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Acta Materialia 61 (2013) 7582–7590
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Atomic-scale investigation of e and h precipitates in bainite

in 100Cr6 bearing steel by atom probe tomography
and ab initio calculations
W. Song a, J. von Appen b, P. Choi c, R. Dronskowski b, D. Raabe c, W. Bleck a,⇑
a
Department of Ferrous Metallurgy, RWTH Aachen University, Aachen, Germany
b
Institute of Inorganic Chemistry, RWTH Aachen University, Aachen, Germany
c
Department of Microstructure Physics and Alloy Design, Max-Planck-Institut für Eisenforschung, Düsseldorf, Germany

Received 14 March 2013; received in revised form 20 August 2013; accepted 25 August 2013
Available online 3 October 2013

Abstract

Carbide precipitation during upper and lower bainite formation in high-carbon bearing steel 100Cr6 is characterized using transmis-
sion electron microscopy and atom probe tomography. The results reveal that both e and h carbides precipitate in lower bainite isother-
mally held at 260 °C and only h precipitates form in upper bainite isothermally held at 500 °C. e and h precipitate under paraequilibrium
condition at 260 °C in lower bainite and h precipitates under negligible partitioning local equilibrium condition in upper bainite at
500 °C. In order to theoretically study e and h precipitation and the e ! h transition in bainite, thermodynamic calculations have been
carried out using ab initio techniques. We find that e and h carbides in ferrite have almost identical thermodynamic stability, and hence
have similar formation probability. In austenite, however, cementite formation is clearly preferred: it is favored by 5 kJ mol1 at room
temperature and still by 4 kJ mol1 at 500 °C. Hence, the thermodynamic predictions agree well with the atom probe tomography results.
Ó 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: e carbide; Cementite; Atom probe tomography; Ab initio

1. Introduction reported that the precipitate microstructure in 100Cr6 not

only determines its static mechanical properties (hardness,
100Cr6 with the nominal composition of 1 wt.% strength and ductility), but also its dynamic response dur-
C–0.3 wt.% Si–0.3 wt.% Mn–1.5 wt.% Cr is a high-carbon ing rolling contact fatigue. Precipitate shearing, particle
steel, which is widely used in automotive and bearing appli- dissolution, dislocation cell and nanocrystal formation as
cations. In order to achieve high strength, high wear resis- well as matrix/carbide debonding are features commonly
tance and good fatigue properties, it is rendered into either observed throughout bearing life. Typically, these micro-
a martensitic and/or bainitic state. Nanosized carbides pre- structural changes are initiated at a scale of only a few
cipitated from martensite and/or bainite play a very impor- nanometers, yet can cause cracks that grow up to several
tant role in determining the mechanical properties of the millimeters during ongoing loading [2]. e carbide precipita-
material. Barrow et al. [1] showed that maximum strength tion during tempering of quenched martensite has been
and hardness can be achieved with high carbon concentra- intensively investigated [3–14]; however, its precipitation
tions and fine e carbides in an early stage of precipitation, from a bainitic matrix has not yet been well understood.
though this results in the material having limited ductility. Lai [15] observed, by transmission electron microscopy
Furthermore, Barrow et al. [1] and Kang et al. [2] recently (TEM), e carbides with the same orientation relationship
of h1 1 0ia jj h1 1 2 0ie in both lower bainite and tempered
⇑ Corresponding author. Tel.: +49 241 80 95782. martensite. This observation would support the view that
E-mail address: [email protected] (W. Bleck). e carbides precipitate directly from supersaturated ferrite

