Comparative study on sigma phase

precipitation of three types of stainless steels:

austenitic, superferritic and duplex
D. M. E. Villanueva, F. C. P. Junior, R. L. Plaut and A. F. Padilha*
The present work studies, in a comparative manner, the sigma phase precipitation of three
stainless steels: austenitic type 316L (17Cr12Ni2.5Mo, wt-%), superferritic type DIN W. Nr.
1.4575 (Nb28Cr4Ni2Mo, wt-%) and duplex type DIN W. Nr. 1.4462 or UNS S31803 (22Cr
5.5Ni3Mo0.14N, wt-%). In austenitic stainless steel, the formation of sigma phase occurred both
at austenite grain boundaries and inside delta ferrite islands. In superferritic stainless steel, sigma
phase occurred both at grain boundaries and in the grain interior. In the ferrites, both in the
duplex and in the austenitic steel, sigma phase formation occurred by eutectoid reaction
ferriteRsigmazaustenite. The tendency towards precipitation of the sigma phase in the
three types of steel investigated can be placed in the following sequence: duplex.superferritic.
austenitic.
Keywords: Stainless steels, Phase transformation, Precipitation, Sigma phase

Introduction Precipitation of sigma phase in stainless steels can

Some dozen phases can occur in the microstructure of
different stainless steels during its processing or usage.
These phases can be classified into six main groups or
categories: martensites, intermetallic phases, carbides,
nitrides, borides and sulphides. Intermetallic phases,
mainly sigma (s), chi (x) and Laves phases, and the
carbides, mainly those of the types MC, M6C, M23C6
and M7C3, are two groups of phases that occur more
frequently in the stainless steels.13
Sigma phase is probably the most studied and
undesirable intermetallic phase of those mentioned
above. In 1907, even before the discovery of the stainless
steels, Treitschke and Tamman4 conjectured that in the
FeCr system, there was a compound in the 30
50 wt-%Cr range. In 1927, Bain and Griffiths5 found
in the FeCrNi system a hard and brittle phase that
they called B constituent where B stands for brittle. In
1936, Jett and Foote6 called it sigma phase and in 1951,
Bergmann and Shoemaker7 studied it in details and
obtained the crystallographic structure of the sigma
phase in the FeCr system.
Sigma phase appears in several binary, tertiary, and
quaternary systems such as FeCr, FeMo, FeV, Fe
Mn, FeCrNi, FeCrMo, FeCrMn and FeCrNi
Mo. The s phase occurs for an electron/atom ratio
between 5.6 and 7 and for an atomic radius ratio
between 0.96 and 1.16 in binary systems.3
Departamento de Engenharia Metalurgica e de Materiais da Escola
Politecnica da Universidade de Sao Paulo, 05508 900, Sao Paulo SP,
Brazil
*Corresponding author, email padilha@usp.br
occur in the austenitic, ferritic and ferriticaustenitic
with duplex structure types. The precipitation of sigma
phase not only causes losses in ductility and toughness
of the steel, but also reduces its corrosion resistance by
removing chromium and molybdenum from the auste-
nitic matrix.
Numerous studies on sigma phase precipitation
available in the literature compare steels of the same
class or type, such as the austenitic,811 ferritic1214 and
duplex,1517 in a general manner, and the studies
comparing the sigma phase precipitation in different
types of stainless steels are practically non-existent. The
main objective of the present work is to study the sigma
phase precipitation in three different types or classes of
stainless steels: one austenitic type Fe17Cr12Ni
2.5Mo (wt-%) (AISI 316L), one superferritic type Fe
28Cr4Ni2MoNb (DIN W. Nr. 1.4575) and one
duplex type Fe22Cr5.5Ni3Mo0.14N (DIN W. Nr.
1.4462 or UNS S31803) in a comparative form. A
specific austenitic cast containing delta ferrite at its
initial stage was selected, in such a way that the three
selected steels would present ferrite after solution
annealing, before precipitation.
Materials and methods
The chemical compositions of the three investigated
steels are given in Table 1. Casts have been selected that
contained low carbon levels, aiming at a diminished
carbide precipitation during subsequent aging heat
treatments. Test samples have been taken from rolled
strips.
Before aging heat treatments, the steels have been
solution annealed at 1050uC (superferritic and duplex

