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M A TE RI A L S CH A RACT ER IZ A TI O N 61 ( 20 1 0 ) 9 6 9 9 7 4

available at www.sciencedirect.com

www.elsevier.com/locate/matchar

Influence of annealing conditions on microstructure and phase

occurrence in high-alloy CrMnN steels
Jana Bakajov a,, Mria Domnkov a , Roman ika a , Sabine Eglser b , Jozef Janovec a
a
Institute of Materials Science, Faculty of Materials Science and Technology, Slovak University of Technology, Bottova 25, 917 24 Trnava,
Slovak Republic
b
Bhler Edelstahl GmbH & Co KG, Mariazeller Strae 25, A-8605 Kapfenberg, Austria

AR TIC LE D ATA

ABSTR ACT

Article history:

The influence of annealing at 750, 800, 850, 900 and 950 C for 4 h on the microstructure and

Received 23 April 2010

the phase occurrence in two high-alloy CrMnN austenitic stainless steels was investigated

Received in revised form

using light microscopy, transmission electron microscopy, and thermodynamic

10 June 2010

calculations. Austenite, , and Cr2N were identified in both steels experimentally. The

Accepted 14 June 2010

experimental results were found to be in good agreement with the thermodynamic

predictions. In one of the steels, M23C6 as a non-equilibrium probably residual phase was
found. Cr2N appeared in the steels either in the form of discrete particles or as a part of cells

Keywords:

consisting of alternate lamellae of Cr2N and austenite.

CrMnN austenitic stainless steels

2010 Elsevier Inc. All rights reserved.

Transmission electron microscopy

Thermodynamic calculations
Cr2N

1.

Introduction

Austenitic stainless steels belong to the favoured construction

materials used for various components in chemical, petrochemical, fertilizer and nuclear industries. Recently, a new
trend in designing the austenitic stainless steels was noticed.
It resides in a partial replacement of the classic CrNi steels
with the CrMnN steels [1]. The latter steels containing cheaper
alloying elements have also high strength and excellent
ductility at room temperature in the solution annealed and
quenched conditions [2,3], excellent resistance to cavitation
erosion [1], satisfactory resistance to pitting and crevice
corrosion [4,5], and good work-hardenability [2,6]. As a result,
the high-nitrogen austenitic stainless steels found broader
application in engineering, particularly when excellent combination of high strength and toughness is required [7].
However, high-nitrogen austenitic stainless steels tend to
form Cr-rich precipitates when annealed at temperatures

Corresponding author. Tel.: + 421 902299159; fax: + 421 335521007.

E-mail address: jana.bakajova@stuba.sk (J. Bakajov).

from 500 to 1050 C. This leads to a significant reduction in

corrosion resistance [1,811]. Besides Cr2N, preferentially
formed during isothermal annealing, small amounts of phase can also precipitate in high-nitrogen austenitic stainless steels on prolonged annealing time. The particles are
expected to precipitate in the nitrogen-depleted zones around
Cr2N, because does not dissolve nitrogen [12]. The presence
of carbide phases in low-carbon CrMnN steels is an open
question. For instance, T.-H. Lee et al. [12] and Y.-X. Ma et al.
[11] predicted the occurrence of M23C6 in 18Cr18Mn2Mo
0.9N and 22Cr14Mn1N steels, respectively, but they did not
confirm this prediction experimentally.
The characteristic discontinuous Cr2N precipitation in the
CrMnN steels leading to the formation of cells containing
alternate lamellae of Cr2N and austenite was studied by
many authors [3,8,1116]. In the recent work of N.C. Santhi
Srinivas and V. V. Kutumbarao [16] the cells, also called
nitrogen pearlite, were considered as products of an
incomplete non-equilibrium reaction controlled by longrange diffusion of interstitial nitrogen over austenite. The
precipitation of Cr2N lamellae is followed by the decrease of
nitrogen content in the adjacent austenite areas, whereas the

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doi:10.1016/j.matchar.2010.06.012

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MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 9 6 99 7 4

chemical composition of untransformed austenite outside of

cells does not change. To restore the equilibrium, nitrogen
solutes start to diffuse from the untransformed austenite
into the cell austenite. After reaching a uniform distribution
of nitrogen in austenite, the growth of Cr2N lamellae is
terminated [16].
The intention of this work is to characterize the type,
morphology, and area fraction especially of the discontinuously precipitated Cr2N particles as a function of the
chemical composition of the investigated high-alloy CrMnN
austenitic stainless steels after annealing at temperatures
between 750 and 950 C. Attention was also paid to the
comparison of experimental and thermodynamically predicted results.

2.

