Assessment of intergranular corrosion (IGC) in 316(N) stainless steel

using electrochemical noise (EN) technique

M.G. Pujar
a,
*
, N. Parvathavarthini
a
, R.K. Dayal
a
, S. Thirunavukkarasu
b
a
Corrosion Science and Technology Division, Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India
b
Non-Destructive Evaluation Division (NDED), Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India
a r t i c l e i n f o
Article history:
Received 19 May 2008
Accepted 26 April 2009
Available online 7 May 2009
Keywords:
A. Stainless steel
B. Electrochemical noise
C. Intergranular corrosion
a b s t r a c t
In the present work, an attempt was made to demonstrate the use of electrochemical noise (EN) tech-
nique in assessment of intergranular corrosion (IGC) in 316(N) stainless steel (SS). Degree of sensitization
(DOS) in the specimens aged at 923 K for 24, 40, 50 and 100 h was determined using double loop elec-
trochemical potentiodynamic reactivation (DLEPR) technique. Immediately after applying a prior precon-
ditioning treatment, current and potential noise measurements were made. The DOS was determined
from standard deviation of current noise (r
I
) versus time plot and it was found to bear a good correlation
with the values obtained by DLEPR. Shot noise analysis of the EN data conrmed the above results.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Sensitization refers to the precipitation of chromium rich car-
bides along the grain boundaries and an associated depletion of
chromium in the adjacent regions which could lead to IGC when
exposed to corrosive media. It is well established that extensive
heating or slow cooling in the temperature range of about 775
1125 K leads to sensitization in austenitic stainless steels. When
exposed to corrosive media the material becomes susceptible to
IGC or intergranular stress corrosion cracking (IGSCC). The typical
tests which are followed to detect IGC in SS qualitatively are as fol-
lows. The samples are electrolytically etched in oxalic acid solution
as per ASTM standard A262 Practice A [1]. The etched surface is
examined at a magnication of 250 and is characterized as step,
dual or ditch structure. Further all the samples are tested in Cu
CuSO
4
H
2
SO
4
solution as per ASTM standard Practice E [1]. The
specimens are bent through 180 over a diameter equal to the
thickness of the specimen being bent. The bent specimens are
examined under low magnication (20) for the appearance of
cracks. If cracks are found it is concluded that the samples are sen-
sitized and hence susceptible to IGC. However, these two tests are
only qualitative in nature, which do not quantify the extent of IGC.
The latter test is also called as go-no-go test which is used more for
accepting or rejecting the steels based on the absence or the pres-
ence of the cracks. Need for a rapid, quantitative and non-destruc-
tive test method, led many researchers to develop electrochemical
potentiodynamic reactivation (EPR) tests. The EPR test is based on
the fact that when a sensitized specimen is kept at passive
potential, the passive lm formed on the chromium depleted zone
along the grain boundaries is defective compared to that formed on
the grain interior. During the rapid reactivation scan, the defective
passive lm breaks down easily and contributes to the measured
anodic current. EPR technique was developed by Cihal et al. [2],
Novak et al. [3] and Clarke et al. [4]. This technique is a quantita-
tive, non-destructive and rapid method, which is essentially suit-
able for eld use. This technique was standardised by ASTM to
quantify the DOS in AISI types 304 and 304L stainless steels [5].
The EPR technique has been successfully used to quantify the
DOS in other stainless steels, alloy 800 and Ni base alloys [68]
too. Two versions of the EPR technique are practiced today, viz.
the single loop technique and the double loop technique [9]. Dou-
ble loop technique has an advantage over single loop technique in
that it automatically compensates for changes in alloy composi-
tion, and in that the surface nish is not very critical, which makes
it an automatic choice for on-eld applications. Reactivation
charge, ratio of reactivation to activation charge, peak reactivation
current density, ratio of peak current densities on reactivation to
activation are some of the parameters used to quantify the DOS.
Though the EPR technique provides a criterion for identifying
the complete absence of sensitization and, thus, is useful in quality
control of fabricated components, it does not readily provide an
acceptance criteria if a certain DOS is present in the material. Many
studies in literature have attempted comparison of DOS measured
using EPR technique with that determined by more established
