ISSN 1063-7834, Physics of the Solid State, 2007, Vol. 49, No. 12, pp. 2298–2302.

© Pleiades Publishing, Ltd., 2007.

Original Russian Text © N.I. Medvedeva, I.R. Shein, O.Yu. Gutina, A.L. Ivanovskiœ, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2192–2195.

MAGNETISM
AND FERROELECTRICITY

Simulation of the Structural, Electronic, and Magnetic Properties

of Fe3C1 – xBx Borocementites
N. I. Medvedeva, I. R. Shein, O. Yu. Gutina, and A. L. Ivanovskiœ
Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences,
Pervomaœskaya ul. 91, Yekaterinburg, 620041 Russia
e-mail: medvedeva@ihim.uran.ru
Received April 11, 2007

Abstract—The structural, electronic, and magnetic properties and the enthalpy of formation of iron boroce-
mentites Fe3C1 – xBx (x = 0, 0.25, 0.50, 0.75, 1.00) are analyzed using ab initio calculations in the framework of
the electron density functional theory. It is found that the unit cell parameter a of the orthorhombic lattice
increases linearly and the parameters b and c decrease as the boron concentration increases. The density of
states at the Fermi level changes only slightly, and the main variations in the band structure occur in the region
of the bottom of the valence bands. The magnetic moment of the iron atoms and the total magnetization and
stability of the Fe3C1 – xBx phases increase linearly with an increase in the boron concentration.
PACS numbers: 71.15.Mb, 71.20.Be
DOI: 10.1134/S106378340712013X

1. INTRODUCTION ite as a function of the boron concentration is an impor-

The great attention paid by researches to the influ-
ence of boron impurities on the physicochemical prop-
erties of cementite Fe3C is explained by a very impor-
tant role played by the Fe–C–B system in metallurgy
and materials science. Introduction of boron into the
composition of industrial alloyed steels has been used
to increase their strength, hardenability, and cold-short-
ness threshold. The presence of boron suppresses the
precipitation of ferrite in austenitic steels during heat
treatment. Boron exhibits a high neutron absorptivity,
and steels alloyed with boron have been used in nuclear
industry. Boride coatings possess a high hardness and a
high wear resistance, which is determined by the pres-
ence of a solid solution based on α-Fe and a number of
carbide (Me3C) and boride (MeB, Me2B, Me23B6) pre-
cipitates. It has been found that boron is readily soluble
in cementite Fe3C, which is one of the main compo-
nents of carbon steels and cast iron [1, 2]. The solubility
of boron in the cementite substantially depends on the
temperature. For example, boron can substitute for up
to 80% C at a temperature of 1000°C and about 60% C
at 600°C, thus forming the so-called borocementites
Fe3C0.2B0.8 and Fe3C0.4B0.6, respectively [1].
Although cementite is of great technological impor-
tance, the influence of boron impurities on the crystal
structure and electronic properties of this compound is
still not clearly understood. It is known that the Fe3C
compound is metastable and easily decomposes with
the precipitation of graphite (the so-called process of
graphitization), whereas the Fe3B boride is stable. In
this respect, investigation of the stability of the cement-
tant problem.
In this work, we performed the ab initio theoretical
investigation of the concentration dependences of the
structural, electronic, energy, and magnetic characteris-
tics of borocementites, namely, a continuous series of
Fe3C1 – xBx solid solutions, on the concentration ratio
C/B in the framework of the electron density functional
theory.
2. COMPUTATIONAL METHOD
AND DESCRIPTION OF THE STRUCTURE
The calculations of the band structure of the solid
solutions Fe3C1 – xBx (x = 0, 0.25, 0.50, 0.75, 1.00) were
performed by projector augmented-wave (PAW)
method [3] with the Vienna ab initio simulation pack-
age (VASP) in the spin-polarized variant. The general-
ized gradient approximation (GGA) was used for the
exchange–correlation term. The integration in the Bril-
louin zone was performed over 6 × 6 × 6 k points, and
the kinetic cutoff energy was taken equal to 400 eV. The
structure was optimized by the minimization of the
forces with a cutoff parameter of 5 meV/Å.
Cementite Fe3C crystallizes in the orthorhombic
system, space group Pbnm, and Z = 4. The unit cell con-
tains four carbon atoms and two types of iron atoms,
which occupy nonequivalent positions: eight iron
atoms are located in the general (Feg) positions and four
iron atoms occupy the special (Fes) positions. Each car-
bon atom is in the trigonal–prismatic environment of

2298
 SIMULATION OF THE STRUCTURAL, ELECTRONIC, AND MAGNETIC PROPERTIES 2299

Table 1. Optimized lattice parameters (Å) and the unit cell volume (Å3) for the Fe3C1 – x Bx borocementites

Fe3C Fe3C0.75B0.25 Fe3C0.5B0.5 Fe3C0.25B0.75 Fe3B

a 5.058 (5.082) 5.126 5.218 5.315 5.397 (5.433)

b 6.703 (6.733) 6.670 6.652 6.629 6.650 (6.656)
c 4.506 (4.521) 4.467 4.438 4.407 4.363 (4.454)
V 152.77 152.73 154.05 155.27 156.59
Note: The experimental data taken from [5] for the Fe3C compound and from [6] for the Fe3B compound are parenthesized.

