Computational Materials Science 67 (2013) 364372

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Computational Materials Science

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Carbide dissolution in bearing steels

J.-H. Kang 1, P.E.J. Rivera-Daz-del-Castillo
SKF University Technology Centre, Department of Materials Science and Metallurgy, University of Cambridge, CB2 3QZ, UK

a r t i c l e

i n f o

Article history:
Received 17 April 2012
Received in revised form 13 August 2012
Accepted 10 September 2012
Available online 27 October 2012
Keywords:
Carbide dissolution
Cementite decomposition
Bearing steels
Rolling contact fatigue
Severe plastic deformation

a b s t r a c t
The conditions leading to precipitate dissolution in a variety of bearing steels are studied. Computational
thermodynamics and kinetics are employed to determine the microstructural effects leading to precipitate instability, and further dissolution. It is found that there exists a characteristic threshold value of the
driving force that induces dissolution and that carbon migration from cementite towards the dislocation
strain elds can play a dominant role. Microstructures not fully precipitated and far from their equilibrium volume fraction appear to be much more stable than their fully developed counterparts. An explanation to the occurrence of lenticular carbides engulng white etching bands and areas is provided. It is
discussed how dislocation development and migration in the neighbourhood of ferrite/carbide interfaces
control carbide dissolution.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Microstructure is one of the most signicant factors that govern
the strength and endurance of materials [1]. In single-phase alloys,
microstructure renement improves strength, generally following
the HallPetch relationship [2,3]. If second phase particles are
introduced, their nature, fraction, size, distribution, and morphology play an important role in strengthening [4].
An effective means for alloy strengthening is microstructure
renement, which can be achieved via severe plastic deformation.
For example, the yield strength of cold drawn pearlitic wire is increased by controlling the dislocation cell size, which decreases
with higher strain during drawing [5]. During that process, not
only deformation but also dissolution of cementite lamellae has
been reported [615]. Dissolution results in the reduction of
cementite fraction, which inuences mechanical properties. The
phenomenon is not limited to cold drawing but extends to other
severe plastic deformation processes, e.g. ball milling, high pressure torsion, cold rolling, and ball drop test [1621].
In high and ultra-high strength steels, microstructure is
believed to evolve during service under extreme operation conditions. Components for railway and bearing applications experience
rolling contact fatigue under very large contact pressures (1.5
3 GPa [22,23]), which assist microstructure alteration including
carbide dissolution [2433]. Since the microstructure degrades
during operation, decay in mechanical properties may lead to
Corresponding author. Tel.: +44 (0)1223 334300; fax: +44 (0)1223 334567.
E-mail addresses: jk515@cam.ac.uk (J.-H. Kang), pejr2@cam.ac.uk (P.E.J. RiveraDaz-del-Castillo).
1
Tel.: +44 (0)1223 334300; fax: +44 (0)1223 334567.
0927-0256/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.commatsci.2012.09.022

failure and carbide stability is reported to strongly inuence bearing performance [34].
In this study, carbide dissolution occurring during rolling contact fatigue in a variety of bearing steel compositions and microstructures is investigated. Through-hardened martensitic and
bainitic bearing steels are tempered at temperatures ranging
150250 C resulting in the formation of e-, g-carbides, and
cementite [3537]. e- and g-carbides are transition carbides believed to grow and disappear prior to cementite formation on prolonged tempering. Temper carbide size is in the range of tens of
nanometres. The particles are often in elongated forms and are
present at grain boundaries, or inside martensite plates or bainite
sheaves [38]. In addition to temper carbides, residual carbides
may also be present. They are remains of the early pearlitic microstructure, which assumes a spherical shape during spheroidisation.
Some carbides remain after subsequent incomplete dissolution
processes in the austenite + cementite phase eld, and are retained
throughout hardening and tempering. The nature of residual carbides is cementite and their size ranges from several hundred
nanometres to about one micrometre [39]. During operation under
heavy loads, bearing steels undergo several microstructural
changes, one of which is dislocation accumulation, particularly
pronounced in heavily deformed regions under the surface [28].
The accumulated dislocations shear carbide particles, which size
is then reduced via dissolution. Such dissolution is clearly observed
inside white etching areas (butteries) and white etching bands,
where carbides are absent. Also, it is interesting to see elongated
(lenticular) carbides surrounding those microstructurally dissimilar areas [26,31,32]. The objective of this study is to propose an
explanation to these phenomena and to explore the conditions
leading to them via appropriately chosen calculations.

