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CORROSION SCIENCE SECTION

Sigma Phase Formation and Polarization Response
of UNS S31803 in Sulfuric Acid

R. Magnabosco‡,* and N. Alonso-Falleiros**

ABSTRACT KEY WORDS: duplex stainless steel, microstructure, sigma
phase, potentiodynamic polarization, sulfuric acid, UNS
For a better understanding of the relationship between the S31803
microstructure of UNS S31803 duplex stainless steel (DSS)
and the shape of the polarization curves, this study evaluated INTRODUCTION
the influence of the microstructure on the potentiodynamic
polarization of the 850°C isothermal-aged UNS S31803 DSS in One of the earliest studies concerning the microstruc-
0.5 M sulfuric acid (H2SO4). In the transpassive region, selec- tural influence on the electrochemical behavior of
tive corrosion of chromium- and molybdenum-rich phases oc-
duplex stainless steels (DSS) was carried out with
curred. In the solution-treated sample, ferrite was selectively
19%Cr-11%Ni steel, solution-treated to obtain a ferrite-
corroded, and in all aged samples, the sigma phase was the
selectively corroded phase. Five current density maxima in the
austenite duplex structure.1 During potentiostatic po-
passive region were found during potentiodynamic polariza- larization at –200 mV vs. saturated calomel electrode
tion, and they can be related to the microstructures formed. (SCE) in 20% sulfuric acid (H2SO4), conducted after
The current density maximum at 564 mV vs. saturated calo- prepolarization in the cathodic region (–600 mVSCE, to
mel electrode (SCE) can be related to secondary ferrite, im- remove the passive film), selective corrosion of the
poverished in chromium and molybdenum, that was formed austenite phase occurred. The potentials used were
during direct precipitation of sigma phase from the original determined after potentiodynamic polarization in the
ferrite. Secondary austenite, impoverished in chromium and same solution of an austenitic stainless steel (18%Cr-
molybdenum and formed together with the sigma phase dur- 9%Ni) and a ferritic one (27%Cr); the results showed
ing eutectoid decomposition of the original ferrite, can be relat-
that the anodic active region of the austenitic sample
ed to the current density maxima at –85 mVSCE and –40 mVSCE.
is located between –300 mVSCE and –100 mVSCE, and
The austenite phase, present in all heat-treatment conditions,
can be related to the current density maxima at –155 mVSCE the anodic active region of the ferritic sample is lo-
and 111 mVSCE. cated between –450 mVSCE and –300 mVSCE. However,
potentiostatic polarization of the duplex sample in the
Submitted for publication November 2004; in revised form, ferrite active region did not lead to selective etching of
December 2004. this phase.1

Corresponding author. E-mail: rodrmagn@fei.edu.br.
* Department of Mechanical Engineering, Ignatian Educational Potentiodynamic polarization curves of DSS simi-
Foundation – FEI, Av. Humberto A.C. Branco, 3972, 09850-901, lar to UNS S31803,(1) in 2 M H2SO4 solutions with 1 M
São Bernardo do Campo, SP, Brazil.
** Department of Metallurgical and Materials Engineering, Polytech-
and 2 M hydrochloric acid (HCl) additions, showed
nic School, University of São Paulo, Av. Prof. Mello Moraes, 2463, selective corrosion of ferrite in potentials near the cor-
05508-900, São Paulo, SP, Brazil. rosion potential, and selective corrosion of austenite
(1)
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers near the passivation potentials.2-3 Heat treatments
(SAE International) and cosponsored by ASTM International. conducted to change the volume fraction of austenite
0010-9312/05/000165/$5.00+$0.50/0
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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

