Corrosion Science 73 (2013) 3243

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

Pitting corrosion of 304ss nanocrystalline thin lm

Chen Pan, Li Liu , Ying Li, Fuhui Wang
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, 62 Wencui Rd., Shenyang 110016, China

a r t i c l e

i n f o

Article history:
Received 5 November 2012
Accepted 25 March 2013
Available online 6 April 2013
Keywords:
A. Sputtered lm
B. AFM
C. Pitting corrosion

a b s t r a c t
Pitting corrosion behavior of coarse crystalline (CC) 304ss and its nanocrystalline (NC) thin lm have
been investigated by electrochemical measurement and in situ AFM observation in 3.5% NaCl solution.
Results show two effects of nanocrystallization on pitting corrosion behavior: (1) more frequent occurrence of metastable pits, but with lower probability of transition to stable pits, which is attributable to
differences in morphologies of sulfur and manganese as well as outstanding repassivation ability of NC
thin lm; (2) nanocrystallization decreases stable pit generation rate and its propensity to form larger
pit cavities, and modies the morphology of stable pit cavity.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Three hundred and four stainless steels have been extensively
used as good corrosion resistant materials. However, resistance
to pitting corrosion of 304ss in solutions containing Cl is not good
enough and adversely inuences the service life and integrity of
structures made of this material. Hence, there is need to improve
the corrosion resistance of 304ss. Some investigations have shown
that nanocrystallization can signicantly enhance the corrosion
resistance of stainless steels [13]. Among several nanocrystallization methods, magnetron sputtering technique has attracted considerable attention. Through the magnetron sputtering technique,
a homogeneous thin lm, having the same composition as the target, but with a smaller grain size, can be deposited on a material.
The sputtered thin lm has the same chemistry with the substrate,
which ensures good adhesion to the thin lm on the substrate [4].
In addition, the sputtered nanocrystalline thin lms have been
found to possess better corrosion resistance than the corresponding conventional coarse crystalline alloys [57] and have been used
successfully in high-temperature applications [810].
It is well known that the corrosion behavior of 304 stainless
steel mainly includes passive and pitting behavior. A previous
study [11] has demonstrated that nanocrystallization changed
the nucleation mechanism and the growth structure of the passive
lm on rolled coarse crystalline (CC) 304ss and also accelerated the
growth rate of the passive lm, thereby enhancing the passivation
ability of the material. On the other hand, the inuence of nanocrystallization on the pitting corrosion mechanism of CC 304ss is
not clearly known; therefore, it is signicant to study the inuence

Corresponding author. Tel./fax: +86 24 2392 5323.

E-mail address: liliu@imr.ac.cn (L. Liu).
0010-938X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.03.022

of nanocrystallization on the pitting corrosion behavior of CC

304ss.
Pitting corrosion is a complicated phenomenon, which is largely
dominated by random parameters [12]. The pit generation event
has been widely considered to be stochastic in nature, and pit initiation processes have been investigated via stochastic analysis
[13,14]. It is believed that both pit initiation rate and pit growth
probability inuence the pitting corrosion resistance. If a material
exhibits high pit initiation rate, metastable pits would spread over
the surface, and the pit would easily become a larger cavity, provided the material has a high pit growth rate. This stochastic approach could indicate the frequency of metastable pit events and
the probability of stable pits being formed, which deeply exposes
the stochastic nature of pitting corrosion [14].
In this work, a stochastic approach and in situ AFM observation
were employed to study the characteristic features of both the pit
initiation and the pit growth processes of the CC 304ss and its
sputtered thin lm in 3.5% NaCl solution. Our goal is to understand
the effect of nanocrystallization on the pitting process.

2. Experimental
2.1. Materials preparation
The composition (in wt.%) of CC 304ss was as follows: 8.054%
Ni, 17.10% Cr, 0.091% Mo, 1.280% Mn, 0.277% Cu, 0.003% As,
0.006% Sn, 0.387% Si, 0.045% C, 0.026% P, 0.002% S, and the rest
Fe. The NC thin lm was deposited on one side of a glass substrate
using the SBH-5115D DC magnetron sputtering system with CC
304ss as target. A glass substrate, much unlike a stainless steel substrate, will not likely interfere with the electrochemical responses
of the thin lm. The magnetron sputtering chamber was evacuated

C. Pan et al. / Corrosion Science 73 (2013) 3243

to 5  103 Pa, then lled with Ar, and maintained at 0.2 Pa. The
temperature of the substrate glass was approximately 200 C.
The DC power was 1800 W and the sputtering duration was 2 h.
The CC 304ss samples (10 mm  10 mm  10 mm) were ground
to 1000 grit SiC paper and degreased in acetone. The CC 304ss and
NC thin lm were either embedded in epoxy resin or parafn-resin,
leaving an exposed working area.

2.2. Materials characterization

The microstructure of the CC 304ss was characterized by optical
metallography. The grain size of the NC thin lm was characterized
by transmission electron microscopy (TEM) (JEM-2000EXII).
Transmission electron microscope, equipped with a high-angle
angular-dark-led (HAADF) detector and X-ray energy-dispersive
spectrometer (EDS) system, was used for electron diffraction,
HAADF imaging, and composition analysis. The cross-section of
the CC 304 was observed by scanning electron microscopy (SEM)
(XL30FEG). The phases of the two materials were analyzed by
X-ray diffraction (XRD) analysis.

