DOI 10.1515/htmp-2013-0004   High Temp. Mater. Proc.
2013; 32(6): 563 – 572
N. Nabiran*, S. Weber and W. Theisen
Ferritic Stainless Steels for High-Temperature
Applications: Stabilization of the Microstructure
by Solid State Precipitation of MX Carbonitrides
Abstract: Ferritic heat-resistant steels are commonly used
for automotive exhaust systems and have replaced cast
iron, the traditional material for this application. Efforts
to improve the efficiency of engines, reduce weight, and
minimize toxic ingredients by increasing the gas tempera-
ture have shifted the requirement for ferritic heat-resistant
steels to a higher hot strength. Methods of improving the
high-temperature strength are solid-solution strengthen-
ing, precipitation hardening, and grain refinement. In this
work, the influence of MX precipitates on the high-­
temperature mechanical properties of three different fer-
ritic Fe-Cr stainless steels was investigated and compared
to a reference material. Investigations were performed
with uniaxial compression tests of samples aged isother-
mally at 900 °C for up to 1440 h. The most effective method
of increasing the high-temperature strength is to alloy the
steel with 2 mass% tungsten. Grain growth during anneal-
ing at 900 °C was decelerated by solid-state formation of
MX carbonitrides. Microstructural investigations also re-
vealed a slow coarsening rate of the MX precipitates.
Keywords: high-temperature strength, long-term ­annealing,
ferritic stainless steels, MX carbonitrides, CALPHAD method
*Corresponding author: N. Nabiran: Institut für Werkstoffe,
Ruhr-Universität Bochum, 44780 Bochum, Germany
E-mail: nilofar.nabiran@rub.de
S. Weber: Helmholtz Zentrum Berlin für Materialien und Energie
GmbH, 14109 Berlin, Germany
W. Theisen: Institut für Werkstoffe, Ruhr-Universität Bochum, 44780
Bochum, Germany
1 Introduction
High-chromium ferritic heat-resistant steels are the most
commonly used materials for automotive exhaust systems
and have replaced cast iron, the traditional material for
this application [1]. This change has been driven by in-
creasing efforts to improve the efficiency of engines and to
reduce their weight. Additionally, the maximum applica-
tion temperature was increased to more than 900 °C in
order to emit cleaner exhaust gas by minimizing toxic pol-
lutants [2].
The use of thinner materials lowers the heat capacity
of the exhaust system so that the exhaust gas flows to the
converter with a higher temperature and heats the cata-
lytic converter more rapidly to the active temperature
range [2]. However, the higher gas temperatures require
enhanced high-emperature mechanical properties of the
materials.
During service, exhaust components undergo thermal
fatigue as a result of heating and cooling cycles caused by
the travel pattern. This load may lead to rupture of the
­material as a result of a local strain concentration due to
thermal expansion. Therefore, the materials must have a
low thermal expansion coefficient and sufficient high-­
temperature strength. Although the high-temperature
strength of ferritic steels is lower than that of austenitic
steels, their excellent thermal fatigue resistance due to
their low thermal expansion is a decided advantage [3]. It
is thus important to exploit the excellent thermal fatigue
resistance of ferritic steels and also improve their high-
temperature strength.
For the alloy design of heat-resistant ferritic steels,
three approaches to improving the high-temperature
strength are feasible: solid-solution strengthening, pre-
cipitation hardening, and grain refinement. In the present
work, three 18 mass% Cr heat-resistant steels with MX
­precipitates were designed and produced in order to in-
vestigate the microstructural changes and the high-­
temperature strength depending on the annealing time at
the prescribed temperature.
2 Experimental
The alloys were designed with the thermodynamic model-
ing software Thermo-Calc® Version S, which is based on
the CALPHAD method [4]. The software was used to calcu-
late the phase equilibria and to evaluate the stabilities of
the respective phases in order to determine the influence
of several alloying elements, including Nb, Si, V, W, C, and
564   N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications

Table 1: Chemical composition of the steels in the initial state (mass%) measured by optical emission spectrometry

Alloy Cr C N Nb V W Si Ti Mn Ni Fe

X4CrWSi18-1-1 17.1 0.05 0.02 0.42 0.52 1.1 0.89 0.09 0.58 0.12 bal.
X4CrWSi18-2-1 17.7 0.04 0.02 0.42 0.54 2.2 0.91 0.08 0.52 0.12 bal.
X4CrWSi18-1 17.8 0.04 0.02 0.41 0.54 1.2 0.33 0.08 0.52 0.12 bal.
X2CrTiNb18 17.8 0.017 0.020 0.39 0.12 – 0.65 0.14 0.46 0.22 bal.

