Corrosion Science 49 (2007) 12661275

www.elsevier.com/locate/corsci

EVects of non-metallic inclusions on the initiation of

pitting corrosion in 11% Cr ferritic stainless steel
examined by micro-droplet cell
Heon Young Ha a, Chan Jin Park b, Hyuk Sang Kwon a,

a
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST),
373-1, GuseongDong, YuseongGu, Daejeon 305-701, Republic of Korea
b
School of Materials Science and Engineering, Chonnam National University, 300, YongbongDong,
BukGu, Gwangju 500-757, Republic of Korea

Received 6 December 2005; accepted 21 August 2006

Available online 17 October 2006

Abstract

This paper explores the eVects of non-metallic inclusions (NMIs) on the initiation of pitting corro-
sion in type 409L stainless steels reWned by the argon oxygen decarburization (AOD) and vacuum
oxygen decarburization (VOD) processes. The dominant NMIs in the AOD and VOD samples were
(Ti, Ca)-oxides and Ti-nitrides, respectively. In-situ electrochemical noise (EN) and micro-electro-
chemical analyses were conducted to investigate quantitatively the inherent eVects of the NMIs on
the pitting corrosion of the alloys. Pitting corrosion was initiated mostly around the (Ti, Ca)-oxides
in the AOD samples, while little such corrosion occurred around the Ti-nitrides in the VOD samples.
In addition, the pitting resistance of the AOD samples increased with increasing Ti content and
decreasing Ca content in the (Ti, Ca)-oxides.
2006 Elsevier Ltd. All rights reserved.

Keywords: A. Stainless steel; A. Non-metallic inclusion; B. Electrochemical noise analysis; B. Micro-droplet cell;
C. Pitting corrosion

*
Corresponding author. Tel.: +82 42 869 3326; fax: +82 42 869 3310.
E-mail address: hskwon@kaist.ac.kr (H.S. Kwon).

0010-938X/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.08.017
 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275 1267

1. Introduction

Type 409L ferritic stainless steel is characterized by a fully ferritic microstructure with
11% Cr [1,2]. In addition, a small amount of Ti is included in the alloy, while C + N contents
are restricted below 200 ppm through the argon oxygen decarburization (AOD) and the
vacuum oxygen decarburization (VOD) processes to enhance intergranular corrosion resis-
tance, weldability, and formability [1]. In particular, during the AOD reWning process, C
content in the alloy is remarkably lowered with a decrease in CO partial pressure in the melt
by blowing a mixing gas of argon and oxygen into the bath. The VOD process is similar in
principle to the AOD process, except that CO partial pressure in the melt is further lowered
in a low vacuum environment [3]. Type 409L stainless steel exhibits acceptable resistance to
corrosion and oxidation and good formability at low cost, and therefore has been widely
used as a material for automotive exhaust parts such as exhaust pipe and muZer.
However, pitting corrosion may occur in the alloy due to Ti containing non-metallic
inclusions (NMIs). It has been reported that NMIs may act as preferential sites for the initi-
ation of pitting corrosion in stainless steels [49]. In particular, the inXuence of manganese
sulWde (MnS) on the pitting in stainless steels has been a main subject of study, due to the
great pitting susceptibility of the inclusions in conventional stainless steels. MnS inclusions
on stainless steels are found to be initiation sites for pitting corrosion in the solution con-
taining Cl ion [59]. Several mechanisms have been postulated to explain pit initiation at
MnS on stainless steel. Cr may substitute for Mn to form (Mn, Cr)-sulWde making Cr-
depleted zone around MnS which is active to pitting corrosion [8]. It was also proposed that
the MnS is more susceptible to dissolution than the surrounding oxide Wlm and dissolves
more easily [5]. Other mechanisms suggest the presence of micro-cavities between MnS and
the metal matrix [7]. However, more recently, improvements in desulfurization technology
have enabled the production of low sulfur grade stainless steels. Therefore, the inXuences of
NMIs other than MnS, such as oxides and nitrides, on the pitting corrosion of stainless steel
have become more important. Nevertheless, thus far, few studies have focused on the inde-
pendent and inherent eVects of Wne oxides and nitrides on the pitting corrosion of stainless
steels, due to the low lateral resolution of conventional electrochemical methods.
Stainless steel is composed of many grains, phases and other heterogeneities, such as
NMIs. The macroscopic electrochemical behavior is the sum of the contributions of these
individual components. Conventional methods of analysis, in which an area of the speci-
men amounting to several mm2 or cm2 is exposed, do not enable us to measure the electro-
chemical behavior of a single heterogeneity, especially an inclusion. Accordingly, a new
electrochemical technique is needed to investigate the individual eVects of oxides and nit-
rides on the pitting corrosion of stainless steels. During the past several years, various
micro-electrochemical techniques have been established [1016]. There have been two basi-
cally diVerent micro-electrochemical methods for local investigations; (1) scanning tech-
nique, where the immersed metal surface is scanned with a micro-electrode [14]; and (2)
micro-area technique, where only small areas are exposed to the electrolyte [15,16]. In the
present study, one of the micro-area techniques, a capillary-based micro-electrochemical
cell was used to examine the resistance to pitting corrosion of each NMI. A capillary based
droplet cell, such as the one represented in Fig. 1 [10], oVers the possibility of conducting
micro-electrochemical investigations at high resolution. The wetted area deWnes the work-
ing electrode, and the reference and counter electrodes are combined with a capillary with
a tip diameter of 20600 m. The small area of the working electrode determined by the tip
1268 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275

