Materials Characterization 58 (2007) 909 916

Effect of stress relief at 350 C and 550 C on the impact

properties of duplex stainless steels
Marcelo Martins a,b,, Sergio Mazzer Rossitti c , Marcio Ritoni a , Luiz Carlos Casteletti d
a
SULZER BRASIL-DIVISO FUNDINOX, Brazil
Centro Universitrio Salesiano de So Paulo-Diviso de Americana, Brazil
c
Grupo MetalStainless Steel and Special Alloys, Brazil
d
Department of Materials, Aeronautics and Automotive Engineering,
So Carlos School of Engineering University of So Paulo at So Carlos, SP, Brazil
b

Received 15 May 2006; received in revised form 1 September 2006; accepted 13 September 2006

Abstract
The production of massive duplex stainless steel castings weighting over 2 t, with thicknesses exceeding 5 in. represents a major
challenge for the foundry industry. The difficulty in manufacturing such castings lies in the fact that thick sections experiment low
cooling rates during the solidification process and during the solution annealing and water quenching heat treatment.
As a result, intermetallic phases such as sigma phase (), Chi phase (), G phase, R phase, and complex carbides may
precipitate, causing the material to be extremely brittle [Martins M, Casteletti LC. Effect of heat treatment on the mechanical
properties of ASTM A890 grade 6A super duplex stainless steel. J ASTM Int 2005;2(1) [January]. [1]].
After solution annealing and water quenching, the steel is, in principle, free of intermetallic precipitates, but will contain
residual stresses resulting from rapid cooling on quenching. During and after machining, these stresses may produce dimensional
distortions in the casting, which can be avoided or at least reduced with stress relief heat treatments at intermediary temperatures,
taking care to prevent the loss of mechanical properties, mainly impact toughness.
The purpose of this study was to investigate the behavior of CD4MCu and CD4MCuN duplex stainless steels in impact tests
under the conditions of solution annealing and water quenching and stress relief at 350 C for 4 h and at 550 C for 2 h. Compared
to CD4MCu the high nitrogen content of CD4MCuN stainless steel has a more balanced microstructure with similar ferrite and
austenite contents, providing it with higher energy-absorbing capacity in impact tests. CD4MCuN fracture surfaces have
predominantly fibrous structures typical of high toughness materials, while the CD4MCu steel's fracture surface shows cleavage
facets typical of low toughness materials. The stress relief heat treatments reduced the impact toughness of the CD4MCu alloy but
did not affect the CD4MCuN alloy.
2006 Elsevier Inc. All rights reserved.
Keywords: Duplex; Impact; Fractography; X-ray

1. Introduction

Corresponding author. SULZER BRASIL-DIVISO FUNDINOX, Brazil. Tel.: +55 11 45892020.

E-mail address: marcelo.martins@sulzer.com (M. Martins).
1044-5803/$ - see front matter 2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2006.09.006

Duplex stainless steels, thus called because their

structure is composed of ferrite and austenite in approximately equal parts, have been known since the early 20th
century. Their use on an industrial scale, however, only

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Table 2
Brinell hardness values for the duplex stainless steels under three
different heat treatment conditions
Material

Condition

CD4MCu

SA + WQ
SA + WQ + 350 C
SA + WQ + 550 C
SA + WQ
SA + WQ + 350 C
SA + WQ + 550 C

CD4MCuN

Hardness (Brinell)
for 4 h
for 2 h
for 4 h
for 2 h

232
235
241
235
231
239

SA + WQ = Solution annealing at 1160 C/2H + Water quench.

Fig. 1. Possible phase precipitations in duplex stainless steel and

influence of the alloy's elements on the TTT curve [2].

began in the second half of the century. Even today, large

castings of these materials are difficult to manufacture
because their metallurgical structure is metastable and,
prone to microstructural alterations.
Intermetallic precipitates that can occur in these
materials when subjected to certain conditions of time
and temperature, are easily found in castings over 125 mm
thick, Fig. 1. The sigma phase () is the most problematic
of all precipitates because it causes a considerable
reduction in toughness and corrosion resistance [35].
The precipitation conditions of this phase have been
exhaustively studied and described in the literature [68].
Considering the production of massive castings that
require strict dimensional control, it may be necessary to
apply a stress relief heat treatment in order to ensure the
dimensional stability. However, few studies have focused
on the microstructural transformations that occur at lower
temperatures and with longer times characteristic of stress
relief heat treatments. After solution annealing and water
quenching, the material is in principle, free of intermetallic
precipitates, but still contains residual stresses resulting
from its abrupt cooling on water quenching. During and
after machining, these stresses can cause dimensional
distortions in the components. However, this can be
avoided, or at least reduced, by applying stress relief heat
treatments at intermediary temperatures (normally below

