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Influence of Sigma Phase Formation on Pitting Corrosion of an Aged UNS

S31803 Duplex Stainless Steel

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DOI: 10.5006/0768

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CORROSION SCIENCE SECTION
Influence of Sigma Phase Formation on Pitting
Corrosion of an Aged UNS S31803 Duplex
Stainless Steel
Daniella Caluscio dos Santos,‡,* Rodrigo Magnabosco,** and Carlos de Moura-Neto***
Abstract
The main purpose of this contribution was the study of the
relation between sigma formation and pitting corrosion resis-
tance of a UNS S31803 duplex stainless steel aged at 850°C.
Solution-treated samples were isothermally aged at 850°C
for up to 360 h. The corrosion resistance of aged UNS S31803
steel was analyzed through cyclic potentiodynamic polariza-
tion tests in 0.6 M sodium chloride (NaCl) solution. The main
mechanism of sigma phase formation was nucleation and
growth from ferrite, in agreement to the Johnson-Mehl-Avrami-
Kolmogorov kinetics model. This model suggests a change on
the mechanisms of sigma phase formation from nucleation
and growth from ferrite to the growth from austenite. Pitting
morphology was related to the material microstructure. The
pitting growth mechanism occurred by selective corrosion of
the chromium-depleted areas of the specimens. Both pitting
and repassivation potentials decreased with an increase of
sigma volume fraction. Recovery of the corrosion resistance
was observed in the early stages of sigma formation, probably
related to chromium redistribution to depleted areas.
KEY WORDS: duplex stainless steel, Johnson-Mehl-avrami,
pitting corrosion, polarization, sigma
Submitted for publication: June 25, 2012. Revised and accepted:
April 16, 2013. Preprint available online: May 31, 2013, doi:
http://dx.doi.org/10.5006/0768.
‡
Corresponding author. E-mail dcaluscio@fei.edu.br.
* Praça Marechal Eduardo Gomes, 50, Vila das Acácias, São José
dos Campos, SP, Brazil 12228-900.
** Ignatian Educational Foundation (FEI), Av. Humberto Castelo
Branco, 3972, São Bernardo do Campo, SP, Brazil, 09850-901.
*** Aeronautics Institute of Technology (ITA/DCTA), Praça Marechal
Eduardo Gomes, 50, Vila das Acácias, São José dos Campos, SP,
Brazil. 12228-900.
ISSN 0010-9312 (print), 1938-159X (online)
900 13/000163/$5.00+$0.50/0  © 2013, NACE International
INTRODUCTION
Duplex stainless steels have two phases in approxi-
mately equal amounts in their structure. These steels
are composed of ferrite (a) and austenite (g), where
both phases may be considered stainless because
of their high chromium content.1 The combination
of these phases leads to high mechanical and corro-
sion resistance, and, as a result of its properties, the
majority of applications of duplex stainless steels is
in chemical, pulp and paper industries, tube manu-
facturing, desalinization plants, and more recently, in
flexible pipes manufacture for offshore oil production.2
Exposure of a duplex stainless steel to high tem-
peratures (typically between 60°C and 1,000°C) may
induce sigma phase (s) formation depending on the
chemical composition of the material. This phase is
considered the most deleterious one given its brittle
behavior.1,3
Sigma phase may be formed by three distinct
mechanisms: eutectoid decomposition of ferrite (gen-
erating secondary austenite), nucleation and growth
from ferrite (generating secondary ferrite that can be
transformed to secondary austenite depending of its
chromium depletion and/or nickel enrichment), or
growth from austenite (after total ferrite consump-
tion).4-6
Some authors5-7 reported that kinetics of sigma
phase formation may be described by the Johnson-
Mehl-Avrami (J-M-A) model. This model is presented
in Equation (1), where f (0 < f < 1) corresponds to
transformed phase fraction, k refers to the activation
energy of the process, and n is the J-M-A exponent,
CORROSION—SEPTEMBER 2013