practices [24,7], but very few of these are quantitative [2,4]. De-
spite all these efforts, EPR technique has not shown much promise
as a tool for quantifying DOS. This is because of its high sensitivity
to the changes in chemical compositions of the stainless steels e.g.
two alloys with different chemical composition but with the same
0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.04.028
* Corresponding author. Tel.: +91 44 27488766; fax: +91 44 27480121.
E-mail address: pujar55@gmail.com (M.G. Pujar).
Corrosion Science 51 (2009) 17071713
Contents lists available at ScienceDirect
Corrosion Science
j our nal homepage: www. el sevi er. com/ l ocat e/ cor sci
DOS need not give the same reactivation ratio. Secondly, inconsis-
tencies exist in the correlation between ASTM A262 Practice E and
EPR DOS results due to effects of temperature, which does not per-
mit a threshold DOS to be dened. Thus, it becomes imperative to
look for an alternative non-destructive technique to assess the DOS
in sensitized SS.
Fluctuations in the electrical quantities of electrochemical sys-
tems, such as cell current and electrode potential are often referred
to as electrochemical noise (EN), wherein the word noise is used
to indicate random, incoherent acoustic or electrical uctuations
[10]. EN technique measures the stochastic uctuations of the cor-
rosion potential and the corrosion current. This technique has been
found to be very useful for studying the corrosion processes. The
information obtained involves the detection of the onset of various
forms of localized corrosion including stress corrosion cracking
(SCC), [1116], the study of corrosion inhibitors [17], the evalua-
tion of the extent of the corrosion process through a correlation
with either the voltage noise or current noise [18,19] and study
of the electrode processes like repassivation [20,21]. Recently,
some workers [22] have shown that EN technique can be success-
fully used to detect the susceptibility to IGC in aluminum alloys.
These workers used both the noise resistance (R
N
) as well as the
shot noise parameters to study the IGC in aluminum alloys
successfully.
However, there is no literature describing the use of EN tech-
nique to detect and quantify the DOS in AISI austenitic stainless
steels of Type 316SS or 316(N). This might also be due to the dif-
culty in collecting the EN signals specically from the sensitized
grain boundaries, which could be correlated with the DOS. In the
present paper, the current and the potential EN signals from the
sensitized grain boundaries of 316(N) SS were collected and ana-
lyzed using the statistical parameters as well as those obtained
using the shot noise theory. A good correlation was found to exist
between the charge values derived from these parameters with the
DOS % values obtained using the conventional DLEPR technique.
Thus, it was demonstrated that EN technique can be successfully
used to detect the IGC in 316(N) SS.
2. Experimental procedure
Nitrogen containing 316 SS was used in this investigation. The
chemical composition of the material is presented in Table 1. As-
received material was in the mill-annealed condition. From the
SS plates, 10 mm 10 mm t mm (thickness) specimens were
cut and following heat treatments were carried out: 316(N) SS:
1323 K-1 h-air cooling (AC), 923 K-24 h-AC, 923 K-40 h-AC,
923 K-50 h-AC, 923 K-100 h-AC.
From each heat treated specimen 10 mm 10 mm t mm
(thickness) specimen were cut for electrochemical tests namely
DLEPR and EN studies. For these tests, specimens were mounted
in epoxy resin (Araldite), after xing small brass rods with M4
threading to them using silver paint for electrical connection. The
specimens were polished up to ne diamond (1 lm) nish. All
the specimens were ultrasonically cleaned in soap solution, de-
greased, rinsed in distilled water and nally dried.
2.1. Double loop EPR test
As received specimen as well as all the heat treated specimens
were subjected to this test. These tests were conducted in the
polarization cell containing 0.5 M sulphuric acid + 0.01 M Ammo-
nium thiocyanate solution. Dry, oxygen free, argon gas was purged
through the solution for 1 h before starting any experiment. The
mounted specimen was immersed in the solution after polishing
to ne diamond nish. Open circuit potential (OCP) was noted.
All the potential measurements were conducted using a saturated
calomel electrode (SCE). The specimen was polarized to 500 mV
(SCE) and kept at that potential for 2 min, then the specimen was
anodically polarized from 500 mV (SCE) to +300 mV (SCE) and
then cathodically polarized to OCP from +300 mV (SCE) at a scan
rate of 100 mV/min using Solartron Model 1287 electrochemical
interface. For each specimen, the activation and reactivation curves