J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

2. Simulation
2.1. Method
MatCalc 5.44 (release 1.012) with thermodynamic database
(mc_fe.tdb) version 1.009 and diffusion database (mc_fe.ddb) version 0.006 was used in this study [40,41]. The program is well
known for precipitation kinetics calculations [4244]. It employs
the classical nucleation theory [45] for computing the nucleation
rate and the SvobadaFischerFratzlKozeschnik (SFFK) growth
model [40] for growth kinetics. Nucleation sites can be selected
among the bulk, grain boundaries, dislocations, and grain boundary edges and corners. The minimum nucleus radius is set to be
0.35 nm and the diffusion enhancement at dislocations and grain
boundaries are set to factors of 104 at grain boundaries and 103
at dislocations, as suggested by MatCalc [46].
There are several aspects to consider when using MatCalc. The
program does not employ different activation energies for the various nucleation sites, but varies their multiplicity instead. Moreover, since there is no thermodynamic database for transition
carbides, cementite was assumed to be present throughout the calculations, and transition carbide effects were incorporated via a
shape factor and a mist strain, which were varied with respect
to carbide size. The linear mist parameter (ek) was taken to be a
function of mean radius (rm) of the precipitate particle as
ek 0:0013r2m  0:0137rm 0:0635 (rm in nm) [35]. The shape factor has been adjusted to asymptotically approach a limit for large
precipitates.

shape factor 3erf

p


r m  3:5 4;

where rm is expressed in nm and is plotted in Fig. 1. The shape factor

stabilises at 7 when rm  5 nm, which is consistent with the experimental observations that the aspect ratio saturates on long-term
tempering at 160 C [35]. Besides, although the interfacial energy
can be calculated by the generalised nearest-neighbour brokenbond (GNNBB) model [47], the resulting value for the ferrite/
cementite interfacial energy is rather low compared with reported
values in the literature (Table 1). This might be because the interfacial energy variations vanish in the absence of the compositional
difference effect across the interface in the GNNBB model. Such
low value predicts very early precipitation and a delay in dissolution. Therefore, the interfacial energy was approximated to be
0.391 J/m2 by comparing the experimental precipitation kinetics
with the simulated results in previous work [35], which is closer

365

to the reported value in the literature (Table 1). Meanwhile, other

factors affecting the nucleation kinetics (e.g. the diffusion enhancement factor, the pre-exponential factor for nucleation rate, and the
incubation time constant) are kept as unity for all calculations.
Hence, the dissolution simulation with the adjusted interfacial energy is believed to provide the expected trends for the different precipitation and dissolution conditions.
2.2. Procedure
A ow diagram showing a summary of the calculations performed is shown in Fig. 2. The simulation is composed of two parts;
the rst deals with precipitation aimed at obtaining the initial precipitate distribution, which becomes the boundary condition for
the onset of dissolution. The precipitation calculations were carried
out so as to reach two values for precipitate volume fraction,
f = 0.05, 0.10, and ve values for the mean radius, rm = 5, 10, 20,
50, 100 nm. The precipitate fraction and size were numerically
controlled by iterating the interfacial energy (cah) and the precipitation time (t), as shown in Simulation I box in Fig. 2.
Nucleation was simulated under paraequilibrium with dislocations acting as nucleation sites at 160 C with 500 classes. The dislocation density is assumed to be 1015 m2 which is typical for a
martensitic microstructure [56], leading to 4.40  1024 m3 nucleation sites [43]. The considered alloy compositions are shown in
Table 2. Since experimental studies show that approximately
4 vol.% cementite is present prior to tempering [38], the temperature for reaching austenite with 4 vol.% cementite was determined
from thermodynamic calculations, and the corresponding austenite composition was taken to be the matrix (ferrite) concentration
for precipitation (Table 3).
The second part of the simulation is carbide dissolution, which
requires the Gibbs free energy of the carbide to be increased with
respect to the matrix (Fig. 3). The extra energy increase can be considered to be the driving force for dissolution (DG). To evaluate the
effects of alloy composition, size and volume fraction of precipitate
on dissolution kinetics, DG = 15 kJ/mol is used; driving forces higher than this value accelerate dissolution. For the inuence of driving force, ve values (DG = 11, 12, 13, 14, and 15 kJ/mol) were
added to the Gibbs free energy of cementite with an initial precipitate distribution of f = 0.10 and rm = 10 nm. The dissolution temperature was set to 50 C as this corresponds with a typical
bearing operation temperature [57].
3. Results
3.1. Simulation I initial precipitate distribution

Fig. 1. Shape factors used in the study (dashed line). Markers show experimental
values.