which is related to the mechanisms of the phase for-
mation:
f = 1 – exp(–kt n ) (1)
8
Christian gives examples of typical n values for
different mechanisms of nucleation and growth. The
typical values of n for discontinuous precipitation,
eutectoid reactions, and interface-controlled growth
vary from 1 to 4. For diffusion-controlled growth, n
values vary from 0.5 to 2.5.
In addition to the reduction on toughness of the
material, sigma phase formation may lead to a reduc-
tion in corrosion resistance. Many authors have re-
ported the corrosion resistance reduction as a result
of sigma phase formation, and pointed out that this
behavior is related to chromium and molybdenum
depletion around sigma phase, mainly in second-
ary ferrite and austenite phases.5,7-8 It was found
that the presence of sigma phase particles in UNS
S31803 duplex stainless steel leads to a reduction
of approximately 1,000 mVSCE on pitting potential
(EPit) of the material, and pitting formation occurred
in chromium-depleted areas associated to sigma
formation.4,9-15 Sridhar, et al.,13 have found that the
same material isothermally aged at 700°C registered
a drop of approximately 450 mV in the repassivation
potentials (ERep) in the beginning of the treatment.
The authors also have found in another aging treat-
ment at 870°C a similar drop in ERep that was partially
recovered with increasing aging time because of the
greater diffusion of alloying elements into the depleted
secondary austenite.
Another work4 presented that between 30 min
and 5 h of aging at 850°C ferrite found in UNS
S31803 duplex stainless steel suffered eutectoid de-
composition, resulting in sigma phase and secondary
austenite formation, both depleted in chromium and
molybdenum. Chromium- and molybdenum-depleted
zones around 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, served as preferential sites for pit nucleation.
However, the mentioned work4 only studied five differ-
ent aging times at 850°C (10 min, 30 min, 1 h, 5 h,
or 100 h), and conclusions on the mechanisms and
kinetics of sigma phase formation require a more
detailed study to clarify the dependence of pitting po-
tential to the material’s microstructure after sigma
formation.
Much information about the sigma phase for-
mation in duplex stainless steels can be found in
literature, and its relation with corrosion resistance
of duplex stainless steels is widely known. However,
there is no agreement on the definition of the mecha-
nisms and kinetics of sigma phase formation. This
work discusses the kinetics and the mechanisms of
sigma phase formation in UNS S31803 aged at 850°C
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CORROSION SCIENCE SECTION
Table 1
Chemical Composition (wt%) of the Studied Material
Cr Ni Mo Mn N C Si Cu Fe
22.48 5.74 3.20 1.42 0.162 0.018 0.35 0.15 Bal.
for 17 different aging times up to 360 h of aging, eval-
uating the influence of sigma phase formation and,
therefore, the chromium depletion on pitting potential
and repassivation potential in a 0.6 M sodium chlo-
ride (NaCl) aqueous solution.
eXPerIMeNtAl PrOceDUres
The chemical composition of UNS S31803 is given
in Table 1. Samples were obtained from 3 mm thick-
ness sheet, with dimensions of approximately 300 mm
long and 600 mm wide. Solution heat treatments were
performed at 1,175°C for 30 min followed by water
quenching, to maintain a homogeneous structure of
ferrite and austenite. After the solution heat treat-
ment, samples were isothermally aged at 850°C be-
tween 10 min and 360 h in a vacuum tubular electric
furnace under nitrogen atmosphere to avoid excessive
oxidation of the samples, and to prevent nitrogen loss
from the material. The aging treatments conducted
between 1 min to 5 min were possible by using an
aluminum bath in a muffle furnace to ensure efficient
heat transfer to the material. Aging treatments were
interrupted by a water quench.
After heat treatments, specimens were abraded
using silicon carbide (SiC) papers to a 220-grit finish
before mounting in thermosetting plastic, leaving an
exposed surface area of approximately 0.5 cm2, paral-
lel to the rolling direction. The mounted specimens
were metallographically polished in a semi-automatic
grounding and polishing machine, with final polishing
provided by 1-μm diamond abrasive. Samples were
then etched with modified Beraha reagent, composed
of 20 mL hydrochloric acid (HCl), 80 mL distilled wa-
ter, and 1 g potassium metabisulfide (K2S2O5); to this
stock solution, 2 g of ammonium bifluoride (NH4F·HF)
were added just before the etching. Selective etch-
ing of sigma phase was obtained through electrolytic
etching in 10% potassium hydroxide (KOH) aqueous
solution (2 Vdc during 1 min). Scanning electron mi-
croscopy (SEM) also was used to evaluate the micro-
structural characterization of polished specimens.
Quantitative metallography of sigma phase was
performed using optical microscopy (OM) connected to
an automated image analysis system, determining the
volumetric percentage of sigma phase (%P[s]). Ferrite
content of the samples (%P[a]) was obtained through
magnetic measurements using a ferritscope. The aus-
tenite content (%P[g]) was determined by Equation (2):
%P( γ ) = 100 – (%P( σ ) + %P( α ) ) (2)
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CORROSION SCIENCE SECTION
Figure 1. Optical microstructure of UNS S31803 duplex stainless
steel after solution treatment. Ferrite (dark) and austenite. Etchant:
Beraha etching.
X-ray diffraction patterns were obtained using
Cu-Ka radiation (wavelength of 1.5418 nm), at 30 kV
and current of 30 mA. Scan rate of 1°/min and scan
step of 0.04° were used.
Cyclic polarization tests were conducted in a
0.6 M NaCl aqueous solution (pH = 6.5), exposed to
laboratory air, at a controlled temperature of 22±2°C,
with a scan rate of 1 mV/s, beginning at the open-
circuit potential (OCP). The scanning was reversed
when the current density reached 1 mA/cm2. The test
cell had a platinum wire as counter electrode, a satu-
rated calomel reference electrode (SCE), and an un-
etched polished specimen as working electrode. The
electrochemical tests were repeated five times for
each heat treatment condition. Immediately after the
polarization, sample surfaces were washed with dis-
tilled water and then with ethyl alcohol (C2H5OH), and
finally dried with hot blown air. The surface of the
samples before and after the polarization tests were
analyzed using OM and SEM.
Results
The microstructure of the solution-treated sample
is presented in Figure 1, which shows the presence of
ferrite (dark) and austenite (light); the ferrite content
was 57.3±2.3%. Figure 2 presents the microstruc-
tures of the aged samples, where the formation of
a new phase (lighter) is observed, with preferential
nucleation at ferrite/austenite interfaces, growing into
ferrite grains with a lamellar morphology. This phase
is probably sigma, considering the evidence of sigma
phase formation in duplex stainless steels aged at
850°C.3-5,7 The same figure shows the formation of a
halo around the austenite grains, probably related to
ferrite/austenite new balance after the solution treat-
ment of the material, together with the presence of
black precipitates in the austenite halo boundaries,
probably associated with chromium nitrides (Cr2N) as
studied previously.16 The formation of sigma (lighter
phase) and nitrides (indicated with white arrows)
902
are seen clearly in SEM images presented in Figure
3. A brighter phase in low volume fraction, prob-
ably related to the chi formation, was also observed
in Figures 3(c) and (d) (indicated with black arrows).
An increase in sigma volume fraction together with
the reduction of ferrite was observed with increasing
aging time, until the total consumption of ferrite (Fig-
ures 2[f] and 3[f]).
Figure 4 shows x-ray diffraction patterns for the
solution-treated sample and for the samples aged for
1 h and 360 h, indicating the presence of only ferrite
and austenite in the solution-treated sample; for the
samples aged for 1 h and 360 h at 850°C, the pres-
ence of sigma phase is clearly observed. Chromium
nitrides (Cr2N) and possibly chi (c) phase formation
also were detected by this technique; however, some
chi and Cr2N diffraction peaks overlap. Considering
that chi is richer in molybdenum in relation to sigma,
and given that it can be identified using back-scat-
tered electrons (BSE) by image contrast in SEM as a
brighter phase in SEM images14 (Figure 3), there are
evidences of chi formation. As observed in BSE images,
the presence of chi occurred in low volume fractions,
and besides that, this phase was not considered for
the mechanisms and kinetic of sigma phase studies.
Figure 5 presents sigma, ferrite, and austenite
volume contents in aged samples, where the increase
of sigma volume fraction together with the consump-
tion of ferrite with increasing aging time is observed,
confirming the microstructural observations. A sharp
decrease of ferrite content is also observed, even for
samples of shorter aging times. Furthermore, the
austenite volume fractions (calculated with Equation
[2]) were higher than the austenite fraction in the
solution-treated sample, which may be related to the
ferrite/austenite re-equilibrium after the heat treat-
ment. Figure 5 is divided into six sections to allow
further discussion of the mechanisms of sigma phase
formation.
Figure 6 presents typical cyclic polarization
curves conducted in 0.6 M NaCl solution. The cyclic
polarization curves exhibit a decrease in pitting poten-
tial values with an increase in aging time, and, con-
sequently, a decrease in pitting corrosion resistance
of the studied material is registered. It was also regis-
tered that in anodic high overpotentials, oxygen evolu-
tion was always observed, as previously published by
one of the authors.4
Furthermore, metastable pitting that is often
found in steels exposed to chloride solutions was
clearly observed in Figures 6(c) and (d) below the pit-
ting potentials. These metastable pits can nucleate
below the pitting potentials, leading to current insta-
bilities in the passive range.
The average EPit and ERep in each aging condition
are presented in Table 2 and in Figures 7 and 8 as a
function of aging time. ERep was defined as the poten-
tial at which the ascendant curve intercepts the de-
CORROSION—SEPTEMBER 2013