N. All calculations were carried out with the database
TCFE6.2 [5].
2.1 Manufacturing of the alloys
The alloys were produced by casting 10 kg ingots and
forging them at 1080 °C to a sheet thickness of 10 mm. The
chemical composition of the alloys is shown in Table 1.
Due to its oxidation resistance, high-Cr steel (Fe-18Cr-
0.45Nb) was chosen as the base composition. The influ-
ence of various alloying elements on the high-­temperature
strength was investigated.
average grain diameter was determined with a minimum
of three images. The orientation of the images was perpen-
dicular to the forging direction.
Quantitative investigations of precipitates were sup-
ported by the software a4i Analysis. The projected area
Ai  of the particles and their diameter were determined
­automatically by means of binary image conversion. The
volume fraction of the precipitates was quantified by mea-
suring the projected area fA, which was obtained by divid-
ing the sum of the projected areas Ai of the particles by the
area of the measuring field s2:
fA = (∑ A ) / s
n
i =1 i
2 (1)

This projected area fraction is a representative measure of

2.2 Compression tests
Compression tests were performed to determine the effect
of microstructural changes during annealing on the high-
temperature strength. Specimens of Ø 5 × 10 mm were an-
nealed under ambient atmosphere in a furnace at 900 °C
for dwell times ranging from 1 to 1440 h. After annealing,
hot compression tests were carried out at 900 °C with a
thermomechanical testing device. Each sample was ini-
tially heated with a rate of 5 K·s-1 to 900 °C and equili-
brated for 2 min. Subsequently, the compression test was
performed at an initial strain rate of 10-3 mm·s-1. After the
compression test, the samples were cooled to room tem-
perature at a rate of 15 K·s-1.
2.3 Microstructural investigations
The microstructure in all states was characterized by light
optical microscopy and scanning electron microscopy.
Grain size measurements were performed with an optical
microscope and a maximum magnification of 1000×.
Scanning electron microscopy was carried out. Secondary
electron contrast was used to measure precipitation, and
a backscattering detector was used for general microstruc-
tural characterization. The grain size was measured using
the standard linear intercept method at magnifications of
50× and 100×, as described in DIN EN ISO 643 [6]. The
the volume fraction of the MX and Laves phases [7]. Four
images from each annealing state were used for these
measurements. The average diameters of the precipitates
were determined by measuring the minimum and
maximum projected diameters (dmin/dmax), respectively, of
all particles in the images.
3 Results
3.1 Alloy design
The alloy design focused on 18 mass% Cr ferritic steels to
provide sufficient oxidation resistance at 900 °C. Two
strengthening mechanisms were used to improve the
high-temperature strength. W offers substantial solid-
solution strengthening on account of its large atomic
radius and high solubility in α-Fe. In order to avoid grain
growth, the microstructures were stabilized by precipita-
tion of niobium rich MX (Nb(C, N)).
Stabilization of the grain structure during the entire
service life can be achieved with a homogeneous distribu-
tion of stable precipitates. In this case, monocarbides of
the type NbC were precipitated in the solid state. Dissolu-
tion of 0.02 mass% N could not be avoided during produc-
tion of the steel. However, the amount of dissolved nitro-
gen in the matrix was lowered by microalloying with Ti to
  N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications   565

