Materials Science and Engineering, A 174 ( 1994 ) 149-156 149

a Phase precipitation and its effect on the mechanical properties of a

super duplex stainless steel

J i a n c h u n Li*, T i y a n W u * a n d Y v e s R i q u i e r
General MetallurgyDepartment, FacultePolytechnique de Mons, Mons (Belgium)
(Received April 13, 1993; in revised form June 18, 1993)

Abstract

A super duplex stainless steel containing nominally (by weight) 25 Cr, 7 Ni, 3.5 Mo and 0.25 N has been investigated for o
phase precipitation and its effect on mechanical properties at elevated temperatures. The specimens were solution treated
and some of these were annealed between 700 and 1050 °C for times ranging between 1 and 60 min. Selective etching,
optical microscopy, X-ray diffraction, bulk extraction and chemical analysis have been used to identify the austenite,
ferrite and o phases, and to construct a time-temperature-precipitation diagram for o phase formation. Hot tensile tests
and subsequent fractography were performed on specimens containing a wide range of o phase volume fractions. The
results indicate the following: the incubation time for o precipitation is about 5 rain at 850-900 °C; the ductility of
specimens deformed at about 600 °C is greatly reduced by o phase precipitation; the effects of this phenomenon increase
with the o phase volume fraction and exhibit quite a marked temperature dependence; at higher temperatures, e.g.
900 °C, o phase particles in the steel are realigned along the shearing direction during deformation and the final fraction
appears ductile

1. Introduction mation exists about its effect on the mechanical pro-

Super duplex stainless steels may be defined as a
family of steels having a ferritic-austenitic structure
and a pitting resistance equivalent (PRE) greater than
40, where P R E = % C r + 3 . 3 % M o + 16%N. Their low
cost and good engineering performance [1, 2] have led
to an increasing number of applications, mainly in
chemical and offshore industries, where high levels of
strength and resistance to corrosion are required.
However, a large variety of undesirable phases (car-
bides, nitrides, intermetallic phases) may appear in
these alloys and greatly affect their properties if appro-
priate manufacturing procedures are not adopted.
Among the phases listed above, the o phase is the most
important because of its drastic effect on the toughness
and corrosion resistance of the material [3, 4]. There-
fore, it is very important to understand clearly the o
embrittlement mechanisms during production as well
as in service.
Although a phase formation has received consider-
able attention in austenitic stainless steels, apart from
the work of Maehara and coworkers [5, 6], little infor-
*Present address: Department of Materials, Central-South
University of Technology, Changsha, China.
perties in highly alloyed duplex stainless steels. The
purpose of this investigation was to examine the o
phase morphologies, the kinetics of formation of this
phase and its effect on hot ductility in a
25Cr-7Ni-3.5Mo-0.25N super duplex stainless steel
after undergoing thermal exposures at temperatures
ranging from 600 to 1100 °C.
2. Experimental procedure
The material used in the present study was a plate
(18 mm thick) produced by hot rolling of a contin-
uously cast slab. The chemical composition of the steel
is given in Table 1.
A solution treatment temperature of 1100 °C was
necessary to dissolve all the o phase in the ferrite, and a
standard treatment of 60 min at this temperature,
followed by water quenching was chosen.
Figure 1 shows the microstructure of the hot-rolled
plate after solution treatment. Island-like austenite
grains can be seen in the ferrite matrix. Isothermal
treatment in the temperature range 700-1050 °C for
times up to 100 min resulted in the transformation of
ferrite to austenite and the a phase. Hot tensile testing,
fractography, hardness measurements, chemical analy-
sis of the o phase and determination of the volume