A total of forty initial precipitate distributions were obtained by

simulating precipitation. As mentioned in the last section, the
interfacial energy (cah) has been iterated and precipitation was
stopped at the desired f and rm values. Large cah suppresses precipitation due to a large energy barrier for precipitation. In other
words, increasing cah causes delay in increasing the precipitate
fraction and in achieving a larger particle size for the given fraction. The precipitation kinetics, precipitate fraction and size are
found to be very sensitive to the cah value. Therefore, the desired
f and rm condition can be obtained by varying cah slightly. The corresponding cah and time (t) values for 100Cr6 were obtained by
trial and error and are given in Table 4. For other steel grades,
the cah and t ratios with respect to 100Cr6 are shown in Fig. 4. It
is noticeable that t to achieve a certain precipitate size and fraction
is higher than in 100Cr6 for other alloy grades. The corresponding
cah is similar for all cases except 100CrMnMoSi8-4-6, which
requires a lower value than the rest, possibly due to the high Si

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J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

Table 1
Ferrite/cementite interfacial energy values reported in the literature and obtained by generalised nearest-neighbour broken-bond (GNNBB) model. The values by GNNBB model
were calculated considering the full composition data and temperature in each work even though only carbon content is mentioned here.
Ferrite/cementite interfacial energy (J m2)

Temperature (C)

C content in alloy (wt.%)

Reference

By GNNBB model

0.2480.417
0.520 0.130
0.56
0.700 0.300
0.731.10
0.851.36

630690
700
588
727
645710
550720

0.33
0.15
0.34 and 0.68
0.80 and 0.81
0.80
0.78, 0.93, and 0.61

[48]
[49]
[50]
[51]
[52]
[53] (using pearlite growth rate data from [54,55])

0.2140.218
0.183
0.1930.199
0.1890.191
0.1730.180
0.1670.284

Start

Input alloy composition

Simulation I

Input

and t

Precipitation simulation

Check f and rm

not ok

ok

3.2. Simulation II dissolution kinetics

= 0.391 J/m2

Input

Input G
Simulation II

deviate from the average if it spreads far from r/rm = 1. Since all alloys show similar distributions in terms of f and rm, only plots of
100Cr6 are shown in Fig. 5. The distribution trends for rm P 20 nm
are convergent for a given precipitate volume fraction (Fig. 5b).
These precipitate distributions are concentrated between
0.74 6 r/rm 6 1.14. As the particle size or volume fraction of precipitates becomes larger, the variance decreases. Precipitates of
rm 6 10 nm display a somewhat larger scatter (Fig. 5a); this may
be due to the precipitate distribution being poorly developed for
low radii, where nucleation still produces new precipitates up to
late precipitation stages, increasing the range of particle sizes
available.
Employing the precipitate distributions as an initial boundary
condition, the inuence of four factors on precipitate dissolution
are studied: alloy composition, precipitate size, precipitate fraction
as well as the driving force for dissolution. The initial precipitate
distributions for the calculations are shown in Fig. 6.

Dissolution simulation
Output f , rm, rmax, N,
and C content in the matrix

The end
Fig. 2. A ow diagram of the two simulations in the study. cah: matrix/precipitate
interfacial energy, t: precipitation simulation time, f: precipitate volume fraction,
rm: particle mean radius, DG: driving force, rmax: particle maximum radius, N:
particle number density.

content, which effectively destabilises precipitation [5860]. The

exact phase fraction and precipitate radius values cannot be obtained; however, the discrepancy for each case does not exceed
1.8% for volume fraction and 2.2% for mean radius.
An overview of the various initial precipitate size distributions
for the considered precipitate radii and volume fractions is shown
in Fig. 5. In this perspective, the precipitate radius (r) is thought to