with intergranular corrosion. The challenge is to select

­adequate monocarbide-forming elements. The propensity
of the elements to form carbides is based on their negative
standard enthalpy of formation on reaction with carbon.
Thus, monocarbides are formed before highly ordered
­carbides with a higher M/C ratio (M23C6). The elements
niobium and vanadium are known to form stable mono-
carbides. Therefore, their influence on MC formation was
calculated for the system Fe-18Cr-2W-0.04C (Figure 2). In
the system with niobium, MC precipitates already ­occurred
in the liquid phase when the niobium content was higher
than 1 mass% (Figure 2a). It is thus difficult to control the
size and distribution of the NbC particles. For a lower
niobium content, the solvus temperature (TSol) and the
amount of MC decreased.
When vanadium was added to the system, no MC pre-
cipitation occurred, even for a content as high as 5 mass%
(Figure 2b). Hence, Nb is necessary for the formation of
Fig. 1: Phase diagram of the system Fe-18Cr-2W-C (Database: MC carbides in the system Fe18Cr2W0.04C. However,
TCFe6.2) the  niobium content should be below 1 mass% to avoid
primary MC carbides precipitating from the liquid phase.
form primary TiN nitrides. Therefore, we focused on the The influence of the MC carbides on the high-­
solubility of carbon in the bcc matrix, in order to prevent temperature strength during long-term annealing was
α-ferrite/γ-austenite phase transformation. In order to de- ­investigated with three high-Cr steels that were used as
termine the solubility of C in bcc, thermodynamic calcula- the basic composition with added niobium and vanadium
tions were performed on the basic system, Fe-18Cr-2W. Its (Table 1). To determine the influence of solid-solution
phase diagram shows that 0.08 mass% C can be dissolved strengthening, the content of tungsten and silicon were
in the matrix without any α/γ phase transformation varied (Table 1).
(Figure 1). However, a high carbon content leads to the The phase diagram of alloy X4CrWSi18-2-1 is shown
­formation of chromium-rich M23C6, which is associated in Figure 3a as a function of the carbon content and the

Fig. 2: Phase diagram of the system Fe-18Cr-2W-0.04C with addition of a) Nb and b) V (Database: TCFe6.2)
566   N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications

Fig. 3: Thermodynamic calculations for alloy X4CrWSi 18-2-1: a) phase diagram, b) volume fraction of the phases MX, TiN and Laves phase
(Database: TCFe6.2)

Table 2: Calculated volume fractions of MX carbides at 900 °C and

solvus temperatures TSol

Alloy MX volume fraction at 900 °C TSol (°C)

(%)

