Electrochimica Acta 85 (2012) 283294

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A novel observation of the interaction between the macroelastic stress and
electrochemical corrosion of low carbon steel in 3.5 wt% NaCl solution
R.K. Ren, S. Zhang, X.L. Pang, K.W. Gao

Department of Materials Physics and Chemistry, University of Science and Technology, Beijing 100083, China
a r t i c l e i n f o
Article history:
Received 25 June 2012
Received in revised form20 August 2012
Accepted 20 August 2012
Available online 28 August 2012
Keywords:
Mechanochemical effect
Microplastic deformation
Surface energy
Electrochemical tests
Acoustic emission
a b s t r a c t
This paper focuses on the interaction of macroelastic stress and electrochemical corrosion of low carbon
steel in 3.5 wt% NaCl solution. The electrochemical impedance spectra (EIS), corrosion current density
and open circuit potential (OCP) tests were used to represent the electrochemical behavior of low carbon
steel. The microplastic deformation was studied through acoustic emission (AE) techniques and sur-
face morphology observation. The results indicated that there was non-linear relationship between the
applied stress and electrochemical corrosion of low carbon steel in 3.5 wt% NaCl solution. At the begin-
ning of macroelastic deformation, the applied mechanical energy would activate the metal surface, so
the corrosive solution would more easily to cover the metal surface and become thin liquid lm, then
accelerate the electrochemical corrosion process. When the gradually increased stress came to a critical
value, the extra mechanical energy would not only affect the surface corrosion behavior of samples, but
also enhance the microplastic deformation at some local regions of metal surface even the applied stress
was far below the yield strength. Usually these two processes competed with each other. The dominated
process at the beginning of elastic deformation is stress accelerating corrosion, and when exceeding the
critical stress, the applied energy would induce microplastic deformation.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Structural materials used in marine atmosphere usually endure
mechanical and electrochemical attacks. Interaction of mechan-
ical and electrochemical effects enhances surface reactions on
metal, resulting in accelerated failure of structural components
[1]. In most cases, mechanical and electrochemical effects inter-
act and accelerate each other concurrently, leading to a dramatic
increase in corrosion rate. This synergistic effect can be dened as
mechanochemical effect (MCE) [2]. Many previous studies focus
on failure of structural components [35], such as stress corrosion
cracking (SCC), corrosion fatigue and hydrogen induced crack-
ing (HIC). On the other hand, most investigation limits to plastic
deformed metal [6,7]. Up to now, less information concerning the
mechanism of the elastic stress interacting with electrochemical
corrosion is available in the literature.
Some researchers [3,810] reported that the mechano-
electrochemical dissolution occurred only in the plastic region;
the stress did not affect the dissolution in elastic deformation.
Guo et al. [11] found that in 0.1M Na
2
SO
4
solution, the impinge-
ment erosion of the sand did not alter the corrosion behavior

Corresponding author. Tel.: +86 10 62334909; fax: +86 10 62334909.

