MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6

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Fe–24 wt.%Cr–4.1 wt.%C hardfacing alloy: Microstructure and

carbide refinement mechanisms with ceria additive

Y.F. Zhoua , Y.L. Yanga , Y.W. Jianga , J. Yanga , X.J. Renb , Q.X. Yanga,⁎
a
State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, PR China
b
School of Engineering, Liverpool John Moores University, Liverpool L3 3AF, UK

AR TIC LE D ATA ABSTR ACT

Article history: The microstructure and carbide refinement mechanisms of Fe–24 wt.%Cr–4.1 wt.%C
Received 25 February 2012 hardfacing alloys with 0 wt.%, 0.5 wt.%, 1.0 wt.%, 2 wt.%, and 4 wt.% ceria additives have
Received in revised form 5 July 2012 been systematically investigated in this work. Optical microscopy, field emission scanning
Accepted 10 July 2012 electron microscopy with energy dispersive spectrometer, and X-ray diffraction were
collectively used to study the microstructure, the phase components, and the chemical
Keywords: formation of inclusion formed in the welding process. Wear-resistance of the alloys was
Fe–Cr–C alloy comparatively studied using an abrasive wear testing machine. The structure analysis results
Hardfacing show that the Fe–Cr–C hardfacing alloy mainly consists of martensite, retained austenite, MC
Carbide carbide and M7C3 carbide. With increasing ceria additive contents, the average size of the
RE additive primary M7C3 carbide decreases and reaches a most refined state in the alloy with 2 wt.%
Refinement mechanism ceria additives. Comparative wear tests data shows that the wear resistance of the hardfacing
alloys with ceria additives is better than that without ceria additive. In a good agreement with
the carbide refinement results, the wear resistance of the alloy reaches an optimum level in
the sample with 2 wt.% ceria additive. The main RE inclusion type identified with in-situ XRD
analysis is RE inclusion Ce2O2S. Thermodynamics calculation confirms that this type of RE
inclusion could precipitate prior to M7C3 carbides, and act as a heterogeneous nucleus for
M7C3 in the welding process, which effectively provides a mechanism for significant
refinement of the M7C3 carbide and improves its wear resistance.
© 2012 Elsevier Inc. All rights reserved.

1. Introduction
With excellent wear-resistance, heat-resistance and lower
price, Fe–Cr–C alloys have been widely used in the fields of
iron and steel industries, mining industry and cement
manufacturing equipment [1–3]. The outstanding perfor-
mance of the material at low stress abrasion conditions is
associated with a large amount of primary M7C3 carbide
within the microstructure [4]. M7C3 carbide, which is the
reinforcing phase in Fe–Cr–C alloy, is well known for high
hardness (1300–1600 HV) [5,6], excellent wear resistance [7] as
well as good corrosion resistance [8]. In many cases, the
failure of components made up of Fe–Cr–C alloy is associated
with excessive surface wear after being used for a certain
period of time. The failed part is commonly repaired to restore
its working shape, dimension and properties through a
variety of processing methods [9]. Hardfacing method by
flux-cored welding wire is one of the best effective ways
among the repairing techniques used [10].
One major technical challenge for Fe–Cr–C hardfacing alloy
is the control of carbide sizes and distributions. Despite its
wide use, several studies have shown that, some large block
primary carbides often form in Fe–Cr–C hardfacing alloy that
deteriorates the continuity between the carbides themselves
and the matrix [11,12]. This made the material prone to peel
off from the surface of the component, and in some cases,

⁎ Corresponding author. Tel.: +86 335 838 7471; fax: + 86 335 807 4545.
E-mail address: qxyang@ysu.edu.cn (Q.X. Yang).