3.2.1. General considerations

Dissolution kinetics was assessed in terms of precipitate volume fraction; mean, maximum and minimum radii; number density of the particles, as well as average carbon content in the
matrix. The representative case of 100Cr6 with initial f = 0.10,
rm = 10 nm, and DG = 15 kJ/mol is shown in Fig. 7. Other conditions
generate similar results. f decreases smoothly with time. f is directly related to the average carbon content in the matrix. As precipitate dissolves, carbon diffuses into the matrix and the carbon
content in the matrix increases smoothly.
The radius and number density evolution take place in a somewhat different manner. The mean radius decreases nearly linearly
until it reaches approximately half of the initial radius, then the
rate of dissolution dramatically increases. This occurs concomitantly with a sudden decrease in precipitate number density.
While the maximum radius shows a smooth curve, the mean radius oscillates as a result of the computational algorithm: the program introduces a nite number of precipitate classes, and when
one class disappears, an abrupt change in mean radius is observed.
However, no sudden change in maximum radius is produced, since
the class representing the maximum radius does not disappear.
3.2.2. Composition and size effect
The dissolution kinetics was calculated for f = 0.10 and
DG = 15 kJ/mol for all alloys, assuming that they display an identical
initial microstructure and driving force for precipitate dissolution.

Table 2
Alloy compositions for the considered bearing steels. R is the overall solute content for each alloy.
Alloy

Fe

C (wt.%)

Cr (wt.%)

Mn (wt.%)

Mo (wt.%)

Si (wt.%)

R (wt.%)

100Cr6
100CrMo7-3
100CrMnMoSi8-4-6
100CrMo7

Bal.
Bal.
Bal.
Bal.

1.00
0.95
0.95
0.95

1.45
1.75
1.90
1.70

0.35
0.70
1.00
0.35

0.35
0.55
0.20

0.50

2.80
3.75
4.90
3.20

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J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

Table 3
The matrix compositions for dissolution kinetics calculation. R is the overall solute content for each alloy. These are the austenite compositions at the temperature where 4 vol.%
cementite exists.
Alloy

Temperature for 4 vol.% cementite (C)

Fe

C (wt.%)

Cr (wt.%)

Mn (wt.%)

Mo (wt.%)

Si (wt.%)

R (wt.%)

100Cr6
100CrMo7-3
100CrMnMoSi8-4-6
100CrMo7

809.0
806.0
820.5
802.5

Bal.
Bal.
Bal.
Bal.

0.80
0.75
0.75
0.75

1.12
1.35
1.50
1.30

0.34
0.68
0.97
0.34

0.32
0.50
0.18

0.52

2.26
3.10
4.24
2.57

by rmax. The dissolution time is also dependent on alloy composition;

the endurance for precipitate dissolution proceeds in the following
order: 100CrMnMoSi8-4-6, 100CrMo7-3, 100CrMo7, and 100Cr6.
It is interesting to notice that dissolution time decreases according
to the overall amount of solute additions, as shown by R in Tables
2 and 3.
In Fig. 8c and d, rm and rmax ratio when dissolution occurs
(f = 0.001) is presented; rm ratio is dened as rm at f 0:001=
initial rm and rmax ratio is r max at f 0:001=initial rmax . Since
dissolution is controlled by rmax, the focus should be on the rmax
ratio (Fig. 8d). The ratio is relatively low for the initial rm = 5 nm
case; this may be attributed to the underdeveloped initial precipitate distribution as mentioned in Section 3.1.
Fig. 3. Schematic Gibbs free energy (G) diagram with respect to carbon concentration (XC). Ga and Gk,j are the Gibbs free energy of the matrix and the precipitate,
respectively. Gk,f is the Gibbs free energy of the precipitate after adding the driving
force for dissolution, DG. X kC is the carbon concentration in the precipitate, and X Ca;i
and X Ca;f are the carbon concentration in the matrix before and immediately after
dissolution has taken place.

The latter assumption is important in that the driving force may differ for different steel grades; this will be treated further in the discussion (Section 4). The resulting kinetics is shown in Fig. 8; 8a
and 8b show the time to reach dissolution with respect to the
squared initial mean radius (r2m ) and the maximum radius (rmax),
respectively. Dissolution was assumed to take place when
f 6 0.001. The linear relationships with squared radii suggest that
dissolution is diffusion controlled as the initial particle size is
proportional to the square root of time to reach dissolution. Considering a diffusion controlled mechanism, dissolution is determined

3.2.3. Volume fraction effects

To study the role of the initial precipitate volume fraction, the
initial mean and maximum radii are very signicant; this is because the maximum radius controls the dissolution kinetics. Even
though the mean radius and volume fraction are the same, a different maximum radius condition can yield to a variation in dissolution kinetics. In this regard, the result of 100CrMo7-3 with initial
rm = 20 nm is presented; the initial precipitation distribution is
very similar (Fig. 6c) and rmax values are 22.57 nm and 22.66 nm
for f = 0.05 and f = 0.10, respectively. The results are shown in
Fig. 9. Fig. 9a shows that the volume fractions of both initial microstructures intersect at 0.32 days. The initial f = 0.10 case completes dissolution around 0.44 days, and initial f = 0.05 is fully
dissolved at 0.48 days. The size decreases much faster with a higher initial volume fraction. This implies that more developed precipitates are more susceptible to dissolution. The reason being that