were recorded. From these curves reactivation current density (I
R
)
and activation current density (I
A
) were measured and (I
R
/I
A
100)
% was calculated. This value represents the DOS % for the specimen
under study.
2.2. EN measurements
Electrochemical current noise is generally measured as the gal-
vanic coupling current between two nominally identical working
electrodes, with the current being measured using a zero resis-
tance ammeter (ZRA) to ensure that the two electrodes are at the
same electronic potential [23]. Electrochemical noise studies on
the specimens were performed such that two nominally identical
specimens of the same area as well as surface nish were taken,
wherein one specimen was the thermally aged whose IGC behav-
iour using EN technique was under study and the other one was
the same SS specimen in the solution-annealed condition. It is re-
ported that the current noise is considered to be produced by a
large number of independent current sources and that the power
of the uncorrelated current noise from the various regions of the
electrode will add [24]. Thus, it is clear that the current signals gen-
erated from the sensitized grain boundaries in the sensitized spec-
imen (working electrode) would be measured compared to the
non-sensitized electrode (held at the ground) which would not
contribute such current signals. The specimens were polished up
to 1 lm nish, washed in soap water and degreased in acetone. Po-
tential and current noise measurements were performed by short-
ing together these two specimens as the two working electrodes.
The current owing between the two working electrodes, as well
as the potential between the working electrode and a reference
electrode are monitored. The area of each electrode exposed to
the solution was about 1.0 cm
2
.
The potentiostat, which can perform this experiment actively,
holds the working electrode connection at the ground potential
by a small amplier circuit. If one working electrode is directly
connected to ground and the other is connected to the working
electrode cable, they are both held at the same potential and are,
in effect, shorted together. Any current, which ows between
the two electrodes, is measured by the instruments of current mea-
surement circuits thus creating a ZRA. The potential is measured
between the working electrodes (since they are shorted together,
both working electrodes are at the same potential) and a refer-
ence electrode.
Table 1
Chemical composition of 316(N) SS.
Elements Weight (%)
316(N) SS
C 0.043
Mn 1.54
Si 0.585
S 0.005
P 0.022
Ni 10.23
Cr 17.18
Mo 1.85
Cu 0.207
B
N 0.075
Fe Balance
1708 M.G. Pujar et al. / Corrosion Science 51 (2009) 17071713
The correlated signals of current and potential were collected at
the sampling frequency of 1 Hz. EN experiments were conducted in
deaerated 0.5 M H
2
SO
4
containing 0.01 M NH
4
SCN at room tem-
perature. The potential signals were measured against a SCE.
2.3. Preconditioning before EN measurements
From the DLEPR experiments, it was noted that the dissolution
of the sensitized grain boundaries took place at 0.150 V (SCE)
during the reverse scan. Therefore it was decided to activate the
grain boundaries by dissolving them at the same potential before
starting the EN measurements. Thus, using the usual arrangement
of three electrodes (working, counter and reference), the DLEPR
experiment was performed. However, the reverse scan was
stopped at 0.150 V (SCE) and immediately the specimen was held
at the same potential for 5 min. As soon as the impressed potential
was removed, the EN measurements were started in the same solu-
tion using a two-electrode arrangement described in the above
section detailing the EN measurement. The current and the poten-
tial EN measurements were continued for 2 h. In the second exper-
iment (on the same specimen, after polishing it freshly), the
activation of the grain boundaries was conducted by applying a po-
tential of 0.150 V (SCE) for 10 min as described above and subse-
quently EN data was collected for 1 h. The specimens were
observed under the optical microscope after the EN measurements
were completed.
The entire data set was rst detrended using the 9th order poly-
nomial. Thereafter, entire data of 7200 (2 h data) and 3600 (1 h
data) points were divided into the data sets of 512 points to calcu-
late the statistical parameters like r
I
and standard deviation of po-
tential (r
V
).
2.4. Shot noise analysis
According to the shot noise theory, the noise signals are com-
posed of the packets of data departing from a base line [24]. After
making certain assumptions, one can estimate the characteristic
charge, q present in each event and the characteristic frequency of
appearance of these events, f
n
using the following formulae [24
27].Characteristic charge, q