1044-5803/$ – see front matter © 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2012.07.004
78 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
even cause the early cracking during the application process
and reduce its service life [13]. Therefore, refinement of the
primary carbide is the key to improve the property and
performance of Fe–Cr–C hardfacing alloys.
In earlier studies, some researchers have reported that the
morphology and size of the primary carbide in Fe–Cr–C alloy
could be improved by controlled alloy design [8,9,13–16]. Lin et
al. [14] investigated the effect of carbon content on morpho-
logical characteristics of the primary carbide in Fe–Cr–C alloys
and discovered that carbon could transit the morphology of
primary phase from dendritic shape with non-faceted struc-
ture to polygonal shape with faceted structure. Meanwhile,
the hardness of the alloys was found to increase with
increasing carbon content [9,13]. Zhi et al. [15] reported that
the microstructure of Fe–Cr–C alloy could be refined by
titanium additive with the TiC carbide acting as the hetero-
geneous nucleus of M7C3 carbide. Azimi and Shamanian [8]
compared Fe–Cr–C and Fe–Cr–Si–C coatings, and found that
the presence of silicon (Si) increased the corrosion-resistance
of the coating. Qi et al. [16] investigated the effect of vanadium
(V) additive on the microstructure, properties and tribological
performance of Fe–Cr–C hardfacing alloy; the results showed
that V additive could effectively refine the hardfacing micro-
structure and improve its wear resistance.
These previous works have achieved some success in
refining the carbides, but the extent of microstructure
improvement was still rather limited. On potential method,
rare earth (RE) elements are used to further improve the
structures and properties of the hardfacing alloys. It has
already been shown that, by adding RE elements in steel, the
crystal grain could be refined, the grain boundary purified and
the plasticity and toughness could be improved [17,18]. Recent
works also showed that, the abrasive wear behavior and
fracture toughness of the 0.16 wt.%C–12 wt.%Cr–Fe hardfacing
alloy can be improved with ceria additive [19]. This has laid a
good foundation for the further study in systematical research
in the effects of RE elements on microstructure and the
properties of Fe–Cr–C hardfacing alloy. However, there were
few reports about the effect of RE element on carbide
refinement [20].
In this work, a series of hardfacing alloys with different
ceria additives was prepared. The effects of cerium on the
microstructure, morphologies of the primary carbides, and
inclusion associated with the RE additives of the alloys were
systematically investigated.
2. Experimental Materials and Methods
2.1. Experimental Materials
The self-shielded flux-cored wires with different ceria addi-
tives were made by a rolling and drawing process. The outer
shell of the flux-cored wire was H08A steel. In order to
Table 1 – Chemical composition of the flux-cored wires.
Elements C Cr Si O Al
Content (wt.%) 4.0–4.2 22–26 0.3–0.5 ~0.02
maintain the chemical compositions of the Fe–Cr–C
hardfacing alloys in the hypereutectic region and achieve a
favorable self-protection function, graphite, ferrochromium,
ferrovanadium, ferromanganese, ferrosilicon, ferrotitanium
and aluminum magnesium alloys were added into the flux
cored wire. Different amounts of ceria were added to
investigate the effect of ceria additive on the primary carbide
in Fe–24 wt.%Cr–4.1 wt.%C hardfacing alloy. The chemical
compositions of the flux-cored wire used in this work are
listed in Table 1.
2.2. Experimental Methods
An automatic welding system was employed for the hardfacing
process. The base metal in the form of a plate with a thickness
of 10 mm (ASTM 1045 plate) was ground and cleaned in
acetone before the welding operations. Hardfacing alloys were
deposited following a multi-track overlapping procedure at a
constant welding speed of 300 mm/min. The welding condition
and key parameters used are listed in Table 2. Specimen
materials with different ceria additives were cut from the
hardfacing alloy by EDM wire cutting machine for chemical and
microstructure analysis. Each sample was polished and etched
in 4 wt.% nitric acid alcohol, the microstructures were observed
and analyzed on an Axiovert 200 MAT optical microscope (OM)
and Hitachi S4800 field emission scanning electron microscope
(FESEM). The inclusions within the hardfacing alloy were
analyzed by EMAX energy dispersive spectrometer (EDS). The
micro-hardnesses of the materials were measured by a FM-700
micro-hardness tester with an applied load of 300 gf and a
dwell testing time of 10 s The key constituent phases of the
specimens were determined using a D/max-2500/PC X-ray
diffraction (XRD) machine with Cu Kα radiation at a scan rate
of 2°·min−1 within an angle range of 20–120°.
Wear tests of the specimens were performed on a belt
abrasion tester in dry frictional condition for 240 min with SiC
80 grit mesh. The testing velocity of abrasive belt was set at
1.8 × 104 mm·min−1. Electronic balance was used during the
wear test to weigh the mass loss of each specimen at a time
interval of 30 min. For each alloy of different chemical
compositions, five wear tests have been performed and the
average mass loss value was calculated to represent the wear
resistance of the material.
3. Results
3.1. Microstructures, Constituent Phases and Micro-hardness
of Fe–24 wt.%Cr–4.1 wt.%C Hardfacing Alloy
Fig. 1 shows a typical microstructural morphology of the
hardfacing specimen on different planes and at different
positions. The planes along or perpendicular to carbide
growth direction (also the welding heat flux direction) were
S P Ce Fe
0.04–0.06 ~0.013 ~0.021 ~0, ~0.5, ~1.0, ~2.0, ~4.0. Bal.
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
Table 2 – Welding condition and key parameters used.
Parameter Wire diameter Voltage Current
(mm) (V) (A)
Value 3.2 22–26 200–220
termed as longitudinal and transverse planes, respectively.
The microstructure on the longitudinal (through-thickness)
section of the top hardfacing layer is shown in Fig. 1(a). On
this plane, the microstructure mostly consists of columnar
primary carbide and eutectic phase with the columnar