0921-5093/94/$7.00 © 1994 - Elsevier Sequoia. All fights reserved

150 J. Li et al. / a Phase precipitation and mechanical properties
TABLE 1. Chemical composition of the steel used (wt.%)
C Si Mn P S
0.018 0.43 0.7 0.02 0.001
Fig. 1. Microstructure of hot-rolled plate after solution heat
treatment at 1100 °C, followed by water quenching.
fractions of 6, 7 and a phases by X-ray diffraction were
performed on these specimens.
For the microscopic examination, 6, ), and a phases
were colored gray, white and black, respectively, by
electrolytic etching in K O H solution. Vickers micro-
hardness measurements with a load of 50 g were
employed to determine the hardness of each phase.
The a phase fraction was determined by X-ray
diffraction as follows. The ratios of the diffraction
intensities of the (331 ), (411 ), (212) and (410) planes to
those of the "reference sample" annealed at 800 °C for
100 min were averaged to eliminate the effect of tex-
ture. In the "reference sample", austenite and a
phases--not ferrite--were detected. The a phase frac-
tion in this "reference" was determined by a bulk
extraction technique. 10% HCI in methanol solution
was used as the electrolytic extraction medium. No
phases other than the a phase was detected in the
extracted powder.
The 6/7 ratio in the plate samples was determined
using the (211) and (200) reflections for ferrite and
(311), (220) and (200) for austenite. Co K a radiation
was used.
Analysis of the alloying elements in each phase was
carried out to reveal the partitioning of the elements
during annealing. The elements were analysed by
means of energy-dispersive X-ray spectroscopy
(EDXS) on the 6 and 7 grains. The composition of the
a phase was determined chemically from the extraction
residues.
Isothermal, hot tensile tests over the temperature
range 600-1100 °C were carried out on a Gleeble
Cu Ni Cr Mo W N B
0.57 7.2 25 3.6 0.65 0.25 0.002
servohydraulic testing machine under a constant strain
rate of 0.01 s -1. Specimens 10 mm in diameter and
160 mm long were prepared parallel to the initial roll-
ing direction. A heating rate of 100 °C s -1 was
obtained by passing an electric current through the
specimen. The temperature was measured and con-
trolled by means of a thermocouple spot welded to the
center of the specimen's surface. After being fractured,
the specimens were quenched by compressed argon to
protect the fractured surface against oxidation and to
warrant a good scanning electron microscopy (SEM)
observation. The microstructure was also examined to
reveal the void formation.
3. R e s u l t s and d i s c u s s i o n
3.1. Precipitation during isothermal annealing
The results obtained from X-ray diffraction and
optical microscopy have been used to establish the
fractional changes of the 6, ), and o phases with the iso-
thermal annealing time. An example of the data relative
to samples annealed at 800 °C is shown in Fig. 2.
When annealing at temperatures below 1000 °C, the
first precipitate detectable in X-ray diffraction, bulk
extraction and optical micrographs consists of austen-
ite. After longer times, the reaction
6--'~+ a
follows the austenite precipitation. When the a phase
volume fraction increases, that of ferrite decreases and
that of austenite increases.
The results obtained from X-ray diffraction have
been used to construct the time-temperature-precipi-
tation diagram shown in Fig. 3. In addition to the a
phase, the starting point of austenite precipitation
(about 3% increasing in austenite volume fraction,
as detected by X-ray diffraction) is also presented. The
curves of o phase precipitation are of C-type, with a
nose at 850-900 °C. At these temperatures, the a
phase appears within 5 min and ferrite decomposes
completely after 30 min. Although the time-tempera-
ture-precipitation diagram is similar to those of
austenitic-ferritic duplex stainless steels [3, 7], the
precipitation in this steel is faster than those in other
cases. This is probably as a result of the higher
molybdenum and tungsten contents, which are found
to favor a phase formation much more strongly than
does chromium [4].
 J. Li et al.
i00
1100°Cxlh W.Q + 8 0 0 ° C x t
Lo
o_
8O
D
# c~
• A /
u_
o BOO
f~
H w
OZ
~ 1~ 2~ 310~
AGING TIME