1359-6454/$36.00 Ó 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.actamat.2013.08.051
 W. Song et al. / Acta Materialia 61 (2013) 7582–7590 7583

in lower bainite. Caballero et al. [16] recently studied a

high-carbon (0.98 wt.%) high-silicon (1.46 wt.%) steel.
Using atom probe tomography (APT), they detected e car-
bide in bainite tempered at 400 °C and observed an e ! h
transition in bainite tempered at 500 °C.
h carbide (cementite Fe3C) is orthorhombic with a car-
bon content of 25 at.%. Hexagonal e carbides are described
as e-Fe2.xC with a carbon content between e-Fe3C and e-
Fe2C. For the carbon-richer version of this carbide, how-
ever, both, composition and crystallographic structure
have been a matter of debate since the 1940s when the first
syntheses of e-Fe2C were reported [17]. It was Jack [18]
who questioned this composition and proposed instead a
partially ordered Fe20C9 (=Fe2.22C) composition as the Fig. 1. Heat treatment cycle of the investigated steel 100Cr6 (ITT stands
upper limit of the carbon solubility. Until now, there are for Isothermal Transformation Temperature).
authors claiming the existence of e-Fe2C [19,20] as well as
other authors who question its existence [21]. Other sources
report carbides that have slightly varying carbon contents temperature (ITT) of 260 °C, the samples were isothermally
(Fe2.2C–Fe2.4C), namely between both stoichiometric held for 2500 s in order to form a lower bainite microstruc-
phases e-Fe3C and e-Fe2C [22,23]. The e carbide discussed ture. At the ITT of 500 °C the samples were isothermally
here is e-Fe2.4C with a theoretical carbon content of held for 1200 s in order to form an upper bainite microstruc-
29.4 at.%. The lattice parameters of this e carbide are ture. The heat-treatment cycles are illustrated in Fig. 1.
ah = 2.752 Å and ch = 4.353 Å [3]. Austenitization and bainitization were performed in a Bähr
In the present work, we study e and h carbide precipita- 805A dilatometer, using specimens 3 mm in diameter and
tion and elemental partitioning features associated with e 10 mm long.
and h precipitation in both upper and lower bainite forma- To characterize the bainitic morphology, a Tecnai
tion, in high-carbon bearing steel 100Cr6 using TEM and F20G2 transmission electron microscope with an embed-
APT. Ab initio (density-functional) predictions together ded US1000 Gatan camera was used. TEM foils were pre-
with quasi-harmonic phonon calculations were further per- pared from the heat-treated specimen with a twin-jet
formed in order to assess the thermodynamics associated electropolishing device, using a chemical solution of
with e carbide (Fe2.4C) formation and its competition with 10 vol.% perchloric acid and 90 vol.% acetic acid. APT
h carbide (cementite Fe3C) precipitation. The possibility of specimens were cut from the heat-treated material and elec-
the existence of e carbide and the arrangement of the car- tropolished with standard electropolishing methods [24].
bon atoms in hexagonal e carbide are further discussed in APT analyses were performed using a Local Electrode
terms of thermodynamic simulations. Atom Probe (LEAP 3000X HR, Cameca Instruments) in
pulsed voltage mode at a pulse fraction of 15% and a pulse
2. Experimental methods and material processing frequency of 200 kHz. The specimen base temperature was
about 60 K [25–28].
The chemical composition of the steel 100Cr6 is given in
Table 1. The material is mainly alloyed with Cr and micro- 3. Simulation methods
alloyed with Mo. Si and Mn are both at a low level, while
the Al content is almost negligible. The N content in the All first-principles electronic-structure calculations were
steel is 75 ppm. based on density-functional theory [29,30]. The simulations
After hot forging, the material was soft annealed at were performed by using the augmented (PAW [31]) plane-
800 °C followed by a subsequent slow cooling to room tem- wave approach using the Vienna Ab initio Simulation
perature. After soft annealing, the microstructure was Package [32–34]. Structural optimizations were carried
characterized by a homogeneous distribution of fine, sphero- out in terms of volume, cell shape and ionic positions. In
idized carbides in a ferritic matrix. Samples were subse- the next step, the lattice vectors were scaled from 91% to
quently heated up at a rate of 3.3 °C s1 and austenitized 104% of those of the equilibrium structure, and optimiza-
at 850 °C for 300 s, followed by rapid cooling to 260 and tions of both the cell shape and the ionic positions were
500 °C at a rate of 55 °C s1. At the isothermal transformation performed using fixed volumes. Phonon properties were

