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Thermal and mechanical treatments effects on phase

transformation in duplex stainless steels

Authors:

Irene Calliari1,a, Emilio Ramous1,b, and Massimo Pellizzari i2,a


1a, 1b
DPCI, Via Marzolo 9, Padova, Italy
2a
University of Trento,Povo-Mesiano, Trento, Italy

Contact details:

irene.calliari@unipd.it, emilio.ramous@unipd.it, Massimo.pellizzari@unitn.it

Keywords:

duplex, phase transformation, heat treatment, martensite

Abstract.

This paper concerns the phase transformation induced by heat treatment and cold rolling
in duplex stainless steels with different compositions. In the 2205 and 2507 grades,
during the isothermal heat treatments, chi-phase precipitates as small particles at the
ferrite/austenite boundaries, followed by sigma precipitation. At the lowest temperature
the kinetic of chi-phase is favoured, with the increasing of time and temperature a
progressive transformation of chi to sigma occurs and the kinetic of sigma is favoured.
During continuous cooling, the chi -phase appears at the lowest cooling rates.
In the low Ni grades (2101 and 2304) the grain boundaries precipitation of chromium
nitrides were detected, but no sigma and chi. In 2101 the austenite transforms to
martensite both after cold rolling and quenching
Introduction

Duplex stainless steels belong to the stainless steels family and are characterized by a
dual-phase microstructure with an almost equal parts of austenite and ferrite [1, 2],
which give them a favourable combination of mechanical and corrosion properties. This
microstructure results from a ferrite->austenite solid phase transformation and is
obtained by an accurate balance of chemical composition and heat treatment. Starting
from a fully ferritic structure, the solid state transformation occurs during cooling and the
resulting phases have different chemical composition: with austenite Ni and N enriched
and ferrite Cr and Mo enriched. This transformation is diffusion controlled and other
phases may precipitate at the grain boundaries in the range 450-1000C: they are
mainly sigma, chi, secondary austenite and nitrides [3, 4].
These precipitates cause a strong deterioration in toughness and corrosion resistance
[5, 6], it has been demonstrated that over 2% secondary phases the toughness of duplex
steels is reduced to values too low for practical applications but some features of the
early stages of precipitation are not yet well understood. The amount of the secondary
phase is related to chemical composition, to cooling rate and to the higher diffusion
ratesof Cr and Mo in the ferrite than in the austenite.
In order to estimate the volume fraction of each phase and their temperature range
stability, some phase diagrams, calculated from thermodynamic data with simulation
program, have been published for the many grades [7]. It is ascertained that as the
temperature increases the amount of ferrite increases and consequently the amount of
austenite decreases, and the formation of sigma chi and nitrides, when it occurs, take
places at 600-900C.
The ranges of each phase stability and their volume fractions are different and depend
on chemical composition of steels, as confirmed by experimental data with several
studies reporting the effects of ageing and continuous cooling experiments on 2205 and
2507 [8, 9]. The kinetics and sequence of precipitation are different with the noses of the
CCT curves from 850 to 950C; in both the grades the cooling rate, solubilisation
temperature and thermo mechanical history affect the fractions and kinetic of
precipitated phases. The quantitative data of volume fractions are otherwise affected by
measurements procedure. Efforts have been made over the years to determine the
volume fraction of sigma phases in austenitic stainless steel and in duplex grades, but at
now it is quite difficult to identify separately chi and sigma and to quantify accurately low
amounts of such phases
These statements confirm that the investigation of the solid state transformation during
cooling plays an important role both for basic physical metallurgy and for technological
aspects: during the production process the solubilisation is the final heat treatment,
aimed to optimize the ferrite /austenite ratio and to redissolve the secondary phases.
The kinetics during cooling after solubilisation affects the maximum size of the bars or
billets which can be produced without dangerous phases. A very low cooling rate may
determine different microstructures from surface to core, especially in large sized bars,
with a surface free of secondary phases and a core with significant amount of them.
Therefore the critical cooling rate for each grade should be determined in order to avoid
or to limit precipitation at core.
The dual phase structure of duplex could rise to both phase transformation : the sigma,
chi and nitrides formation mainly involve the ferrite transformation by diffusion
mechanism and lattice arrangement, while in austenite could occur a martensite
transformation induced by cold working, as well known in fully austenitic stainless steels.
Some preliminary studies have been published, concerning the low Ni grade 2101 [10].
This alloy has been recently developed for structural and transport applications,its Ni
content is about 1%, so the alloy is cheaper than the traditional ones but it is promising
for its good mechanical and corrosion resistance properties. The Ni gamma-stabilizing
role is partially compensated by Mn and N addition, but the resulting austenite could be
instable.