Fig. 1. The capillary based micro-droplet cell.

size of the capillary enables the investigation of localized corrosion or the passivation of
small areas within a single grain or phase. This device enables a complete range of poten-
tiostatic (or dynamic) and galvanostatic (or dynamic) techniques to be performed, includ-
ing impedance spectroscopy. Thus, it is well adapted to the micro-electrochemical
observation of the pitting initiation induced by NMIs in stainless steels.
The objective of this study is to elucidate the inherent eVects of oxides and nitrides on
the initiation of pitting corrosion in type 409L stainless steel with the aid of various elec-
trochemical techniques including a micro-droplet cell.

2. Experimental

Table 1 shows the chemical compositions of the two types of 409L stainless steel used
in this study. One alloy was reWned by the vacuum oxygen decarburization (VOD) process
and the other by the argon oxygen decarburization (AOD) process. These two alloys are
 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275 1269

Table 1
Chemical compositions (wt.%) of the 409L stainless steels used
Cr Ni Mn Si Ti Al C N S P Ca
409L VOD 11.32 <0.5 0.5 0.39 0.209 0.027 0.005 0.007 0.001 0.025 8 ppm
409L AOD 11.34 <0.5 0.5 0.55 0.141 0.006 0.011 0.009 0.003 0.025 8 ppm

referred to as VOD and AOD, respectively, after their reWning process. The extremely low
S content around 0.0010.003 wt% in the alloy enabled the suppression of the formation
of MnS. In addition, small amounts of Ti, Al, and Ca were added to the alloys as a deoxi-
dizer.
The distribution and composition of the NMIs were analyzed by means of a scanning
electron microscope (SEM) and an energy dispersive spectroscope (EDS) attached to the
SEM. The specimens used for the SEM observation were polished to a 1 m surface Wnish.
Macroscopic anodic polarization tests on the alloys were performed to evaluate the
resistance to pitting corrosion and determine the applied potential (Eapp) for the subse-
quent electrochemical noise analysis (ENA). Potentiodynamic tests were conducted on the
alloys in a 0.5 M NaCl solution at 25 C with a scan rate of 1 mV s1. The electrochemical
system consisted of a stainless steel coupon as the working electrode, a platinum plate as
the counter-electrode and a saturated calomel electrode (SCE) as the reference electrode.
All of the potentials used in this study were relative to the SCE. The stable pitting potential
(Epit) was determined as the potential at which the current just exceeded 100 A during the
anodic polarization.
In addition, electrochemical noise measurements were carried out in a 0.5 M NaCl solu-
tion at 25 C with an applied potential (Eapp) of 0 VSCE at which metastable pitting can
occur on the specimens. The current signal was recorded at a sampling frequency of 10 Hz
during a period of 10,800 s.
Finally, microscopic potentiodynamic tests were conducted on the alloys using a micro-
droplet cell, as shown in Fig. 1. The diameter of the working electrode was about 60
170 m, which enabled the micro polarization test to be performed on a single inclusion.
After the potentiodynamic tests, the pitting sites on the specimen surface were analyzed by
SEM.

