Met. Mater. Int., Vol. 23, No. 2 (2017), pp.

313~319
doi: 10.1007/s12540-017-6266-z

Crystallographic Characterizations of Eutectic and Secondary Carbides

in a Fe-12Cr-2.5Mo-1.5W-3V-1.25C Alloy
1,2 1,3,* 2 1 4 1,*
Jing Guo , Ligang Liu , Yunli Feng , Sha Liu , Xuejun Ren , and Qingxiang Yang

1
State Key Laboratory of Metastable Materials Science & Technology, Yanshan University,
Qinhuangdao 066004, China
2
College of Metallurgy and Energy, North China University of Science and Technology,
Tangshan 063009, China
3
College of Mechanical Engineering, Yanshan University, Qinhuangdao 066004, China
4
School of Engineering, Liverpool John Moores University, Liverpool L3 3AF, UK
(received date: 20 April 2016 / accepted date: 13 September 2016)

In this work, the morphology and structures of the eutectic and secondary carbides in a new high chromium
Fe-12Cr-2.5Mo-1.5W-3V-1.25C designed for cold-rolling work roll were systematically studied. The pre-
cipitated carbides inside the grains and along the grain boundaries were investigated with optical microscope,
scanning electron microscopy with energy dispersive spectroscopy, transmission electron microscopy and
X-Ray diffraction. Selected area diffraction patterns have been successfully used to identify the crystal formation
and lattice constants of the carbides with different alloying elements. The results show that the eutectic carbides
precipitated contain MC and M2C distributed along the grain boundaries with dendrite feature. The composition
and crystal structure analysis shows that the eutectic MC carbides contain VC and WC with a cubic and hexago-
nal crystal lattice structures respectively, while the eutectic M2C carbides predominantly contain V2C and Mo2C
with orthorhombic and hexagonal crystal lattices respectively. The secondary carbides contain MC, M2C,
M7C3 formed along the grain boundaries and their sizes are much larger than the eutectic carbides ones.
The secondary M23C6 is much small (0.3-0.5µm) and is distributed dispersively inside the grain. Similar to
the eutectic carbides, the secondary carbides also contain VC, WC, V2C, and Mo2C. M7C3 is hexagonal
(Fe,Cr)7C3, while M23C6 is indexed to be in a cubic crystal form.
Keywords: alloys, cold working, phase diagram, scanning electron microscopy (SEM), transmission electron
microscopy (TEM)