Table 4
Interfacial energy and precipitation time pairs, (cah, t), for different mean radii (rm) when the precipitate fraction (f) is 0.05 and 0.10. The units for interfacial energy and time are
J m2 and s, respectively.

f = 0.05
f = 0.10

(a)

rm = 5 nm

rm = 10 nm

rm = 20 nm

rm = 50 nm

rm = 100 nm

(0.283, 0.220)
(0.240, 0.245)

(0.347, 1.49)
(0.333, 1.70)

(0.371, 4.81)
(0.364, 5.92)

(0.392, 26.3)
(0.387, 33.7)

(0.405, 95.3)
(0.401, 130)

(b)

(c)

(d)

Fig. 4. (a and b) Interfacial energy and (c and d) precipitation time ratios of all steel grades in respect to those of 100Cr6, (a and c) for f = 0.05 and (b and d) for f = 0.10.

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J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

(a) 0.03

0.05, 5 nm

Frequency

0.025

0.05, 10 nm
0.10, 5 nm

0.02

0.10, 10 nm

0.015
0.01
0.005
0
0

0.5

1.5

r/rm

(b)0.015

0.05, 20 nm

Frequency

0.05, 50 nm
0.05, 100 nm

0.01

0.10, 20 nm
0.10, 50 nm
0.10, 100 nm

0.005

the matrix containing underdeveloped precipitates displays a higher carbon supersaturation, which results in a lower carbon concentration gradient to drive dissolution.

0.75

1.25

3.2.4. Driving force effects

The dissolution kinetics of 100Cr6 for different driving forces is
shown in Fig. 10. The results for other compositions show similar
behaviour so they are excluded from this work for conciseness. It
is clear that there is a threshold driving force DGth for dissolution;
in the case of 100Cr6, it is between 14 and 15 kJ/mol. For driving
forces higher than DGth, dissolution occurs, showing a decrease
in phase fraction, size and number density of precipitates, as well
as an increase in the carbon content in the matrix. Conversely,
the opposite trend is seen for driving forces slightly lower than
DGth; coarsening continues until the fraction reaches equilibrium.
The kinetics is so sensitive to DG value that a difference of 1 kJ/
mol can determine whether the precipitate would dissolve or
coarsen.
DGth varies with alloy composition. For an initial value of
rm = 10 nm, DGth is between 14 and 15 kJ/mol for 100Cr6 and
100CrMo7; between 13 and 14 kJ/mol for 100CrMo7-3; and between 12 and 13 kJ/mol for 100CrMnMoSi8-4-6. This reconrms
that each alloy displays different dissolution endurance, which is
consistent with Section 3.2.2.

r/rm
Fig. 5. Precipitate distribution in 100Cr6 for (a) rm 6 10 nm, and (b) rm P 20 nm.
The conditions are given as (f, rm) pairs.

(a)

4. Discussion
The results shown in this work provide an interesting insight
into the mechanisms of precipitate dissolution under severe operation conditions such as rolling contact fatigue. The analysis can
readily be extended to steels subjected to severe plastic deformation. A more detailed explanation on the origin of composition effects and the driving force for dissolution follows.
4.1. Compositional effects and precipitate stability

(b)

(c)

Considering the result that dissolution is controlled by carbon

diffusion, there are two ways that composition can affect dissolution kinetics: altering the diffusion coefcient of carbon and the
precipitate thermodynamic stability. The diffusion coefcient of
carbon DaC in each alloy system and the driving force for precipitation (DGpcpt) obtained from MatCalc are presented in Table 5. The
driving force is calculated for equilibrium at 50 C. The changes in
diffusion coefcient are very small, but the driving force for precipitation increases for grades showing more stable precipitates
(Fig. 8). It follows that precipitate stability is responsible for delaying the dissolution other than the diffusion coefcient of carbon. It
is noticeable that DaC is the highest and the driving force is the lowest for 100CrMnMoSi8-4-6, which explains its signicant dissolution rate (Fig. 8). Note that the magnitude of DGpcpt is similar to
the DGth obtained from the calculation. However, it is not exactly
the same because DGpcpt depends on the initial conditions and it
even varies in the course of simulation. One interesting result is
that even though DG is larger than |DGpcpt| to induce dissolution
at the beginning of dissolution, the precipitate coarsens after partial dissolution if |DGpcpt| becomes larger than DG.
4.2. Size effects and diffusion
The size effect originates from the difference in diffusion distance of carbon. The volume fraction (f) of precipitate can be expressed in terms of mean radius (rm) and number density (N) of
precipitate:

Fig. 6. Precipitate size distributions for studying the effects of: (a) composition and
driving force, (b) initial mean radius, and (c) precipitate volume fraction.

