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A comparative study of Cr7C3, Fe3C and Fe2B in cast iron both from ab initio
calculations and experiments

Article in Journal of Physics D Applied Physics · May 2009

DOI: 10.1088/0022-3727/42/11/115415

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 42 (2009) 115415 (16pp) doi:10.1088/0022-3727/42/11/115415

A comparative study of Cr7C3, Fe3C and

Fe2B in cast iron both from ab initio
calculations and experiments
B Xiao1,2,3 , J D Xing1,4 , J Feng2,4 , C T Zhou1 , Y F Li1 , W Su1 , X J Xie3
and Y H Cheng3
1
State Key Laboratory of Mechanical Behavior of Materials, School of Materials Science and
Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
2
Key Laboratory of Advanced Materials of Precious-Nonferrous Metals, Education Ministry of China,
and Key Lab of Advanced Materials of Yunnan Province, Kunming University of Science and
Technology, Kunming 650093, People’s Republic of China
3
State Key Laboratory of Electrical Insulation and Power Equipment, Xi’an Jiaotong University,
Xi’an 710049, People’s Republic of China
E-mail: [email protected] (J D Xing) and [email protected] (J Feng)

Received 12 November 2008, in final form 9 April 2009

Published 14 May 2009
Online at stacks.iop.org/JPhysD/42/115415

Abstract
The ground state properties of three compounds, Cr7 C3 , Fe3 C and Fe2 B, are investigated using
ab initio calculations based on density functional theory. Formation enthalpy values indicate
that Cr7 C3 is the most stable crystal among the three compounds. Fe3 C is metastable which
has a positive heat of formation value. The calculated bulk modulus, shear modulus and
Young’s modulus value of Cr7 C3 are 311 GPa, 143.8 GPa and 374 GPa, respectively. The bulk
modulus values of Fe2 B and Fe3 C are 194 GPa and 258 GPa. We also find that both the
hardness and the stiffness of the Cr7 C3 type carbides can be improved by doping with B, W,
Mo, etc. The bulk modulus of transition metal doped Fe2 B is considerably higher than pure
Fe2 B. The electronic structures of Fe2 B and Fe3 C are ferromagnetic and the evaluated average
magnetic moment of Fe is 2.09µB /atom for Fe3 C and 2.02µB /atom for Fe2 B, respectively.
Micro-indentation test results indicate that Cr7 C3 is the hardest phase among the three phases
and shows excellent wear resistance performance under three-body abrasive experiments. The
experimental results are in agreement with the theoretical prediction that Cr7 C3 is the best both
in stability and mechanical performance.
(Some figures in this article are in colour only in the electronic version)

Introduction during the solidification of the melt iron. To control the

shapes and sizes of these compounds is always important so
Wear resistant materials have been widely used in the industrial as to obtain excellent mechanical performance for the whole
field since the beginnings of industrialization. Efforts to material. Much experimental study has been conducted on
develop advanced wear resistant materials have never ceased. this aspect [1–12]. The single phase of these compounds
Cast iron could be the most important one among them. The has already been synthesized by various non-equilibrium
mechanical performance of cast iron can be greatly improved methods. For example, Hirota et al [13] used pulsed electric-
by precipitated compounds, such as Cr7 C3 in high content current pressure sintering to fabricate Cr7 C3 , Cr23 C6 and Cr3 C2
Cr cast iron [1–9], Fe3 C in white cast iron [7] and Fe2 B in simultaneously. Iron borides can be obtained by ball milling.
boron cast iron [10, 11]. All of these phases could be formed Other methods such as sputtering deposition, chemical vapour
deposition (CVD) and physical vapour deposition (PVD) can
4 Authors to whom any correspondence should be addressed. also be used to prepare the single phases of these compounds.

0022-3727/09/115415+16$30.00 1 © 2009 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

However, the ground state properties of Cr7 C3 , Fe3 C and Fe2 B to verify our calculation results. Finally, we discussed the
have long remained unclear. In recent years, first principles tribological behaviour and dynamic damage mechanisms of
calculations based on density functional theory (DFT) have these compounds in wear resistant cast iron briefly based on
become a powerful tool to investigate the electronic, stability our previous works.
and mechanical properties of condensed matter. It is very
suitable to study the equilibrium properties of compounds that 1. Calculation details and experimental procedures
cannot be synthesized on a large scale or are very difficult to
obtain enough samples for mechanical tests. Many carbides 1.1. Models and algorithm
and borides of transition metals show excellent physical or
chemical properties, such as high melting point, high hardness, All the calculations in this paper were carried out using
high temperature oxidation resistance and can also be used as the ab initio method based on DFT [26–29]. A plane
catalysts for many important organic reactions (hydrogenation, wave expansion technology as implemented in the CASTEP
dehydrogenation) [14, 15]. Many calculations are devoted code was applied with a kinetic energy value of 350 eV.
to investigating these aspects. Shein et al [16] studied the The interactions between valence electrons and the ionic
electronic and magnetic properties of X3 C (X = Fe, Co, Ni) core were represented by ultra-soft pseudo-potentials (USPP).
by applying DFT calculations. They found that Fe3 C was A k point mesh of 10 × 10 × 10 was selected for the
metastable and had a positive value of formation enthalpy. energy integrations in the first irreducible Brillouin zone with
Liao et al [15] investigated three low index planes of Fe3 C the Monkhorst–Pack scheme [30]. We employed gradient
((1 0 0), (0 1 0) and (0 0 1) planes) that were absorbed with a corrected exchange-correlation energy of the PBE (Perdew–
carbon monoxide (CO) molecule with the CASTEP code. The Burke–Ernzerhof) scheme to represent many body interactions
effect of magnetic state on the equation of state (EOS) of Fe3 C among electrons [31]. The Pulay density mixing scheme
has also been studied by Vočadlo et al [17] by first principles was applied for the electron energy minimization process
calculations (VASP code). Chen and co-workers [18] have [32]. Crystal optimization was conducted by the BFGS
applied empirical potentials to study the stability, mechanical (Broydene–Fletchere–Goldarbe–Shanno) method where both
and thermodynamic properties of X7 C3 (X = Mn, Cr, Fe). atomic positions and lattice parameters were optimized based
They concluded that Cr7 C3 was the most stable structure on total energy minimization [33]. The total energy changes
among the three compounds. Music et al [19] investigated during the optimization process were finally converged to
the electronic structures and mechanical properties of Cr7 C3 1 × 10−6 eV and the force per atom was reduced to
using the VASP code and found the bulk modulus value of this 0.01 eV Å−1 . The valence electrons considered in this study
compound to be near 308 GPa, for Young’s modulus it was are 3s2 3p6 3d5 4s1 4p, 3d6 4s2 , 2s2 2p2 and 2s2 2p1 for Cr, Fe, C
371 GPa. They also discovered a very interesting chemical and B, respectively.
bonding feature that the strong covalent Cr–C–Cr chains were We have studied three pure compounds in this paper;
immersed in the delocalized free electron gas of metallic bonds. they are Cr7 C3 , Fe2 B and Fe3 C. The space group is Pnma,
Sterneland et al [20] studied the solubility of Co in Cr7 C3 both I -4/mcm and Pnma for Cr7 C3 , Fe2 B and Fe3 C, respectively.
from the ab initio method and experiment. More recently, The corresponding cell parameters and Wyckoff positions for
the electronic structure, stability and elastic constants of three distinct atoms are listed in table 1. Since the ground states of
Fe2 B polymorphs were calculated using DFT in [21, 22]. It is Fe3 C and Fe2 B are ferromagnetic, the spin polarized scheme
indicated that one of the polymorphs of Fe2 B is unstable and should be considered [16, 34, 37]. In order to estimate the
can be prepared by applying non-equilibrium methods. Several relative stability of these compounds, we need to investigate
multi-component carbides in the irons were investigated by the the thermodynamic properties such as cohesive energy and
first principles calculations, such as (Fe,Si)3 C, (Fe,Cr)3 C and formation enthalpy which can be calculated using equations (1)
Fe12 Cr12 W4 C8 B4 [23–25]. These calculations may provide and (2).
more information on the electronic properties and mechanical Etotal (Cell)−7nEisolate (Cr)−3nEisolate (C)
performances of real carbides in steels and irons. Ecohesive (Cr 7 C3 ) = ,
n
In this paper, we have also used first principles calculations (1)
to investigate the ground state properties of these compounds
Etotal (Cell)−7nEbinding (Cr)−3nEbinding (C)
(both the pure compounds and the corresponding multi-
r Hm (Cr 7 C3 ) = .
component carbides), but our main emphasis is on the n
(2)
mechanical aspect. The calculated electronic structure and
stability order of Cr7 C3 , Fe2 B and Fe3 C may be extremely Here, Ecohesive (Cr 7 C3 ) and
r Hm (Cr 7 C3 ) are the cohesive
useful for us to clearly understand the origin of such energy and formation enthalpy of Cr7 C3 , respectively.
mechanical performance, because the mechanical response Etotal (Cell) is the total energy of a calculated cell; Ebinding (X) is
of solids, as we knew, is determined by chemical bonding the cohesive energy of pure element X per atom and Eisolate (X)
among distinct atoms. The mechanical properties, electronic indicates the total energy of an isolated X atom; finally n refers
structure and stability of these compounds were compared and to the formula number of Cr7 C3 contained in each cell. The two
discussed in detail. Moreover, we prepared three kinds of cast energy definitions for the other compounds are the same and
iron and conducted micro-indentation tests on the (Fe, Cr)7 C3 , are eliminated here. In order to calculate the cohesive energy
(Fe, Cr)3 C and Fe2 B phases in these cast iron samples in order and the corresponding chemical potential of the single element,