2.3. Electrochemical experiments

All electrochemical measurements were performed using an
Autolab Electrochemical Measurement System (EG&G) in a conventional three-electrode cell, with a large platinum plate as the
counter electrode and a saturated calomel electrode (SCE) as the
reference electrode. All potential values reported in this paper
are with reference to SCE in saturated KCl solution whose potential
value vs. SHE is 0.2438 V. The aggressive medium used in all experiments was 3.5% NaCl solution prepared from reagent grade chemicals and distilled water. The test solution was degassed with
nitrogen for 1.5 h before experiment. A water bath was used to
maintain the solutions at 30 1 C during testing.
Prior to all electrochemical measurements, the specimens were
initially reduced potentiostatically at 1 VSCE for 2 min to remove
air-formed oxides on the surface and then kept in solution until a
stable corrosion potential was attained.
For the polarization measurements, the specimens were kept in
the NaCl solution until a stable corrosion potential was attained
and then scanned in 0.333 mV/s. For the induction time measurement, a potentiostatic technique (0.25 VSCE and 0.9 VSCE for CC
304ss and NC thin lm, respectively) was used to measure the anodic current trace. The current response to the applied potential was
recorded within a data-sampling interval of 0.2 s. A sudden increase was the result of the pit corrosion, which was conrmed
by morphology observation. The time interval for this sudden current increase is dened as the pit induction time.

33

2.5. In situ AFM measurements

For AFM measurements, the NC thin lm was cut into coupons
of dimensions 20 mm  20 mm  2 mm and xed in a Teon electrochemical cell with an O-ring to prevent the liquid from leaking
out. The measurements were carried out with a three-electrode
setup: the working electrode was the sample on the bottom of
the cell, the counter electrode was a Pt ring line with 0.25 mm
diameter around the cell, and an Ag line with 0.51 mm diameter
was used as the reference electrode. All the AFM experiments were
carried out in contact mode. In situ AFM scanning was performed
under anodic potential at 0.9 VSCE for NC thin lm. To calibrate
the potential of the Ag reference electrode with respect to the
SCE used for polarization experiments, the OCP differential was
determined using both reference electrodes, and a corresponding
potential (anodic) was imposed on the samples during AFM
measurements.
3. Results
3.1. Microstructure
The microstructural characteristics of the CC 304ss and NC thin
lm have been extensively described in a previous report [11]. The
grain sizes of the CC 304ss and the NC thin lm were found to be
about 100 lm and 50 nm, respectively. The possible occurrence
of austenite to ferrite transition in the NC thin lm is still being
investigated; nonetheless, such transition, for single phase structured sputtered thin lms, has been shown to have negligible inuence on corrosion resistance [16,17].
3.2. Potentiodynamic polarization measurements
The potentiodynamic polarization curves of the CC 304ss and
NC thin lm in 3.5% NaCl solution are presented in Fig. 1. It is obvious that the NC thin lm possesses superior pitting resistance compared to CC 304ss. The pitting corrosion morphologies of the
samples after polarization are shown in Fig. 2a and b for the CC
304ss and NC thin lm, respectively. In order to properly accommodate measurement errors, each experiment was replicated severally. Statistical analysis of the obtained results conrmed larger
size pits (with diameter of about 70 lm) on the CC 304ss, whereas
the pits formed on the NC thin lm had diameter of about 10 lm.

2.4. Pit diameter and pit depth measurements

For CC 304ss, the radius of pit mouth (a) was determined from
photomicrography by measuring the area of the pit mouth with a
planimeter in the microscope. The estimated error in a is 5%. Pit
depths, h, were measured by applying the Fine Focus Technique
[15], where the distances required shifting the optical objective between the focal points on the original surface of sample and on the
bottom of the pit are compared. The estimated error in h is 1 lm.
For the NC thin lm, the radius of pit mouth a and pit depth h
was obtained by AFM observation. The AFM resolution is 1.4 nm
in XY scan size and 0.5 nm in Z scan range. The AFM observation
was replicated severally on different samples. The results shown in
the paper are the average sizes.

Fig. 1. Potentiodynamic polarization plots of CC 304ss and NC thin lm in 3.5% NaCl

solution.

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C. Pan et al. / Corrosion Science 73 (2013) 3243

(a)

50 m

(b)

10 m

Fig. 2. SEM morphologies of CC 304ss (a) and NC thin lm (b) after corrosion.
Fig. 3. Potentiostatic polarization plots of CC 304ss (a) and NC thin lm (b) in 3.5%
NaCl solution.

The above results imply that both materials had pitting corrosion
behavior within the studied polarization range. Therefore, 0.25
VSCE and 0.9 VSCE were, respectively, chosen as the applied anodic
polarization potential for CC 304ss and NC thin lm to investigate
the differences in pitting corrosion behavior of the two materials.