primary carbide growing epitaxially from the substrate.
Fig. 1(b) shows the microstructure of the main hardfacing
layer on the transverse section, the morphology of the
primary carbide is hexagonal-shaped in the cross-section
perpendicular to the heat flux direction. The micro-hardness
of the primary carbide tested on transverse plane is 1536 ±
27 HV, which is much higher than the carbide hardness on the
longitudinal section (1215 ± 21 HV). This agrees with the
finding of other published works that the Fe–Cr–C hardfacing
alloy presented higher wear resistance on the transverse
section than that on the longitudinal section [7].
As shown in Fig. 1(c), the structure of the transitional
region shows a smooth jointing region at the interface
between the substrate and hardfacing alloy. The microstruc-
ture across the top layer (as shown in Fig. 1(a)) is significantly
different from the bottom region (Fig. 1(c)). The microstructure
of the bottom section of the hardfacing alloy is of a typical
hypoeutectic microstructure consisting of primary dendrite
and eutectic phase. The primary dendrite has a hardness
Fig. 1 – Microstructural morphology of the hardfacing specimen: (a) top layer in longitudinal section (along the carbide growth
direction); (b) top layer in transverse section (perpendicular to the carbide growth direction); (c) hardfacing-substrate
transitional zone in longitudinal section.
79
Travel speed Layer thickness Tracks overlap
(mm·min−1) (mm) (%)
300 5.8–6.2 45–50
value of 550 ± 35 HV, which is the phase of lowest-hardness in
the Fe–Cr–C hardfacing alloy. As shown in the figure, the
dendrites grow from the substrate at a direction opposite to
the resultant heat flux. The primary phase and the micro-
structure of the hardfacing alloy in the bottom section reveal
that the growth of the dendrite is dependent upon the dilution
of composition due to mixing with the substrate. As the
dilution level decreases gradually away from the interface
between the substrate and hardfacing alloy, the microstruc-
ture changes from hypoeutectic to hypereutectic type along
the thickness of the hardfacing layer.
Fig. 2 shows a typical XRD pattern taken on the longitudi-
nal plane of the top hardfacing layer of the specimen without
ceria additive. It clearly demonstrates that main phases in the
specimen included M7C3 carbide, martensite, retained aus-
tenite and a little amount of MC carbide.
In order to examine the microstructure of the as-welded
Fe–Cr–C alloy in further details, transverse section of the top
hardfacing layer without ceria additive was analyzed using
FESEM and a typical image is presented in Fig. 3. As labeled on
the figure, the primary carbide is in the form of a block with a
hexagonal shape, while the eutectic carbide is in the form of
fine strips. The matrix is mainly of martensite and small
amount of retained austenite. The primary carbide formed a
80 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
Fig. 2 – XRD pattern of Fe–24 wt.%Cr–4.1 wt.%C hardfacing
alloy without ceria additive.
large fraction of the Fe–Cr–C hardfacing alloy surrounded by
the eutectic structure. All the primary and eutectic carbides
are M(Cr,Fe)7C3 carbide with the same crystal type and similar
lattice parameter [21]. During the solidification process, the
composition of surrounding liquid gradually reaches the
eutectic point with the shell of primary carbide polygon
constantly thickening [22]. As shown in Fig. 1(b), the primary
M7C3 carbide distributed in an isolated pattern as it is difficult
for these carbides to gather into a network due to the fast
welding cooling rate. This potentially could be a beneficial
feature as it will avoid causing excessive brittleness of the
hardfacing alloy.
The composition of different micro-zones labeled in Fig. 3
was semi-quantitatively determined by EDS; the results are
listed in Table 3. As shown by the data, the compositions of both
the primary M7C3 carbide and the eutectic carbides are mainly
Fe, Cr, and C. However, the primary M7C3 carbide has a relatively
higher amount of elements C and Cr than that of the eutectic
carbide. The matrix has the lowest C and Cr contents and the
highest Fe content. According to the precipitation sequence of
each phase and its mass fraction, the microstructure of the Fe–
Fig. 3 – FESEM image of Fe–Cr–C hardfacing alloy.
Table 3 – EDS results and the micro-hardness of
micro-areas in the Fe–Cr–C hardfacing alloy.
Marked Structure Hardness Chemical composition
position (HV) (wt.%)
C Cr Fe Mn
A Primary M7C3 1536 ± 27 18.13 43.58 35.44 1.28
carbide
B Eutectic M7C3 793 ± 20 8.684 24.45 65.52 1.72
carbide
C Eutectic γ 5.04 17.39 71.46 1.62
Cr–C alloy can be treated of having two main parts: primary
M7C3 carbide and eutectic (M7C3 + γ) structure.
The micro-hardness of primary M7C3 carbide and the
eutectic structure (M7C3 + γ) is also listed in Table 3. The
micro-hardness of primary M7C3 carbide is 1536 ± 27 HV, while
the hardness of the eutectic (M7C3 + γ) structure is 793 ± 20 HV.
The high micro-hardness of primary M7C3 carbide could be
attributed to its complex HCP crystal structure. The strong
atomic bonds of Cr\C give the carbide a high micro-hardness,
but a relatively weaker toughness in comparison to the eutectic
structure.
3.2. Effect of Ceria Additive on the Primary M7C3 Carbide
in Fe–Cr–C Hardfacing Alloy
The microstructures on the transverse plane of hardfacings
with different ceria additions (0 wt.%, 0.5 wt.%, 1.0 wt.%,
2 wt.%, and 4 wt.%) are shown in Fig. 4(a–e) As shown in
Fig. 4(a), the primary M7C3 carbide of polygonal form is
unevenly distributed with an irregular shape in the alloy
without ceria additive. In some regions carbides were closely
packed together, which could have adverse effects on the
properties of the material (such as reduced toughness). With
increasing amount of ceria additive (Fig. 4(b–e)), the primary
M7C3 carbide becomes more evenly distributed, the shape of
the carbides became more regular and its size becomes much
smaller. As shown in Fig. 4(d), the carbide size is the smallest
in the alloy with a ceria addition of 2 wt.% rather than 4 wt.%
(Fig. 4(e)), indicating an optimum level of carbide refinement.
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6 81

