Applied Surface Science 273 (2013) 192–198

Contents lists available at SciVerse ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Experimental study of corrosion behavior for burnished aluminum

alloy by EWF, EBSD, EIS and Raman spectra
Lv Jinlong, Luo Hongyun ∗ , Xie Jinpeng
School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, Xueyuan Road 37, Beijing, 100191, China

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

Article history: The effect of burnish process on 2024 aluminum alloy was studied by electron work function and electron
Received 16 September 2012 backscattered diffraction (EBSD). Moreover, the corrosion resistance of thin passive films formed on 2024
Received in revised form 1 February 2013 aluminum alloy in borate buffer solutions was studied by the electrochemical impedance spectroscopy
Accepted 2 February 2013
(EIS), the Mott–Schottky plots and the galvanostatic techniques. The composition of passive films was
Available online 10 February 2013
analyzed by Raman spectra. The results obtained indicated that the impedance increased due to burnish
and this was attributed to decreased electron work function and higher current efficiency in the burnished
Keywords:
aluminum alloy which led to thicker passive films. It was further supported by Raman spectra experiment.
Electron work function
Electron backscattered diffraction
Moreover, the donor and acceptor concentration of passive films and their the semiconductor type have
Electrochemical impedance spectroscopy changed due to burnish.
Raman spectra © 2013 Elsevier B.V. All rights reserved.
Burnish

1. Introduction
The severe surface plastic deformation was used to refine grain
and improve corrosion resistance. However, its effects on corrosion
resistance were contradictory. The refine grain could improve and
decrease corrosion resistance. Meng et al. [1] showed that the cor-
rosion resistance of aluminum film with grain size of about 400 nm
was significantly improved compared with that of pure coarse grain
aluminum in NaCl containing acidic solution. Moreover, a dense
passive film was formed on modified nanocrystalline layer of 2024
aluminum by mechanical attrition treatment (SMAT) [2]. While
Barbucci et al. [3] found a deteriorated protective properties of the
oxide film on the nanostructured alloy in neutral chloride solu-
tion and proposed sintering defects and increased amount of grain
boundary in the nanostructured alloy resulted in the deterioration.
Moreover, decreasing the grain size of pure titanium further down
to 90 nm using hydrostatic extrusion did not result in any signifi-
cant change in the corrosion resistance [4]. In addition, the texture
significantly affected the corrosion behavior [5]. Sample with the
most densely packed crystallographic plane parallel to the surface
was found to offer the highest corrosion resistance, regardless of
their grain size [5].
It was well recognized that the corrosion processes and mech-
anism were strongly associated with surface electronic structures
such as electron work function (EWF), the grain size and chemical
∗ Corresponding author at: Tel.: +86 10 82339905; fax: +86 10 82317128.
E-mail addresses: ljlhit@126.com (L. Jinlong), luo7128@163.com (L. Hongyun).
composition of passive film [6]. Therefore, it is also crucial and sig-
nificant to understand the relationships between EWF and grain
size and corrosion behaviors. It was theoretically demonstrated
that roughness could decrease the average EWF but increase the
fluctuation of the local EWF which could promote the formation of
microelectrodes and, therefore, accelerate corrosion [6]. It was also
revealed that the corrosion rate of Cu increased with an increase in
surface roughness, whereas its surface EWF accordingly decreased
[7,8].
As mentioned above, the serious plastic deformation affects
grain size which will affect the work function. The work function
must affect electrochemical impedance and semiconductor prop-
erties of passive film on the surface of burnished samples. There is
little research in this aspect, therefore, from the point of view of
fundamental and applied studies, it is very necessary to investigate
EWF, grain size and corrosion resistance of burnished aluminum
alloy and the their relationship.