3.3. Potentiostatic polarization measurement

The current traces for both samples under anodic potential are
shown in Fig. 3. The initial rapid decrease in current density corresponds to the formation of passive lms on the electrode surfaces.
After about 700 s of anodic polarization, the current density of CC
304ss shows a sudden rapid increase, which occurs after about
900 s for NC thin lm. The time interval for this sudden current increase is dened as the pit induction time. It is clear that the current traces of the two materials both comprise of two distinctive
stages: metastable pit (before induction time) and stable pit (after
induction time).
Fig. 3 shows the metastable pit current transients of CC 304ss
and NC thin lm, which reects the generation, growth, and
repassivation of the metastable pits. It is obvious that within
200 s, large metastable pits appeared on CC 304ss (in Fig. 4a). However, metastable pit events on NC thin lm (in Fig. 4b) are signicantly different from that of CC 304ss, with shorter transient

lifetime and lower spike height compared to CC 304ss. Fig. 4a also

displays the shape of a metastable pit current transient of CC
304ss: the slow rise of the current followed by a sharp decay of
the current corresponds to slow growth and rapid repassivation
of the metastable pits. The same metastable pitting events happened on the NC thin lm (shown in Fig. 4b), indicating that nanocrystallization did not alter the formation mechanism of the
metastable pit.

4. Discussion
4.1. Effect of nanocrystallization on metastable pit process
4.1.1. Effect of nanocrystallization on pit location
Pit initiation has been reported to proceed via initial dissolution
of MnS at the MnCr2O4/MnS interface in the presence of salt water
[18]. Webb et al. [19] proposed that the shape, size, and distribution of inclusions inuenced the pit initiation. The coarse crystalline CC 304ss usually undergoes hot-rolling or cold-rolling before
component-making, during which MnS inclusions were deformed
to be needle-shaped. Fig. 5 depicts an SEM image showing the typically needle-like MnS inclusions within the present stainless steel

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C. Pan et al. / Corrosion Science 73 (2013) 3243

specimen. However, the MnS inclusions in NC thin lms have not

been previously characterized, at least not in terms of shape and
size. The NC thin lm used in this experiment was prepared by
the magnetron sputtering technique which is a non-equilibrium
method employed to develop materials with ne crystalline structure that often exhibit high corrosion resistance. Therefore, the
shape and size of MnS inclusions in NC thin lm may differ from
that in CC 304ss, and could be responsible for the observed differences in metastable pitting events on the two materials. Fig. 6 displays a high-angle angular-dark-eld (HAADF) image (a) of NC thin
lm and the EDS results (b) of a scan made along the red line in (a).
It is obvious that there are no noticeable inclusions embedded in
NC thin lm (Fig. 6a). However, the EDS prole (in Fig. 6b) obtained
from the line-scanning along the red line reveals that the component element of MnS, sulfur and manganese, exists in NC thin lm.
That is to say, sulfur and manganese may melt into the a-Fe phase
as atoms instead of forming MnS inclusion embedded in the NC
thin lm. This seeming absence of MnS inclusions on the NC thin
lm should be responsible for the difference in the metastable pitting events compared with CC 304ss.
Since pit initiation in stainless steel has been conrmed to be
associated with MnS dissolution, and there is no MnS inclusion
in the NC thin lm, it is necessary to identify the pit initiation process for the NC thin lm. In order to illustrate clearly the differences in pit initiation mechanisms of the two materials, the
following experiments were carried out. The potentiostatic polarization of CC 304ss was performed under anodic polarization and

(a)

280nm

Fig. 4. Current transient features of CC 304ss (a) and NC thin lm (b) in 3.5% NaCl
solution.

(b)

Fe

MnS

Cr
Ni

Ti

Mn

10 m
Fig. 5. SEM morphology of MnS inclusion embedded in CC 304ss.

Fig. 6. (a) An HAADF image of NC thin lm and (b) EDS results of a scan made along
the red line in (a).

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C. Pan et al. / Corrosion Science 73 (2013) 3243

B
S

5m
Fig. 7. SEM morphology of CC 304ss after anodic polarization stopped at the time when current suddenly increased.

then stopped at the time when the current suddenly increased, the
time interval of which is dened as the pit induction time. Fig. 7
displays the morphology of CC 304ss after polarization (chemical
compositions of corresponding sites are shown). It is clear that
the pit initiation sites are within the dark gray area. The light gray
area is comprised mainly of alloy elements, such as Fe, Cr, Ni, and
Mn (shown in spectrum A). However, the composition of the dark
gray area includes not only alloy elements but also S (shown in
spectrum B), which suggests that the dark gray area should be
MnS inclusions. Replicate experiments on several samples conrmed that the pit initiation site on CC 304ss was on the MnS
inclusion. Analysis of the pit initiation site on NC thin lm was
by in situ AFM observation. Fig. 8ac illustrates the morphology
changes of the NC thin lm with progressing anodic polarization.
Fig. 8a shows that a lot of particles piled up on the surface of the
NC thin lm after 170 s of polarization. Also, there were many
voids in the boundaries of these observed particles piled up in different layers [20]. It is, however, difcult to determine the composition of these particles because they quite minute and formed
directly in the solution. However, XPS analysis of the passive lm
formed on NC thin lm in acid NaCl solution in a previous study
[21] showed the lm to be primarily composed of chromium oxide
and iron oxide.
In the subsequent 60 s, the void (in green1 circle) expanded and
deepened (Fig. 8b), which may indicate the growth of a metastable
pit. After that, the void became reduced at 340 s (shown in Fig. 8c).
Thus, the pit initiation site of NC thin lm could be said to be at the
boundaries of observed particles. Although 304 stainless steel has a
high C content (0.045%), the carbide was not observed clearly on
the surface of CC 304ss and NC thin lm by SEM and TEM in this
work, respectively.
4.1.2. Effect of nanocrystallization on pit initiation process
The above observations indicate that metastable pit events on
NC thin lm differed from that of CC 304ss. In order to elucidate
the metastable pit events of both materials in more detail, further
analysis of metastable pit transients was performed by counting
the number of current spikes as a function of time interval and
as a function of amplitude, and their corresponding distribution
using the method described by Burstein and co-workers [2224].
The analytical method counted the total number of spikes between
any two adjacent points in the data set whose amplitude differed
by an amount greater than or equal to an imposed threshold amplitude. The imposed thresholds had been taken to values low enough
1

