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SECONDARY PHASES PRECIPITATION IN

DUPLEX STAINLESS STEEL WITH
WIDMANSTATTEN AUSTENITE
MICROSTRUCTURE
Conference Paper September 2001

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Image Anal Stereol 2001;20(Suppl 1):151-156

SECONDARY PHASES PRECIPITATION IN DUPLEX

STAINLESS STEEL WITH WIDMANSTATTEN AUSTENITE
MICROSTRUCTURE
ZORICA CVIJOVI, ABDULWAHAB MA IBRAHIM AND DRAGINJA MIHAJLOVI
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O.Box 3503, 11120
Belgrade, Yugoslavia
e-mail: zocvij@elab.tmf.bg.ac.yu
ABSTRACT
The extent and kinetics of secondary phases precipitation in Widmanstatten austenite (WA)
microstructure of a cast 26.6Cr-7.6Ni-2.5Mo-2.9Cu-0.06C duplex stainless steel (DSS) heated in
the 750oC to 1100oC temperature range were quantified in order to determine the thermal stability
of this steel. It was established that the WA microstructure with the ratio of : = 89-85:11-15 and
32.0-34.0 vol.% metastable -ferrite is very unstable and susceptible to secondary austenite (2),
M23C6 carbide and -phase formation. The nucleation of 2 and carbide is more favorable and
faster than the nucleation of -phase. However, at all temperatures the -ferrite decomposition is
primarily attributed to the -phase formation. On the other hand, its amount varies significantly
with the annealing temperature. The estimated value of VV first increases with increasing
temperature, reaches a maximum in the intermediate part of the investigated temperature range and
then decreases as temperature further increases. A similar acceleration in the rate of -phase
formation was found. At 800oC and 900oC the process kinetics are so fast that the precipitation is
almost complete within 120 min. This indicates that reaction displays the classical C curve
behavior. From a drawn TTT diagram, the -phase precipitation is fastest at about 950oC. During
isothermal annealing 5 vol.% of -phase is expected to form after about 6 min at this temperature,
while almost 85 min is required to form 95 vol.%.
Keywords: duplex stainless steel, heat treatment, precipitation kinetics, secondary phases, TTT
diagram, Widmanstatten austenite microstructure.

INTRODUCTION
The need for high strength and corrosion resistance in chloride-containing media has made duplex
stainless steels (DSSs) composed of -ferrite and -austenite an attractive alternative to the singlephase ferritic and austenitic grades (Walker, 1988; Sedriks, 1989). Since these materials offer a
remarkable combination of properties, they are suitable for many industrial applications. However,
some problems can appear due to microstructural modifications provided by inappropriate heat
treatment or prolonged exposure at elevated temperatures. Namely, during heating the precipitation of
various secondary phases, like secondary austenite (2), chromium carbides, nitrides and some other
intermetallic phases, such as -phase can take place, causing the time-dependent degradation of the
material (Shek et al., 1994; Nilsson et al., 1996; Cortie and Jackson, 1997). The unequilibrium
microstructure produced in a weld metal by higher cooling rate is particularly sensitive to subsequent
heating. The metastable -ferrite may decompose, leading to decrease in the weld metals properties.
The presence of undesirable secondary phases is especially detrimental to the localized corrosion
resistance (Nilsson et al., 1995). The balance of alloying elements corresponding to equal pitting
resistance in -ferrite and can be disturbed even by excessive precipitation of 2, having a different
composition from the primary (Cortie and Jackson, 1997). Hence, a through knowledge of the
kinetics of precipitate formation is important in determining the heat treatment and cooling rates
required during production to ensure a precipitate-free material.

