j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782

journal homepage: www.elsevier.com/locate/jmatprotec

Effect of the annealing temperature on the mechanical

properties, formability and corrosion resistance of
hot-rolled duplex stainless steel

G. Fargas, M. Anglada, A. Mateo ∗

Dept. Ciència dels Materials i Enginyeria Metal.lúrgica, Universitat Politècnica de Catalunya, 08028 Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The industrial sequence for obtaining duplex stainless steels by rolling includes two anneal-
Received 14 September 2007 ing steps: one intermediate after the hot rolling, and the final one after the cold rolling. The
Received in revised form aim of this paper is to study the consequences of deviations from the current industrial inter-
10 April 2008 mediate annealing temperature. Optical microscopy (OM), scanning electron microscopy
Accepted 11 April 2008 (SEM) and transmission electron microscopy (TEM), together with X-ray diffraction (XRD),
were used to investigate the microstructural changes of the steel. The only transformation
observed was the precipitation of sigma phase for all the considered annealing conditions. A
Keywords: decrease in the heat treating temperature augmented the percentage of sigma phase, which
Duplex stainless steel generated an increase in tensile strength and hardness, concurrently with drastic reductions
Rolling on ductility and impact resistance. In addition, compression testing and cold rolling at labo-
Annealing ratory scale were done in order to compare the formability of the steel subjected to the new
Sigma phase annealing conditions with the current industrial rolled products. On the other hand, the
pitting potential of the thermo-mechanically treated samples was determined by potencio-
dynamic polarization tests. The electrochemical results showed that sigma phase markedly
decreases the pitting potential. SEM observations revealed that pits appear mainly in regions
adjacent to sigma phase, where secondary austenite forms.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction whereas more recently Johansson (2000) made a complete

Duplex stainless steels (DSS) are defined as a family of steels
having a two-phase microstructure with roughly the same vol-
ume fractions of ferrite (˛) and austenite (). Solomon and
Devine (1983) reported, in a comprehensive review article, the
attractive combination of mechanical properties and corro-
sion resistance of these steels. Thanks to these characteristics,
DSS are widely used in different sectors of the industry (typi-
cal areas are petrochemical, desulphurization, pulp and paper,
chemical tankers and architecture). Olsson and Liljas (1994)
presented a report about six decades of duplex applications,
revision of past, present and future of DSS. Also Charles (1991)
made an interesting correlation between microstructure and
properties but concentrated on the third generation of duplex,
often designed as superduplex. On the other hand, Gironès et
al. (2007) studied the fatigue behaviour of duplex when chlo-
rides are present and proved the good performance of these
steels under this aggressive environment. This fact made DSS
very adequate materials for desalination plants, as explained
by Jacques et al. (2007).
However, DSS present some technical limitations when
considering thermal cycles acceptable for the material dur-