2. Experimental procedure
2.1. Materials preparation
The material used in this paper is 2024 aluminum alloy with
a chemical composition as follows: (wt.%): Cu 3.8–4.9, Mg 1.2–1.8,
Mn 0.3–1.0, Zn 0.25, Cr 0.1, Fe 0.5, Si 0.5 and balance Al. The burnish
process is performed through a cylindrical-ended PCD tool accord-
ing to ref [9]. The schematic illustration of the burnish device is
shown in Fig. 1a. The diameter of the sample is 46.6 mm. A is as-
received sample, while the B and C samples are burnished. The tool

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.02.012
 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198
rotational speed is 3000 rpm and the burnish depths are 15 ␮m
for B sample 60 ␮m for C sample, respectively. Fy is 8.87 N and Fz
−1.35 N for B sample, while Fy is 9.74 and Fz is −1.64 for C sample,
respectively. Therefore, the burnish force of B sample is higher than
that of C sample.
2.2. SKP measurements
The EWF was measured using a scanning Kelvin probe (SKP) sys-
tem, which was provided by the KP Technology Ltd. (Caithness, UK).
The measurement was performed on the as-received and burnished
samples through Nanoman VS atomic force microscope. In the sur-
face potential model, the potential distribution in 5 × 5 ␮m2 area
was obtained. Prior to SKP measurements, samples were polished
with #3000 sand papers.
2.3. EBSD measurements
EBSD scans were conducted on the X (the axis of bar) - Z (bur-
nish direction) section in ZEISS ULTRA 55 field emission gun SEM,
equipped with an HKL Technology Channel 5 EBSD detector. The
area mapping for the tested samples was 165 ␮m × 124 ␮m with
a step size of 0.35–0.4 ␮m, operating at an accelerating voltage of
20 kV.
2.4. Electrochemical measurement
For electrochemical experimental purposes, the hole was drilled
on the reverse side of burnish surface. Then the insulated cop-
per wires were inserted into all the samples which act as working
electrodes due to difficulty in aluminum alloy welding. The work-
ing electrodes were embedded in epoxy resin with an exposure
area of 1.0 cm2 in Fig. 1b. The electrochemical cell employed in
this study was made of glass beaker with the three electrodes.
Very high density graphite and a saturated calomel electrode (SCE)
were used as the counter and the reference electrodes, respectively.
The electrochemical measurements were performed using 660B
model (CHI company) controlled by a PC. Before each experiment,
the samples were polished with silicon carbide papers up to 3000
grit finish and then rinsed in doubly-distilled water and imme-
diately immersed in borate buffer solution (0.5 mol dm3 H3 BO3
and 0.05 mol dm3 Na2 B4 O7 ·10H2 O; pH 7.8). The electrochemical
impedance spectroscopy (EIS) at open circuit potential (OCP) was
performed in a wide frequency range, from100 kHz to 0.1 Hz, with
ac voltage amplitude of 5 mV. To examine oxide film growth on as-
received and burnished samples under conditions of galvanostatic
Fig. 1. (a) Sample reference system in burnish and sample cut diagrammatic sketch for electrochemical measurement. (b) Schematic diagram of sample for electrochemical
measurement.
193
anodising, anodic charging curves were recorded in 100 ␮A cm−2
for 200 s. Then, the EIS at OCP was used to determine the charac-
teristic sizes of oxide films formed anodically on the samples. The
equivalent circuit model and ZsimpWin software were utilized to
fit the Nyquist plots of all the samples.
2.5. Raman measurement
Raman measurements were performed using a Jobin Yvon
(Laboratory RAM HR800) confocal micro-Raman spectrometer
backscattered geometry through a 10 × (NA = 0.25) microscope
objective. Ar+ laser emitting at a wavelength of 514.5 nm was
used as a source of excitation (5.5 mW laser power available at
sample). The number of grating in the Raman spectrometer was
1800 grooves/mm. The scattered light was analyzed with a Dilor
XY triple spectrometer and a liquid-nitrogen-cooled CCD multi-
channel detector with the accuracy better than 1 cm−1 . The Raman
band of a silicon wafer at 520 cm−1 was used to calibrate the
spectrometer. The Raman spectra were recorded in the range of
200–1300 cm−1 and were collected three points of each sample for
reproducibility.
