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Pit Morphology and Its Relation to

Microstructure of 850°C Aged Duplex
Stainless Steel

Article in Corrosion -Houston Tx- · February 2005

DOI: 10.5006/1.3278167

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CORROSION SCIENCE SECTION
Pit Morphology and its Relation to Microstructure
of 850°C Aged Duplex Stainless Steel
R. Magnabosco‡,* and N. Alonso-Falleiros**
ABSTRACT
The relation between pit morphology and microstructure
formed during 850°C isothermal aging of UNS S31803 duplex
stainless steel (DSS) could be reached through the explanation
of pit nucleation and growth during potentiodynamic polariza-
tion in 3.5 wt% sodium chloride (NaCl) aqueous solution. Aging
times up to 10 min at 850°C led to sigma formation by direct
precipitation from ferrite, resulting in Cr- and Mo-depleted fer-
rite, or secondary ferrite. Between 30 min and 5 h of aging,
the ferrite suffered eutectoid decomposition, resulting in sigma
phase and secondary austenite, also impoverished in Cr and
Mo. Those Cr- and Mo-depleted zones around the sigma phase
were preferential sites for the nucleation of pits. At those sites,
the passive film breakdown was easier, as shown by the low
pitting potential values found in aged samples. Pit growth
occurred as selective corrosion of the metallic matrix surround-
ing the sigma phase, as a consequence of the lower corrosion
resistance of the secondary ferrite and austenite phases
found. The low passivation potential values indicated the
difficulty in repassivation of the pits formed, probably related
to the Cr and Mo depletion of the regions surrounding the
sigma phase.
Submitted for publication December 2003; in revised form, May
2004.
‡
Corresponding author. E-mail: rodrmagn@fei.edu.br.
* Department of Mechanical Engineering, Ignatian Educational
Foundation, FEI, Av. Humberto A.C. Branco, 3972, 09850-901,
São Bernardo do Campo, SP, Brazil.
** Department of Metallurgical and Materials Engineering, Polytech-
nic School, University of São Paulo, Av. Prof. Mello Moraes, 2463,
05508-900, São Paulo, SP, Brazil.
(1)
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
0010-9312/04/000027/$5.00+$0.50/0
130 © 2005, NACE International
KEY WORDS: duplex stainless steel, pit morphology, poten-
tiodynamic polarization, sigma phase, sodium chloride, UNS
S31803
INTRODUCTION
Duplex stainless steels (DSS) were created to com-
bine the stress corrosion cracking resistance of fer-
ritic stainless steels with the excellent toughness and
pitting corrosion resistance of austenitic stainless
steels.1-2 They are produced by hot deformation and
solution treatment of Fe-Cr-Ni-Mo-N alloys at tem-
peratures up to 1,200°C, followed by rapid quenching,
with a resulting microstructure of approximately
40% to 45% of ferrite, rich in Cr and Mo, and 55%
to 60% of austenite, with high fractions of Cr—up to
20%—as a consequence of the high nitrogen content
found in those alloys, which is frequently 0.2%.3-4
One of the most common DSS is the UNS
S31803(1), which has a nominal chemical composi-
tion 22% Cr-5% Ni-3% Mo-0.15% N-0.02% C, a ten-
sile strength of 770 MPa, a yield strength of 515 MPa
(twice the typical value found in austenitic stainless
steels UNS S30400 and UNS 31600), and a total
elongation in 50 mm up to 32%.1,3 Accompanying
this excellent mechanical behavior is a higher corro-
sion resistance than low-carbon austenitic stainless
steels,4-6 especially high pitting corrosion resistance.7
Potentiodynamic polarization of solution-treated
DSS in 3.5 wt% sodium chloride (NaCl) aqueous
solution, at room temperature, usually led to pitting
potential values (Epit) between 1,000 mV vs saturated
calomel electrode (SCE) and 1,200 mVSCE.7-8 However,
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 CORROSION SCIENCE SECTION

TABLE 1
Chemical Composition of the Investigated Steel (wt%)
Cr Ni Mo Mn Si V N C S
22.2 5.7 2.98 1.60 0.44 0.07 0.161 0.016 0.001

(a) (b)

(c) (d)
FIGURE 1. Typical microstructures found in the UNS S31803 DSS studied: (a) solution-treated, showing ferrite (dark) and
austenite; (b) aged at 850°C for 10 min, sigma selectively etched; (c) aged at 850°C for 30 min, showing ferrite (dark),
austenite (gray), and sigma; (d) aged at 850°C for 100 h, with austenite (gray) and sigma. Optical microscopy. Etchants: (a),
(c), and (d) modified Behara; (b) electrolytic etching in KOH.