∗
Corresponding author at: ETSEIB-UPC, Avda Diagonal 647, 08028 Barcelona, Spain. Tel.: +34 93 4011089; fax: +34 93 4016706.
E-mail address: antonio.manuel.mateo@upc.edu (A. Mateo).
0924-0136/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2008.04.026
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782
ing fabrication or in service. An inappropriate heating cycle
may cause the precipitation of secondary phases and, as a
consequence, a decrease of toughness and reduction of cor-
rosion resistance, becoming a serious problem both for the
service reliability of products made of these steels, as demon-
strated by Chen and Yang (2001). Karlsson (1999) reported that
the same effect can appear after welding operations, and even
as a consequence of exposures at intermediate temperatures
as demonstrated by Otárola et al. (2005), who tried to find
an appropriate range of temperatures for post-welding heat
treatments without inducing embrittlement. Moreover, if the
inadequate time-temperature excursion takes place during
the forming operations, it can induce a loss of formability
which will hinder to continue with the regular production
process. Huchtemann and Wulfmeier (2000) deal with this
question in their paper about production of long products
made of duplex.
In addition to ferrite and austenite, a variety of secondary
phases may form in the temperature range from 300 to 1000 ◦ C.
According to Jolly and Hochmann (1973) this is basically due
to the instability of ferrite. An extensive dissertation including
almost all the possible secondary phases was made by Nilsson
(1992). The severity of the precipitation depends on temper-
ature, time and chemical composition of the DSS. Carbides,
nitrides and secondary austenite often coexist with differ-
ent intermetallic phases, such as sigma, chi, R, G, pi and tau.
The literature about these phases is abundant, but several
remarkable articles can be cited: Beckitt (1969) dealing with
the mechanisms of sigma phase precipitation; Kasper (1954)
concerning chi phase structure; Redjaimia et al. (2002) made
a complete study of the Frank-Kasper R-phase crystallogra-
phy; G-phase composition and crystallography was reported
by Mateo et al. (1997), Evans and Jack (1957) detected the less
common pi phase; the article by Redjaimia et al. (1991) whose
the first one reporting the precipitation of a new intermetallic
phase that they called tau. Among all these phases, sigma is
the most important because it has fast formation kinetics in a
wide range of temperatures and numerous studies proved that
it induces a severe embrittlement, some significant examples
of them are: Nilsson et al. (2000), who studied the embrit-
tlement by sigma phase of a superduplex steel with a high
chromium and nitrogen content; and the recent publication
by Storz et al. (2007) whose relevant point is the fact of relat-
ing the morphology of sigma particles with their influence on
the mechanical properties.
Sigma phase can appear during slow cooling from high
temperatures, when passing through its temperature range
of stability, which extends from 600 to 1000 ◦ C. Moreover,
Karlsson (1999) proved that slow heating through this range
may lead to the formation of sigma phase too and annealing
Fig. 1 – Orientations of the Charpy V specimens.
1771
Table 1 – Chemical composition of the studied duplex
stainless steel E.N. 1.4462 (wt%)
C Mn P S Si Cr Ni Mo N
0.023 1.55 0.026 0.006 0.45 22.62 5.92 3.02 0.158
temperatures may not always cause the re-dissolution of this
intermetallic phase. Consequently, some manufacturing pro-
cesses of DSS are limited, i.e. the production of thick pipes
and bars with large diameter, because of the sigma phase pre-
cipitation in the inner part of those products, where cooling
and heating rates are relatively slow. In this sense, Cozar et al.
(1993) evaluated the problems when producing forges pieces
of heavy section. A recent study by Ferro et al. (2007) has found
that a minimum cooling rate of 0.3 ◦ C/s must be reach to avoid
sigma precipitation in the standard 2205 DSS.
According to the review by Johansson (2000), DSS are
mainly used in form of flat products, i.e. plates, strips and
sheets. The processing route to manufacture DSS sheets
generally consists in two alternative steps of rolling and
annealing, as presented in Fig. 1. After continuous casting,
the slab is hot rolled in several passes in order to attain large
thickness reduction. Then, the material is annealed to recover
the ductility for the subsequent cold rolling up to the required
final thickness. The process ends with a final annealing which
provides the steel product with the appropriate characteris-
tics for future applications. The parameters, i.e. temperatures
and times, of both annealing treatments are selected to avoid
the formation of precipitates. Furthermore, in the case of the
intermediate annealing, temperature uses to be higher and
soaking time longer in order to dissolve the precipitates that
could have appeared during the last hot rolling passes.
The aim of the work presented here was to evaluate the
effect that a change in the temperature of the intermedi-
ate annealing could produce on the mechanical properties
and corrosion resistance of the hot-rolled DSS. This change
tries to simulate a possible fault in the industrial furnace
calibration or operation. As previously commented, this