3. Results and discussion
3.1. Characterization of surface layer
Fig. 2a–c exhibit three-dimensional surface potential of A, B
and C samples. Each point value is fluctuant due to polishing with
sand papers. Fig. 2d illustrates the change trend of the EWF due to
burnish. The EWF decreases dramatically due to the plastic defor-
mation, and then the EWF decreased slightly with the increasing
of burnish force. Some studies showed the EWF could change due
to grain orientation [10] and strain [11]. The texture was shown to
significantly affect the EWF and sample with close packed plane for
FCC metal was found to offer the lowest value of EWF [10]. However,
at present the mechanism of EWF change has not been completely
understood and some results were even controversial. For exam-
ple, Song et al. [7] found a decrease in EWF with surface roughness,
while Beierlein et al. [12] observed an increase in EWF at the rough
surface induced by surface treatment of oxygen plasma.
The quantification of low angle grain boundary (marked LAGB
with misorientation angle in range of 1.5–15◦ ) and high angle grain
boundary (marked HAGB with misorientation angle >15◦ ) are listed
in Fig. 3a–c. It can be seen that the volume fraction of LAGB increases
due to the burnish and higher burnish force. It indicates the disloca-
tions generate during burnish process. After burnish process many
194 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198

Fig. 2. Three-dimensional scanning image of potential at the surface of (a) A, (b) B and (c) C; (d) variations of the EWF of the samples with respect to burnish process.

grains were refined. The grain size of C sample is slightly smaller
than that of B sample, except for slightly more area which is not
indexed (Green area). Apparently the more dislocation will help
to refine grain and reduce the surface work function of burnished
samples. Therefore, it is necessary to study the effect of changed
EWF due to refine grain by burnish process on corrosion resistance
by electrochemical techniques.
3.2. The electrochemical analysis
3.2.1. The electrochemical impedance spectroscopy and the
Mott–Schottky analysis
Generally, to determine the stability of the passive film, the EIS
is carried out by the Nyquist plot. In this plot, the real impedance is
plotted vs. the imaginary impedance at each frequency. As the fre-
quency increases, the impedance of the capacitor decreases [13].
For this purpose, all the samples were passivated at the OCP for
24 h, just at which the impedance spectra were measured. Typical
Nyquist plots are illustrated in Fig. 4a which shows the partial semi-
circle Nyquist plots of A, B and C in the aerated borate buffer solu-
tion. It can be noticed that the Nyquist plots are depressed semicir-
cles. However, the semicircle diameters are different. The increase
in capacitive semicircle due to burnish and higher burnish force is
related to thickening or compactness and stability of oxide film [14].
Several models of circuits to fit these experimental data were
attempted. The best agreement between experiment and fitting
results was circuit shown in Fig. 4a. The equivalent electron cir-
cuit with one time constant was more suitable in the present study
according to Bode plots in Fig. 4b. It included a solution resistance
Rs, constant angle element (CPE) and the charge transfer resistance
Rt in Fig. 4a.
The maximum value of polarization resistance in Fig. 4c coin-
cides with the minimum EWF in Fig. 2d. Taking into account similar
grain size due to burnish in Fig. 3b and c and comparing Fig. 4c
and Fig. 2d, it may be concluded that the effects of EWF and grain
size on corrosion resistance are very important in the present test

Fig. 3. Frequencies of low angle grain boundaries  < 15◦ (blue lines) and high angle grain boundaries (black lines) for (a) A, (b) B and (c) C samples, respectively. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198
Fig. 4. (a). Nyquist plots for samples in borate buffer solution after 24 h stabilization at the OCP for A, B and C samples in borate buffer solution and equivalent circuit
proposed. (b) Bode plots for samples in borate buffer solution after 24 h stabilization at the OCP for A, B and C samples in borate buffer solution. (c) The dependence of Rt on
burnish process. (d) Anodic potentiodynamic curve of all the samples in borate buffer solution (pH 7.8). Scan rate, 0.00167 V s−1 .