1. INTRODUCTION
With excellent mechanical properties and performances,
Fe-Cr-Mo-W-V-C alloy was an important steel system prin-
cipally for manufacturing cold-rolling work roll [1-3]. The
main strength enhancing mechanisms are associated with the
carbides precipitated during the solidification process [4,5].
With a complex alloying system, the type, size, quantity of the
carbides and their distributions are directly related to a series
of complicated phase transformations during solidification pro-
cess including austenite crystallization, eutectic reaction, primary
and secondary carbides precipitations [6,7]. The primary (includ-
ing pro-eutectic carbide and eutectic carbides) and secondary
carbides tend to segregate along the grain boundary forming
a coarse network after the casting and/or heat treatment pro-
cess, which would adversely affect the working performance
*Corresponding authors: lgliu@ysu.edu.cn, qxyang@ysu.edu.cn
KIM and Springer
of the roll during service. One potential way to break the car-
bides network is through a hot forging process following the
casting operation. However, due to the brittleness of the carbides,
cracks could easily initiate and propagate in the carbides and
surrounding structures. It is of great significance to analyze
the precipitation, growth and transformation of the primary and
secondary carbides during a solidification process in order to
design an optimum materials systems and/or forging process
based on the composition and structure of the materials.
The structure and properties of the carbides have been a
main research focus in traditional cold-rolling work roll alloys.
Serna et al. [8] studied the morphology and crystal structure
of the extracted MC in spray formed AISI M2 high speed
steel. Zhou et al. [9] investigated the microstructure of M2C
in high speed steel and indicated that the morphology of M2C
is changed from the plate-like type to the fibrous one with
increasing cooling rates. Hwang et al. [10] analyzed the effects
of the alloying elements on carbide types and microstructure
in six cast high speed steel rolls, and the results showed that
314 Jing Guo et al.
the MC inside the grains and the M7C3 carbides along the
grain boundary are primarily formed with high Cr content, while
fibrous M2C carbides in the intercellular regions is predomi-
nantly formed with high W and Mo contents. These published
works have greatly contributed to the understanding of car-
bide precipitation and structure-properties relationships of the
steels. However, crystallographic characteristics of the car-
bides precipitated during solidification were not provided in
details, which is not sufficient to guide the development of new
material systems with complex alloying system.
In a recent work, a novel Fe-Cr-Mo-V-W-C alloy system
for cold-rolling work roll was developed, which has achieved
a good combination of properties and formability. The newly
design alloy contains an increased Cr content and decreased
W, Mo contents [11]. During the design and development of
the steel, the stability of the eutectic carbide has been ana-
lyzed by experimental research and first-principles calcula-
tion [12,13]. With increased Cr content, the carbides inside the
grain may increase and play an active role.
In this work, the organizational characteristics of this newly
developed alloy with high Cr and low Mo/V is further inves-
tigated. The structures of carbides inside the grains and along
the grain boundaries were characterized. The crystallographic
characteristics of the carbides with different alloying elements
were established and key crystal parameters were determined,
which would provide a theoretical basis for materials design
and process optimization of the heat treatment and forging
process in order to produce cold-rolling work roll with an opti-
mum balance of working performance and formability.
2. EXPERIMENTAL PROCEDURES
The specimens were taken from the self-designed Fe-12Cr-
2.5Mo-1.5W-3V-1.25C alloy for cold-rolling work roll.
The Fe-C isopleths of the alloy were calculated by Thermo-
Calc according to its chemical composition. Based on the
Fe-C isopleths and Differential Scanning Calorimeter (DSC)
data [11], 1240 °C and 900 °C are chosen as the characteristic
temperatures of the carbides precipitation. The specimens were
firstly heated up to 1400 °C, then cooled slowly to 1240 °C
and 900 °C in a furnace, and quenched quickly into water to
freeze the microstructures for future analysis.
The specimens were polished and etched using Murakami
etchant [14] (3 g K3Fe(CN)6 + 10 g NaOH + 100 ml H2O), in
which black M2C, brown M7C3, and gray MC were selectively
etched, and then observed by a Axiovert 200 MAT Optical
Microscope. Additionally, the matrix was deep etched in an
etchant (5 g FeCl3 + 10 ml HNO3 + 3 ml HCl + 87 ml ethylal-
cohol) [15] to reveal the three-dimensional morphologies of
the eutectic carbides with a S4800-II Field Emission Scanning
Electron Microscope (FESEM). The compositions of the dif-
ferent carbides precipitated were analyzed quantitatively by
Energy Dispersive Spectroscopy (EDS). The deeply etched
specimens after quenching from 1240 °C and 900 °C were
analyzed by X-Ray Diffraction (XRD) with Cu K radiation
-1
at a scan rate of 2°·min within an angle range of 20-120° in
order to determine the phase structures.
The specimens for TEM experiments were prepared by ion
milling with a precision ion polishing system (Model691 PIPS)
and the specimens were studied by a JEM-2010 transmission
electron microscope. The microscopy was performed using
bright field and SADPs to identify the lattice structures and
constants of the carbides with different alloying elements.
3. RESULTS AND DISCUSSION
3.1. Carbide types and critical temperatures
Figure 1 shows Fe-C isopleths of the alloy between 800 °C
and 1500 °C. The carbon content of the steel is 1.3 wt%, as
marked by the straight line on the diagram, and the intersec-
tion points between the line and phase line correspond to the
temperatures of the phase transformation or carbide precipi-
tation. During equilibrium solidification process, ferrite pre-
