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 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲 B291
0013-4651/2004/151共6兲/B291/8/$7.00 © The Electrochemical Society, Inc.

New Interpretation of the Effect of Hydrogen on the Ion

Distributions and Structure of Passive Films on Microalloyed
Steel
Y. M. Zenga J. L. Luo,a,*,z and P. R. Nortonb
a
Department of Chemical and Material Engineering, University of Alberta, Edmonton, Canada T6G 2G6
b
Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7

It has been reported that hydrogen decreases the stability of the passive films on iron and stainless steel and promotes their
localized corrosion. However, the mechanism of hydrogen-promoted corrosion is still not clear. Potentiostatic, electrical imped-
ance spectroscopy measurements, and Mott-Schottky analysis were used to investigate the effect of hydrogen on the properties of
the passive film on X70 microalloyed steel. In the range of passive potentials, hydrogen retards the passive film formation and
decreases its stability. Impedance spectra of passive film on X70 steel show that hydrogen decreases the resistance towards charge
transfer and ion diffusion and increases the capacitance of the passive film. Mott-Schottky analyses show that hydrogen increases
the capacitance and donor density, and decreases the flatband potential and the space-charge layer thickness of the passive film. A
new explanation is proposed for the effects of hydrogen on the properties of the passive films. According to this explanation,
hydrogen creates an additional electric repulsion on Fe2⫹ or Fe3⫹ and oxygen vacancies, and enhances the diffusion rate of cations
and anion vacancies. At steady state, hydrogen will not only decrease the concentrations of O2⫺ and Fe3⫹, but also increase the
concentration of Fe2⫹ in the passive films, resulting in changes in the structure and a decrease in the thickness of the passive films.
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1737383兴 All rights reserved.

Manuscript submitted March 31, 2003; revised manuscript received November 25, 2003. This was in part Paper 275 presented at
the Salt Lake City, NV, Meeting of the Society, October 20-24, 2002. Available electronically April 30, 2004.

