Corrosion Science 52 (2010) 2758–2765

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Evaluation of hydrogen entry into high strength steel under atmospheric corrosion
Eiji Akiyama *, Katsuhiro Matsukado 1, Maoqiu Wang 2, Kaneaki Tsuzaki
Structural Metals Center, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan

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

Article history: Hydrogen entry into high strength steels by atmospheric corrosion has been investigated to evaluate
Received 11 September 2009 their susceptibility to hydrogen embrittlement. High strength steels were corroded by dry/wet cyclic cor-
Accepted 13 November 2009 rosion after NaCl deposition. The maximum diffusible hydrogen concentration around the surface was
Available online 27 April 2010
successfully obtained by means of thermal desorption analysis after keeping the specimens at high
humidity to reproduce enhanced hydrogen entry influenced by the rust layer and to homogenize the
Keywords: hydrogen distribution. Despite decrease in corrosion rate, hydrogen content in specimens did not
A. Steel
decrease. Decrease of pH in inner rust layer is responsible for the enhanced hydrogen entry into steel.
B. Thermal desorption spectroscopy, cyclic
corrosion test
Ó 2010 Elsevier Ltd. All rights reserved.
C. Atmospheric corrosion, hydrogen
embrittlement, delayed fracture

1. Introduction
Tailoring new high strength steels is expected in the field of
construction, civil engineering, auto engineering, etc., to scale up
constructions, to reduce costs for constructions, to save resources,
and to reduce the weight of vehicles for low fuel consumption.
However, as it is widely known, the susceptibility of high strength
steel to hydrogen embrittlement is increased with its strength le-
vel [1], and this restricts the practical use of high strength steels
whose tensile strength exceeds 1100 MPa [2]. For safe and reliable
usage of high strength steels, establishment of an evaluation meth-
od for hydrogen embrittlement property is strongly expected. Be-
cause of recent progress of thermal desorption analysis (TDA) of
hydrogen, critical diffusible hydrogen concentration for hydrogen
embrittlement fracture, HC, has become to be recognized as one
of the parameters to evaluate the susceptibility of high strength
steels to hydrogen embrittlement quantitatively [3,4]. This is be-
cause diffusible hydrogen which can evolve out from specimens
at ambient temperature is considered to be responsible for hydro-
gen embrittlement of high strength steels [5].
HC has been obtained by means of constant load test (CLT) of cir-
cumferentially notched round bar specimens pre-charged with
hydrogen [3,4,6–8]. Slow strain rate test (SSRT) of hydrogen-pre-
charged specimens has been also applied to obtain fracture stress
in wide range of hydrogen content by the present authors [9–13].
* Corresponding author. Tel.: +81 29 859 2122; fax: +81 29 859 2101.
E-mail address: AKIYAMA.Eiji@nims.go.jp (E. Akiyama).
1
Now at Kobe Steel, Ltd., 15 Kinugaoka, Moka, Tochigi 321-4367, Japan.
2
On leave from Institute for Structural Materials, Central Iron and Steel Research
Institute, No. 76 XueYuanNanLu, Haidian District, Beijing 100081, PR China.
From the obtained relation between hydrogen content and fracture
stress, HC can be estimated at any applied stress. As well as the
importance of the influence of hydrogen content in steels on their
mechanical property, the amount of hydrogen entering into steel
at service environment, HE, is also essential because the balance be-
tween HC and HE is considered to be determining the occurrence of
hydrogen embrittlement fracture. Researchers have investigated HE
of high strength steels under atmospheric corrosion environment
by measuring hydrogen content in specimens after outdoor expo-
sure [6,14–16] and cyclic corrosion test (CCT) [6,14,17], and by
measuring accumulated hydrogen gas in an atmospherically ex-
posed hollow bolt by means of a gas sensor [18]. The obtained HE
is useful to evaluate hydrogen uptake behaviour of steels under
atmospheric corrosion. However, quantitative measurement of HE
which can be compared with HC is not easy because the activity
of hydrogen absorption/desorption changes with the change in
environmental factors, such as humidity and temperature, and
the diffusible hydrogen concentration is not stable.
In order to observe hydrogen intrusion behaviour, electrochem-
ical hydrogen permeation test [19,20] has been utilized. Omura
et al. have reported that hydrogen entry strongly depended upon
the time in a day, seasons and exposure locations [21,22]. The elec-
trochemical hydrogen permeation test is an useful technique
which allows us to observe time-dependent hydrogen entry behav-
iour qualitatively. By using this technique it is also possible to esti-
mate the surface diffusible hydrogen concentration, though
quantitative measurement of surface hydrogen concentration is
not straightforward when the surface hydrogen concentration is
changing with time.
Fig. 1 shows a schematic drawing of assumed change of hydro-
gen distribution in steel under atmospheric corrosion. When