At the moment a lack of investigation exists on the physical metallurgy, concerning the
phase stability, which correlate the phase transformation with all the experimental
parameters (heat treatment temperature and time, cooling media), chemical composition
and phase ratio.
In the present paper the results concerning the formation of secondary phases and
austenite transformation in commercial DSS (2205, 2507, 2101 and 2304) are
presented.

Experimental part

Four steels of different composition were considered: two highly alloyed steels, 2205 and
2507, and two low Ni grades, 2101 and 2304. The chemical compositions are reported in
Table 1.

C Si Mn Cr Ni Mo Cu W P S N
2205 0.030 0.56 1.46 22.75 5.04 3.19 - - 0.025 0.002 0.16
2507 0.030 0.43 0.54 24.48 6.36 4.0 0.67 0.72 0.020 0.008 0.263

2101 0.026 0.69 3.95 22.57 1.1 0.07 - - 0.03 0.001 0.13
2304 0.03 0.56 1.4 23.20 4.3 0.18 - - 0.027 0.001 0.10

Table 1: chemical composition of the examined steels (wt %)

Isothermal heat treatments were carried out for 102-104 sec., in the 700-1000C
temperature range followed by water quenching, while continuous cooling tests have
been performed in a Setaram Labsys TG machine, in Argon atmosphere. Samples
(diameter 6 mm, length 8 mm) were solution treated (5 min) at temperatures of 1020-
1080C, cooled in Argon in the range 0.02-0.7C/s.
Cold rolling was performed to 10-85% final thickness reduction. Characterization of the
samples was performed by OM, SEM (EDS and BSE), XRD, TEM and EBSD. The
secondary phases have been identified by SEM-BSE signal and quantified by image
analysis. The chemical composition of the phases was determined by SEM- EDS.

Results and discussion

2205: effects of isothermal treatment


In the SEM-BSE images, ferrite and austenite appear in the background, with the ferrite
darker than the austenite; the secondary phases appear as small bright regions (the -
phase brighter than the -phase). Their quantitative measurement is actually reliable on
samples treated at 850 and 900C (Fig.1) and the precipitation sequence can be
summarized:
780 C: the first precipitates appear after 30' ageing and become more evident
after 40', with small bright particles identified as chi by EDS, just within the beam
resolution limit.
850 C: chi appears after 10', while sigma after 20'; after 30'chi and sigma are
both present: chi is always at the boundaries / and /. Sigma penetrates the
ferrite or grows along the / boundary...
900 C: also at this temperature chi is the first precipitating phase, generally
decorating the grain boundaries. By increasing the time, the amount of chi
increases and also sigma appears, in the form of coarser precipitates at the /
boundary, but growing into the ferrite (Fig.2). Although sigma particles are, at the
beginning, less numerous than the chi particles, they are coarser, and grow more
rapidly, quickly reaching almost the same volume fraction. By increasing the
time, sigma grows to large particles, moving from the boundaries into the ferrite,
embedding some small chi particles. This looks like a progressive transformation
of chi to sigma (Fig.3).