and ferrite led to changes in the shape of the polariza- 600-grit finish before mounting in thermosetting
tion curves, which was attributed to the rise of anodic plastic, leaving an exposed surface area of ~0.5 cm2,
areas (related to the ferrite phase) and the reduction parallel to the rolling direction. The mounted samples
of cathodic areas (related to the austenite phase).3 were metallographic polished in a semi-automatic
Selective corrosion of the ferrite phase occurred grounding and polishing machine, with final polishing
during potentiodynamic polarization at 60°C and 80°C provided by 1-µm diamond abrasive. Samples were
of UNS S31803 DSS in 1 M H2SO4, if sodium chloride then etched for 40 s in modified Behara reagent, com-
(NaCl) additions were higher than 0.2 M. NaCl addi- posed of 20 mL HCl, 80 mL distilled water, and 1 g
tions of 0.05 M and 0.1 M led to generalized corrosion potassium metabisulfide (K2S2O5); to this stock solu-
of the two phases. However, in the absence of chlo- tion, 2 g of ammonium bifluoride (NH4F·HF) were
rides the austenite phase was selectively corroded at added just before the etching. This etching procedure
the corrosion potential.4 clearly distinguished the ferrite, austenite, and sigma
The presence of the sigma phase reduced the phases.
corrosion potential measured before the potentiody- Selective etching of the sigma phase was obtained
namic polarization of UNS S31803 (SAF 2205) in through electrolytic etching in 10% potassium hydrox-
10% H2SO4 solution; the higher the sigma phase con- ide (KOH) aqueous solution, using 2 Vdc for 1 min.
tent, the lower the corrosion potential, which varied Quantitative metallography of the sigma phase
from 299 mVSCE in the solution-treated sample (with- was performed with an automated image analysis
out the sigma phase) to 78 mVSCE in samples with system attached to an optical microscope. The ferrite
21% of the sigma phase. No active peaks were ob- content of the samples was obtained using magnetic
served in the polarization curves, and the transpas- measurements; the austenite content was calculated
sive potential remained relatively constant (around using Equation (1):
1,040 mVSCE).5
Potentiodynamic polarization of the solution- % γ = 100 – %α – % σ (1)
treated UNS S31803 (SAF 2205) in 1 M H2SO4, at
25°C, yields polarization curves that exhibit two cur- Potentiodynamic polarization tests were conduct-
rent density maxima: at –200 mVSCE in the active-pas- ed in a 0.5-M H2SO4 aqueous solution (pH 2), exposed
sive transition and at 650 mVSCE in the passive region. to laboratory air, at a controlled temperature of 22°C
The transpassive potential was around 1,050 mVSCE.6 ± 2°C. The test cell had a platinum wire as a counter
To better understand the relationship between electrode and an SCE as a reference electrode. The
the microstructure of DSS and the polarization electrochemical tests were repeated 20 times for each
curves, this work evaluated 850°C isothermal-aged heat-treatment condition.
UNS S31803 DSS in 0.5 M H2SO4. Immediately after polishing, sample surfaces were
washed with ethyl alcohol (C2H5OH) and dried with
EXPERIMENTAL PROCEDURES hot blown air. Within 6 s, the sample was immersed
in the test solution, and the electrode potential (E)
The studied material had the chemical composi- was continuously changed from a potential 300 mV
tion given in Table 1, and was received as a 3-mm- below the open-circuit potential to 1,200 mVSCE, at a
thick sheet, solution-treated at 1,120°C and water- scan rate of 1 mV/s.
quenched. Specimens of 20 mm length and 15 mm The corroded sample surfaces were examined
width were machined, with its length parallel to the using optical microscopy and scanning electron mi-
rolling direction. After machining, specimens were croscopy using secondary electron imaging (SEI); the
isothermically aged for 10 min, 30 min, 1 h, 5 h, or identification of corroded phases was possible using
100 h at 850°C, in a tubular electric furnace that con- energy-dispersive spectroscopy (EDS).
trolled the aging temperature to within 1°C. All heat
treatments were conducted in a 99.9% N2 atmosphere RESULTS
to suppress oxidation of the sample surfaces and pre-
vent nitrogen loss from the DSS. Following heat treat- Figure 1 shows the microstructure evolution of
ments, the material was water-quenched. the aging process at 850°C. The solution-treated ma-
After the heat treatments the specimens were terial (Figure 1[a]) presented 40.9 ± 1.9% of ferrite and
abraded using silicon carbide (SiC) papers to a 59.1 ± 1.9% of austenite, distributed as alternated

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CORROSION SCIENCE SECTION

(a) (b)

(c) (d)