E-mail address: kwgao@mater.ustb.edu.cn (K.W. Gao).
of carbon steel signicantly because the mass transfer step was
not the rate-determined step and the corrosion product was not
protective. But more workers held the opposite points. Du et al.
[12] employed electrochemical noise (EN) and acoustic emission
(AE) techniques and found the corrosion behavior of 304 stain-
less steel would be changed in 1.5mol/L H
2
SO
4
+0.5mol/L NaCl
under slow strain rate test (SSRT) condition, pitting corrosion,
crack propagation and general corrosion would appeared succes-
sively. Li and Chen [13] reported that an elastic stress of 308MPa
which was close to the yield strength, performed on 1420 AlLi
alloy caused denser and smaller pits in 3.5% NaCl. Some people
researched on the mechanochemical effect (MCE) through electro-
chemical techniques. Despic et al. [14] found the elastic stress only
affected cathodic hydrogen evolution reaction and led to a rise of
corrosion potential with 0.8mV in H
2
SO
4
solution per 1000MPa
external stress. H.H. Huang [15] showed the polarization resis-
tance R
p
of EIS measurements of titanium in NaF solution, which
was inversely proportional to the corrosion rate, decreased on
increasing the NaF concentration and the elastic strain. Gutmans
theory [2] concerning mechanochemical effect (MCE) and chemo-
mechanical effect (CME) was proven by many workers [1618].
They insisted there was linear relationship between external stress
and corrosion potential.
Although the problem caused by the interaction of stress and
electrochemical corrosionis very serious, the mechanismis still not
0013-4686/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.08.079
284 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
Table 1
Nominal composition of the tested steels (mass fraction, wt%).
Steel no. C Si Mn S Cu Cr Ni Nb P RE Fe
Lowcarbon bainitic steel 0.081 0.35 1.12 0.0083 0.38 0.52 0.31 0.0037 0.008 Balance
Low carbon ferritic steel 0.0055 0.16 0.79 0.054 Balance
thoroughly understood. Some researchers worked on the inuence
of stress on surface and bulk structure of metal. Kiejna and Pogosov
[19] modied the jelliummodel and derived surface energy, stress
and work function of elastically deformed metal. Ciuplys [20]
thought during the deformation process, the arrangement and the
density of dislocations varied at moving away fromthe surface into
depth of the metal. Gutman [21] pointed out that an extra disloca-
tion ux would appear in the surface layer while anodic dissolution
presented at the surface and resulted in a degradation of resistance
in the surface layer to the plastic deformation. All of these could
help us to study the interaction and synergismbetween stress and
electrochemical corrosion in an active dissolution system.
The primary aim of the present investigation is to study the
inuence of tensile stress on electrochemical effect during macroe-
lastic deformation process of low carbon steel. The mechanism of
mechano-chemical interaction is discussed.
2. Experimental procedures
2.1. Material
In this research, two kinds of low carbon steels with different
microstructure were tested. The chemical compositions of these
steels are listed in Table 1.
Samples for metallographic observations were preparedby con-
ventional grinding and polishing techniques, and then etched with
3% nital solution. Fig. 1 exhibits the different microstructure of the
samples along the hot-rolled direction. The microstructure of the
ferritic steel is polygonal ferrite (PF). While in the bainitic steel,
the grain is ner and the predominant microstructures are lath
bainite, granular bainite, a small amount of acicular ferrite and
quasi-polygonal ferrite.
Themechanical properties wereevaluatedthroughuniaxial ten-
siletests andtheresults exhibitedinTable2. Theferritic steel shows
lower yieldandtensile strength, the yield-strengthratiois 0.56. The
ner grain and the bainitic microstructure led to higher yield and
tensile strength, the higher yield-strength ratio is 0.84.
In order to investigate the interaction of mechanical and elec-
trochemical effect duringthemacroelastic deformation, static loads
and dynamic tensile tests were adopted to exert the tensile defor-
mation respectively. In the rst way, the sample was loaded by
a constant loading machine at 30%, 50%, 70% or 90% of its yield
strength (i.e., 0.3o
s
, 0.5o
s
, 0.7o
s
or 0.9o
s
). In the second way, slow
strain rate test (SSRT) was performed at a strain rate of 10
4
s
1
.
The maximumload was belowthe yield strength to ensure that the
macro-deformation was in an elastic region.
2.2. Electrochemical measurement system
The electrochemical measurement was carried out in a 3.5wt%
NaCl aqueous solution using the sample shown in Fig. 2. The
Table 2
Mechanical properties of the tested steels (os the yield stress, o
b
the tensile
stress, elongation to failure).
Steel no. os (MPa) o
b
(MPa) (%) os/o
b
Lowcarbon ferritic steel 173 307 43 0.56
Lowcarbon bainitic steel 906 1083 8 0.84
specimen was ground by emery paper to 1200-grit, and washed
with ethanol. The working surface of the specimen was exposed to
the NaCl solution; the other parts were covered by silicone rubber.
All the measurements were performed at room temperature by
means of CORRTEST CS350 electrochemical workstation using a
saturated calomel electrode (SCE) with a Luggin capillary as the
reference electrode and graphite as the counter electrode. The
electrochemical impedance spectra (EIS) measurements were
carried out to evaluate the anti-corrosion performance of the
matrix. The sinusoidal potential was close to open circuit potential,
amplitude 5mV, and frequency ranged from10
5
Hz to 10
2
Hz.
2.3. Surface energy tests
Throughthecritical surfacetensiontheory, thecontact anglecan
qualitatively characterize the surface energy of metals. Ordinarily,
the higher the surface energy of a metal is, the easier it can be
wetted by liquid, so the contact angle between the metal surface
Fig. 1. Metallographic images of samples: (a) low carbon ferritic steel and (b) low
carbon bainitic steel.
R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294 285
Fig. 2. Schematic of the specimen for electrochemical measurement.
and the solution is smaller. The contact angle measurements were
performed on Dataphysics OCA15 with 10l 3.5wt% NaCl drop, the
data was analyzed and simulated through computer automatically.
The specimen used here was shown in Fig. 3.
2.4. Acoustic emission (AE) tests
Acoustic emission (AE) has been proved to be an appropriate
method to research the deformation mechanisms in metals during
different deformation modes, since AE originates from transient
elastic waves generated within the material as a result of sud-
den localized irreversible structure changes. A threshold of 35dB
was maintained throughout the experimental study. A simulated
specimen was employed to verify that the background signals
which came from the machine or surrounding were removed in
the results. Because the probe of the sensor can not work properly
in solution, the signals were collected simultaneously during the
SSRT of the lowcarbon bainitic steel in the air.
2.5. Surface morphology observation after anodic polarization
A ferritic sample was ground by emery paper to 1200-grit, and
washed with ethanol. The sample with the applied stress of 0.5o
s
was potentiostatically polarized at +200mV above the open circuit
potential in 3.5wt% NaCl solution. After the potentiostatic anodic
polarization, the surface morphology was observed by SEM.
2.6. Grain boundary misorientation and CSL analyses
The microstructure especially the grain boundary misorienta-
tion and coincident site lattice (CSL) were analyzed using electron
backscattered diffraction (EBSD) technique. The specimen was
electrochemical polished and then examined by SUPRA
TM
55 eld
emission scanning electron microscope.
3. Results
3.1. Electrochemical characteristic of the elastically tensiled low
carbon steels
Figs. 4 and 5 presented the electrochemical impedance spec-
tra (EIS) and the open circuit potential/corrosion current density
of the low carbon ferritic and bainitic steel under various applied
constant loads. InFig. 4, all of these Nyquist plots includedtwo time
constants. The low frequency loop was related to inductive shrink
in both steels with different microstructure, indicating that it was
in the induction period of the pitting corrosion in NaCl solution
[22,23]. In some researches, the applied stress would cause a more
active surface resulting in a decrease of anti-corrosion [1,2,13]. An
increase in current density with applied stress during corrosion has
been reported in previous study [2,7]. However, in this study the
electrochemical characteristic of the loaded steels did not follow
this way.
In Fig. 4, for the bainitic steel, as the applied stress increased
from0o
s
to0.3o
s
thento0.5o
s
, theradius of thecapacitivearc grad-
ually reduced. This phenomenon showed the applied elastic stress
would result in a decrease of resistance of corrosion. The result
that, when the applied stress was below 0.7o
s
, mechanical effect
would accelerate the electrochemical corrosion of bainitic steel in
NaCl solution, could also be approved through the measurements
of thermodynamics parameter of open circuit potential (OCP) and
kinetics parameter of corrosion current density. The results were
Fig. 3. Schematic of the specimen for the contact angle measurement.
286 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
1000 800 600 400 200 0
0
200
400
600
800
1000
without constant stress
with 30% yield strength
with 50% yield strength
with 70% yield strength
with 90% yield strength
(b)
-
Z
i
m
/
o
h
m