“faulty-annealed” DSS may have experienced a loss of forma-
bility which would difficult the subsequent cold rolling stage,
therefore compression tests and cold rolling at laboratory
scale were performed for each annealing temperature to sur-
vey their influence. This type of research approach is relevant
for improving reliability and performance of the materials and
processes studied.
2. Experimental procedure
The studied material is an EN 1.4462 (often designed as 2205) duplex
stainless steel, whose chemical composition is given in the Table 1.
It was supplied as plates with a thickness of 6 mm, produced by ALZ
(Belgium) through the forging of a cast slab and subsequent hot rolling.
When the hot rolling began the temperature of the slab was 1250 ◦ C
and it decreased up to 1100 ◦ C at the exit of the last rolling mill.
The conditions established by the steelmaking company for the
annealing that follows the hot rolling were in the temperature range of
1000–1050 ◦ C, with soaking times around 15–20 min and a final quench
in water. The material supplied after this industrial processing will
be hereinafter designated as IA (industrial annealing), whereas the as
hot-rolled DSS, prior to any annealing treatment, will be called HR (hot
rolled).
1772 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782
Fig. 2 – Microstructure of hot rolled DSS: (a) rolling plane; (b) longitudinal section; (c) transversal section.
On the other hand, six experimental annealing treatments were car-
ried out in the laboratory furnaces. A range of temperatures from 850
to 975 ◦ C was selected. These temperatures are lower than the indus-
trial conditions in order to enter in the domain where the precipitation
of secondary phases becomes feasible. Time was kept in 20 min in all
cases.
The microstructural characterization of the DSS after the differ-
ent annealing treatments was done by means of optical microscopy
(OM), scanning electron microscopy (SEM) and transmission electron
microscopy (TEM), together with X-ray diffraction (XRD). For the OM
study, mechanically polished samples were etched by immersion in a
solution of 1 g K2 S2 O5 , 15 mL HCl and 85 mL H2 O. This etching proce-
dure makes sigma appear white, ferrite reddish-brown and austenite
yellow-brown. Quantitative metallographic measurement of sigma
phase content was carried out using image analysis software. Precipi-
tates formed after the experimental heat treatments were identified by
XRD. The selected-area diffraction patterns on TEM obtained from the
precipitates were analyzed to elucidate their crystallographic structure.
The evolution of the mechanical properties related with the
microstructural changes after the annealing treatments were evalu-
ated by tensile, impact and hardness tests. Vickers hardness (HV) was
measured in the plane of the sheet for each heat-treated sample with
a load of 10 kg. Three orientations with respect to the rolling direction
were considered for tensile tests: longitudinal (L), transversal (T) and
diagonal (D). Specimens were machined following the standard ASTM
E 8M and tested at a cross-head speed of 2 mm/min. Impact testing was
carried out using Charpy V specimens, taking the total thickness of the
plate and with a notch of 2 mm in depth. L–T, T–L and D orientations
(Fig. 1), as defined by the standard ASTM E 399, were machined. All the
mechanical evaluation was done at room temperature.
Corrosion resistance is another property that can be affected by
the changes on the annealing temperature. In order to confirm the
alterations on corrosion behaviour of the “faulty-annealed” DSS, poten-
ciodynamic polarization studies were carried out in a three electrodes
cell with platinum counter-electrode and Ag/AgCl reference electrode.
Pitting potential (Ep ) was evaluated by anodic polarization testing in a
3.5% NaCl solution at room temperature. Sample surfaces were previ-
ously polished with alumina up to 1 ␮m. Potentials were scanned from
−100 to +1200 mV at a scan rate of 1 mV/min. Each test was repeated
at least three times in order to assure its repeatability.
Cold rolling is the subsequent step after the intermediate anneal-
ing in the industrial process of rolled DSS. Therefore, microstructural
modifications produced by altering the annealing conditions will affect
the cold rolling. Compression tests and cold rolling at laboratory scale
were performed for each annealing treatment condition to survey their
effect. Compression testing was done at room temperature with cylin-
drical specimens of 4 mm in diameter, according to standard ASTM E
9. The initial strain rate was 1.38 × 10−3 s−1 and tests were continued
until thickness reductions of 11, 33 and 67%, values that correspond
to the last step of industrial cold rolling practice. Specimens subjected
to compression were afterwards analyzed by OM, SEM and TEM. Also,
considering the results of compression tests, several heat-treated DSS
plates were selected for cold rolling using the laboratory scale equip-
ment of Ghent University (Belgium). This cold rolling was continued up
to achieve sheets of 2 mm in thickness.
3. Results and discussion
3.1. Microstructural characterization
The microstructure of the hot rolled DSS studied is shown
in Fig. 2. It can be seen that during rolling both constitutive
phases align in the rolling direction and the microstructure
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782 1773