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Of the secondary phases mentioned above, -phase is by far the most important because of its
large volume fraction, and its adverse effect on the embrittlement and corrosion resistance of DSSs
(Kuroda et al., 1999). However, the tendency toward -phase formation, as well as the precipitation
kinetics, mechanism and stability range of -phase may vary considerably, depending on the exact
steel composition (Kotecki, 1989; Tseng et al., 1994). Thus, the precipitation of -phase is accelerated
by increased amount of chromium and molybdenum, as a result of which C curve of -phase are
shifted toward to shorter times (Kuroda et al., 1999). Moreover, Kotecki (1989) reported that
increasing chromium and molybdenum in nickel-rich DSSs causes not only the faster precipitation
kinetics, but also a higher dissolution temperature of -phase. On the other hand, a few alloying
elements such as copper and nitrogen are known to retard the -phase formation (Nilsson et al., 1996).
Another factor that may influence the -phase precipitation behavior is the size and shape, i.e., the
crystallographic characteristics of / interfaces as the preferential nucleation sites (Kokawa et al., 1989).
Consequently, it is necessary to clarity the behavior of -phase precipitation in high alloy DSSs
and their weld metal. As little data concerning this topic are available for commercial steels, this
investigation was undertaken to examine in detail the effects of annealing temperature on the kinetics
of secondary phases precipitation in 26.6Cr-7.6Ni-2.5Mo-2.9Cu-0.06C DSS solidified at moderate
high cooling rate, which approaches those achieved in the weld metal. In addition, the goal was to establish
time-temperature-transformation (TTT) diagram with respect to the formation of dominant -phase.

MATERIAL AND METHODS

The base material used in this work was produced in the ordinary production process of an
industrial foundry by sand cast technique in the form Y blocks, each weighing 20 kg. Its chemical
composition is such that should promote the formation of -ferrite as the primary solidification phase.
In accordance to calculated Creq/Nieq ratio of 2.61, under equilibrium condition selected steel solidifies
in the fully ferritic (F) mode (Elmer et al., 1989). Just after the solidification, the steel attains a ferritic
single phase, which then undergoes a solid-state transformation to austenite. The low cooling rate of
the order 10-1 101 oC/s (Elmer et al., 1989), related to conventional casting process, enables the cast
structure to reach close to equilibrium state. Hence, the microstructure of the as-received cast block
consists of a -ferrite matrix with 39.0 vol.% austenite, 8.4 vol.% (total fraction) M23C6 carbide and phase particles as well as small amounts of non-metallic inclusions. Namely, the cooling time is long
enough for diffusion-controlled processes, leading to precipitation of secondary phases. These phases
normally appear after reheating to high temperatures, but high carbon content of the steel studied
makes it more feasible for carbide and -phase to precipitate.
In order to realize a faster cooling during solidification and subsequent solid-state transformation,
the surface melting by the gas tungsten arc (GTA) welding techniques was performed on small
specimens (151510 mm) each cut from the bulk of the as-received block. After stationary remelting
carried out under the following conditions: current 120 A, voltage 12 V, arc time 20 sec, the specimens
were air cooled to room temperature.
The microstructural changes that occur after heat treatment of the resolidified material were
examined in the central zone of the upper parts of the surface melted layer. Annealing of GTA melts
was carried out in a muffle furnace in air at temperatures from 750oC to 1100oC. After holding at each
temperature for 30 min, the specimens were quenched into water. Since these experiments showed that
the transformation of -ferrite is the fastest in the intermediate part of this temperature range, all
subsequent studies were performed on GTA melts isothermally annealed at 800oC, 900oC and 980oC
for periods of time from 5 to 120 min followed by water quenching.
Phase identification and image analysis were undertaken after electrolytic etching in aqueous 20%
sodium hydroxide solution. The volume fractions of , and -phase were estimated for every
microstructural state using the line-intercept method. No attempt to quantify the volume percentage of
M23C6 particles was made, owing to the fact that the carbides were, in general, too small to be fully
resolved by light optical microscopy (LOM). Based upon these results, the kinetic curves and TTT

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diagram for precipitation of -phase were drawn. The Avrami curves were found to be suitable to
establish the TTT curves, since they could be used for extrapolating to shorter times and for
interpolating between discrete experimental values.

RESULTS
The initial as-resolidified microstructure of the GTA melts is presented in Fig. 1a. Apart from the
non-metallic inclusions, the austenite (white) and particles of secondary phases in the form of lamellar
structure observed in a -ferrite matrix (relatively dark).