c
m
2
-
Z
i
m
/
o
h
m

c
m
2
1800 1500 1200 900 600 300 0
0
300
600
900
1200
1500
1800
(a)
Z
re
/ohm cm
2
Z
re
/ohm cm
2
without constant stress
with 30% yield strength
with 50% yield strength
with 70% yield strength
with 90% yield strength
Fig. 4. Electrochemical impedance spectra (EIS) of the tested steels with different
stress (i.e. 0, 0.3os, 0.5os, 0.7os, 0.9os) loadedin3.5wt% NaCl solution: (a) lowcarbon
bainitic steel and (b) lowcarbon ferritic steel.
illustrated in Fig. 5. For the potential, in line with the Gutmans
assumption [2], for a uniform corrosion system, the variety of the
electrochemical potential ^ caused by the applied stress can be
characterized as:
^ =
^Pv
zF
(1)
where ^P is the residual stress, z is the ionic valency, V is the gram
molecular volume and F is Faradays constant. For the low carbon
bainitic steel, with z =2, F =96,485 C/mol and V7cm
3
, ^ from
unstressed to 0.5o
s
was calculated to be 16.4mV, which is smaller
than the experimental value 33.8mV. The variation was resulted
from the stress concentration at pits which were caused by the
chloride ion. So for the bainitic steel, when the applied stress was
below 0.7o
s
, the increscent stress would promote the corrosion
tendency of bainitic samples in NaCl solution. In actual corrosion
behavior, the current density i would also linearly increased, as
shown in Fig. 4(a).
But when the applied elastic stress increased to a critical value,
for bainitic steel which was 0.7o
s
, the initial linear relationship
between the mechanical stress and electrochemical corrosion was
broken. When the applied stress came to 0.7o
s
, the elastic mechan-
ical energy no longer resulted in a decrease in EIS with corrosion
potential and linear increase of corrosion current. Instead, a break
point would disturb the linear relationship at 0.7o
s
.
Table 3
The contact angles of 10l 3.5wt% NaCl solution of the tested steels under various
applied stress (

).
Steel no. 0 0.3o
S
0.5o
S
0.7o
S
0.9o
S
Lowcarbon ferritic steel 61.13 52.33 76.75 61.68 70.63
Lowcarbon bainitic steel 67.48 64.53 50.48 73.00 62.67
For the ferritic steel, interactionof mechanical andelectrochem-
ical effects during macroelastic deformation was similar with that
of bainitic steel. At the beginning of elastic deformation (applied
stress below0.5o
s
), the stress would make the corrosion potential
a linear decrease with tens of millvolts as well as a decrease in EIS,
and make the current density a linear increase of microamperes
per 1000MPa. As the applied elastic stress increased to 0.5o
s
, the
break point emerged.
Inordinarycourse, the electrochemical behavior is relatedtothe
status of metal surface. For low carbon steel under various loads,
the applied stress would supply extra energy. Usually, the extra
mechanical energy would affect the systemstability. So its neces-
sary to investigate the surface energy of the elastically deformed
metal.
3.2. Surface energy of the elastically tensiled low carbon steels
The early experimental investigations have proved that the cor-
rosion behavior of metals under an applied stress is related to
surface diffusion which is determined by surface energy [2,24].
But it is difcult to measure the surface energy exactly. A qualita-
tive comparison can be made through contact angle measurement.
The variations of the contact angle of 3.5wt% NaCl solution on the
surface of bainitic and ferritic steels under various applied static
stresses were illustrated in Figs. 6 and 7 respectively. The val-
ues of contact angles of the tested steels under various applied
stress were shown in Table 3. The fact that all values of the con-
tact angle were below90