Fig. 1: amounts of secondary phases in 2205 after 900C treatment

Fig. 2: SEM-BSE micrograph of a 2205 sample treated for 30 at 900C


Fig 3 SEM-BSE micrograph of a 2205 sample treated for 40 at 900C with chi
transforming to sigma

The transformation of chi to sigma phase is faster at 900C than at 850C, as the
diffusion coefficients of Mo and Cr are higher than at 850C, and the lattice arrangement
from cubic -phase to tetragonal -phase is favoured. Moreover, these considerations
confirm and suggest that chi could act as preferential sites for the sigma nucleation [11].
The effect of secondary phase precipitation has been investigated by the Charpy
instrumented test and by hardness test [10] and a drastic droop of toughness (from 250J
to 50J) was verified at very low intermetallic phases (0.5-1%) before sigma formation,
when only a few small chi particles can be detected by metallographic techniques
(2500X, SEM-BSE image). On the contrary, low intermetallic contents scarcely affect the
hardness values.

2205: effects of continuous cooling after solubilisation

The morphology and localization of the new phases after continuous coolings are very
similar to that observed in the isothermal ageing tests (the precipitation occurs at the
alfa/gamma grain boundaries and at the triple points), while the formation sequence of
secondary phases seems to be different.
The total amount of secondary phases is the lowest for the highest solubilisation
temperature, in agreement with [9], and is strongly dependent both on the cooling rates
and on the solubilisation temperature. The critical cooling rate for sigma formation is
0.35C/s, when a final sigma content of 0.2% is obtained. With a further lowering of the
cooling rate, the sigma content gradually increases and at about 0.1-0.15C/s a small
amount of chi appears. Therefore the chi appears at lower cooling rates than the sigma.
The final amount of sigma and chi is strongly dependent on the solubilisation
temperature. The sigma amount is higher in the samples treated at 1020C, the lowest
solubilisation temperature. On the contrary, the chi amount is larger in the samples
quenched from 1050C, the highest temperature.
Fig.4 SEM-BSE micrograph of a 2205 sample cooled at 0,35 C/m

2507: effects of isothermal treatment:

The effects of ageing in the range 850-1000 C can be summarized:


800C: no precipitation has been detected,
850C: chi-phase is the only one phase to precipitate at the alfa/gamma (volume
fraction <0.1%).
900C: chi and sigma are present, but the formation kinetic of chi -phase is favoured
(Figs 5 and 6)
950C chi is the first phase to precipitate after 3, followed by sigma after 5. By
increasing the holding time, sigma grows to large particles, moving from the
boundaries into the ferrite, embedding some small chi particles. The progressive
transformation of chi to sigma occurs mainly after 4800s but the ferrite transformation
is not complete.
1000C ageing: After 5 chi and sigma are at grain boundaries and inside the ferrite
grains ( 0.5%). By increasing the time, the chi content slowly decreases while sigma
amount rises its maximum value (4%) after 15. These data confirm that the 2507
grade must be solubilised at T>1050, if the phase free structure is mandatory. In all
samples treated at 900-950C small nitrides were detected at grain boundaries. It
can be explained as during quenching N probably diffuses from ferrite to austenite
but the high density of dislocations may obstacle its diffusion and the nitrides
precipitation is favoured.

Figs 5 and 6: SEM-BSE image of 2507 treated at 900C for 5 (left),and at 950 for 80
with small nitrides and the chi-phase transforming to sigma phase
In this grade chi transforms to sigma and the transformation is faster at 950C than at
900C and the nose of the TTT curve is approximately at 950C.At all the temperatures
the total amount of secondary phases is about 3% after less than 10.It may be
dangerous as, in a previous paper [12], a drastic drop of toughness in a 2205 with 1% of
secondary phases has been measured. The shift of the curves nose to high temperature
of the 2507 grade can be justified by the highest alloying elements content.

Fig. 7: Volume fractions of secondary phases in 2507 aged at 950C

2507: effects of continuous cooling after solubilisation:

The effects of continuous cooling treatments can be summarized


the amount of secondary phases and the relative morphology are quite similar for
both the solution temperatures; the secondary phases volume fraction increases
if the cooling rate decreases the total amount is slightly lower for the highest
solubilisation temperature (1120C), in agreement with the results obtained for
2205
no nitrides neither carbides are detected.
it is not possible to asses the cooling rate corresponding to precipitation less than
1%, but it can be estimated to be 0.8-0.9Cs-.

