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Intermetallic Phase Precipitation in Duplex Stainless Steels During High

Temperature Exposition

Conference Paper · August 2018

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 Intermetallic Phase Precipitation in Duplex Stainless Steels
During High Temperature Exposition

D. M. Escriba1,a, E. Materna-Morris2,b , R. L. Plaut1,c and A. F. Padilha1,d

1
Department of Metallurgical and Materials Engineering, University of S. Paulo, S. Paulo, Brazil
2
Institute für Materialforschung I, Forschungszentrum Karlsruhe (FZK), Karlsruhe, Germany
a
[email protected], [email protected], [email protected], [email protected]

Keywords: Precipitation, duplex stainless steel, superduplex, sigma phase, chi phase.

Abstract. The intermetallic phase precipitation, mainly sigma (σ) and chi (χ) phases, was studied in
a comparative manner in two stainless duplex steels: a duplex type UNS S31803 and a superduplex
type UNS S32520. The χ-phase precipitated at ferrite/ferrite grain boundaries prior to the σ-phase
precipitation, which occurred preferentially at ferrite/austenite interfaces and at ferrite/ferrite grain
boundaries. The σ-phase precipitation is a eutectoid type reaction of ferrite, leading to σ-phase and
austenite (γ). The χ-phase precipitated at lower temperatures and in smaller amounts than sigma.
The χ-phase is metastable in the studied steels and was consumed during the σ-phase precipitation.

Introduction
Duplex stainless steels (DSSs), with ferritic-austenitic microstructure, have excellent mechanical
properties and corrosion resistance. DSSs are widely used in the chemical industry and in offshore
technologies, where a combination of high corrosion resistance and good tensile strength is required
[1,2]. The continuing development of the duplex stainless steels has resulted in complex steel
compositions containing substantial amounts of alloying elements. Alloying elements are, of
course, introduced in the steel for one or more reasons, but the final aim is mainly to obtain better
mechanical properties and/or higher corrosion resistance. Duplex stainless steels presenting Pitting
Resistance Equivalent (PRE = %Cr + 3.3 %Mo + 16 %N) higher than 40 are known as
superduplex. As usual, the benefits of such additions invariably come attached to unavoidable
disadvantages, the most important being the potential microstructural instability of the material.
When exposed to temperatures lower than 1000 ºC, DSSs are subject to various phase
transformations. In the 970 to 600 ºC temperature range, intermetallic phase precipitation may
occur, mainly the sigma (σ) and the chi (χ) phases [3,4]. The formation of such phases is
undesirable so that careful processing and use of the steel are needed to avoid or, at least, to
minimize them.
The sigma phase formation in ferritic-austenitic duplex stainless steels can be represented by a
eutectoid type reaction of ferrite (δ) into sigma phase (σ) plus austenite (γ) as follows: δ → σ + γnew,
where γnew is known as new austenite [5-7]. This reaction may consume totally the ferrite phase of
the steel. Sigma phase nucleates at ferrite-austenite interface and grows inwards into the ferrite
phase. The χ-phase has been less studied than the σ-phase. In DSSs, it occurs in lesser amounts
than sigma; nonetheless its presence is also considered to be detrimental to the steel properties [6].
The high susceptibility of the duplex stainless steels to intermetallic phase formation is frequently
attributed [6,7] to the ferrite chemical composition; richer in sigma forming elements (Cr, Mo and
Si) and poorer in austenite stabilizing elements (C, N and Ni).
The main objective of the present work is to study the intermetallic phase precipitation, mainly
sigma and chi phases, in two stainless duplex steels: duplex 45N (type UNS S31803 with 0.16%N,
22.5 %Cr, 5.5%Ni and 3%Mo) and superduplex 52N+ (type UNS S32520 with 0.22 %N, 24.9 %Cr,
6.5%Ni and 4.0%Mo) in a comparative manner.
Experimental procedures
The investigated materials (for chemical composition see Table 1) were a duplex type UNS S31803
and a superduplex type UNS S32520 stainless steels. Test samples have been taken from rolled
strips. Before aging heat treatments, the samples have been solution annealed at 1050 °C for 30
min, followed by water quenching to produce a balanced ferrite/austenite microstructure. The aging
heat treatments were then carried out at 750 ºC for 1, 2, 4 and 8 h.

Table 1: Chemical composition of the investigated duplex stainless steels (wt-%).