600 C), while taking care to prevent the loss of

mechanical properties, specifically impact toughness.
Even today, one of the duplex steels most widely
used for valve and centrifugal pump components is the
CD4MCu, whose microstructure contains up to 70% of
ferrite. This high ferrite content renders the material
more prone to the formation of solidification and heat
treatment cracks and favors the formation of sigma
phase. With a view to reducing these adverse effects, the
CD4MCuN material was developed from the through
the addition of 0.10% to 0.25% in weight of Nitrogen to
its chemical composition. This chemical modification
increases the austenite content improving the material's
weldability [9]. These materials contain copper in their
chemical composition and their stress relief heat
treatment may cause precipitation of the phase,
which is basically a copper precipitate. This precipitation may degrade the material's tensile strength, impact
resistance and increase hardness [10].
2. Experimental procedure
Duplex stainless steels cylindrical test specimens
260 mm long and 25 mm diameter were cast from
CD4MCu and CD4MCuN. The casting process employed
was silica sand with phenolurethane type organic resin
binder (PepSet). The casting design was made using
Autocad 2002 software and the solidification of the
castings was simulated with another software package,
called SOLSTAR, whose physical principle is based on
the determination of heat conduction through finite
elements. The metal was melted in a vacuum induction
furnace with network frequency (60 Hz) and a maximum
power of 400 KW, lined with predominantly magnesium

Table 1
Chemical composition of the steels studied (% in weight)
Alloy

C (%)

Cr (%)

Ni (%)

Mn (%)

Si (%)

Mo (%)

S (%)

P (%)

Cu (%)

N (%)

Cr/Ni equiv

CD4MCuN
CD4MCu

0.027
0.032

25.01
24.67

5.70
5.43

0.88
0.77

0.49
0.87

1.88
1.86

0.004
0.011

0.024
0.028

2.89
3.03

0.172
0.077

1.72
2.14

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911

Table 3
Results of the Charpy impact tests for diferent heat treatment
conditions
Material

Condition

Energy (J)

CD4MCu

SA + WQ
SA + WQ + 350 C for 4 h
SA + WQ + 550 C for 2 h
SA + WQ
SA + WQ + 350 C for 4 h
SA + WQ + 550 C for 2 h

66
55
26
119
140
116

CD4MCuN

SA + WQ = Solution annealing at 1160 C/2H + Water quench.

refractory cement (magnesium oxide base). Chemical

analysis was done by optical emission spectroscopy on
solid samples. The material was solution annealed at
1160 C for 2 h, followed by water quenching and subsequent stress relief at 350 C for 4 h and at 550 C for 2 h.
A scanning electron microscope with an EDS
detector was used and the secondary electron images
were obtained digitally.

Fig. 3. Aspects of the fracture of CD4MCuN in the condition of

solution annealing at 1160 C and water quenching.

Brinell hardness was measured using a Universal

Testing Machine with a capacity of 300,000 N and a
10 mm diameter sphere with a load of 3000 Kgf and the
impact tests were done using a OTTO WOLPERTWERKE-GMBH, type PW 30K machine, with maximum capacity of 294J. X-ray diffraction patterns was
performed using copper K1 radiation and a scanning
velocity of 1/min to characterize the structures for each
alloy.
Table 4
Electron microprobe analysis of the particles contained in the dimples
Material
CD4MCu
CD4MCuN
Material
Fig. 2. Aspects of the fracture of CD4MCu in the condition of solution
annealing at 1160 C and water quenching.

O (%)

Al (%)

Si (%)

Zr (%)

S (%)

Ca (%)

9.77
5.51

0.86
0.35

62.72
10.25

ND
6.52

4.77
2.90

Zero
1.17

Cr (%) Mn (%) Fe (%) Ni (%) Cu (%)

CD4MCu
6.33
CD4MCuN 31.04

6.51
14.63

8.47
25.29

0.35
1.53

0.23
0.81

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3. Results and discussion

The chemical compositions of the materials studied
are shown in Table 1. The Crequivalent/Niequivalent ratios
obtained through Eqs. (1) and (2) were: 2.14 for the
CD4MCu steel and 1.72 for the CD4MCuN. According
to ASTM Standard A800/800M [11] for these
Crequivalent/Niequivalent CD4MCu has 69% of ferrite
and CD4MCuN has 49% of ferrite.
Creq Cr% 1:5%Si 1:4%Mo
%Nb4:99

[11].
Nieq Ni% 30%C 0:5%Mn
26N0:02 2:77

[11].
Results from quantitative metallography was 63%
ferrite for the CD4MCu and 46% ferrite for the

Fig. 5. Appearance of the fractures in CD4MCu (A) and CD4MCuN

(B) solution annealed and stress relieved at 550 C for 2 h.

