MAT ER IA LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9) 5 0– 5 5

Effect of ageing on precipitation and impact energy of 2101

economical duplex stainless steel

Zhang Weia,b , Jiang Laizhua,⁎, Hu Jinchenga , Song Hongmeia

a
Shanghai Baosteel Technology Center, Baosteel Co., LTD. Shanghai 200431, PR China
b
College of Materials Science and Engineering, Shanghai Jiaotong University, Shanghai 200240, PR China

AR TIC LE D ATA ABSTR ACT

Article history: The impact energy and microstructure of a thermally aged 2101 duplex stainless steel with
Received 11 June 2008 composition of Fe–21.4Cr–1.2Ni–5.7Mn–0.23 N–0.31Mo were studied. The results showed
Accepted 5 July 2008 that the room temperature impact energy of specimens decreased gradually with ageing
temperature up to 700 °C and then increased with aging over 700 °C. The minimum value of
Keywords: impact energy was 37 J after 700 °C aging, which was only 34% of that for as-annealed
Duplex stainless steel specimens. For specimens aged at 700 °C, the room temperature impact energy decreased
Impact energy significantly after 3 min and was halved after 10 min. Fractographs showed that, with
Ageing increasing aging time, the fracture morphology changed from fibrous fracture to
Cr2N transgranular and intragranular fracture. Scanning electron micrographs revealed that
many precipitates were distributed along α/γ and α/α interfaces. The precipitates were
extracted and confirmed by X-ray diffraction to be Cr2N. Therefore, it can be concluded that
precipitation of Cr2N is the main reason for the decrease of impact energy in aged 2101
duplex stainless steel.
© 2008 Elsevier Inc. All rights reserved.

1. Introduction Since 2000, significant research has been devoted to the

Austenitic stainless steel has good corrosion resistance and
high toughness but it has high sensitivity of localized
corrosion in chloride environments. Ferritic stainless steel
also has good stress corrosion resistance, but it exhibits low
ductility. Duplex stainless steels (DSS) combine aspects of
each of these stainless steel classes and are characterized by a
two-phase structure with approximately equal volume frac-
tions of ferrite and austenite, offering an attractive combina-
tion of corrosion resistance and mechanical properties [1]. In
these duplex stainless steels, 2205 type DSS of composition
22Cr–5Ni–3Mo–0.16N have been widely used in many applica-
tions such as oil, petro-chemical, desalination service, and
paper mill. To support these applications, substantial research
has been performed on the mechanical properties [2–4],
corrosion resistance [5–6], second phase characteristics [4,7–
8] and weldability [9–11] of 2205 DSS.
development of cost-efficient DSS containing low Ni and low
Mo. Wang et al. [12] investigated the microstructure and
properties of a nickel-free DSS Fe–22Cr–10Mn–0.35N and found
that a dual-phase structure with approximately 50% austenite
could be attained after completely replacing Ni by Mn and N;
moreover, the steel had high yield strength and good corrosion
resistance. Merello et al. [13] evaluated the pitting corrosion
resistance of a family of non-standard low-Ni high-Mn–N
duplex stainless steels and determined an exponential
equation for estimating the pitting resistance of these steels.
In particular, Outokumpu Stainless developed a kind of
economical DSS LDX2101 of the typical composition 21.5Cr–
5Mn–1.5Ni–0.22 N–0.3Mo–0.3Cu. LDX2101 showed wide appli-
cation potential due to its higher yield strength, better pitting
resistance and lower cost than traditional 304 austenite steel.
However, limited research [14–15] has been dedicated to
studies of the microstructure and properties of LDX2101.

⁎ Corresponding author. Tel.: +86 021 26034501; fax: +86 021 26034622.
E-mail address: zwatt@163.com (J. Laizhu).

