MA TE RI A L S CH A R A CT ER IZ A TI O N 60 ( 20 0 9 ) 7 9 2 7 9 5

Sigma phase morphologies in cast and aged super duplex

stainless steel
Marcelo Martins a,b,, Luiz Carlos Casteletti c,1
a

SULZER BRASIL S/A, Brazil

So Paulo Salesian University Center (UNISAL), Americana Division, Av. Eng. Joo Fernandes G. Molina, 905 Distrito Industrial 13.213-080
Jundia-SP Brazil
c
Department of Materials, Aeronautical and Automotive Engineering, So Carlos School of Engineering, University of So Paulo (USP), Av. Trabalhador
So Carlense, 400 13.566-590 So Carlos SP Brazil
b

AR TIC LE D ATA

ABSTR ACT

Article history:

Solution annealed and water quenched duplex and super duplex stainless steels are

Received 22 July 2008

thermodynamically metastable systems at room temperature.

Accepted 15 January 2009

These systems do not migrate spontaneously to a thermodynamically stable condition

because an energy barrier separates the metastable and stable states. However, any heat

Keywords:

input they receive, for example through isothermal treatment or through prolonged

Metals

exposure to a voltaic arc in the welding process, cause them to reach a condition of stable

Heat treatment

equilibrium which, for super duplex stainless steels, means precipitation of intermetallic

Electron microscopy

and carbide phases. These phases include the sigma phase, which is easily identified from

Optical microscopy

its morphology, and its influence on the material's impact strength.

The purpose of this work was to ascertain how 2-hour isothermal heat treatments at 920 C
and 980 C affect the microstructure of ASTM A890/A890M GR 6A super duplex stainless
steel. The sigma phase morphologies were found to be influenced by these two aging
temperatures, with the material showing a predominantly lacy microstructure when heat
treated at 920 C and block-shaped when heat treated at 980 C.
2009 Elsevier Inc. All rights reserved.

1.

Introduction

The sigma phase in 2205-type duplex stainless steels

solution annealed at 1080 C and water quenched, precipitates through the diffusion of chromium and molybdenum
from the delta ferrite to the ferrite/austenite interfaces [1].
The / interface with high interfacial energy is considered
the most favorable site for precipitation of this intermetallic
phase. Nucleation of the sigma phase may also occur at the
twin boundaries in the austenitic phase and in stacking
dislocations.

Small M23C6-type chromium carbide particles of about 0.1 m

can also be found associated with the sigma phase at /
interfaces. The interfacial precipitation of M23C6-type carbides is
associated with the partition of carbon and chromium in the
austenite and ferrite phases, respectively. M23C6 carbide particles
are sometimes found completely surrounded by rod-shaped
sigma phase particles.
Research has focused on the role of preformed particles of
M23C6 in the precipitation of the sigma phase in duplex stainless
steels. It is thought these M23C6 particles may be preferential sites
for nucleation of the sigma phase [1].

Corresponding author. So Paulo Salesian University Center (UNISAL), Americana Division, Av. Eng. Joo Fernandes G. Molina, 905 Distrito
Industrial 13.213-080 Jundia-SP Brazil. Tel.: +55 11 45892020; fax: +55 11 45892102.
E-mail addresses: marcelo.martins@sulzer.com (M. Martins), castelet@sc.usp.br (L.C. Casteletti).
1
Tel.: +55 16 33739580; fax: +55 16 33739590.
1044-5803/$ see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2009.01.005

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M A TE RI A L S CH A RACT ER IZ A TI O N 60 ( 20 0 9 ) 7 9 2 7 9 5

Table 1 Concentrations of the chemical elements in weight percent.

C(%)

Cr(%)

Mo(%)

Ni(%)

Si(%)

Mn(%)

Cu(%)

W(%)

N(%)

P(%)

0.016
Nb(%)
0.014

25.69
Ti(%)
0.005

3.80
Al(%)
0.016

7.18
V(%)
0.049

0.74
Zr(%)
0.065

0.52
Co(%)
0.055

0.716
Sn(%)
0.007

0.736
Pb(%)
0.002

0.22
S(%)
0.008

0.027
Fe(%)
Rest.

The delta ferrite of the duplex structure is usually a

metastable phase at temperatures below 1000 C. The austenitic
phase grows spontaneously toward regions of delta ferrite when
the material is cooled slowly after being solution annealed.
M23C6 particles initially precipitated at the / interface can
become trapped in the regions of newly grown austenite. The
preservation of M23C6 particles in the sigma phase can be
attributed to the low solubility of carbon in this phase.
A lamellar structure composed of M23C6 and particles can
develop isothermally in 2205-type duplex stainless steels [2].
However, no lamellar mixture of and M23C6 can be found in the
same material when it is cooled continually, as in the case of
solidification cooling, particularly if the carbon content is very
low [2]. The preferential growth of these particles in the direction
of the delta ferrite is due to the fact that the ferritic phase has a
larger quantity of chromium atoms and offers greater diffusivity
to this element than the austenitic phase. Hence, migration of the
interface toward the ferrite is associated with growth of M23C6
carbides and secondary austenite (2). Finally, after the lamellar
precipitation is completed, the sigma phase is formed at the front
of the lamellar precipitates as a result of the second eutectoid
decomposition.