For interpretation of color in Fig. 8, the reader is referred to the web version of
this article.

to include the background noise as well. Fig. 9 shows the electrochemical noise data of both materials in 3.5% Na2SO4 and 3.5% NaCl
solutions, respectively. Since the present study assumes that there
is no pitting corrosion on both materials in 3.5% Na2SO4 solution,
the electrochemical noise results of CC 304ss and NC thin lm in
this solution could be considered as background noise. Separation
of the background noise from the metastable pit current transients
can be made by detecting the point at which the graphs deviates
from one another (about 22 nA in this case). In order words, all
peaks of amplitude greater than 22 nA are metastable pit spikes,
while those of amplitude less than 22 nA were not considered
further.
Figs. 10 and 11 depict the average frequency and distribution of
metastable pitting events with various transient lifetimes and with
different spike heights on CC 304ss and NC thin lm, respectively.
The large error bars on the data points show that metastable pit
formation is a random process which is stochastic in nature [14].
For NC thin lm, the average frequency of metastable pit events
with shorter transient lifetime (25 s) is higher than that of CC
304ss, while that with longer transient lifetime (710 s) is a little
lower than that of CC 304ss (shown in Fig. 10a). Fig. 10b indicates
that the higher percent of the events accumulate at shorter time
intervals, which implies that metastable pits occurred more frequently on the NC thin lm compared with CC 304ss. In addition,
CC 304ss exhibits a higher average frequency than NC thin lm
at the range of larger spike height (Fig. 11a). Also, there is a greater
proportion of larger spikes height on CC 304ss (Fig. 11b). The larger
the spike height of the metastable pit, the more probable the transition from metastable pit to stable pit. Therefore, it can be observed that there is an increased probability of occurrence of
stable pits which develop from metastable pits for CC 304ss.
In summary, the pit initiation site on NC thin lm is at the
boundaries of the oxide particles. Because of so many boundaries
on the surface, metastable pit events on NC thin lm occur more
readily compared with CC 304ss, indicating that nanocrystallization promotes the metastable pit process. However, the outstanding repassivation ability of NC thin lm results in a decrease in the
probability of stable pits developing from metastable pits. In other
words, nanocrystallization promotes the occurrence of metastable
pitting events and inhibits the transition from metastable pits to
stable pits.
4.2. Effect of nanocrystallization on stable pit process
4.2.1. Effect of nanocrystallization on stable pit formation mechanism
The time when current increased rapidly is called the induction
time (s). Repetition of the same experiment yielded a number of

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C. Pan et al. / Corrosion Science 73 (2013) 3243

(a)

170s

(b)

230s
230s

39nm

44nm

(c)

340s

42nm

Fig. 8. In situ AFM images of NC thin lm (scale 2 lm  2 lm) in initial pitting stage under anodic polarization in 3.5% NaCl solution.

induction time values. The stable pit generation has been widely
considered as a stochastic process. Shibata and co-workers [25
29] proposed a stochastic theory of pitting corrosion, which assumed various models including the series or parallel combination
of an elemental birth stochastic process as well as the death stochastic process. The stochastic model could rationally explain stochastic distributions of induction time for pit formation. The
proposed theory recognizes two models:
Type A: Pure birth stochastic models, which only consider pit
generation events.
Type B: Birth and death stochastic models, which assume stochastic pit generation and pit repassivation.
The expected equations for the survival probability (Psur) and
time for pit initiation formulated for each model are shown in
Table 1, and corresponding curves between ln (Psur) and time are
illustrated in Fig. 12. The survival probability could be dened as:
Fig. 9. Determination of the threshold current required to distinguish pit current
transients from background noise.

Psur 1 

i
1N

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C. Pan et al. / Corrosion Science 73 (2013) 3243

Fig. 10. (a) Average frequencies of metastable events with different transient
lifetime for both materials and (b) transient lifetime distribution for the both
materials under anodic polarization in 3.5% NaCl solution.

where the symbol i is the order in the total number, N, the total
number of measured induction time.
To dene the exact model, the distribution of the induction time
has to be tted to a specic model by numerical or graphic simulation using the equations for an assumed model. Fig. 13 displays
the logarithm of the survival probability (Psur) as a function of
induction time (s) for CC 304ss (a) and NC thin lm (b), respectively. It is obvious that both plots exhibit linear behavior. This distribution type is the specic character of A2 model (a series birth
stochastic model of stable pit generation process), which is expressed in the equation:

Pt expmkt  t0 

where k is the stable pit generation rate, t0 is the incubation time,

and m is the number of incorporated processes. The stable pit generation rate k is calculated according to Eq. (2). From the results of
Fig. 13, two kinds of information can be obtained: Firstly, plots of
the distribution of induction time for CC 304ss and NC thin lm display analogous shapes, which suggest that nanocrystallization has
no inuence on the stable pit generation mechanism. A series of
stochastic birth models could be used to describe the stable pit generation mechanism of both materials. Secondly, the stable pit generation rate of NC thin lm (2.40  103 s1) is lower than that of
CC 304ss (2.69  103 s1), which means that nanocrystallization
inhibits the stable pit formation process of CC 304ss.