(a)
(c)
(e)
Figure 2. Optical microstructures of UNS S31803 duplex stainless steel aged at 850°C for: (a) 1 min, (b) 30 min, (c) 1 h,
(d) 6 h, (e) 240 h, and (f) 360 h. Ferrite (dark), austenite (gray), and sigma (light). Etchant: Modified Beraha - OM.
scendant curve. However, Figures 6(c) and (d) showed
that for aging times greater than 20 min there was
no interception, leaving an open loop in polarization
curves. In those cases, ERep was considered equal to
OCP, showing an inability to repassivation of the ma-
terial after pit nucleation and growth. Figure 7 is also
divided into the same six sections already used in Fig-
ure 5, allowing the further analysis of the relationship
between pitting corrosion resistance and mechanisms
of sigma phase formation.
After the polarization tests, the surface of the
samples were analyzed using OM (Figure 9) and SEM
(Figure 10) techniques. In these figures it is observed
that in the samples aged for shorter aging times
(Figures 9[a] and 10[a]) pitting formation occurs pref-
erably on grain boundaries or on ferrite/austenite
CORROSION—Vol. 69, No. 9
CORROSION SCIENCE SECTION
(b)
(d)
(f)
interfaces. Meanwhile, in the samples aged for more
than 30 min, pitting formation is observed related to
selective corrosion with a lamellar morphology (Figure
9[b]), indicating that these affected areas are related
to sigma phase formation. In particular, Figure 10(c)
shows lacy pattern morphology on the corroded sur-
face, which begins primarily on ferrite/ferrite and fer-
rite/austenite interfaces. In Figure 10(d), where the
absence of ferrite is registered, the pitting formation
occurs close to sigma phase.
Discussion
Mechanisms of Sigma Phase Formation
To define the mechanisms of sigma phase forma-
tion, the plot presented in Figure 5 is divided into six
903
CORROSION SCIENCE SECTION
(a)
(c)
(e)
Figure 3. SEM images of UNS S31803 duplex stainless steel aged at 850°C for: (a) 5 min, (b) 10 min, (c) 20min, (d) 2 h,
(e) 36 h, and (f) 360 h. Etchant: Modified Beraha.
sections. The first aging section (between 1 min and
5 min) does not show sigma phase formation; how-
ever, the austenite volume fraction rises from
42.7±2.3% to 59.4±2.2% and ferrite decreases from
57.3±2.3% to 40.6±2.2%. The decrease of ferrite and
the increase in austenite volume fractions may be
related to the new balance of these phases after the
solution treatment of the material, considering that
in solution treatment temperature, the austenite frac-
tion is smaller than the equilibrium austenite fraction
on aging temperature. This new austenite is probably
904
(b)
(d)
(f)
formed as a result of the balance of phases after the
solution treatment is originated from ferrite, and
therefore may not contain nitrogen on its composi-
tion.16 The austenite volume fraction of the first aging
section corresponds to the sum of original austenite
(g) and the new austenite, which will be called re-
equilibrium austenite (gr) to differentiate this phase
from the original one. The formation of re-equilibrium
austenite could be observed in Figures 2 and 3 as
the formation of austenite halos around the original
austenite grains. This phenomenon probably induces
CORROSION—SEPTEMBER 2013
 CORROSION SCIENCE SECTION

