Research Article

Received: 24 July 2007

Revised: 13 December 2007

Accepted: 18 December 2007

Published online in Wiley Interscience: 13 February 2008

(www.interscience.com) DOI 10.1002/sia.2759

Characterization of the carbides in the steel

X20CrMoV12.1 used in thermal power plants
Danijela Anica Skobir,a Matjaz Godec,a Monika Jenkoa and
Bostjan Markolib
Microstructure of the steel X20CrMoV12.1, used for thermal power plants, after tempering at approximately 500 C consists of
tempered martensite with carbide precipitates.
The evolution of the chemical and phase composition of carbide precipitates in X20CrMoV12.1 steel was studied in the
as-received state after 56 000 h at 470530 C under load and in heat-treated state (11344 h at 800 C) using transmission
electron microscopy (TEM) and electron backscatter diffraction (EBSD) technique.
The precipitates found in service-loaded state as well as in heat-treated state were of M23 C6 type. In all samples two
c 2008 John Wiley & Sons, Ltd.
morphologically different types of carbides were established. Copyright

Keywords: chromium steel; X20CrMoV12.1 steel; carbide morphology; tempering

Introduction

Experimental

The 912% Cr martensitic steels have been widely used as

pipework in the power-generating industry. The first 912%
chromium steel, X20CrMoV12.1, was developed in Germany
and it was standardized for use in steam pipes under the
German standard DIN17175 designation. Since 1960s it has been
widely used for steam pipes in power plants in Europe and
elsewhere.[1 3]
The heat-treatment of 912% chromium steels includes
austenitizing, quenching and high-temperature tempering (at
730780 C) in order to achieve a good combination of hightemperature strength, toughness and creep strength. The microstructure of such a steel is composed of highly tempered
martensite with finely dispersed carbide precipitates along the
boundaries of ex-austenitic grains and ferritic sub-boundaries.
An important aspect of the microstructural stability is the distribution of carbide precipitates. Carbides change their chemical
and phase composition as well as their size with time and temperature until equilibrium is reached. The carbides which can
be expected in steel depend strongly on the service temperature, initial composition, amount and kind of carbide-forming
elements and thermodynamic stability of carbides. Steels destined for power plant applications might contain any of the
following precipitates M23 C6 , M7 C3 , M2 X, and MX (M stands
for the metal elements and X for nonmetallic elements of C
and N).[4]
The aim of this work was to investigate the morphological
and compositional changes of carbides in X20CrMoV12.1 steel
after long-term service of 56 000 h within a temperature range
of 470530 C at pressures up to 18 MPa. In order to study the
evolution of the carbide precipitates, some samples were heattreated at 800 C for different periods of time (11344 h) and
investigated.
Transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD) techniques were used to determine the type
of carbides.

Steel pipes manufactured from X20CrMoV12.1 were cut from a 325

MW steam boiler after long-term service for 56 000 h (470530 C
at up to 18 MPa) and investigated. The chemical composition
of the investigated steel was performed using optical emission
spectroscopy (OES) and is presented in Table 1. Specimens were
prepared from the wall of an industrial 42 4.5 mm pipe in the
as-received state after long-term service. In order to simulate the
evolution sequence of carbides, some specimens of the same
material were prepared, but they were first quenched in oil at a
temperature of 1040 C. This temperature ensured the solution of
all carbide particles in austenite.[3] Specimens of steel were then
tempered from 1 to 1344 h at 800 C.
Microstructures of the sample in as-received state and samples
tempered at 800 C at different times were investigated by
field emission scanning electron microscope JEOL JSM 6500F
supplemented by energy dispersive spectroscopy (EDS) and EBSD
analytical techniques. EDS analyses were performed at 13 kV
accelerating voltage and a probe current of 0.35 nA, while EBSD
analyses were done at 15 and 20 kV and a probe current of 1.2 and
2 nA, respectively.
Samples for EBSD measurements were finally polished for 3 min
by colloidal silica oxide (Struers OPS). Extraction carbon replicas
were prepared from the material, tempered 1344 h at 800 C for
the investigation on TEM. The crystallographic characterisation of
precipitates was performed on a JEOL AEM 2000 FX.