2
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Table 1. Cell parameters of the studied structures determined both by experimental analysis and calculations.

Lattice parameters (Å)

Atomic positions
Species Space group Point group a b c Wyckoff symbols Reference
Cr7 C3 Pnma mmm 4.526 7.010 12.142 Cr C [35]
4c 4c
8d 8d
Fe2 B I -4/mcm 4/mmm 5.11 5.11 4.249 Fe B [21]
5.109 5.109 4.249 8h 4a [34]
Fe3 C Pnma mmm Fe C
5.09 6.748 4.523 8d 4c [16]
Pnma mmm 5.0875 6.7484 4.5219 4c [56]
Theoretical results of cell constants
Species Methods a b c Volume Reference
Cr7 C3 CASTEP-GGA 4.519 6.890 12.102 376.766 This work
Fe2 B CASTEP-GGA 5.016 5.016 4.216 106.119 This work
CASTEP-GGA 4.838 4.838 4.208 98.488 [21]
CASTEP-GGA 5.017 5.017 4.217 106.138 [22]
Fe3 C CASTEP-GGA 4.9959 6.6828 4.4467 148.461 This work
CASTEP-GGA 5.058 6.703 4.506 152.77 [16]
VASP-GGA 5.02 6.74 4.50 153.01 [15]
FLAPW-GGA 5.1281 6.6512 4.4623 152.20 [23]
CASTEP-GGA 4.9938 6.6962 4.4424 148.559 [24]
LMTO 5.089 6.743 4.523 155.207 [37]
VASP 5.036 6.724 4.480 151.7 [38]
VASP 5.058 6.703 4.506 152.77 [39]

graphite C, BCC Fe, BCC Cr and α-boron were used in this increases up to 4% for the non-spin polarized case and much
paper [36]. For the practically used irons or steels, the chemical better results can be achieved by considering the spin polarized
compositions of the borides and carbides usually deviate calculation (reduced to 1.45%). In [19], another polymorph
from the corresponding stoichiometric formula. Instead, they of Cr7 C3 (Pmcn) has been investigated by DFT with the
can be properly designated as multi-component compounds, GGA scheme and the same trend is obtained. More recently,
for example (Fe, Cr)3 C, (Fe, Cr)7 (C, B)3 , etc. During the Shein et al [16] applied the ab initio algorithm to investigate
preparation of the paper, we also calculated several multi- the stability and electronic structure of M3 X(M = Fe, Co,
component carbides of the Fe3 C and Cr7 C3 type, respectively. Ni; X = C or B). When comparing the calculated cell
Their mechanical properties will be reported in this paper for a parameters of Fe3 C with those of the experimental results, they
better comparison with experimental results. The electronic got the same conclusion. The valence electrons in metallic
structures and crystal structures of these multi-component compounds are distributed almost uniformly in the space.
carbides will be published in other papers [22, 24, 25]. This means that the exchange-correlation energy errors caused
Figure 1 shows the crystal structures of these compounds. by the variation of electron density are less important and
The complete descriptions of these crystals can be found in the cell constants obtained with local density approximation
[6, 9, 16, 21, 35]. Atomic configurations in Cr7 C3 and Fe3 C (LDA) are close to generalized gradient approximation (GGA)
are similar to each other; and the carbon atom is placed at the results. In order to verify the above conjecture, we recalculated
centre of the triangular prisms of metal atoms. However, in the cell constants of Fe2 B both by LDA and GGA. With
Fe2 B, we can see a sheet structure along the z axis where the spin polarized method, the calculated cell constants are
the B layer and the Fe layer are configuring alternately. a = b = 4.80 Å, c = 4.145 Å and a = b = 5.02 Å,
Structural differences may lead to different chemical bonding c = 4.226 Å for LDA and GGA, respectively. On the other
features and can profoundly affect the mechanical properties hand, for the spin non-polarized GGA calculation, they are
and chemical stability of the compound. a = b = 4.85 Å, c = 4.21 Å, clearly indicating that both
Since we have applied the gradient corrected exchange- the exchange correlation scheme and the magnetic state are
correlation scheme in this study, one could observe the important to obtain the correct ground state properties of Fe2 B.
overestimated results of the cell parameters. However, as Therefore the spin polarized GGA method was applied for most
can be seen from table 1, the cell parameters for all these of the calculations in this paper.
compounds are underestimated. The average deviations of
the theoretical results from the experiments are all less than 1.2. Experimental procedures
2% except for Fe2 B. In the case of Fe2 B, we have observed an
enormous displacement of Fe and B atoms at the (0 0 1) plane 1.2.1. Preparation of samples. In this study, three specimens
during the optimization and consequently the cells are clearly were prepared from high boron cast iron, high chromium cast
contracted along the x and y axes. The average deviation iron and hypereutectic white cast iron, respectively. These

3
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

(a) (b)

(c)

Figure 1. Crystal structures considered in this study: (a) Cr7 C3 (Pnma); (b) Fe2 B (I 4/mcm); (c) Fe3 C (Pnma); projection direction and
symbols for different atoms are also illustrated in the figure.