conditions. Fig. 4d contains representative potentiodynamic curves
of different burnish processes. When the potential changes in the
anodic direction, the examined samples show increased current
with the occurrence of a current peak. Polarization behavior shows
different corrosion current icorr , passive current ipass and corrosion
potential Ecorr. In general, the burnished samples have the lower
icorr , ipass and higher Ecorr. The higher burnish force decreases icorr
and ipass and improves Ecorr.
There was no doubt about that the improved corrosion resis-
tance of burnished sample was correlated with its semiconducting
properties of passive film [15]. The most common in situ method
for probing these conducting properties of passive films was the
Mott–Schottky plots of the electrode capacitance vs. potential
dependence. It has been shown [16,17] that in high frequency
domain, the Mott–Schottky approach can be a good tool for char-
acterizing the semiconducting properties of passive films.
According to the Mott–Schottky theory, the space charge capac-
itances of n-type and p-type semiconductor were given by the
following the Mott–Schottky relationships (1) and (2), respectively,
assuming that the capacitance of the Helmholtz layer could be
neglected [18]:
2 KT
C −2 = CH−2 + CSC
−2
= (U − Ufb − ) (1)
εS ε0 qND e
−2 KT
C −2 = CH−2 + CSC
−2
= (U − Ufb − ) (2)
εS ε0 qNA e
 
where ε0 is the vacuum permittivity 8.854 × 10−12 Fm−1 , ε is
the dielectric constant of the sample, q is the electron charge
 3−
1.6 × 10−19 C , K is the Boltzman constant 1.38 × 10−23 JK −1 , ND
and NA are the donor or acceptor density, respectively, T is the abso-
lute temperature and Ufb is the flatband potential. KT/q is neglected
as it is only about 25 mV at room temperature. From the slope and
the intercept of linear plot zones, the donor and acceptor densi-
ties and the flatband potential can be determined, respectively.
The dielectric constant εs is assumed as 10 for the passive films
on aluminum oxide [19]. Sikora et al. [20] pointed out that the
defect structure was “frozen-in” at a sufficiently high sweep rate. So
the potential sweeping rate was selected to be 50 mV/s in present
195
study. The sweeping rate was fast enough to satisfy the assump-
tion of “frozen-in defect structure” for the Mott–Schottky theory
[21], and hence the defect density of the passive film should not be
affected by the change of applied potential. The capacitance values
were calculated from C = (−Zim 2f)1 , where Zim was the imaginary
part of the impedance and f was the frequency which was 1000 Hz
in the present study.
Fig. 5a shows the effect of burnish process on the Mott–Schottky
plots of the samples after 24 h at OCP in the aerated borate buffer
solution. It shows the passive film on A sample is n-type semi-
conductor (with positive slope in the Mott–Schottky plot) in the
solution. While the passive films on B and C samples are n-type
semiconductor (positive slope in the Mott–Schottky plot) and p-
type semiconductor (negative slope in the Mott–Schottky plot) in
the same solution. The donor and the acceptor concentrations in
the passive film calculated from the slopes are presented in Fig. 5b.
It is clear that the dopant concentration in A sample is higher than
those in B and C samples and dopant concentration in B sample is
higher than that in C sample.