(e) (f)
FIGURE 1. Typical microstructures found in UNS S31803 DSS studied: (a) solution-treated, showing ferrite (dark) and
austenite, and aged at 850°C for (b) 10 min, (c) 30 min, (d) 1 h, and (e) 5 h, showing ferrite (dark), austenite (gray), and
sigma. In (f), sample aged for 100 h, with austenite (gray) and sigma. Optical microscopy. Etchant: modified Behara.

bands throughout the sheet thickness. The sigma samples aged 30 min at 850°C, with lamellar growth
phase was nucleated in the interfaces between fer- of sigma together to the formation of austenite, called
rite and austenite (Figure 1[b]) in the initial period of secondary austenite (γs), which is probably impover-
aging, and grew preferentially, consuming the ferrite ished in chromium and molybdenum compared to
phase (Figures 1[c] through [e]). Indications of the the original austenite present in the solution-treated
eutectoid decomposition of ferrite could be noted in sample. However, the eutectoid decomposition of fer-

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CORROSION SCIENCE SECTION

(a) (b)

(c) (d)
FIGURE 2. Typical microstructures found in 850°C aged UNS S31803 DSS after selective etching to sigma phase. Aging
times: (a) 10 min, (b) 30 min, (c) 1 h, and (d) 100 h. Optical microscopy. Electrolytic etching in KOH.

results, together with the magnetic measurements
of the ferrite content and the use of Equation (1), al-
lowed the determination of the volume fraction of the
phases as a function of aging time (Figure 3).
Figures 4 through 6 show the potentiodynamic
polarization curves for the material in all heat-
treatment conditions. The corrosion potential of all
samples remained constant at –200 mVSCE. The trans-
passive potential also remained unchanged at about
900 ± 25 mVSCE.
In the passive region, reproducible current den-
sity maxima occurred at specific potentials for each
sample, identified from E1 to E5 in Figure 5. For each
heat-treatment condition, the mean values of poten-
FIGURE 3. Phase content of UNS S31803 DSS as a function of
aging time at 850°C.
tials where the current density maxima occurred, and
the standard deviation associated with the results ob-
tained in the 20 tests, are listed in Table 2.
rite could also generate divorced microstructures. After potentiodynamic polarization, sample sur-
After total ferrite consumption, the sigma phase could faces were observed in a scanning electron micro-
be formed inside the original austenite (Figure 1[f]). scope. Figure 7(a) shows the solution-treated sample,
Figure 2 shows examples of aged samples after and EDS analysis confirmed that the ferrite phase
electrolytic etching in KOH; this procedure allowed was selectively corroded. In aged samples (Figures
the determination of the sigma phase content. Those 7[b] through [f]), the sigma phase was preferably cor-

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CORROSION SCIENCE SECTION

roded. Some polarization curves were interrupted at
the transpassive potential (900 mVSCE); in those cases,
the sample surfaces remained in the as-polished con-
dition, confirming that the selective corrosion of fer-
rite in the solution-treated material, and the selective
corrosion of the sigma phase in the aged samples, oc-
curred in the transpassive region.

DISCUSSION
In aging times up to 10 min, the sigma phase
was formed by consuming the original ferrite phase,
and the austenite content remained unchanged, as FIGURE 4. Potentiodynamic polarization curves in 0.5 M H2SO4 of
showed in Figure 3. This is an indication that direct UNS S31803 DSS solution-treated or aged 10 min at 850°C.
precipitation from ferrite is the primary mechanism
of the sigma phase formation at aging times up to
10 min, and this probably leads to an impoverishment
in chromium and molybdenum in the remaining fer-
rite, which could be called secondary ferrite (αs).
The progress of the aging process leads to the
continuous growth of sigma phase content (Figure
3), but there were modifications in the mechanism of
the sigma phase formation. If aging was conducted
for 30 min, a reduction in the volume fraction of fer-
rite and austenite was observed, indicating growth of
the sigma phase (rich in chromium and molybdenum)
through the consumption of the ferrite and austenite.
After 30 min of aging, the microstructure probably
had larger amounts of αs and γs. FIGURE 5. Potentiodynamic polarization curves in 0.5 M H2SO4 of
The presence of lamellar microstructures after UNS S31803 DSS aged 30 min or 1 h at 850°C. Current density
30 min of aging (Figure 1[c]) is an indication of sigma maxima are identified from E1 to E5.
phase formation from the eutectoid decomposition
of ferrite, with the formation of γs. This is clearly ob-
served after 1 h of aging, when the austenite content
was higher than after 30 min of aging (Figure 3). Af-
ter 5 h of aging the ferrite consumption was almost
complete, but the sigma content continued to grow
up until 100 h of aging. This, and the formation of the
sigma phase inside the austenite (Figure 1[f]), are oth-
er indications of sigma phase nucleation and growth
from austenite, and the formation of the γs. Table 3
summarizes the major mechanisms of sigma phase
formation and the probable related phases formed as
a function of aging time.
From the analysis of polarization curves shown in
Figures 4 through 6 it was concluded that the micro- FIGURE 6. Potentiodynamic polarization curves in 0.5 M H2SO4 of
UNS S31803 DSS aged 5 h or 100 h at 850°C.
structural complexity of the samples did not affect the