1044-5803/$ – see front matter © 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2008.07.002
 MAT E RI A LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9 ) 5 0 –5 5 51

Table 1 – Composition of the 2101 duplex stainless steel

Elements C Si Mn P S Cr Ni N Mo

Content (wt.%) 0.03 0.4 5.7 0.019 0.005 21.4 1.2 0.23 0.31

Research on the nature of precipitation and its effects on

properties in LDX2101 was still lacking. By comparison,
precipitation in 2205 DSS was investigated by a number of
researchers [7–8,16], that showed that 2205 DSS was prone to
sigma phase formation, which could drastically decrease the
toughness properties. In related work, Duprez et al. [17]
revealed that Mo was the main element controlling the
sigma precipitation because sigma phase had a high content
of Cr and Mo. The lower concentration of Mo in DSS 2101
suggested a lower likelihood for the precipitation of sigma Fig. 2 – Impact energy of specimens aged at different
phase. This interest prompted the current effort to more temperatures for 30 min.
closely examine the precipitation characteristics and impact
strength of as-=annealed and thermally aged DSS 2101.
Fracture micrographs after impact testing were observed in an
FEI Quarter 400 SEM.
2. Experimental Materials and Procedures To observe the microstructure, each specimen was electro-
chemically etched in a 40 g KOH + 50 ml H2O solution and the
The experimental steel was prepared by induction melting in a volume fraction of austenite was measured by a CARL ZEISS
ZG-50 vacuum induction furnace, using high purity iron, optical microscope equipped with a KS400 quantitative
manganese, silicon, chromium, nickel, molybdenum and a metallographical analysis system. The as-aged specimens
Fe(CrN) alloy. The chemical composition of the steel is listed in were etched by the same method and observed in an FEI
Table 1. After homogenization at 1200 °C for 2 h, the ingot was Quarter 400 SEM. To determine the type of precipitation,
hot forged into 48-mm thick plates at 1200 °C, and then hot precipitates were extracted by special solution and then
rolled into 8-mm diameter bars. The as-rolled bars were then examined in a Panalytical X′ Pert XRD, using Co Kα radiation.
annealed at 1050 °C for 30 min—referred to here as as- To observe the precipitates in detail, specimens aged at 700 °C
annealed specimens. Some of the as-annealed specimens for 240 min were examined in a JEOL JEM 200CX TEM, operated
were subjected to thermal ageing at temperatures from 500 °C at 200 kV.
to 1050 °C for 30 min and at 700 °C for different times.
Charpy specimens for impact testing were machined from
both the as-annealed and as-aged plates along the rolling 3. Results
orientation with diameters of 5 × 10 × 55 mm. Charpy impact
tests were carried out at room temperature, using an AHC-
Fig. 1 shows the optical microstructure of the specimen as-
3000/2-AT impact machine with maximum capacity of 290 J.
annealed at 1050 °C for 30 min. The bright phase was defined

Fig. 1 – Optical microstructure of DSS 2101 as-annealed at Fig. 3 – Impact energy of specimens aged at 700 °C for
1050 °C for 30 min. different times.
52 MAT ER IA LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9) 5 0– 5 5

as austenite and the dark as ferrite. The volume fraction of the
austenite phase was 55 vol.% calculated by the quantitative
analysis system. No precipitates were observed in the as-
annealed microstructure.
Fig. 2 presents the impact energy of specimens aged at
various temperatures for 30 min. For specimens aged at
500 °C–950 °C, the impact energy was lower than that of the
as-annealed specimens. When the ageing temperature was
increased from 500 °C to 950 °C, the impact energy initially
decreased and reached the minimum value at 700 °C of 37 J,
which was only 34% of the as-annealed specimen value of
108 J. For ageing temperatures over 750 °C, the impact energy
increased again and reached 106 J after aging at 1050 °C,
almost equaling the value of the as-annealed specimens.
Fig. 3 presents the impact energy of specimens aged at
700 °C for varying times. It can be seen that the impact energy
decreased rapidly with the time of heat treatment. After
ageing times as little as 6 min and 10 min, the impact energy
decreased to 78 J and 55 J, being 30 J and 53 J lower than that of
the as-annealed specimen, respectively. After aging for
30 min, the impact energy decreased to 34.7 J. Beyond
30 min a further increase of aging time had little effect on
impact energy.
Fractographs of specimens subjected to various heat-
treatments are shown in Fig. 4. The fractograph of the as-
annealed specimen, Fig. 4(a), showed predominantly ductile
fracture, where a large number of deep dimples could be
observed and the size of the dimples was uniform. For the
specimen aged at 700 °C for 6 min, a ductile fracture
mechanism was still dominant, Fig. 4(b), but the size of the
dimples was varied and some transgranular cracking could be
observed. After aging for 15 min at 700 °C, the fracture
appearance (Fig. 4(c)) provided evidence to show that
the transgranular facets were distributed over the entire
fracture surface and a slight river pattern can be seen within
some facets. Meantime, these facets were connected by
shallow dimples. In the specimen aged at 700 °C for 240 min,
the fracture surface showed that transgranular and