Experimental Procedure

The chemical compositions of the investigated high-nitrogen

austenitic stainless steels are given in Table 1. The steels
produced by Bhler Edelstahl GmbH & Co KG, Kapfenberg
(Austria) were solution heat treated at 1100 C for 0.5 h
and then annealed at 750, 800, 850, 900 and 950 C always for
4 h.
The specimens for light microscopy were polished up to fine
diamond finish (1 m) and then electrolytically etched for 10 s
using 10% oxalic acid at the current density 1 A cm 2. The
metallographic sections were observed by a light microscope
NEOPHOT 32 equipped with a CCD camera. The grain sizes were
determined according to STN EN ISO 643 using the linear
intercept segment method. The area fraction of precipitates was
determined by quantitative metallographic analysis based on
the gray levels of the microstructural constituents. The
magnifications of 250 and 400 were used and the measurement was made on 10 fields per magnification.
The identification of the secondary phases was done by
selected area electron diffraction using transmission electron
microscopy (TEM) of dual stage replicas and thin foils. Dual
stage replicas were made by evaporating carbon onto celluloid
squares skinned from polished and subsequently etched
surface of metallographic specimens. The etching taking 60 s
was done using an agent consisting of 10 ml H2SO4, 10 ml
HNO3, 20 ml HF and 50 ml H2O. Thin foils suitable for TEM
observations were prepared by jet-electropolishing (TENUPOL
5) in electrolyte HNO3:CH3OH = 3:7, at 30 C and 19 V. Both
carbon replica and thin foils were studied using a microscope
JEOL 200CX operating at 200 kV. Metal compositions of Cr2N
particles extracted into carbon replicas were determined by
energy dispersive X-ray spectroscopy (EDX) using software for
thin samples. No corrections for absorption or fluorescence
were made.

Table 1 Chemical composition of investigated steels.

Alloy

Cr

Mn

Ni

Mo

CrMnN1
CrMnN2

21,05
17.75

23.00
18.50

0.85
0.85

1.50
0.08

0.04
0.05

0.06
0.03

0.25
2.00

3.

Thermodynamic Calculations

The phase equilibria and the molar fractions of equilibrium

phases were calculated for systems corresponding to the
investigated steels in the temperature range of 6001200 C by
Thermocalc software [17] using the database STEEL17X
formulated by Kroupa et al. [18]. In the calculation procedure
the total Gibbs energy of the system consisting of contributions of individual phases is minimized at constant temperature and pressure. The particular phases were modelled as a
sum of the reference level of Gibbs energy, entropy term,
excess Gibbs energy, and magnetic term (if plausible the
magnetic ordering). In the calculations, the elements Fe, C, N,
Si, Mn, Cr, Mo, Ni and V were considered, and the phases ferrite (b.c.c.), austenite (f.c.c.), Cr2N (h.c.p.), M6C (f.c.c.), M23C6
(f.c.c.) and (tetragonal) were taken into account.

4.

Results

The microstructures of both steels in solution annealed

condition are fully austenitic with polyhedral grains containing annealing twins as shown in Fig. 1. The grain boundaries
as well as the grains in both cases are free of precipitates.
Medium grain sizes of 25 and 40 m were determined for steels
CrMnN1 and CrMnN2, respectively. During annealing, secondary phases start to precipitate in the form of discrete particles
and/or lamellar cells. The discrete particles were observed
mainly along the grain boundaries (Fig. 2). Cells consisting of
the alternate particle/austenite lamellae were found to be
adjacent to the grain boundaries (Figs. 2 and 3). The cells were
observed in the CrMnN1 and CrMnN2 steels annealed at
temperatures of 750850 and 800900 C, respectively. The
area fraction of precipitates was found to be temperature
dependent (Fig. 4); the highest values of the fraction were
observed at 800 and 850 C for CrMnN1 and CrMnN2 steels,
respectively. In the central part of the larger cells, however,
grey areas resembling an optical merger of coterminous
lamellae are also observable (Fig. 2). These areas were
considered as particles at the evaluation of the area fraction
of precipitates.
The substructure of the CrMnN1 steel after annealing at
800 C/4 h containing a trigonally particle is documented in
Fig. 5. The particle was identified as -phase (see the
diffraction pattern in the upper left corner of Fig. 5). Fig. 3
shows the morphology of precipitates in cells after annealing
at 800 C. As follows from the respective diffraction patterns,
the lamellas are formed by Cr2N. Besides the prevailing Cr2N
particles, the occurrence of and M23C6 particles (Table 2) was
also proved by electron diffraction. The thermodynamically
calculated isopleths showing phase equilibria in dependence
on both temperature and bulk nitrogen content are illustrated
in Fig. 6a and b for systems corresponding to CrMnN1 and
CrMnN2 steels, respectively. The molar fractions of equilibrium phases (e.g. , , Cr2N) are plotted in Fig. 7a (CrMnN1) and b
(CrMnN2) in dependence on temperature.
Chromium (8295 wt.%), manganese, iron, and traces of
molybdenum and nickel were identified in the metallic part of
Cr2N particles. This means, the formula Cr2N represents in this

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Fig. 1 Microstructures of CrMnN1 (a) and CrMnN2 (b) steels

after solution heat treatment at 1100 C for 0.5 h.