Fig. 3 – X-ray diffraction pattern of the hot rolled DSS.

becomes morphologically anisotropic. A characteristic lami-

nated structure, composed of alternating bands of ferrite and
austenite, can be distinguished in the rolling plane (Fig. 2a) and
in the longitudinal section (Fig. 2b). In the transversal section,
elongated blocks of ferrite oriented in the transversal direc-
tion combine with ellipsoids of austenitic phase (Fig. 2c). The
volume fractions of the two-phase microstructure consist of
approximately 60 vol% ˛ and 40 vol% . X-ray diffraction spec-
tra of the hot rolled DSS (Fig. 3) shows peaks for austenite and
ferrite with no evidence of any other precipitates.
After the industrial annealing, the microstructure
still remains markedly oriented in the rolling direction
(Fig. 4). However, the wavy morphology of ferrite observed
after hot rolling has disappeared and the microstructure is
characterized by thicker bands of austenite and ferrite.
The examination of the “faulty-annealed” samples evi-
denced the effect of the annealing temperature on the
microstructure. Peaks corresponding to sigma phase were
clearly observed in the XRD pattern in all of them (Fig. 5),
whereas other secondary phases were not detected. Accord-
ing to the data given by Nilsson (1992), the presence of ␹ phase
in the samples treated under 900 ◦ C was also feasible. The
absence of ␹ phase after 20 min of annealing may be attributed
to the precipitation of . As demonstrated by Duprez et al.
(2000), ␹ particles start to dissolve from the moment that they
are completely surrounded by  and austenite.
Fig. 6 shows the microstructures obtained after annealing
at 875 and 975 ◦ C. The evolution of the sigma phase content for
the studied range of temperatures is shown in Fig. 7. The high-
est values appeared at 875 ◦ C (more than 20%), while a contin-
uous decrease was observed for more elevated temperatures. Fig. 4 – Microstructure of industrial annealed DSS: (a) rolling
Storz et al. (2007), studying the same type of DSS, the standard plane; (b) longitudinal section; (c) transversal section.
1.4462, pointed out that the shortest time for the nucleation
of sigma phase during isothermal treatments corresponds at
temperatures around 850 ◦ C. However, Jackson and Matthews
(1991) reported that when the DSS comes directly from the hot face, because of the high energy of this interface, and grown
rolling process, without a prior annealing, like in the present into the adjacent ferrite grains via a eutectoid reaction
case, precipitation of sigma takes place earlier and the peak which led to the decomposition of ferrite into an aggre-
temperature moves to slightly higher values. gate of sigma and secondary austenite. Depending on the
Sigma particles are easily distinguished in the SEM images temperature, different morphologies of sigma phase were
recorded with the back-scattered mode because they look observed. At high temperatures (925–975 ◦ C) diffusion is eas-
brighter than the surrounding matrix owing to its higher ier but the nucleation driving force is lower, and then coarse
molybdenum content compared with ferrite and austenite sigma particles appeared (Fig. 9). Meanwhile, in the range
phases (Fig. 8). TEM observations by Evans and Jack (1957) between 850 and 900 ◦ C the nucleation force is maxima so
showed that sigma particles had nucleated at the ˛/ inter- more nuclei are formed and, as a result, two morpholo-
1774 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782

Fig. 5 – X-ray diffraction pattern of the sample heat treated

at 900 ◦ C.

gies were produced: elongated bands of sigma following the Fig. 7 – Percentage of sigma phase for the different studied
˛/ interfaces (Fig. 10a) and a clear eutectoid microstructure heat treatments.
(Fig. 10b). These results are in agreement with other research
works previously cited in this paper, such as Beckitt (1969),
Mateo et al. (1997), Nilsson et al. (2000) and Redjaimia et al.
(2002).

4. Mechanical properties

Hardness, tensile strength and impact resistance were the

properties measured in order to evaluate the effect of the dif-

Fig. 8 – SEM micrograph showing sigma phase for the

heat-treated sample at 875 ◦ C.