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.11.046
 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765 2759

Table 2
Heat treatment conditions and tensile strengths of the steels used in this study.

Sign Quenching Tempering Tensile strength/MPa

A13 880 °C, 60 min/water 290 °C, 90 min/water 1339
B13 860 °C, 60 min/oil 460 °C, 110 min/water 1286

in a project of Japanese Society of Steel Construction started in

2005. The chemical compositions of the steels, A13 and B13 are
presented in Table. 1. Heat treatment conditions and tensile
strengths of the steels are shown in Table. 2. The body of the bolts
of A13 and B13 with a diameter of 22 mm was sliced and coin-
shaped specimens with a diameter of 20 mm and a thickness of
5 mm were machined. Both surfaces of the specimens were pol-
ished with Emery paper up to #400, and the side of the specimens
Fig. 1. Schematic drawing of the change in the in-depth profile of hydrogen
was coated.
concentration in a high strength steel under atmospheric corrosion.
2.2. Cyclic corrosion test and hydrogen homogenization procedure

hydrogen entry proceeds due to corrosion, the surface hydrogen

Cyclic corrosion test (CCT) was carried out with dry/wet cycles
concentration becomes high and when the hydrogen entry is sup-
consisting of 50%RH (relative humidity) and 98%RH at 30 °C as
pressed the surface hydrogen concentration seem to be decreased
shown in Fig. 2. Before the CCT NaCl was deposited on both spec-
than that in the interior if the rate of hydrogen release is controlled
imen surfaces by applying NaCl solution and drying. The NaCl con-
mainly by diffusion. Because of the changing hydrogen uptake and
centration deposited on the surfaces was varied from 0.00143 to
release behaviour, homogeneous distribution of hydrogen cannot
1.43 mol m2. The crack initiation of hydrogen embrittlement frac-
be expected. Thermal desorption analysis (TDA) is useful to mea-
ture of construction bolts occurs in the vicinity of the surface of
sure the average hydrogen concentration quantitatively. However,
thread groove [23], and it is required to obtain the hydrogen con-
neither TDA nor any other currently used techniques can measure
centration around the surface. In order to obtain the surface hydro-
the distribution of hydrogen. On top of that, the average hydrogen
gen concentration, rusted specimens were kept in a constant
content is changing with the change of the environment. Thus,
temperature and humidity chamber at 60–98%RH and 30 °C for
measurement of diffusible hydrogen concentration under atmo-
24 h after CCT, and then hydrogen content in the specimens were
spheric corrosion is not easy.
measured by means of thermal desorption analysis (TDA) (route
In the case of hydrogen embrittlement fracture of high strength
b in Fig. 2).
bolts with a thread, crack initiation occurs in the vicinity of the sur-
The purpose of this procedure is to keep hydrogen entry caused
face of thread groove where stress is concentrated [23]. Therefore,
by corrosion long enough to homogenize diffusible hydrogen con-
for evaluation of hydrogen embrittlement property of high
centration throughout the specimen as schematically shown in
strength steels for fasteners, the most important hydrogen concen-
Fig. 3. Here, it is assumed that the surface concentration of hydro-
tration is that in the vicinity of the surface. In this study, a simple
gen is determined by corrosion influenced by environmental fac-
technique as will be explained in the experimental section has
tors such as humidity, temperature, concentration of chloride
been proposed in order to evaluate the surface concentration of
ions and the property of the rust layer formed on the surface. It
hydrogen absorbed under atmospheric corrosion environment,
is also assumed that the hydrogen concentration level in the inte-
and the validity of the technique has been examined. Furthermore,
rior of the specimen increases with time by diffusion of hydrogen
the influences of salt concentration, corrosion rate and pH value of
and eventually the hydrogen concentration will become homoge-
inner rust layer have been investigated to know the effect of atmo-
neous at the level of the surface hydrogen concentration. If the
spheric corrosion on hydrogen entry.
hydrogen homogenization is achieved, the surface hydrogen con-
centration can be equal to the average hydrogen concentration.
2. Experimental procedure