According to the point defect model [22], the movement of point
defects, such as cation vacancies (acceptor) and oxygen vacancies
(donor), through anodic oxides films on metals, contributed to the
formation and dissolution of the passive films. The electrochemical
reactions at the aluminum/oxide film interface could be written
[23]
3 2+
Al(m) = AlAl(ox) + V (OX) + 3e (3)
2 O
Al(m) + VAl (OX) = AlAl (OX) + 3e (4)
where Al(m) is the aluminum atom in the regular metal site;
AlAl (OX) is the aluminum atom in the regular site of oxide film;
VO2+ (OX) is the positively charged oxygen vacancy in the oxide film;
3−
e is the electron and VAl (OX) represents the negatively charged alu-
minum vacancy in the oxide film. The field-assisted reactions at the
oxide film/solution interface are given by
H2 O + Vo2+ (OX) = OO (OX) + 2H + (aq) (5)
196 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198
Fig. 5. (a) The Mott–Schottky plots for A, B and C samples in borate buffer solution after 24 h stabilization at the OCP (b) The dependence of donor and acceptor concentration
on burnish and burnish force.
2 3−
H2 O = OO (OX) + V (OX) + 2H + (aq)
3 Al
3−
AlAl (OX) = Al3+ (aq) + VAl (OX)
where OO (OX) is the oxygen ion in the regular site of the oxide film,
H + (aq) is the hydrogen ion in the aqueous solution and Al3+ (aq)
represents the aluminum ion in the aqueous solution.
The relationship between passive film stability and semicon-
ductor property was as yet not universally acknowledged. Della
Rovere et al. [24] suggested that the low value of concentrations of
the donor and the acceptor lead to the formation protection against
corrosion. Moreover, Zhang et al. [25] suggested that the p-type film
could possess a relative higher stability. Although it was suggested
that n-type semiconductor in which oxygen vacancies were exces-
sive as major carriers facilitated oxygen anions migration, resulting
in the further thickening of the passive film in A sample. How-
ever, the cation vacancies in B and C samples could facilitate metal
cation migration from the metal/oxide film interface to the oxide
film/solution interface then a new layer of oxide formed at oxide
film/solution interface [25], which improved corrosion resistance
of the sample. In short, burnish process and higher burnish force
improved corrosion resistance, which was proved by the results of
the EIS and the Mott–Schottky plots.
3.2.2. Current efficiency analysis
It was well known that anodizing could improve protec-
tive property of aluminum. This was because that oxide layers
were formed, which provided greater resistance to the charge
passing through metal/oxide/electrolyte interfaces [26,27], when
aluminum was anodized. Anodic film growth mechanism of alu-
minum and aluminum alloys in borate buffer solution has been
studied by means of anodic charging and impedance techniques
[28,29]. Impedance measurements provided an insight into the
characteristic sizes of oxide films. Therefore, the current efficiency
in the formation of the oxide film could be calculated.
The anodic charging curves for A, B and C samples in the borate
buffer solution are shown in Fig. 6a. The obtained results indicate
linear increase of potential with time for all the samples. The slope
of the potential with time in A sample is higher than those in B
and C samples and the slope of the potential with time in C sample
is higher than that in B sample. The rate of potential increase with
time represents the rate of oxide formation [28]. Therefore, the rate
of oxide film formation also increases due to burnish and higher
burnish force.
After anodization for 200 s and after reaching a certain potential
and the impedance measurements were performed after 30 min
at the OCP. Fig. 6b shows the Nyquist plots for A, B and C sam-
ples obtained after anodic current is switched off. It is clear that
the semicircle in A sample is lower than those in B and C sam-
ples and semicircle in B sample is lower than that in C sample. The
diameter of the capacitive loop increases due to burnish and higher
(6)
burnish force. The equivalent electron circuit with one time con-
stant was suitable in the present study according to Bode plots in
(7)
Fig. 6c. The model of circuit to fit these experimental data is also
used in Fig. 4a. In mathematical analysis of impedance diagrams
the constant phase element, CPE, is used instead of an ‘ideal’ capac-
itor to account for the deviations observed as capacitive loops are
depressed. The impedance, ZCPE of CPE is described by the expres-
sion [30]:
n −1
ZCPE = [Q (jω) ] (8)
After the values are deduced from the equivalent circuit, the
capacitance C related to the CPE (Q) can be calculated by the fol-
lowing equation [31]:
(QR)1/n
C= (9)
R
where the Q is a constant phase element, n is the exponent of the
Q, The thickness increase is formulated according to EIS data of the
oxide layer, using the relation as follows [32]:
εε0 A
d = (10)
C
where A is the effective area.