these values could be influenced by the oxygen evolu-
tion reaction (4OH– → O2 + 2H2O + 4e),7 which in-
creases the total current density measured, and
generates oxygen bubbles at the sample surface, mak-
ing the passive film breakdown an easier process. In
more concentrated NaCl solutions, the Epit is reduced,
reaching 800 mVSCE in 1 M NaCl solution.9 Pits de-
velop a surface morphology of “lacy metallic covers,”
which has been explained in terms of passivation and
undercutting near the pit mouth.10
However, undesired phases can form during iso-
thermal aging or welding procedures, resulting in a
reduction of toughness, ductility, and corrosion resis-
tance. Aging between 700°C and 900°C results in the
formation of the sigma phase, a hard and brittle inter-
metallic phase rich in Cr and Mo, by eutectoid decom-
position of ferrite or by nucleation and growth from
ferrite and austenite.3,11 Cr- and Mo-depleted zones
form around the sigma phase precipitated at those
temperatures, and their presence probably leads to a
reduction in localized corrosion resistance.12-16 It was
found that 6 vol% of sigma in UNS S31803 reduced
Epit in 3.5 wt% NaCl solution to values near 300 mVSCE.8
This work details the relation between pit morphol-
ogy and microstructure formed during 850°C isother-
mal aging of UNS S31803 DSS, through the explanation
of pit nucleation and growth during potentiodynamic
polarization in 3.5 wt% NaCl aqueous solution.

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TABLE 2
Phase Content of UNS S31803 DSS as a Function of Aging Time at 850°C
Phase Content Solution
(vol%) Treated 10 min
σ — 7.5 ± 2.2
α 40.9 ± 1.9 32.8 ± 3.0
γ 59.1 ± 1.9 59.7 ± 3.7
FIGURE 2. Typical potentiodynamic polarization curves in 3.5%
NaCl for UNS S31803 DSS solution treated and aged at 850°C for
10 min and 100 h.
FIGURE 3. Measured values of Epit and Epp for UNS S31803 DSS in
3.5 wt% NaCl as a function of aging time at 850°C. Mean values and
standard deviations from them were calculated with the results of
five to 10 electrochemical tests for each heat treatment condition.
EXPERIMENTAL PROCEDURES
The studied material had the chemical composi-
tion given in Table 1, and was received as a 3-mm-
thick sheet, solution treated at 1,120°C, and water
quenched. Specimens of 20 mm length and 15 mm
wide were obtained, and the length described was
maintained parallel to the rolling direction. All speci-
mens were isothermically aged for 10 min, 30 min,
1 h, 5 h, or 100 h at 850°C, in a tubular electric
furnace with a solid-state controller, which main-
tained the aging temperature to 1°C around the cho-
sen temperature. All heat treatments were conducted
132
Aging Time at 850°C
30 min 1h 5h 100 h
35.7 ± 5.7 38.3 ± 5.1 44.9 ± 2.3 50.8 ± 3.2
12.6 ± 1.2 7.7 ± 1.0 1.6 ± 0.1 —
51.7 ± 5.9 54.0 ± 5.2 53.5 ± 2.4 49.2 ± 3.2
under a 99.9% N2 atmosphere, to suppress oxidation
of the sample surfaces and prevent nitrogen loss
from the DSS. Water quenching interrupted the
heat treatments.
After the heat treatments the specimens were
abraded using silicon carbide (SiC) papers to a
600-grit finish before mounting them in thermosetting
plastic, leaving an exposed surface area of ~0.5 cm2,
parallel to the rolling direction. The mounted samples
were metallographically polished in a semiautomatic
grinding and polishing machine, with final polishing
provided by a 1-µm diamond abrasive. After metallo-
graphic polishing, the samples were etched for 40 s
in modified Behara reagent, composed of 20 mL
hydrochloric acid (HCl), 80 mL distilled water, and
1 g potassium metabissulfide (K2S2O5); to this stock
solution, 2 g of ammonium bifluoride (NH4HF2) were
added just before the etching. This etching procedure
allowed a distinction to be made between the ferrite,
austenite, and sigma phases.
Selective etching of the sigma phase was obtained
through electrolytic etching in 10% potassium hydrox-
ide (KOH) aqueous solution, using 2 direct current
volts (Vdc) during 1 min. Quantitative metallography
of the sigma phase was performed with an automated
image analysis system attached to an optical micro-
scope. Ferrite content of the samples was obtained
through magnetic measurements; austenite content
was calculated using Equation (1):
% γ = 100 – %α – %σ (1)
Before the potentiodynamic polarization tests, the
mounted samples had their testing surface abraded
with 600-grit paper. These tests were carried out in a
stagnant 3.5 wt% NaCl aqueous solution exposed to
air at a controlled temperature of 22°C ± 2°C. The
test cell had a platinum wire as the counter electrode
and an SCE as the reference electrode. The sample
was immersed in the solution for 5 min before starting
the test.
The technique used in the potentiodynamic test
was cyclic polarization. The electrode potential (E) was
continuously changed at a scan rate of 1 mV/s; when
a sharp increase in the current density (i) occurred,
the pitting potential (Epit) could be determined easily.
When the current density reached 1 mA/cm2, scan-
ning was reversed, and the protection potential or
passivation potential (Epp) was determined as the point
CORROSION—FEBRUARY 2005