samples were fabricated by melting the raw materials through 3.5Cr, 0.8Si and trace amounts of Mn. The obtained phases
the intermediate frequency electric induction furnace and the were cementite (Fe3 C type carbides) and ferrite. No further
processing is summarized as follows. heat treatment was conducted for the samples of white cast
The first step was the fabrication of high boron cast iron in order to preserve the coarse Fe3 C.
alloy. Raw materials were prepared using pig iron, scrap We prepared three specimens from the above materials
steel, pre-alloy powders of Fe–Si and Fe–B, Mn–Fe alloy respectively, in order to compare the mechanical properties of
and copper plate, etc. The boron cast iron samples were each compound (Fe2 B, (Cr, Fe)7 C3 , and (Fe, Cr)3 C). Since
produced by investment casting. First, raw materials were the Fe3 C phase is metastable, the appropriate amount of Cr
added into the induction furnace except Fe–B pre-alloy. Before
should be added in the raw materials in order to obtain the
beginning to pour molten alloy (overheated up to 1873 K)
coarse Fe3 C compound in the white cast iron. In the case of
into the mould, Fe–B pre-alloy was added into the molten
high content Cr cast iron, the Cr7 C3 type multi-component
steel. The prepared boron cast iron has the following chemical
carbides are thermodynamically stable when the Cr content
composition (wt%): 0.39C, 2.04B, 1.33Mn, 1.12Cr, 0.29Cu,
is above 20 wt%. In both cases, the hypereutectic conditions
1.17Si, 0.044S, 0.031P (a negligible amount of P and S) and
the rest Fe. The typical microstructure of the boron cast ensured that the precipitated primary carbides are sufficiently
iron in the cast state consists of three phases, coarse Fe2 B, large for the micro-indentation tests. The observation of the
ferrite and cementite. In order to improve the hardness of microstructures was conducted both by optical microscopy
the matrix, the boron cast iron was heated at 950 ◦ C for (NEOPHOT-21) and scanning electron microscopy (CSM-950
1.5 h, and then quenched in water and finally annealed at SEM, Germany); the phase identification was carried out by
180 ◦ C for 4 h. Therefore, the obtained phases were martensite using an x-ray diffraction analyzer (MXP21VAHF), Cu Kα was
and Fe2 B. used for the diffraction and the scanning step was 2◦ min−1
High content chromium cast iron was prepared using from 10◦ to 90◦ . The micro-composition of the phase was
commercially available 3Cr15 with a chemical composition determined with an electron probe micro-analyzer (EPMA-
of (wt%): 15.0Cr, 3.1C, 1.0Mo, 1.0Cu and the rest Fe. The 1600, Japan). Figure 2 illustrates the microstructures of the
fabricated samples were held at 980 ◦ C for 2 h, then cooled two cast iron samples, the high B cast iron and the high Cr
in air and then annealed at 300 ◦ C for 2 h and cooled slowly cast iron, in figures 2(a) and (b), respectively. It is evident
in the furnace. The microstructure was attributed mainly to that the obtained carbides or borides in the prepared cast iron
Cr7 C3 type carbides and martensite. are sufficiently large for the micro-indentation tests. The
The last step was an effort to achieve hypereutectic white diffraction patterns for the studied phases and matrix are not
cast iron. The chemical composition was (in wt%): 4.0C, shown here.

4
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

(a) (b)

Figure 2. The optical microstructures of the cast iron studied in this paper: (a) boron cast iron; (b) high Cr cast iron; in both (a) and (b) the
dark-grey regions represent the martensite and the light areas are the boride (Fe2 B) or carbide (Cr7 C3 ).

1.2.2. Micro-indentation tests. Micro-indentation tests were or elongated) by a specific strain value, for example −0.1 to
carried out on a micro-hardness apparatus (HXD-1000TMC, +0.1 for a, b and c simultaneously. Only the internal freedoms
China). The applied loads during the tests were 50 g, 100 g and of the atoms were re-optimized and the single point energy for
200 g, respectively, and the loading or unloading time was set each strain was calculated. Besides the EOS, one can calculate
as 5 s. All the specimens for the tests were ground carefully the full set of elastic constants for the compound, and then other
with silicon carbide paper first and then polished following mechanical parameter such as bulk modulus and shear modulus
the metallographic level, and finally eroded in 5% nitric acid can be easily calculated by a Voigt–Reuss–Hill approximation.
alcoholic solution. In order to compare the toughness or The details can be found elsewhere [44–48]. Cell energy as a
brittleness of the above specimens, the patterns and sizes of the function of cell volume for the three pure phases Fe2 B, Fe3 C
cracks in these compounds were recorded and analysed under and Cr7 C3 are illustrated in figure 3. Then we applied EOS
each load. Each alloy sample which contains a specific kind to fit these curves and obtained the bulk modulus (B0 ), the
of carbide or boride was examined by 20 sites under each load. pressure derivative of B0 (B0 ) and the equilibrium cell volume
The load was added up to 200 g until both carbide and boride (V0 ) for the corresponding crystal.
fractured. The surface morphologies of the tested samples
7/3
were recorded using a charge coupled device (CCD) camera 9 V3 V
E(V ) = − B0 (4 − B0 ) 02 − (14 − 3B0 ) 04/3
which was incorporated with the micro-hardness equipment. 16 V V
The microstructures under the subsurface were also observed
5/3

both by optical microcopy (NEOPHOT-21, Germany) and  V0
+ (16 − 3B0 ) 2/3 + E0 ,
scanning electron microscopy (CSM-950 SEM, Germany) V
after three-body abrasive experiments. (3)

 7/3  5/3 
3 V0 V0
P (V ) = B0 −
2. Theoretical study of Cr7 C3 , Fe2 B and Fe3 C 2 V V

  
In this section, we discuss the mechanical, thermodynamic and 3  V0 2/3
electronic properties of Cr7 C3 , Fe2 B and Fe3 C and compare × 1 + (B0 − 4) −1 .
4 V
these properties with each other. The results of several multi-
component carbides are compared with the corresponding Here total energy E and pressure P are functions of cell volume
single phases. Our main purpose is to provide guidance for V ; B0 is the bulk modulus and V0 represents the equilibrium
applying and designing excellent wear resistant materials in lattice volume; B0 is the pressure derivative of B0 and E0
cast iron, including high content Cr cast iron and boron cast is the equilibrium energy. From figure 3 it can be clearly
iron. seen that the calculated data are fitted well by equation (3).
This implies that our calculations are accurate. The obtained
2.1. Mechanical properties bulk modulus, Young’s modulus, shear modulus and first
pressure derivative of B0 are listed in table 2 and the available
The mechanical properties of materials can be characterized results estimated by DFT calculations are also included.
by several parameters, such as isothermal bulk modulus, The shear modulus and Young’s modulus for anisotropic
shear modulus and Young’s modulus. All these values polycrystalline material can be calculated with equations (4)
can be calculated by the DFT method directly if the cell and (5).
size is moderate. In this paper, we have calculated the 2(1 + ν)
mechanical response of these compounds by fitting the solid B0 = G, (4)
3(1 − 2ν)
state of equation with Birch–Murnaghan third order EOS
(equation (3)) [40–43]. At first the crystal structure was fully 1
G= E. (5)
relaxed, then the cell parameters were deformed (compressed 2(1 + ν)