Fig. 6 – Optical microstructures corresponding to Fig. 9 – Transmission electron microscopy showing sigma
longitudinal section of heat-treated samples: (a) 875 ◦ C; (b) phase for the heat treatment sample at 975 ◦ C.
975 ◦ C.
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782
Fig. 10 – Transmission electron microscopy for the heat
treatment sample at 875 ◦ C showing sigma phase: (a)
interface ˛/; (b) eutectoid transformation.
ferent annealing treatments on the mechanical response of
hot-rolled DSS.
4.1. Hardness
Vickers hardness values of the heat-treated samples are
plotted in Fig. 11 compared with the steel annealed fol-
lowing industrial conditions, i.e. IA. If Figs. 7 and 11 are
compared, the same trend is clearly observed in both. This
means that hardness is strongly related to the percentage
of sigma phase formed. Nevertheless, this is not the only
factor which must be taken into account. Annealing treat-
1775
Fig. 11 – Hardness evolution of heat-treated samples and
steel IA.
ments also induce changes on the microstructure, internal
stresses, dislocations substructures and crystallographic tex-
tures which could influence the mechanical response of DSS.
Duprez et al. (2000) analyzed these factors for isothermal
treatments, whereas in another paper the same authors,
Duprez et al. (2002), did it for hot rolling processes. Jiménez
et al. (2000) studied the hot formability characteristics of DSS
too.
However, the present work concentrates in the compari-
son of annealing treatments performed in a relatively narrow
range of temperatures and all of them of the same duration,
consequently it is expected that the effect of the above cited
factors will be similar for all the cases, leaving the amount
of intermetallic precipitates as the most important difference
among them.
4.2. Tensile tests
Fig. 12 shows the ultimate tensile stress ( UTS ) and the elon-
gation to fracture (A%) for three different conditions: samples
annealed at 875 ◦ C (high percentage of  phase), at 975 ◦ C (low
percentage of  phase) and IA.
Fig. 12 – Ultimate tensile stress ( UTS ) and ductility (A%) for
the samples heat-treated samples at 875 ◦ C (high
percentage of  phase), 975 ◦ C (low percentage of  phase)
and IA.
1776 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782

Fig. 13 – SEM micrographs showing the cracks originated in

sigma phase after tensile test for samples heat treated at
875 ◦ C.

A tensile strength increment of around 30% was observed

for the heat treatment with the highest sigma content. It was Fig. 15 – Fracture surfaces after impact tests for TL oriented
accompanied with very large ductility decay, leading to a brit- specimens: (a) IA; (b) 875 ◦ C.
tle behaviour. As Storz et al. (2007) demonstrated, not only the
amount of intermetallic phases is relevant, its morphology is

Fig. 14 – Charpy impact results of heat-treated samples at Fig. 16 – Variation in the pitting potential of specimens
875 and 975 ◦ C compared with IA. heat treated at 875, 925 and 975 ◦ C, and IA steel.
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782 1777

Fig. 19 – Macroscopic aspect of heat-treated specimens

after compression testing.

Fig. 20 – SEM micrograph corresponding to a transversal

Fig. 17 – SEM micrograph of sample heat treated at 925 ◦ C section of a sample heat treated at 875 ◦ C after a thickness
after corrosion test observed at the same zone by: (a) reduction of 67%.
secondary electrons and (b) back-scattered electrons.

important too. The linking of sigma particles observed for tem-

peratures under 900 ◦ C assists the nucleation of long cracks
which are probably the starting point of the brittle fracture.
SEM observations of the lateral surfaces close to the fracture
zone revealed the occurrence of this mechanism (Fig. 13).

Fig. 21 – TEM micrograph corresponding to the ferritic

Fig. 18 – Compression test curves for the different
phase of one sample with a thickness reduction of 11%.
treatment conditions.
1778 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782

Fig. 22 – TEM micrographs corresponding to the austenitic phase of a sample with a thickness reduction of 11%. (a) Shear
bands; (b) magnification of the shear bands; (c) patches of dislocation and stacking-faults.

After annealing at 975 ◦ C tensile strength increased slightly,
approximately 5%. More noticeable was the ductility decrease,
about 15% lower than the industrial treatment, even though
the fracture was still ductile with a minimum elongation value
of 40% corresponding to D specimens. The low percentage of
sigma phase precipitated, together with the morphology con-
sisting in big and isolated particles, explains this behaviour.
DSS produced by rolling have a significant anisotropy in
mechanical properties. Unusually large strength directionality
effect on an EN 1.4462 DSS was documented by Hutchinson et
al. (1985), and similar results were also reported by UlHaq et al.
(1994). More recently, Mateo et al. (2003) studied the anisotropy
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782 1779

Fig. 23 – TEM micrographs corresponding to the austenitic phase of a sample with a thickness reduction of 11%. (a)
First-order twins; (b) diffraction pattern corresponding to the {1 1 1} habit plane of Fig. 19a; (c) complex system of
intersections of deformation twins; (d) second-order twins.