2.

room temperatures [4]. Niobium is kept at a low concentration

because, at concentrations exceeding 0.10% in weight, this
element also embrittles super duplex stainless steels [5]. Fig. 1
depicts the microstructures of the material in the conditions
of as cast and solution annealed heat-treated at 1160 C
followed by quenching.
Fig. 1(a) shows a microstructure composed of a ferritic
matrix in the background, clearly outlined austenite and
sigma phase, which nucleated at the / interfaces and grew in
the direction of the ferrite. The ferrite provides stabilizing
elements such as chromium and molybdenum. Fig. 1(b) shows
only ferrite and austenite precipitated in the shape of an
island. The ferrite/austenite interfaces, as well as the ferrite
grain boundaries, are devoid of precipitated secondary phases.
The solution annealing heat-treatment at 1160 C followed by
water quenching altered the morphology of the austenite,
leaving it more refined and elongated.
The aging heat treatments at 920 C and 980 C produced
significant changes in the microstructure. The ferrite became

Experimental Procedure

The material super duplex stainless steel was prepared in a

foundry in a vacuum induction furnace with a 60 Hz network
frequency and maximum power of 400 kW. The first step
consisted of the foundry design of the test specimens measuring
25 mm in diameter by 300 mm in length using standard software,
followed by simulation of the solidification process. The material's chemical composition was identified by optical emission
spectroscopy, using a spectrometer with 47 different channels.
The solution annealing heat treatments recommended for
these materials, as well as aging treatments, were applied in an
electric furnace with a capacity of up to 1300 C. The temperature
employed for the solution heat treatment was 1160 C and the
aging temperatures were 920 C and 980 C applied for 2 h.
Microstructural analysis was conducted in a light optical
microscope equipped with a 35 mm film camera, and also with
a scanning electron microscope.

3.

Results and Discussion

The chemical composition of the material (ASTM A890/A890M

Grade 6A [3]), identified by optical emission spectrometry, is
described in Table 1.
Low titanium and aluminum contents are employed to
avoid the formation of nitrides of these elements, which cause
severe embrittlement of the material at both cryogenic and

Fig. 1 Optical micrographs of the 6A super duplex stainless

steel: (a) in the as cast condition, and (b) solution annealed at
1160 C and water quenched.

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MA TE RI A L S CH A R A CT ER IZ A TI O N 60 ( 20 0 9 ) 7 9 2 7 9 5

Fig. 2 Microstructures after isothermal heat treatments at

(a) 920 C, and (b) 980 C.

filled with precipitates and, in the specific case of the

treatment at 920 C, it was almost completely consumed
through the following eutectoid reaction:

Fig. 3 SEM micrographs showing: (a) Sample aged at 920 C

using secondary electrons, and (b) Sample aged at 980 C
using back-scattered electrons.

+ 2 :
Fig. 2 depicts optical micrographs of the ASTM A890 GR 6A
super duplex stainless steel aged for 2 h at 920 C and 980 C.
The aging heat treatment at 920 C caused precipitation of the
sigma phase with a predominantly lacy morphology, while the
morphology of the austenitic phase, which precipitates in the
solid state of these materials, showed a predominantly
dendritic formation, unlike the solution annealed condition.
On the other hand, the isothermal heat treatment at 980 C
also promoted precipitation of sigma phase in the form of
blocks, albeit in smaller quantity. Note the small quantities of
ferritic matrix and secondary austenite with a more refined
morphology. In this case, the dendritic characteristic of the
austenitic phase is less marked than in the sample treated at
920 C.
Scanning electron microscopy images, using secondary
and back-scattered electrons, depict in great detail the
morphologies of sigma phase precipitated at two different
temperatures (Fig. 3).
Back-scattered electrons provide an image that takes into
account the atomic weight of the chemical elements. Because
it contains high concentrations of chromium and molybdenum, the sigma phase appears in a lighter shade of gray than

ferrite and austenite [6]. The ferrite and austenite phases,

which appear in relief, are clearly visible because of mechanical polishing that has worn down the softer phase () more
than the harder one (). This is not visible in the sample
treated at 920 C, which shows only two phases: austenite and
sigma phase; the delta ferrite was completely consumed
through the eutectoid reaction that produced the intermetallic
phase () and the secondary austenite (2) [6].

4.

Conclusions

Solution annealing at 1160 C led to complete dissolution of

the sigma phase, which precipitated during solidification
cooling.
Aging at 920 C for 2 h caused precipitation of the sigma
phase through the eutectoid dissolution of the delta ferrite
in secondary austenite and sigma phase. The morphology of
the intermetallic phase was mostly lacy, with no sign of
precipitations in other geometric shapes.
The isothermal aging treatment at 980 C altered the
morphology of the lacy sigma phase into a block-shaped

M A TE RI A L S CH A RACT ER IZ A TI O N 60 ( 20 0 9 ) 7 9 2 7 9 5

morphology with nucleation at the / interfaces and

growth in the direction of the delta ferrite. At this specific
temperature, the delta ferrite was not totally consumed
through the eutectoid reaction.
The morphology of the austenite in the aged material,
especially the material aged at 920 C, was predominantly
dendritic, while the same phase was more refined in the
solution heat-treated material.

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