Fig. 2 Microstructures of CrMnN1 (a) and CrMnN2 (b) steels

after annealing at 850 C for 4 h.

work a complex nitride containing besides chromium also other

metallic elements. In general, the Cr2N particles present in the
CrMnN1 steel contain more chromium than those present in the
CrMnN2 steel. Vanadium in contents up to 4 wt.% was found in
Cr2N appearing in the CrMnN1 steel after annealing at 850, 900,
and 950 C.

solution of this steel, Table 1. If it is taken into account that the

cells contribute decisively to values of the area fraction of
precipitates and that Cr 2 N in the CrMnN steels is in
equilibrium in a broad temperature range (Figs. 6 and 7), the
higher activity of nitride-forming elements in austenite is
expected to shift the intensive formation of the Cr2N containing cells to lower temperatures.
Broader grain boundaries and smaller cells observable in
the microstructure of the CrMnN1 steel (Fig. 2a) annealed and
etched at the same conditions as the CrMnN2 steel (Fig. 2b)
confirm indirectly a higher density of discrete particles along
the grain boundaries in the former steel. It is indirect evidence
about the different mechanisms of the secondary phase
precipitation in the investigated steels. In the CrMnN1 steel,
the intensive precipitation of particles (Cr2N and ) starts at
lower temperatures, and it is localized mainly to the grain
boundaries. On the other hand, the intensive precipitation in
the CrMnN2 steel starts at higher temperatures, and the
formation (growth) of cells is preferred. With respect to both
the above suggestions and the predicted molar fraction of
Cr2N (Fig. 7), the grain boundaries in the CrMnN1 steel can be
considered as the most convenient places for the precipitation (Fig. 5).
For the investigated steels, three phases (austenite, Cr2N, )
were predicted to be in equilibrium at temperatures between

5.

Discussion

The annealing activated the precipitation of particles of

different size and morphology (Fig. 2) in the plain austenite
(Fig. 1) formed on the prior solution heat treatment in both
steels. It was found out that the area fraction of precipitates is
strongly influenced by the occurrence of the Cr2N containing
cells in the steel microstructure (Figs. 24). The course of the
temperature dependence of the area fraction of precipitates
for the CrMnN2 steel with the maximum at 850 C (Fig. 4) fits
very well the course of the same dependence presented by
Yuan et al. [19] for the Fe24Mn18Cr3Ni0.62 N steel
annealed at temperatures between 750 and 900 C for times
up to 12 h. The lower temperature of the maximum value of
the area fraction of precipitates for the CrMnN1 steel (800 C,
Fig. 4) resides probably in the higher bulk concentration
(activity) of nitride-forming elements (e.g. Cr, V) in the solid

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Fig. 5 TEM micrograph (thin foil) showing substructure of

the CrMnN1 steel annealing at 800 C for 4 h; the diffraction
pattern corresponding to the -phase particle of trigonal
shape is shown in the upper left corner.

Fig. 3 Cr2N particles and corresponding diffraction pattern

in CrMnN1 (a) and CrMnN2 (b) steels after annealing at 800 C
for 4 h, TEM of carbon extraction replicas.
750 and 950 C (see dashed lines in Fig. 6). The transition
temperatures between the areas austenite + Cr2N + and austenite + Cr2N were predicted at 834 and 812 C for CrMnN1 and
CrMnN2 steels, respectively. As follows from Fig. 6, the area
austenite + Cr2N is wider and the upper temperature of Cr2N
occurrence in equilibrium is higher for the CrMnN2 steel
(1115 C) compared to the CrMnN1 steel (1058 C). This fact can
be explained by differences in bulk compositions of the steels.

Higher chromium content increases the nitrogen solubility in

the austenite phase [20]. Therefore the formation of Cr2N is
shifted to lower temperatures for CrMnN1 steel alloyed with
about 2% more chromium than CrMnN2 steel. On the other
hand the higher vanadium content in CrMnN1 steel probably
leads in to the formation of more stable vanadium nitrides
exhibiting a more negative enthalpy of formation compared to
Cr2N [21]. Unfortunately, this suggestion was not confirmed
experimentally, because particles of vanadium nitrides were
not identified in the microstructure of the CrMnN1 steel.
Anyway, the interactions between vanadium and nitrogen in
the solid solution can reduce the concentration of free
nitrogen available for nucleation and growth of Cr2N particles.
According to the calculations, the conditions annealed at 750
and 800 C should contain two types of secondary phases
(Cr2N and ). The only secondary phase (Cr2N) was predicted
to be present in conditions annealed at 850, 900, and 950 C. As
follows from the comparison of data in Fig. 6 and Table 2, the
calculated results are in excellent agreement with the
experimental results for the CrMnN2 steel. Good agreement
was also obtained for the CrMnN1 steel, except for the
discrepancy at 800 C. For this temperature, the experimentally evidenced M23C6 (Table 2) was not predicted thermodynamically. This carbide is rather a low-temperature phase in
CrMnN steels. For instance, Y. X. Ma et al. [11] predicted the
coexistence of M23C6 and at temperatures up to 750 C for the
22Cr14Mn1 N steel. Moreover, T. H. Lee et al. [12] conceded
the formation of in the carbon depletion zones surrounding
the growing M23C6 particles. It cannot be therefore excluded