2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 7 December 2005; accepted 4 February 2006
1098 DOI 10.1179/174328406X109230 Materials Science and Technology 2006 VOL 22 NO 9
 Villanueva et al.
a V2A etchant, OM; b acqua regia etching, SEM
1 Austenitic stainless steel 316L microstructure in initial condition after solution annealing and before precipitation
steel) or at 1100uC (austenitic steel) for 30 min, followed
by water quenching. In the case of the austenitic steel,
the creep samples, which have been tested at 550 and
600uC, have been taken from rolled strips.18,19
Microstructural characterisation of the samples has
been performed using several complementary techniques
such as optical microscopy (OM), scanning electron
microscopy (SEM) coupled with energy dispersive
chemical microanalysis (EDX), X-ray diffraction
(XRD) and magnetic measurements (ferritoscope).
The samples for OM or SEM analysis have been hot
embedded in phenolic resin. Metallographic sample
preparation has been carried out using grinding (320,
400, 600, 1000 and 1500) papers and polishing with
diamond paste (6, 3, 1 and 1/4 mm). Microstructures
have been revealed by chemical and electrolytic etchings.
The chemical etchants and conditions used were:
(i) acqua regia: 50 mL distilled water, 10 mL HCl
and 5 mL HNO3. This has been used for duplex
stainless steel samples in the initial condition
and after solution annealing, and for the
austenitic stainless steel samples in the initial
condition. Etching was performed by immer-
sion, at room temperature, immediately after
preparation of the solution. Etching time was
y2 min
(ii) V2A-Beize: 100 mL distilled water, 100 mL
HCl, 100 mL HNO 3 and 3 mL Vogels
Sparbeize heated between 50 and 70uC for 10
50 s. This etchant has been used for the super-
ferritic stainless steel in the initial condition and
after solution annealing and for the austenitic
stainless steel in its initial condition and after
creep testing
(iii) KOH: 45 g KOH in 60 mL distilled water. This
solution has been used for electrolytic etching of
superferritic stainless steel, following sigma
phase precipitation heat treatments, at 22.5 V
for a few seconds
Table 1 Chemical composition of three investigated stainless steels, wt-%
Steels C Mn Si P S
316L 0.02 1.80 0.32 0.020 0.006
1.4575 0.01 0.22 0.35 0.014 0.003
UNS S31803 0.025 1.72 0.47 0.021 0.01
Comparative study on sigma phase precipitation of three types of stainless steels
(iv) oxalic acid: 10 g oxalic acid in 100 mL distilled
water. This solution has been used for electro-
lytic etching of duplex stainless steel samples,
following sigma phase precipitation heat treat-
ments, at 22.5 V for a few seconds.
X-ray diffraction analysis has been performed on a
Philips diffractometer model MPD 1880. The analysis
have been carried out on polished samples using 1 mm
diamond paste and Cu Ka1 (l51.5405 A) radiation, with
an angular step of 0.04u and counting time of 2 s.
Ferritoscope measurements are based on the magnetic
induction method. In the present work, this technique
has been employed in order to assess the ferrite
(ferromagnetic) phase fractions that are presented in
the austenitic, superferritic and duplex stainless steels. A
Fisher, model MP3 ferritoscope has been used.
Detection limit of this equipment is 0.1% ferrite.
Results and discussion
In the following the results of the three steels will be
presented in a specific order: austenitic, superferritic and
duplex steels.
Austenitic steel
The austenitic stainless steel (AISI 316L) microstructure
in its initial condition is presented in Fig. 1. It may be
observed that this microstructure presents austenitic
recrystallised grains containing several annealing twins
and elongated delta d ferrite islands.
Annealing twins are typical of a FCC crystal structure
with low stacking fault energy. The delta ferrite comes
from the solidification. The ferrite islands are in an
elongated form and are parallel to the rolling direction
in all microstructures. Volume fraction of delta ferrite,
evaluated with the ferritoscope technique is 0.26
0.03%. This small quantity, ,1%, did not allow the
identification of the phase by XRD. Austenite lattice
parameter evaluated by XRD is 0.3604 nm.
Cr Ni Mo N Other
17.34 12.50 2.40 0.08 Cu50.12
28.12 3.91 2.44 0.011 Nb50.31
22.04 5.49 2.91 0.14 Cu50.09
Materials Science and Technology 2006 VOL 22 NO 9 1099
Villanueva et al. Comparative study on sigma phase precipitation of three types of stainless steels