TABLE 2
Identification of Current Density Maxima Potentials for All Heat-Treatment Conditions
Identification Solution- Aging Time at 850°C Mean
(mVSCE) Treated 10 min 30 min 1h 5h 100 h Potential
E1 –171 ± 17 –137 ± 35 — –161 ± 13 –149 ± 37 –158 ± 12 –155
E2 — — –85 ± 37 — — — –85
E3 — — — –40 ± 18 — — –40
E4 113 ± 34 129 ± 45 — 86 ± 18 108 ± 16 117 ± 31 111
E5 — 542 ± 31 562 ± 26 603 ± 37 550 ± 31 — 564

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(a) (b)

(c) (d)

(e) (f)
FIGURE 7. Scanning electron micrographs (SEI) of sample surfaces after polarization tests: (a) solution-treated, showing
selective corrosion of ferrite. Specimens aged at 850°C for (b) 10 min, (c) 30 min, (d) 1 h, (e) 5 h, and (f) 100 h, showing
selective corrosion of sigma. α and γ identify ferrite and austenite, respectively.

transpassive potential, which was always about 1,074 mVH (832 mVSCE) in the 0.5-M H2SO4 solution
900 ± 25 mVSCE, or 1,142 ± 25 mV vs. hydrogen elec- (pH 2), confirming that the transpassive region begins
trode (H); this behavior had already been observed near 900 mVSCE:
in an earlier work.5 In fact, the reaction described in
Equation (2),7 associated with the beginning of the Cr 3+ + 4 H2O = HCrO 4– + 7H + + 3 e
(2)
transpassive region, has an equilibrium potential of E o = 1, 350 – 137.9pH (mVH )

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TABLE 3
Mechanisms of Sigma Phase Formation and Probable Related Phases Formed as a Function of Aging Time at 850°C
Aging Time at 850°C
1-h Eutectoid 100-h
10-min Direct Decomposition Nucleation
Major Mechanism Precipitation 30-min Growth of α and Growth 5-h Growth and Growth
of Sigma Formation from α from α and γ from α and γ from α and γ from γ
Related phases αs α s, γ s α s, γ s α s, γ s γs