Table 1
Chemical composition of the investigated steel 100Cr6 (wt.%).
Fe C Si Mn P S Cr Mo Ni Al Cu N
Bal. 0.967 0.30 0.23 0.003 <0.001 1.38 0.02 0.07 0.026 0.05 0.0075
7584 W. Song et al. / Acta Materialia 61 (2013) 7582–7590

computed by the direct force constant method [35] as 25 at.% as cementite (h) and the particle with a carbon
implemented in the FROPHO code [36,37]. To avoid self- content of 29.4 at.% as e carbide Fe2.4C, both owing to
interactions while calculating the Hellmann–Feynman their respective stoichiometries. To further analyze these
forces [38,39], supercells were used with lattice parameters two particles, two regions of interest (ROI) were selected.
>10 Å. Volume expansions and temperature-dependent On the other hand, the distribution of the carbon atoms
thermodynamic properties were evaluated in the frame- within the bainitic ferrite aB matrix is not uniform either.
work of the quasi-harmonic approximation [40,41], taking The carbon content ranges from 0.3 to 1.2 at.%. The car-
into account the electronic ground state and the harmonic bon atom map in Fig. 3a shows small regions of carbon
vibrational contributions to the Helmholtz free energy for agglomeration which might be caused by carbon concen-
various volumes. The vibrational free energy was fitted as tration perturbation in the bainitic ferrite aB matrix, such
a linear function of the volume in order to reduce calcula- as possibly caused by carbon-enriched internal interfaces.
tion time. In order to precisely analyze the compositional distribu-
tion of carbon and the other alloying elements in the par-
4. Results and discussion ticles, more detailed mass spectrum analyses of ROI1 and
ROI2 in Fig. 3a were separately carried out on these spe-
4.1. Morphology cific subvolumes. The chemical compositions in the parti-
cles observed in ROI 1 and ROI 2 are listed in Table 2.
Fig. 2 shows TEM micrographs of bainite microstruc- Spectrum peaks with a mass-to-charge ratio of 24 Da can
tures in the investigated steel 100Cr6. Lower bainite and be either assigned to Cþ 2 or C4
þþ
ions [42,43]. Using the
upper bainite in 100Cr6 exhibit distinct morphological fea- mass-to-charge ratio of 24.5 Da, which can be unambigu-
13 þþ
tures. The bright-field TEM image in Fig. 2a shows lower ously assigned to Cþþ4 ions, namely ðC12
3 C Þ , we applied
bainite microstructure in the sample isothermally heat-trea- a peak devolution algorithm for the mass-to-charge peak
ted at 260 °C for 2500 s. As shown in Fig. 2a, nanosized 24 Da. We found that Cþþ 4 ions make up 90 % of the peak
carbides precipitate within bainitic ferrite aB plates and at 24 Da and hence assigned this peak to Cþþ 4 for plotting
the particles precipitate with an angle of 60° to the longi- the 1-D concentration profiles. This procedure leads to a
tudinal direction of bainitic ferrite aB. The boundaries of slight overestimation of the carbon concentration inside
the bainitic ferrite aB subunits are indicated in Fig. 2a in the particles, as determined from the 1-D concentration
terms of dashed lines. profiles.
The bright-field TEM image in Fig. 2b shows the upper Fig. 3b and c display 1-D concentration profiles (fixed