2.1. Materials

The high strength steels used in this study are high strength bolt
steels of boron baring steel (A13) and AISI 4135 steel (B13) which
were used in a joint research project between Building Research
Institute, The Japan Iron and Steel Federation and National Insti-
tute for Materials Science (1999–2005). In the project, fastened
bolts made of the high strength steels were exposed in exposure
sites and probability of hydrogen embrittlement fracture was
examined. After the project the exposure test of bolts is continued

Table 1
Chemical compositions (mass%) of the steels used in this study.

C Si Mn P S Cr Mo B
A13 0.20 0.076 1.01 0.013 0.014 0.16 0.011 0.0015 Fig. 2. Dry/wet cyclic corrosion test condition for NaCl-deposited specimens.
B13 0.34 0.18 0.76 0.015 0.015 1.01 0.17 0.0001 Thermal desorption analysis (TDA) was carried out with/without hydrogen
homogenization process after CCT.
2760 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765

Fig. 3. Schematic drawing of a procedure to homogenize hydrogen distribution in a corroded sample. After the hydrogen homogenization, the surface hydrogen
concentration is expected to be obtained by measurement of average hydrogen concentration by means of thermal desorption analysis (TDA).

Therefore, the surface hydrogen concentration can be obtained by

measuring the average hydrogen concentration by means of TDA.
In this study, hydrogen homogenization process was applied for
24 h before TDA because the homogenization is thought to be
achieved in a sample with a thickness of 5 mm by a calculation
using a diffusion coefficient of hydrogen of 4.5  1011 and
3.9  1011 m2 s1 for A13 and B13, respectively, obtained by elec-
trochemical hydrogen permeation test [24].

2.3. Thermal desorption analysis of hydrogen

After CCT, with and without hydrogen homogenization, route b

and a in Fig. 2, respectively, hydrogen content in a rusted specimen
was measured by means of thermal desorption analysis (TDA)
using a ‘Thermal Desorption Spectroscopy System for Hydrogen
Analysis’ (R-DEC Co. Ltd.) equipped with quadrupole mass spec-
trometer. Heating rate was 100 °C/h. The hydrogen desorbed from
room temperature to 327 °C was regarded as diffusible hydrogen.
Prior to TDA, rust layer formed on the surface was removed by
means of sand blast to avoid influence of hydroxyl group and
adsorbed water in the rust on hydrogen measurement. Liquid
nitrogen was used to preserve the specimens to avoid hydrogen
release after CCT until TDA was carried out.