4 3
pr N:
3 m

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J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

(a)

(b)

(c)

(d)

Fig. 7. Precipitate dissolution kinetics of 100Cr6 for f = 0.10, initial value of rm = 10 nm, and DG = 15 kJ/mol in terms of: (a) phase fraction, (b) mean radius, and (c) number
density of precipitates, and (d) carbon content in the matrix.

(a)

(b)

(c)

(d)

Fig. 8. Precipitation dissolution kinetics of all steel grades for different particle size conditions. (a and b) Necessary time to reach f = 0.001 in terms of initial r 2m and r 2max ,
respectively. (c and d) The ratio of rm and rmax to their initial values at f = 0.001.

(a)

(b)

(c)

(d)

Fig. 9. Precipitate dissolution kinetics of 100Cr6 for an initial value of rm = 10 nm, and DG = 15 kJ/mol in terms of: (a) phase fraction, (b) mean (solid line) and maximum
(dotted line) radius, and (c) number density of precipitate, and (d) carbon content in the matrix. The markers are shown to distinguish each curve and do not represent
experimental values.

When the carbon diffusion distance (k) is assumed to be the half

distance between the precipitate particles, it is proportional to rm
by following equation:

2
N

2r m
1=3

 1=3
4p
:
3f

q
Since k can be approximated as DaC t in a diffusion controlled
process, it follows that diffusion time (t) is proportional to r 2m .
Hence, the results shown in Fig. 8a and b conrms that the dissolution is driven by the diffusion of carbon atoms away from the
precipitate.
4.3. The nature of the driving force for dissolution
Precipitate dissolution is driven by supplying an amount of energy sufcient to destabilise the precipitate. Such approach has
been adopted by Languillaume et al. [7] and Sauvage et al. [8],
who suggested that an interfacial energy increase should be added
to the cementite Gibbs free energy. The interfacial energy increase

is caused by a surface to volume ratio increase due to cementite

deformation and fragmentation. However, the increase in interfacial energy is not the only possible force driving dissolution; other
forces include (i) the interfacial energy, (ii) the elastic energy increase in heavily dislocated regions, and (iii) the difference in binding energy of carbon with iron in cementite and of carbon with a
dislocation [7,8,18,31,6164].
The increase in the matrix/precipitate interfacial area to volume
ratio, due to carbide deformation and fragmentation, is considered
rst [7,8]. Accordingly, the overall interfacial energy increases
causing the carbide to be unstable. Sauvage et al. calculated such
increment for a pearlitic structure, adding it to the cementite Gibbs
free energy, and by calculating the resulting dissolution kinetics by
considering carbon diffusion [8]. This approach enabled them to
calculate the degree of cementite dissolution according to strain.
The interfacial energy contribution (DEcah ) can be approximately
given by capillarity. Assuming that the carbides are fragmented
down to spherical particles of radius r = 10 nm right before
dissolution,

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J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

Fig. 10. Precipitate dissolution kinetics for 100Cr6 for f = 0.10 and rm = 10 nm. (a and e) Phase fraction, (b and f) mean (solid line) and maximum (dotted line) radius, and (c
and g) number density of precipitate, and (d and h) carbon content in the matrix. The markers are shown to distinguish each curve and do not represent experimental values.