bainite microstructure in the sample isothermally heat-trea- sample count profiles, using a bin size of 5000 atoms) of
ted at 500 °C for 1200 s. Unlike the plate-like morphology carbon and alloying elements in nanosized carbides and
of bainitic ferrite aB observed in lower bainite it adopts a the adjacent bainitic ferrite aB matrix region in lower bai-
more lath-type shape in upper bainite. As shown in nite in the investigated material 100Cr6 isothermally
Fig. 2b, nanosized carbides are precipitated between the heat-treated at 260 °C for 2500 s. The 1-D concentration
bainitic ferrite laths in the upper bainite. Several carbides profile of the carbon-enriched particle in ROI1 is plotted
precipitate from the grain boundary (GB) shown at the in Fig. 3b, showing the compositions of carbon and alloy-
right bottom of Fig. 2b. The carbides found in the upper ing elements in bainitic ferrite matrix aB and cementite (h)
bainite are much longer and thicker than the carbides in with a carbon concentration of 25 at.%. The substitu-
the lower bainite. Some of these precipitates have already tional elements are distributed with the same compositions
merged to a larger carbide particle. The TEM images reveal in both bainitic ferrite and cementite (h). More specifically,
that the average size of nanosized carbides in lower bainite the concentration profile indicates no significant enrich-
is about 30 nm in width and about 80 nm in length, while in ment of substitutional elements at the interface between
upper bainite, the coarsened carbides are even as large as bainitic ferrite and cementite (h). In addition, the 1-D con-
100 nm in width and 0.5–1 lm in length. centration profile of the carbon-enriched particle observed
in ROI2 is plotted in Fig. 3c, showing the compositions of
4.2. Atom probe tomography carbon and the other alloying elements in the bainitic fer-
rite aB matrix and also in the e carbide Fe2.4C with a car-
The 3-D carbon atom map of the sample isothermally bon concentration of 29.4 at.%. The data reveal that
heat-treated at 260 °C for 2500 s is shown in Fig. 3a. It pro- the substitutional elements are distributed homogeneously
vides a local overview of the carbon distribution in bainitic in both bainitic ferrite and e carbide Fe2.4C. The carbon
ferrite aB matrix and carbides. As shown in Fig. 3a, the dis- atoms are near-equilibrated and there is no partitioning
tribution of the carbon atoms in the analysis volume is not of any substitutional elements between the bainitic ferrite
uniform. The carbon-depleted region with a carbon con- aB and the e carbide Fe2.4C. Therefore, we conclude that
tent of <1.2 at.% represents the bainitic ferrite aB, which both cementite (h) and e carbide Fe2.4C precipitate without
is supersaturated with carbon [25]. The carbon-rich regions partitioning of substitutional elements in lower bainite in
correspond to h carbide (cementite Fe3C) and e carbide the investigated material 100Cr6 when isothermally heat-
Fe2.4C. We identify the particle with a carbon content of treated at 260 °C for 2500 s. The features of substitutional
 W. Song et al. / Acta Materialia 61 (2013) 7582–7590 7585