(a)

(b)

(c)

Fig. 1. LOM micrographs of a GTA melt before (a) and after annealing at 800oC for 15 min (b) and
900oC for 30 min (c) showing the presence of austenite (a = austenite allotriomorphs, w =
Widmanstatten type austenite, i = intragranular austenite), -phase and mixed constituent (M) of
M23C6 carbide and austenite in the matrix of -ferrite.
A fine mixed structure (M) generally formed at slightly curved boundaries could not be clearly
resolved. Based on the morphological appearance of precipitated particles, which is consistent with a
lamellar structure formed in a base material and proposed model for M23C6 formation by eutectoid
reaction (Shek et al., 1994) it is concluded that the fine particles presented in a mixed constituent are
M23C6 carbides. No evidence of the -phase was found.
But, an increase in the cooling rate seems to have a very significant effect on the volume fraction
of the retained -ferrite and structure morphology. In addition to a reduction in the carbide content, the
higher cooling rate promotes a greater -ferrite and lower content to exist at room temperature. As a
result, the volume fraction of retained -ferrite is high and found to be 85.0 89.0 vol.%. The
microstructure consists of -ferrite grains, which are decorated by continuous networks of the
austenite allotriomorphs (a). The thin Widmanstatten type side plates (w) either nucleated from this a
layer or intragranularly within the grains growth along preferred crystallographic directions into the matrix, leading to a low-energy / boundary and higher boundary coherency. Within the grains, a fine
austenite precipitates (i) can be also observed. Regardless of the noticed differences in morphology,
the fineness of resolidified microstructure is exceptionally increased.
A significant deviation from equilibrium results in a rapid decomposition of metastable -ferrite
during subsequent annealing. Figures 1b and c show the various stages of the -ferrite decomposition.
As can be seen, the precipitation proceeds extensively causing a drastic decrease in the volume fraction of
retained -ferrite. The precipitates are of three kinds, viz., 2, M23C6 carbide and -phase. At each
temperature a first transformation product is M23C6 formed by eutectoid reaction M23C6+2, Fig. 1b.
The increase in content of M23C6 particles already present in resolidified material indicates that this
reaction precedes nucleation of the -phase. The isolated intragranular 2 precipitates are also formed at
this stage. At later stages, the -phase formation was observed to occur. At temperatures up to 900oC,
the -phase precipitation was indicated by dark patches, Fig. 1b, which are (+2) aggregates. They are
composed of a numerous small particles densely packed on the curved / phase boundary sites and in
the process of growth with the new 2 into the adjacent -ferrite. Rarely, the fine particles precipitated in
the form of (+2) eutectoid structure were also formed ahead of the mixed (M23C6+2) constituent.

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Annealing at 900oC accelerates the formation of -phase particles by a typical eutectoid reaction
(Tseng et al., 1994), Fig. 1c. At higher temperatures, the -phase forms directly from the -ferrite.
But, although the nucleation of carbide is more favorable and faster than the nucleation of -phase,
the vast majority of precipitates are found to be -phase. Exposure of the GTA melts for 30 min
showed that the amount of -phase varies significantly with the annealing temperature, as indicated in
Table 1. Its formation is fastest in the intermediate part of the investigated temperature range.
Table 1. Amount of the -phase formed after 30 min of annealing at different temperatures.
Parameter
VV , vol.%

750
1.36

Annealing temperature, oC
800
900
1050
14.37
35.81
2.98

1100
1.41

At 800oC and 900oC the decomposition of -ferrite is so rapid that at both temperature is
essentially complete within the first 60 min and then a steady state is established, Fig. 2. At 980oC and
above, however, the precipitation of -phase is retarded so it is possible to speculate that this
temperature is close to the high-temperature plateau of the TTT curve. The corresponding TTT
diagram is shown in Fig. 3.

Fig. 2. Volume fraction of precipitated -phase

as a function of annealing time.

Fig. 3. TTT diagram for precipitation of phase in annealed GTA melt.