5
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Cr7 C3 Fitted by EOS ( 3 )

of G and 374 GPa of E for Cr7 C3 , which show obvious
-70975
mechanical advantages when comparing with Fe2 B and Fe3 C.
The mechanical properties of Fe3 C are also better than Fe2 B.
-70980
EOS fitted bulk modulus of Fe3 C is 259 GPa and it is
Total energy (eV/cell)

larger than the theoretical value of 230 GPa [23] and the
-70985
experimental value of 170–200 GPa [17], but smaller than
276 GPa calculated by VASP [38]. On the other hand, we
-70990
observe a significant difference of B0 calculated between the
ab initio method and the EOS fitting method for Fe2 B. More
-70995
recently, Chen has used x-ray diffraction to study Fe2 B at high
pressure and the obtained B0 and B0 values are 164 ± 14 GPa
-71000
and 4.4 ± 0.5, respectively [34]. In [21, 22], the DFT values
300 350 400 450 500
of B0 for Fe2 B are 194 GPa and 249 GPa, respectively. Both
(a) 3 of them are considerably larger than the experimental value of
Cell volume ( A )
164 GPa reported in [34], since GGA still underestimates the
Fe2 B EOS ( 3 )
cell constants of Fe2 B which leads to overestimation of the bulk
-7233.6
modulus [21, 22]. In other words, the bulk modulus of Fe2 B
varies below the upper bound value 250 GPa. The calculated
B0 for all the compounds is greater than 4, and this implies
Total energy (eV/cell)

-7234.0
that the mechanical performance of these compounds could be
affected enormously by the variation of external pressures as
-7234.4 shown in figure 4. The curve for the hardest material is situated
in the upper part of the figure and is close to the pressure axis.
In order to illustrate the mechanical response of Cr7 C3 , Fe3 C
-7234.8 and Fe2 B at high pressure qualitatively, the results for Al and
diamond are also shown. It is evident that Cr7 C3 is the best
among the three crystals. We also calculated the mechanical
90 95 100 105 110 115 parameters of several multi-component carbides, such as (Cr,
(b) Cell volume (A3 ) Fe)7 C3 and (Fe, Cr)3 C, and the results are listed in table 2. In
the case of (Fe, Cr)3 C, the bulk modulus of Fe11 CrC4 (260 GPa)
-11003.1 Fe3C (Pnma) EOS ( 3 ) is improved slightly when compared with the pure Fe3 C
(259 GPa) phase, but still smaller than the Cr3 C (298 GPa)
-11003.4
phase. Jae et al [23] calculated the B0 and B0 for (Fe, Si) 3 C;
Total energy (eV/cell)

the results indicate that the bulk modulus of Fe3 C is reduced

step by step by Si doping. For the Cr7 C3 type multi-component
-11003.7 carbides Fe16 Cr12 C12 , Fe12 Cr12 W4 C12 and Fe12 Cr12 W4 C8 B4 ,
the corresponding B0 is 330 GPa, 358 GPa and 306 GPa,
-11004.0 respectively. Although the mechanical performance of the
W + B co-doped (Fe, Cr)7 C3 crystal is less remarkable than
that of Fe16 Cr12 C12 and Fe12 Cr12 W4 C12 , its chemical stability
-11004.3
is much better than that of Fe16 Cr12 C12 and Fe12 Cr12 W4 C12
[25]. The B0 of Fe12 Cr12 W4 C8 B4 is close to Cr7 C3 . On the
135 140 145 150 155 160 165 other hand, the mechanical properties of Fe2 B could be greatly
(c) Cell volume (A3) improved by doping with strong carbide forming elements,
Figure 3. Total energy of cell as a function of cell volume changes such as Nb and Ti, and the EOS fitted B0 is near 300 GPa.
and fitted by equation (3): (a) Cr7 C3 cell; (b) Fe2 B; (c) Fe3 C (Pnma). In summary, applying the empirical method to calculate the
mechanical parameters of Fe2 B, Fe3 C, Cr7 C3 and other multi-
component carbides is reliable and efficient. In fact, there
Here, B0 is the isothermal bulk modulus; G and E are the are 40 atoms in the primitive cell of Cr7 C3 crystal, thus
shear modulus and Young’s modulus; ν represents Poisson’s DFT calculations can hardly be used to calculate the full
ratio. For a metal or a metallic bond dominated solid, a good set of elastic constants of it. Finally we conclude that for
approximation of this value equals 0.3. This assumption is the bulk modulus, (Fe, Cr, W/Mo)7 C3 > (Fe, Cr)7 C3 >
valid in our case. From table 2 we conclude that Cr7 C3 Cr 7 C3 ≈ (Fe, Cr, W/Mo)7 (C, B)3 > (Fe, Cr)3 C > Fe3 C ≈
has the largest bulk modulus value among the three pure Fe2 B. The relationship between the hardness and bulk
compounds and the corresponding value is slightly larger modulus values is still unclear, a superhard compound usually
than the result obtained by Music [19]. This value could favors large bulk modulus [49, 50]. This cannot completely
be acceptable because in that study a Cr rich cell was used. exclude the possibility of using B0 as an indicator for
By applying equations (4) and (5), we obtain 143.85 GPa superhard materials designing. The B/G value is also

6
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Table 2. The evaluated mechanical parameters by using equations (3)–(5), the results of Al and diamond are also depicted for comparisons.
Species Method B0 (GPa) B0 G (GPa) E (GPa) B/G Reference
Cr7 C3 EOS 311.68 4.26 143.85 374 2.16 This work
EOS 309 — — 371 [19]
Fe2 B EOS 331.04 4.44 152.77 397.22 2.16 This work
DFT 194.00 — 67 190 2.89 [21]
DFT 249.73 60.24 184.3 4.0 [22]
EOS 164 ± 14 4.4 ± 0.5 — — [28]
Fe3 C EOS 259.20 4.25 119.63 311.04 2.17 This work
EOS 174.0 5.1 — — [17]
FLAPW 235 [23]
FLAPW 226.8 [23]
VASP 276 106 2.60 [38]
Fe11 CrC4 EOS 260.55 4.75 120.25 312.66 2.16 This work
Cr3 C EOS 298.24 4.23 137.70 358.00 2.18 This work
Fe16 Cr12 C12 EOS 330.19 4.42 152.3954 396.228 2.17 This work
Fe12 Cr12 W4 C12 EOS 358.56 5.81 165.4892 430.272 2.17 This work
Fe12 Cr12 W4 C8 B4 EOS 306.64 4.29 141.5262 367.968 2.17 This work
Fe12 Cr12 Mo4 C12 EOS 355.45 3.65 164.0538 426.54 2.16 This work
C (diamond) EOS+DFT 436.8 3.30 — — [43]
Al EOS+DFT 81.92 4.49 — — This work

frequently used to indicate the hardness of the compound. Compressibility of various materials
1.00
In table 2, the calculated B/G for all the compounds is
shown. The largest B/G is attributed to Fe2 B and for the
Cr 7 C 3
other compounds that value is near 2.17. The critical B/G 0.98
value is 1.75, the carbides and borides studied in this paper Fe 7 NbB 4
are all metallic in nature, indicating that Fe3 C, Cr7 C3 and Fe 3 C
0.96
the corresponding multi-component compounds are harder Fe 2 B
V/Vo

than the Fe2 B phase. More recently, Gao proposed that Al

the hardness of materials could be highly dependent on the 0.94 Diamond
band gap value and also established a semi-empirical method
to estimate the hardness of various covalent crystals [50].
They concluded that the criteria for superhard compound 0.92