Fig. 2. TEM micrographs of 100Cr6 steel: (a) lower bainite at 260 °C for 2500 s, (b) upper bainite at 500 °C for 1200 s; aB: bainitic ferrite, h: cementite,
GB: grain boundary.

Fig. 3. (a) Carbon atomic map and 13 at.% iso-concentration surface in lower bainite in 100Cr6 isothermally heat-treated at 260 °C for 2500 s; ID
concentration profile in ROI1 (b) and ROI2 (c) in Fig. 3(a); aB: bainitic ferrite, h: cementite, e: e carbide Fe2.4C.

Table 2 element distribution across the bainitic ferrite aB/cementite

Chemical compositions in the particles in ROI1 and in ROI2.
(h) interface and the bainitic ferrite aB/e carbide Fe2.4C
Element C Si Mn Cr Ni Al Cu interface hence imply that both cementite (h) and e carbide
ROI1 (at.%) 25.58 0.474 0.298 1.879 0.065 0.028 0.042 Fe2.4C precipitation in lower bainite occur under paraequi-
ROI2 (at.%) 30.79 0.521 0.293 1.836 0.049 0.034 0.032 librium mode [44,45]. “Paraequilibrium mode” refers to the
7586 W. Song et al. / Acta Materialia 61 (2013) 7582–7590

phase transformation mode which assumes that only inter- by TEM, we find that the thicknesses of these carbides that
stitial alloy elements, e.g. C, N, redistribute by long-range are revealed by APT are much smaller. Therefore, when
diffusion, whereas substitutional alloy elements, e.g. Cr, blending the TEM observations on the average width and
Mn, Si, are considered to be frozen in the sublattice. length of the nanosized carbides in the lower bainite with
Both cementite (h) and e carbide Fe2.4C in lower bainite the current APT results, we conclude that both cementite
isothermally heat-treated at 260 °C for 2500 s were repeat- (h) and e carbide Fe2.4C adopt plate-like carbide shapes.
edly observed in the current APT measurements. The par- The 3-D carbon atom map of the sample isothermally
ticles which were detected in this current investigation show heat-treated at 500 °C for 1200 s is shown in Fig. 5a.
small dimensions in thickness, i.e. 3–10 nm, in lower bai- Fig. 5a shows a local overview of the carbon distribution
nite. An e carbide Fe2.4C particle with a thickness of in bainitic ferrite aB and cementite (h) in upper bainite in
10 nm and a cementite particle with a thickness of 100Cr6. The carbon-rich region with a carbon content of
5 nm are indicated in Fig. 3a. From Fig. 3, these nano- 25 at.% corresponds to cementite (h). The carbon-
sized precipitates are inferred to form under paraequilibri- depleted region in the bulk represents bainitic ferrite aB.
um mode. Likewise, the same stoichiometry of e carbide The carbon content in the aB bulk phase amounts to only
Fe2.4C and the same elemental partitioning behavior of 0.0173 at.%. The carbon largely partitions to the austen-
interstitial and substitutional elements across the bainitic ite during upper bainite formation at 500 °C, which leads
ferrite aB/e carbide Fe2.4C interface are revealed in to carbide precipitation directly from austenite.
Fig. 4. The e carbide Fe2.4C particle indicated in Fig. 4 Fig. 5b displays the proxigram of carbon and alloying
shows a thickness of 4 nm. Small regions of carbon elements at the interface of bainitic ferrite aB and cementite
agglomeration in the bainitic ferrite aB matrix are again (h) in upper bainite. The proxigram reveals the partitioning
detected in this dataset (Fig. 4a). e carbide Fe2.4C precipi- characteristics of carbon and alloying elements at the bain-
tation in lower bainite is repeatedly proved to occur under itic ferrite (aB)/cementite (h) interface. As shown in Fig. 5b,
paraequilibrium mode. the carbon partitions according to the local equilibrium
These results help us to gain further knowledge of the between bainitic ferrite (aB) and cementite (h), while the
shapes of cementite (h) and e carbide Fe2.4C in lower bai- substitutional elements Cr, Mn and Si redistribute over a
nite in three dimensions together with the chemical compo- short range and exhibit enrichment at the aB/h interface.
sition and the local partitioning behavior. The TEM Si is mostly dissolved in the bainitic ferrite matrix and
observations also show these nanocarbides in the lower exhibits a relatively low solubility in cementite (h).
bainite, however, only in the form of 2-D projections, as Fig. 5b shows that Si is highly enriched at the interface
indicated in Fig. 2a. The TEM results also suggest that between the bainite and the cementite (h), which kinetically
the nanocarbides in the current lower bainite assume elon- impedes the further growth of cementite (h). However, the
gated shapes with an average size of 30 nm in width and data also reveal that there is no long range redistribution of
80 nm in length. On the other hand, in our APT measure- the substitutional elements Cr, Mn and Si.
ments we detected additional nanocarbides in lower bainite It is assumed in the paraequilibrium mode that only
even with a much smaller size of 3–10 nm in thickness. interstitial elements are considered to be equilibrated, while
When compared to the average width and length values in the non-partitioning local equilibrium/negligible
of the nanosized carbides in the lower bainite observed partitioning local equilibrium (NPLE) mode, interstitial