Selective corrosion of chromium- and molybde- TABLE 4
num-rich phases was observed in the transpassive Relation Between Current Density
region: in the solution-treated sample, ferrite was Maxima Potentials and Microstructure
selectively corroded, and in all aged samples, the of Solution-Treated or 850°C Aged UNS S31803 DSS
sigma phase was selectively corroded. This is associ- Identification Mean Related
ated with an increase in the current density in the (mVSCE) Potential Microstructure
transpassive region. Another reason for the increase E1 –155 γ
in current density in the transpassive regions is O2 E2 –85 γs
evolution (Equation [3]), whose equilibrium potential E3 –40 γs
in a solution of pH 2 is 1,110 mVH (868 mVSCE): E4 111 γ
E5 564 αs
2 H 2O = O 2 + 4H + + 4 e
(3)
E o = 1, 228 – 59.1pH (mVH )
chromium and molybdenum of γs is greater, and this
The current density maximum identified in Table happens in the sample aged 30 min at 850°C. After
2 as E5 was seen in all aged samples that contained 1 h of aging, together with the rise in the γs content, a
secondary ferrite (αs), and was related to the presence chromium and molybdenum redistribution could oc-
of this phase in the microstructure. Between E5 cur in the earlier formed γs: the anodic reaction occurs
(564 mVSCE) and the corrosion potential (–200 mVSCE), with lower current density, and E1, E3, and E4 could
two current density maxima were observed in all sam- be observed separately. For aging times of 5 h or
ples, except for the one aged 30 min. These two cur- more, despite the higher sigma phase and γs contents,
rent density maxima, identified in Figure 5 and Table the chromium and molybdenum redistribution re-
2 as E1 and E4, are probably related to the austenite duced the probability of those anodic reactions, lead-
phase, the only one present in all samples. Note that ing to the absence of E3 current density maximum.
E1 (–155 mVSCE) occurs in the anodic region of 18%Cr- The relation between current density maxima and
9% Ni austenitic steel in 20% H2SO4.1 However, the the microstructure of 850°C aged UNS S31803 DSS is
association of E1 and E4 with austenite is valid only summarized in Table 4.
if the electrochemical behavior of the sample aged
30 min at 850°C can be explained. In those samples, CONCLUSIONS
these two current density maxima are not present,
and a new current density maximum occurs at ❖ Selective corrosion of chromium- and molybdenum-
–85 mVSCE (identified as E2 in Figure 5 and Table 2). rich phases occurred in the transpassive region of
This maximum could be explained as an increase in UNS S31803 DSS in 0.5 M H2SO4 aqueous solution:
the corrosion rates of the reactions that occur at E1, in the solution-treated sample, ferrite was selectively
E3, and E4, which are the current density maxima corroded, and in all aged samples, the sigma phase
found in the sample aged 1 h at 850°C (Figure 5). was selectively corroded.
Besides, the occurrence of the E3 maximum only in ❖ Five current density maxima in the passive region
the sample aged for 1 h suggests that the same elec- were found during potentiodynamic polarization in
trochemical reactions occur in this sample and in the 0.5 M H2SO4 of 850°C aged UNS S31803 DSS, and
sample aged for 30 min, with differences in corrosion those maxima were related to the microstructures
rates, which are lower in the 1-h-aged sample. The E3 formed.
current density maxima are related to anodic electro- ❖ Current density maximum occurred at 564 mVSCE
chemical reactions over γs, which are present in the and can be related to secondary ferrite, impoverished
microstructure after 30 min of aging, and probably in chromium and molybdenum, which was formed
become prominent in the microstructure after 1 h of during direct precipitation of the sigma phase from
aging, as a result of the eutectoid decomposition of the original ferrite.
ferrite in sigma and γs. Those anodic electrochemical ❖ Secondary austenite, impoverished in chromium
reactions are more intense if the impoverishment in and molybdenum and formed together with the sigma

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phase during eutectoid decomposition of the original 2. E. Symniotis-Barrdahl, “Selective Corrosion of Duplex Stainless
Steels,” Proc. Stainless Steels ’87 (York, U.K.: The Institute of
ferrite, is responsible for the current density maxima Metals, 1988), p. 176.
occurring at –85 mVSCE and –40 mVSCE.5 3. E. Symniotis, Corrosion 46, 1 (1990): p. 2.
❖ The austenite phase, present in all heat-treatment 4. J.W. Fourie, F.P.A. Robinson, “Mechanistic Aspects of Selective
Corrosion of a 22% Cr Duplex Stainless Steel in Acid Chloride
conditions, is responsible for the current density Mixtures,” Proc. Int. Conf. on Stainless Steels (Chiba, Japan:
maxima that occurred at –155 mVSCE and 111 mVSCE. ISIJ, 1991), p. 11.
5. J.H. Potgieter, Br. Corros. J. 27 (1992): p. 219.
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7. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous So-
1. E. Mor, A. Carlini, V. Scotto, E. Traverso, Metall. Ital. 64, 6 lutions, trans. J.A. Franklin (Houston, TX: NACE International,
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