2.4. Weight loss and pH of inner rust layer

pH of rust layer was measured by using a W/WO3 electrode

[25,26] which was prepared by an immersion of tungsten wire
with a diameter of 0.3 mm in a 10 vol.% HNO3 solution for about
12 h at RT. 0.1 M NaCl solution was put on the rust layer and the
open circuit potential of the W/WO3 electrode vs Ag/AgCl reference
electrode in the solution droplet was recorded. Prior to the pH
measurement, W/WO3 electrode was calibrated by using standard
pH solutions. The rust layer was scratched off by using a knife and
the pH measurement was carried out in order to measure the pH
value of inner rust layer.
The corrosion loss was measured after removing rust layer by
immersion of the specimens in a 10% ammonium citrate solution
at 80 °C after removal of most of rust layer by using metal wire
brush.
Fig. 4. Change in the average hydrogen concentration (Haverage
E ) and the hydrogen
concentration measured after homogenizing hydrogen distribution (Hhomogenized
E ) with
dry/wet cycle number. The concentration of deposited NaCl was 0.143 mol m2.
3. Results and discussion
3.1. Hydrogen entry by cyclic corrosion test and effect of hydrogen
homogenization
The change in the diffusible hydrogen concentration in A13 and
B13 steels measured after CCT with deposition of NaCl of
 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765
Fig. 5. Dependence of Haverage
E and Hhomogenized
E on the concentration of NaCl
deposited on a sample for an accelerated atmospheric corrosion test.
0.143 mol m2 on the sample surface is shown in Fig. 4. The hydro-
gen concentration measured by means of TDA after the CCT (route
a in Fig. 2) is represented as Haverage
E because the hydrogen concen-
tration is an average value normalized by the weight of the whole
specimen. The hydrogen concentration measured after hydrogen
homogenization at 90%RH and 30 °C for 24 h (route b in Fig. 2) is
represented as Hhomogenized
E . Though the data points are scattering,
the hydrogen concentrations in both steels tend to increase with
increase in the number of dry/wet cycle initially, and after a while
the hydrogen concentration becomes roughly independent on the
cycle number. The increase of hydrogen concentration for A13 is
faster than that of B13, but the levels of hydrogen concentration
for both steels after 21 cycles of CCT are similar. The roughly con-
stant hydrogen concentration suggests that hydrogen entry does
not change so much with increase of CCT cycle number.
Hhomogenized
E generally show higher value than Haverage
E . This fact sug-
gests that the hydrogen distribution is heterogeneous during CCT
and that Hhomogenized
E reflects the surface hydrogen concentration
better than Haverage
E .
Fig. 5 shows the influence of the concentration of NaCl-depos-
ited on the sample surface before the dry/wet CCT. The NaCl con-
centration was varied from 0.00143 to 1.43 mol m2. Both Haverage E
and Hhomogenized
E with hydrogen homogenization at 90%RH and
30 °C for 24 h are plotted. Without the hydrogen homogenization
process, Haverage
E for 0.143 and 1.43 mol m2 NaCl deposition are al-
most the same, and they are higher than that for the lower NaCl
concentrations. Haverage
E for 0.0143 mol m2 NaCl deposition is
slightly higher than that for 0.00143 mol m2 NaCl. Although
Hhomogenized
E for both A13 and B13 for 0.143 mol m2 NaCl deposi-
2761
Fig. 6. Dependence of Hhomogenized
E on the relative humidity of hydrogen homoge-
nization process for (a) A13 and (b) B13 steels corroded by 21 cycles of dry/wet
cyclic corrosion test with a deposition of 0.143 mol m2 of NaCl on the specimen
surfaces. Open triangle shows Haverage
E without hydrogen homogenization process.
tion shows scattering, the value of Hhomogenized
E tends to be higher
than that for the other salt concentrations and to be higher than
Haverage
E . Thus, chloride concentration influences hydrogen intrusion
behaviour.
The effect of relative humidity of hydrogen homogenization
process on the resulted value of Hhomogenized
E is shown in Fig. 6. For
comparison, Haverage
E is also plotted. Specimens with 0.143 mol m2
NaCl after 21 cycles of CCT which showed high Hhomogenized
E in the
previous figure were used for this comparison. Hydrogen homoge-
nization was done at 60–98%RH and 30 °C. Hhomogenized
E of A13 mea-
sured after hydrogen homogenization at 60%RH and 80%RH
showed slightly lower value than Haverage E . This can be interpreted
in terms of hydrogen release during the hydrogen homogenization
process at the relatively low humidity. At higher relative humidity
of hydrogen homogenization, A13 showed obviously higher value.
Hhomogenized
E of B13 also has an inclination to show higher value at
higher humidity. The results suggest that hydrogen entry into
specimens rusted by the simulated atmospheric corrosion condi-
tion is enhanced at higher humidity. Therefore, in order to repro-
duce active hydrogen entry into steel covered with rust layer and
to evaluate possible maximum HE for risk management of hydro-
gen embrittlement fracture, application of higher humidity is suit-
able. The inflection point of Hhomogenized
E seems to be at around
90%RH. The wide scattering of Hhomogenized
E with hydrogen homoge-
nization at 90%RH is probably because the hydrogen entry behav-
iour changes abruptly at around this relative humidity.
3.2. Corrosion behaviour under cyclic corrosion test
Weight loss and estimated change in corrosion rate as a func-
tion of dry/wet cycle number are presented in Fig. 7. A13 and
2762 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765