Fig. 4. Fractures in the CD4MCu (A) and CD4MCuN (B) steels

solution annealed and stress relief at 350 C for 4 h.

CD4MCuN in a good agreement with A800/800M.

The presence of nitrogen strongly favors the formation
of austenite in the microstructure.
Table 2 lists the Brinell hardness values found for the
materials when solution heat-treated at 1160 C and
water quenched and stress relieved at 350 C for 4 h and
550 C for 2 h. In the case of the CD4MCu steel, stress
relief at 350 C for 4 h promoted an insignificant
increase in hardness, on the order of 2.6%, which is
within the range of accuracy of the test. Although the
material contains 2.89% copper, the temperature and
heat treatment time were insufficient to promote the
precipitation of phase particles, which are rich in this
element [12]. However, the same alloy, when subjected
to stress relief at 550 C for 2 h, showed a 5.2% increase
in hardness, possibly indicating that submicroscopic
phase particles began to precipitate in the ferritic phase.
The CD4MCuN steel remained practically unaltered,
indicating greater stability of Cu in solid solution in the
austenite phase.

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913

Fig. 6. Magnified region of the diffractograms of Fig. 7.

Although the microstructure of the CD4MCuN steel

has a higher volume of austenite, the hardness of the
CD4MCu and CD4MCuN materials in the solution
annealed state was very similar, i.e., 232HB and 235HB,
respectively. This behavior is probably due to the fact
that the nitrogen in solid solution in the CD4MCuN
promotes hardening by interstitial solid solution.
The energy absorbed in the Charpy impact tests at room
temperature by the two materials is shown in Table 3. The
values represent the arithmetic mean of three test speci-

mens. The CD4MCuN steel containing nitrogen has

greater impact toughness under all the conditions studied.
The presence of nitrogen in the material's composition
leads to a greater concentration of the austenitic phase in
the microstructure, increasing the energy absorption
capacity in the Charpy impact test. The face-centered
cubic crystalline structure has greater plasticity than the
body-centered cubic crystalline structure.
In the solution annealed condition, the energy
absorbed by the CD4MCuN steel was 80% greater

Fig. 7. Diffractograms of the CD4MCu and CD4MCuN materials in the solution annealing condition.

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M. Martins et al. / Materials Characterization 58 (2007) 909916

than that absorbed by the CD4MCu steel. In the case of

the materials stress relieved at 350 C, the energy
absorbed by CD4MCuN was 154% greater than in
CD4MCu, while the impact test showed that the
nitrogenized steel stress relieved at 550 C absorbed
346% more energy than the steel without nitrogen.
In the case of the CD4MCu, the stress relief at 350 C
for 4 h reduced the absorbed energy by 16.7% in relation
to the sample only solution heat-treated, while stress
relief at 550 C for 2 h decreased the absorbed energy by
60.6% when compared with the same steel in the
solubilized state.
This behavior was not repeated by the CD4MCuN
steel, in which the stress relief at 350 C for 4 h
increased the absorbed energy by 17.6% in relation to
the sample only solution annealed at 1160 C. This
increase may be associated with the effect of the relief of
all stresses originated during cooling on quenching.
Stress relief at 550 C for 2 h hardly altered the energy
absorbed in the Charpy impact test when compared with
the sample only solution annealed. Nitrogen increases
the austenite content in the microstructure and austenite,
in turn, dissolves higher concentrations of copper in
solid solution compared to ferrite. Hence, the stress
relief at both 350 C and 550 C in the samples containing nitrogen were probably insufficient to promote
precipitation of the phase in the microstructure.
Figs. 2 and 3 illustrate the aspect of the fracture
surfaces of the CD4MCu and CD4MCuN after solution
annealing and water quenching. CD4MCu has fracture
predominantly faceted, with few areas of ductile
fracture, due to the mostly ferritic microstructure. The