Fig. 11. (a) Average frequency of metastable events with different spike height and
(b) spike height distribution for the both materials under anodic polarization in
3.5% NaCl solution. The height ranges are as follows: (A) 22100 nA, (B) 100
200 nA, (C) 200300 nA, (D) 300400 nA, (E) 400500 nA, (F) 500600 nA, (G) 600
700 nA, (H) 700800 nA, and (I) >800 nA.

Table 1
Analytical expressions of the survival probability function for various stochastic
models.
Model

Survival probability function

Birth process
A1 simple
A2 series
A3 parallel
A4 combination

P(t) = exp[k(t  t0)]

P(t) = exp[mk(t  t0)]
P(t) = 1  {1  exp[k (t  t0)]}m
P(t) = Rfi exp[ki (t  t0)]

Birth and death process

B1 parallel
B2 series

P(t) = l/(k + l) + k/(k + l) exp[(k + l)(t  t0)]

P(t) = exp[ak(t  sc) exp (lsc)]

4.2.2. Effect of nanocrystallization on stable pit growth

Beyond the induction time, the current densities of both materials (Fig. 3) showed a sudden rapid increase, indicating passive
lm break down and subsequent occurrence of stable pits. Pit
growth is usually modeled using a non-homogeneous Markov process [30,31]. To achieve this, the theoretical foundations of extreme
value statistics have been employed. The solution of the Kolmogorov forward equations [30,31], governing the growth of an individual pit, is in the domain of attraction of the Gumbel distribution
[32]. In many applications, the Gumbel-type distribution has been

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C. Pan et al. / Corrosion Science 73 (2013) 3243

Fig. 14. The charge results from the formation of a stable pit and
can be related to the physical volume of the stable pit via Faradays
equation, Eq. (3), which is based on the correlation between optical
pit size and anodic current trace charge [36]. If the pits are assumed to be hemispherical, then the pit radius/depth can be calculated, using Eq. (4).

Fig. 12. A schematic illustration of ln Psur vs. time for various stochastic models.

CM
nFD

r!
3 3V
 10; 000
2p

where V (cm3) is the volume of largest stable pit, C is the quantity of

charge passed from the largest current spike within each of the
potentiostatic measurements, M is average molecular mass of CC
304ss and NC thin lm (55.35 g/mol), D is density of both materials
(7.93 g/cm3), F is Faraday constant, and R (lm) is the radius of largest stable pit.
Extreme value statistical analysis was employed according to
the following procedure [32]: (1) all calculated extreme value data
were arranged in ascending order from the smallest to the largest
value; (2) the probability F(Y) is dened as M/(N + 1), where M is
the rank in the ordered extreme values (M = 1, 2, 3, . . . , M) and N
the total number of extreme value data. The reduced variant (Y)
can be calculated by the formula Y = ln{ln[F(Y)]}.
The largest stable pit size within each potentiostatic measurement was calculated, and the values were subjected to extreme
value statistics analysis according to the above mentioned
procedure. Fig. 15 shows the relationship between values of the
reduced variant and the ordered pit sizes. The linearity of the points
demonstrates that the data actually did t the Gumbel distribution.
The scale parameter a and location parameter l for CC 304ss and NC
thin lm were obtained by the linear tting and are shown in
Table 2. These values describe the shape and center of the
probability distribution of the largest stable pit sizes expected from
electrodes identical to that used for the measurements and treated
in the same manner for the same period of time.
The probability that the largest pit depth is described by a
double exponent (Gumbel-type extreme value distribution) can
be calculated by the following equation [35]:




D  l a ln S
P 1  exp  exp

where P is probability of the pit depth, D is pit depth, l is the central

parameter (the most frequent value), S is the ratio of the area over

Fig. 13. Plots of survival probability (Psur), vs. time for CC 304ss and NC thin lm in
3.5% NaCl solution.

found to account for the stochastic nature in the observed behavior

of pitting corrosion systems [3335].
The extreme value in the present study is dened as the largest
pit depth in each of the potentiostatic measurements. The largest
pit depth can be determined by considering the quantity of charge
passed from the largest current spike. This was achieved by integrating the current trace over time as illustrated schematically in

Fig. 14. A scheme about the determination method of stable pit charge.

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C. Pan et al. / Corrosion Science 73 (2013) 3243

for the CC 304ss, which is prone to formation deep stable pits in

the test solution.
The current transient in Fig. 3 exhibits two straight lines with
different slopes beyond the induction time (s). The rst and the
second straight lines are associated with the periods of stable pit
growth [37]. The increase in current transient after s can be represented by the EngellStolica equation for pitting corrosion [37]:

log I log B b log t

Fig. 15. Gumbel distribution parameters for CC 304ss and NC thin lm in 3.5% NaCl
solution.