Fig. 8. A model for dry/wet cyclic corrosion test. The surface hydrogen concentra-
tion is assumed 1 and 0 for wet and dry stages, respectively.

Fig. 7. The change in weight loss and corrosion rate of (a) A13 and (b) B13 steels
with dry/wet CCT cycle number. NaCl deposition concentration was 0.143 mol m2.
The dotted line is approximated curve of weight loss.

B13 steels show similar corrosion behaviour under the CCT condi-
tion. The approximated curve of weight loss was calculated by
assuming that the weight loss follows the exponential equation;

WL ¼ AN B ð1Þ
Here, WL is the weight loss, N cycle number, and A and B con-
stants. Corrosion rate, d(WL)/dN, is calculated by using the approx-
imated weight loss expressed by Eq. (1). The resulted weight loss
and corrosion rate, CR, for A13 and B13 are expressed as follows

WLA13 =mg cm2 ¼ 4:1N0:61 ð2Þ

2 1 0:39
CRA13 =mg cm cycle ¼ 2:5N ð3Þ
WLB13 =mg cm2 ¼ 6:5N0:48 ð4Þ
2 1 0:52
CRB13 =mg cm cycle ¼ 3:1N ð5Þ
Corrosion rate of the steels decreases with cycle number. This is Fig. 9. The calculated distribution of hydrogen concentration in a steel sample with
probably because effective chloride concentration in the formed a thickness of 5 mm after (a) wet stage and (b) after dry stage.
rust layer is decreased with growth of the rust layer. Despite the
decrease of corrosion rate, both Haverage
E and Hhomogenized
E do not show
decrease with cycle number as shown in Fig. 4. This fact suggests dry stages of CCT are 3 and 5 h, respectively. Though the change of
that the corrosion rate is not directly determining the activity of humidity between wet and dry stages takes about quarter of an
hydrogen entry into steels. hour in the actual experimental condition, the change of humidity
and corresponding change in the surface hydrogen concentration is
3.3. Model calculation of hydrogen entry behaviour assumed to be clear-cut as shown in Fig. 8 for the calculation. The
thickness of a specimen is 5 mm and its surface area is infinite. The
As has been shown in Fig. 4, hydrogen concentration increases diffusion coefficient of hydrogen in the steels are regarded as
with cycle number of CCT initially. Mathematical simulation of 4.3  1011 m2 s1 which is the average of diffusion coefficients
the change of hydrogen distribution and increase in hydrogen con- of A13 and B13 obtained by electrochemical hydrogen permeation
centration with CCT cycle has been carried out. The assumed tests [24]. In-depth hydrogen distribution was calculated by differ-
change in the surface hydrogen concentration is shown in Fig. 8. ence method. The calculated in-depth hydrogen distributions after
At wet and dry stages of CCT, the surface concentration of hydro- wet and dry stages are shown in Fig. 9. Hydrogen diffuses into inte-
gen is assumed 1 and 0 (arbitrary unit), respectively, for simplifica- rior of the specimen gradually with increase of CCT cycle number.
tion. Similarly to the experimental condition, durations of wet and After 9 cycles of CCT the hydrogen distribution becomes to repeat
 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765 2763

Fig. 10. The change in average hydrogen concentration after wet and dry stages.
The curve between the data points is hand-written.