In aqueous systems, the generation of hydrogen can arise through
corrosion processes or the action of cathodic protection.1,2 Hydrogen
degradation of materials is complex and depends on many variables,
and various mechanisms have been proposed to interpret hydrogen
induced-damage and material failures.2-5 The nature of such damage
and failures depends on the hydrogen concentration, stress, solution,
temperature, material composition, and microstructure.
A passive film acts as a reacting ion barrier between the metal
surface and the aggressive environment present in corrosive solu-
tions, and thereby protects the underlying metal from corrosion. Hy-
drogen is known to decrease the stability of the passive film and
promote the localized corrosion of iron and stainless steel.1,6-9 The
current explanations for hydrogen-promoted localized corrosion are
based primarily on the following possible reactions.
Hydrogen atoms reduce Fe3⫹ to Fe2⫹ at the metal/film interface
by Reactions 1 and 2, resulting in an increase in the concentration of
Fe2⫹ in the passive films
H → H⫹ ⫹ e⫺
Fe3⫹ ⫹ e⫺ → Fe2⫹
Hydrogen increases OH⫺/O2⫺ ratio in passive films, and then
accelerates pit initiation due to the relatively easy substitution of
OH⫺ ions in the film by Cl⫺ in the solution
⫺ ⫺ ⫺ ⫺
OHfilm ⫹ Clsolution → Clfilm ⫹ OHsolution
Hydrogen might decrease the thickness of passive films.
However, the mechanism by which hydrogen promotes localized
corrosion is still far from being fully understood. The existing ex-
planations for hydrogen-promoted corrosion have not considered the
effects of hydrogen on the transport and distribution of cations and
anion in the passive films. First, for iron and microalloyed steels
with passive films, the following reaction occurs at the metal/film
interface
Fe → Fe2⫹ ⫹ 2e⫺
* Electrochemical Society Active Member.
z
E-mail: jingli.luo@ualberta.ca
It is less favorable for iron to exist in the form of Fe3⫹ at the
metal/film interface due to thermodynamic instability. Even though
a very small amount of Fe3⫹ might exist at this interface, Fe3⫹
would be reduced to Fe2⫹ by iron rather than by hydrogen atoms at
the interface through Reaction 2 since an iron atom has stronger
reduction ability than a hydrogen atom. Hence, it is not convincing
to explain hydrogen-promoted corrosion by considering that hydro-
gen reduces Fe3⫹ to Fe2⫹ at the metal/film interface, resulting in an
increase in the concentration of Fe2⫹ in the films. Second, it is
generally accepted that oxygen ions (O2⫺) are transported from the
film/solution interface to the metal/film interface, resulting in the
growth of the passive layer into the substrate. At the same time,
cations are transported in the reverse direction. Knowledge of the
transport processes of cations and anions in the passive film is very
important to any understanding of the mechanism of film formation
and breakdown; but there have been very few such investigations.
Moreover, it is expected that when passive films are formed on iron
and carbon steels, the continuous permeation of hydrogen from
关1兴 metal to film should not only change the ratios of OH⫺/O2⫺ and
O2⫺/Fe2⫹ or O2⫺/Fe3⫹, but also influence the distribution of cations
关2兴 and anions in the films.
To our knowledge, little work has been performed on studying
the effect of hydrogen on local corrosion of microalloyed steels.
Microalloyed steels are widely used as pipeline materials in industry
and are always under the condition of cathodic protection. The pur-
pose of the present work is to investigate the effect of hydrogen on
the properties of the passive film on microalloyed steel, and then
关3兴
propose a new theoretical explanation, based on thermodynamics,
ion transport, and electrochemical theories. It is anticipated that this
will help to advance the understanding of the mechanism by which
hydrogen promotes localized corrosion.
Experimental
Materials and solutions.—The interest in X70 microalloyed steel
originates from Syncrude Canada, and this material was therefore
used for testing the effect of hydrogen in the following experiments.
The composition and mechanical properties of the material are listed