designing are strong covalent bond, shorter bond length and

denser covalent bond number. The method proposed by Gao 0.90
cannot be used to calculate the hardness of the metals or 0 10 20 30 40 50
metallic bonds dominated compounds. All the compounds Pressure (GPa)
considered here are dominated by metallic bonds. Even
Figure 4. The calculated V /V0 versus external pressure curves for
if the hardness of several covalent bonds (such as Cr–C various compounds; Al and diamond are also included as two
and Fe–C) can be calculated, the physical meaning of such extremes.
calculations is less important for metals than for typical
covalent crystals. Based on the B/G and B0 values of each most stable structure is Cr7 C3 , the calculated cohesive energy
compound, we may conclude that both for the hardness and is −109.939 eV/f.u. and the formation enthalpy value is
stiffness (Fe, Cr, W/Mo)7 C3 > (Fe, Cr)7 C3 > Cr 7 C3 ≈
−1.210 eV/f.u. Both are the smallest values among them. The
(Fe, Cr, W/Mo)7 (C,B)3 > (Fe, Cr)3 C > Fe3 C ≈ Fe2 B.
cohesive energy of all these compounds has negative value
and increases from −109.939 for Cr7 C3 up to −26.77 for Fe2 B.
2.2. The relative stability of Cr7 C3 , Fe2 B and Fe3 C However, the calculated formation enthalpy of Fe3 C is positive
In this section, we have used two thermodynamic parameters as 0.19 eV/f.u., which indicates the metastable nature of this
to determine the relative stability of Cr7 C3 , Fe2 B and Fe3 C. structure. This value agrees with 0.22 eV/f.u. obtained by
They are the cohesive energy and formation enthalpy. As Shein [16]. When comparing the calculated formation energy
defined in equations (1) and (2), the larger the negative values of these compounds with that of experimental results, they are
of these two parameters, the more stable the compound. in agreement especially for Fe2 B and Fe3 C. The formation
Not the cohesive energy but the formation enthalpy is enthalpy of Fe3 C is slightly greater than zero, which implies
used to estimate the chemical stability of the compound this compound can be easily prepared by non-equilibrium
in the bulk state. Metastable structure is less important methods. The LDA results of cohesive energy and formation
for practical applications because it cannot be synthesized enthalpy of Fe2 B are −30.18 eV/f.u. and −1.918 eV/f.u.,
by the equilibrium method. Table 3 shows the calculated respectively, as shown in table 3. Thus we conclude that
energy values of these compounds. It is obvious that the LDA systematically overestimated the energy parameters of

7
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Table 3. Theoretical evaluated cohesive energy and heat of formation values of Cr7 C3 , Fe2 B and Fe3 C; useful data for pure elements and
other theoretical works are also shown.
Cohesive energy Formation enthalpy Formation enthalpy
Species Methods (eV/f.u.) (eV/f.u.) (kJ mol−1 )
Cr (BCC) GGA-PW91 −11.343 0.00 0.00
C (graphite) GGA-PW91 −9.776 0.00 0.00
B (alfa) GGA-PW91 −6.98a — —
Fe (BCC) GGA-PBE −9.4a — —
Cr7 C3 GGA-PBE −109.939 −1.210 −116.55
Fe3 C GGA-PBE −37.926 0.1973 19.00
Fe2 B GGA-PBE −26.77 −0.991 −96.27
Fe3 C GGA — 0.22b 21.19
LMTO −33.48c
FLAPW 21.5d
LMTO −33.7e

Cr7 C3 Empirical potential −90f — —

Fe2 Bg DFT-GGA −26.67 −0.891 −85.50
Fe2 B LDA −30.1809 −1.918
Cr7 C3 −181.17h
Fe2 B −71.13h
Fe3 C 22.19h
a
Theoretical calculated value from [21].
b
Calculated by VASP with GGA scheme in [16].
c
Linear muffin-tin orbital method (LMTO) in [23].
d
Full-potential linearized augmented plane wave method (FLAPW) in [23].
e
LMTO method in [37].
f
Calculated by empirical potentials in [18].
g
DFT calculations with non-spin polarized calculations in [21].
h
Experimental results measured at 298 K under ambient pressure in [51].

Fe2 B. For the other compounds such calculations were not up channel and the down channel, respectively; E is the energy
conducted. and µB is the Bohr magneton. The integral is calculated from
the lowest energy level to the Fermi level for the specific orbital
2.3. Electronic structure and population analysis only.
The evaluated average moment values of Fe are 2.09µB
More details about the electronic structure of Fe2 B and Fe3 C and 2.02µB for Fe3 C and Fe2 B, respectively. This is slightly
are available in [21] and [15–17]. Recently, the authors larger than the values of 1.96µB (Fe3 C) obtained in [15, 16],
have also applied first principles calculations to investigate 1.921µB (Fe3 C) in [23], 1.95µB (Fe3 C) in [39] and 1.90µB
the electronic and mechanical properties of Cr7 C3 polymorphs (Fe2 B) in [34]. In fact, only the local moment for the 3d orbital
[52]; Cr doped Fe3 C type carbides [24] and Cr7 C3 type multi- of Fe is calculated in this paper, and including the contributions
component carbides [25]. Hence in this paper our main focus from the 4s and 4p bands will reduce the magnetic moment
will be to make a comparative study of the electronic structures value. Thus the observed discrepancies between our results
of these compounds and to provide some useful information and the other references can be rationalized. From figure 6 we
that can be used for wear resistant materials design. The can conclude that the local magnetic moment of Fe3 C is almost
magnetic states of Fe3 C and Fe2 B will be discussed first. attributed to the polarization of the 3d bands of Fe atoms. The
The magnetic states of Fe3 C and Fe2 B and the net spin polarized electrons, total valence electrons and d bands
corresponding local magnetic moments of Fe were calculated. electrons in Fe3 C are 24.24, 112 and 72, respectively. This
Figure 5 shows the spin polarized density of states (DOS) of indicates that the corresponding spin polarization strength is
Fe3 C and the integrated spin DOS for 3d bands of Fe atoms 21.6% for the whole cell and 33.67% for d bands only. In
(in order to save space, the results for Fe2 B, being analogous the case of Fe2 B, that value is 21.5% and 33.33% accounting
to those for Fe3 C, are omitted here). The average magnetic for total electrons and d band, respectively. Previous studies
moment of Fe can be evaluated using equation (6). for many ferromagnetic compounds such as CrAs, CrN, CrP

and MnS, reveal that the magnetic moment of non-metal
Ef
elements always has a small ‘negative’ value because of the
u= g(DOS, Spin-up) dE negative exchange mechanism. In the case of Fe3 C and Fe2 B,
E0
 the local magnetic moment value for C is near 0.12µB with
Ef opposite direction to metal atom. A similar value is also
− g(DOS, Spin-down) dE µB , (6) obtained in [39]. The spin polarized calculations were not
E0
carried out for Cr7 C3 and the corresponding multi-component
where u refers to magnetic moment; g(DOS, spin-up) and carbides for two reasons. Firstly, the crystal structures of the
g(DOS, spin-down) represent the spin polarized DOS for the Cr7 C3 type multi-component carbides have a large number

8
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al
50
15 Spinup 3d p bands
Spindown 3d Cr 3p
Ef Spinup sum C 2p
10 Cr 4 p
Spindown sum
DOS (electrons/eV.Cell)

DOS (electrons/eV.Cell)
5 Majority Spin channel
-80 - 60 -40 -20 0 20 40
50

Ef
s bands
0
Cr 3 s
-5 C 2s
Minority Spin channel Cr 4 s

-10 0
-80 - 60 -40 -20 0 20 40
100
-15 d bands
-15 -10 -5 0 5 10 15 10
50
(a) Energy (eV) Cr 3d

0.6 Spin up 2s 0
2s Spin down 2s -80 - 60 -40 -20 0 20 40
2p Ef
Spin up 2p (a) Energy (eV)
DOS (electrons/eV.Cell)

0.3 Spin down 2p

Majority Spin Channel 20 Fe 3 d 3d bands
0.0 10
0
-0.3 -15 -10 -5 0 5 10 15
Minority Spin channel
20 p bands
B 2p Fe4p
DOS (electrons/eV.cell)