The values of a constant phase element (approximately
inversely proportional to thickness of passive films) decrease after
anodic charging due to burnish and higher burnish force in Fig. 7a.
The charge transfer resistance and passive film thickness increase
after anodic charging due to burnish and higher burnish force in
Fig. 7b, c, respectively. It can be seen that passive film thickness
and polarization resistance in Fig. 4d increase due to the burnish
and higher burnish force.
Oxide films can be also formed by counter migration of Al 3+ and
O2− ions through the film thickness under the high electric field.
The thickness of oxide layer increases because anodic oxidation
was measured using the relation as follows
Mq
dcharge = (11)
zF
where  is the oxide density, M is the molecular mass of oxide, z is
the number of electrons used up in the anodizing process, F is the
Faraday constant and  is the roughness factor. Using data in ref
[28], the oxide film thickness is calculated.
Current efficiency has been determined by comparing the oxide
film thickness as determined by capacity measurements to that
determined by the quantity of charge used up per surface unit dur-
ing the anodising process [33]. Therefore, the current efficiency
could be given by the following the relationship
dcapacity
= (12)
dcharge
 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198 197

Fig. 6. (a) Anodic charging curve of the A, B and C samples in the borate buffer solution at current density 100 ␮A cm−2 , (b) Nyquist plots for the impedance of the anodic
formed film on A, B and C samples after anodic charging. (c) Bode plots for the impedance of the anodic formed film on A, B and C samples after anodic charging.

The formation of oxide films on Al alloys is obviously a process
that takes place with current losses. Fig. 7d shows that the current
efficiency in the oxide film growth is largely affected by the burnish
and higher burnish force.
During corrosion, the exchange of electrons between metal
and surrounding medium constituted an electric circuit at the
interface. Corrosion was related to the surface electron behavior
or electron activity. The EWF was an informative parameter for
further understanding the corrosion behavior or electrochemical
stability of a material. For example, the EWF increased as the grain
size decreased for Cu-30Ni alloy tube, which was a good indication
that the passive film on a nanocrystalline surface was more
effective to reduce the electron activity and enhanced the resis-
tance of the surface to corrosion [34]. It was also observed that the
EWF decreased and the corrosion rate increased with an increase
in plastic strain, indicating that the strained surface layer became
more electrochemically active [35]. However, in present study,
corrosion resistance increases with a decrease in the EWF after
burnish process. This is because the EWF is the minimum energy
required to move an electron from inside a metal to its surface
[6,36]. Therefore, burnished surface layer is more electrochemi-
cally active, which facilitates to form compactness and stability
of the passive film in Fig. 5b and improves current efficiency in
Fig. 7d which enhance thickness of passive film in Fig. 7c.

Fig. 7. Dependence of (a) constant phase element, (b) polarization resistance, (c) passive film thickness increase and (d) current efficiency on burnish and burnish force in
the borate buffer solution.
198 L. Jinlong et al. / Applied Surface Science 273 (2013) 192–198
Fig. 8. Raman spectra of the A, B and C samples in the borate buffer solution at
current density 100 ␮A cm−2 .
3.3. The component analysis of passive film
To further prove above about composition change of passive film
due to burnish process, Raman spectra was used to analyze com-
ponents of passive film. Fig. 8 shows the Raman spectra of the A, B
and C samples after being passived at current density 100 ␮A cm−2
for 200 s in the borate buffer solution. The vibrational modes of
aluminum species are known from the literature. The broad peak
near 1056 and 1068 cm−1 indicates the Al O bending mode [37].