Fig. 4 – Optical microstructure images of top Fe–Cr–C hardfacing alloy in transverse section with (a) 0 wt.% ceria additive;
(b) 0.5 wt.% ceria additive; (c) 1 wt.% ceria additive; (d) 2 wt.% ceria additive and (e) 4 wt.% ceria additive.

The primary M7C3 carbide with 4 wt.% ceria addition begins to
turn coarser but overall structure is still much finer than the
alloy without ceria additive.
The average diameter of the primary M7C3 carbide in
hardfacing alloys was measured by a quantitative metallographic
method; the results are shown in Fig. 5. The data clearly shows
that the average carbide size decreases with the amount of RE
addition and reaches an optimum level with a ceria addition of
2 wt.%. The average diameter of primary M7C3 carbides in the
hardfacing alloy without ceria additive is 18.0 μm, which is
decreased to 6.8 μm in the alloy with 2 wt.% ceria addition. With
further increase of ceria addition, the primary M7C3 carbide
begins to coarsen reversely, and the average carbide size in the
alloy with 4 wt.% ceria addition is 10.5 μm. In addition to the
carbide size refinement, the uniformity of carbide size is also
improved with ceria addition. As shown in the figure, the
standard deviation of the measured carbide size decreased from
4.97 μm (0 wt.% ceria addition) to 1.32 μm (2 wt.% ceria addition).