Steel C Si Mn P S Cr Ni Mo Cu N
S31803 0.023 0.28 1.80 0.04 0.001 22.52 5.54 3.25 0.15 0.157
S32520 0.023 0.29 0.87 0.05 0.0004 24.90 6.50 4.04 1.40 0.218

Metallographic sample preparation has been carried out by grinding (320, 400, 600 and 1000
papers) and polishing with diamond pastes (6, 3, and 1µm). The microstructures were analyzed by
several complementary techniques. They were examined by optical microscopy after electrolytic
etching in 20% NaOH solution and by scanning electron microscopy (SEM) after etching with V2A
or Glyceregia. Chemical microanalysis of individual phases was performed by energy dispersive X-
ray system (EDX) coupled to the SEM. The amount of ferromagnetic phases was determined using
the magnetic induction method (Feritoscope) with a 0.1% ferrite detection limit. Vickers hardness
(with a 1 kg load; HV 1) of all the specimens polished and etched was measured using a durometer.

Results and discussion

Overall views of the microstructures of the duplex and superduplex stainless steels after solution
annealing and before precipitation aging are shown in Fig. 1. The chemical compositions of both
phases (austenite and ferrite) in the two steels are shown in Table 2.

a) b)

γ γ
α
α

Fig. 1: Optical micrographs of duplex stainless steels: duplex 45N (a) and super duplex 52N+
(b) after solution annealing and before precipitation. Etching: Electrolytic etching with NaOH.

Banded microstructures of elongated austenite islands in a ferrite matrix can be observed in the
longitudinal section. The volumetric percentages of ferrite and austenite phases were measured on
the longitudinal section, evaluated by the magnetic method and by quantitative metallography (see
Table 3). The magnetic measurements are strongly influenced by the crystallographic texture
present in the rolled strip. Hence, the ferrite volume fraction evaluated by quantitative stereology is
more reliable. No intermetallic phases have been observed after solution annealing.
 Table 2: Chemical composition, obtained via EDX analysis (wt-%), of ferrite and austenite phases
for both steels after solution annealing.
Phase Si Mo Cr Mn Fe Ni Cu
α 0.5 ± 0.1 3.9 ± 0.1 24.5 ± 0.1 2.1 ± 0.1 64.5 ±0.1 4.2 ± 0.1 0.2 ± 0.1
Duplex
γ 0.4 ± 0.1 2.6± 0.1 21.1 ± 0.1 2.3 ± 0.1 66.4± 0.1 6.7 ± 0.1 0.3 ± 0.1
α 0.5 ± 0.1 4.8 ± 0.1 27.3 ± 0.1 1.1 ± 0.1 59.8 ±0.1 4.7 ± 0.1 1.5 ± 0.1
Superduplex
γ 0.4 ± 0.1 3.1 ± 0.1 23.6 ± 0.1 1.3 ± 0.1 61.7 ± 0.1 7.6 ± 0.1 1.9 ± 0.1

Table 3: Volumetric percentages of ferrite and austenite in the solution annealed stainless steels.
Volumetric percentage (%) Volumetric percentage (%)
Phase Feritoscope Metallography
Duplex Superduplex Duplex Superduplex
Ferrite 37.4 ± 0.2 31.7 ± 0,2 51.3 ± 4,7 51.2 ± 5.5
Austenite 62.6 ± 0.2 68.3 ± 0,2 48.8 ± 4,7 48.8 ± 5.5

After aging heat treatments performed at 750 °C, the magnetism of all the samples was measured
using a feritoscope. The results given in Table 4 show that the precipitation reactions consume the
ferrite phase.

Table 4: Magnetic measurements (in vol %) on duplex and on super duplex stainless steels after
ageing heat treatment at 750 °C for 1,2,4 e 8 h.
Volumetric percentage of ferrite
Time (h)
phase (%)
Duplex Superduplex
1 27.3 ± 0.2 12.8 ± 0.2
2 22.7 ± 0.2 2.4 ± 0.1
4 14.0 ± 0.1 0.6 ± 0.1
8 6.9 ± 0.1 0

Table 5 shows the results of Vickers hardness measurements of the samples aged at 750°C. High
hardness values are related to the abundant intermetallic phase precipitation in the microstructure.