Fig. 2. Fractional variations of 6, }, and o phases with annealing
time at 800 °C, based on X-ray diffraction data.
3.2. Morphology and chemical composition of the
phase
Figures 4(a)-4(c) show the morphology of the o
phase at different stages of precipitation. In an austeni-
tic-ferritic duplex stainless steel, o phase particles
normally nucleate at the ferrite-austenite interfaces
and grow into the adjacent ferrite grains, developing a
cellular structure consisting of the o phase and new
austenite. In the former austenite, as far as the optical
microscopic observation is concerned, only traces of
the o phase can be identified at the grain boundaries
after complete ferrite decomposition.
The EDXS results for the ferrite and austenite of the
specimen after solution treatment are shown in Table
2, and the results of chemical analysis of the o phase
precipitates extracted after isothermal annealing at
800 °C for different times are shown in Table 3. From
these data listed in Tables 2 and 3, the chromium and
molybdenum enrichments in the o phase are remark-
able. The variation in chemical composition of the o
phase precipitates indicates that the molybdenum con-
tent is a function of time. As the molybdenum content
in the o phase increases, the chromium content
decreases.
3.3. Effect of o phase precipitation on mechanical
properties
Figure 5 shows the effects of the o phase and
temperature on the tensile properties for specimens
containing no o phase (as-solution-treated) and 16% o
phase (annealed for 20 min at 800 °C). The variations
in strength and ductility with temperature are signifi-
cant. In both cases, the strength decreased with increas-
ing temperature. However, the characteristics of the
reduction in area vs. the temperature are quite different
/ o Phase precipitation and mechanicaI properties 151
~100 1100°Cxlh W.Q +_xtT _- --_
- - f e r r i t e ~ austenite
/ o.~" o,~
-~000 '~ • • " " • ...... • 1%o
' / - ~ - - ~ 5%~
o
cc ~.o •J,o 6.0 ~2 016..C 30
k~
... ,~
• "/4
70o 2 , 5, , 10 , 2o 3o 6~ 1£0
AGING TIME (min)
:C~I 6 10
Fig. 3. Time-temperature-precipitation of o phase ill a duplex
stainless steel, based on X-ray diffraction data.
(min)
in the two cases examined. For a specimen containing
16% o phase, the ductility decreases progressively with
increasing temperature over the entire temperature
range investigated. In contrast, for the as-solution-
treated sample, the ductility decreases with increasing
temperature before rising again, so that a minimum
appears on the curve of ductility vs. temperature.
The microstructures in longitudinal cross-section
ch)se to the fractured surface after testing at 1100 and
600 °C are illustrated in Figs. 6(a) and 6(b), respect-
ively, for the specimens without any o phase. Although
the reductions in area are reasonably high (95% and
70%), the grain size of austenite in these two cases is
quite different. When deforming at 600 °C, austenite
islands were elongated extensively along the tensile
axis, while, at 1100 °C, the austenite islands underwent
less deformation before fracture occurred. This can be
seen by comparing Figs. 6(a) and 6(b) with Fig. 1.
The Vickers hardness of the y and 6 phases at room
temperature in the deformed zone are HV 230 (7), 260
(6) and HV 320 (y), 260 (6), respectively, before and
after tensile testing at 1000 °C. These values indicate
that ferrite could be fully dynamically recovered during
testing, while austenite partially retains its work hard-
ening. In the temperature range 600-1000 °C, the self-
diffusion rate in the ferrite is about 100 times that in
the austenite [8]. The remarkable difference in
recovery kinetics could be responsible for this argu-
ment.
Figure 6(b) shows that, at about 600 °C, both the
ferrite and austenite were plastically deformed to
approximately the same degree. When the temperature
rises, ferrite can recover more easily than austenite
during the deformation process. The difference in
deformation behavior between the 7 and 6 phases
increases and the ductility of the duplex stainless steel
decreases with temperature. Despite this, the ductility
is improved at even higher temperatures, e.g. 1100 °C,
where ferrite dominates the deformation process.
 152 J. Li et al. / a Phase precipitation and mechanical properties