The peak at 1290 cm−1 originates from aluminum oxide mode [37],
which is stronger in B and C samples than that in A sample. This
can further support the results of current efficiency. The peak at
460 cm−1 characterizes amorphous alumina films, especially for B
and C samples, which grows at the oxide/electrolyte interface by
the outward migration of aluminum [38]. It was suggested that
surface film on aluminum was duplex layer, where the inner layer
was a compact amorphous layer and the outer layer was a perme-
able hydrated oxide layer [39]. This can affect the semiconductor
type of surface passive film in Fig. 5. The burnish process facili-
tates form of metal vacancies in the oxide film/solution interface
and promotes p-type passive film to form, which improve sta-
bility and corrosion resistance corrosion of samples. In addition,
weak peaks at 566 cm−1 706 cm−1 840 cm−1 and 896 cm−1 are ␥-
Al(OH)3 and Weak peaks at 334 cm−1 and 705 cm−1 are ␣-AlOOH
[40].
4. Conclusions
The refined grain on surface layers were obtained on a 2024
aluminum alloy by means of surface burnish process. The EWF and
EBSD were used to analyze microscopic characteristic. The corro-
sion resistance of passive films was analyzed by electrochemical
impedance spectroscopy, current efficiency analysis and Raman
spectra. The results could be summarized as:
(1) The EWF decreased due to burnish process and higher burnish
force.
(2) The burnish process and higher burnish force improved
corrosion resistance, which was proved by the results
of the electrochemical impedance spectroscopy and the
Mott–Schottky plots.
(3) The semiconductor type of surface passive film was changed by
burnish process.
(4) The current efficiency in the oxide film growth was largely
affected by burnish and higher burnish force. The higher bur-
nish force, the higher the current efficiency, which facilitated
growth of thicker passive film. It was supported by Raman spec-
tra experiment.
(5) The decreased EWF improved surface electrochemically active
and increased the value of current efficiency, which could
explain improved passive film growth mechanism.
References
[1] G.Z. Meng, L.Y. Wei, T. Zhang, Y.W. Shao, F.H. Wang, C.F. Dong, X.G. Li, Corrosion
Science 51 (2009) 2151–2157.
[2] L. Wen, Y.M. Wang, Y. Zhou, L.X. Guo, J.H. Ouyang, Corrosion Science 53 (2011)
473–480.
[3] A. Barbucci, G. Farne, P. Matteazzi, R. Riccieri, G. Cerisola, Corrosion Science 41
(1998) 463–475.
[4] H. Garbacz, M. Pisarek, K.J. Kurzydlowski, Biomolecular Engineering 24 (2007)
559–563.
[5] M. Hoseini, A. Shahryari, S. Omanovic, J.A. Szpunar, Corrosion Science 51 (2009)
3064–3067.
[6] W. Li, D.Y. Li, Acta Materialia 54 (2006) 445–452.
[7] G.L. Song, D. Haddad, Materials Chemistry and Physics 125 (2011) 548–552.
[8] W. Li, D.Y. Li, Journal of Chemical Physics 122 (2005) 064708.
[9] H.Y. Luo, J.Y. Liu, L.J. Wang, Q.P. Zhong, International Journal of Advanced Man-
ufacturing Technology 25 (2005) 454–459.
[10] J.K. Grepstad, P.O. Gartland, B.J. Slagsvold, Surface Science 57 (1976) 348–362.
[11] Y. Zhou, J.Q. Lu, W.G. Qin, Materials Chemistry and Physics 118 (2009) 12–14.
[12] T.A. Beierlein, W. Brutting, H. Riel, E.I. Haskal, P. Muller, W. Rieb, Synthetic
Metals 111–112 (2000) 295–297.
[13] Z.X. Zhang, G. Lin, Z. Xu, Journal of Materials Processing Technology 205 (2008)
419–424.