cipitates from high temperature firstly, followed by peritectic
reaction and then austenite. Since the region of the peritectic
reaction is relatively narrow, it is reasonable to treat the pro-
cess as that austenite precipitates from liquid directly without
taking into account of the peritectic reaction. From Fig. 1, it can
be seen that the starting transformation temperatures of the
primary austenite, eutectic reaction, MC, M7C3 and M23C6 are
1379 °C, 1257 °C, 1203 °C, 1186 °C and 937 °C, respectively.
The eutectic carbides formed as part of the eutectic reaction
belong to the primary carbides, while the carbides subsequently
precipitated from the austenite below the eutectic tempera-
ture are secondary carbides. From our previous work with a
similar steel of 10-11 wt% Cr [11], an exothermic peak appears
at about 1250 °C in the DSC curve corresponding to the eutectic
Fig. 1. Fe-C isopleths of Fe-Cr-Mo-W-V-C alloy for cold-rolling
work roll.
 Crystallographic Characterizations of Eutectic and Secondary Carbides in a Fe-12Cr-2.5Mo-1.5W-3V-1.25C Alloy
Fig. 2. XRD pattern of deep-etched sample after quenching from
1240 °C.
reaction temperature. According to Fig. 1, M23C6 precipitates
at 937 °C, but no corresponding exothermic peak was observed
in the DSC curve. This is probably due to the small size of
M23C6 particles, which is below the resolution of the DSC.
Therefore, slightly lower temperatures, 1240 °C and 900 °C, are
chosen as characteristic temperatures in this work in order to
investigate the type, morphology and crystallographic char-
acteristics of the eutectic carbides and secondary carbides.
3.2. Crystallographic characteristics of the eutectic car-
bides
Figure 2 shows the XRD pattern of the deeply etched speci-
men after quenching from 1240 °C. It is clearly shown that
-Fe (martensite), MC and M2C exist at 1240 °C. Based on
Fig. 1, the ternary eutectic reaction, L→γ + MC + M2C, occurs
at 1240 °C and the microstructure consists of austenite (γ–Fe),
eutectic MC and eutectic M2C. When the specimen is quenched
from 1240 °C, the austenite is transformed into martensite,
which appears in the form of -Fe in the XRD pattern.
Figure 3 shows the microstructures of the eutectic carbide
quenched at 1240 °C. From Fig. 3a, the eutectic carbides are
mixed fine structures along the crystal grain boundaries. The
black part is eutectic M2C after etched by Murakami etchant,
while the gray one is eutectic MC, which distributes sparsely.
Three-dimensional morphologies of the eutectic carbide are
further observed after deep etching as shown in Fig. 3b and
Fig. 3c. It can be seen that both the eutectic MC and M2C exhibit
a dendritical feature. The eutectic MC is large and grows dis-
persedly with fibrous-like feature inside, whereas the leaf-like
eutectic M2C is of closely arranged finer features.
In order to determine the lattice structures of eutectic carbide,
TEM observation after quenching from 1240 °C has been car-
ried out. Figure 4 shows typical high-resolution bright-field
TEM images and SADPs of the eutectic carbides. It should
315
Fig. 3. Morphologies of eutectic carbides after quenching from 1240 °C:
(a) metallographic structure etched by Murakami etchant; (b), (c) three
dimensional morphologies of eutectic MC and M2C deeply etched by
5 g FeCl3 + 10 ml HNO3 + 3 ml HCl + 87 ml ethylalcohol.
be noted that the branch lengths of the eutectic MC and M2C
reach tens even dozens of microns due to their dendritical growth,
so the full morphologies could not be revealed on the TEM
images.
As shown in Fig. 4, the eutectic carbides contain VC, WC,
V2C and Mo2C. Each carbide has a clear unique diffraction
patterns representing a different crystal structure and lattice
constants. Figure 4a represents eutectic VC, which belongs
to the cubic system and Fm3m space group with lattice con-
stants of a = b = c = 0.4167 nm. The eutectic WC is indexed
to be of a hexagonal system and P6m2 space group with lattice
constants of a = b = 0.2900 nm, c = 0.2831 nm (Fig. 4b). Figure
4c represents eutectic V2C, which is a orthorhombic system
and Pbcn space group with lattice constants of a = 0.4577 nm,
b = 0.5742 nm, c = 0.5037 nm. Figure 4d shows that eutec-
tic Mo2C is the hexagonal system and P63/mmc space group
with lattice constants of a = b = 0.3012 nm, c = 0.4735 nm.
3.3. Crystallographic characteristics of the secondary
carbides
Figure 5 shows the XRD pattern of the deeply etched speci-
mens after quenching from 900 °C. It clearly shows that α-Fe,
MC, M2C, M7C3 and M23C6 exist in the steel at 900 °C, which
indicates that the Fe-C isopleths (Fig. 1) is relatively accurate
in predicting the secondary carbides precipitation. There are
clear index peaks corresponding to M2C on the XRD analysis
(labeled with ‘Δ’), while the carbide didn’t appear on the Fe-C
isopleths since it is a meta-stable phase as confirmed in pre-
vious work based isopleths calculation [16].
3.3.1. Compositional and crystallographic characteristics
of the secondary carbides precipitated at the grain boundaries.
316
Fig. 4. TEM images and corresponding selected area diffraction patterns (SADPs) of eutectic carbides: (a) VC, (b) WC, (c) V2C, and (d) Mo2C.
Fig. 5. XRD pattern of deep-etched sample after quenching from
900 °C.
Figure 6 shows a typical microstructure of the secondary
carbides formed along the grain boundary in the specimen
quenched at 900 °C. As illustrated in Fig. 6a, the secondary
MC, M2C and M7C3 are etched into gray, black and brown by
Murakami etchant and became easily distinguishable. Com-
pared with the eutectic carbides, the secondary carbides along
Jing Guo et al.
Fig. 6. Morphologies of secondary carbides after quenching from
900 °C: (a) metallographic structure showing mixed MC, M2C and
M7C3 distribute along the grain boundary distinguished by special
color differences etched by Murakami etchant; (b), (c), and (d) three
dimensional morphologies of secondary M7C3, MC and M2C etched
by 5 g FeCl3 + 10 ml HNO3 + 3 ml HCl + 87 ml ethylalcohol.
 Crystallographic Characterizations of Eutectic and Secondary Carbides in a Fe-12Cr-2.5Mo-1.5W-3V-1.25C Alloy 317

