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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


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

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 (iv) oxalic acid: 10 g oxalic acid in 100 mL distilled
by water quenching. In the case of the austenitic steel, water. This solution has been used for electro-
the creep samples, which have been tested at 550 and lytic etching of duplex stainless steel samples,
600uC, have been taken from rolled strips.18,19 following sigma phase precipitation heat treat-
Microstructural characterisation of the samples has ments, at 22.5 V for a few seconds.
been performed using several complementary techniques X-ray diffraction analysis has been performed on a
such as optical microscopy (OM), scanning electron Philips diffractometer model MPD 1880. The analysis
microscopy (SEM) coupled with energy dispersive have been carried out on polished samples using 1 mm
chemical microanalysis (EDX), X-ray diffraction diamond paste and Cu Ka1 (l51.5405 A) radiation, with
(XRD) and magnetic measurements (ferritoscope). an angular step of 0.04u and counting time of 2 s.
The samples for OM or SEM analysis have been hot Ferritoscope measurements are based on the magnetic
embedded in phenolic resin. Metallographic sample induction method. In the present work, this technique
preparation has been carried out using grinding (320, has been employed in order to assess the ferrite
400, 600, 1000 and 1500) papers and polishing with (ferromagnetic) phase fractions that are presented in
diamond paste (6, 3, 1 and 1/4 mm). Microstructures the austenitic, superferritic and duplex stainless steels. A
have been revealed by chemical and electrolytic etchings. Fisher, model MP3 ferritoscope has been used.
The chemical etchants and conditions used were: Detection limit of this equipment is 0.1% ferrite.
(i) acqua regia: 50 mL distilled water, 10 mL HCl
and 5 mL HNO3. This has been used for duplex Results and discussion
stainless steel samples in the initial condition
and after solution annealing, and for the In the following the results of the three steels will be
austenitic stainless steel samples in the initial presented in a specific order: austenitic, superferritic and
condition. Etching was performed by immer- duplex steels.
sion, at room temperature, immediately after
preparation of the solution. Etching time was Austenitic steel
y2 min The austenitic stainless steel (AISI 316L) microstructure
(ii) V2A-Beize: 100 mL distilled water, 100 mL in its initial condition is presented in Fig. 1. It may be
HCl, 100 mL HNO 3 and 3 mL Vogels observed that this microstructure presents austenitic
Sparbeize heated between 50 and 70uC for 10 recrystallised grains containing several annealing twins
50 s. This etchant has been used for the super- and elongated delta d ferrite islands.
ferritic stainless steel in the initial condition and Annealing twins are typical of a FCC crystal structure
after solution annealing and for the austenitic with low stacking fault energy. The delta ferrite comes
stainless steel in its initial condition and after from the solidification. The ferrite islands are in an
creep testing elongated form and are parallel to the rolling direction
(iii) KOH: 45 g KOH in 60 mL distilled water. This in all microstructures. Volume fraction of delta ferrite,
solution has been used for electrolytic etching of evaluated with the ferritoscope technique is 0.26
superferritic stainless steel, following sigma 0.03%. This small quantity, ,1%, did not allow the
phase precipitation heat treatments, at 22.5 V identification of the phase by XRD. Austenite lattice
for a few seconds parameter evaluated by XRD is 0.3604 nm.