Table 2 Secondary phases in investigated steels

identified experimentally.
Alloy
Fig. 4 Temperature dependence of the area fraction of
precipitates/cells for CrMnN1 and CrMnN2 steels. The error
bars represent the standards deviation of measurements.

CrMnN1
CrMnN2

Annealing temperature [C]

750

800

850

900

950

Cr2N,
Cr2N,

Cr2N, , M23C6
Cr2N,

Cr2N
Cr2N

Cr2N
Cr2N

Cr2N
Cr2N

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Fig. 6 Isopleths showing calculated phase equilibria for

systems corresponding to CrMnN1 (a) and CrMnN2 (b) steels.
The bulk nitrogen content in particular steel is illustrated by
dashed line. The experimental results are documented by
solid (austenite + + Cr2N) and empty (austenite + Cr2N)
circles.

Fig. 7 Calculated molar fractions of , Cr2N and phases for

CrMnN1 (a) and CrMnN2 (b) steels.

6.
that the precipitation of a non-stable M23C6 preceded the
formation of equilibrium also in the investigated steels.
M23C6 identified in the CrMnN1 steel after annealing at 800 C
for 4 h can be also considered as a residual phase present in
the microstructure already before the solution heat treatment.
The precipitation of particles along the cell boundaries in
the CrMnN steels was reported by many authors [3,12,22]. As a
driving force for this process either the chromium enrichment
[3] or the nitrogen depletion [12] near the cell boundaries were
proposed. In the present work, particles were observed
mainly along the boundary segments where the grain and cell
boundaries are overlaid. These segments were considered as
the most convenient places for the formation (Fig. 5). It is
highly probable that the formation of phase is promoted by
both diffusion related compositional changes and microstresses along the grain and/or cell boundaries.

973

Conclusions

The influence of annealing at 750, 800, 850, 900 and 950 C for
4 h on the microstructure and the phase occurrence in the
austenitic stainless steels CrMnN1 and CrMnN2 was studied
using experimental techniques (light microscopy, TEM, EDX,
electron diffraction) and thermodynamic predictions (Thermocalc). The obtained results can be summarized as follows:
1. Austenite, and Cr2N after annealing at 750, 800 C, and
austenite and Cr2N after annealing at 850, 900 and 950 C
were identified in the microstructure of both steels
experimentally. These results are in good agreement with
the thermodynamic predictions. In the CrMnN1 steel
discrete particles of the non-equilibrium probably residual
carbide M23C6 were also found after annealing at 800 C for
4 h.

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2. Cr2N appeared in the steels either in the form of discrete

particles or as a part of cells. The cells formed by alternate
lamellae of austenite and Cr2N were observed in the
CrMnN1 and CrMnN2 steels at temperatures 750850 and
800900 C, respectively.
3. The highest values of the area fraction of precipitates were
observed at 800 and 850 C for CrMnN1 and CrMnN2 steels,
respectively. The lower temperature of the maximum
value of the area fraction of precipitates for the CrMnN1
steel resides probably in the higher bulk concentration
(activity) of nitride-forming elements (e.g. Cr, V) in the solid
solution of this steel.
4. The phase precipitated mostly along boundaries in the
form of discrete particles. The boundary segments formed
by the overlaid grain and cell boundaries were found to be
the most convenient places for the formation. According
to the thermodynamic predictions, in the CrMnN1 steel is
in equilibrium to higher temperatures than in the CrMnN2
steel.
5. Chromium (8295 wt.%), manganese, iron, and traces of
molybdenum and nickel were identified in the metallic
part of Cr2N. Particles of this nitride present in the CrMnN1
steel contained more chromium than particles present in
the CrMnN2 steel. Vanadium (up to 4 wt.%) was found in
the metallic part of Cr2N after annealing of the CrMnN1
steel at 850, 900, and 950 C.
6. The experimental studies as well as the thermodynamic
calculations showed that the precipitation behaviour of
high-nitrogen CrMnN steels is significantly influenced by
the steel bulk composition. Therefore a deep understanding of the precipitation behaviour is of high importance if
designing this kind of steels.

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