effects on the fatigue response and found a marked influence.
This anisotropy is attributed to the presence and interplay of
sharp preferred crystallographic orientation in the two sep-
arate constitutive phases, whereas there is no evidence of a
significant fibre reinforcement effect arising from the duplex
structure. In the present work, the anisotropy effect due to the
rolling process remains practically the same for samples with
and without sigma phase in their microstructure. Transver-
sal direction exhibits the highest values of strength and the
lowest ductility.
4.3. Impact tests
The same three annealing conditions selected for tensile test-
ing were chosen for Charpy impact. Investigations on DSS use
to rely in notch-bar-impact-energy as the most sensible prop-
erty to detect the beginning of embrittlement problems. As it
can be observed in Fig. 14, impact toughness was extremely
sensitive to the presence of  phase, even more than ductility.
Samples heat treated at 975 ◦ C, with only 4% of sigma phase,
experienced an impact resistance reduction of more than 70%
1780 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782
of the value obtained for IA conditions. In the case of the
annealing at 875 ◦ C, the percentage of sigma phase is higher
and, as a consequence, extremely brittle behaviour took place,
with values under 5 J/cm2 . On the other hand, impact tests
are very sensitive to anisotropy effects too. For example, T–L
type specimens exhibited more than double impact resistance
than L–T ones. The reason is related with the highly oriented
microstructure observed in Fig. 2. In the former case the crack
had to cross a higher number of phase boundaries, whereas
for L–T specimens a delamination effect was observed due
to the easy crack propagation along the bands of ferrite and
austenite. Differences among the three orientations remained
even when the amount of sigma phase was increased. Due to
the harmful role on the mechanical behaviour of this phase,
the three orientations exhibited brittle fracture and the num-
ber of delaminations increased indicating preferential crack
growth along sigma particles aligned in the rolling direction
(Fig. 15).
5. Corrosion resistance
Fig. 16 plots the variation in the pitting potential (Ep ) of spec-
imens annealed at 875, 925 and 975 ◦ C, compared with the IA
condition, during tests in an aqueous solution of 3.5% NaCl.
A marked displacement of the pitting potential towards less
noble values is observed when the percentage of sigma phase
increases.
Surfaces of the samples subjected to anodic polariza-
tion tests where afterwards analyzed by SEM. Fig. 17a
shows a high density of corrosion pits after the treat-
ment at 925 ◦ C. The same area was observed with the
back-scattered mode, technique that makes appear sigma
in white and pits in black (Fig. 17b). The image exposes
that pits were originated in zones close to sigma phase,
where previous studies by Adhe et al. (1996) demonstrated
the formation of secondary austenite, fact corroborated by
Perren et al. (2001). This austenite, produced via eutec-
toid decomposition of ferrite, is poorer in Cr and Mo
because these elements migrate to sigma phase. As a
consequence, secondary austenite has a lower corrosion resis-
tance.
For the annealing treatment at 975 ◦ C, the Ep value was
identical to the result obtained for samples without sigma
phase, i.e. IA condition. In this case, not only the low per-
centage of sigma phase was important, also the chemical
composition of secondary austenite must be considered. The
higher the annealing temperature, the faster the diffusion
rates of Cr and Mo, fact that enhances the replenishment of
depleted zones and, for that reason, preferred sites for pitting
attack are reduced.
6. Cold working
During the industrial processing of rolled DSS, cold rolling
is performed after the intermediate annealing treatment.
Therefore, it is important to explore how the presence of
sigma phase, consequence of an inappropriate annealing
temperature, can influence the cold rolling step. This study
was made in two stages: first, compression tests were per-
formed for the different annealing conditions, and second,
cold rolling at laboratory scale was done only for sev-
eral conditions selected from the results of compression
testing.
6.1. Compression tests
The mechanical response during compression testing is
shown in Fig. 18. A clear correlation between the stress level
and the amount of sigma phase was observed. To achieve the
same thickness reduction, almost double load was required
for the samples with a high content of sigma phase compared
to the sigma free condition.
As a consequence of the global embrittlement of the DSS
due to sigma phase precipitation, macroscopic cracks were
observed in the tested specimens even for the conditions with