3 Sigma phase precipitation at grain boundaries on

2 Sigma phase precipitation inside ferrite on gauge
length of creep sample of 316L steel tested at 550uC
for 85 000 h with load of 150 MPa: etchant V2A
Beize, SEM
Creep samples given in Table 2 have been tested at the
Karlsruhe Research Center (Germany). Detailed infor-
mation on these tests can be found in previous
publications.18,19
In all tested samples, sigma phase has been detected.
Precipitation of sigma phase occurred preferentially in
the delta ferrite islands (Fig. 2) that are present in the
microstructure before creep testing, however occurring
also for longer exposure times at grain boundaries,
specially at triple points (Fig. 3). No sigma phase
precipitation has been detected in the grain interior.
Precipitation mechanisms in the different places are not
identical. While ferrite decomposes through a eutectoid
reaction (ferriteRsigmazaustenite), at grain boundaries
and triple points the precipitation occurred in the
traditional manner, i.e. by non-cooperative and contin-
uous precipitation.
The chemical compositions of the austenite, delta
ferrite and of the sigma phase have been evaluated using
energy dispersive spectroscopy (EDS). Results obtained
are presented in Table 3. Delta ferrite is richer in sigma
forming elements mainly Cr, Mo and Si, as compared
with austenite, which facilitates sigma precipitation. The
chemical composition of the sigma phase formed in the
ferrite islands is different to the one that is formed at
gauge length of creep samples of 316L steel tested at
550uC for 85 000 h with load of 150 MPa (SEM): etchant
V2A Beize
grain boundaries (triple points). In delta ferrite, the
sigma phase that is formed is richer in sigma forming
elements, mainly Si, Mo and Cr and poorer in Fe, Ni
and Mn. Furthermore, sigma formation via a coopera-
tive eutectoid type reaction is easier and faster.
Moreover, the rate of Cr and Mo diffusion in ferrite is
almost 100 times greater than that in the austenite.3 A
comparison of the present data with previously pub-
lished results8 about the precipitation behaviour of type
AISI 316L steel suggests that the effect of delta ferrite on
the sigma phase precipitation kinetics is stronger than
the effects of minor compositional changes of the steel
casts.
The direct precipitation of sigma phase in austenite is
in general very sluggish and takes thousands of hours.8
The main reasons for that are:3
(i) sigma phase has very low carbon and nitrogen
solubility, hence carbide and nitride precipitation
should happen before sigma precipitation
(ii) diffusion of substitutional elements is very slow
in austenite
(iii) sigma phase is incoherent with austenite and its
nucleation is difficult.
In the investigated samples, it has not been possible to
observe any significant differences between sigma phase
precipitations in the head or gauge length of the test

Table 2 Creep test samples investigated in present work

Temperature, uC Stress, MPa Time, h Initial elongation, %

550 250 6100 7.5

550 210 60 000 4.8
550 135 70 000 0.34
550 180 85 000 2.85
600 200 5481(rupture) 3.7
600 170 7500 3.03
600 120 41 015 0.32
600 70 85 000 0.055

Table 3 Chemical composition of various phases evaluated by EDX, wt-%

Phase Si Mo Cr Mn Fe Ni

Austenite c 0.540.02 2.60.1 17.40.2 2.00.1 64.90.3 12.40.1

Ferrite d 0.510.05 4.70.1 23.90.2 1.510.04 63.20.2 6.110.02
Sigma in c 0.470.04 4.30.3 251 1.510.03 582 92
Sigma in d 0.420.02 6.00.3 39.00.1 1.30.1 472 6.00.6