Table 2
Gumbel distribution parameters for CC 304ss and NC thin lm in 3.5% NaCl solution.
Samples

Scale parameter (a)

Location parameter (l)

CC 304ss
NC thin lm

11.57
3.56

33.95
5.98

where b is a constant depending on the applied potential and the

concentration of NaCl and is given by the slope of the log i vs. log t
curve. The values of b relates to the stable pit growth. It can be observed that both rst and second slopes of the straight lines of CC
304ss (shown in Fig. 3a): b1 = 39.65, b2 = 3.28, are larger than those
of NC thin lm (shown in Fig. 3b): b1 = 9.41, b2 = 2.32. These results
suggest that the growth rates of stable pit on the CC 304ss are signicantly faster than those of the NC thin lm. That is to say, nanocrystallization indeed retards the growth process of stable pit
formed on CC 304ss.
4.2.3. Effect of nanocrystallization on pit morphology
The above experimental results demonstrate that nanocrystallization inhibits formation and growth of stable pits on CC 304ss.
However, it is uncertain how nanocrystallization inuences the
morphology of the resulting stable pits. It has been suggested that
pit geometry could be described by the ratio of the radius of pit
mouth (a) to pit depth (h) (a/h) [38]:
a/h < 1, pit geometry exhibits deep-hole shape.
a/h = 1, pit geometry shows hemispherical shape.
a/h > 1, pit geometry displays shallow-disk shape.
In order to illustrate the morphology of stable pits on both materials, optical microscopy and AFM were employed to measure (a)
and (h) for stable pits on CC 304ss and NC thin lm, respectively.
Fig. 17 shows the ratio of the radius of pitting mouth to pitting
depth for CC 304ss. Most of the values of a/h distributed around
11.5, indicates that the pitting geometry of stable pits is described
by shallow-disk shape. This result is in accordance with the results
reported elsewhere [39]. Fig. 18 illustrates the SEM micrographs of
the surface (a) and the cross-section (b) along the red line in (a) of
stable pit on CC 304ss, which demonstrates that the geometry of

Fig. 16. Probabilities of various diameters pits occurring for CC 304ss and NC thin
lm in 3.5% NaCl solution.

which prediction is to be made to the area over which the data was
measured, and a is the scale parameter which denes the width of
the distribution.
The probabilities of a series of given pit depths were calculated
using Eq. (5) in terms of obtained a and l values for CC 304ss and
NC thin lm, respectively, and the results are shown in Fig. 16. It is
obvious that the smaller the depth of the stable pit, the higher the
probability. The probability of larger stable pits (>5 lm) is much
higher for CC 304ss than NC thin lm. The reciprocal of the probability of the given pit depth corresponds with the expected time for
this given pit depth to occur. According to Fig. 16, the probability of
generating a 10 lm stable pit is larger on the CC 304ss than on the
NC thin lm. That is to say, the expected time for generating a
10 lm stable pit is shorter on the CC 304ss. This implies that it is
very hard to form deeper stable pits on the NC thin lm, unlike

Fig. 17. Pitting geometry of CC 304ss in 3.5% NaCl solution.

41

C. Pan et al. / Corrosion Science 73 (2013) 3243

plots of AFM images (shown in Fig. 20). Compared with CC 304ss,

most of the values of a/h are much higher and fall within 35.
Hence, the geometry of stable pits on NC thin lm is more shallow-disk than that on CC 304ss. In order to distinguish the morphology of stable pits on the two materials, semi-elliptic shape and
shallow-disk shape are used to describe the geometry of stable pits
for CC 304ss and NC thin lm, respectively. In addition, it can also be
seen from Figs. 17 and 19 that the measured stable pits depth on CC
304ss and the NC thin lm are, respectively, of the same order of
magnitude with the calculated ones shown in Fig. 15. From the

(a)

300 m

(b)

300 m

4.7 m

28.7 m

Fig. 18. SEM geometry of stable pit for surface (a) and cross-section (b) of CC 304ss.

Fig. 20. AFM image of stable pit on NC thin lm.

Fig. 19. Pitting geometry of NC thin lm in 3.5% NaCl solution.

stable pits on CC 304ss is shallow-disk indeed. Fig. 19 displays the

a/h ratio for NC thin lm, which was obtained by measuring the
width and depth of stable pits with the corresponding linear scan

Fig. 21. Lacy cover of stable pit grown on CC 304ss in 3.5% NaCl solution.

42

C. Pan et al. / Corrosion Science 73 (2013) 3243

above results, it is obvious that the values of a/h did depend on

nanocrystallization and increased signicantly with decreasing
grain size. Thus, nanocrystallization changes the morphology of stable pits from semi-elliptic shape to shallow-disk shape.
It is believed that stable pits are covered with a nely perforated cover, acting as a diffusion barrier which stabilizes pit
growth. In the present study, majority of the stable pits formed
on CC 304ss were enclosed with a perforated cover. And Fig. 21 displays the SEM micrograph of a stable pit on CC 304ss with a lacy
metal cover which helps to maintain the aggressive local chemistry
within the pit and stabilizes pit growth. However, it has not been
reported whether or not there is a pit cover on NC thin lm. To gain
insight into the growth mechanism of stable pit on NC thin lm,
in situ AFM was employed to record the entire pitting growth
process.
Fig. 22 shows that stable pits appeared on the NC thin lm with
prolonged potentiostatic polarization. According to in situ AFM
observation, the stable pit was initially about 650 nm wide and
140 nm deep after polarization 10 min, as determined from linear