X4CrWSi18-1-1 0.44 1367

X4CrWSi18-2-1 0.39 1346
X4CrWSi18-1 0.39 1339

temperature. Ferrite, TiN, and niobium-rich MX carboni-

trides are present as equilibrium phases in the phase field
of interest at 900 °C. The calculated volume fractions of
TiN, MX (NbCN), and Laves phase in X4CrWSi18-2-1 are
plotted against the temperature in Figure 3b. The equilib-
rium volume fraction of MX decreases with increasing
temperature. At the proposed application temperature of
900 °C, the calculated equilibrium volume fraction of the
MX is about 0.4 vol.% and the calculated solvus tempera-
ture (TSol) was calculated to be 1346 °C. The calculated
equilibrium volume fraction of MX and TiN as well as the
calculated solvus temperature of all three steels are listed
in Table 2.
3.2 Compression tests
The results of the compression tests follow from the offset
yield strength as a function of the isothermal aging time at
900 °C (Figure 4). In the as-solution-annealed state, steel
X4CrWSi18-2-1 possessed the highest offset yield strength
Fig. 4: Offset yield strength as a function of the logarithm of the
annealing time at 900 °C (IS = initial state). For reasons of clarity,
the error bar is only given for steel X4CrWSi18-2-1. For all steels
and ranges, the error bar is in the range of -/+2.55 MPa
of 35 MPa. Steel X4CrWSi18-2-1 exhibited a higher strength
at 900 °C than the reference steel. The lowest high-­
temperature strength of 27 MPa at 900 °C in the as-­solution-
annealed state was exhibited by steel X4CrWSi18-1. After
annealing for 1 h, the strength of the reference steel de-
creased, whereas X4CrWSi18-2-1 did not show any change
in its high-temperature strength. Steels X4CrWSi18-1-1 and
X4CrW18-1 showed a slight increase in their strength. After
additional annealing for up to 192 h, the high-temperature
strength of all steels steadily decreased. After annealing
for 720 h (30 d), all three newly developed materials
  N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications   567
e­xhibited a large decrease in their high-temperature
strengths. This trend continued for steel X4CrW18-1 after
annealing for 1440 h. In contrast, steel X4CrWSi18-2-1
showed an increase in its high-temperature strength. In
conclusion, steel X4CrWSi18-2-1 consistently exhibited
the  highest strength, even after annealing for 1440 h at
900 °C. The high-temperature strength of the reference
steel steadily decreased as the annealing time increased.
3.3 Microstructural changes during
isothermal annealing
Figure 5 shows the evolution of the mean grain size in all
three steels as a function of the isothermal annealing time
at 900 °C. In the initial state, steels X4CrWSi18-2-1 and
X4CrW18-1 had a grain size of about 150 µm. Steel
X4CrWSi18-1-1 featured an almost 95 % larger grain size in
the initial state. After a dwell time of 1 h, all three steels
did not show any significant grain growth. Further
­annealing for 24 h led to a grain growth of 40 µm for
X4CrWSi18-2-1. For the other two steels, there was still no
significant change in their grain size. This trend contin-
ued for steels X4CrWSi18-1-1 and X4CrW18-1 at longer dwell
times. Steel X4CrW18-1 exhibited a slight grain growth of
10 µm after longer annealing dwell times. Steel X4CrWSi18-
2-1 showed the greatest grain growth during long-term
­annealing, with a change of 70 µm compared to the initial
state. Steel X4CrWSi18-1-1 exhibited only 10 µm grain
growth after annealing for 1440 h.
SEM investigations of alloy X4CrWSi18-2-1 in the initial
state (0 h) revealed a ferritic matrix and two kinds of
Fig. 5: Average diameter of grain size as a function of the isothermal
annealing time at 900 °C (IS = initial state)
­ recipitates (Figure 6a). One type is an MX carbonitride
p
(NbCN), which appears white in the SEM image, and the
other type is TiCN, featuring a dark contrast in the SEM
image.
It is crucial to note that TiCN precipitates primarily
from the liquid state and MX (NbCN) precipitates from the
solid state, especially at the interface with TiCN. Forma-
tion of Ti-rich carbonitrides from the liquid phase can be
also deduced from the phase diagram (Figure 3a). An
­additional Laves phase formed after annealing for 1 h at
900 °C (Figure 6b). It precipitated mostly at the grain
boundaries, but also within the grains in an acerous type.
The Laves phase can be still detected after an annealing
time of 24 h. However, after a longer annealing time, the
Laves phase within the grains gradually disappeared but
coarsened at the grain boundaries (Figure 6d). After
­annealing for 720 h at 900 °C, the Laves phase had com-
pletely disappeared so that even the grain boundaries
were free of Laves phase precipitates. No change in the
microstructure was observed for the MX and TiN precipi-
tates between the initial state and after annealing for 1440
h at 900 °C (Figure 6a–e).
The volume fraction of the precipitates during long-
term annealing is quantified in Figure 7. In the initial state,
the volume fraction of NbCN is about 0.4 %, which agrees
with the value calculated by means of the Calphad
method. After 24 h at 900 °C, the entire volume fraction of
the precipitates increased. However, distinction of the
precipitates indicated that the volume fraction of the MX
was around 0.4 %. This behavior was also seen for a dwell
time of 192 h. After annealing for 720 h at 900 °C, the entire
volume fraction decreased. It is important to note that the
Laves phase appeared after annealing for 1 h and disap-
peared after 720 h. The measured value of the MX precipi-
tates agrees quite well with the calculated value (dashed
line in Figure 7).
The average particle diameter of MX is given in
Figure  8a. In the initial state, the particle size was
about  0.5  µm. The particle diameter increased with
the  ­annealing time. After aging for 1440 h, the particle
size  increased to about 0.8 µm. Figure 8b shows the
particle size of MX precipitates as a function of the
­
­annealing time and frequency of the precipitate particles.
The size of the small particles started with 80 nm to
100  nm, and their frequency for a short annealing time
was high, but decreased significantly after annealing
for  24 h. This behavior dominated at longer annealing
times, whereas the frequency of the larger particles (1.0–
3.0 µm) increased continuously. This classification also
shows the low frequency of the medium-sized particles
(0.2–1.0 µm).
568   N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications

Fig. 6: Microstructure of steel X4CrWSi18-2-1 after isothermal annealing at 900 °C