, indicated that the surfaces of both steels

were hydrophilous to the solution. Generally, the higher the sur-
face energy is, the more powerful the adhesion of the drop is, and
the smaller the contact angle is [25].
Kiejna and Pogosov [19] suggested that for the ideal metal sub-
jected to deformation, changes only happen on its surface area, the
electron concentration in its bulk remains unchanged. The sumof
surface energy will increases with the applied tension, which was
formulated as follows:
d
s
= /

+
d
d

(2)
Here E
S
is the sum of surface energy, is surface energy per unit
area, and denote directions in the plane along the x axis and
the direction perpendicular to the x axis, and

is the Kronecker
delta. A is area, is uniaxial strain.
According to the OwensWendtKaelbleUy theory [2628],
the relationship between the contact angle and the surface energy
of the interfaces at two of the three phases is,

Lv
(1 +cos 0) = 2

d
S

d
Lv
+2

p
S

p
Lv
(3)
where the subscripts are solid S, liquid L and gas V, superscripts
p and d are the effect factor of polar force and dispersion force
between the solid and liquid. 0 is the contact angle. So when
an applied tensile stress loaded on metal, the sum of surface
energy would increase, with the contact angle decreased. But in
our research, the contact angles of elastically deformed samples
with 3.5wt% NaCl solution did not always followthis pattern. Fig. 8
gave the contact angles change tendency with the applied stress
of the samples.
R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294 287
0.9 0.6 0.3 0.0
-0.54
-0.53
-0.52
-0.51
-0.50
-0.49
-0.48
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

v
s

S
C
E
/

V
stress / yield strength
4
5
6
7
8
9
10
4.39
4.68
9.54
i
/

A

c
m
-
2
(a)
OCP
i
-0.5022
-0.5242
-0.5360
-0.4878
-0.4924
5.77
7.62
0.9 0.6 0.3 0.0
-0.570
-0.555
-0.540
-0.525
-0.510
-0.495
-0.480
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

v
s

S
C
E
/

V
stress / yield strength
OCP
i
2
3
4
5
6
7
8
9
i
/

A

c
m
-
2 5.40
6.89
2.78
8.11
-0.4880
-0.5273
-0.5039
-0.5601
(b)
-0.5219
4.46
Fig. 5. Open circuit potential (OCP) and current density i of the tested steels loaded in 3.5wt% NaCl: (a) lowcarbon bainitic steel and (b) lowcarbon ferritic steel.
InFig. 8(a) for the bainitic steel, as the appliedstress increasedto
0.5o
s
, theextramechanical energywouldactivatethemetal surface
andinduce a decrease of contact angles betweenthe sample surface
and solution. Then the corrosive solution would easier to cover the
metal surface and become thin liquid lm, indicating the tendency
of accelerated corrosion of bainitic steel. It was the essential reason
that mechanical effect accelerated the electrochemical corrosion
(decrease of EIS/OCP and increase of corrosion current density)
of bainitic steel in 3.5wt% NaCl solution. For the ferritic steel,
when the applied stress below 0.5o
s
, the interaction of mechan-
ical and electrochemical effects could also be described by this
way.
But when the elastic stress increased to the critical break point,
0.7o
s
and 0.5o
s
for the bainitic and ferritic steel respectively, the
contact angles were no longer decreased as the stress increased.
This nonlinear regularity of contact angles/surface energy with
applied elastic stress was similar to that of the electrochemical
behavior of samples. This means increasing the surface energy is
no longer the only way to consume the extra mechanical energy.
The higher applied stress would lead to some irreversible structure
changes.
3.3. Microplastic deformation of the macroelastic deformed metal
As we know, the deformation of metal near surface layer essen-
tially inuences the common character of plastic ow. In spite of
the fact that in macro-elastic deformation region, residual macros-
trains practically equals to zero, the metal microplastic strain takes
place [20]. It has been proved that acoustic emission (AE) origi-
nates from transient elastic waves as a result of sudden localized
irreversible structure changes such as the glide of dislocation or
crack propagation [29]. For elastic deformed metal AE signals are
mainly associated with the generation and motion of dislocations.
In order to investigate why the regularity (that the applied stress
would linearly enhance the electrochemical corrosion of low car-
bon steel in 3.5wt% NaCl solution) was broken at the critical stress,
288 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
Fig. 6. Contact angles of 3.5wt% NaCl solution on the surface of low carbon bainitic steel under various applied stress: (a) without load; (b) o/o
S
=0.3; (c) o/o
S
=0.5; (d)
o/o
S
=0.7 and (e) o/o
S
=0.9.
Fig. 7. Contact angles of 3.5wt% NaCl solution on the surface of low carbon ferritic steel under various applied stress: (a) without load; (b) o/o
S
=0.3; (c) o/o
S
=0.5; (d)
o/o
S
=0.7 and (e) o/o
S
=0.9.
1.0 0.8 0.6 0.4 0.2 0.0
50
60
70
80
(a)
c
o
n
t
a
c
t

a
n
g
l
e

/

d
e
g
r
e
e
stress / yield strength
contact angle of the bainitic steel in 3.5% NaCl
1.0 0.8 0.6 0.4 0.2 0.0
50
60
70
80
(b)
c
o
n
t
a
c
t

a
n
g
l
e

/

d
e
g
r
e
e
stress / yield strength
contact angle of the ferritic steel in 3.5% NaCl
Fig. 8. Variation of contact angles of tested steels under different constant stress with NaCl solution drops: (a) lowcarbon bainitic steel and (b) lowcarbon ferritic steel.
R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294 289
1400 1200 1000 800 600 400 200 0
0
200
400
600
800
1000
1200
s
t
r
e
s
s