PSD
E
PSD
I
p
B
and characteristic frequency,
f
n

B
2
PSD
E
A
where PSD
E
and PSD
I
are the low frequency PSD values of
the current and the potential noise, B is the SternGeary coefcient
and A is the area of the electrode surface exposed. In this paper PSD
E
and PSD
I
were estimated using fast Fourier transform(FFT). In these
calculations theBvalue was takentobe 0.026 Vper decade [24]. This
result is obtained for common values of the Tafel slopes for the ano-
dic and cathodic reactions. These two parameters derived from the
shot noise analysis have been reported to provide information re-
lated to the nature of the corrosion processes [25,2730]. Thus, q
gives an indication about the mass of the metal lost in the event,
while f
n
provides the information about the rate at which these
events are happening. Therefore, a system undergoing active uni-
formcorrosion can have both large charge and frequency. Localized
corrosion, such as pitting and IGC, can be characterized by a small
number of events, and is therefore expected to have a lowfrequency
and high charge. Finally, in the case of passivity, the charge is ex-
pected to be low, while the frequency will depend on the processes
occurring on the passive lm [27].
Thus, the q and the f
n
values were calculated using the PSD val-
ues of the current and the potential noise obtained using FFT. This
analysis was done for all the data les in sets of 512 points. In order
to know the increase in DOS with the increase in the ageing dura-
tion at the same temperature, the cumulative values of the q (to
signify the total metal lost due to IGC) as well as the f
n
(total num-
ber of events of IGC) were calculated and plotted.
3. Results and discussion
Fig. 1 shows the typical microstructures of 316(N) SS after com-
pleting the DLEPR test. After the DLEPR test it was observed that
there was an increase in the attack on the grain boundary area with
increase in the ageing time from 24 to 50 h; the width of the at-
tacked zone too was found to have increased. These features indi-
cated clearly an increase in the DOS; the DOS value was found to
have increased from 7.09% to 18.93%. A typical DLEPR curve is
shown in Fig. 2 for the 316(N) specimen aged at 923 K for 24 h.
It is noted that during the reverse or the cathodic scan, while the
entire grain interior is passive, grain boundaries dissolved freely
at about 0.15 V (SCE) even at the scan rate of 100 mV/min.
The visual record of the current and the potential EN data for
the 923 K-24 h specimen before and after detrending is shown in
Fig. 3(a and b). It is known that the EN signal starts to drift due
to the instability of the test electrodes during the measurement
period. This phenomenon is referred to as DC trend and the process
of removing it is called trend removal; trend removal is important
in order to avoid calculating the erroneous values of r
I
and r
V
. Drift
or trend elimination is a form of high-pass (HP) ltering, consisting
of suppressing the components of the signal below a certain fre-
quency [31]. Bertocci et al. [31] have reported that subtracting a
polynomial tting curve to the time records is an example of digital
HP ltering. These authors reported that depending on the order of
the polynomial, the lowest frequencies could be drastically atten-
Fig. 1. Photomicrographs of the specimens 316(N) after DLEPR experiments, (a)
923 K-24 h and (b) 923 K-50 h.
M.G. Pujar et al. / Corrosion Science 51 (2009) 17071713 1709
uated and that if the order of the polynomial was 5k (k integer), all
frequencies equal to or lower than k/T (where T is the time dura-