(a)
(c)
FIGURE 4. Scanning electron micrographs (SEI) of sample surfaces after polarization tests with scanning reversal occurring
at a current density of approximately 1 mA/cm2. (a) A solution-treated sample. Samples were aged at 850°C for: (b) 10 min,
(c) 30 min, and (d) 100 h.
where the descending curve intercepted the ascend-
ing curve; it was assumed that the growing pits or
pits formed at Epit become passive at this potential. To
determine the pit nucleation sites, cyclic polarization
tests were conducted on polished surfaces provided
by the 1-µm diamond abrasive, with scanning reversal
at a current density of approximately 0.01 mA/cm2.
Description of pit growth was carried out through ob-
servation of the polished transversal sections of pits
formed during cyclic polarization with scanning re-
versal occurring at a current density of approximately
100 mA/cm2. The electrochemical tests were repeated
five to 10 times. The corroded sample surfaces were
examined by optical microscopy and scanning elec-
tron microscopy using secondary electron image (SEI)
and backscattered electron image (BEI).
RESULTS
Typical microstructures of the samples studied
are shown in Figure 1. The solution-treated material
contained only ferrite and austenite, as can be seen in
CORROSION—Vol. 61, No. 2
CORROSION SCIENCE SECTION
(b)
(d)
Figure 1(a). The sigma phase was formed during
aging at 850°C, as a result of both direct precipitation
from ferrite, resulting in sigma and a Cr- and Mo-
impoverished ferrite, as well as eutectoid decomposi-
tion of ferrite, resulting in sigma and austenite phases
in massive morphology (Figure 1[b]) or lamellar mor-
phology (Figure 1[c]). After 100 h at 850°C, the sigma
phase formed inside the austenite phase (Figure 1[d]).
Volume fraction of the phases as a function of aging
time are given in Table 2. The austenite formed during
eutectoid decomposition of ferrite, and the remaining
austenite after long-term aging were probably Cr-
and Mo-impoverished. Those facts probably created a
Cr- and Mo-depleted metallic matrix surrounding the
sigma phase.
Figure 2 shows potentiodynamic polarization
curves obtained in 3.5% NaCl. The sharp increase in
the current density that marks Epit, as well as the Epp
at the intercept between the ascending and descend-
ing polarization curves, are clearly seen. Figure 3
presents values of Epit and Epp for all samples studied,
as mean values and standard deviations from them,
133
CORROSION SCIENCE SECTION

(a) (b)

(c) (d)
FIGURE 5. Scanning electron micrographs (BEI) of sample surfaces aged at 850°C after polarization tests with scanning
reversal occurring at a current density of approximately 0.01 mA/cm2, showing pit nucleation sites (black areas) always
associated with interfaces between the sigma (lighter phase) and the surrounding metallic matrix. Samples were aged for:
(a) 10 min, (b) 1 h, and (c) 5 h with ferrite (dark), austenite (gray), and sigma. In (d), the sample was aged for 100 h, showing
only austenite (gray) and sigma.

calculated with the results of five to 10 electrochemi-
cal tests for each heat treatment condition.
Examples of sample surfaces after cyclic polar-
ization with scanning reversal at a current density of
approximately 1 mA/cm2 are shown in Figure 4. The
solution-treated sample presented very small pits (Fig-
ure 4[a]), in agreement with the excellent pitting cor-
rosion resistance expected.7-8 Aged samples, however,
presented extensive pitting corrosion. Figures 4(b)
and (d) showed a lacy pattern of pits, while Figure 4(c)
shows the inner walls of an “open mouth” pit in the
sample aged for 30 min at 850°C. The similarity be-
tween the microstructure found after heat treatments
and the pit growth morphology is evident.
In Figure 5, typical sample surfaces after po-
larization tests with scanning reversal occurring at
a current density of approximately 0.01 mA/cm2
showed that pit nucleation sites are always associated
with interfaces between the sigma phase and the sur-
rounding metallic matrix, suggesting selective corro-
sion of those regions. This is confirmed by scanning
electron micrographs from transverse sections of the
samples aged at 850°C, after polarization tests with
scanning reversal occurred at a current density of
approximately 100 mA/cm2, shown in Figure 6, which
presents pit growth by selective corrosion of the me-
tallic matrix surrounding the sigma phase.
DISCUSSION
Data in Table 2 show a very small change in
austenite volume fraction after 10 min aging, which
is a strong indication of sigma formation from direct
precipitation from ferrite, resulting in Cr- and Mo-
depleted ferrite, or secondary ferrite. Between 10 min
and 30 min, the austenite volume fraction decreased,
indicating that austenite could be consumed to allow
sigma volume fraction growth. However, austenite vol-
ume fraction increased in aging between 30 min and
5 h, indicating eutectoid decomposition of ferrite,