/

M
P
a
time / s
Fig. 9. Variation of the applied stress with time during tensile test along with simul-
taneous AE measurement.
AE technique was used here to ensure whether it is the results of
generation and motion of dislocations.
The comparison of stress-time and the AE hits-time (bainitic
steel deformed in the air) was analyzed (Figs. 9 and 10). In case of
lowcarbon steel, the deformation process can be divided into three
stages. The rst stage is macroelastic deformation. This stage lasts
fromthe beginning to the occurrence of yield. The second stage is
the yield stage and the third is strain hardening (postyield stage).
The rst macro-elastic stage is the major subject of our research.
As the degree of deformation increased, the activization of disloca-
tion sources in near surface layer, in comparison with the sources
in the bulk, caused the emission and propagation of dislocations
and this process generated more and more AE hits. The maximum
hits appeared at 105s corresponding to stress 634MPa in Fig. 10
where the fraction of stress to elastic limit was 0.79 (just near the
break points in the above experiments), implied the formation of
microplastic deformation.
In previous studies it is believed that local stress concentration
leads to local plastic ow (no cracking occurs). The grain bound-
aries are main sources of dislocations. Some authors think that the
main source of AE at the rst stage of deformation is the grain
boundary [29]. In this model of boundary sources, the number of
dislocations gathered in grain boundary is a sensitive function of
grain size and boundary geometry. To investigate the microplas-
tic deformation at the grain boundaries when the electrochemical
current interacts with applied elastic stress, a sample was anodic
polarized 200mV above the open circuit potential in 3.5wt% NaCl
solution during the SSRT. The maximal applied stress was under
50% of the yield strength. Fig. 11 exhibited the SEM morphology
of the sample surface after the corrosion product was removed.
Fig. 11. Surface morphology of sample after potentiostatic polarization 200mV
above the open circuit potential in 3.5wt% NaCl solution during SSRT to the maxi-
mum applied load of 0.5o
S
.
Due to the electrochemical anodic dissolution current, the metal
surface was corroded in NaCl solution. The grain boundaries were
rstly suffered severe corrosion because of the higher activity. The
corroded grain boundaries divided the original glazed surface into
massive lumpish regions. At the grain boundaries, a few disloca-
tions slip bands were found as the white arrows shown in Fig. 11.
This means that, when there was anodic current, even the applied
elastic load was far below the yield strength, some microplastic
deformations were carried out near the grain boundaries. The local
surface microplastic deformation was the reason caused the novel
relationship between the macroelastic stress and electrochemical
corrosion of lowcarbon steel in 3.5wt% NaCl solution.
4. Discussion
4.1. The inuence of macroelastic stress on electrochemical
response of low carbon steel in NaCl solution
Through the above results about the interaction of applied elas-
tic stress with electrochemical corrosion behavior, we found there
was a non-linear relationship between those two factors. During
the macroelastic deformationprocess of lowcarbonsteel in3.5wt%
NaCl solution, at beginning, the applied elastic stress only has an
inuence on the energy state and anodic polarization behavior of
metal surface in the NaCl solution. The extra mechanical energy
would activate the metal surface and induce a drop of the contact
angles between the sample surface and solution. Then the corro-
sive solution would easily cover the metal surface and become thin
liquid lm, indicating the tendency of accelerated corrosion of low
carbon steel. The applied stress would make the corrosion poten-
tial a linear decrease with tens of millvolts as well as a decrease
Fig. 10. Acoustic emission hits distribution with time of the bainitic steel during tensile test.
290 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
1200 1000 800 600 400 200 0
-0.63
-0.60
-0.57
-0.54
-0.51
-0.48
-0.45
time / s
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
OCP
i
i

/

A

c
m
-
2
(a)
1200 1000 800 600 400 200 0
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
(b)
time / s
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
OCP
i
i
/

A

c
m
-
2
Fig. 12. Variation of open circuit potential (OCP) and current density i of the stress free specimens immersed in a 3.5wt% NaCl solution with time during the stabilizing
procedure: (a) lowcarbon bainitic steel and (b) lowcarbon ferritic steel.
1.0 0.8 0.6 0.4 0.2 0.0
-0.64
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
-0.50
(a)
OCP
i
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0
100
200
300
400
500
i
/

A

c
m
-
2
1.0 0.8 0.6 0.4 0.2
-0.60
-0.58
-0.56
-0.54
-0.52
-0.50
-0.48
-0.46
(b)
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
OCP
i
0.3
0.4
0.5
0.6
0.7
i
/