关4兴 in Table I. Samples were cut into 10 ⫻ 10 ⫻ 1.8 mm coupons. The
samples were spot-welded to a copper wire for electrical contact.
Prior to measurements, both surfaces of the specimen were ground
mechanically with emery papers up to 600 grit, and then rinsed
using deionized water and ethanol successively.
B292 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲
Table I. Composition and mechanical properties of X70 microalloyed steel.
Elements C Mn S P Si Cu
Weight
共%兲 0.04 1.46 0.003 0.008 0.24 0.22
YS 共MPa兲 UTS 共MPa兲 EL 共%兲
545 642 41
All solutions were prepared with deionized water and analytical-
grade reagents. The test solutions were 0.5 M NaHCO3 with or
without NaCl. 0.5 M H2 SO4 ⫹ 0.25 g/L As2 O3 solution were used
for precharging with hydrogen. The addition of As2 O3 to the charg-
ing solution is designed to inhibit the hydrogen recombination reac-
tion, and therefore, promote the entry of hydrogen atoms into the
metal.10
Electrochemical cell setup.—As shown in Fig. 1, a Devanathan-
type double cell was used in this study with one side as the hydro-
gen charging cell and the other as the test cell.1 Electrolyte A was in
a two-electrode cell and used for charging hydrogen. Hydrogen
charging was carried out by applying various constant cathodic cur-
rent densities for designed times. Electrolyte B was in a three-
electrode cell and used for measurement. In the system, a saturated
calomel electrode 共SCE兲 was used as a reference electrode and two
platinum sheets 50 ⫻ 20 mm were used as counter electrodes in
electrolytes A and B. Potentials cited in this paper are all referred to
SCE.
Potentiostatic measurements were recorded with an EG&G PAR
model 273 potentiostat. Electrical impedance spectroscopy 共EIS兲
measurements were carried out with a Gamry CMS300. The ampli-
tude of the ac signal was 10 mV, and the test frequencies ranged
from 10,000 Hz to 0.005 Hz. For both current density vs. time and
EIS measurements, after the specimens were precharged with hydro-
gen at 2 mA/cm2 for 1 h, the hydrogen charging was switched off.
For the current density vs. time measurements, current responses of
the specimens at 0.1 VSCE were recorded immediately after the
charging was switched off. EIS measurements were conducted at
⫺0.1 VSCE after the specimens were passivated at ⫺0.1 VSCE for
1.5 h.
Mott-Schottky measurements were conducted by a 1287 electro-
chemical interface equipped with a 1255 frequency response ana-
lyzer 共FRA, Solatron, Inc.兲. To obtain Mott-Schottky plots, the
specimens were prepassivated at the chosen film formation potential
for 80 min, and then the measurement potential was scanned at 2
mV/s from ⫺0.4 to 0.6 VSCE in the anodic direction. For the
hydrogen-charged case, the specimen was precharged for 2 h, and
then the test side of the specimen was passivated at 0.2 VSCE for 80
min, followed by capacitance measurements with concurrent hydro-
gen charging. An ac signal with amplitude of 10 mV and a fre-
quency of 1000 Hz were superimposed on the scanning signal. The
Figure 1. Schematic drawing of the electrochemical cell for measurements.
Ni Cr Nb Mo Al Ti Fe
0.10 0.05 0.073 0.20 0.028 0.024 98.5
capacitance was calculated from the imaginary part of the imped-
ance, assuming a series resistance-capacitance 共RC兲 circuit for the
system.
Results
Effect of hydrogen on formation of passive
films.—Potentiodynamic measurements have shown that X70 steel
exhibits passive behavior in the potential range from open-circuit
potential to 1 VSCE in 0.5 M NaHCO3 共see Fig. 2兲. To study the
passivation process on X70 steel, the current densities of the speci-
men were measured at various film formation potentials. For the
hydrogen-charged case, the specimens were precharged with hydro-
gen at 2 mA/cm2 for 1 h and then the hydrogen charging was switch
off.
Figure 3 shows the effect of hydrogen on the passivation process
of X70 steel at ⫺0.1 VSCE constant potential. An uncharged sample
reached stable current density after about 800 s i.e., a stable passive
film would be formed on the X70 steel after 800 s immersion at
⫺0.1 VSCE . After the film formed on the surface of the sample, the
current density smoothly decreased with time and approached 1.5