tion of the record) were eliminated without any visible leakage
into the adjacent frequencies. Thus, all the data les were detrend-
ed by tting them to a 9th order polynomial using MATLAB soft-
ware. It is clear from Fig. 3(a and b) that the detrending using
9th order polynomial had effectively eliminated the trend without
eliminating the important features of the original signal. The detr-
ended data showed that the random current and the potential EN
uctuations occurred around some mean value; in case of potential
noise, the mean value is the corrosion potential [32].
Standard deviation is one of the simplest parameters for mea-
suring the magnitude of uctuations in electrochemical noise
[33,34]. Recently, Aballe et al. [35] reported the evolution of corro-
sion activity of AlMg alloy AA 5083 with and without the addition
of CeCl
3
in 3.5% sodium chloride solution using the robust statisti-
cal parameters. The r
I
values calculated after detrending were
plotted (Fig. 4) for the experiments conducted for 1 and 2 h,
respectively. It has been reported that the change in the trend of
r
I
as well as r
V
values indicated the change in the corrosivity of
the solution [36,37]. It is reported that, Gusmano et al. [36] esti-
mated the corrosion rates of the carbon steel specimens using a
LPR probe in sodium phosphate solution (Na
3
PO
4
) at different con-
centrations as a function of time and compared them with the r
I
values measured simultaneously using EN technique and found
that there was a perfect correlation between the two parameters.
In a very recent reference it was reported by Cuevas-Arteaga [38]
that the r
I
values and the corrosion rates measured for HK-40m al-
loy exposed to molten sulfate/vanadate mixtures showed an excel-
lent correlation. Time-dependent uctuations in corrosion current
are described by electrochemical current noise, and corrosion po-
tential are described by electrochemical potential noise [39]. Thus,
it was obvious that as the corrosivity of the experimental solution
was the same throughout the experiment, the change in the trend
of r
I
values directly reected the extent of the dissolution of the
grain boundaries. Therefore, the area under each curve shown in
Fig. 4 represented the charge in Coulomb; thus the area under
the curve gives the DOS. As it is important to compare the DOS %
values obtained using the conventionally accepted technique like
DLEPR, with those obtained using the EN technique, the plots of
DOS % obtained using DLEPR were plotted against the charge val-
ues obtained using EN (Fig. 5) as a scatter and a best t regression
line was plotted. Best t regression lines were obtained with
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
-0.6
-0.4
-0.2
0.0
0.2
0.4
Cathodic scan
Anodic scan
923K-24h
E
l
e
c
t
r
o
d
e

p
o
t
e
n
t
i
a
l
,

V
(
S
C
E
)
Log (c.d., A/cm
2
)
Fig. 2. DLEPR curve for 316(N) specimen aged at 923 K-24 h.
0 1000 2000 3000 4000 5000 6000 7000 8000
-12
-10
-8
-6
-4
-2
0
-410
-405
-400
-395
-390
923K-24h
Raw data
C
u
r
r
e
n
t
,

A
Time, s
a
P
o
t
e
n
t
i
a
l
,

m
V
(
S
C
E
)
0 1000 2000 3000 4000 5000 6000 7000 8000
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
-6
-5
-4
-3
-2
-1
0
1
2
3
b
Detrending using 9
th
order polynomial
923K-24h
P
o
t
e
n
t
i
a
l
,

m
V
(
S
C
E
)
C
u
r
r
e
n
t
,

A
Time, s
Fig. 3. Current and potential noise data for 316(N) specimen aged at 923 K-24 h (a)
before detrending and (b) after detrending with a polynomial of the 9th order.
500 1000 1500 2000 2500 3000 3500 4000
10
-8
10
-7
10
-6
a
1h data