Table 5
Diffusion coefcient of carbon in the matrix (DaC ) and driving force of precipitation (DGpcpt ) at 50 C.
100Cr6
a

1)

DC (m s
DGpcpt (kJ mol1)

100CrMo7-3
20

4.63  10
14.62

2cah
2cah
2:867  1010 3

Vm
 NA ;
9
r
2
10  10

4.72  10
14.12

20

100CrMnMoSi8-4-6
5.25  10
13.90

20

100CrMo7
4.51  1020
14.30

contributions are schematically shown in Fig. 11. The binding energy between carbon and iron atoms in cementite can be obtained
from the reported heat of solution of cementite (DHsol), which is given in Table 6. Note that the heat of solution is different from the
heat of formation: the reference state of a carbon atom is solid
solution in ferrite for the former, whereas it is graphite for the latter. In Table 6, there are two DHsol values obtained from Swartz
[66] by internal friction: self-stressed from a quenched and aged
specimen, and stress-free from ageing 3 days at 715 C to relieve
the transformation strain. DHsol is smaller for the self-stressed
specimen implying less stability. The DHsol values from various
works (Table 6 [7072]) show a large discrepancy between the
minimum and maximum value (26.8 kJ/mol), which might be
due to the transformation stress. The stress state of carbides in
the real system would be affected by the heat-treatment history.
For example, it is expected that cementite in tempered martensite
is more stressed than cementite in coarse pearlite. Moreover, it
should be noted that the effect of alloying elements on the
heat of solution is not taken account in these values. Some

where l is the shear modulus, b is the magnitude of burgers vector,

q is the dislocation density, and Vm is the molar volume of the matrix [67]. Taking l  80 GPa, b  2.48 , Vm as in Eq. (2), and by
assuming q  1017 m2 for a heavily dislocated structure, DEel is
1.75 kJ/mol.
The third contribution focuses on the dislocation-carbon interaction [18,61,63]. Since the binding energy of a dislocation with
a carbon atom (DEb) exceeds that of Fe atoms with a carbon atom
in cementite, carbon atoms tend to reside in dislocation strain
elds rather than within cementite. This concept has been also employed to explain strain-ageing behaviour [68,69]. When a high
dislocation density region is adjacent to a ferrite/carbide interface,
the dislocations are likely to draw carbon atoms from the carbide
until the dislocation becomes saturated; the relevant energy

Fig. 11. A schematic showing energy states of a carbon atom in solid solution
ferrite, in cementite, and in a dislocation.

DEcah

where cah is the ferrite/cementite interfacial energy, Vm is the molar

volume of the matrix, and NA is the Avogadros number. The matrix
molar volume is calculated using a ferrite lattice parameter of
2.867 . If we take the cah values shown in Table 1 (0.248
1.36 J m2), then DEcah is in the range of 0.3521.93 kJ/mol; a value
much lower than the DGth values in Fig. 10.
The second mechanism for dissolution is based on the increase
of carbon solubility in ferrite under pressure [65,66]. Buchwald and
Heckel suggested that the huge hydrostatic stress causes carbon
activity increase in the carbide leading to the dissolution and carbon diffusion is assisted by a high density of dislocations generated
during deformation [31]. However, no quantitative analysis was
carried out. The stored energy (DEel) in the dislocation strain elds
can be expressed as:

DEel

1 2
lb qV m ;
2

J.-H. Kang, P.E.J. Rivera-Daz-del-Castillo / Computational Materials Science 67 (2013) 364372

Table 6
Reported values for the heat of solution of cementite.
Condition

DHsol
(kJ mol1)

Reference

Quenched
Quenched (self-stressed)
Quenched
Quenched and aged at 715 C for 13 days
(stress-free)
Various

50.5
50.6
52.3
61.9

[70]
[66]
[71]
[66]

77.3

[72]