140nm
650nm

scanning plots. Afterward, the particles dissolved gradually and

the pit propagated, until the dimensions of the stable pit were
about 750 nm wide and 141 nm deep. Within some minutes, the
width and depth of the stable pit was about 910 nm and 148 nm,
suggesting that the stable pit became larger with increasing polarization time. From the in situ AFM results, two conclusions could
be drawn; rstly, the width of stable pit on NC thin lm changes
more rapidly than the depth, which could explain the geometry
of stable pits on NC thin lm being shallow-disk shape; secondly,
no lacy cover existed during stable pit growth, which indicates that
the growth mechanism of stable pits on NC thin lm is different
from that on CC 304ss.
The present study proposes that the absence of the lacy pit cover on the NC thin lm could be related to internal residual stress
induced by the nanocrystallization process [40]. Internal residual
stresses in nanocrystalline thin lm prepared by magnetron sputtering technique are extremely high [41]. These stresses are normally comprised of two types of stress, namely thermal and
intrinsic stresses. The thermal contribution results from the differ-

141nm
750nm

148nm
910nm

Fig. 22. In situ AFM images of NC thin lm (scale 2 lm  2 lm) in stable pitting formation stage under anodic polarization in 3.5% NaCl solution.

C. Pan et al. / Corrosion Science 73 (2013) 3243

ence in temperatures of deposition and stress measurements when

thin lms and substrates exhibit different thermal expansion coefcients. The intrinsic stress is introduced and built up in the lms
during deposition. The occurrence of internal residual stress in NC
thin lm may inhibit the formation of lacy cover during stable pit
growth and furthermore, change the growth mechanism of stable
pits on NC thin lm. In other words, nanocrystallization retards
the nucleation and growth process of stable pits and changes the
geometry and growth mechanism of stable pits.
5. Conclusions
Nanocrystallization leads to the existence of the chemical elements, sulfur and manganese (in the uncombined state) in the
CC 304ss, leading to differences in the pit initiation sites on CC
304ss and NC thin lm: the former is on the MnS inclusions, and
the latter is at the boundaries of observed particles. The pit initiation site and outstanding repassive ability of NC thin lm ensure
that metastable pit events occur more frequently, and the probability of stable pits developing from metastable pits is lower compared with that of CC 304ss. Nanocrystallization retards the
formation and growth process of stable pits, changes the geometry
and growth mechanism of stable pits, which enhance the pitting
corrosion resistance of CC 304ss.
Acknowledgements
The investigation was supported by the National Natural Science Fund of China under the Contract No.50801063 and 512.
The authors acknowledge Dr. Tao Zhangs contributions to the discussion on stochastic analysis of metastable pit events and Emeka
E. Oguzie (Nigeria) for suggestions and modication of English.
References
[1] R.B. Intrui, Z. Szklarska-Smialowsska, Localized corrosion of nanocrystalline
304 type stainless steel lm, Corrosion 48 (1992) 398403.
[2] N. Li, Y. Li, S.G. Wang, F.H. Wang, Electrochemical corrosion behavior of
nanocrystallized bulk 304 stainless steel, Electrochim. Acta 52 (2006) 760
765.
[3] X.Y. Wang, D.Y. Li, Mechanical and electrochemical behavior of nanocrystalline
surface of 304 stainless steel, Electrochim. Acta 47 (2002) 39393947.
[4] F.H. Wang, H.Y. Lou, Factors affecting adhesion between magnetron sputter
deposited stainless steel coating and a carbon steel substrate, Mater. Sci. Prog.
3 (1989) 133137.
[5] W. Ye, Y. Li, F.H. Wang, Effects of nanocrystallization on the corrosion behavior
of 309 stainless steel, Electrochim. Acta 51 (2006) 44264432.
[6] M.P. Ryan, N.J. Laycock, H.S. Isaacs, R.C. Newman, Corrosion pits in thin lms of
stainless steel, J. Electrochem. Soc. 146 (1999) 9197.
[7] G.Z. Meng, Y. Li, F.H. Wang, Electrochemical behaviour of Fe20Cr
nanocrystalline coatings, J. Soc. Corros. Prot. 26 (2006) 1118.
[8] H.Y. Lou, F.H. Wang, S.L. Zhu, B. Xia, L. Zhang, Oxide formation of K38G
superalloy and its sputtered micrograined coating, Surf. Coat. Technol. 63
(1994) 105114.
[9] F.H. Wang, H.Y. Lou, S.L. Zhu, W.T. Wu, The mechanism of scale adhesion on
sputtered microcrystallized CoCrAl lms, Oxid. Met. 45 (1996) 3949.
[10] F.H. Wang, Oxidation resistance of sputtered Ni3(AlCr) nanocrystalline coating,
Oxid. Met. 47 (1997) 247254.
[11] C. Pan, L. Liu, Y. Li, S.H. Wang, F.H. Wang, Passive lm growth mechanism of
nanocrystalline 304 stainless steel prepared by magnetron sputtering and
deep rolling techniques, Electrochim. Acta 56 (2011) 7740.
[12] T. Shibata, T. Takeyama, Pitting corrosion as a stochastic process, Nature 260
(1976) 315316.