3. Results and discussion

Fig. 2 shows the SEM images of the NMIs distributed in the AOD and VOD samples.
On the whole, the AOD specimen exhibited larger inclusion densities than the VOD speci-
men. The NMIs in the AOD sample had a globular shape with a diameter of up to 15 m,
while those in the VOD sample were rectangular with a width of less than 2 m. The EDS
analysis of the inclusions indicated that the globular inclusions in the AOD sample were
(Ti, Ca)-oxides, while the rectangular inclusions in the VOD samples were Ti-nitrides. In
particular, many of the NMIs in the AOD specimen were found to be composed of two
parts distinguished by their contrast, as shown in Fig. 2. The relatively dark part (Fig. 2b-
(1)) contained more Al and Ca and less Ti as compared with the bright part (Fig. 2b-(2)), as
shown in Table 2.
Anodic polarization tests were conducted to investigate the eVects of the NMIs on the
pitting corrosion of the alloys, and to determine the applied potential (Eapp) for the subsequent
1270 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275

Fig. 2. SEM images showing the NMI distributions in the (a) 409L AOD specimen and (b) 409L VOD specimen.
Enlarged micrographs of a single NMI are also included.

Table 2
Chemical compositions (wt.%) of each inclusion in VOD and AOD specimens
Ti N O Fe Al Ca Cr Si C Mg
VOD (Fig. 2a) 55.39 15.67 23.46 0.43 4.57 0.22 0.26
AOD (Fig. 2b-(1)) 26.04 22.93 24.33 10.25 11.03 3.98 0.82 0.62
AOD (Fig. 2b-(2)) 64.41 30.86 1.69 0.78 2.26

electrochemical noise analysis (ENA). Fig. 3 shows the anodic polarization curves and the
pitting potential (Epit) for the AOD and VOD samples in 0.5 M NaCl solution at 25 C. The
corrosion potentials (Ecorr) of both specimens were around 0.13 VSCE and their passive
 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275 1271

VOD

0.1 AOD

Potential / V 0.0

E pit /V

-0.1 VOD 0.127

AOD 0.068
1E-8 1E-7 1E-6 1E-5
Current density / A cm-2
Fig. 3. Potentiodynamic curves for the 409L VOD and AOD specimens in 0.5 M NaCl solution at 25 C with a
scan rate of 1 mV s1.

behaviors were nearly identical. However, stable pitting corrosion occurred at a higher
potential of 0.127 VSCE for the VOD sample, as compared with 0.068 VSCE for the AOD
sample. The higher Epit for the VOD sample indicates its greater pitting resistance com-
pared with the AOD sample. In addition, from the polarization curves shown in Fig. 3,
0 VSCE in the passive range was selected as the Eapp for the ENA.
An electrochemical noise analysis was performed to examine the metastable pitting
behavior of the samples, in order to obtain information on the initiation stage of the pit-
ting corrosion. Fig. 4 shows the current versus time for the AOD and VOD samples mea-
sured in 4 M NaCl solution at 25 C with an applied potential of 0 VSCE. The stabilized
passive current of the AOD sample was found to be higher than that of the VOD sample.
In addition, the current spikes indicating the initiation and repassivation of metastable pits
appeared more frequently for the AOD sample than for the VOD sample. This indicates
that the passive Wlm formed on the AOD sample was less protective than that formed on
the VOD sample. Furthermore, the current transients were transformed into a histogram

Fig. 4. Potentiostatic current versus time for the (a) VOD specimen, and (b) AOD specimen in 0.5 M NaCl solu-
tion at 25 C with an applied potential of Eapp D 0 VSCE.
1272 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275

75000
50000 (a) VOD
25000

Peaks 5
0

75000
50000 (b) AOD
Peaks

25000

0 -7 -7 -7 -7 -6
2.0x10 4.0x10 6.0x10 8.0x10 1.0x10
Current /A
Fig. 5. Histograms indicating the number of current peaks versus current for the (a) VOD and (b) AOD samples,
obtained from the current transient curves shown in Fig. 4.