The effect of the o phase on the mechanical proper-

ties is significant at lower temperatures, e.g. 600 °C;
however, this effect quite strongly depends on tempera-
ture, as can be seen in Fig. 5. At higher temperatures,
e.g. 900 °C, the ductility and ultimate tensile strength
(UTS) for both solution-treated and annealed speci-
mens are very near. The reduction in area against
temperature curve for the annealed specimen shows no

c
TABLE 3. Phase composition (wt.%), determined by chemi-
cal analysis, for specimens annealed at 800 °C

Annealing time Si Ni Cr Mo Cu
(min)

8 0.48 3.50 37,12 5.70 0.15

12 0.50 3.51 35.70 7.02 0.16
20 0.53 3.73 33.34 7.86 0.17
100 0.58 3.72 31,15 8.35 0.16

,600.@

400
S"
E

-300 \ \

t~

E-,
.200 ~@
.:too @~'~'~
0 6(pO 7qO 8qO 900 lqO0 11p0

-:too (;,/,
0

"80 0~/ .
Fig. 4. Typical microstructure of specimens after annealing for a
phase precipitation: (a) 800 °C for 8 min, following solution
treatment; (b) 800 °C for 20 min, following solution treatment;
(c) 800 °C for 30 min, following solution treatment. ~:

40 ~ | o 0 ~ o

TABLE 2. Ferrite and austenite composition (wt.%), deter- 20"~~ @16 % o

mined by EDXS
6~)0 7q0 8013 91~0 10~30 :tlp0
Phase Si Ni Cr Mo Cu
TEMPERATURE (°C)
Ferrite 0.46 5.49 28.03 4.28 0.41 Fig. 5. Variation of tensile properties with deformation tempera-
Austenite 0.39 9.27 25.18 2.79 0.76 ture: o, specimens solution treated at 1100 °C for 1 h; o, speci-
mens annealed at 800 °C for 20 min.
 J. Li et al. / a Phase precipitation and mechanical properties 153

-700 0 /

600
E
• 500--~ ~ 0 0 0 6(]0 C
• 900°C
.400

,BOO

/ -
200 / ~ /

- EO0

0 10 20
[) I I i I I I

\ Ov
-7O
O ~ 0 600%
-G~..~......~xX • .9oooc

.10

(b) I 100 r, P , i,o , 2?

Fig. 6. Microstructure in longitudinal cross-section close to the FRACTION OF SIGNA PHASE (%)
fractured surface, showing specimens after being solution treated Fig. 7. Variation of tensile properties at 600 and 900 °C with
at 1100 °C, followed by water quenching: (a) deformed at volume fraction of a phase.
110(/°C (95% reduction in area); (b) deformed at 600 °C (70%
reduction in area).

turning point. T h e ductility increases monotonically

with temperature. In this case, the a phase in the
annealed steel is the dominant factor in the ductility.
T h e difference in deformation behavior between the
ferrite and austenite phases, which caused a minimum
in the ductility in the as-solution-treated specimen, was
suppressed here by the hard and brittle a phase.
To evaluate the effect of the a phase content on the
mechanical properties, the reduction in area and UTS
at two temperatures are plotted as a function of the o
phase fraction in Fig. 7. At 600 °C, the reduction in
area decreases from 70% to as low as 5% when the
fraction of a phase raises from 0% to 26%. However, at
900 °C, this variation is not significant. Only a slight Fig. 8 Fracture surface of specimen after solution treatment at
1100 ~C. followed by water quenching, and deformation at
decrease in ductility is shown when the fraction of o 600 °C.
phase increases from 0% to 26%.

3.4. F r a c t o g r a p h y from the decohesion of the inclusion-matrix interfaces,

A typical example of a fractured surface in the solu- exhibit high ductility. Indeed, deep dimples with fine
tion-treated condition tested at 600 °C is shown in Fig. structure lines are clearly shown in Fig. 8. T h e size and
8. Transgranular ductile dimples, which originated distribution of these lines correspond to the deformed
 154 J. Li et al. / cr Phase precipitation and mechanical properties

substructures, such as slip bands or subgrains, in the
austenite as well as in the ferrite. The longitudinal
section of this sample, which appears to be of excellent
quality, is shown in Fig. 6(b).
In contrast, the fracture surface of the same kind of
specimen exhibits relatively poor ductility when
ruptured at 900 °C (Fig. 9(a)). The longitudinal section
of this fracture is also shown in Fig. 9(b). In this case, a
large number of voids were formed around the )'-6
interfaces close to the fractured surface. These voids
were linked by shear fracture of the ferrite, with cracks
propagated in directions along the tensile axis as well
as at about 45 ° to it. Austenite islands are surrounded
by the more ductile ferrite at 900 °C. The decohesion
of austenite from the ferrite matrix has occurred and
can be clearly recognized, as indicated by the arrows in
Fig. 9(b). Only the ferrite phase is responsible for the
final ductile fracture. Less deformation substructures
are observed on the dimples in Fig. 9(a) (unlike the
fracture at 600 °C, where both phases took part in the
final fracture and more plastic deforamation has taken
place before failure). The decline in ductility with
increasing temperature in the range 6 0 0 - 8 0 0 °C can
also be explained in terms of this fracture mechanism.
Figures 10(a) and 10(b) present the fracture surface
and longitudinal section of a specimen annealed at
800 °C for 20 min (16% o phase) and tested at 600 °C.
Very low elongation has been observed. The appear-
ance of the fracture surface was granular and no ductile
dimples could be observed. Cleavage cracks were
linked by thin shearing fracture, where austenite was
plastically deformed; however, ductile austenite could
not compensate for the brittleness of the a phase.
Many "river" patterns are visible on the cleavage
facets, as shown by the arrows in Fig. 10(a). In the
longitudinal section (Fig. 10(b)), transverse micro-

Fig. 9. (a) Fracture surface and (b) corresponding microstructure in the longitudinal cross-section of specimen after solution treatment
at 1100 °C and deformation at 900 °C.