Table 5: Vickers hardness measurements on duplex and on super duplex stainless steels after
solution annealing and after ageing heat treatment at 750 °C for 0 (solution annealed), 1,2,4 e 8 h.
Time (h) Hardness (1 HV)
Duplex Superduplex
0 241.0 ± 1.8 267.0 ± 2.0
1 243.5 ± 3.6 340.6 ± 4.8
2 265.6 ± 3.2 438.2 ± 11.9
4 314.4 ± 3.8 447.0 ± 4.2
8 350.7 ± 5.2 482.2 ± 10.2

Comparing Tables 4 and 5 it may be concluded that the magnetic measurements are more
sensitive than the hardness measurements to follow the precipitation reaction kinetics.
Microstructures of the steels after several aging times at 750 °C are displayed in Fig. 2.
 a) b)

1h σ
α

γnew
σ
α
2h

4h

8h

Fig. 2: Scanning electron microscopy micrographs of the samples aged at 750 °C for 1,2,4 and 8 h.
a) duplex 45N (type UNS S31803) and b) super duplex 52N+ (type UNS S32520). Electrolytic
etching with NaOH.

Details of sigma- and chi- precipitates are shown in Fig. 3. The formation of the sigma phase in
the superduplex stainless steel is faster and the ferrite decomposition is more complete than that in
the duplex stainless steel. The χ-phase presents more molybdenum and less chromium than the
sigma phase and the results of this investigation are in good agreement with the results of the
literature [3-6]. The two intermetallic phases (sigma and chi) can be easily identified on the basis of
the BSE (back scattered electrons) contrast in SEM because the chi phase is richer in the heavy
element molybdenum than in the σ-phase (Tables 6 and 7), hence chi is the brightest phase [3-6].

a) b)

σ
χ
1h
χ σ
γnew
γ

Fig. 3: Scanning electron micrographs of both steels aged at 750 °C for 1 h: a) duplex steel, etching
with V2A-Beize. b) superduplex steel, etching with Glyceregia.

Table 6: Main metallic elements in chi and sigma phases as determined by energy-dispersive X-ray
spectroscopy after ageing at 750 °C for 1h in the duplex stainless steel (wt%).
Si Mo Cr Mn Fe Ni
χ 1.1 ± 0.1 10.6 ± 0.7 24.2 ± 0.9 1.8 ± 0.5 59.5 ± 0.5 4.2 ± 0.4
σ 0.8 ± 0.1 6.8 ± 0.7 29.5 ± 2.6 1.8 ± 0.1 53.5 ± 0.7 5.6 ± 0.4

Table 7: Main metallic elements in chi and sigma phases as determined by energy-dispersive X-ray
spectroscopy after ageing at 750 °C for 1h in the superduplex stainless steel (wt%).
Si Mo Cr Mn Fe Ni
χ 0.5 ± 0.1 9.7 ± 0.6 26.3 ± 0.6 1.6 ± 0.3 54.8 ± 0.7 5.5 ± 0.6
σ 0.5 ± 0.1 5.9 ± 0.1 28.7 ± 0.4 1.8 ± 0.6 57.4 ± 0.2 3.8 ± 0.1

The precipitation of χ-phase at 750 °C occurred before the σ-phase precipitation. It nucleated at
the ferrite/ferrite interface, then, both phases coexist in the microstructure. Following, the χ-phase
is consumed by σ-phase precipitation.
Fig. 4 presents in a schematic form the precipitation sequence of the chi and sigma phases in the
duplex and superduplex stainless steels.
 Fig. 4: Proposed schematic representation for the chi- and sigma- phase precipitation sequence in
duplex stainless steels.

Summary
The sigma phase formation in ferritic-austenitic duplex stainless steels can be represented by a
eutectoid type reaction of ferrite (δ) into sigma phase (σ) plus austenite (γ) as follows: δ → σ + γnew,
where γnew is known as new austenite. This reaction may consume totally the ferrite phase of the
steel. Sigma phase nucleated at the ferrite-austenite interface and grew inwards into the ferrite
phase. The high susceptibility of the duplex stainless steels to sigma phase formation is attributed to
the ferrite chemical composition; richer in sigma forming elements (Cr, Mo and Si) and poorer in
austenite stabilizing elements (Ni and Mn). The ferrite phase of the investigated superduplex
stainless steel presents higher Cr and Mo contents than the ferrite of the duplex stainless steel,
resulting in a faster sigma and chi phase precipitation kinetics for the superduplex steel. Chi phase
nucleates mainly at the ferrite/austenite interface but also at the ferrite/ferrite grain boundaries. It
precipitates at lower temperatures and in a narrower temperature range than the sigma phase, but
chi phase appears to be metastable in these steels and transforms into sigma after long aging time.

References
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