Fig. 4 – Impact fracture micrographs of the specimens subjected to different heat-treatments: (A) as-annealed specimen; (B) aged
at 700 °C for 6 min; (C) aged at 700 °C for 15 min; (D) aged at 700 °C for 240 min.
 MAT E RI A LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9 ) 5 0 –5 5
intragranular facets were distributed over the entire fracture
surface, Fig. 4(d).
Fig. 5 shows the SEM analysis of specimens aged at 700 °C for
240 min. The basic microstructure still consists of austenite and
ferrite dual-phase; the bright phase is austenite. Note that many
particles were distributed along the austenite/ferrite interfaces
and grew into the adjacent ferrite region as shown in Fig. 5(a).
Between these particles and the austenite phase, bright areas
with widths of 0.3 μm were also observed to surround the
austenite phase. In Fig. 5(b), some precipitates could also be
observed along the ferrite grain boundaries. To determine the
identity of these precipitates, the particles were extracted by a
special solvent method and then examined by XRD (Fig. 6). The
results of XRD showed that these precipitates were mainly Cr2N,
together with some Cr23C6 carbides. Fig. 7 presents a TEM
micrograph of the DSS aged at 700 °C for 30 min. Needle-like
Cr2N precipitates (arrow marks) were found in the ferrite grains.
These particles had an average thickness of 0.05–0.1 μm and a
length of 0.2–1 μm. In addition, some coarse Cr2N precipitates
were observed at the phase interfaces. These particles had an
average thickness of 0.1–0.2 μm and a length of 0.3–0.5 μm.
Fig. 5 – SEM micrographs of specimens aged at 700 °C for
240 min: (A) ferrite/austenite interfaces; (B) ferrite/ferrite
interfaces.
53
4. Discussion
Precipitates often exist in duplex stainless steel due to high
concentrations of Cr, N and Mo and the partitioning of these
elements in different phases. Research [7,8] reveals that in DSS
2205, the undesirable phases such as sigma phase (σ), Chi phase
(χ), R phase, M7C3 and M23C6-type carbides and chromium
nitrides (Cr2N) may exist in the steels following thermal aging.
Among these secondary precipitates, sigma phase with fast
formation kinetics has been considered as the most critical
because it can cause a drastic deterioration in toughness and in
corrosion resistance. Ahn and Kang [18] studied a series of DSS
2205 compositions, and claimed that the steels containing 2–
5 vol.% sigma phase in the microstructure had an impact energy
of 32 J, being 288 J lower than precipitation-free specimens.
Martins and Casteletti [16] studied the effects of thermal ageing
on toughness property of a 25.84Cr–5.94Ni–3.79Mo–0.25N–
0.88Mn super DSS and found that sigma phase began to
precipitate for temperatures above 760 °C and reached its
highest concentration at 840 °C–850 °C. At the same time, the
impact energy declined sharply due to the precipitation of sigma
along the ferrite/austenite interfaces.
The values of impact energy in DSS 2101 in the paper show
a similar trend to that of DSS 2205 following to thermal aging,
except that the nose temperature for minimum impact energy
of DSS 2101 is 700 °C, which is lower than the 850 °C of DSS
2205. This indicates that the precipitation causing the impact
energy decreases in DSS 2101 may not be sigma phase. This
assumption is confirmed by the results of XRD analysis in
Fig. 6, which indicates that Cr2N particles are the main
precipitation in DSS 2101. In fact, as Duprez et al. [17] have
shown, in 2205 DSS containing 3.0 wt.% Mo sigma precipita-
tion occurs in the ferrite and a decrease of Mo in the ferrite is
pronounced; this forces the Mo to diffuse from the inner
regions of the ferrite matrix and further indicates that Mo is
the main element controlling the sigma formation. However,
the concentration of Mo is only about 0.3% in DSS 2101. As a
result, the nucleation and growth of sigma phase is more
constrained than in DSS 2205.
Some research [2,19] has indicated that Cr2N precipitates
are distributed along ferrite/ferrite and ferrite/austenite inter-
faces in 00Cr25Ni7Mo4N0.25 (SAF2507) super duplex stainless
steel aged at 700–900 °C. These Cr2N precipitates have a high
concentration of Cr and N and sometimes contain Fe, Ni and
Mo. Meantime, the precipitation of Cr2N is often accompanied
by the formation of γ2 due to a decrease of Cr in the ferrite.
However, few researchers have noted the effect of Cr2N
precipitation on the impact energy of duplex stainless steels
because in DSS 2205 and 2507 sigma phase has the most
noticeable impact on loss of impact toughness.
Conversely, precipitation of Cr2N in high-N austenitic
stainless steels has been reported in the literature [20–22].
Maribe and Saucedo-Munoz [20] revealed that in a 24.32Cr–
15.07Ni–0.32 N–3.88Mn–0.04C austenitic stainless steel aged at
700 °C for 6 min, 0.5–1.0 vol.% Cr2N precipitates at the grain
boundaries. In fact, the formation of Cr2N in a duplex stainless
steel will be faster than in an austenitic stainless steel because
diffusion of elements such as N and Cr in the b.c.c ferrite phase
is faster than in the f.c.c austenite phase.
54 MAT ER IA LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9) 5 0– 5 5