Fig. 4. (a) 3-Dimensional atomic map and 5.8 at.%C iso-concentration surface in lower bainite in 100Cr6 isothermally heat-treated at 260 °C for 2500 s;
(b) proxigram showing carbon and alloy concentrations across bainitic ferrite and e carbide Fe2.4C interface; aB: bainitic ferrite, e: e carbide Fe2.4C.
 W. Song et al. / Acta Materialia 61 (2013) 7582–7590 7587

Fig. 5. (a) Carbon atomic map and 12.5 at.% iso-concentration surface in upper bainite in 100Cr6 isothermally heat-treated at 500 °C for 1200 s; (b)
proxigram showing carbon and alloy concentrations across bainitic ferrite and cementite (h) interface; aB: bainitic ferrite, h: cementite.

elements partition according to the local equilibrium and also e-Fe2.4C [4]. In a recent experimental contribution, Du
substitutional elements redistribute over a short range. Plessis synthesized a mixture of iron carbides with e-Fe2.3C
The various interstitial and substitutional elemental parti- (the carbon content is somewhat sample dependent [22])
tioning features in the current APT investigation indicate being the main phase [23]. Rietveld refinement of X-ray
that cementite (h) and e carbide Fe2.4C precipitate under data, however, did not show any indications for carbon
paraequilibrium mode in lower bainite at 260 °C, while ordering but suggested that the disordered [NiAs] structure
cementite (h) precipitates under NPLE mode in upper bai- type (with space group P63/mmc; Strukturbericht Designa-
nite at 500 °C. tion: B81) is more likely, thereby questioning the theory. In
Unlike the nanosized carbides in lower bainite, the other words, the C atoms would then randomly occupy
cementite (h) that precipitated in the upper bainite exhibits 41.7% of each of the Wyckoff positions 2b, 2c and 2d
a much larger average size. The coarsened carbides even (Fig. 6d). Therefore we first clarified the situation by inde-
achieve a size of up to 1 lm in length. Thus, APT maps pendent theoretical means. In the most common descrip-
are not capable of revealing the complete size information tion of the ordered variant of Fe2C (note that the only
of a coarse cementite (h) in upper bainite. published structure of Fe2C in the ICSD database [50] is
obviously incorrect) the C atoms occupy all the 2d sites
4.3. Ab initio calculations such as in Fe3C and, additionally, a single position, or
50%, of the 2b sites (see Fig. 6c). This leads, next to the cor-
Ab initio calculations were performed in order to assess ner-sharing octahedra described above, to additional edge-
the thermodynamic probability of e carbide Fe2.4C forma- sharing octahedra with a C–C distance of 2.73 Å. Nonethe-
tion, competing with the precipitation of cementite (Fe3C, less, face-sharing octahedra with a C–C distance of 2.17 Å
h). As the most crucial prerequisite for total-energy calcu- do not occur in the ordered variant because carbon does
lations, a reliable structural model for e carbide is needed, not occupy the 2c sites. According to Pauling’s third rule
in particular because the distribution of the n carbon atoms of crystal chemistry, the latter polyhedral connectivity is
over the 2.4n available octahedral sites is not fully resolved. energetically unfavorable [51]. Our density-functional com-
For the structure of the hexagonal e-Fe3C, on the other parison of both candidates confirms Pauling’s rule because
hand, the situation is clear ever since its first synthesis in the calculation of the ordered distribution of e-Fe2C indi-
1950 [46]. For illustration, Fig. 6a depicts the commonly cates this to be 41 kJ mol1 more stable at 0 K than the dis-
used unit cell of the hexagonal Fe carbide structures ordered one; this is an extremely large difference between
containing six Fe atoms. For carbon, three different inde- two different interstitial configurations. For the same rea-
pendent crystallographic positions, called Wyckoff sites, son, the phase dubbed Fe2.4C would also have the 2d sites
are available (2b, 2c, 2d). Each site corresponds to two completely occupied by carbon and the 2b site only par-
indistinguishable atomic positions which can be occupied tially occupied (25%). If we compare this structure with a
by C atoms. In e-Fe3C (Fig. 6(b)), only the 2d position is disordered e-Fe2.4C, the energy gain amounts to
fully occupied, thereby leading to the widest possible 39 kJ mol1 at 0 K (Fig. 7). At higher temperatures the
C–C distances (d = 3.49 Å) and corner-sharing octahedra energetic difference of the disordered structure gets slightly
throughout. reduced since it is stabilized by the configuration entropy
For this work, the question of carbon ordering is of par- term. The latter term, however, will never compensate this
amount importance. Indeed, the aforementioned ordering large enthalpy difference up to the melting point. There-
proposed by Jack [18] for Fe2.2C was corroborated by sev- fore, the existence of a disordered e-Fe2.4C can be safely
eral DFT total-energy calculations for e-Fe2C [47–49] and excluded at any temperature.
7588 W. Song et al. / Acta Materialia 61 (2013) 7582–7590