The work is in progress in order to determine, by simulation program, the maximum bar
size of each grade that can be obtained after solubilisation with a non dangerous phase
content.

2101 and 2304: effects of isothermal treatment:


600 C and 650C, for t> 2400s some small dark particles were detected at the
ferrite grain boundaries. They were identified by TEM and SEM-EDS chromium
nitrides.
750 C: nitrides precipitation has been detected in the range 103-105 s,
increasing the temperature, particles became larger (Fig. 8), no sigma or chi
were detected

In 2304 at 750 and 850C for t>2400s nitride precipitation is also evident just below the
austenite grain boundary, as they have moved towards the austenite giving the
precipitation inside the austenite grains. A similar grain boundaries precipitation was
observed after long treatment (10 hrs) at 850C but the kinetic is slower than at 750C.
The main effect of the 600-850C treatment on 2304 is the increasing of the austenite
volume fraction, with values from 44% (as received) 62% ( 850C, 15 hours),
accompanied by a decreasing of the austenite Cr content and by its ferrite increasing.
These results confirm that in 2101 and 2304 no sigma and chi precipitation was
observed, neither after long time exposures in the temperature ranges 650-900C,
typical of the phases formation in the common DSS. Indeed the reduction of Ni and
mainly of Mo contents seems to allow avoiding the precipitation of intermetallic phases.
These results partially agree with Thermocalc (Fig. 9) and Lee [13] calculations, showing
for T>800C ferrite austenite and no sigma, while for T<800C our experimental data do
not confirm the Thermocalc calculations which indicate the substitution of austenite by
ferrite, sigma (about 30%) and nitrides. Any -phase precipitation nor significant
transformation of austenite to ferrite has been verified in the range 600-800C after 50-
100 hours ageing The main microstructure modifications observed during isothermal
annealing is the nitrides precipitation (in good agreement with Thermocalc) which occur
in rather short times. More generally the resulting microstructures are established after
few hours of treatment, depending on temperature value, and do not change further,
also during treatments of some hundreds hours. These results confirm that the solution
annealing treatment allows obtaining a microstructures close to the equilibrium ones.

Fig. 8: SEM-BSE image of 2101 (750C, 60)

Fig. 9: 2101 phase diagram (Thermocalc) of 2101


In these lean DSSs the lack of dangerous phases precipitation allows to avoid the
consequent drop of the toughness; therefore the impact energy after isothermal
treatment in the 2101 grade is never lower than 30 J, while in the 2304 is never lower
than 200 J, the impact toughness after solution annealing treatment is very good and
after isothermal treatment the impact energy is never lower than 50 J.

Martensitic transformation

Small amounts of martensite laths in 2101 have been detected, both after cold rolling
(Fig.10) and after quenching from 750-850C, as revealed by OM and XRD. The
increased manganese content may induce the instability of the austenite, as suggested
in previous researches, which report of a probable transformation to martensite during
cold forming [11]. Moreover the martensite formation has been confirmed [14] in some
low-Ni DSS after cold rolling and annealing (1040C, air quenched).In the 2304 grade
the austenite is more stable, having higher Ni content and martensite transformation was
not detected. An accurate investigation of the structure of the martensite is in progress,
to determine the lattice parameter and the crystallographic orientation.

Fig.10: martensite laths in 2101>


Top: 750C, 1500s, WQ. Bottom: cold working 25% reduction
Conclusions

The 2205 and 2507 grades are very prone to chi and sigma precipitation in the
range 800-1000C, with chi as the first precipitating phase, and a progressive
transformation of chi to sigma.
The noses of the TTT curves are at 900C (2205) and 950C (2507)
The critical cooling rate in 2205 is about 0.35C/s, in 2507 can be estimated about
0.8-0.9C/s
The 2101 and 2304 are not prone to sigma and chi precipitation, only nitrides
were detected
The austenite to martensite transformation has been evidenced in 2101 after
thermal treatment and after cold rolling.

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