting
Newton's method is used for curve tting. Consider the
function
f =

M
j=1
[i
j
theo
(D,k,t
j
) i
j
exp
(D,k,t
j
)]
2
(A1)
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5032
where i
j
theo
(D,k,t
j
) is the normalized theoretical current
density expressed by equation (5), i
j
exp
(D,k,t
j
) the normal-
ized experimental current density and M the number of
the experimental data. f = min requires
&
f
1
= dfadD = 0
f
2
= dfadk = 0
X (A2)
From Newton's theory, the unknown parameter can be
evaluated by the following iteration formula:
D
n1
= D
n

1
J
n

df
1
adk f
1
df
2
adk f
2

D=Dn,k=kn
k
n1
= k
n

1
J
n

f
1
df
1
adD
f
2
df
2
adD

D=Dn,k=kn
V
b
b
b
`
b
b
b
X
(A3)
where
J
n
=

df
1
adD df
1
adk
df
2
adD df
2
adk

D=Dn,k=kn
(A4)
is the Jacobi matrix, and subscript n is the iteration
number.
If the permeation tests were performed for dierent
sample thicknesses, more accurate results can be obtained
by tting the curves for dierent sample thicknesses. At
this time, the function f in equation (A1) can be rewritten
as
f =

M1
j=1
[i
j
theo
(D,k,L
1
,t
j
) i
j
exp
(D,k,L
1
,t
j
)]
2

M2
j=1
[i
j
theo
(D,k,L
2
,t
j
) i
j
exp
(D,k,L
2
,t
j
)]
2

Mn
j=1
[i
j
theo
(D,k,L
n
,t
j
) i
j
exp
(D,k,L
n
,t
j
)]
2
(A5)
where M
n
is the maximum number of experimental data
when the sample thickness is L
n
. In order to keep the
same weight for each curve, M
1
= M
2
= = M
n
is used
for curve tting. Then, following the same procedure
above, the unknown D and k can be evaluated.
ZHANG and ZHENG: ABSORPTION/DESORPTION ON HYDROGEN PERMEATIONI 5033