the alloy elements’ redistribution between the re-

equilibrium austenite and the original austenite,
and this promoting the local saturation of chromium
and nitrogen, and consequently the observed nitride
formation.
Analyzing the second aging section (marked as
“2” in Figure 5), corresponding to the samples aged
between 5 min and 1 h, a decrease in ferrite volume
fraction from 40.6±2.2% to 17.5±2.9% was observed
together with a significant increase in sigma content,
up to 22.1±4.02%. Therefore, considering that the
austenite fraction remains almost constant (from
59±2.2% to 60.4±4.95%), the sigma phase formation
occurs by nucleation and growth from ferrite since
there is not an increase on austenite content arising
from secondary austenite formation.
The same analysis was used in the third section
of Figure 5, related to the aging between 1 h and 2 h:
an increase in sigma volume fraction from 22.1±4.0%
to 35.2±2.9% occurs simultaneously with a decrease
in ferrite from 17.5±2.9% to 13.1±2.8% and austenite
from 60.4±5.0% to 51.68±3.3%. Therefore, in this sec-
tion the sigma phase formation is not only related to
ferrite, but also to the austenite consumption. There-
fore, sigma phase formation may be related to both
nucleation and growth from ferrite and growth from
austenite, resulting in a secondary austenite (g2) gen-
eration. However, given the decrease of austenite vol-
ume fraction, the hypothesis of secondary austenite
formation from secondary ferrite or from eutectoid de-
composition of ferrite seems unreasonable, especially
considering that an increase on austenite volume
fraction should be observed. The microstructure of the
samples aged between 1 h (Figure 2[c]) and 2 h (Fig-
ure 3[d]) shows that the morphology of sigma evolves
from massive to lamellar, probably because of the dis-
continuous precipitation of sigma from ferrite.
Figure 4. X-ray diffraction patterns of solution-treated sample and
In the fourth section of aging (Figure 5), corre- samples aged for 1 h and 360 h.
sponding to the samples aged between 2 h and 72 h,
it is observed that the total consumption of ferrite
after 36 h aging, an increase of sigma phase (from
35.2±2.9% to 43.2±3.5%), and the maintenance of
austenite volume fraction considering the standard
deviation of the measurements (from 51.7±3.4% to
56.8±3.5%). Therefore, in this section, sigma phase
formation probably occurred by nucleation and
growth from ferrite, generating secondary ferrite until
the total ferrite consumption. The microstructure of
the samples in this section (Figures 2[d] and 3[d])
shows the growth of the sigma particles in comparison
with the other sections.
In a similar analysis, the fifth section of Figure 5,
from 72 h to 144 h of aging, presents an increase in
sigma volume fraction from 43.2±3.5% to 51.56±4.2%
and the decrease in austenite volume fraction from
56.8±3.5 to 48.4±4.2%. This behavior indicates the
Figure 5. Ferrite, austenite, and sigma volume contents (%) as a
growth of sigma from austenite in the absence of fer-
function of aging time at 850°C.
rite, as observed by previous researchers.4