Fig. 6. Hexagonal close-packed unit cell of Fe (in red) containing all possible octahedral Wyckoff sites 2b (white), 2c (black), and 2d (grey) for the carbon
atoms (a); the ordered e-Fe3C has only carbon-filled corner-sharing octahedra (grey) by occupying all 2d sites (b). In the ordered variant of the carbon-
richer Fe2.4C, edge-sharing octahedra (red line between grey and yellow octahedra) also occur by filling 25% of the 2b site (c) while in disordered Fe2.4C
they would also be face-sharing (common plane between blue and grey octahedra; tagged with a red triangle) since Wyckoff site 2c is partially occupied.
Red lines emphasize common edges and faces (in d) between adjacent octahedra. The Wyckoff positions have been indicated.

the Gibbs free energies for the aforementioned reaction as a

function of temperature and the results are shown in Fig. 8. A
positive value of the Gibbs free energy indicates an e favored
region and a negative value indicates a cementite favored re-
gime. In a bainitic ferrite matrix and at 0 K, the Gibbs free
energy of the reaction is 1.5 kJ mol1 which means that
the formation of cementite (h) is slightly more favorable than
the formation of the hexagonal carbide. Upon increasing the
temperature, however, the reaction becomes more equili-
brated (DGR  0) because the slightly higher configurational
entropy contribution (due to more degrees of freedom be-
cause of partial carbon disorder) of the e carbide reduces
this energy difference. At 260 °C, the Gibbs energy is
0.1 kJ mol1 only and the formation of h-Fe3C and
Fig. 7. Comparison of stabilities (Gibbs free energies of formation) of e-Fe2.4C have nearly the same probability from a thermody-
randomly occupied and ordered e carbide Fe2.4C as a function of namic standpoint. In an austenitic environment, however,
temperature. the formation of cementite (h) is clearly preferred at any tem-
perature; for example, at 500 °C it is favored by 4 kJ mol1.
Since cementite (h) and e-Fe2.4C have different stoichi- The theoretical results reveal that the formation of epsilon
ometries, a direct comparison of their enthalpies is not pos- carbide does not directly depend on the temperature because
sible such that we have to generate a realistic cementite is even more favored at low temperatures. Indi-
thermodynamic balance between both phases in order to rectly, however, it does depend on the temperature since
compare the competing products. The obvious reaction in the formation benefits from a ferritic matrix. As carbides pre-
an iron matrix is the transition between e carbide/iron cipitate exclusively from austenitic matrix in upper bainite, it
and cementite (h): is inferred in terms of thermodynamics that only cementite
(h) can precipitate at 500 °C in upper bainite, while both
e-Fe2:4 C þ 0:6 Fe ¢ h-Fe3 C cementite (h) and e-Fe2.4C precipitation can occur at
where Fe is either body-centered cubic (bcc) iron in a bainit- 260 °C in lower bainite. Furthermore, e carbide is more
ic–ferritic matrix at low temperatures or face-centered cubic prone to precipitate from lower bainite than from upper
(fcc) iron in austenite at higher temperatures. We calculated bainite.
 W. Song et al. / Acta Materialia 61 (2013) 7582–7590 7589