I
,

A
Time, s
923K-24h
923K-40h
923K-50h
923K-100h
0 1000 2000 3000 4000 5000 6000 7000 8000
10
-7
10
-6
10
-5
b 2h data

I
,

A
Time, s
923K-24h
923K-40h
923K-50h
923K-100h
Fig. 4. The plots of the r
I
values for 316(N) specimens (a) 1 h data and (b) 2 h data.
1710 M.G. Pujar et al. / Corrosion Science 51 (2009) 17071713
R = 0.92 and R = 0.85 for 2 h and 1 h data, respectively. Thus, using
the EN charge one can obtain the DOS % from these linear plots.
Typical photomicrographs of the specimens after the EN mea-
surements are shown in Fig. 6. The excellent grain boundary attack
observed in both the specimens aged at 923 K-24 h and 923 K-50 h
(Fig. 6a and b) emphasized the validity of the EN measurement
technique as well as the data obtained from this technique; the
microstructures clearly showed an increased grain boundary at-
tack from the increased grain boundary width with increase in
the DOS % for these specimens.
In order to reduce the time of the EN measurements, the charge
values were calculated from the available data and plotted at the
shorter time intervals (Fig. 7) as a function of ageing time. The plots
for 1 h and the 2 h data are linear, except for the 100 h aged spec-
imen (2 h data) which showed somewhat scattered values particu-
larly at the lower measurement times of 1024, 2048 and 3072 s.
From the 1 h data it was also clear that the EN measurements
can be done for as low as 1024 s to know the DOS value of the sen-
sitized specimen using the experimental technique described
above.
Since, the q and the f
n
values were calculated from the PSD plots
obtained at every 512 s for the entire data record length, a typical
PSD plot for 923 K-100 h is shown in Fig. 8. Since the sampling fre-
quency is 1 Hz (therefore sampling interval, DT is 1) nd the data re-
cord length, N is 512, f
min

1
DTN
which is equal to 1.9510
3
Hz
and f
max

1
2DT
which is 0.5 Hz. As the q value indicates the mass
of the metal lost during a certain time interval due to a corrosion
process, the cumulative q value indicates the total mass of the me-
tal lost during a certain measurement interval due to the same cor-
rosion process. Similarly, the cumulative f
n
value indicates the total
frequency of such events during a certain measurement interval
due to the corrosion process under study. All the data les (2 h
as well as 1 h) with a data record length of 7200 and 3600 points
were analyzed in sets, each set being of 512 points. Thus, q and
f
n
were calculated for each interval. Since every interval provides
a different value of q and f
n
, they were summed up (integrated)
in order to know the total mass lost (total q) and the total number
of events (total f
n
) over 2 and 1 h data length. Thus, the cumulative
values of q and f
n
would effectively show the total mass lost due to
intergranular corrosion and the intergranular corrosion events,
respectively, during the measurement time (1 and 2 h). Fig. 9(a
and b) show the plots of the cumulative q as well as the cumulative
f
n
calculated over 1 and 2 h, respectively. The best t lines drawn in
Fig. 9(a and b) indicated that the q as well as the f
n
values increased
as a function of increase in ageing time at the given temperature
which is commensurate with the increase in the DOS values as
indicated by the DLEPR values. Thus, the shot noise analysis results
were found to conform with those results obtained using the sta-
tistical parameters earlier and were supportive in explaining the
EN results.
4. Conclusions
In this paper it was demonstrated that EN studies could be con-
ducted on the sensitized austenitic SS of Type 316(N) to detect and
quantify the IGC. The special experimental procedure developed in
order to achieve the results was described and the results ex-
plained. The conclusions drawn from these studies are given
below:
(1) The preconditioning treatment before EN measurements
was evolved in such a way that a combination of the prior
potentiodynamic as well as the potentiostatic experiments
created a galvanic couple between the dissolving grain
boundaries and the passive grain interior. Current and
potential EN immediately following this pretreatment ascer-
tained that the signals resulted from the galvanic coupling
described above.
(2) The area under the curve of r
I
versus time was found to give
DOS of the specimen in Coulombs and the values of DOS so
obtained were found to have good correlation with those
obtained by DLEPR tests.
0 1 2 3 4
5
10
15
20
25
30
D
O
S