Table 1 Chemical composition of three investigated stainless steels, wt-%

Steels C Mn Si P S Cr Ni Mo N Other

316L 0.02 1.80 0.32 0.020 0.006 17.34 12.50 2.40 0.08 Cu50.12
1.4575 0.01 0.22 0.35 0.014 0.003 28.12 3.91 2.44 0.011 Nb50.31
UNS S31803 0.025 1.72 0.47 0.021 0.01 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 gauge length of creep samples of 316L steel tested at
length of creep sample of 316L steel tested at 550uC 550uC for 85 000 h with load of 150 MPa (SEM): etchant
for 85 000 h with load of 150 MPa: etchant V2A V2A Beize
Beize, SEM
grain boundaries (triple points). In delta ferrite, the
Creep samples given in Table 2 have been tested at the sigma phase that is formed is richer in sigma forming
Karlsruhe Research Center (Germany). Detailed infor- elements, mainly Si, Mo and Cr and poorer in Fe, Ni
mation on these tests can be found in previous and Mn. Furthermore, sigma formation via a coopera-
publications.18,19 tive eutectoid type reaction is easier and faster.
In all tested samples, sigma phase has been detected. Moreover, the rate of Cr and Mo diffusion in ferrite is
Precipitation of sigma phase occurred preferentially in almost 100 times greater than that in the austenite.3 A
the delta ferrite islands (Fig. 2) that are present in the comparison of the present data with previously pub-
microstructure before creep testing, however occurring lished results8 about the precipitation behaviour of type
also for longer exposure times at grain boundaries, AISI 316L steel suggests that the effect of delta ferrite on
specially at triple points (Fig. 3). No sigma phase the sigma phase precipitation kinetics is stronger than
precipitation has been detected in the grain interior. the effects of minor compositional changes of the steel
Precipitation mechanisms in the different places are not casts.
identical. While ferrite decomposes through a eutectoid The direct precipitation of sigma phase in austenite is
reaction (ferriteRsigmazaustenite), at grain boundaries in general very sluggish and takes thousands of hours.8
and triple points the precipitation occurred in the The main reasons for that are:3
traditional manner, i.e. by non-cooperative and contin- (i) sigma phase has very low carbon and nitrogen
uous precipitation. solubility, hence carbide and nitride precipitation
The chemical compositions of the austenite, delta should happen before sigma precipitation
ferrite and of the sigma phase have been evaluated using (ii) diffusion of substitutional elements is very slow
energy dispersive spectroscopy (EDS). Results obtained in austenite
are presented in Table 3. Delta ferrite is richer in sigma (iii) sigma phase is incoherent with austenite and its
forming elements mainly Cr, Mo and Si, as compared nucleation is difficult.
with austenite, which facilitates sigma precipitation. The In the investigated samples, it has not been possible to
chemical composition of the sigma phase formed in the observe any significant differences between sigma phase
ferrite islands is different to the one that is formed at 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. Comparative study on sigma phase precipitation of three types of stainless steels

4 Schematic representation of sigma phase precipitation in AISI 316L austenitic stainless steel

samples. In no sample was there any evidence of then precipitation progresses in the grain interior. On the
porosity or grain boundary cracking, indicating that other hand, it is important to mention also that
the third creep stage has not been reached. precipitation in the grain interior is present since the
Figure 4 summarises the precipitation sequence of the beginning of precipitation; however it only progresses
sigma phase in various sites of the investigated stainless substantially after saturation of the boundaries. It is
steels in a schematic form. interesting to mention also that sigma phase particles that
are in the interior of the grains are more faceted than those
Superferritic steel precipitated at the boundaries, which are more rounded.
The microstructure of the superferritic steel after solution Precipitation temperature had a significant effect on the
annealing is shown in Fig. 5. From this figure it may be morphology and distribution of the phases, as illustrated
observed that the microstructure is monophasic with in Fig. 6. In this figure, the microstructures of the samples
equiaxed grains. Average ferritic grain size diameter is aged for y60 h at four different temperatures: 600, 700,
592 mm. Ferrite lattice parameter is 0.2874 nm. 800 and 900uC are compared. While at 600uC (Fig. 6a)
Precipitation has been studied in the 600900uC precipitation was practically initiating, at 800uC precipita-
temperature range. For the four temperatures that have tion was practically finished. It may be observed also that
been investigated, sigma phase precipitation started at the precipitation temperature increase is associated with
grain boundaries, especially at the triple points. the more rounded morphologies and precipitations at the
Therefore, there is a local saturation at these sites and 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
5 Optical micrograph of superferritic stainless steel (DIN
W. Nr. 1.4575) microstructure after solution annealing 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
for 30 min at 1050uC: etchant V2A-Beize

