J. Mater. Sci. Technol., 2011, 27(8), 725-728.

Modeling of Nucleation and Growth of M23 C6 Carbide

in Multi-component Fe-based Alloy
Naqiong Zhu1) , Yanlin He1) , Wenqing Liu1) , Lin Li1) , Shuigen Huang2) , Jef Vleugels2) and
Omer Van der Biest2)
1) Department of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
2) Department of Metallurgy and Materials Engineering, Katholieke Uniersiteit Leuven, Kasteelpark Arenberg 44, B3001 Heverlee, Belgium
[Manuscript received September 29, 2010, in revised form December 23, 2010]

Three-dimensional atom probe (3DAP) technique has been used to study the nucleation and growth of M23 C6
carbide in a supersaturated multi-component Fe-based alloy aged at 800 C. 3D images indicate that the radius
of M23 C6 carbide after ageing for 10 min is about 9 nm. Concentration profiles of alloy elements in the carbide
are also obtained. Combined with PANDAT and Thermo-Calc software, attempts to model the early stages of
precipitation are present. The calculated particle size and composition of M23 C6 carbide is in good agreement
with 3DAP data.
KEY WORDS: Nucleation and growth; M23 C6 ; Three-dimensional atom probe (3DAP); Modeling

1. Introduction
Evolution of alloy carbides during ageing treatment greatly influences the overall properties of steels.
In spite of the classical theories of nucleation, growth
and coarsening, the prediction of precipitation limited by calculation and analysis technology is not
satisfactory. In recent years, it is reported that
early stages of precipitation can be detected by
three-dimensional atom probe (3DAP) technique[13] .
Moreover, the new generation of phase diagram calculation software PANDAT designed the PanPrecipitation module for simulating precipitation kinetics
during heat treatment processes[4] . Two built-in kinetic models: KWN[5] and Fast-Acting[6] can be used
to simulate the co-precipitation of phases with various morphologies, with concurrent processes of nucleation, growth and coarsening. TC-PRISMA software
also proposed a new model for simulating precipitation in multi-component systems taking both crossdiffusion and high supersaturation into account[7,8] .
Corresponding author. Assoc. Prof., Ph.D.; Tel.: +86
21 56331472; Fax: +86 21 56382976, E-mail address:
ylhe@staff.shu.edu.cn (Y.L. He).

Much work has been done to study the growth

and coarsening of chromium carbide[813] . However,
little work focusing on the prediction of early stages
of chromium carbide precipitation has been reported.
The aim of the present study is to investigate the
nucleation and growth of M23 C6 carbide in a multicomponent Fe-based alloy by 3DAP technique experimentally and modeled with the combination of PANDAT (Version 8.0) and Thermo-Calc (Version P) software.
2. Experimental
2.1 Material
Raw materials used in the present study were electrolytic iron, white cast iron and iron-chromium interalloy. The materials were first induction melted in an
argon atmosphere and then homogenized at 1200 C
for 5 days. After homogenization, composition of the
alloy was tested as shown in Table 1. The samples encapsulated in evacuated quartz tubes were austenized
at 1200 C for 2 h and isothermally treated at 800 C
for 10 min and then quenched into water.

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Table 1 Alloy composition in wt%

Si
0.3

C
0.85

Cr
12.78

V
0.035

Fe
Bal.

2.2 3DAP

Fig. 1 3D elemental maps obtained in the alloy aged at

800 C for 10 min: (a) maps of Cr and C atoms
in a volume of 13 nm13.5 nm102 nm, (b) elemental maps in the selected box
100
90
80
Concentration / at.%

The 3DAP instrument used in the study is a kind

of position-sensitive probe (POSAP)[14] to yield the
original 3D position of detected Cr, C, V and Si
atoms.
To prepare the 3DAP specimens, small rods
(0.7 mm0.7 mm21 mm) were first cut from the
heat-treated samples and mechanically polished to
pins of about 0.5 mm0.5 mm cross section. With
a two-stage electropolishing technique[15] first in an
electrolyte consisting of 25% perchloric acid and 75%
acetic acid, a neck was made on the pins. The neck
was further electrolytically thinned in a 2% solution
of perchloric acid in butyl cellosolve until it broke
to ensure the tip radius of less than 100 nm. Field
ion microscopy (FIM) was performed at 60 K with
(2.02.5)103 Pa of neon as the imaging gas. Atom
probe analysis was performed with the vacuum pressure of 1108 Pa at 70 K and with a pulse fraction
of 20% and a pulse repetition rate of 5000 Hz. All
the 3DAP results were analyzed using the specialty
software Posap.