3.3. Effect of Ceria Additive on the Wear Resistance of the

Fe–Cr–C Hardfacing Alloy

Fig. 5 – Average diameter of primary M7C3 carbide with
different ceria additives.
The mass loss vs. wear time data of hardfacing alloys with
different amount of ceria additives is plotted in Fig. 6. In all
cases, the mass loss of the alloy increased with the wear time
exhibiting a much sharper increase in the initial testing stage.
All the alloys with ceria additive showed higher wear
resistance than the alloy without ceria additive. The wear
resistance of the alloy with 2 wt.% ceria additive is the highest
among the samples comparatively tested with a wear loss
82 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
Fig. 6 – Relationship between the wear time and mass loss.
reduction of about 50% in comparison to the alloy of no ceria
additive. When the amount of ceria additive is further
increased to 4 wt.%, the mass loss increased reversely. It was
known that wear resistance is dependent on morphology,
size, amount and distribution of carbides [23]. From the
previous works, the main failure forms of Fe–Cr–C alloys
were micro-scratches and craters [22]. When the carbides
were refined, the scratches became discontinuous and the
fracture of carbides was avoided, which therefore corresponds
well to the carbide size measurement results (Figs. 3 and 4);
the optimum wear resistance with the alloy with smallest
carbide size showed that refining the carbides with optimum
amount of ceria additive could effectively enhance the wear
resistance of the Fe–Cr–C hardfacing alloy.
3.4. Analysis of the Inclusions Related to Ceria Additive in
Hardfacing Alloy
Fig. 7(a) shows a typical FESEM image of primary carbide with
an RE rich inclusion. As shown in the image, one of the
inclusions is embedded in the primary M7C3 carbide. XRD
Fig. 7 – FESEM image and EDS analysis of the inclusion in hardfacing alloy with ceria additive.
analysis has been performed on the inclusion labeled as EDS
position in Fig. 7(a); the result (Fig. 7(b)) revealed the inclusion
as a phase enriched by RE element Ce. This confirmed that the
RE inclusion is distributed within the primary M7C3 carbides.
From the XRD pattern of the hardfacing (Fig. 8), apart from
M7C3 carbide, MC carbide, martensite and retained austenite,
RE phase Ce2O2S is also observed in the alloy. However, CeO2,
which was originally added into the flux cored wire, was not
observed in this experiment. This suggests that, during the
hardfacing process, the element Ce changes its chemical form
from CeO2 to Ce2O2S. Details of the transformation mecha-
nism based on thermodynamics calculation are presented in
the Discussions section.
4. Discussions
4.1. Thermodynamics Calculation for the Formation of RE
Inclusion in the Fe–Cr–C Alloy System
As shown in the microstructure analysis, the primary M7C3
carbide in the Fe–Cr–C hardfacing alloy has shown significant
refinement with the use of ceria additive. In order to
investigate the mechanism of carbide refinement, the ther-
modynamics for the formation of the inclusions and related
chemical reactions in the weld pool were calculated to
establish the effect of RE inclusions on the primary carbides
formation in Fe–Cr–C alloy.
Assuming all the elements in the welding pool existed in a
dissolved form, the reactions related to element Ce may occur
with element oxygen (O), sulfur (S), aluminum (Al), or a
combination of O and S when ceria additive is added into the
melt. The occurrence of the reactions in the weld pool is
mainly determined by the free energy for formation ΔG, which
can be calculated by Eq. (1).
α resultant
ΔG ¼ ΔG0 þ RT lnJ ¼ ΔG0 þ RT ln ð1Þ
α reactant
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6 83