scarce presence of sigma (Fig. 19). Specimens were cut and the
transversal sections observed by SEM to analyze the different
behaviour of the two-phase matrix and the secondary phases.
As it can be seen in Fig. 20, during compression the bands of
the softer austenite/ferrite matrix were forced to run around
the harder particles of sigma phase.
TEM micrographs demonstrated the dissimilar mecha-
nisms for strain accommodation activated in ˛ and  during
compression testing. While the ferritic phase showed a high
dislocation density of wavy character (Fig. 21), in the austenite
shear bands, stacking-faults and twins were observed (Fig. 22),
features typical of low stacking fault energy structures. Com-
plex twinning systems were present in most of the austenitic
grains. Fig. 23a shows first-order twins with a diffraction pat-
tern corresponding to the {1 1 1} habit plane, as identified
in Fig. 23b, whereas Figs. 23c and present intersections of
deformation twins and second-order twins, respectively. On
the other hand, Sachdev and Shea (1985) reported martensite
transformation induced by deformation, but signs of these
transformation, characteristic of some austenitic stainless
steels, were not observed in the present research, neither
by X-ray diffraction nor by TEM for any of the studied
samples.
6.2. Cold rolling
Cold rolling at laboratory scale was performed in the facili-
ties of the Department of Metallurgy and Materials Science of
Ghent University (Belgium) in order to corroborate the results
obtained by compression testing.
For those plates subjected to annealing in the range from
850 to 900 ◦ C, it was impossible to complete the reduction
from the initial thickness of 6 mm thickness up to the final
industrial product, i.e. sheets of 2 mm in thickness. Fractures
of “alligatoring” type resulted from the brittleness introduced
by the precipitation of interconnected sigma phase particles
(Fig. 24).
After annealing at temperatures higher than 925 ◦ C, despite
the low percentages of sigma phase, it was necessary to apply
elevated rolling loads to achieve the required industrial thick-
ness reduction. On the other hand, large edge cracks appeared
even for heat treatment at 950 ◦ C where the percentage of
sigma phase was under 5% (Fig. 25).
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 9 ( 2 0 0 9 ) 1770–1782
Fig. 24 – Longitudinal cracks or alligatoring fracture. (a) Schematic representation; (b) macroscopic aspects of the cold rolled
plates at the laboratory scale after a heat treatment of 875 ◦ C.
Fig. 25 – Edge cracks. (a) Schematic representation; (b)
macroscopic aspects of the cold rolled plates at the
laboratory scale after a heat treatment of 950 ◦ C.
7. Conclusions
During the industrial production of rolled duplex stainless
steels, the annealing treatment previous to cold rolling is usu-
ally done at temperatures around 1050 ◦ C. The present paper
has evaluated the consequences of changing this annealing
temperature towards lower values, in the range from 975 up
to 850 ◦ C. For all the annealing temperatures studied, the only
secondary phase detected was the intermetallic sigma phase.
However, taking into account the amount and also the mor-
phology of its precipitation, two temperature ranges can be
distinguished:
1781
• Annealing treatments at temperatures around 875 ◦ C
enhanced the formation of sigma phase and also the inter-
connection between sigma particles. As a consequence,
mechanical properties, corrosion resistance and forma-
bility were severely affected, as compared with those of
the DSS subjected to the industrial annealing treatment.
Hardness and strength of the steel increased, together
with important ductility and impact toughness reductions.
Formability was very poor and it became impossible to
reach the required thickness reduction by cold rolling due
to the development of alligatoring fracture. Corrosion resis-
tance is not directly related to the presence of sigma phase,
although it is associated with the secondary austenite
originated during the eutectoid transformation of ferrite.
This reaction was observed to take place mainly at low
annealing temperatures in the range considered, producing
a clear decrease in the pitting potential.
• After annealing at higher temperatures, i.e. 925–975 ◦ C, the
amount of sigma phase precipitated was low and in the
form of isolated particles. Therefore, tensile properties and
corrosion resistance were only slightly affected. A more
marked and deleterious effect was observed in the impact
toughness. Also, edge cracks developed during cold rolling.
Acknowledgements
The authors thank ALZ-ARCELOR GROUP (Belgium) for
supplying the material. We acknowledge the contribution
of M. Marsal and J.M. Manero (UPC) in SEM and TEM
studies.
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