[14] Z.J. Zheng, Y. Gao, Y. Gui, M. Zhu, Corrosion Science 54 (2012) 60–67.
[15] A. Shahryar, S. Omanovic, Electrochemistry Communications 9 (2007) 76–82.
[16] D.J. Blackwood, Electrochimica Acta 46 (2000) 563–569.
[17] H.H. Ge, G.D. Zhou, W.Q. Wu, Applied Surface Science 211 (2003) 321–334.
[18] W.P. Gomes, D. Vanmackelbergh, Electrochimica Acta 41 (1996) 967–973.
[19] J. Hitzig, K. Jüttner, W.J. Lorenz, W. Paatsch, Corrosion Science 24 (1984)
945–952.
[20] J. Sikora, E. Sikora, D.D. Macdonald, Electrochimica Acta 45 (2000) 1875–1883.
[21] M.G.S. Ferreira, C. Melendres, Electrochemical, Optical Techniques for the Study
and Monitoring of Metallic Corrosion, Kluwer Academic publishers, Dordrecht,
The Netherlands, 1991, p. 219.
[22] C.Y. Chao, L.F. Lin, D.D. Macdonald, Journal of the Electrochemical Society 128
(1981) 1187–1194.
[23] S.M. Moon, S.I. Pyun, Electrochimica Acta 43 (1998) 3117–3126.
[24] C.A. Della Rovere, J.H. Alano, R. Silva, P.A.P. Nascente, J. Otubo, S.E. Kuri, Corro-
sion Science 57 (2012) 154–161.
[25] B. Zhang, Y. Li, F.H. Wang, Corrosion Science 52 (2010) 2612–2615.
[26] S.E. Frers, M.M. Stefenel, C. Mayer, T. Chierchie, Journal of Applied Electrochem-
istry 20 (1990) 996–999.
[27] J.B. Bessone, D.R. Salinas, C.E. Mayer, M. Ebert, W.J. Lorenz, Electrochimica Acta
37 (1992) 2283–2290.
[28] S. Gudić, J. Radošević, D. Krpan-Lisica, M. Kliškić, Electrochimica Acta 46 (2001)
2515–2526.
[29] S. Gudić, J. Radošević, A. Višekruna, M. Kliškić, Electrochimica Acta 49 (2004)
773–783.
[30] Z. Stoynov, Electrochimica Acta 35 (1990) 1493–1499.
[31] G.J. Brug, A.L.G. van der Eeden, M. Sluyters-Rehbach, J.H. Sluyters, Journal of
Electroanalytical Chemistry 176 (1984) 275–295.
[32] D.D. Macdonald, Journal of the Electrochemical Society 139 (1992) 3434–3449.
[33] J.A. Bardwell, M.C.H. McKubre, Electrochimica Acta 36 (1991) 647–653.
[34] X.Y. Mao, D.Y. Li, F. Fang, R.S. Tan, J.Q. Jiang, Materials Science and Engineering,
A 527 (2010) 2875–2880.
[35] W. Li, D.Y. Li, Applied Surface Science 240 (2005) 388–395.
[36] N.W. Ashcroft, N.D. Mermin, Solid State Physics, Saunders College Publishing,
New York, 1976.
[37] N.J. Cherepy, T.H. Shen, A.P. Esposito, T.M. Tillotson, Journal of Colloid and
Interface Science 282 (2005) 80–86.
[38] M. Ghrib, R. Ouertani, M. Gaidi, N. Khedher, M.B. Salem, H. Ezzaouia, Applied
Surface Science 258 (2012) 4995–5000.
[39] M. Schutze, Corrosion Environmental Degradation, vol. II, Wiley-VCH, Wein-
heim New York, 2000, p113.
[40] A. Lekatou, A.K. Sfikas, A.E. Karantzalis, D. Sioulas, Corrosion Science 63 (2012)
193–209.