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CORROSION SCIENCE SECTION
Figure 6. Typical cyclic polarization curves in 0.6 M NaCl solution of UNS S31803 duplex stainless steel aged at 850°C:
(a) solution-treated sample, (b) 3 min to 10 min of aging, (c) 20 min to 40 min of aging, and (d) 1 min to 360 min of aging.
Finally, in the last section of aging comprised
between 144 h and 360 h, it was observed that sigma
and austenite volume fractions were approximately
constant, indicating that the volume fractions of these
phases became stable. The microstructures presented
in Figures 2(e) and (f) and Figure 3(f) show only the
presence of sigma and austenite in the aged samples.
This remaining austenite is called final austenite
(gfinal). A summary of the proposed phase transforma-
tions that occur in aging treatment is presented in
Table 3.
Kinetics of Sigma Phase Formation
From sigma volume fraction data as a function
of aging time and J-M-A equation (Equation [1]), the
J-M-A constant (k) and the J-M-A exponent (n) can be
determined using the linearized form of Equation (1),
presented in Equation (3):
ln[– ln(1 – f )] = n[ln(t )] + ln(k)
The maximum value for the transformed sigma
volume fraction (f = 1) is established in the aging time
(t) correspondent to the absence of ferrite, because
from this time, sigma volume fraction tends to stabi-
lization. With the values of transformed fraction and
the aging time, the plot presented in Figure 11 is ob-
tained, and it can be observed that the experimental
data leads to two different slopes. This trend suggests
that there is a change on the main mechanism of
906
sigma phase formation with increasing of aging time,
and, consequently, with the increase of sigma volume
fraction, as previously mentioned by other authors.6
The parameters k and n obtained from J-M-A plots
are presented in Table 4. Even though the determina-
tion of J-M-A parameters cannot specify precisely
the mechanisms of sigma formation, it can indicate
what kind of nucleation or growth conditions are
occurring.15
For the first slope, which includes the aging be-
tween 1 min and 1 h at 850°C, the J-M-A coefficient
(n) corresponds to 1.57. According to Christian,8
this value may be related to the nucleation on grain
boundaries (1.0), or nucleation in triple points (2.0)
if the process is related to discontinuous precipita-
tion; and the growth from small dimensions with
decreasing nucleation rate (1.5 to 2.5), if the process
is controlled by diffusion. As mentioned earlier, the
mechanisms of sigma phase formation indicates that
(3) in this aging section, after the new balance of fer-
rite and austenite (until 5 min of aging), the sigma
phase formation occurs by heterogeneous nucleation
and growth from ferrite (between 5 min to 1 h of ag-
ing). Furthermore, as indicated in this section by
microstructural analysis, the sigma phase formation
preferably occurs on ferrite/ferrite or ferrite/austenite
interfaces; therefore, it seems valid to consider the
occurrence of nucleation and growth after saturation.
Nevertheless, the possibility of the beginning of sigma
growth in the first section of aging cannot be ruled
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 CORROSION SCIENCE SECTION