  N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications   569

Fig. 7: Microstructure evolution of steel X4CrWSi18-2-1 after

annealing at 900 °C: Volume fraction of NbCN + metastable Laves
phase

4 Discussion

4.1 Influence of the alloying elements

One of the most important challenges for ferritic steels in

exhaust systems is to improve the high-temperature
strength with maintain sufficient oxidation resistance.
Several other engineering requirements should also be
achieved, such as sufficient toughness, good weldability,
as well as adequate hot and cold workability. Therefore,
the alloy design focused on high chromium steels with a
basic composition of 18 mass% Cr. In order to increase the
high-temperature strength of these steels during their
service life, solid-solution strengthening and precipita-
tion of MX carbonitrides were used to stabilize the micro-
structure at elevated temperatures.
The elements Mo and W are known to increase solid-
solution strengthening as a consequence of their large
atomic radius. In the present work, only the element W
was used in varied amounts (1–2 mass%) for the solid-
solution strengthening effect. Indeed, according to Fujita
et al. [1], Mo is believed to improve the thermal fatigue life
of ferritic stainless steels. However, Mo promotes forma-
tion of the sigma phase (σ) and shifts the phase boundary
in the Fe-Cr system to a lower chromium range [8]. The
sigma phase (σ) is hard and brittle, and it reduces the
toughness properties of the alloys. Due to the fact that
the  exhaust manifold cycles through a wide operating
temperature range from room temperature to 900 °C, the
formation of a brittle sigma phase (σ) can be detrimental.
Fig. 8: Microstructure evolution of steel X4CrWSi18-2-1 after
annealing at 900 °C: a) average particle size of MX, b) size
distribution of MX precipitates
To achieve sufficient high-temperature strength
during the entire service life, it is important to stabilize the
microstructure to avoid microstructural coarsening.
Stable and finely dispersed precipitates are known to
­stabilize the microstructure. There are several types of
precipitates (M23C6, MX, Laves phase) with different nucle-
ation and growth kinetics, which can be used. However,
selection of the right type of precipitate is associated with
several requirements. Due to the low stability of M23C6 in
low-carbon ferritic steels at higher temperatures, this
phase can be excluded (Figure 3a). In previous works the
influence of Laves phase in ferritic stainless steels during
long-term annealing was investigated [9]. An analysis of
the microstructure in different states annealed at 900 °C
showed that the Laves phase precipitates grow and rapidly
570   N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications
coarsen. This insight is in good agreement with the results
of Morris et al. [10]. They noted that initial treatment of
Fe-25Al-2Nb at 900 °C led to coarsening of the Laves phase.
Sim et al. [11] also reported a rapid coarsening rate of
Laves phase precipitates at high temperatures (700 °C).
These precipitates coarsen rapidly and their contribution
to precipitation hardening is comparatively small, al-
though they inhibit grain growth and thus stabilize the
microstructure [9]. However, coarse Laves phase precipi-
tates on the grain boundaries can have a detrimental
effect on the toughness of these steels [12]. Therefore, the
basic principle for designing the alloy was to develop
steels with more stable precipitates. According to several
publications, monocarbides/carbonitrides (MX) seem to
have a low coarsening rate compared to those of the Laves
phase. Prat et al. [13] simulated and measured the coars-
ening rate of MX of the type V(C,N) and predicted no
coarsening at 650 °C. Aghajani et al. [14] also reported a
low coarsening rate of MX (V(C,N)) at 650 °C. Sim et al. [11]
compared the coarsening rate of Laves phase Fe2Nb and
MX (Nb(C,N)) in ferritic stainless steels at 700 °C, and they
found that the coarsening rate of Laves phase Fe2Nb is
higher than that of MX (Nb(C,N)). Due to the high stability
compared to that of the Laves phase, MX precipitation was
selected for stabilization of the microstructure in this
work. However, in order to avoid brittleness of the micro-
structure, the precipitates should be finely distributed.
Therefore, it is important to determine the solvus tem-
perature of the phase so that the precipitates do not occur
primarily as large particles, especially at the grain bound-
aries. Previous studies have revealed that the carbon and
niobium contents have a strong influence on the solvus
temperature of monocarbides (Figure 2). It is important to
choose an adequate content of both elements in order to
form fine MC precipitates. Nitrogen also greatly affects the
solvus temperature. Incorporation of 0.02 mass% N could
not be avoided during production of the steels. In order to
capture this nitrogen, the system was microalloyed with
Ti, thus minimizing the effect of nitrogen on the precipita-