70

Figure 1(a) is the 3D elemental map of Cr and C

atoms obtained from the specimen aged at 800 C for
10 min. Two clusters rich in chromium and carbon
correspond to M23 C6 carbide, of which the radius is
about 9 nm. Figure 1(b) plots the atom distribution
in the selected box. In Fig. 2, concentration profiles
are derived by analyzing the selected box with the
volume of 4 nm6 nm18 nm.
3. Modeling and Discussion
The precipitation kinetics of a secondary phase including nucleation and growth are controlled by thermodynamic driving force and diffusion. In the present
study, SSOL4 and MOB2 databases in Thermo-Calc
software provide necessary thermodynamic and kinetic data for simulation. PanPrecipitation module in
PANDAT software is used to model the early evolution stages of M23 C6 carbide. Ferritic phase is defined
as matrix in the simulation according to Thermo-Calc
calculation.
3.1 Nucleation
Classical nucleation theory gives the equation[16]
for time dependent, homogeneous nucleation, as

J = Nv Z exp

G
kT

exp

Cr
Fe

50

V
Si

40
30
20
10
0

2.3 Results

60

(1)

12

14

16

18

Fig. 2 Concentration profiles derived from 3D images of

M23 C6 carbide
2

where G = 4
3 (R ) , R is the critical radius,
which a cluster must reach to become a nucleus equal2
; GV , the chemical driving force for nuing to G
V
cleation; , the interfacial energy between the matrix
and particle interface; Nv , the nucleation site density;
Z, the Zeldovich factor; , the atomic attachment
rate; t, the time; , the incubation time for nucleation;
k, the Boltzmann constant and T , the temperature in
Kelvin.
Using Thermo-Calc software, Chen et al.[8] calculated the critical nucleation radius of M23 C6 for
the supersaturated alloy quenched after austenization, taking fully into account the thermodynamic
properties of the multi-component alloys. , the interfacial energy between the ferritic matrix and M23 C6
carbide is set to be 0.37 J/m2 according to Leitner
et al [17] . Vm , the molar volume of M23 C6 is set
to be 6106 m3 /mol[8] . GV is calculated to be
1.71109 J/m3 .
Then, R can be calculated by the following equation,

R =

10

Distance / nm

2
Gv

The calculated R equals 0.43 nm.

(2)

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N.Q. Zhu et al.: J. Mater. Sci. Technol., 2011, 27(8), 725728

0.20

10

C / nm

0.15

23

0.10

Radius of

Volume fraction of

23

Experimental data

0.05

0.00
-6

-5

-4

-3

-2

-1

0
-6

log(time/h)

R
-5

-4

-3

-2

-1

log(time/h)

Fig. 3 Predicted evolution of volume fraction of M23 C6

precipitates
Table 2 Composition of M23 C6 carbide in at.%
Calculation result
Experiment result

Fe
29.16
36.0

Cr
49.87
47.3

C
20.71
16.4

V
0.26
0.3

Si
0
0

The calculated nucleus composition compared with

the average composition obtained by 3DAP inside
M23 C6 particle is listed in Table 2. Comparison of
the two data sets reveals good agreement with each
other.
3.2 Growth
Using PANDAT software, we try to simulate the
nucleation and growth of M23 C6 carbide. The input
parameters for the matrix and precipitate phase organized in Extensible Markup Language (XML) format are listed in Table 3. The atomic spacing usuTable 3 Parameter values used in PanPrecipitation
module
Parameters
Values
Molar volume of ferritic matrix 7.1106 m3 /mol[19]
Molar volume of M23 C6
6106 m3 /mol[8]
Interfacial energy of M23 C6
0.37 J/m2[17]
Atomic spacing of M23 C6
10.9031010 m[18]

ally refers to the lattice constant of the precipitate

phase. Xie et al.[18] reported the lattice constants of
Cr23x Fex C6 with content x. Since the value changes
of lattice constant due to the solubility of Fe is too
small to have a great impact on the simulation results, here we neglect the effects of solubility of Fe
and V on the lattice constant of Cr23 C6 and set it to
be 1.0903 nm for M23 C6 .
Figure 3 plots the evolution of the volume fraction
of M23 C6 with ageing time. It shows that the volume
fraction increases dramatically after about 0.02 s and
before that time it is quite low. Figure 4 indicates
that before 0.02 s, the average particle size of M23 C6
almost remains the value of about 0.4 nm. Thus, the
critical nucleation radius of M23 C6 is assumed to be
0.4 nm, which meets well with the value of 0.43 nm

Fig. 4 Predicted evolution of average particle size of

M23 C6 precipitates compared with the experimental data characterized by 3DAP

calculated by Thermo-Calc. In addition, the simulated radius of M23 C6 with the value of 8.6 nm after
ageing for 10 min is in reasonable agreement with the
value of 9 nm characterized by 3DAP.
4. Conclusion
The early evolution stages of M23 C6 carbide precipitating in a supersaturated Fe-12.78Cr-0.035V0.3Si-0.85C (wt%) alloy aged at 800 C is characterized by 3DAP technique. An attempt to model
the nucleation and growth process of M23 C6 is
also present with the combination of PANDAT and
Thermo-Calc software. The nucleation radius of
M23 C6 carbide precipitated in the supersaturated alloy is assumed to be 0.4 nm. After ageing for 10 min,
the radius of M23 C6 carbide is about 9 nm and the
concentration profiles of alloy elements in the precipitate are also obtained. The calculated particle size
and composition of M23 C6 is in good agreement with
3DAP observation.

Acknowledgements
This study was financially supported by the National
Natural Science Foundation of China (Nos. 50971137 and
50934011).
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