Table 5 – Approximating composition of the Fe–Cr–C alloy

for thermodynamics calculation.
Elements C Cr Si Al O S P Ce
Content (wt.%) 4 24 0.5 0.04 0.02 0.013 0.021 2

½Ce þ ½O þ 1=2½S ¼ 1=2Ce2 O2 S ð6Þ

½Ce þ ½S ¼ CeS ð7Þ

½Ce þ 3=2½S ¼ 1=2Ce2 S3 ð8Þ

½Ce þ 4=3½S ¼ 1=3Ce3 S4 : ð9Þ

The standard free energyΔGΘ of the above reactions can be

Fig. 8 – XRD pattern of the Fe–Cr–C hardfacing alloy with ceria obtained by Eqs. (10)–(15) [23].
additive.
ΔGΘEq:ð4Þ ¼ −1366460 þ 427:12T ð10Þ

ΔGΘEq:ð5Þ ¼ −714380 þ 265:53T ð11Þ

where αresultant and αreactant are the activities of the resultant and
reactant in the weld pool, respectively. The activity αi and the ΔGΘEq:ð6Þ ¼ −790567 þ 142:8T ð12Þ
activity coefficient fi can be calculated by Eq. (2) and Eq. (3).
ΔGΘEq:ð7Þ ¼ −721130 þ 294:0T ð13Þ
α i ¼ f i ½%i ð2Þ

X
n ΔGΘEq:ð8Þ ¼ −536420 þ 242:7T ð14Þ
lgf i ¼ eji ½%j ð3Þ
j¼1
ΔGΘEq:ð9Þ ¼ −497670 þ 157:15T: ð15Þ
where [%i] is the mass percentage of element i in the weld pool,
eji is the interaction coefficient between elements i and j. For If the reaction products CeAlO3, Ce2O3, Ce2O2S, CeS, Ce2S3
Ce and Ce3S4 exist in the welding pool as independent phase, the
example, the interaction eO represents the coefficient between
element Ce and O in the weld pool. The interaction coefficient eji activity of the each resultant αresultant of Eqs. (4)–(9) equals to 1.
between different elements in the hardfacing pool is listed in Thus, the formation free energy ΔG of Eqs. (4)–(9) can be
Table 4 [15,24]. obtained by Eqs. (1)–(3) and Eqs. (10)–(15).
In order to simplify the calculation, the mass percentage of
the main element is estimated based on approximate values ΔGEq:ð4Þ ¼ −1366460 þ 526:54T ð16Þ
and listed in Table 5. The activity αi and activity coefficient fi
are calculated by Eq. (2) and Eq. (3) and listed in Table 6. The ΔGEq:ð5Þ ¼ −714380 þ 334:08T ð17Þ
formation temperature of primary M7C3 carbide used in the
calculation was 1553 K [25–29]. ΔGEq:ð6Þ ¼ −790567 þ 232:41T ð18Þ
For the RE compounds to be related with carbide refine-
ment mechanisms during the welding process, the RE
ΔGEq:ð7Þ ¼ −721130 þ 337:85T ð19Þ
compounds should precipitate prior to the primary M7C3
carbide. The reaction products of RE oxides, RE doped
oxysulfides and RE sulfides may be formed according to ΔGEq:ð8Þ ¼ −536420 þ 374:44T ð20Þ
Eqs. (4)–(9).
ΔGEq:ð9Þ ¼ −497670 þ 332:74T: ð21Þ
½Ce þ ½Al þ 3½O ¼ CeAlO3 ð4Þ

Combining Eqs. (4)–(9) and Eqs. (16)–(21), it can be conclud-

½Ce þ 3=2½O ¼ 1=2Ce2 O3 ð5Þ ed that, RE compounds CeAlO3, Ce2O2S, CeS, and Ce2O3 form