-0.6 10
0
-15 -10 -5 0 5 10 15
-0.9
E s bands
-15 -10 -5 0 5 10 15 20 25 20 f

(b) Energy (eV)

10 B 2s Fe 4s

Figure 5. Spin polarized DOS of 3d bands and 2s, 2p bands for Fe 0

(a) and C (b), the dotted line is the Fermi level. -15 -10 -5 0 5 10 15
Sum
20
of atoms in the cell, using the spin polarized GGA method 10
is extremely expensive; secondly, Cr and related compounds
0
are always anti-ferromagnetic or non-magnetic in their ground -15 -10 -5 0 5 10 15
state. We performed the spin polarized calculations for ( b)
Energy (eV)
(Fe, Cr)3 C and Cr3 C, the local magnetic moments for both
metals and C decrease from Fe3 C to Fe11 CrC4 and completely 30
Fe 3 d 3d bands
annihilate for Cr3 C. In [23], the bulk modulus of Fe3 C is 20

calculated for both the ferromagnetic and non-magnetic states, 10

0
they concluded that the bulk modulus is overestimated in the -15 -10 -5 0 5 10 15 20
DOS (electrons/eV.Cell)

latter case. In addition, in [25], all the calculations for Cr7 C3 30

p bands
20 C 2p
type carbides were carried out without considering the spin Fe 4 p
10
state of Cr; the obtained results are in good agreement with 0
experiments. The electronic structures of Cr doped Fe3 C -15 -10 -5 0 Ef 5 10 15 20
30
type carbides and Cr7 C3 type multi-component carbides are 20
C 2s s bands
analogous to the corresponding Fe3 C and Cr7 C3 phases. In 10
Fe 4 s
the following subsections, only the results for Fe2 B, Fe3 C and 0
Cr7 C3 are discussed. 30
-15 -10 -5 0 5 10 15 20
Sum
Now we will discuss the electronic structures of Cr7 C3 , 20
Fe2 B and Fe3 C by comparing the DOS. Figure 6 displays 10
the calculated partial densities of states (PDOS) of these 0
-15 -10 -5 0 5 10 15 20
compounds. In figure 6(a), 3s and 3p bands of Cr are semi- (c ) aergy (eV)
core states which are only important for energy calculations.
These orbitals are highly localized around the ionic core Figure 6. The angular momentum projected PDOS for distinct
compounds: (a) Cr7 C3 ; (b) Fe2 B; (c) Fe3 C; dotted lines refer to
region, implying that they could be delocalized in k space, Fermi level.

9
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

which corresponds to flat energy dispersion relations in band non-metal atoms in Cr7 C3 , Fe2 B and Fe3 C increase from 0.53
structures and also leads to sharp peaks in DOS. The semi-core up to 0.71. The ionicity of chemical bonds in these compounds
orbitals of 3s and 3p for Cr locate very deep in energy, below is induced by the electron transfer process as mentioned above.
−40 eV. The common features of PDOS for these compounds This indicates that more ionicity could be expected for Fe2 B
are summarized as follows: than the others.
(2) In all of these compounds, the metal’s 4s bands lose
(1) These compounds are metallic-like, the d bands of the
electrons significantly and may transfer to the 4p bands of
transition metal dominate the Fermi level. The conduction
metal atoms and the 2p bands of B or C atoms. Besides Cr7 C3 ,
bands consist mainly of the metal’s 4s and 4p orbitals,
electron gains can be seen for the d bands in Fe2 B and Fe3 C.
but the contributions from the B and C atoms cannot be
In the case of Cr7 C3 , the d orbital is half occupied and can
neglected.
be stabilized by the exchange energy based on Hund’s rule.
(2) The p bands of the B or C atoms locate near the Fermi
So it is inert in nature. But for Fe3 C and Fe2 B the electron
level. As can be seen from figure 6, they are all overlapped
accumulation in the d bands may occur in two ways. They can
with the d bands in some degree, which indicates covalent
either come from the 4s orbital of metal atoms or the 2p bands
interactions between the transition metal and C atoms
of B (C) atoms due to p–d hybridization.
in terms of p–d hybridization. That is very prevalent
(3) The variations of the bond length in these compounds are
in transition metal compounds. However, the centre of
quite different from each other. In Fe3 C and Cr7 C3 , we observe
gravity of non-metal atoms p bands does not completely
only two types of bonds, the metal–C and the Fe (Cr)–Fe (Cr)
coincide with the d bands. Since the electronegative values
bond. But for Fe2 B, an additional B–B bond type should be
for these elements are different, one may expect some
included. The calculated bond length of B–B is 2.1169 Å,
ionicity of metal–B or C bonds.
very close to the value of the Fe–B bond in Fe2 B, and it is
(3) The 2s orbitals of B or C locate in the energy range
much shorter than any metal–metal bond in the calculated
between −15 and −20 eV in these compounds. In Fe3 C
compounds. These results can be understood when noticing
and Cr7 C3 , one could observe a relatively strong DOS
the layered structure of Fe2 B. In the case of Fe3 C and Cr7 C3 ,
peak of 2s bands. On the other hand, for Fe2 B this peak
carbon atoms locate at the interstitial sites of metal polyhedrons
is rather dispersive in energy and almost overlaps with the
and then form three-dimensional networks in space. As a
2p bands. This may be attributed to the strong covalent
result, the distance between these non-metal atoms should be
bonds between B atoms in Fe2 B.
sufficiently large and the chemical interactions are negligible.
More information on chemical bonding will be provided The equilibrium bond length between different atoms is also
by population analysis results in table 4. Here we define the determined by the atomic radius. The distance for the Fe–Fe
other two parameters to characterize the chemical bonds in bond is shorter than that for the Cr–Cr bond, which is consistent
these compounds; the average bond length (7) and the average with the contraction of the atomic radius from Sc to Cu.
bond overlap population (8). (4) A net bonding interaction could be deduced for Cr7 C3 , since
the calculated average bond population values are positive
Li Ni both for the Cr–Cr bond (0.294 electrons) and the Cr–C bond
L(AB) = i
(7)
i Ni (0.021 electrons). In Fe2 B, the strongest covalent bond may
be attributed to B–B and the corresponding overlap population
nAB
i Ni is 0.66, almost 4 times larger than the value of the Fe–B bond.
nAB = i
(8)
i Ni Interestingly, the net population for the Fe–B bond in Fe2 B has
the smallest value among the three crystals. When considering
Here L(AB) and nAB represent the average bond length and
the crystal structure of Fe2 B in figure 1, one may expect that
the mean bond population, respectively; Ni is the total number
boron and iron sheets can easily glide relative to each other by
of the i bond in the cell and Li the bond length of the i
shearing force at the x–y plane. The calculated mean bond
type. The Mulliken population method was applied to calculate
population of Fe–C is 0.27 electrons which is comparable
the overlap population for a specific kind of bond and the
to that of the Cr–C bond in Cr7 C3 . On the other hand, the
nominal charges carried by distinct atoms [53]. Using the
existence of repulsive force between Fe atoms in Fe2 B and
Mulliken method to study the chemical bonds in metals or
Fe3 C may deteriorate the mechanical properties of these two
metallic bonds dominated compounds has its own limitations;
compounds.
most importantly, the metallic bond cannot be accounted for
(5) The total numbers of valence electrons are 440, 76 and
properly in this case. So we are aware that the population
112 for Cr7 C3 , Fe2 B and Fe3 C, respectively. The net bonding
results listed below are only responsible for the covalent and
electrons of these compounds can be calculated using table 4.
ionic bonds and the results listed below can only provide
It is found that in Cr7 C3 the net bonding electrons account for
a qualitative picture of the chemical interactions for each
6.568% of total valence electrons, and this value is 4.921%
compound. From the results listed in table 4, we could draw
and 4.392% for Fe2 B and Fe3 C, respectively. In other words,
the following conclusions:
Cr7 C3 is the most stable structure among the three and agrees
(1) The positive charges carried by metal atoms in Fe2 B have well with the stability ordering obtained by formation enthalpy
the largest value of 0.33, and the values of Fe3 C and Cr7 C3 are calculations. Although the evaluated population value of
similar to each other. However, negative charges carried by the Fe–C bond in Fe3 C is large enough, it is less sufficient