Fig. 10. (a) Fracture surface and (b) corresponding microstructure in the longitudinal cross-section of specimen after solution treatment
at 1100 °C, annealing at 800 °C for 20 min and deformation at 600 °C.
 J. Li et al. / o Phase precipitation and mechanical properties 155

cracks across the o-austenite cellular structures are
formed by brittle fracture.
However, a specimen with the same structure as that
shown in Fig. 10(b) exhibited ductile fracture when
deformed at 900 °C, as can be seen in Fig. 1 l(a). The
longitudinal section of this specimen close to the frac-
ture is shown in Fig. 1 l(b). In this case, although voids
formed by the decohesion of ~-austenite interfaces,
the orientation of the o phase had been changed during
the deformation process. By comparing Fig. 1 l(b) with
Fig. 4(b), it is clear that the o phase particles had
realigned in the direction about 45 ° to the tensile axis
after deformation. This contrasts with Fig. 4(b), where
the o phase bands are perpendicular to the d - 7 inter-
face.
The realignment of the a phase demonstrates that
quite an amount of ductility was preserved in the
former ferrite region, where large amounts of ~ phase
particles existed. On the fracture surface, fine dimples
corresponding to the shearing process are displayed in
Fig. l l(a). Furthermore, when a specimen with the
same structure as that shown in Fig. 10(b) was
deformed at 1000 °C, plastic shearing predominates in
the fracture surface, which declines in a direction about
45 ° to the tensile axis, indicating excellent ductility (Fig.
12(a)).
The corresponding microstructure (Fig. 12(b))
showed that no a phase was present. Nevertheless, a
very fine secondary austenite phase can be observed in
the former ferrite regions. There are two possible reac-
tions responsible for this phenomenon. Firstly, the o
phase is dissolved at 1000 °C but the secondary
austenite formed by the eutectoid reaction d - - ' o + 7
remains partially. Alternatively, ferrite, which is

Fig. 11. (a) Fracture surface and (b) corresponding microstructure in the longitudinal cross-section of specimen after solution treatment
at 1100 °C, annealing at 800 °C for 20 min and deformation at 900 °C.

Fig. 12. (a) Fracture surface and (b) corresponding microstructure in the longitudinal cross-sections of solution treatment at 1100 °C.
followed by water quenching, annealing at 800 °C for 20 min and deformation at 1000 °C.
156 J. Li et al. / o Phase precipitation and mechanical properties
thermodynamically unstable at 1000 °C, may trans-
form to austenite. This process would be accelerated
by plastic deformation during testing.
At this point, ferrite was hardened slightly by the
dispersion of secondary austenite. This results in a
higher UTS of the annealed specimen than that of a
specimen without previous o phase precipitation, as
can be seen in Fig. 5. Granular roughening on the frac-
ture surface corresponds to this dispersion in some
places, as indicated by an arrow in Fig. 12(a). An exam-
ple of the microhardness measurements is shown in
Fig. 12(b), where the sizes of the Vickers hardness
indentations within the ferrite and austenite demon-
strate clearly the difference between these two phases.
After hot deformation at 1000 °C, austenite is much
harder than ferrite, although it is well known that, in
the solution-treated condition, these values are
reversed.
4. Conclusions
(1) The o phase has C-curve transformation
kinetics with a minimum transformation time of the
order of 5 min at 850-900 °C.
(2) After nucleation at the austenite-ferrite inter-
face, the o phase grows into the ferrite in a cellular
morphology. As the o phase grows, its molybdenum
content increases and its chromium content decreases.
(3) The ductility of the steel in the solution-treated
condition presents a minimum value at 800-900 °C.
(4) The o phase embrittlement depends on the a
phase content even more strongly than on the deforma-
tion temperature.
(5) At temperatures below 600 °C, the ductility is
greatly reduced by o phase precipitation.
(6) During deformation at higher temperatures, e.g.
900 °C, the o phase particles are realigned in the shear-
ing direction and the final fracture exhibits a ductile
morphology with a large reduction in area.
(7) The effects of o phase precipitation on the
mechanical properties disappear at 1000 °C.
Acknowledgment
The authors wish to thank Fabrique de Fer de
Charleroi for supplying the alloy used in this study.
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