Table 4 – Interaction coefficient eji of the different elements in the melted hardfacing pool.
eij C O S P Si Mn Ni Cr Al Ce V B

O −0.45 −0.20 −0.133 0.07 −0.131 −0.021 0.006 −0.04 −3.9 −0.57 −0.3 −2.6
S 0.112 −0.27 −0.028 0.029 0.063 −0.026 – −0.011 0.035 −1.91 −0.016 0.13
C 0.14 −0.34 0.086 0.042 0.088 −0.012 0.012 −0.024 0.043 −0.0067 −0.077 0.24
Ce −0.077 −5.03 −3.94 1.76 0.013 0.13 – – −2.25 −0.003 –
Al 0.091 −6.6 0.03 – 0.0056 – – – 0.045 −0.43 0.045
84 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
Table 6 – Activity coefficient and activity of alloy element
of the Fe–Cr–C alloy.
Activity ai aO aS aCe aC
0.063 0.005 1.025 2.346
Activity coefficient fi fO fS fCe fC
3.166 0.420 0.512 0.586
in the welding pool in sequence at 1600 K. While, the Ce2S3
and Ce3S4 cannot exist as their formation free energy ΔG are
far greater than zero. Based on the XRD analysis, the existence
of CeAlO3, CeS, and Ce2O3 was not observed in the hardfacings
with, RE doped oxysulfides Ce2O2S being the main RE related
inclusion in Fe–Cr–C alloy. The carbide refining mechanism to
be analyzed in the next section will then be focused on
Ce2O2S. The result also suggests that the ceria additive has
played an active role of deoxygenation and desulfurization
during the Fe–Cr–C alloy hardfacing.
4.2. Refinement Mechanism of Primary M7C3 Carbide with
Ce2O2S as the Heterogeneous Nucleus
Due to the fast cooling rate in a hardfacing process, the critical
nucleation dimension of the primary M7C3 carbide is small
and a large number of nuclei formed during the solidification
process. In this situation, the resistance of the heterogeneous
nucleation, which is mainly the interfacial energy between
the substrate and the nucleated solid phase, can be deter-
mined by calculating the lattice misfit δ. The one-dimensional
lattice misfit can be defined as [30]:
δ ¼ Δa0 =a0
where Δa0 is the interatomic spacing difference between the
substrate and the nucleated solid phase, and a0 is the
interatomic spacing on the nucleated solid phase.
By considering the angle difference between the substrate
and the nucleated solid phase, Bramfitt [31] has proposed a
theory that, two-dimensional lattice misfit is more rational
than one-dimensional one for estimating the effectiveness of
some inclusions acting as the heterogeneous nuclei. A
Fig. 9 – Crystal structure of (a) nucleated solid phase Ce2O2S [32] and (b) substrate Cr7C3 [33].
mathematical model of the two-dimensional lattice misfit
was defined as:
aAl
0.025
3 h
X   i
fAl ðhklÞ  i i  i
0.623 δðhklÞs ¼ d½uvws cosθ−d½uvwn =d½uvwn =3  100 ð23Þ
n
i¼1
where
(hkl)s is a low-index plane of the substrate;
[uvw]s is a low-index direction in (hkl)s;
(hkl)n is a low-index plane in the nucleated solid phase;
[uvw]n is a low-index direction in (hkl)n;
d[uvw]n is the interatomic spacing along [uvw]n;
d[uvw]s is the interatomic spacing along [uvw]s;
θ is the angle between the [uvw]s and [uvw]n (θ ≤ 90°).
According to Bramfitt's theory, a nucleation system with
δ < 6% is the most effective, while that with δ = 6–12% is
medium effective and that with δ > 12% is ineffective during
heterogeneous nucleation [31]. In this system concerned in
this work, the space group of Ce2O2S is rhombohedra. Its
lattice parameters are as follows: a = b = 4.01 nm, c = 6.83 nm
[32]. M7C3 has a hexagonal structure. Its lattice parameters are
as follows: a = b = 6.88 nm, c = 4.54 nm [15,33]. The crystal
structure of Ce2O2S and Cr7C3 is shown in Fig. 9 [32,33]. In
the calculation, the formula of the two-dimensional lattice
misfit has been revised for a better interface matching by
selecting the interatomic spacing on certain low-index plane.
The calculated crystal relationship between Ce2O2S and Cr7C3
is shown in Fig. 10, and the calculated lattice misfit results
ð22Þ
between the (001) plane of Ce2O2S and selected active planes
of Cr7C3 are listed in Table 7.
The two-dimensional lattice misfit between (001)Ce2O2S and
(110)M7C3, (001)Ce2O2S and (100)M7C3, (001)Ce2O2S and (111)M7C3 is
6.2%, 8.2%, and 7.4%, respectively. According to the Bramfitt's
theory, Ce2O2S acting as heterogeneous nuclei of the primary
M7C3 carbide is middle effective, which could provide an
effective mechanism to refine the primary carbide in the
Fe–Cr–C hardfacing alloy.
 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6 85