Table 2
Pitting (EPit), Repassivation (ERep), and Open-Crcuit (OCP) Potentials for all Studied Conditions
Aging Time EPit (mVSCE) ERep (mVSCE) OCP (mVSCE) ERep–OCP
Solution-treated 1,085±98.4 857.1±15.9 –211.0±35.5 1,068.1
1 min 1,098±46.0 930.5±25.1 –326.4±168.3 1,256.9
3 min 1,067±31.5 905.1±22.8 –205.1±118.2 1,110.2
5 min 1,084±43.4 907.8±61.6 –264.9±61.4 1,172.7
10 min 1,083.2±96.8 199.6±533.5 –305.2±52.2 504.8
20 min 732.4±458.3 –206.7±53.3 –204.8±54.1 1.94
30 min 1,081.6±46.3 –201.7±38.1 –201.7±38.1 0
40 min 784.8±149.3 –207.9±61.5 –207.9±61.5 0
1 h 579.8±291.1 –224.3±61.5 –224.3±61.5 0
2 h 548.6±112.3 –212.1±46.4 –212.1±46.4 0
4 h 457±109.9 –215.8±43 –215.8±43 0
6 h 382.6±44.9 –214.0±31.4 –214.0±31.4 0
18 h 256.4±151.0 –250.3±23.8 –250.3±23.8 0
36 h 402±92.8 –230.4±20.8 –230.4±20.8 0
72 h 409.6±76.1 –215.9±27 –215.9±27 0
144 h 422.8±40.3 –206.5±24.6 –206.5±24.6 0
240 h 316±58.6 –212.4±34.1 –212.4±34.1 0
360 h 386±187.3 –282.6±81.7 –282.6±81.7 0

out. In addition, the previous analysis indicates that

in this section the sigma transformation was diffu-
sion-controlled, supporting the depleted ferrite forma-
tion assumption.
In the second slope of the plot presented in Fig-
ure 11, related to the aging between 2 h and 18 h,
the J-M-A exponent value of 0.67 was determined.
Considering this value close to 1, and according to
Christian,8 in this section the growth of sigma parti-
cles probably occurred with an appreciable initial vol-
ume; and considering this value close to 0.5, occurs
the thickening of sigma particles. Both hypotheses
may be considered since the growth of sigma phase
was observed in Figures 2 and 3. Analyzing the mech-
Figure 7. Epit of UNS S31803 duplex stainless steel as a function
anisms of sigma phase formation, from 1 h of aging, of time at 850°C.
the growth of sigma from austenite occurs, and it is
also possible the nucleation and growth of sigma from
ferrite, which may occur also between 2 h and 72 h
of aging. Once again, sigma particle growth occurs
probably by diffusion process from ferrite or austen-
ite, and it perhaps led to the increase in chromium-
and molybdenum-depleted areas, which may cause
a decrease in corrosion resistance of the material.
Furthermore, the J-M-A constant (k) remained
approximately constant on both slopes (1.12 and
1.08) increasing aging time. Therefore, in the begin-
ning of aging (first slope), sigma phase formation
would occur by diffusion-controlled mechanisms.
At the beginning of the second slope, the ferrite vol-
ume fraction is low in comparison to the initial vol-
Figure 8. ERep of UNS S31803 duplex stainless steel as a function
ume fraction. Therefore, sigma growth in the second of time at 850°C.
slope probably occurred by a diffusion-controlled
process from austenite to sigma, as identified previ-
ously. The sigma particle growth leads to the growth From the values of n and k obtained through
of chromium-depleted areas and, consequently, to the plot of Figure 11, Equation (4) can be considered
the decrease of pitting corrosion resistance of the valid. In this equation, the sigma equilibrium volume
eq
material. fraction (%P[s] ) is determined from the aging time from