1100 Materials Science and Technology 2006 VOL 22 NO 9

 Villanueva et al.
4 Schematic representation of sigma phase precipitation in AISI 316L austenitic stainless steel
samples. In no sample was there any evidence of
porosity or grain boundary cracking, indicating that
the third creep stage has not been reached.
Figure 4 summarises the precipitation sequence of the
sigma phase in various sites of the investigated stainless
steels in a schematic form.
Superferritic steel
The microstructure of the superferritic steel after solution
annealing is shown in Fig. 5. From this figure it may be
observed that the microstructure is monophasic with
equiaxed grains. Average ferritic grain size diameter is
592 mm. Ferrite lattice parameter is 0.2874 nm.
Precipitation has been studied in the 600900uC
temperature range. For the four temperatures that have
been investigated, sigma phase precipitation started at
grain boundaries, especially at the triple points.
Therefore, there is a local saturation at these sites and
5 Optical micrograph of superferritic stainless steel (DIN
W. Nr. 1.4575) microstructure after solution annealing
for 30 min at 1050uC: etchant V2A-Beize
Comparative study on sigma phase precipitation of three types of stainless steels
then precipitation progresses in the grain interior. On the
other hand, it is important to mention also that
precipitation in the grain interior is present since the
beginning of precipitation; however it only progresses
substantially after saturation of the boundaries. It is
interesting to mention also that sigma phase particles that
are in the interior of the grains are more faceted than those
precipitated at the boundaries, which are more rounded.
Precipitation temperature had a significant effect on the
morphology and distribution of the phases, as illustrated
in Fig. 6. In this figure, the microstructures of the samples
aged for y60 h at four different temperatures: 600, 700,
800 and 900uC are compared. While at 600uC (Fig. 6a)
precipitation was practically initiating, at 800uC precipita-
tion was practically finished. It may be observed also that
the precipitation temperature increase is associated with
the more rounded morphologies and precipitations at the
boundaries (Fig. 6d), while for lower temperatures
(Fig. 6b) more faceted with a needle like morphology,
especially at grain interior, are frequent.
Table 4 presents the composition of the matrix and
sigma phase evaluated by EDX in the aged sample for
94 h at 850uC.
Analysing the values given in Table 4, it may be
observed that the sigma phase in richer in Cr, Mo and Si
and poorer in Ni and Fe when compared with the
matrix. On the other hand, it is interesting to observe
that the sigma phase composition does not vary
significantly from the matrix composition. Moreover,
Table 4 Chemical composition of sigma phase and of
ferritic matrix evaluated by EDX in sample aged
for 94 h at 850uC, wt-%
Phase Fe Cr Ni Mo Si
Sigma 56.70.4 33.60.3 3.60.2 5.10.2 0.60.1
Matrix 64.00.5 29.90.3 3.80.2 2.70.2 0.30.1
Materials Science and Technology 2006 VOL 22 NO 9 1101
Villanueva et al. Comparative study on sigma phase precipitation of three types of stainless steels
a 600uC, 60 h; b 700uC, 58 h; c 800uC, 64 h; d 900uC, 57 h
6 Optical micrographs of superferritic stainless steel (DIN W. Nr. 1.4575) microstructures after solution annealing at dif-
ferent temperatures for different times: etchant V2A-Beize
the sigma phase chemical composition of the austenitic
stainless steel type AISI 316L does not differ substan-
tially from the sigma phase composition found in the
superferritic stainless steel. This means that the main
implication of the high Cr level (and low Ni level) of the
superferritic steel is in the quantity of the sigma phase
formed and not in its composition.
The difference in the Mo content in the observed
sigma phase when compared the AISI 316L steel with
the superferritic steel can also be attributed to the much
larger quantity of sigma phase that is formed in the
superferritic steel. Lattice parameters evaluated by
XRD for the sigma phase are a5 0.88021 nm and c5
0.4583 nm.
Figure 7 summarises the precipitation sequence of the
sigma phase in the investigated superferritic stainless
steel in a schematic form.
Duplex stainless steel
Figure 8 illustrates the microstructure of the duplex
stainless steel DIN 1.4462 before sigma phase precipita-
tion. Ferrite per cent volume fraction was y60%.
Austenite and ferrite lattice parameters evaluated by
XRD are 0.3615 and 0.2871 nm respectively. The
chemical composition of the two phases (austenite and
ferrite) is shown in Table 5, along with the chemical
composition of the sigma phase.
The results of this series illustrate that the duplex
stainless steel DIN W. Nr. 1.4462 (UNS S31803), is
highly susceptible to sigma phase precipitation. This
sigma phase is formed quickly in the 650950uC Sigma
temperature range, attaining its maximum precipitation
velocity at y850uC. The present work, in agreement
1102 Materials Science and Technology 2006 VOL 22 NO 9
with previous ones,1517 illustrates that sigma phase
formation occurs in ferrite, as shown in Fig. 9. Exposing
the steel for a few hours at 850uC consumes practically
all the ferrite in the steel. The high susceptibility of the
duplex stainless steels to the sigma phase formation is
frequently attributed to the ferrite composition, richer in
the sigma forming elements (Cr, Mo and Si) and poorer
in the elements that are less soluble in sigma (C, N and
Ni) than in austenite.1517 On the other hand, ferrite of
the superferritic stainless steel investigated in the present
work has a richer composition in elements that favour
sigma formation than ferrite of the duplex stainless steel.
However, the formation of the sigma phase in the duplex
stainless steel is faster and more complete than that in
the superferritic stainless steel.20 Therefore, another
explanation is necessary, apart from chemical composi-
tion, in order to explain the greater susceptibility to the
sigma phase formation in the duplex stainless steel. A
probable explanation is that in the duplex stainless steel
sigma formation is facilitated by the cooperative
eutectoid reaction of the type: ferriteRsigmaz
austenite. The occurrence of this eutectoid reaction
seems to demand a minimum amount of austenite
(gammagenic) forming elements (mainly Ni, N and C) in
the steel composition. The new austenite formed in the
Table 5 Chemical composition of phases evaluated by
EDX in duplex stainless steel after slowly heating
(1 uC min21) of sample up to 850uC, wt-%
Phase Si Mo Cr Mn Fe Ni
0.6 4.5 25.2 1.6 63.8 4.3
Ferrite 0.8 6.2 29.7 1.8 58.8 2.7
Austenite 0.5 2.5 20.3 2.1 67.5 7.2
 Villanueva et al. Comparative study on sigma phase precipitation of three types of stainless steels