tion of MX (Nb(CN); however, it is still involved in their
formation (Figure 3).
4.2 Relationship between mechanical
properties and microstructure
The offset yield strength of steel X4CrWSi18-2-1 in the
initial state (IS) was approximately 29 % higher than that
of steel X4CrWSi18-1-1 and 13 % higher than the reference
steel (Figure 4). After annealing for 1 h at 900 °C, the
­difference in the high-temperature strength between the
reference steel and X4CrWSi18-2-1 increased to 24 %. Steel
X4CrWSi18-2-1 possessed the highest offset yield strength
for all dwell times. This considerable difference in the
high-temperature strength is due to the solid-solution
strengthening effect of 2 mass% W. Solid-solution strength-
ening is caused by the interaction of an alloying element
with dislocations, which results in increased glide resis-
tance. There are different ways in which solute atoms can
interact with dislocations. One of these is a paraelastic
interaction due to the different sizes of solute atoms and
matrix atoms. Their incorporation into the crystal lattice
causes compressive or tensile stresses, depending on
whether the solute atom is larger or smaller than the
matrix atom [15]. On alloying with W, the high-­temperature
strength can be significantly increased due to its large
atomic radius. However, this effect greatly depends on the
amount of W. The measured high-temperature strengths
showed no difference between steels X4CrWSi18-1-1 and
X4CrWSi18-1 with 1 mass% W and the reference steel
without added W. Fujita et al. [1] investigated the effect of
alloying elements on the 0.2 % proof strength at 950 °C
with 0.02 (C+N)-19Cr steels. He reported that 2 mass% W
has the greatest influence on the high-temperature strength,
which is in a good agreement with the present findings.
In order to investigate the influence of the element Si
on the high-temperature strength, it was added in various
amounts to the alloying system. At first sight, it seems that
Si does not significantly influence the high-temperature
strength. However, it is important to note that the grain
size of steel X4CrWSi18-1-1 (~0.9 mass% Si) is about 95 %
higher than that of steel X4CrWSi18-1 with 0.33 mass% Si
(Table 1).
The offset yield strength of all investigated steels de-
creased with increasing annealing time at 900 °C (Figure
4). Steel X4CrWSi18-2-1 featured a considerable drop in the
high-temperature strength after annealing for 192 h. The
high-temperature strength decreased continuously after
exceeding a dwell time of 720 h. However, after aging for
1440 h, the offset yield strength increased, so that it was at
the same level as the high-temperature strength after 192
h. This deviation is not caused by microstructural changes,
but it is within the range of the error bar. Nevertheless, it
can be concluded that long-term annealing decreases the
high-temperature strength.
The general reduction in high-temperature strength
after long-term annealing could be explained by grain
growth. However, these steels exhibited only minimal
grain growth during aging at 900 °C (Figure 5). Only steel
X4CrWSi18-2-1 showed a grain growth of 50 µm after an-
nealing for 1440 h. This could explain the drop in the high
temperature strength after annealing for 720 h. However,
  N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications   571
steel X4CrWSi18-1 also exhibited a drop in the high-­
temperature strength, although there was no significant
grain growth. In conclusion, the minimal grain growth
could have only a small impact on lowering the high-­
temperature strength. This means that the concept to
counteract microstructural coarsening via MX precipita-
tion was s­ uccessful. The slow growth of the grains could be
due to the pinning effect of the precipitates (MX). This be-
havior depends on the Zener force, which strongly affects
grain growth and frequently suppresses it completely [15].
A further reason for the slight drop in the high-­
temperature strength could be the evolution of precipi-
tates during long-term annealing. Steel X4CrWSi18-2-1
reached a state close to thermodynamic equilibrium after
annealing for approximately 1 h, as indicated by the con-
stant volume fraction of the precipitates (Figure 7). Indeed,
the entire volume fraction of precipitates increased after a
dwell time of 1 h, but decreased again after a 720 h dwell.
This behavior was affected by precipitation of a metasta-
ble Laves phase. The Laves phase precipitated after 1 h
and disappeared after annealing for 720 h (Figure 6). In
order to illustrate the influence of the volume fraction
of  the precipitates (Laves phase + MX) on the high-­
temperature strength, the results of the volume fraction
and offset yield strength at 900 °C are compared directly
in Figure 9a. After annealing for 24 h, the entire volume
fraction of the precipitates increased and the high-­
temperature strength decreased slightly. After annealing
for 192 h, the high-temperature strength decreased contin-