consisting of the number of peaks versus current, as represented in Fig. 5. The number of
current peaks for the AOD specimen was much larger than that for the VOD specimen.
This suggests that the AOD sample, which exhibits poorer passivation behavior, is more
susceptible to the initiation of metastable pitting than the VOD sample.
The results of the polarization tests and electrochemical noise analysis show that pitting
corrosion can occur more easily on the AOD sample than on the VOD sample. These
results also indicate that the initiation of pitting corrosion may be closely associated with
the type and density of the NMIs. To clarify the relation between pitting initiation and the
NMIs, potentiodynamic tests were carried out for a single NMI in 0.5 M NaCl solution
with the aid of a micro-droplet cell. Fig. 6 shows the surface morphologies of the VOD and
AOD samples after the potentiodynamic tests. The potentiodynamic curves for each inclu-
sion are also indicated. The Ti-nitrides in the VOD specimen appear to be immune to pit-
ting corrosion in the solution used in the potentiodynamic test, given that no pitting
corrosion occurred in this region. In contrast, for the AOD sample, pitting corrosion
occurred around the (Ti, Ca)-oxide at an potential of approximately 0.45 VSCE during
anodic polarization. This suggests that the round (Ti, Ca)-oxide in the AOD sample can act
as an active site for the initiation of pitting.
In particular, based on the observation of a (Ti, Ca)-oxide complex in the AOD speci-
mens after the potentiodynamic tests, it was inferred that pitting was initiated around the
Ca-rich and Ti-depleted part of the inclusion complex, as shown in Fig. 6(b) and Fig. 7.
This result suggests that the pitting susceptibility of the inclusions in the AOD specimen
may be related to the Ti and Ca contents of the (Ti, Ca)-oxide.
Fig. 8 represents the variation of the pitting potential with the Ti and Ca contents in a
single inclusion in the AOD specimen, as examined by the micro-droplet cell. The pitting
potentials (Epit) for the single inclusion ranged from 0.1 VSCE to 0.7 VSCE. On the whole,
Epit, which can be considered as a measure of the pitting resistance of the inclusion,
increased with increasing Ti content and decreasing Ca content. This suggests that those
inclusions with higher Ca contents and lower Ti contents are more susceptible to pitting
initiation.
 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275 1273

Fig. 6. Surface morphologies of the (a) VOD and (b) AOD specimens after the potentiodynamic tests conducted
with the aid of a micro-droplet cell. The corresponding polarization curves are also indicated.

4. Conclusions

The NMIs in the type 409L stainless steels exhibited diVerent volume fractions, mor-
phologies and chemical compositions, depending on the reWning method that was used.
The total amount of NMIs in the alloy produced by the argon oxygen decarburization
(AOD) process was signiWcantly larger than that in the alloy produced by the vacuum oxy-
gen decarburization (VOD) process. The NMIs in the AOD alloy were round (Ti, Ca)-
oxides with a diameter of 1015 m, while those in the VOD alloy were angular Ti-nitrides
with a diameter of less than 2 m.
The resistance of the VOD alloy to pitting corrosion, in terms of the pitting potential
and metastable pitting density, was much higher than that of the AOD alloy. In addition,
1274 H.Y. Ha et al. / Corrosion Science 49 (2007) 12661275

Fig. 7. SEM micrograph of an inclusion complex in 409L AOD specimen after potentiodynamic test in 0.5 M
NaCl solution at 25 C.

0.6 0.6

0.4 0.4
Epit / V
Epit / V

0.2 0.2

0.0 0.0

20 30 40 50 60 0 2 4 6 8 10 12 14
Ti / wt% (in NMI complex) Ca / wt% (in NMI complex)
Fig. 8. EVects of (a) Ti and (b) Ca concentration in single (Ti, Ca)-oxide inclusion in AOD specimen on the pitting
potential measured in 0.5 M NaCl solution at 25 C.

based on the micro analysis using a micro droplet cell, pitting corrosion was found to be
initiated at the interface between the round (Ti, Ca)-oxide and the matrix. In contrast, the
Ti-nitrides in the VOD alloy appeared to be immune to pitting corrosion. For the 409L
alloy reWned by AOD, the resistance to pitting corrosion increased linearly with increasing
Ti content, but decreased with increasing Ca content, in the (Ti, Ca)-oxide.

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