%
Charge (EN), mC
2h data
1h data
Fig. 5. The values of DOS % obtained by DLEPR were plotted against the charge (mC)
obtained using EN technique for 316(N) specimens.
Fig. 6. Photomicrographs of 316(N) aged at (a) 923 K-24 h and (b) 923 K-50 h after
the EN measurements showing the grain boundary attack.
M.G. Pujar et al. / Corrosion Science 51 (2009) 17071713 1711
(3) It was shown that the DOS values could be calculated even
for the smaller time intervals, thus reducing the time of EN
measurement.
(4) Shot noise analysis, which is fairly recent, was used to con-
rm the above results and it was found that the cumulative
q as well as the f
n
values increased linearly with increase in
the DOS i.e. linearly with the ageing time at 923 K.
(5) Thus, it was concluded that the combination of the prior
potentiodynamic and the potentiostatic experiments fol-
lowed by the EN measurements can detect and quantify
the IGC in 316(N) SS successfully.
References
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[3] P. Novak, R. Stefec, F. Franz, Corrosion 31 (1975) 344.
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0 20 40 60 80 100 120
10
-4
10
-3
10
-2
a 1h data
C
h
a
r
g
e
,

C
Ageing time, h
1024s
1536s
2048s
2560s
3072s
3584s
0 20 40 60 80 100 120
10
-4
10
-3
10
-2
10
-1
b 2h data
C
h
a
r
g
e
,

C
Ageing time, h
1024s
2048s
3072s
4096s
5120s
6144s
7168s
Fig. 7. The plots of the charge (C) values for 316(N) specimens at different
measurement times (a) 1 h data and (b) 2 h data.
10
-3
10
-2
10
-1
10
0
10
-18
10
-17
10
-16
10
-15
10
-14
10
-13
10
-12
10
-11
10
-13
10
-12
10
-11
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
923K-100h
P
o
t
e
n
t
i
a
l

P
S
D
,

V
2
/
H
z
C
u
r
r
e
n
t

P
S
D
,

A
2
/
H
z
Log (Frequency, Hz)
Fig. 8. The PSD plot for the current and potential EN for 316(N) specimen aged at
923 K-100 h. Data record length = 512 points.
0 20 40 60 80 100 120
9.0x10
-7
1.0x10
-6
1.1x10
-6
5.0x10
3
1.0x10
4
1.5x10
4
2.0x10
4
1h data
C
u
m
u
l
a
t
i
v
e

q
,

C
Ageing time, h
q
C
u
m
u
l
a
t
i
v
e

f
r
e
q
u
e
n
c
y

(
f
n
)
,

H
z
.
c
m

2
f
n
0 20 40 60 80 100 120
0.0
2.0x10
-6
4.0x10
-6
6.0x10
-6
8.0x10
-6
1.0x10
-5
1x10
4
2x10
4
3x10
4
4x10
4
5x10
4
b
a
q
2h data
C
u
m
u
l
a
t
i
v
e

f
r
e
q
u
e
n
c
y

(
f
n
)
,

H
z
.
c
m

2
C
u
m
u
l
a
t
i
v
e

q
,

C
Ageing time, h
f
n
Fig. 9. The plots of the cumulative characteristic charge (q) and cumulative
characteristic frequency (f
n
) values for 316(N) specimens at different measurement
times (a) 1 h data and (b) 2 h data.
1712 M.G. Pujar et al. / Corrosion Science 51 (2009) 17071713
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