⫻ 10⫺6 mA/cm2 after 5400 s. For the sample with precharged hy-
drogen at 2 mA/cm2 for 1 h, the current density reached relative
stability after 1500 s, i.e., a longer time is needed to form the pas-
sive film on microalloyed steel when hydrogen atoms are present in
the steel. Even in the range of stable current density, small current
density fluctuations were present. This means that the stability of the
passive film was decreased by hydrogen and was more readily at-
tacked by the aggressive ions (Cl⫺). It is also noted that the oxida-
tion of H in the passive film could also contribute the increment of
current density. At the stable stage, the passive current density was
close to 5.2 ⫻ 10⫺6 mA/cm2 , which was about 3.5 times that of the
uncharged sample. At a higher passive potential 共0.2 VSCE), similar
results were observed, as shown in Fig. 4. The release of hydrogen
from the film could lead to a decrease in the difference in current
Figure 2. Polarization curve of X70 microalloyed Steel in 0.5 M NaHCO3
solution.
 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲
Figure 3. Variations of current density with time for X70 steel in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution at ⫺0.1 VSCE .
between the charge and uncharged specimens as time goes on as
shown in Fig. 4.
Effect of hydrogen on impedance response of passive films.—In
order to investigate the effect of hydrogen on the impedance re-
sponse of the passive films, the hydrogen charging was switch off
after the specimens were charged with hydrogen at 2 mA/cm2 for 1
h. Then the test side of specimen was consecutively passivated in
the solution of 0.5 M NaHCO3 containing 0.001 M Cl⫺ for 1.5 h,
followed by impedance measurements. For comparison, the imped-
ance of the passive film on the uncharged specimen was also mea-
sured in the same solution. The results are shown in Fig. 5 and 6.
Although it is still controversial, there seems to be general agree-
ment that the impedance characteristics of a passive film include ion
electromigration, diffusion transport, and dissolution.11-13 In this
case, an equivalent circuit, as shown in Fig. 7, was set up to interpret
the impedance data. Here, R ct is charge-transfer resistance, C film is
the capacitance of the passive film, R film is the resistance to ion
diffusion in the passive film, including the relaxation of mass trans-
port, R s is the resistance of the solution, and the constant phase
element 共CPE兲 is related to the double-layer capacitor. For the
double layer capacitor
Z CPE ⫽ A 共 j␻ 兲 ⫺␣ 关5兴
Figure 4. Variations of current density with time for X70 steel in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution at 0.2 VSCE .
B293
Figure 5. Impedance spectra for passive films on X70 steel preformed in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution at ⫺0.1 VSCE for 1.5 h.
where the constant A ⫽ 1/C dI 共the inverse of the double-layer ca-
pacitance兲 and the exponent ␣ was less than one. Figure 8 shows the
comparison of the fit data obtained by modeling the equivalent cir-
cuit and our experimental results for X70 steel in 0.5 M NaHCO3
⫹ 0.001 M NaCl solution at 0.2 VSCE for 1.5 h. Good agreement is
obtained between the measured and the fitted spectra at high and
low frequencies.
The calculated results of R s CPE, Rct, C film , and R film are shown
in Table II. The results show that hydrogen increases the film ca-
pacitance and decreases the resistance of charge transfer and ion
diffusion of the passive film. At a higher passive potential 共0.2
VSCE), the resistance toward ion diffusion is significantly decreased
from 156.9 to 78.4 k⍀ cm2 by hydrogen precharging at 2 mA/cm2
for 1 h.
Effect of hydrogen on electronic properties of passive
films.—The electronic properties of passive films are often investi-
gated by Mott-Schottky analysis based on the measurement of the
electrode capacitance as a function of the electrode potential 共U兲,
assuming that the capacitance of the space-charge layer, C SC , is
Figure 6. Impedance spectra for passive films of X70 steel preformed in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution at 0.2 VSCE for 1.5 h.
B294 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲

Figure 7. The equivalent circuit for the passive film on X70 steel in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution.

much less than that of the Helmholtz layer, and thus the electrode
capacitance is equal to C SC . For an n-type semiconductor, the Mott-
Schottky relationship can be expressed as14
1
2
C SC
⫽
2
eN D␧ 0 ␧ 冉
U ⫺ U FB ⫺
kT
e 冊 关6兴
Figure 9. Mott-Schottky plots of the passive films on X70 steel in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution with different hydrogen-charged
where ␧ 0 is the vacuum permittivity, ␧ the dielectric constant, e the current densities. The passive films were formed at 0.2 VSCE for 80 min
electron charge, U the applied potential, U FB the flatband potential, before the Mott-Schottky measurements.
N D the donor density, and kT/e is about 25 mV at room temperature.
The donor density N D can be estimated from the slope of linearly
fitted Mott-Schottky plots, while the flatband potential U FB can be films formed on X70 steel are n-type semiconductors due to the
obtained from the extrapolation of 1/C ⫺2 to 1/C ⫺2 ⫽ 0. In addition, positive slopes. The capacitance of the films increased with the
the thickness W of the space-charge layer at a film formation poten- hydrogen-charging current densities. At lower measurement poten-
tial can be calculated by14 tials, the influence of hydrogen on capacitance is not noticeable. The

冉 冊冉 冊
1/2 1/2
2␧␧ 0 kT
W⫽ U f ⫺ U FB ⫺ 关7兴
eN D e that there are linear regions of 1/C 2 vs. potential, and the slopes of
where U f is the film formation potential, and the other parameters
have the same physical meanings as those in Eq. 1. In this paper, the
value of the dielectric constant ␧ is taken as 15.6 for calculation of
N D and W.15,18
To study the electronic structure of the passive film, the electrode
capacitance was measured after the specimen had been previously
passivated at 0.2 VSCE for 80 min. For the hydrogen-charged case,
the specimen was precharged for 2 h, and then the test side of the
specimen was passivated at 0.2 VSCE for 80 min, followed by ca-
pacitance measurements with concurrent hydrogen charging. Figure
9 shows the Mott-Schottky plots of the passive films on the un-
charged and charged specimens.
The slope of a Mott-Schottky plot is an indication of the conduc-
tivity type of the semiconductor. It can be concluded that the passive
Figure 8. Comparison of experimental data for X70 steel in
0.5 M NaHCO3 ⫹ 0.001 M NaCl solution with the fitted data obtained by
the equivalent circuit shown in Fig. 7. The specimen was prepassivated at
0.2 VSCE for 1.5 h. 共 兲 Fitted data, 共⽧, 䊉兲 measured data.
effect of hydrogen on the capacitances becomes significant when the
measurement potential exceeds ⫺0.2 VSCE . It was also observed
the straight lines decrease with increasing hydrogen charging current
densities.
Since a linear relation between 1/C 2 and the potential was ob-
served, the data in the range of ⫺0.2-0.35 VSCE measurement po-
tentials were linearly fitted with a confidence of 95%. According to
Eq. 6 and 7, the values of N D , V FB , and W were calculated and are
shown in Table III. As shown in Table III, hydrogen increases the
donor density N D , decreases the thickness of space-charge layer,
and results in a more negative flatband potential for the passive films
formed at 0.2 VSCE . This effect became more significant with the
increase of the hydrogen-charging current densities.
A competitive adsorption model16 has been generally used to
describe the inhibition of pitting on low carbon steel and microal-
loyed steel, in which aggressive ions (Cl⫺) and inhibitive ions
(HCO⫺ 3 ) compete for the adsorption sites on the metal surface. If
bicarbonate adsorption predominates, metastable films consisting of
FeCO3 and Fe(OH) 2 will be formed, and Fe2⫹ is finally oxidized to
ferric oxide at the passive potential. Our previous studies17 have
shown that the passive film on X70 steel is mainly composed of
Fe3 O4 and ␥-Fe2 O3 layers, which is similar to that of the film on
iron. Stimming18,19 claimed that the donors in the passive film on
iron were Fe2⫹ ions, which occupied part of the octahedral and
tetrahedral sites in the passive film on pure iron. Macdonald,20 on
the other hand, proposed that the oxygen vacancies acted as donors
in the passive film. Since hydrogen increases the concentration of
donors in the passive film, the films on hydrogen-charged specimens
may have a higher concentration of Fe2⫹ ions or oxygen vacancies.
According to the point defect model 共PDM兲,28 a higher concentra-
tion of oxygen vacancies in the films should enhance the pitting
susceptibility of the passive films on X70 steel.
Theoretical Analysis of Hydrogen Effect
Distribution of hydrogen ions in the passive films.—For a mi-
croalloyed steel coupon in a Devanathan cell 共see Fig. 1兲, when the
potential on one side of the specimen is maintained in the passive
 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲 B295