Correspondence to: Danijela Anica Skobir, Institute of Metals and Technology,

Lepi pot 11, SI-1000 Ljubljana, Slovenia.
E-mail: danijela.skobir@imt.si

a Institute of Metals and Technology, Lepi pot 11, SI-1000 Ljubljana, Slovenia
b University of Ljubljana, Faculty of Natural Sciences and Engineering, Ljubljana,
Slovenia

c 2008 John Wiley & Sons, Ltd.

Copyright

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Surf. Interface Anal. 2008; 40: 513517

D. A. Skobir et al.

Table 1. Chemical composition of the steel of the investigated pipe

(mass%)
Steel

Si

Mn

Cr

Mo

Ni

X20CrMoV12.1 0.18 0.24 0.51 0.009 0.014 11.7 0.96 0.66 0.27

Results and Discussion

Some of the steam pipes have been in service more than 20 years.
Owing to high-operating temperatures, long-exposing time and
high pressure, the mechanical properties and the microstructure
changed significantly. In order to prolong the service time and to
predict the life time it is of great importance to understand the
evolution of the carbide precipitates in microstructure.
Figure 1(a) shows the microstructure of the as-received material
as well as microstructures of material, tempered at temperature
800 C for 1,336 and 1344 h (Fig. 1(b)(d)). In the as-received state
there is still a typical tempered martensite microstructure with
carbide precipitates along martensite laths and previous austenite
grain boundaries. After tempering for 1 h at 800 C the microstructure is similar to that in as-received state. Morphologically, two
types of carbides were distinguished, in the shape of laths and
octahedral (Fig. 1(e)). The size of the first ones was about 200 nm
and the size of the octahedral was about 500 nm. After 336 h the

coarsening of the precipitates was observed. The precipitates of

the lath shape disappeared or coarsened into octahedral shape.
In the microstructure after 1344 h of tempering at 800 C the
martensite habitus is not present any more. There are still two
sizes of carbides, the larger one up to 4 m and smaller one
around 500 nm. The octahedral shape is preserved.
The smaller carbides were examined by TEM and it was found
that they are of the type M23 C6 (Fig. 2). Identical results were
obtained also by Zheng-Fei and Zhen-Guo.[5] Thermo-Calc (version
1.4.4. Software AB 2000) simulation was also performed and
showed that the composition given in Table 1 corresponds to
the microstructure of -ferrite and M23 C6 carbides. The chemical
composition given by Thermo-Calc was very close to that, obtained
by EDS measurement on larger carbide precipitates. Table 2
presents the comparison of chemical compositions in at.% for the
M23 C6 carbide phase, calculated with Thermo-Calc and obtained

Table 2. Chemical composition of M23 C6 obtained by EDS measurement and calculated with Thermo-Calc (at.%)

Thermo-Calc
EDS

Cr

Fe

Mo

20.8
29.4

1.0
0.7

52.8
47.2

20.2
19.4

5.2
3.3

514

Figure 1. SEM images of microstructure (a) in as-received state; and after tempering at 800 C for (b) 1 h; (c) 336 h; (d) 1344 h; (e) higher magnification
image of (b) of two morphologically different carbides, laths, and octahedral shape.

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Surf. Interface Anal. 2008; 40: 513517

Characterization of the carbides in the steel X20CrMoV12.1

Figure 2. (a) Transmission electron image of an extraction carbon replica with (b) corresponding diffraction pattern and (c) indexing of the diffraction
pattern of M23 C6 carbide. This figure is available in colour online at www.interscience.wiley.com/journal/sia.

Surf. Interface Anal. 2008; 40: 513517

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515

Figure 3. SEM image and corresponding EBSD patterns of the material in the as-received state. The point of the EBSD analysis is marked by cross on the
SEM image. This figure is available in colour online at www.interscience.wiley.com/journal/sia.