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CORROSION SCIENCE SECTION
(a)
Figure 9. OM of the specimen’s surface after cyclic polarization tests in 0.6 M NaCl solution of the samples aged at
850°C for (a) 30 min and (b) 144 h.
which it is registered the absence of ferrite, after 36 h
of aging, with a value of 40.7%:
%P( σ ) = %P(eq
σ ) ⋅ [1 – exp(–kt )]
n
(4)
The comparison between J-M-A-estimated sigma
content and experimental results is presented in Fig-
ure 12, where it is evident the good agreement of
experimental and calculated data for the first slope
(R2 = 0.89). For the second slope, the same relation is
not so good if compared to the first (R2 = 0.6). This
behavior indicates that for this section the J-M-A
kinetics model may not be valid, since sigma growth
is controlled by chromium diffusion to the depleted
areas. Since the presence of sigma within the begin-
ning of aging time is deleterious to the material’s cor-
rosion resistance, as will be further discussed, the
description of the kinetics of sigma phase formation
by this method is relevant for the purpose of this
work.
Relation Between Microstructure and Corrosion
Resistance
The solution-treated and the aged samples’ cyclic
polarization behavior, presented in Figure 6, showed
a strong correlation with the material microstructure.
The relationship between pitting potential and the ag-
ing time is presented in Figure 7, where the depleted
phases formed in each section are also indicated,
according to the study of the mechanisms of sigma
phase formation. In addition, the analysis of the re-
lationship between repassivation potential and aging
time is presented in Figure 8.
In the first section of Figure 7, it was observed
that the pitting potential of solution-treated sample
was 1,000 mV vs. saturated calomel electrode (SCE).
Meanwhile, as previously discussed by Magnabosco
and Alonso-Falleiros,4 this pitting potential value may
have been influenced by anodic current correspond-
ing to the oxygen evolution reaction (2H2O ↔ O2 + 4H+
+ 4e for acid solutions) on a steel surface. This reac-
908
(b)
tion may increase the total current density, generat-
ing oxygen bubbles on the sample surface, making
the passive film-breaking process easier and, conse-
quently, leading to the pit nucleation on the metal/
gas/solution interface. After polarization tests, the
solution-treated sample surface was analyzed by opti-
cal microscopy (Figure 9[a]), showing the presence of
isolated pits preferably on ferrite/austenite interfaces,
probably related to the oxygen evolution.
It is also observed that the pitting potential of the
aged samples in the first section of Figure 7, showing
the beginning of the aging treatment (between 1 min
to 40 min), were similar to the solution-treated ones.
Here, the major phase transformations were ferrite/
austenite new balance generating re-equilibrium
austenite, followed by sigma phase formation by
nucleation and growth from ferrite generating chro-
mium-depleted ferrite. Therefore, the presence of new
equilibrium austenite (gr), which probably does not
have nitrogen in their composition, since it arises
from ferrite, does not cause a decrease in pitting po-
tential of the material. There are three hypotheses for
this behavior:
—The re-equilibrium austenite may not be ni-
trogen-depleted in comparison to the original
austenite.
—There is a nitrogen redistribution between origi-
nal austenite and re-equilibrium austenite be-
cause of the high temperature treatment.
—The available chromium content at the begin-
ning of the aging is high enough to ensure the
corrosion resistance of material.
The formation of isolated pits, preferably on ferrite/
ferrite and ferrite/austenite interfaces (Figure 10[a]),
was probably related to the formation of oxygen
bubbles, as suggested previously. Moreover, high ERep
were observed until 10 min of aging, confirming high
corrosion resistance of these samples (Figure 8).
Between 10 min and 1 h of aging, represented as
the second section in Figure 7, the polarization curves
showed, in particular for the sample aged for 20 min
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 CORROSION SCIENCE SECTION

(a) (b)

(c)

(d) (e)
Figure 10. SEM images of specimen surface after cyclic polarization tests in 0.6 M NaCl solution aged at 850°C for: (a)
10 min (SEI), (b) 1 h (left - BSC; right - SEI), (c) 1 h (SEI), (d) 240 h (left - BSC; right - SEI), and (e) 240 h (SEI).

(Figure 6[c]), fluctuations in pitting potential values,
probably related to the increasing of chromium-de-
pleted areas formed as a consequence of nucleation
and growth of sigma from ferrite, causing composition
heterogeneities in the metallic matrix. Fluctuations
also were observed in repassivation potentials in the
sample aged for 10 min of aging (Figure 8), probably
related to chromium-depleted phase formation, espe-
cially secondary ferrite (a2). Although, in the sample
aged for 30 min, the increase of pitting potential to
values close to the less aged samples occurs, probably
because of the chromium redistribution enabled by
high-temperature aging. The surface sample analysis
shows the beginning of selective corrosion formation
mainly on ferrite/ferrite interface, as presented in
Figure 9(a), emphasizing the hypothesis of chromium-
depleted area formation. A decrease of pitting poten-
tial values is registered from 40 min to 18 h of aging.
In particular, in the fourth section of Figure 7, the de-
crease of pitting potential to values close to 300 mVSCE
for samples aged for 1 h is observed, and a severe
selective corrosion of the samples mainly on sigma/
ferrite interfaces is observed, as shown Figures 10(b)
and (c).

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CORROSION SCIENCE SECTION

Table 3
Phase Transformation Related to Aging Treatment
at 850°C
Section Transformation

Until 5 min a/g re-equilibrium-gr formation

5 min to 1 h a → s + a2
1 to 2 h a → s + a2/a → s + g2
2 to 72 h a → s + a2
72 to 144 h g → s + g2
144 to 360 h s stabilization
a, original ferrite; g, original austenite; s, sigma; a2, secondary ferrite;
g2, secondary austenite; gr re-equilibrium austenite.