A

c
m
-
2
Fig. 13. OCP and current density i response of the tested steels during tensile tests in 3.5wt% NaCl solution: (a) lowcarbon bainitic steel and (b) lowcarbon ferritic steel.
R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294 291
0.0 0.2 0.4 0.6 0.8 1.0
-0.76
-0.74
-0.72
-0.70
-0.68
-0.66
-0.64
(a)
OCP
i
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
50
100
150
200
250
300
350
400
0.0 0.2 0.4 0.6 0.8 1.0
-0.66
-0.64
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
OCP
i
(b)
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
i
/

A

c
m
-
2
i
/

A

c
m
-
2
i
/

A

c
m
-
2
i
/

A

c
m
-
2
0.0 0.2 0.4 0.6 0.8 1.0
-0.70
-0.68
-0.66
-0.64
-0.62
-0.60
-0.58
-0.56
OCP
i
(c)
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0
40
80
120
160
200
240
0.0 0.2 0.4 0.6 0.8 1.0
-0.76
-0.74
-0.72
-0.70
-0.68
-0.66
-0.64
-0.62
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2 OCP
i
(d)
Fig. 14. OCP and current density i response of the metals (with passivation lm) during tensile tests: (a) low carbon bainitic steel with procedure A; (b) low carbon ferritic
steel with procedure A; (c) lowcarbon bainitic steel with procedure B and (d) lowcarbon ferritic steel with procedure B.
in EIS, and make the current density a linear increase of microam-
peres per 1000MPa. When the applied elastic stress increases to a
critical value, the initial linear relationship between the mechan-
ical and electrochemical effects is broken. The extra mechanical
energy applied by the tensile stress would enhance the microplas-
tic deformation at some local regions even the applied stress is far
below the yield stress. Especially when anodic dissolution current
presents at the metal surface, the electrochemical current activates
the dislocations more easily and make the appearance of an extra
dislocation ux in the surface layer.
The most effective method to investigate the change of the
interaction process of mechanical stress with electrochemical fac-
tor during the macroelastic deformation of low carbon steel is
to observe the electrochemical response of tensile strain at every
moment of deformation procedure.
Without any elastic stress, the OCP and current density were
recorded simultaneously along with the dynamic tensile tests as
shown in Fig. 12. The whole procedure lasted for 20min, and we
could call it stabilizing condition. In Fig. 12, the electrochemi-
cal behaviors of bainitic steel and ferritic steel shared a similar
trend although the quantitative values were different. The open
circuit potential decreased sharply with time initially and then
subsequently decreased slightly until it reached a steady value.
The current density was almost the same. Through the stabiliz-
ing procedure, a stable electrostatic double layer was built up at
the interface between the electrode surface and the solution. After
that, we set slowstrain rate tensile test (SSRT) on the samples and
the electrochemical responses were shown in Fig. 13. Because the
samples hadcome to the stabilizing condition, comparedto the sta-
bilizing procedure with a stress free condition (as in Fig. 12), there
was almost no change of the OCP. But the current soared rapidly
during tensile tests. Because it can indicate the dynamic process of
electrochemical corrosion, the variation of current density with the
applied stress was analyzed to describe the behavior of deformed
metal.
As shown in Fig. 13, the current density response curves of the
bainitic and ferritic steel were both divided into three stages. For
bainitic steel, at the beginning of the tensile tests, the current den-
sityalmost kept the same until it came tothe elastic stress of 0.55o
s
.
Then the curves went into the second part and the current rose
slightly with the deformation. When the applied stress reached to
0.75o
s
, a drastic jump of current density appeared and the value
reached up to hundreds of microampere per square centimeter.
For ferritic steel, the current density response was similar to that
of bainitic steel and there were also three parts in the curve. The
differences lay intwo aspects. First, the break points were different.
For ferritic steel, the break points appeared at 0.3o
s
and 0.55o
s
. At
0.3o
s
the current would increase slightly and at 0.55o
s
the current
would jump drastically. Secondly the maximum value of current
density was apparently different. For bainitic steel, it can reach up
to 400A/cm
2
, but for ferritic steel the maximumvalue was below
1A/cm
2
. These differences resulted fromthe higher strength and
more dislocations inmicrostructure of bainitic steel. It is worthnot-
ing that the second sharp rise were near the 0.75o
s
for bainitic steel
292 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
0.0 0.2 0.4 0.6 0.8 1.0
-0.70
-0.68
-0.66
-0.64
-0.62
-0.60
-0.58
-0.56
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0
100
200
300
400
500
600
OCP
i
i
/

A

c
m
-
2
(a)
0.0 0.2 0.4 0.6 0.8 1.0
-0.52
-0.50
-0.48
-0.46
-0.44
-0.42
-0.40
-0.38
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0
100
200
300
400
500
600
i
/

A

c
m
-
2
OCP
i
(c)
0.0 0.2 0.4 0.6 0.8 1.0
-0.74
-0.72
-0.70
-0.68
-0.66
-0.64
-0.62
-0.60
(b)
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

