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.
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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
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10
-3
10
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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.
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