10
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Table 4. Population analysis results of Cr7 C3 , Fe3 C and Fe2 B, the calculated average bond length and the mean bond population are also
shown.
Species s p d Total electrons Charge states
Cr7 C3 C1 1.39 3.15 0 4.54 −0.54
Cr1 2.1 6.64 5 13.74 0.26
Cr2 2.11 6.67 5 13.78 0.22
Fe2 B B 1.14 2.53 0 3.67 −0.67
Fe 0.49 0.43 6.75 7.67 0.33
Fe3 C C 1.47 3.24 0 4.71 −0.71
Fe1 0.52 0.53 6.69 7.74 0.26
Fe2 0.51 0.62 6.68 7.81 0.19
Bond population analysis
Net bonding
Species Lmax (AB) (Å) Lmin (AB) (Å) L(AB)(Å) nAB (electrons) electrons
Cr7 C3 Cr–C 2.4167 1.9942 2.1016 0.294 25.88
Cr–Cr 2.9600 2.4857 2.6215 0.021 3.02
Fe2 B B–B 2.1169 2.1169 2.1169 0.66 1.32
Fe–B 2.1049 2.1049 2.1049 0.15 4.9
Fe–Fe 2.6734 2.3091 2.5348 −0.103 −2.48
Fe3 C Fe–C 2.3720 1.9444 2.0741 0.2775 8.88
Fe–Fe 2.6192 2.4280 2.5533 −0.0792 −3.96

Table 5. Proportion of cracks emerging for studied compounds. the load increases to 100 g, cracks initiated and appeared more
Proportion of cracks emerging under certain load easily for (Fe,Cr)3 C and Fe2 B. At the largest load value of
200 g, the probabilities of the presence of cracks for Fe2 B
Structure 50 (g) 100 (g) 200 (g) and (Fe,Cr)3 C are 80% and 70%, respectively. For the multi-
Fe2 B 0% 70% 100% component carbides, (Cr, Fe)7 C3 , the values are reduced below
(Fe,Cr)7 C3 0% 50% 80% 80%. It can be seen that the cracks appearing around the
(Fe,Cr)3 C 0% 50% 70% Fe2 B and (Fe,Cr)3 C indentations are wider and deeper than
in multi-component carbides under the same load. In table 2
we can see that the DFT predicted E and G values of Fe2 B are
to eliminate the strong repulsion forces among Fe atoms in rather small, and both values are less than 80 GPa and much
contrast to Fe2 B. The chemical bonding is highly anisotropic smaller than Cr7 C3 ((Fe,Cr)7 (C,B)3 and W doped structures)
for Fe2 B which differs from Fe3 C and Cr7 C3 . As a result, Fe2 B and Fe3 C ((Fe,Cr)3 C). One may expect that Fe2 B should be
is not suitable to be used as hard phase in boride cast iron. soft at low pressure but brittle at high stress. This kind of
At the end of this part, by considering all aspects of strange mechanical response is caused by the layered structure
these compounds, we conclude that both the stability and the of Fe2 B and strong chemical repulsion forces among Fe atoms
mechanical properties of Cr7 C3 and the corresponding multi- at Fe layers. Most importantly, the Fe–B bond between layers
component carbides are much better than Fe2 B and (Fe, Cr)3 C. is weak when compared with the B–B bond at the B layers.
In the next section, we will conduct indentation tests to verify Mechanical grinding caused decomposition or phase transition
this conclusion. of Fe2 B has been reported elsewhere [34]. The mechanical
properties of the (Fe,Cr)3 C phase are slightly better than Fe2 B.
3. Experimental results
3.2. Three-body abrasive performances of (Fe,Cr)7 C3
3.1. Indentation test and Fe2 B
Under each load, we selected 20 points to perform indentation In this section, we will discuss the mechanical performance of
fracture toughness tests for the specific compound on one the studied compounds in high chromium content cast iron and
sample. The microstructure morphologies of the examined boron cast iron by applying three-body abrasive wear tests. The
samples were recorded by a CCD camera incorporated with pure Fe3 C phase in white cast iron is rarely used in practice
a micro-hardness test apparatus. Table 5 shows the micro- and the abrasive tests are not conducted in this paper. Our
indentation tests data by calculating the percentage of the main purpose will be focused on the mechanical performance
fractured sites with respect to the total indentation points of these precipitated compounds in iron but not the whole
at each load. The Vickers indentations of the compounds material. In fact, the tribological properties of materials are
are shown in figure 7. At the small load of 50 g, all highly dependent on many factors, such as the composition,
these compounds show good performance without any cracks mechanical performance of the matrix, hardness of dispersed
appearing besides Fe3 C. However, as can be seen from particles and the toughness and hardness of the precipitated
figure 7(a), the indentation size of (Fe,Cr)7 C3 is the smallest phase. Figure 8 illustrates the tribological behaviour of
among the three, the largest one corresponding to Fe2 B. As these compounds by applying three-body abrasive experiments

11
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Fe2B without cracks (Fe, Cr) 7 C3 without cracks

(a)
(Fe, Cr) 3C without crack

Figure 7. The indentation shape under certain load observed using optical microscopy: (a) 50 g; (b) 100 g; (c) 200 g.

Fe2B with cracks (Fe, Cr) 7 C3 with cracks

(b)
(Fe, Cr) 3 C with cracks

Figure 7. Continued.

at ambient temperature. The details of the materials and are attributed mainly to the broken fracture of the Fe2 B phase.
experimental apparatus can be found elsewhere [54]. Cracks The damaged part of Fe2 B will protrude out of the surface
can be frequently observed in the Fe2 B phase in figures 8(a) later. Ruptured debris can be completely pulled out of the
and (b). In fact, in boron cast iron, the damage mechanisms matrix, which leads to large weight loss. As a result, the

12
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

Fe2B with cracks (Fe,Cr)7C3 with cracks

(c)
(Fe,Cr)3C with cracks

Figure 7. Continued.