Fig. 12. pH measured by means of W/WO3 electrode for 0.1 M NaCl droplet on the
rust layers formed on (a) A13 and (b) B13 specimens after 27 cycles of CCT. Position
1 is the top rust layer. With increase of the position number the depth is increased.
Position 4 is the most inner layer of rust above the substrate metal.

Fig. 11. The ratio of Haverage measured after wet stage of CCT to Hhomogenized for A13,
E E
3.4. Influences of corrosion rate and pH of inner rust layer
B13 and model calculation. The concentration of deposited NaCl for CCT experi-
ments was 0.143 mol m2.
In order to investigate the influence of the property of rust layer
on hydrogen entry, pH of the inner rust layer was evaluated by
measuring pH of a droplet of 0.1 M NaCl solution put on a rust
the same change between wet and dry stages. The hydrogen con-
layer by using a W/WO3 electrode. The rust layer was scratched
centration calculated for the center of the specimen is about 0.4.
step by step and pH measurement was carried out. Fig. 12 presents
The average hydrogen concentration, Haverage E is calculated by
the measured pH value for rust layer formed by 27 cycles of CCT
using the obtained hydrogen distribution. The change in Haverage E
with NaCl deposition of 0.143 mol m2. Although the measured
with CCT cycle number is plotted in Fig. 10. The calculated
pH is indirect and qualitative value, it is noteworthy that the pH
Haverage
E gradually increases with CCT cycle number showing oscilla-
value is decreased with depth, and the pH of inner rust layer is
tion corresponding to the change of the surface hydrogen concen-
obviously lower than that of outer layer. The decrease in pH is con-
tration between wet and dry stages. After several cycles the change
sidered to be caused by hydrolysis reactions of ferrous ions as fol-
of Haverage
E repeats the same oscillation where Haverage
E after wet stage
lows [27];
is 0.51 and that after dry stage is 0.27.
In Fig. 11 the ratios of Haverage
E to Hhomogenized
E for the experimental
data and the calculation are compared. Hhomogenized
E for the calcula- Fe2þ þ 2H2 O ! FeðOHÞ2 þ 2Hþ ð6Þ
tion is equal to the surface concentration which is defined as 1. 2þ þ
2Fe þ 1=2O2 þ 3H2 O ! 2FeOOH þ 4H ð7Þ
Both ratios of Haverage
E to Hhomogenized
E for experimental data and for
the calculation reach roughly 0.5 after a while. This agreement sug- The lowering of pH of rust layer should increase the efficiency of
gests that the hydrogen homogenization process applied before hydrogen entry [28].
TDA is effective to obtain the surface concentration of hydrogen Fig. 13 shows the pH measured for inner rust layer formed by
quantitatively as expected. The slower increase of the ratio for 15, 21 and 17 cycles of CCT with NaCl deposition of 0.143 mol m2.
the experimental data is probably because the actual surface The position of the measurement is on the most inner layer of rust
hydrogen concentration is increasing with CCT cycle. Presumably above substrate metal, which corresponds to position 4 in Fig. 12.
the increase of coverage of rust layer and the growth of rust The change of hydrogen concentration measured after hydrogen
layer are influencing on the increase of the surface hydrogen homogenization, Hhomogenized
E , which has been shown in Fig. 4 and
concentration. the change in corrosion rate in Fig. 7 are also plotted. Note that
2764 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765
Fig. 13. The change in Hhomogenized
E , corrosion rate and pH of inner rust layer of (a)
A13 and (b) B13 steels with the cycle number of dry/wet CCT. The concentration of
deposited NaCl was 0.143 mol m2.
the specimens used for hydrogen concentration measurement are