D. A. Skobir et al.
by EDS measurement. The results of EDS measurements given
in Table 2 are an average of three carbides shown in Figs 3, 4
and 5. The amount of carbide-forming elements, measured by
EDS coincides very well with the calculated values. Carbon value
obtained by EDS measurement was larger, due to carbon built-up
under electron beam.
In the literature there is not much found about the investigations
of the carbides by EBSD technique, which is a rather new technique.
This technique was primarily developed for texture measurements,

but also phase analysis can be successfully provided.[6] The carbide

precipitates are usually studied by TEM technique, which requires
very difficult and time consuming preparation of thin foils as well
as carbon replicas. The main advantage of EBSD is because this
technique works by positioning a stationary beam of electrons on
selected sampling points on the specimen surface.
Figure 3 shows 70.5 tilted and tilt-corrected SEM image of
as-received material. Final polishing of microstructure leads to
surface topography. The harder carbide phase is slightly above

Figure 4. SEM image and corresponding EBSD patterns of the material tempered for 1 h at 800 C. The point of the EBSD analysis is marked by cross on
the SEM image. This figure is available in colour online at www.interscience.wiley.com/journal/sia.

516

Figure 5. SEM image and corresponding EBSD patterns of the material tempered for 1344 h at 800 C. The point of the EBSD analysis is marked by cross
on the SEM image. This figure is available in colour online at www.interscience.wiley.com/journal/sia.

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Surf. Interface Anal. 2008; 40: 513517

Characterization of the carbides in the steel X20CrMoV12.1

the surface. EBSD measurements were performed on a larger
carbide phase and also on the small one. Both Kikuchi patterns
confirm Cr23 C6 carbide types. It has been quite an effort to
distinguish between Cr7 C3 and Cr23 C6 , because patterns are
very similar. At higher accelerating voltage the diffraction lines
are narrower and can be easily distinguished between similar
patterns. To avoid overlapping of patterns it is better to use
lower accelerating voltage for the determination of small carbide
precipitates. On the Fig. 3 there is also a pattern of -Fe. The same
type of carbide was also found on the samples, tempered for 1,
336 and 1344 h at 800 C. Figures 4 and 5 show EBSD carbides
analyses of sample tempered for 1 and 1344 h, respectively. In
the cases when carbides are smaller than 400 nm some patterns
overlapping appeared, as shown in Fig. 5. On the SEM image
(Fig. 5) the coarsening of carbides is clearly seen. There are
two carbides 3 and 4 m diameter with orientation differing
by a few degrees. From this image, we might suppose that two
carbides grow together and when they coalesce one orientation
predominates. The other explanation might be in connection with
the orientation of martensite matrix. Therefore, the orientations
of two close carbides which mostly nucleate from the same
martensite habitus have similar orientation. The phenomenon
of carbides coalescence was quite frequently observed. Such
coalescent carbides have mostly the same orientation within
5 differences. The exact mechanism of the coarsening is not
completely known.

Conclusions
The samples, taken from the steam pipes manufactured from
the X20CrMoV12.1 steel after 56 000 h in service within the
temperature range of 470530 C and pressures up to 18 MPa,
have carbides in various morphologies and coarsened during
exposure. The martensite structure changed from the primarily
needle-like martensite to ferritecarbide microstructure with still
noticeable martensite habitus.
The microstructure obtained after tempering for 336 h at 800 C
is very similar to that in as-received state. In all samples two
morphologically different types of carbides were found but both
were proven by EBSD and TEM to be of the type M23 C6 .

References
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[3] Foldyna V, Kubon Z, Filip M, Maier KH, Berger C. Steel Res. 1996; 67:
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[4] Fujita N, Bhadeshia HKDH. ISIJ Int. 2002; 42: 760.
[5] Zheng-Fei H, Zhen-Guo Y. Journal of Materials Engineering and
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[6] Michael JR. In Electron Backscatter Diffraction in Materials Science
Schwartz AJ, Kumar M, Adams BL (eds). Kluwer Academic Press: New
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