Table 4
Values of n and k Parameter from J-M-A Calculations Figure 11. J-M-A model applied to sigma phase formation at
850°C: (1) initial slope between 1 min and 1 h of aging and (2) final
First Slope Second Slope
slope between 2 h and 18 h of aging.
n 1.57 0.67
k 1.12 1.08

The repassivation potential (Figure 8) was main-

tained approximately constant for aging times greater
than 20 min until the end of the aging treatment,
probably related to the intensive sigma formation
and consequently by chromium-depleted areas for-
mation, as secondary ferrite or austenite (a2 or g2).
This is related to the assumption of the inability of
repassivation of the material after pit nucleation and
growth, since ERep was considered equal to OCP. Table
2 shows this behavior by the calculation of the differ-
ence between ERep and OCP, indicating a drop in cor-
rosion resistance of the material.
In addition to the severe sigma phase formation,
the kinetic analysis indicates that after 1 h of aging,
intensive sigma growth and sigma phase formation
from austenite take place (between 1 h and 2 h of ag-
ing), increasing both chromium-depleted ferrite and
austenite (Figure 6[d]). Therefore, the pitting potential
values decrease continuously until 18 h of aging. It is
also observed, in an opposite behavior in relation to
the beginning of aging, the selective corrosion of re-
equilibrium austenite (Figure 9[b]). This phase, as a
result of the formation of chromium nitrides, is prob-
ably depleted on both alloy elements, allowing the se-
lective corrosion of these areas.
In the aging treatment between 18 h and 72 h,
also in the same section of Figure 7, the increase of
pitting potential values from the chromium redistri-
bution from austenite is registered. Considering that
ferrite volume fraction in this section of aging are very
low, the chromium redistribution may not be enough
to restore completely the corrosion resistance.
At 72 h of aging, the pitting potentials reached
the lowest values, probably because of the general
chromium depletion of the samples. Therefore, from
this aging time the chromium concentration gradient
between original (g) and secondary austenite (g2) was
Figure 12. Comparison between experimental data and J-M-A
analysis of sigma volume fraction as a function of aging time at
850°C.
smaller, making the chromium redistribution diffi-
cult. The surface sample analysis shows the selective
corrosion of austenite, as a consequence of the total
consumption of ferrite, indicating that this phase was
also chromium-depleted. In particular, analysis of Fig-
ures 9(b) and 10(d) and (e) indicates that the pitting
formation occurs mainly close to nitrides formation.
In general it is clear that once the pitting forma-
tion on the aged samples started, it tended to grow by
selective corrosion of chromium-depleted areas.
Both EPit and ERep may be analyzed as a function
of sigma volume fraction, as presented in Figures 13
and 14. As expected, for low sigma contents, high val-
ues of pitting and repassivation potentials were regis-
tered. In Figure 13 for a sigma content of about 15%,
the beginning of the decrease of pitting potential is
registered, culminating in a drop of about 1,000 mVSCE
with 41% of sigma, probably related to the decrease
of corrosion resistance from the formation of depleted
areas in a consequence of sigma phase formation.
Likewise, a recovery of corrosion resistance with a

910 CORROSION—SEPTEMBER 2013


Figure 13. EPit as a function of sigma volume fraction (%s).
slight increase of pitting potential to approximately
420 mVSCE was also observed for the sample with 51%
of sigma, probably as a result of the chromium redis-
tribution to depleted areas, which was commented on
previously in the discussion of mechanisms of sigma
phase formation. From approximately 2% sigma vol-
ume fraction, a drop of about 1,213 mVSCE in repas-
sivation potentials was observed (Figure 14). But, the
recovery in repassivation potential was not registered,
indicating that the chromium redistribution may not
be enough to restore completely the corrosion resis-
tance of the material.
Conclusions
The study of the influence of sigma phase forma-
tion on the corrosion resistance of aged UNS S31803
duplex stainless steel in 0.6 M NaCl solution shows
a strong dependency between pitting corrosion and
microstructure, mechanisms, and kinetics of sigma
phase formation. The conclusions can be summarized
as follows:
v  The main mechanism of sigma phase formation
was the nucleation and growth from ferrite.
v  The kinetics of sigma phase formation study by the
J-M-A model confirmed the change on the mechanism
of sigma phase formation from nucleation and growth
from ferrite to the growth from austenite with increas-
ing aging time as a double slope on J-M-A plots.
v  The pitting morphology of the samples after cyclic
polarization tests were related to the material micro-
structure, and the pitting growth mechanism occurred
by selective corrosion of chromium-depleted areas.
CORROSION—Vol. 69, No. 9
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CORROSION SCIENCE SECTION
Figure 14. ERep as a function of sigma volume fraction (%s).
v  The corrosion resistance analysis showed a severe
drop in pitting potentials and repassivation potentials,
probably related to the increase of secondary chro-
mium-depleted phases formed in consequence of sigma
phase formation. A partial recovery of the pitting po-
tentials at some aging periods was also registered,
probably because of the chromium redistribution to
depleted areas. However, the recovery in repassivation
potential did not occur, indicating that the chromium
redistribution may not be enough to restore com-
pletely the corrosion resistance of the material.
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