/

V
stress / yield strength
0.8
1.0
1.2
1.4
1.6
1.8
OCP
i
i
/

A

c
m
-
2
0.0 0.2 0.4 0.6 0.8 1.0
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
-0.50
-0.48
(d)
o
p
e
n

c
i
r
c
u
i
t

p
o
t
e
n
t
i
a
l

v
s

S
C
E
/

V
stress / yield strength
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
i
/

A

c
m
-
2
OCP
i
Fig. 15. OCP and current density i response of the naked metals (without passivation lm) during tensile tests: (a) lowcarbon bainitic steel with procedure C; (b) lowcarbon
ferritic steel with procedure C; (c) lowcarbon bainitic steel with procedure D and (d) lowcarbon ferritic steel with procedure D.
and 0.55o
s
for ferritic steel which were perfectly consistent with
the break points in the constant loading tests (0.7o
s
for bainitic
steel and 0.5o
s
for ferritic steel).
It is widely believed that the surface condition such as the pres-
ence of oxide or accumulation of corrosion product would have a
great inuence on the corrosion process. To investigate what is the
reason to cause the break points; four kinds of experimental design
were employed.
Procedure A: rstly cathodic polarized at 1Vvs. SCE for 10min
to remove the pre-existed oxide lm which unavoidably formed
during the preparationof specimen, thenanodic polarizedat 0.4V
for 10min to form passivation layer, these were conducted in
3.5wt% NaCl mixed with 0.5M NaHCO
3
solution. (The stable pas-
sivation section of the specimen in this solution was among 0.5V
to 0.3V.)
Procedure B: only anodic polarized at 0.4V for 10min in
3.5wt% NaCl mixed with 0.5MNaHCO
3
solution.
Procedure C: cathodic polarized at 1V for 10min in 3.5wt%
NaCl.
After the above treatments respectively, the specimens were
tensile tested in 3.5wt% NaCl as usual respectively.
Procedure D: tensile tested in 20% H
2
SO
4
solution.
Procedure A and B can be classied as the passive lm formed
treatment and the remained two are tested in active naked surface
conditions.
Fig. 14 presents the OCP and current density curves after the
surface passive lm formed treatment. As Fig. 14(a) and (c) illus-
trated, the current density curves of the bainitic steel with passive
lm also composed of three parts. The rst parts were almost the
same with that in Fig. 13(a). After lm formed treatments, how-
ever, the rst break stress moved to lower stress, near 0.4o
s
. Then
the current density gradually increased in the second part until the
second break point appeared. The second break stress was 0.8o
s
, a
little higher than the results in Fig. 13(a) and static loading tests.
Finally the current density jumped to the maximumvalue, almost
300A/cm
2
. For the ferritic steel with passivation lm, the current
density curves in Fig. 14(b) and (d) are looked so much like the
curve in Fig. 13(b). Also the break stress had a little shift. The shift
of lower break point came fromthe quality variation with different
treatments.
Incomparison, for the specimens after passivationlmremoved
(Fig. 15), the curves of current density composed of two parts,
instead of three. After procedure D, for example, at the rst stage
the current density of the bainitic steel increased little with grad-
ually rising applied stress, and then jumped up to hundreds of
microampere per square centimeter when the break point stress
0.5o
s
came up. By comparing the values of current density, we
thought that the rst and third stages in current density curves
of Fig. 13 kept the same, but the second part disappeared by
removing the passivation lm. Another difference shown in Fig. 15
was that the break stress was a little lower than the higher
break stress in Figs. 14(a), (c) and 13(a). The negative move of
its stress may be attributed to the change of surface condition
in cathodic polarization and the acid dissolution. Similar expla-
nation can be applied to the results of the other three curves in
Fig. 15.
R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294 293
48 44 40 36 32 28 24 20 16 12 8 4 0
0
1
2
3
4
5
6
(a)
N
u
m
b
e
r

F
r
a
c
t
i
o
n

(
%
)
CSL
the coincident site lattice (CSL)
distribution of the bainitic steel
48 44 40 36 32 28 24 20 16 12 8 4 0
0
1
2
3
4
5
6
(b)
N
u
m
b
e
r

F
r
a
c
t
i
o
n

(
%
)
CSL
the coincident site lattice (CSL)
distribution of the ferritic steel
60 56 52 48 44 40 36 32 28 24 20 16 12 8 4 0
0
5
10
15
20 (c)
N
u
m
b
e
r

F
r
a
c
t
i
o
n

(
%
)
Misorientation angle (deg)
the grain boundary misorientation
distribution of the bainitic steel
60 56 52 48 44 40 36 32 28 24 20 16 12 8 4 0
0
5
10
15
20 (d)
N
u
m
b
e
r