DISCUSSION
From the results reported here, it is evident that the microstructure of a cast DSS with main
composition in mass.% 26.6Cr-7.6Ni-2.5Mo-2.9Cu-0.06C is very sensitive to the variation in the cooling
rate during solidification. Namely, the increase of the cooling rate to the order 101 103 oC/s, typical for
conventional arc melting process (Elmer et al., 1989), does not change the F solidification mode. At this
cooling rate the investigated steel exhibited a same duplex (+) microstructure. The increase of the
cooling rate to this level, however, suppressed the subsequent transformation in solid state to a great
extent. The volume fraction of untransformed -ferrite is greater and found to be about 32.0 34.0 vol.%.
Besides the low realization of the transformation, the achieved cooling rate completely removed the
-phase and retarded the onset of M23C6 precipitation very significantly, so that the carbide volume fraction
is quite small, i.e., less than 1.0 vol.%. As a result, the WA plate-like morphology is obtained.
A highly metastable WA microstructure is prone to formation of -phase. As it can be seen from
the data presented in Table 1, this secondary phase is likely to be stable at temperatures up to or above
1100oC. The amount of precipitated -phase increases rapidly with annealing temperature and reaches
maximum of 35.81 vol.% at the 900oC. At higher temperatures, however, the -phase precipitation is

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retarded, so that after 30 min at 1100oC its content is about 25 times lower than that at 900oC. Thus, to
eliminate -phase from the structure annealing temperatures of 1150oC or higher are appropriate.
The formation of the -phase is always preceded by M23C6 carbide precipitation and inhibits phase nucleation. Hence, the formation of -phase precipitates occurred after an incubation period.
The sluggish formation in early stage of transformation process is due to an absence of appropriate
heterogeneous nucleation sites. But, after 5 to 15 min, depending on the temperature, the amount of ferrite transformed to -phase increases rapidly with reaction time and temperature and reaches almost
a maximum of about 47.0 and 58.0 mas.% after 60 min of annealing at 800oC and 900oC, respectively.
The kinetics of -phase precipitation show an overall sigmoidal form, Fig. 2. Since after 120 min there
was no evidence of significant changes in amount of -phase, it is assumed that the material is not far
from equilibrium. Also, an increase in the amount of precipitated phases with increasing annealing
temperature at any given annealing time indicates that the process kinetics are faster at 900oC.
The transformation to -phase in the annealed material, as a function of time and temperature, is
most vividly illustrated on TTT diagram plotted in Fig. 3. It has been constructed by interpolating through
raw experimental data of the kind presented in Fig. 2. The times of VV/VVs = 5% and VV/VVs = 95%
are defined as the precipitation start and finish times (VV is the volume fraction of -phase formed
after time t, and VVs is the saturation level of -phase, i.e., the equilibrium volume fraction which
depends on temperature). These curves are typical C curves, with their noses at minimum times of
about 6 and 85 min, respectively. Although the exact nose positions are not established, it is apparent
that nose of precipitation is located at a temperature very close to 950oC.
There is also evidence that the precipitation rate and extent depend strongly on the composition of
the alloy, particularly, the key elements chromium and molybdenum, and on the amount of metastable
-ferrite. Namely, the precipitation of -phase in the chosen steel exhibiting WA microstructure is
much faster and much more than in a lathy ferrite (LF) microstructure of 22.5Cr-7.8Ni-2.3Mo-3.5Cu0.1N-0.08C DSS with 43.5 vol.% retained -ferrite and 10 vol.% metastable -ferrite, which has been
investigated in our earlier study (Cvijovi et al., 1999). An additional factor contributing to enhanced
formation of secondary phases in the case of WA microstructure is the lower / boundary coherency.
Despite the much greater amount of interphase boundary surface present in the LF microstructure
(Cvijovi et al., 1999), the easier precipitation in WA microstructure with the larger degree of semiand non-coherent /a boundaries suggests the nature of interphase boundary has a decisive influence
on the rate of precipitation reactions in the investigated steels.

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