43

[13] T. Shibata, Y. Zhu, The effect of lm formation temperature on the stochastic

processes of pit generation on anodized titanium, Corros. Sci. 36 (1994) 1735
1739.
[14] T. Zhang, Y.G. Yang, Y.W. Shao, G.Z. Meng, F.H. Wang, A stochastic analysis of
the effect of hydrostatic pressure on the pit corrosion of Fe20Cr alloy,
Electrochim. Acta 54 (2009) 39153922.
[15] ASTM Stand G46-94. Standard Guide for Examination and Evaluation of Pitting
Corrosion. ASTM International, West Conshohocken, PA, 2005.
[16] D.C. Liu, F.H. Wang, C.N. Cao, H.Y. Lou, The pitting corrosion resistance of
microcrystalline coatings of sputtered 321 stainless steel, Corrosion 46 (1990)
975982.
[17] D.C. Liu, F.H. Wang, C.N. Cao, H.Y. Lou, Inuence of phase composition on
pitting corrosion resistance of sputtered layer of 1Cr18Ni9Ti stainless steel,
Acta Metall. Sin. 25 (1989) B299B302.
[18] S.J. Zheng, Y.J. Wang, B. Zhang, Y.L. Zhu, C. Liu, P. Hu, X.L. Ma, Identication of
MnCr2O4 nano-octahedron in catalyzing pitting corrosion of austenitic
stainless steels, Acta Mater. 58 (2010) 50705085.
[19] E.G. Webb, T. Suter, R.C. Alkire, Microelectrochemical measurements of the
dissolution of single MnS inclusions, and the prediction of the critical
conditions for pit initiation on stainless steel, J. Electrochem. Soc. 148 (2001)
B186B195.
[20] L. Liu, Y. Li, F.H. Wang, Inuence of nanocrystallization on pitting corrosion
behavior of an austenitic stainless steel by stochastic approach and in-situ AFM
analysis, Electrochim. Acta 55 (2010) 24302436.
[21] C. Pan, L. Liu, Y. Li, B. Zhang, F.H. Wang, The electrochemical corrosion behavior
of nanocrystalline 304 stainless steel prepared by magnetron sputtering, J.
Electrochem. Soc. 159 (2012) C453C460.
[22] G. Ilevbare, G. Burstein, The role of alloyed molybdenum in the inhibition of
pitting corrosion in stainless steels, Corros. Sci. 43 (2001) 485513.
[23] G. Burstein, S. Vines, Repetitive nucleation of corrosion pits on stainless steel
and the effects of surface roughness, J. Electrochem. Soc. 148 (2001) B504
B516.
[24] G. Burstein, R. Soutob, Improvement in pitting resistance of stainless steel
surfaces by prior anodic treatment in metasilicate solution, J. Electrochem. Soc.
151 (2004) B537B542.
[25] T. Shibata, Stochastic studies of passivity breakdown, Corros. Sci. 31 (1990)
413423.
[26] T. Shibata, M. Ameer, Stochastic processes of pit generation on zirconium with
an anodic oxide lm, Corros. Sci. 33 (1992) 16331643.
[27] T. Shibata, Y. Zhu, The effect of lm formation potential on the stochastic
processes of pit generation on anodic titanium, Corros. Sci. 36 (1994) 153163.
[28] T. Shibata, Y. Zhu, A stochastic analysis of ow velocity effects on the pit
generation process on anodized titanium, Corros. Sci. 37 (1995) 853862.
[29] T. Shibata, Statistical and stochastic approaches to localized corrosion,
Corrosion 52 (1996) 813830.
[30] J. Provan, E. Rodriguez, Development of a Markov description of pitting
corrosion, Corrosion 45 (1989) 178188.
[31] P. Aziz, Application of the statistical theory of extreme value to the analysis of
maximum pit, Corrosion 12 (1956) 495505.
[32] E.J. Gumbel, Statistics of Extremes, Columbia University Press, New York, 1957.
[33] G. Engelhardt, D. Macdonald, Unication of the deterministic and statistical
approaches for predicting localized corrosion damage. I. Theoretical
foundation, Corros. Sci. 46 (2004) 27552780.
[34] A. Valor, F. Caleyo, L. Alfonso, D. Rivas, J. Hallen, Stochastic modeling of pitting
corrosion: a new model for initiation and growth of multiple corrosion pits,
Corros. Sci. 49 (2007) 559579.
[35] T. Zhang, Y. Yang, Y. Shao, G. Meng, F. Wang, A stochastic analysis of the effect
of hydrostatic pressure on the pit corrosion of Fe20Cr alloy, Electrochim. Acta
54 (2009) 39153922.
[36] S. Pride, J. Scully, J. Hudson, Metastable pitting of aluminum and criteria for the
transition to stable pit growth, J. Electrochem. Soc. 141 (1994) 30283040.
[37] H.H. Hassan, Effect of chloride ions on the corrosion behaviour of steel in 0.1 M
citrate, Electrochim. Acta 51 (2005) 526535.
[38] D. Sun, Y. Jiang, Y. Tang, Q. Xiang, C. Zhong, J. Liao, J. Li, Pitting corrosion
behavior of stainless steel in ultrasonic cell, Electrochim. Acta 54 (2009) 1558
1563.
[39] P. Ernst, R.C. Newman, Pit growth studies in stainless steel foils. I. Introduction
and pit growth kinetics, Corros. Sci. 44 (2002) 927941.
[40] R. Daniel, K.J. Martinschitz, J. Keckes, C. Mitterer, The origin of stresses in
magnetron-sputtered thin lms with zone T structures, Acta Mater. 58 (2010)
26212633.
[41] N.R. Shamsutdinov, A.J. Bottger, F.D. Tichelaar, The effect of Cu interlayers on
grain size and stress in sputtered FeCu multilayered thin lms, Scripta Mater.
54 (2006) 17271732.