Table II. The values of R s , CPE, R ct , R f , and C f for passive films on charged and uncharged X70 microalloyed steel in 0.5 M NaHCO3
¿ 0.001 M NaCl solution. The specimens were prepassivated at different potentials for 1.5 h.

CPE
iH Rs R ct
Potential 共mA/cm2兲 共⍀兲 C dI 共␮F/cm2兲 ␣ 共k⍀ cm2兲 R f 共k⍀ cm2兲 C f 共␮F/cm2兲

⫺0.1 VSCE 0 8.90 67.6 0.87 26.3 47.9 45.9

2 9.11 58.7 0.88 24.6 41.5 74.6
0.2 VSCE 0 8.63 48.2 0.91 66.4 156.9 7.8
2 8.77 37.7 0.91 63.1 78.4 29.7

potential region, a passive film will be formed on this side in an
aqueous solution. If hydrogen is constantly charged into the film
from the other side of the specimen, hydrogen would continually
diffuse from the metal to the film and it would be ionized by Reac-
tion 1 at the metal film interface. The resultant electrons will leave
the specimen through the external circuit, and the protons will dif-
fuse from the metal/film interface to the film/solution interface un-
der the force of the electric field and finally dissolve into the solu-
tion. In this situation, the concentration distribution of hydrogen in
the films is shown in Fig. 10. For uncharged specimens, the concen-
tration distribution of hydrogen ions in the film is quite different
from that in the hydrogen-bearing film 共see Fig. 10兲.
Effect of hydrogen on the diffusivity of ions and vacan-
cies.—Ingress of hydrogen into a passive film will result in a struc-
ture and/or composition change of the passive film when the con-
centration of hydrogen is high enough.8,21 It will cause lattice ex-
pansion when the concentration of hydrogen is low. This paper only
deals with the latter case. In the passive film on X70 microalloyed
steel, the force, F, on a Fen⫹ (n ⫽ 2 or 3兲, would be the sum of
electrical field force, F f , and electric attraction force, F a , between
Fen⫹ and O2⫺
F ⫽ Ff ⫹ Fa 关8兴
The electric attraction force, F a , may be simply expressed as
q Fen⫹q O2⫺
Fa ⫽ 兺K d2
关9兴
where K is a constant (9 ⫻ 10⫺9 N m2 /C2 ), d the distance between
Fen⫹ and O2⫺, q Fe2⫹ and q O2⫺ represent the charges of Fen⫹ and
O2⫺, respectively. When hydrogen ions exist in the passive film,
they might have a negative effect on the strength of the interaction
between Fen⫹ and O2⫺. When hydrogen ions enter a Fe3 O4 or
␥-Fe2 O3 unit of the film and stay at interstitial lattice sites, they
should add an additional repulsive force to Fen⫹. For the same rea-
son, there also exists an additional repulsive force to an oxygen
vacancy in the unit cell.
Several models have been developed to describe the growth of an
anodic oxide film on metals.22-28 Although different approaches
were used, certain conclusions were reached unanimously; at pas-
sive potentials, cations are injected into the film from the metal and
move to the film/solution interface mainly by an interstitial diffusion
mechanism, oxygen vacancies are created at the metal/film interface,
and then oxygen ions are injected from the solution into the film and
move to the metal/film interface by a vacancy diffusion mechanism.
In the process of cation interstitial and oxygen vacancy diffusions,
the diffusion coefficient D can be simply expressed by the Nernst-
Einstein equation29,30
D ⫽ M RT 关10兴
where M is the ion mobility constant, R is the gas constant, and T the
temperature. Due to the additional electric repulsion force formed
between H⫹ and Fen⫹ ions or oxygen vacancies, the diffusion coef-
ficient of cations or oxygen vacancies would be increased by hydro-
gen.
For a microalloyed steel coupon in a Devanathan cell, hydrogen
constantly diffuses from the metal to the film. The effect of hydro-
gen on diffusivity should be less significant at the outer layer of the
passive film than at the inner layer because the concentration of H⫹
gradually decreases along the direction of the electric field 共see Fig.
10兲. Thus, the change of diffusivity of Fen⫹ and oxygen vacancies at
the outer layer of the passive film will not be as great as that in the
inner layer. Moreover, the passive current densities of the films on
the microalloyed steel are related to the transport rate of cations and
anions. Therefore, the enhancement of oxygen vacancies and inter-
stitial Fe2⫹ transport by hydrogen might lead to a higher passive
current density of the film, which is consistent with the potentio-
static results.
Effect of hydrogen on the concentration of ions and vacan-
cies.— Effect of hydrogen on the concentration of Fe 2⫹..—For an
uncharged specimen, at steady state, Reaction 4 occurs at the metal/
film interface as mentioned above. After Fe2⫹ ions are generated at
the metal/film interface, a fraction of them enter the cation sites in
the first monolayer of the oxide closest to the metal. This diffusion
process is expressed as
Fe2⫹  M Fe2⫹ ⫹ V O.. 关11兴