Fig. 8. Gibbs free reaction energies between e-Fe2.4C and cementite (Fe3C, h) as a function of temperature in a ferritic (left) and an austenitic matrix
(right). Both experimental isothermal transformation temperatures (ITT) are indicated.

5. Conclusions and outlook 5. Ab initio calculations reveal that the e carbide must be a
partially ordered structure with respect to the carbon
e and h carbide precipitation and elemental partitioning distribution.
behavior in both upper and lower bainite were investigated 6. From a thermodynamic point of view, the probability of
in high-carbon bearing steel 100Cr6 using TEM and APT forming cementite and e carbide in a bainitic ferrite
in combination with ab initio (density-functional theory) cal- matrix is comparable. In austenite, however, the forma-
culations. The long-lasting questioning of e carbide existence tion of cementite is clearly preferred, namely favored by
and its transition to h carbide is proved in terms of elemental 5 kJ mol1 at room temperature and still by 4 kJ mol1
concentrations detected by APT and explained by thermody- at 500 °C. This indicates that e carbide is more prone to
namic simulations. The nanosized metastable carbides pre- precipitation from lower bainite than from upper
cipitate from upper bainite and from lower bainite under bainite.
different mechanisms. The difference of the two precipitation
mechanisms within bainite is revealed for the first time by
means of atomic-scale investigation on the elemental parti- Acknowledgements
tioning behaviors. Deeper insights into the nature of e and
h carbide precipitation were gained at the atomic scale. In This work has been performed partly within the Inter-
the future, in order to prove our APT observations in a crys- disciplinary Centre for Advanced Materials Simulation
tallographic manner and to further explore the metastable (ICAMS) at Ruhr University Bochum and partly within
carbide precipitation within bainite structure as well as the the collaborative research center (SFB) 761 of the Deutsche
e ! h transition during bainitic phase transformation, Forschungsgemeinschaft at RWTH Aachen University.
time-resolved in situ high-energy synchrotron X-ray and The authors would like to express their thanks to
TEM analysis will be carried out. In the present work, the Dr. Christoph Somsen in Ruhr-University Bochum for
results can be summarized as follows: his support with the TEM experiment and the Center for
High Performance Computing of RWTH Aachen Univer-
1. APT measurements show that both e and h precipitate sity for providing us with computational time for the ab
in lower bainite isothermally held at 260 °C and only h initio investigations. ICAMS gratefully acknowledges
precipitates in upper bainite isothermally held at 500 °C. funding from ThyssenKrupp Steel Europe AG, Bayer
2. TEM and APT reveal different sizes of e and h carbides Material Science AG, Salzgitter Mannesmann Forschung
at 260 and 500 °C. Both, e and h carbides adopt plate- GmbH, Robert Bosch GmbH, Benteler Steel/tube Man-
like shapes in lower bainite. agement GmbH, Bayer Technology Services GmbH and
3. APT reveals that e and h precipitate under paraequilib- the state of North Rhine-Westphalia as well as the
rium mode at 260 °C in lower bainite, and h precipitates European Commission in the framework of the European
under NPLE mode in upper bainite at 500 °C. Regional Development Fund (ERDF).
4. In lower bainite formation at 260 °C, a high amount car-
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