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 with previous ones,1517 illustrates that sigma phase
stainless steel type AISI 316L does not differ substan- formation occurs in ferrite, as shown in Fig. 9. Exposing
tially from the sigma phase composition found in the the steel for a few hours at 850uC consumes practically
superferritic stainless steel. This means that the main all the ferrite in the steel. The high susceptibility of the
implication of the high Cr level (and low Ni level) of the duplex stainless steels to the sigma phase formation is
superferritic steel is in the quantity of the sigma phase frequently attributed to the ferrite composition, richer in
formed and not in its composition. the sigma forming elements (Cr, Mo and Si) and poorer
The difference in the Mo content in the observed in the elements that are less soluble in sigma (C, N and
sigma phase when compared the AISI 316L steel with Ni) than in austenite.1517 On the other hand, ferrite of
the superferritic steel can also be attributed to the much the superferritic stainless steel investigated in the present
larger quantity of sigma phase that is formed in the work has a richer composition in elements that favour
superferritic steel. Lattice parameters evaluated by sigma formation than ferrite of the duplex stainless steel.
XRD for the sigma phase are a5 0.88021 nm and c5 However, the formation of the sigma phase in the duplex
0.4583 nm. stainless steel is faster and more complete than that in
Figure 7 summarises the precipitation sequence of the the superferritic stainless steel.20 Therefore, another
sigma phase in the investigated superferritic stainless explanation is necessary, apart from chemical composi-
steel in a schematic form. 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
Duplex stainless steel sigma formation is facilitated by the cooperative
Figure 8 illustrates the microstructure of the duplex eutectoid reaction of the type: ferriteRsigmaz
stainless steel DIN 1.4462 before sigma phase precipita- austenite. The occurrence of this eutectoid reaction
tion. Ferrite per cent volume fraction was y60%. seems to demand a minimum amount of austenite
Austenite and ferrite lattice parameters evaluated by (gammagenic) forming elements (mainly Ni, N and C) in
XRD are 0.3615 and 0.2871 nm respectively. The the steel composition. The new austenite formed in the
chemical composition of the two phases (austenite and
ferrite) is shown in Table 5, along with the chemical Table 5 Chemical composition of phases evaluated by
composition of the sigma phase. EDX in duplex stainless steel after slowly heating
(1 uC min21) of sample up to 850uC, wt-%
The results of this series illustrate that the duplex
stainless steel DIN W. Nr. 1.4462 (UNS S31803), is Phase Si Mo Cr Mn Fe Ni
highly susceptible to sigma phase precipitation. This
sigma phase is formed quickly in the 650950uC Sigma 0.6 4.5 25.2 1.6 63.8 4.3
temperature range, attaining its maximum precipitation 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
velocity at y850uC. The present work, in agreement

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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


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-
8 Optical micrograph of duplex stainless steel (DIN W. num content of the 904L and the 254SMO steels leads to
Nr. 1.4462 or UNS S31803) in initial condition, dark a greater tendency towards the appearance of the Laves
phase a and light phase c: etchant acqua regia (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

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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 3. A. F. Padilha and P. R. Rios: ISIJ Int., 2002, 42, (4), 325
may be stated that the propensity towards sigma phase 337.
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precipitation of the superaustenitic stainless steels22,23 411.
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The propensity towards sigma phase precipitation in the 24362444.
three investigated steels can be placed in the following 15. L. A. Norstrom, S. Petterson and S. Nordini: Z. Werkstofftech.,
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cal composition of the steel seems to have a major
Met. Sci., 1983, 17, 541547.
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kinetics and the chemical composition of the sigma zum kriechverhalten des strukturwerkstoffes 316-L(N) - DIN
phase. Sigma formation via a cooperative eutectoid type 1.4909 in niedrigen spannungsbereich bei 550u und 600uC
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Karlsruhe, Germany, 2002.
19. M. Rieth, A. Falkenstein, P. Graf, S. Reger, U. Jantsch,
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(Brazil) for the financial support of the present work. 20. A. F. Padilha, W. Reick and F. C. Pimenta, Jr: Z. Metallkd., 2001,
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