134 CORROSION—FEBRUARY 2005

 CORROSION SCIENCE SECTION

(a) (b)

(c) (d)
FIGURE 6. Scanning electron micrographs from transverse sections of the pits formed after polarization tests with scanning
reversal occurring at a current density of approximately 100 mA/cm2, showing pit growth by selective corrosion of the
metallic matrix surrounding the sigma phase. (a) Sample aged for 30 min, ferrite (dark), austenite (gray), and sigma (lighter
phase). In (b) through (d), samples aged for 100 h. BEI in (a) and (d); SEI in (b) and (c).

resulting in secondary austenite, also impoverished
in Cr and Mo. This result was confirmed by the mi-
crostructure shown in Figure 1(c). Regardless of this
fact, the austenite volume fraction after 100 h became
smaller than the value found after 5 h aging, indicat-
ing nucleation and growth of the sigma phase from
austenite in the absence of the ferrite phase, which
was confirmed in Figure 1(d).
This phase transformation involving sigma for-
mation could lead to the development of Cr- and
Mo-depleted zones around the sigma phase, formed
preferably by secondary ferrite in aging times up to
10 min, and by secondary austenite in aging times
greater than 30 min. The Cr- and Mo-impoverished
zones around the sigma phase were preferential sites
for nucleation of pits, as shown in Figure 5, where the
passive film breakdown was easier, in agreement with
the low Epit values found (Figure 3).
Figure 6 shows that pit growth occurs as selec-
tive corrosion of the metallic matrix surrounding the
sigma phase, which is explained by the presence of
Cr- and Mo-depleted ferrite or austenite phases sur-
rounding the sigma, as a consequence of the lower
corrosion resistance of those secondary phases. The
small Epp values found after aging at 850°C (Figure 3)
were an indication of the difficulty surrounding the
repassivation of the pits formed, probably related to
the Cr depletion, and especially the Mo depletion, of
those regions.
The pit morphology after potentiodynamic po-
larization in 3.5 wt% NaCl aqueous solution was a
consequence of the lower corrosion resistance of sec-
ondary austenite and ferrite and their distribution,
always associated with the sigma phase formed at the
ferrite/ferrite or ferrite/austenite boundaries. The se-
lective corrosion of those regions, as shown in Figures
5, 6(a), and 6(d), led to the lacy pattern over the pit-
ting corroded surface shown in Figures 4(b) and (d).
The high Epit value found for the solution-treated
material was expected. This could be influenced by
the oxygen evolution reaction (4OH– → O2 + 2H2O +
4e),7-8 as mentioned earlier.

CORROSION—Vol. 61, No. 2 135

CORROSION SCIENCE SECTION
The small increase of Epit and Epp values with in-
creasing aging time (Figure 3) is another indication of
the influence of Cr- and Mo-depleted zones on pitting
mechanisms of aged UNS S31803 DSS. With increas-
ing aging time, Cr and Mo diffusion from the original
metallic matrix to the Cr- and Mo-impoverished re-
gions could contribute to the small increase in the
pitting corrosion resistance observed.
CONCLUSIONS
❖ Aging times up to 10 min at 850°C of UNS S31803
DSS led to sigma formation by direct precipitation
from ferrite, resulting in Cr- and Mo-depleted ferrite,
or secondary ferrite.
❖ Between 30 min and 5 h of aging at 850°C, the
ferrite found in UNS S31803 DSS suffered eutectoid
decomposition, resulting in the sigma phase and sec-
ondary austenite, impoverished in Cr and Mo.
❖ Cr- and Mo-depleted zones around the sigma
phase, formed preferably by secondary ferrite in ag-
ing times up to 10 min, and by secondary austenite
in aging times greater than 30 min, were preferential
sites for nucleation of pits. At those sites, the passive
film breakdown was easier, as shown by the small Epit
values found.
❖ Pits growing in 850°C, aged UNS S31803 DSS oc-
curred as selective corrosion of the metallic matrix
136
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surrounding the sigma phase composed of second-
ary ferrite and austenite phases, as a consequence of
their lower corrosion resistance.
❖ The small Epp values found after aging at 850°C of
UNS S31803 DSS were an indication of the difficulty
in repassivation of the pits formed, probably related to
the Cr and Mo depletion of such regions.
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