particles visible in the dimples probably originate from

the deoxidization process of the metal.
CD4MCuN has fracture predominantly ductile, i.e.,
with fibrous regions, due to the large quantity of austenite
in the microstructure, which, being a very tough phase,
absorbs the impact energy in the test to deform itself
plastically, making difficult for cracks to propagate.
Analysis of Figs. 2 and 3 indicates that the
morphologies of the particles found in the two materials
are completely dissimilar, for the CD4MCu particles are
basically spherical while those of the CD4MCuN are
angular and smaller. Electron microprobe analyses of
the particles indicated that they are probably inclusions,
but have different chemical compositions, as shown in
Table 4. In the case of the CD4MCu steel, the particles
are basically silica inclusions originating from the
deoxidization process and the Cr and Fe elements that
appear in the microanalysis are due to the small size of
the analyzed particles, which produce an effect on the
adjacent matrix. With regard to the CD4MCuN steel, the
particles are complex silicon, zirconium, chromium,
manganese and iron oxides. This is because the
materials were deoxidized differently. Only a metallic
silicon was used to deoxidize the CD4MCu. A calcium
siliconmanganese, ironsiliconzirconium, and metallic silicon was used to deoxidize the CD4MCuN steel.
Moreover, since the same electron beam phenomenon
reached the matrix of this material, the chromium and
iron contents, in particular, must have significantly
influenced its effect.
Fig. 4 (A) and (B) depict the fractures in both steels in
the condition of solution annealed and stress relief at

Fig. 8. Diffractograms of the CD4MCu and CD4MCuN materials after solution annealing and stress relief at 350 C for 4 h.

M. Martins et al. / Materials Characterization 58 (2007) 909916

915

Fig. 9. Diffractograms of the CD4MCu and CD4MCuN materials after solution annealing and stress relief at 550 C for 2 h.

350 C for 4 h. Similarly, Fig. 5 shows the appearance of

the fractures that occurred in the two materials solution
annealed and stress relieved at 550 C for 2 h. An
analysis of Figs. 4 and 5 reveals that the CD4MCu
stainless steel subjected to stress relief at both 350 C
and 550 C displayed fractures with cleavage facets
typical of brittle materials. These same heat treatments
did not affect the impact behavior of CD4MCuN, which
showed predominantly fibrous fractures characteristic of
ductile materials.
The X-ray diffraction results for the two steels indicate
the major phases present are ferrite () and austenite ().
This means that after the solution annealing at 1160 C,
the microstructure of these steels is composed solely of
these two phases. Fig. 6 shows only a small region of the
diffraction pattern of Fig. 7, but on a magnified scale,
clearly revealing the peaks corresponding to the (111),
(110) and (200) planes. Similarly, Figs. 8 and 9 show
the diffraction patterns of the CD4MCu and CD4MCuN
materials after solution annealed followed by stress relief
at 350 C and 550 C, respectively. These figures show
only peaks corresponding to the reflections of ferrite and
austenite crystalline planes. No secondary phase was
identified by this technique, although there was evidence
of its occurrence, mainly in the Charpy impact tests on the
CD4MCu steel.
Stress relief above 550 C in duplex stainless steels
containing copper normally causes the precipitation of
phase particles extremely rich in this element [12]. The
fact that the X-ray test did not detect other precipitates in
the material's microstructure does not mean they do not

exist, but that they may be present in concentrations of

less than 3%, which is the lowest detection limit, or that
there are only atom clusters in the initial stages of
formation of a precipitate coherent with the matrix.
4. Conclusions
The two materials showed very different values of
absorbed energy in the Charpy impact tests under the
various conditions of heat treatment. In the solution
annealing condition at 1160 C followed by water
quenching, the higher volumetric concentration of
austenite in the microstructure of CD4MCuN led to
high energy absorption when compared with the energy of
CD4MCu. The stress relief treatments at both 350 C and
550 C significantly reduced the impact energy of
CD4MCu but did not have the same effect on CD4MCuN.
Although the microstructure of the nitrogenized
CD4MCuN presented more austenite, the hardness of
the CD4MCu and CD4MCuN steels in the solubilized
and quenched condition was practically the same. The
hardening effect caused by N in interstitial solid solution
probably explains this fact.
The stress relief heat treatment at 350 C for 4 h did
not significantly alter the materials' hardness, but the
treatment of CD4MCu at 550 C for 2 h increased its
hardness by 9 HB, while the change in this property was
not very significant in CD4MCuN.
The fracture surfaces of CD4MCu were predominantly faceted under all the conditions, while those of
CD4MCuN were typically fibrous.

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M. Martins et al. / Materials Characterization 58 (2007) 909916

The X-ray diffraction tests indicated the presence of

only two phases: ferrite and austenite in the materials'
microstructures under all the conditions studied.
Although the absorbed energy values of CD4MCu
declined in response to the stress relief heat treatment
the presence of a secondary crystalline phase responsible for this behavior was not detected in X-ray.
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