Fig. 6 – X-ray diffraction results of extracted phase from specimen being aged at 700 °C for 240 min.

To further confirm the conclusion offered here, a phase-
diagram of DSS 2101 was calculated by Thermo-Calc software
as shown in Fig. 8. After being annealed at 1050 °C, the volume
fraction of austenite is 57%, which is accordance with the result
of 55 vol.% calculated by metallographical observations, Fig. 1.
At 900 °C, Cr2N is precipitated preferentially as shown in Fig. 8
and then Cr23C6 is precipitated at about 800 °C, while a very low
fraction of sigma phase precipitates at temperatures below
700 °C. Therefore, phase-diagram analysis also confirms that
Cr2N is the main precipitate in thermally aged DSS 2101.
Similar to the effect that sigma precipitation has in
drastically decreasing the impact energy of DSS 2205, Cr2N
precipitation can also decrease the impact energy of DSS 2101.
As shown in Figs. 2 and 3, the nose temperature for the
minimum impact energy is 700 °C. Note that for specimens
aged at 700 °C, the precipitation of Cr2N is rapid, corresponding
to the drastic drop of impact energy. With increasing ageing
time, more Cr2N particles are precipitated at phase interfaces
and grain boundaries, causing the continuous decrease of
impact energy. After being aged for 10 min at 700 °C, the
impact energy decreases to 55 J due to the Cr2N precipitation.
For times greater than 30 min, the nucleation of Cr2N becomes
more difficult and thus the impact energy changes little with
increasing time.

Fig. 7 – TEM micrograph of DSS 2101 aged at 700 °C for Fig. 8 – Phase-diagram of as-received DSS 2101 calculated by
240 min. Thermo-Calc software.
 MAT E RI A LS CH A R A CTE R IZ A TI O N 6 0 (2 0 0 9 ) 5 0 –5 5
5. Conclusions
The room temperature impact energy of DSS 2101 after
thermal ageing is drastically decreased and reaches the lowest
value after aging at 700 °C. When aged at 700 °C for 10 min, the
impact energy is reduced by half comparing with as-annealed
specimens. Microstructural analysis shows many particles are
distributed along the austenite/ferrite and ferrite /ferrite
interfaces. XRD analysis identifies these particles are mainly
Cr2N. It is thus concluded that precipitation of Cr2N is the
dominant reason for the drop of impact energy in DSS 2101
subjected to thermal aging.
Acknowledgments
The authors would like to thank Prof. M.O. Speidel for fruitful
discussion. The work was sponsored by the key project of
Shanghai Postdoctoral Science Foundation under contract
No.07R214201.
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