Fig. 7. EDS analysis of secondary carbides: (a) FESEM image and (b) EDS line analysis of AB line.

the grain boundary are significantly large. From the three-dimen-

sional morphologies of M7C3, MC and M2C in Fig. 6b-d, the
secondary MC is a bulk-like structure embeded in the matrix;
the secondary M2Cs are strip-like structure. Secondary M7C3
is relatively large with chrysanthemum-like feature and irreg-
ular bulk-like feature.
EDS analysis was performed to reveal the element compo-
sitions of the carbides along the grain boundary in specimen
quenched from 900 °C. A typical result is shown in Fig. 7.
As shown in Fig. 7a, the mixed carbides in the FESEM image
can be distinguished with different contrast. Figure 7b plots
the EDS line analysis along line A-B in Fig. 7a. The carbides
identified according to the element compositions of the carbides,
are Mo-rich M2C, V-rich MC and Cr-rich M7C3, respectively.
TEM experiment was carried out in order to determine the
specific types of the secondary MC, M2C and M7C3 along the Fig. 9. TEM image and SADP of M7C3.
grain boundary. From TEM results, it is found that, similar to
the eutectic carbides, the secondary MC and M2C consist of
VC, WC, V2C and Mo2C. Comparing the EDS results of the corresponding secondary carbides. However, the contents of
eutectic and secondary carbides (Fig. 8), the element compo- the main elements V and Mo in the secondary MC and M2C
sitions of the eutectic carbides are also similar to those of are slightly high, which is probably related to more complete
diffusion of the alloying elements after longer time heat preser-
vation at high temperatures.
Figure 9 shows the TEM morphology and SADP of M7C3.
From Fig. 9, the large bulk-like M7C3 embeded in the matrix
is (Fe,Cr)7C3. Accurate Fe/Cr ratio and Fe, Cr positions in the
crystal lattice are still unclear due to the fact that (Fe,Cr)7C3
is known to have a very wide composition range in terms of
Fe/Cr ratio with different conditions. However, the result is a
good match to hexagonal crystal system and P63mc space
group with lattice constants of a = b = 0.9135 nm, c = 0.3782 nm.

3.3.2. Compositional and crystallographic characteristics

of precipitated secondary carbides inside the grain.
As shown in Fig. 10a, a large number of the granular pre-
cipitates can be found in the specimen quenched at 900 °C.
Fig. 8. EDS analyses between eutectic and secondary MC, M2C. These carbides are distributed dispersively inside the grain.
318 Jing Guo et al.

Fig. 10. Morphologies of M23C6 inside the grain: (a) FESEM image and (b) TEM image and SADP of M23C6.

Table 1. Type, composition, morphology and crystallographic characteristics of eutectic and secondary carbide at 1240 °C and 940 °C
T (°C) Type Composition Morphology Crystallographic Characteristics
MC: fibrous-like MC: VC, WC
1240 eutectic γ–Fe, MC, M2C
M2C: leaf-like M2C: V2C, Mo2C
MC: bulk-like MC: VC, WC
M2C: strip-like M2C: V2C, Mo2C
940 secondary α–Fe, MC, M2C, M7C3, M23C6
M7C3: chrysanthemum-like M7C3: (Fe,Cr)7C3
M23C6: granular M23C6: Cr23C6

The statistic dimension measurements shows that the average
carbide size range is about 0.3-0.5 μm, which is much smaller
than the secondary carbides precipitated at grain boundaries.
TEM study of these particles shows that carbide type is Cr23C6
(Fig. 10b). The size of the particles from the TEM data is compa-
rable to the measurement data with the FESEM analysis.
The carbide type identified is also consistent with the Fe-C
isopleths data (Fig. 1). Based on the TEM SADP data (Fig. 10b),
Cr23C6 belongs to the cubic system and Fm3m space group
with lattice constants of a = b = c = 1.0659 nm. Clearly, the amount
and morphology of the carbide is associated with the higher
Cr content.
According to quench temperature (1240 °C and 940 °C),
Table 1 is provided to summarize compositional, morphological
and crystallographic characteristics of eutectic and second-
ary carbide.
are larger than the corresponding primary carbides and mixed
together along the grain boundary. M23C6 is much small with
a size of 0.3-0.5 μm and is distributed dispersively inside the
grain. The secondary MC and M2C also contain VC, WC, V2C
and Mo2C, which are similar to the eutectic carbides. M7C3 exists
in the form of hexagonal (Fe,Cr)7C3, while M23C6 is indexed
to be cubic Cr23C6. The contents of main elements V and Mo
in the secondary MC and M2C are slightly higher than those
of the corresponding eutectic carbides.
ACKNOWLEDGEMENT
The authors would like to express their gratitude for projects
supported by National Natural Science Foundation of China
(51271163) and (51471148), and program for Hebei province
Basic Research Foundation of China (16961008D).

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