7 Schematic representation of sigma phase precipitation in superferritic stainless steel

eutectoid reaction is poorer in Cr, Mo and N than the

8 Optical micrograph of duplex stainless steel (DIN W.
Nr. 1.4462 or UNS S31803) in initial condition, dark
phase a and light phase c: etchant acqua regia
original austenite and this causes considerable drop in
the corrosion resistance of the steel.21
Figure 10 presents in a schematic form the precipita-
tion sequence of the sigma phase in the duplex stainless
steel.
Finally, it is interesting to compare the sigma phase
precipitation behaviour of the three steels studied in the
present work with the new generation of superaustenitic
stainless steels, such as the 904L and the 254SMO. The
term superaustenitic relates to austenitic stainless steels
containing high amounts of chromium, nickel, molyb-
denum, copper and frequently also nitrogen, resulting in
an iron content close to or even less than 50 wt-% and
presenting high values of pitting resistance equivalent
(PRE). It must be pointed out that the high molybde-
num content of the 904L and the 254SMO steels leads to
a greater tendency towards the appearance of the Laves
(Fe2Mo type) and chi (x) intermetallic phases. Relative
to the sigma phase precipitation, the higher content of
molybdenum displaces the temperature range of sigma

a after etching with V2A, SEM with secondary electrons; b after etching with oxalic acid, SEM with back scattered electrons
9 Duplex stainless steel (DIN W. Nr. 1.4462 or UNS S31803) microstructure slowly heated at 1 uC min21 within sigma
phase field up to 850uC

Materials Science and Technology 2006 VOL 22 NO 9 1103

Villanueva et al. Comparative study on sigma phase precipitation of three types of stainless steels
10 Schematic representation of sigma phase precipitation in duplex stainless steel
phase precipitation to higher temperatures.3 In short, it
may be stated that the propensity towards sigma phase
precipitation of the superaustenitic stainless steels22,23
can be placed in the following sequence: duplex.
superferritic.superaustenitic.austenitic.
Conclusions
In the austenitic stainless steel, sigma phase formation
occurred both at grain boundaries and in the delta
ferrite islands. In the superferritic stainless steel, sigma
phase precipitation occurred both at boundaries and in
the grain interior. In the ferrites, being in the duplex or
in the austenitic steels, sigma phase formation occurred
by eutectoid reaction ferriteRsigmaznew austenite.
The propensity towards sigma phase precipitation in the
three investigated steels can be placed in the following
sequence: duplex.superferritic.austenitic. The chemi-
cal composition of the steel seems to have a major
influence on the volume fraction of the sigma phase that
is formed, when compared with the precipitation
kinetics and the chemical composition of the sigma
phase. Sigma formation via a cooperative eutectoid type
reaction is easier and faster.
Acknowledgements
The authors are grateful to CAPES, CNPq and FAPESP
(Brazil) for the financial support of the present work.
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