different from the specimens used for weight loss and pH measure-
ments. The pH values measured for the inner rust layer for both
steels are obviously low. The pH for B13 decreases from 15th to
21st cycle, while the pH for A13 shows no clear tendency. The
pH change of B13 may have a correlation with the increase of
Hhomogenized . On the other hand, the increase in Hhomogenized of B13
E E
is faster than that of A13, and Hhomogenized does not change obvi-
E
ously from 15 to 21 cycles where the pH was measured. This
may be related with that the change of pH for A13 has no clear
tendency.
The corrosion rate decreases with CCT cycle number. This
means that the cathodic reaction taking place as the counter of
anodic dissolution is also decreasing. Nevertheless, the diffusible
hydrogen concentration does not show obvious decrease. This im-
plies that the efficiency of hydrogen reduction reaction is not de-
creased with the decrease of corrosion rate. The ratio of
hydrogen reduction reaction to the total cathodic reaction may
be increased by the decrease of pH in the inner rust layer. Thus,
the property of rust layer such as pH has an important role to
determine hydrogen entry behaviour.
The relation between initially deposited NaCl concentration on
specimens before dry/wet CCT and Hhomogenized
E (Fig. 5), corrosion
rate (Fig. 13) and the pH value of inner rust layer measured for
21st cycle are shown in Fig. 14. At 0.143 mol m2 of NaCl deposi-
tion, Hhomogenized
E of both A13 and B13 show the maximum value
though the corrosion rates at that NaCl concentration is almost
the same as that at 1.43 mol m2. The pH of inner rust layer for
0.143 mol m2 NaCl is apparently lower than that for 1.43 mol m2.
Fig. 14. The dependence of Hhomogenized , corrosion rate and pH of the inner rust layer
E
of (a) A13 and (B) B13 steels on the concentration of deposited NaCl. The Hhomogenized
E
and pH were measured after 21 cycles of CCT. The corrosion rate is for 21st cycle
estimated from approximated curve shown in Fig. 13.
This lower pH of inner rust layer for 0.143 mol m2 NaCl is consid-
ered to be responsible for the higher hydrogen entry. The highest
Hhomogenized
E at 0.143 mol m2 NaCl for both steels is attributed to
the low pH of inner rust layer and the high corrosion rate. Chloride
concentration affects corrosion rate and pH of inner rust layer, and
consequently it influences the hydrogen entry behaviour.
4. Conclusions
Evaluation of diffusible hydrogen concentration near the sur-
face of specimens of high strength steels corroded by simulated
atmospheric corrosion has been intended by applying hydrogen
homogenization process before hydrogen measurement by means
of thermal desorption analysis (TDA). The conclusions can be sum-
marized as follows:
(1) The surface concentration of diffusible hydrogen has been
successfully estimated by means of TDA after hydrogen
homogenization process for specimens corroded by dry/
wet cycles with NaCl deposition.
(2) Higher humidity for hydrogen homogenization process
results in higher diffusible hydrogen concentration.
(3) Hydrogen entry is influenced by humidity, chloride concen-
tration, corrosion rate and pH of inner rust layer. Higher cor-
rosion rate and lower pH of inner rust layer which are
influenced by chloride concentration results in enhanced
hydrogen entry into steels.
 E. Akiyama et al. / Corrosion Science 52 (2010) 2758–2765
Acknowledgements
The authors thank Mr. T. Tsuchida, Ms. Y. Hirota and R. Araki for
help in TDA and for their assistance of experiments. The authors
also thank Dr. T. Takahashi and Dr. S. Sakashita for profitable
discussions.
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