abrasive performance of the boron cast iron is damaged. In the indenter [50]. This resistance force is determined both by
the case of Cr7 C3 , these dynamic damage processes are less the band gap value and valence electron density. The plastic
important. Weight loss of the Cr7 C3 phase is caused by micro- deformation mechanism plays a key role during the indentation
cutting at the working surface. As can be seen in figure 8(c), test. In metals, the metallic bond among atoms is isotropic
the Cr7 C3 phase shows excellent mechanical properties and and weak; dislocations can be easily created by external force.
is tightly bounded with the matrix (martensite in this case). In contrast, in covalent compounds the chemical interactions
Based on the experimental results, we conclude that Cr7 C3 type are highly anisotropic and also very strong along a certain
carbides are harder than Fe2 B. Through the micro-indentation direction, and the deformation process is always associated
tests, we also verify that Fe2 B is brittle because of the small B0 with the breaking and re-creation of the covalent bond. Ionicity
and G values. The hardness of Fe3 C or (Fe,Cr)3 C lies between should always be avoided since it can promote the crack
Fe2 B and Cr7 C3 type carbides. initiation and fracturing process in materials. It is also reported
that the hardness of the compound is closely related to the shear
3.3. Discussions modulus, because the correlation between the hardness and
the bond length is proposed to be HV ∝ 1/d 6 , and for shear
In section 2, we applied first principles calculations to modulus it is proportional to 1/d 5 in covalent and partially
investigate the various properties of these compounds, and ionic compounds [57]. Although the DOS near the Fermi
then micro-indentation tests were carried out in section 3 surface is dominated by the partially occupied 3d band of
to study the hardness and toughness. As we mentioned metals in Cr7 C3 , Fe3 C and Fe2 B, the covalence is significant,
in section 2, the most stable phase is Cr7 C3 , and Fe3 C is which affects the hardness of these compounds. The strongest
a metastable structure. Most importantly, the calculated covalent bond is attributed to Cr7 C3 and should be the hardest
mechanical parameters of Cr7 C3 are superior to Fe3 C and material among the three compounds. Recently, the single
Fe2 B. The bulk modulus value of Cr7 C3 is near 310 GPa, phases of Cr7 C3 and Cr23 C6 have been synthesized by the
which is comparable to c-CSi2 N4 (309.5 GPa) [55], c-Si3 N4 pulsed electric-current pressure sintering method in [13]. Their
(280 GPa) [55], OsB2 (239.80 GPa) [43], but smaller than measured average Vickers hardness values are 16 GPa and
BN (367 GPa) [56] and c-C3 N4 (377.6 GPa) [55]. The bulk 14.5 GPa, respectively. The corresponding fracture toughness
modulus of it can be further improved by doping with W, Mo, is 6.3 MPa m1/2 for Cr7 C3 and 4.4 MPa m1/2 for Cr23 C6 .
Cr and B. Cr7 C3 has a relatively large B0 value which can For comparisons, we also mention several hardness values
deteriorate its performance at high pressure. The presence calculated by empirical methods based on Gao’s theory in
of strong directional bonds can improve the hardness and [50]: Diamond (93.6 GPa); c-BN (64.5 GPa); GaN (18.1 GPa);
toughness of Cr7 C3 considerably. Based on Gao’s theory, the Al2 O3 (20.6 GPa). We conclude that the hardness value of
hardness of covalent solids is intrinsic and can be calculated Cr7 C3 is close to Al2 O3 and GaN, but less hard than other
by the sum of the resistance of each bond per unit area to covalent compounds. The micro-hardness of the Fe2 B phase

13
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

(a) (b)

(c)

Figure 8. Morphologies of Fe2 B and Cr7 C3 phases in boron cast iron and high Cr content cast iron after abrasive tests. The arrows indicate
the boride and carbide. (a) Optical microscopy view of cracks in Fe2 B phase (white color) after abrasive test; (b) fractured debris of Fe2 B at
sub-surface (SEM image); (c) tribological performance of Cr7 C3 (dark-grey region) at sub-surface (SEM).

in boron cast iron is near 1400 HV , which is 14 GPa, and is Table 6. The calculated mechanical parameters of transition metal
very close to the pure Cr7 C3 phase. The fracture toughness of doped Fe2 B.
the mono-phase of Fe2 B ranges from 2.79 to 4.79 MPa m1/2 , Structure B (GPa) B0
which is considerably smaller than the single Cr7 C3 phase.
Fe7 TiB4 299.8 3.522
For the pure Fe3 C phase in white cast iron the hardness is Fe7 VB4 311.6 3.166
at least above 8 GPa (8–11 GPa), whereas the reported value Fe7 CrB4 327.8 5.077
in [58] is 10 GPa for pure Fe3 C and 13.5 GPa for Fe10 Cr2 C4 , Fe7 NbB4 321.6 5.049
respectively. The low hardness values of the three compounds Fe7 MoB4 323.2 4.382
are caused mainly by metallic bonds among metal atoms. They Fe7 WB4 329.52 4.418
are much harder than the corresponding pure metals because of
the strong covalent bonds introduced by interstitial atoms. This
implies that the mechanical performance of these compounds Both the chemical stability and the hardness are important for
can be further improved by doping with the strong carbide practical applications. Addition of Cr in Fe3 C improves the
or boride forming elements such as Nb, Ti, V, W and Mo. hardness and compression strength of Fe3 C [58]. However,
In the case of Fe2 B, the bulk modulus value increases above the solubility of Cr in Fe3 C is below 20 wt%. As shown in
300 GPa by doping with strong carbide forming elements as table 5, both the hardness and the stiffness of (Fe,Cr)3 C are
shown in table 6. The results were obtained by fitting the EOS better than Fe3 C. The hardness of Fe2 B is comparable to Fe3 C
(3). Figure 9 shows the calculated compressibility curves of and Cr7 C3 at small loads. Increasing the load value up to
transition metal doped Fe2 B. The experimental verification of 100 g, Fe2 B mechanically failed and no hardness value can be
such predictions is still being carried out and will be published calibrated.
in the future. The chemical compositions of borides in boron The morphologies of these compounds after three-body
cast iron are complicated because of the alloying elements. For abrasive tests are shown in figure 8. We can clearly see that
example, (Cr, Fe)2 B and Fe2 (B,C) can be frequently observed there are many cracks, fractured debris of the Fe2 B phase in
in the experiments. Other compounds are also possible such boron cast iron. This morphology appears less frequently in the
as FeB, Fe3 B, (Fe,Cr)23 (C,B)6 and so on. High temperature Cr7 C3 phase. The micro-indentation tests can also verify the
oxidation resistance and hardness of Cr7 C3 can be improved brittle nature of the Fe2 B phase in boron cast iron, and Cr7 C3
by doping with Mo, W, Ti [25], the obtained Cr7 C3 type multi- shows the best function among the three. The tribological
component carbides could have a high hardness, at least close behaviour of Fe3 C is not considered here, because it is a
to Cr7 C3 . The chemical stability is also greatly enhanced. metastable phase and the pure phase is rarely used in practice.

14
J. Phys. D: Appl. Phys. 42 (2009) 115415 B Xiao et al

1.00 phase. Tribological behaviours of these phases are different

Fe7 XB4 from each other; the main damage form of boron cast iron
Ti during abrasive experiments is fracturing of the precipitated
0.98 V phase (Fe2 B). The Fe2 B phase can be completely pulled out of
Compressibility (V/V0)

Cr the matrix and leads to large mass lost. On the other hand, the
Nb Cr7 C3 (the exact formula is (Cr, Fe)7 C3 ) phase in Cr cast iron
0.96 Mo is tightly bound with the martensite matrix, dynamic damage
W
of this compound only occurs near the surface and the fracture
Cr 7 C 3
0.94
debris can also be observed.

Acknowledgments
0.92

This research is supported by the Natural Science Foundation

0 5 10 15 20 25 30 35 40
of China under Contract number of 50571078; we would also
Pressure (GPa) like to thank the Ministry of Science and Technology of China.
Figure 9. The compressibility curves of Fe7 XB4 compounds, the Part of the investigations are supported by State 863 Projects
results are compared with Cr7 C3 . with contract No 2007AA032510. The authors also appreciate
Dr X H Zhi and Dr Z F Huang for fruitful discussions. All the
4. Conclusions calculations were performed on a SGI working station at Xi’an
Jiaotong University.
We have used both the DFT calculations and experiments to
investigate the mechanical performance of three compounds,
Cr7 C3 , Fe3 C and Fe2 B. The calculated cohesive energy for
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