Fig. 10 – Relationship of crystallizing planes and their diagrammatic drawings of Ce2O2S and M7C3: (a) crystal faces (001)Ce2O2S to
(110)M7C3; (b) crystal faces (001)Ce2O2S to (100)M7C3; (c) crystal faces (001)Ce2O2S to (111)M7C3. The gray solid circle represents the
atoms in Ce2O2S, and the hollow circle represents the atoms in M7C3 carbide, respectively.

21 HV on the transverse plane and longitudinal planes,

5. Conclusions
• The microstructure of Fe–24 wt.%Cr–4.1 wt.%C hardfacing
alloy mainly consists of martensite, retained austenite,
M7C3 carbide and a small amount of MC carbide. The
primary M7C3 carbide grows epitaxially from the substrate
opposite to the resultant heat flux direction. The micro-
hardness of primary M7C3 carbide is 1536 ± 27 HV and 1215 ±
respectively; the hardness of the eutectic (M7C3 carbide + γ)
is 793 ± 20 HV.
• The primary M7C3 carbide could be modified by ceria
addition. The carbide size decreased with ceria addition
and reached an optimum (most refined state) value (6.8 μm)
with 2 wt.% ceria addition. The Fe–Cr–C hardfacing alloys
with ceria additive exhibited higher wear-resistance than
that of alloy without ceria additive. The alloy with 2 wt.%

Table 7 – Planar misfit between M7C3 and Ce2O2S.

Matching interface (001)Ce2O2S//(110)M7C3 (001)Ce2O2S//(100)M7C3 (001)Ce2O2S//(111)M7C3
h i h i h i h i h i h i h i h i h i
[uvw]Ce2O2S 121 220 201 120 210 100 120 230 210
h i h i h i h i
[uvw]M7C3 [111] 111 110 [110] [011] [001] 110 120 [011]
cos θ 0 5.26 0 0 15 0 0 0 0
dCe2O2S 11.27 11.34 10.53 8.97 8.97 4.01 8.97 14.56 8.97
dM7C3 10.73 10.73 9.73 9.73 8.24 4.54 9.73 15.38 8.24
δ, % 6.2 8.2 7.4
86 MA TE RI A L S CH A R A CT ER IZ A TI O N 7 2 (2 0 1 2) 7 7–8 6
ceria, showed the highest wear-resistance with a 50%
increase, which corresponds well to the microstructure
analysis results of optimum carbide size and distribution.
• The formation of RE inclusion Ce2O2S, which precipitates
prior to M7C3 carbides. The calculated two-dimensional
lattice misfit between (001)Ce2O2S and (110)M7C3, (001)Ce2O2S
and (100)M7C3, (001)Ce2O2S and (111)M7C3 is 6.2%, 8.2%, and
7.4%, respectively, which indicates that RE inclusion Ce2O2S
is middle effective as a heterogeneous nucleus for M7C3 and
ceria additive could be effectively used to refine the M7C3
carbide in Fe–Cr–C hardfacing alloy.
Acknowledgments
The authors would like to express their gratitude for the
project support by the Program for one Hundred Excellent
Talents of Hebei Province of China and the Key Project of
Science and Technology of Hebei Province (09215106D).
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