Table III. Effect of hydrogen on the electronic properties of pas-

sive films on X70 steel in 0.5 M NaHCO3 ¿ 0.001 M NaCl solu-
tion. The specimens were prepassivated at 0.2 VSCE for 80 min. i H
is hydrogen charging current densities.

iH ND U fb LW
共␮A/cm2兲 共m⫺3兲 共V兲 共Å兲
0 (1.32 ⫾ 0.01) ⫻ 1027 ⫺0.35 ⫾ 0.01 8.10 ⫾ 0.01
20 (1.54 ⫾ 0.01) ⫻ 1027 ⫺0.33 ⫾ 0.01 7.53 ⫾ 0.01 Figure 10. Schematic drawing of the concentration distribution of H⫹ in the
100 (2.08 ⫾ 0.01) ⫻ 1027 ⫺0.34 ⫾ 0.01 6.48 ⫾ 0.01 films on the uncharged and charged specimens.
B296 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲

Figure 11. Schematic of hydrogen effect on 共a兲 the diffusion process and 共b兲
concentration of M Fe2⫹.
Figure 12. Schematic of hydrogen effect on 共a兲 the diffusion process and 共b兲
concentration of oxygen vacancies in the passive film.

where M Fe2⫹ represents Fe2⫹ at cation sites and V O.. the oxygen
vacancy. The concentration of Fe2⫹ at the interface is determined by
Reaction 4.
Earlier studies have shown that hydrogen enhances the anodic
dissolution of metals and alloys.31-33 For a charged microalloyed
steel coupon, hydrogen can also enhance the anodic dissolution rate
and result in an increase of the concentration of Fe2⫹ at the metal/
film interface. This should promote the forward reaction of Reaction
11, i.e. the concentration M Fe2⫹ at the metal/film interface would be
increased by hydrogen. Hence, at steady state, the concentration of
M Fe2⫹ at the metal/film interface for a hydrogen-containing speci-
men is higher than that for a hydrogen-free specimen.
When hydrogen ions exist in the passive film, they should accel-
erate the transport of M Fe2⫹, as mentioned above. Since a higher
concentration of M Fe2⫹ appears at the metal/film interface for a
hydrogen-containing specimen, an increase in the mobility of M Fe2⫹
would result in a higher flux of M Fe2⫹ in the film. Moreover,
J MFe2⫹( leave) is less than J MFe2⫹( enter) at the initial stage, as shown in
Fig. 11a, because the effect of hydrogen on diffusivity of Fe2⫹ is
more significant at the side close to the metal/film interface than at
the side close to the film/solution interface. Therefore, the concen-
tration of M Fe2⫹ in any section, such as section A in Fig. 11a would
be increased with time. When a new steady state is established, the
concentration of M Fe2⫹ in section A is higher for a hydrogen-
containing specimen than that for a hydrogen-free specimen, as
shown in Fig. 11b.
Effect of hydrogen on the concentration of oxygen vacan-
cies.—According to the P.D.M. model,28 Reaction 11 occurs at the
metal/film interface and causes the formation of oxygen vacancies.
Since hydrogen enhances Reaction 11, the concentration of oxygen
vacancies at the metal/film interface should also increase for a
hydrogen-charged specimen. At the film/solution interface, the fol-
lowing reaction occurs
section in the film, such as section B in Fig. 12a, J Vo( enter) would be
larger than J Vo( leave) because the effect of hydrogen on the transport
of oxygen vacancies is more significant at the side close to the
metal/film interface. The concentration of oxygen vacancies in sec-
tion B would increase with time before a new steady state is estab-
lished. The rate of increase of oxygen vacancy concentration in the
film will gradually reduce to zero when a new steady state is estab-
lished. Finally, the concentration of oxygen vacancies would be
higher in the hydrogen-containing film than in the hydrogen-free
film 共see Fig. 12b兲.
Effect of hydrogen on the concentration of Fe 3⫹.—During the trans-
port of Fe2⫹, the following reaction occurs in the film
⬙ 2⫹ ⫹ e
M Fe2⫹ → Fe3⫹ ⫹ V Fe 关13兴
As discussed above, this reaction is less likely to occur at the metal/
film interface. For uncharged specimens, it is assumed that Reaction
13 occurs in the film between D, the plane close to the metal/film
interface as shown in Fig. 13a, and the film/solution interface. Be-
cause the oxidation power decreases as the oxygen vacancy concen-
tration increases, the concentration of Fe3⫹ increases outwardly
from the metal/film interface, as shown in Fig. 13b. When hydrogen
is present in the passive film, as discussed above, hydrogen in-
creases the amount of the oxygen vacancies in the film. Therefore,
the tendency for oxidation of Fe2⫹ to Fe3⫹ would decrease since a
higher concentration of oxygen vacancies contributes more free
electrons, which would retard Reaction 13 in the forward direction.
The retarding effect of hydrogen on Reaction 13 decreases with
decreasing hydrogen concentration. For the same reason, the plane