F
r
a
c
t
i
o
n

(
%
)
Misorientation angle (deg)
the grain boundary misorientation
distribution of the ferritic steel
Fig. 16. Coincident site lattice (CSL) and grain boundary misorientation distribution of bainitic (a and c) and ferritic (b and d) steels.
So through the analysis and comparison of Figs. 14 and 15, we
would be able to infer that the rupture of oxide lm on the metal
surface led to the rise of current density at the rst lower break
stress. Nomatter whether therewas oxidelmonthemetal surface,
the second critical break point always existed and broke the con-
tinuous increase of electrochemical corrosion of low carbon steel
in NaCl solution. This critical stress state could be corresponding
to the irreversible structure changes at metal surface. Just as the
results shown in AE tests (Figs. 9 and 10) and surface morphology
observation (Fig. 11), this irreversible change was the microplastic
deformation at some local regions.
During the elastic deformation of low carbon steel in 3.5wt%
NaCl solution, the applied mechanical energy was transferred to
two aspects. One was to raise the surface energy and accelerate
the electrochemical corrosion. Another is to induce the motion of
surface dislocations. These two procedures competed with each
other, and occupied different dominant positions at different elas-
tic deformation stages. The rst stage lasted from the beginning
to the critical stress. At this period, the applied mechanical energy
was so low that it could not activate the surface dislocations. The
applied energy was transferred to raise the surface energy, and
make the solution easier to become thin liquid lm at metal sur-
face, and accelerate the corrosion. Of course the increasing applied
tensile stress would destroy the oxide lm on metal surface, but
the growth of current density was so lowthat this inuence could
be ignored. So at the rst period, applied mechanical energy accel-
erating electrochemical corrosion was the dominant process. The
second stage lasted from the critical point to the yield strength.
During this period, the appliedmechanical energy was highenough
to activate the surface dislocations, and led to microplastic defor-
mation. If there was anodic dissolution current at metal surface,
the current would enhance the microplastic deformation even the
applied stress was far belowthe yield strength.
4.2. The inuence of microstructure on interaction of mechanical
and electrochemical effects
For both bainitic and ferritic steels, the interaction between
mechanical and electrochemical effects could be divided into two
stages, and the dominant factor at each stage was the same. The
only difference of the interaction of these two steels was that the
critical stress of the interaction effect was different. For the bainitic
steel, the critical point was 0.7o
s
, but for ferritic steel it was 0.5o
s.
Through our researches, when the applied stress increased to the
critical value, the partial applied mechanical energy would lead to
microplastically deformation in the metal surface layer. In Fig. 11
we found that the slip bands usually generated from the grain
boundaries then extended into the grains. So the differences of
grain boundaries maybe cause the different break/critical stresses
of the bainitic steel and ferritic steel.
So, in this study, the electron backscattered diffraction (EBSD)
technique was used to check the different activity of the two kinds
of steels. Fig. 16 exhibits the coincident site lattice (CSL) and grain
boundary misorientation distribution of the steels. According to
294 R.K. Ren et al. / Electrochimica Acta 85 (2012) 283294
the coincident site lattice theory, the reciprocal number density
of lattice sites that are common to both crystals could be dened
as

CSL and generally the CSL boundaries are regarded as low-
energy boundaries, and the energy of low-

CSL boundaries is
lower than that of high-

CSL boundaries [30]. It can be seen that

the CSL boundaries were very little in both bainitic and ferritic
steel. This indicatedthat the boundaries inthe specimens were ran-
domboundaries with high-energy. The boundaries became highly
active to generate defects. Fromthe grain boundary misorientation
of bainitic steel, large amount of boundaries falls into the range
of below 20

, which should be related to a large number of sub-

boundary between bainitic ferritic laths in a packet. Comparing
with the bainitic steel, the grain boundaries in the ferritic steel dis-
tributed more averagely, and the proportion of high angle grain
boundaries increased apparently.
So owing to high energy and more defects at the grain bound-
aries, a large number of local plastic ows would generate at
grain boundaries and lead the deformed metal into microplastic
region even in macroelastic deformation region. This was the rea-
son which causes the break point in the electrochemical behavior
of mechanochemical effect. Due to the different microstructure of
bainitic andferritic steel, the differences of grainboundaries maybe
cause the different break stress. Sub-boundaries with low misori-
entationof bainitic steel concentratedthestress at 70%of theelastic
limit stress while that fraction was 50% of ferritic steel with much
more high angle grain boundaries.
5. Conclusions
(1) For low carbon steel in 3.5wt% NaCl solution, the applied
mechanical stress and the electrochemical corrosion of the
samples wouldinteract andaccelerate eachother concurrently.
(2) The relationship between the mechanical and electrochemical
effects is non-linear. The interactionprocess canbe dividedinto
two stages. At the beginning of the macroelastic deformation,
the applied elastic stress only has an inuence on accelerating
the electrochemical corrosion of lowcarbon steel in NaCl solu-
tion. The applied mechanical energy would activate the metal
surfaceandmakethecorrosivesolutioneasilycover thesurface.
When the applied elastic stress increases to the critical value,
the partial applied mechanical energy is used to enhance to
microplastic deformationat some local regions of metal surface
even the tensile stress is far belowthe yield strength.
(3) The microplastic deformation of the macroelastic deformed
metal in NaCl solution usually generates at grain boundaries
and then extends into the grains. The microstructure especially
the activity of grain boundaries may have an inuence on the
critical stress beyond which the sample would microplastically
deformed.
Acknowledgement
This study was supported by National Natural Science Founda-
tion of China (No. 51071029).
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