substitutional elements (e.g. Mn, Cr, Mo) can be incorporated in

cementite, resulting in different DHsol values. In our case, DHsol is
considered as 5053 kJ/mol, which is for the quenched condition.
For the binding energy of carbon atoms with dislocations (DEb)
77.2 kJ/mol is adopted2 [73]. Assuming this mechanism to operate,
the driving force for carbide dissolution becomes DEdisl, i.e. the energy for carbon migration from cementite to the dislocation strain
eld; this can be obtained by subtracting DHsol from DEb (Fig. 5),
resulting DEdisl to be 2427 kJ/mol.
Assuming that the precipitates are surrounded by a heavily dislocated area able to host all carbon atoms in cementite, the driving
force (DG) for precipitate dissolution is the sum of DEcah , DEel, and
DEdisl. It should be noted that the energy resulting from the third
mechanism (2427 kJ/mol) surpasses the other two, which are in
the order of 12 kJ/mol. However, it worth mentioning again that
estimated DEdisl value is somewhat speculative because (i) compositional effects are not considered at all for DHsol and DEb, (ii) DHsol
may have discrepancy due to the dependence on the microstructure, (iii) |DEb| decreases as the dislocation strain eld becomes
saturated with carbon. Accordingly, it is found that the alloying
elements effect on carbide decomposition is somewhat complex
[61,64,73,74]. Considering these factors, the DG  15 kJ/mol for
calculation can be a reasonable value to induce the dissolution.
Furthermore, even though DEcah and DEel are signicantly smaller
than DEdisl, they can lead to a difference of 1 kJ/mol in DG. Such
variation can control the precipitate behaviour: whether it dissolves or coarsens (Section 3.2.4). This suggests an explanation
for the occurrence of carbide dissolution inside white etching areas
(butteries) and white etching bands, as well as the coalescence of
lenticular carbides around such regions. The driving force can exceed DGth in heavily deformed regions, resulting in precipitate dissolution, while in the surrounding areas the stress level is less and
the driving force can be lower than DGth, causing carbides to coarsen until they reach an equilibrium fraction.
4.4. Additional considerations for dissolution3
All calculations presented in this work have been made by
considering the energetic instability of precipitates. Instability is
a necessary condition, but it may not sufce for dissolution since
other limiting factors may be present. One of them can be an insufcient mobile dislocation density to carry away the carbon atoms
associated to dissolution. The calculations show that carbon migration from cementite towards dislocations may be the highest contribution to instability. Dislocations should migrate away from the
2
According to [73], 77.2 kJ/mol is in the case of 0.0060.007 wt.% steel. Effect of
alloying element is also shown for some compositions; however, the inuence seems
signicant (greater than 1 eV in some cases). Therefore, the alloying element effect
has been neglected in this study.
3
Another way to simulate dissolution is to introduce the deformed matrix which
can trap more carbon than normal matrix in MatCalc [75]. Still, it cannot explain the
dislocation evolution at the localised region and the given thermodynamic parameter
for the deformed matrix phase could not reproduce dissolution when substitutional
element is introduced with paraequilibrium nucleation condition.

371

interface, while carbon-unsaturated ones should continuously approach it for dissolution to take place uninterruptedly. However,
it is known that dislocations cannot move freely once carbon atom
trapping occurs and Cottrell atmospheres are formed [76]. Accordingly, when sufcient fresh dislocations are not provided at the ferrite/carbide interface, dissolution may not continuously occur
[62,77]. Then, the dissolution kinetics is controlled by the interface
reaction. There can be other means of transporting carbon atoms
away of the interface; (i) wear due to the deformation strain difference between ferrite and cementite [19], and (ii) the formation of
vacancy-carbon atom complexes [78,79]. Overall, this implies that
dislocation evolution is a key factor controlling dissolution, which
is the reason why different deformation processes result in different dissolution behaviours [63].
In spite of their complexity, the calculation results shown in this
work are a good approximation to cementite dissolution, given
that a large density of mobile dislocations is present. The relative
effects of the microstructural factors are plausible. Further studies
are required to determine the conditions leading to the development and evolution of such a high mobile dislocation density.
5. Conclusions
Precipitate dissolution as a result of damage accumulation in
bearing steels has been presented. The estimation of the driving
force based on a number of dissolution mechanisms shows that
the interaction between carbon atoms in the precipitate and dislocations in a heavily dislocated matrix plays the most important
role in dissolution. The calculations for four different bearing steel
grades show that:
1. Precipitate dissolution is faster with increasing alloying content:
the most stable alloy being 100Cr6, followed by 100CrMo7,
100CrMo7-3, and 100CrMnMoSi8-4-6. The elemental content
inuences the thermodynamic stability of precipitates.
2. Smaller precipitate particles tend to dissolve faster than larger
particles. The dissolution rates imply that the dissolution is diffusion controlled.
3. A lower initial precipitate volume fraction displays a lower dissolution rate. This is consistent with industrial practice in which
a non-fully developed precipitate microstructure is employed
for bearings.
4. There is a threshold driving force value (1215 kJ/mol), below
which precipitate coarsening will occur other than dissolution.
This is experimentally observed in the surroundings of certain
white etching areas such as bands and butteries, which display
long lenticular carbides.
5. Provided that a high dislocation density has formed, the migration of carbon from cementite towards dislocations is the prevailing mechanism controlling dissolution. This requires a
constant supply of carbon-unsaturated dislocations in the
neighbourhood of dissolving carbide particles.

Acknowledgements
The authors are grateful to Prof. A.L. Greer for provision of laboratory facilities, and to SKF for nancial support.
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