V O ⫹ H2 O → O O ⫹ 2H⫹ 关12兴

••
where O o represent oxygen ions in anion sites and V O the oxygen
⫹
vacancies. A higher concentration of H at the film/solution inter-
face would retard Reaction 12 in the forward direction. Hence, the
concentration of oxygen vacancies at both interfaces may stay at a
higher level at steady state for a hydrogen-charged specimen.
After the passive film reaches the steady state, the concentration
of oxygen vacancies remains constant at any location in the passive
film, i.e., the flux of oxygen vacancies entering the film, J V O( enter) ,
equals the flux of oxygen vacancies leaving the film, J V O( leave) , as
shown in Fig. 12a. When protons exist in the passive film, they
should enhance the formation of oxygen vacancies at the metal/film
interface and accelerate their transport as discussed above, resulting Figure 13. Schematic of hydrogen effect on 共a兲 the diffusion process and 共b兲
in an increase in the flux of oxygen vacancies. Meanwhile, at any concentration of M Fe3⫹.
 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲
Figure 14. Schematics of the structures of passive films on 共a兲 an uncharged
and 共b兲 a charged X70 microalloyed steel.
where Reaction 13 starts to occur will be further away from the
metal/film interface. At the same time, Fe3⫹ migrates from the film
to the solution under an electric field. As noted above, hydrogen also
enhances the transport of Fe3⫹, resulting in a lower concentration of
ferric ions in a hydrogen-containing film than in a hydrogen-free
film.
Two factors that may cause an increase in the concentration of
ferric ions in the charged film are the flux of Fe3⫹ and the concen-
tration increase of Fe2⫹ due to the presence of hydrogen in the
passive film. The flux of Fe3⫹ is proportional to both diffusivity and
concentration of ferric ions. Although the diffusivity of ferric ions
on the left side of section C 共Fig. 13兲 is higher than on the right side,
this effect on the flux may be compensated by the lower concentra-
tion on the left side than on the right side. Therefore, the flux of
Fe3⫹ entering section C, J Fe3⫹( enter) , may not be larger than that
leaving section C, J Fe3⫹( leave) . The second factor, an increase in the
concentration of Fe2⫹ caused by hydrogen, may favor the oxidation
of Fe2⫹ to Fe3⫹ through Reaction 13. All influences would be
gradually counteracted. The concentration of Fe3⫹ in the passive
film would reach a relatively lower level when a steady state is
reached for the charged specimen, as shown in Fig. 13b.
Effect of hydrogen on the structures of passive films.—Although
the structure of the passive films on iron is still controversial, it
seems to be agreed that the structure of the film is composed of two
layers, an inner layer of Fe3 O4 and outer layer of ␥-Fe2 O3 . As
mentioned earlier, the passive film on X70 steel has a similar struc-
ture to that of the film on iron, as shown in Fig. 14a. When hydrogen
is charged into the metal substrate, the film has less Fe3⫹ and more
Fe2⫹, as we deduced before. Hence, the thickness of the inner layer
(Fe3 O4 ) would be increased due to the presence of hydrogen in the
passive film, as shown in Fig. 14b. When hydrogen is continually
charged into a metal substrate, the flux of Fe3⫹ from the passive film
to solution would be increased, i.e., the dissolution rate of the film
will be increased. Thus, the thickness of the outer layer ␥-Fe2 O3
should be decreased by hydrogen when a new steady state is estab-
lished, as shown in Fig. 14b.
At the same time, due to the high concentration of hydrogen ions
at the metal/film interface, there would be a combination of FeO
with H⫹, i.e., a FeO1⫹x H2x compound also exists at that interface. It
is generally accepted that the thickness of a passive film formed on
B297
iron and microalloyed steel in neutral or alkaline solution is less
than 5 nm.23,26,28 However, the length of a unit cell (a 0 ) for both
bulk crystalline ␥-Fe2 O3 and Fe3 O4 is about 0.84 nm. This means
that the thickness of the passive film contains less than ten unit cells.
The structure of the passive film, hence, would be significantly in-
fluenced if even one unit of FeO1⫹x H2x exists in the film.
Effect of hydrogen on the capacitance of passive films.—The
capacitance of the passive films on X70 microalloyed steel, C film ,
could be considered as the capacitances of the Fe3 O4 inner layer,
C Fe3 O4 , in series with that of the ␥-Fe2 O3 outer layer, C ␥-Fe2 O3 .
Therefore, the capacitance of the passive films can be expressed as
1 1 1
⫽ ⫹ 关14兴
C Film C Fe3 O4 C ␥-Fe2 O3
Meanwhile, the capacitance of the inner or outer layer can be simply
expressed by
␧ 0 ␧A
C⫽ 关15兴
d
where ␧ 0 is electrical permittivity, ␧ relative electrical permittivity
of the oxide, and A and d are the surface area and thickness of the
oxide layer, respectively. Assuming that the surface area of the inner
layer is equal to that of the outer layer, the capacitance of the film
could be given by
1 d1 d2
⫽ ⫹ 关16兴
C Film A␧ 0 ␧ Fe3 O4 A␧ 0 ␧ Fe2 O3
where d 1 and d 2 are the thickness of inner Fe3 O4 and outer ␥-Fe2 O3
layer, respectively. Since the dielectric constants34,35 of Fe3 O4 and
␥-Fe2 O3 are 20 and 10, respectively, the capacitance of the film can
be simply expressed as
20A␧ 0
C Film ⫽ 关17兴
d 1 ⫹ 2d 2
As noted above, the thickness of the ␥-Fe2 O3 outer layer and the
total passive film would be decreased due to the presence of hydro-
gen in the passive film. Hence, the capacitance of passive films
would be increased by hydrogen.
Conclusions
At the range of the passive potential, hydrogen retards the pas-
sive film formation on X70 steel and decreases the film stability.
Hydrogen also decreases the resistance of charge transfer and ion
diffusion, and increases the capacitance of the film.
Hydrogen increases the capacitance and donor density, and re-
sults in a more negative flatband potential and thinner space-charge
layer in the passive film on X70 steel. The influence of hydrogen on
the electronic property becomes more noticeable with the increase in
the hydrogen charging current densities.
A new explanation was proposed for the effects of hydrogen on
the passive films on X70 microalloyed steel. According to this new
explanation, hydrogen enhances the transport of interstitial cations
and anion vacancies in the passive film, resulting in increase in the
concentrations of ferrous ions and oxygen vacancies in the film; this
therefore leads to a deterioration of the film structure.
Acknowledgments
This project was supported by a Strategic Project grant of Natu-
ral Sciences and Engineering Research Council of Canada, Syn-
crude Canada, Ltd., Dow, IPSCO, and NOVA.
University of Alberta assisted in meeting the publication costs of this
article.
B298 Journal of The Electrochemical Society, 151 共6兲 B291-B298 共2004兲
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