uously, whereas the volume fraction remained at the same
level. The volume fraction increased with longer anneal-
ing times, but the offset yield strength decreased.
Consequently, the high-temperature strength does
not seem to be affected by the deviation of the volume
fraction and hence by precipitation of the Laves phase.
Fig. 9: Comparison of the high-temperature strength and the microstructural evolution of steel X4CrWSi18-2-1 after annealing at 900 °C:
a) volume fraction of the precipitates (MX + Laves phase), b) particle size of MX precipitates
On this account, it can be noted that the quantified
volume fraction of MX precipitate was in good agreement
with the calculated thermodynamic equilibrium value at
900 °C (Figure 7). This means that the volume fraction of
MX precipitates quickly reaches a state close to equilib-
rium. On reaching thermodynamic equilibrium, the pre-
cipitates undergo Ostwald ripening [16]. The driving force
for the Ostwald ripening process is a reduction in the
­interfacial free energy [16]. Smaller particles in solution
have a higher surface-to-volume ratio than larger parti-
cles. This means that smaller particles coarsen faster com-
pared to larger particles due to their higher surface energy.
An increase in the average particle size will thus reduce
the total free energy of the system, and this reduction is
the driving force for the coarsening effect.
Based on the theory of coarsening, the MX precipi-
tates undergo Ostwald ripening after annealing for 1 h,
which is in good agreement with the obtained results
(Figure 8). After annealing for 24 h, there was a slight
growth in the average particle size, and it increased con-
tinuously for longer annealing dwell times. Simultane-
ously, the amount of small particles decreased, whereas
the amount of large particles increased (Figure 8b).
In order to estimate the influence of precipitate coars-
ening on the high-temperature strength, both results are
compared in Figure 9b. There appears to be a relationship
between the drop in the high-temperature strength and
coarsening of the MX particles during annealing. However,
it is important to examine the contribution made by the
MX particles to the strengthening effect. This is due to the
fact that the effect of precipitation hardening strongly
depends on the particle size [15]. It is most effective if
the particles are very small [15]. Indeed, the classification
of the precipitates shows that the amount of small parti-
cles is for short annealing times. However, the smallest
572   N. Nabiran et al., Ferritic Stainless Steels for High-Temperature Applications
particle size is 80 nm. Therefore, the contribution of the
MX particles to strengthening or rather to softening of the
­microstructure could be small.
Softening of the material with respect to the anneal-
ing time could also be explained by the reduction in the
dislocation density during annealing. The deformed state
of the material (hot- or cold-rolled) is unstable because the
dislocation structure is not in thermodynamic equilibrium
[15]. The dislocation mobility is strongly controlled by the
temperature. At low temperatures, the deformed state is
retained due to the mechanically stable structure. Increas-
ing the temperature activates thermally induced pro-
cesses, cross slip of screw dislocations, and climb of edge
dislocations [15]. Through climb, dislocations can leave
their glide planes, annihilate one another, or leave the
crystal altogether. These processes are subsumed under
recovery, which is always associated with a decrease in
the dislocation density and formation of low-angle grain
boundaries (polygonization) [15].
In conclusion, the high service temperature (900 °C) and
time leads to a reduction in the dislocation density, which
is associated with a reduction in the mechanical strength.
5 Conclusion
The present study focuses on the high-temperature
strength of ferritic stainless steels with stabilization of the
microstructure using MX precipitates:
1. The solid-solution strengthening effect of W increased
the high-temperature strength of ferritic stainless
steel. This enhancement was retained during long-
term annealing.
2. Thermodynamic calculations (CALPHAD) proved to
be a reliable tool for developing ferritic stainless steels
with respect to the effect of Nb, V, C, N, and W on the
formation of MX carbonitrides
3. Investigations of the microstructure of different an-
nealing states (900 °C) showed growth and coarsen-
ing of MX precipitates. After 1 h, MX precipitates
achieved a constant volume fraction and thus a state
close to the thermodynamic equilibrium.
Acknowledgments: The authors gratefully acknowledge
the financial support of the Bundesministerium für Bildung
und Forschung (BMBF) for the project “Entwicklung
von  Höchstleistungswerkstoffen für Hochtemperatur-
Wärmeträger und PKW-Abgasanlagen” with the contract
number 03X3520G.
Received: January 11, 2013. Accepted: June 12, 2013.
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