s g
the iron atoms [ Fe 2 Fe 4 ] with the average Fe–C dis-
tance of ~2.018 Å [4].
3. RESULTS AND DISCUSSION
3.1. Structural Properties
It follows from the data presented in Table 1 that, for
the Fe3C and Fe3B compound, the calculated values of
the lattice parameters (a, b, c) and the unit cell volumes
(V) are in good agreement with the available experi-
mental data. The calculations performed have demon-
strated that, for the Fe3C1 – xBx solid solutions, the unit
cell volume of the borocementite increases with an
increase in the concentration ratio B/C, i.e., with the
sequential replacement of the carbon atoms with a
small radius (0.77 Å) by the boron atoms with a large
radius (0.91 Å). However, it is found that, in this case,
the lattice parameters (a, b, c) vary oppositely; more
specifically, as the boron concentration increases, the
lattice parameter a increases linearly, whereas the lat-
tice parameters b and c decrease. The lattice parameter
a varies more significantly (by 6.7% upon changing
over from Fe3C to Fe3B). The changes in the lattice
parameters b (0.8%) and c (3.2%) are considerably
smaller, i.e., an increase in the volume in the series
Fe3C Fe3C1 – xBx Fe3B is determined by an
3d states with spin down (3d↓ ). The magnetic moments
(MM) of the iron atoms are equal to 1.96 and 1.86µB
(for the Fes and Feg atoms, respectively). The magnetic
moments of the carbon atoms are equal to 0.12µB.
Upon replacement of carbon by boron in the
Fe3C1 – xBx solid solutions, an additional band A'
formed by the B 2s states appears in the energy region
from –9.5 to –7.5 eV (Fig. 1). The B 2p states are
shifted to the region of higher energies as compared to
the C 2p states. As the boron concentration increases,
the A' band regularly broadens, whereas the lower-
energy C 2s band (A) correspondingly narrows. This is
accompanied by changes in the relative contributions of
the C 2p–B 2p states to the region of the valence band.
Since the B 2p states reside in the region of the Fe 3d
band C, an increase in their concentration leads to an
increase in the overlap of the Fe 3d and B 2p states, i.e.,
to an enhancement of the Fe 3d–Fe 2p hybridization
upon changing over from carbide to boride. For all the
compositions Fe3C1 – xBx, the Fermi level is located in
the region of almost completely occupied Fe 3d↑ states
and in a local minimum of the unoccupied Fe 3p states.
As a result, the total density of states at the Fermi level
20 C
Density of states, states/eV

Fe3B
increase in the lattice parameter a. 10 B
A'
0
3.2. Electronic Properties 10 Fe3C0.25B0.75
The total densities of electron states of the Fe3C1 – xBx 0
solid solutions are presented in Fig. 1. It can be seen 10 Fe3C0.5B0.5
from this figure that the valence band of the Fe3C com- 0
pound (in accordance with the results of the previous Fe3C0.75B0.25
calculations [7–11]) involves three subbands, namely, 10
A'
the A, B, and C subbands. The lower band A is formed 0
by the C 2s states, and the B band contains predomi- C
10 Fe3C B
nantly the contributions of the C 2p states. The upper A
edge of the valence band (the C band) is formed prelim- 0
–20 –15 –10 –5 0 5 10
inarily by the Fe 3d states. The hybridization of the Fe E, eV
3d–C 2p states is rather small, which is indicated by the
small contributions of the C 2p and Fe 3d states in the
region of the C and B bands, respectively. The Fermi Fig. 1. Total densities of states for the Fe3C1 – xBx solid
level (EF = 0) is located between almost completely solutions. The solid and dotted lines correspond to the spin-
occupied 3d states with spin up (3d↑) and partially free up and spin-down states, respectively.

PHYSICS OF THE SOLID STATE Vol. 49 No. 12 2007

2300 MEDVEDEVA et al.

Table 2. Averaged atomic magnetic moments (MM, µB), the total magnetization M µB/form. unit), and the enthalpies of for-
mation ∆H (eV/form. unit) for cementite-like phases in the system under investigation
Parameters of the
Fe3C Fe3C0.75B0.25 Fe3C0.5B0.5 Fe3C0.25B0.75 Fe3B
phases
MM [C] –0.12 –0.12 –0.12 –0.12 –
MM [B] – –0.14 –0.15 –0.15 –0.16
MM [Fes] 1.96 2.04 2.15 2.22 2.28
(1.99) (2.06)
MM [Feg] 1.86 1.89 1.90 1.91 1.94
(1.95) (1.89)
M 22.25 22.75 23.23 23.64 24.10
∆H +0.22 –0.06 –0.33 –0.59 –0.87

in the series Fe3C Fe3C1 – xBx Fe3B varies
insignificantly and increases linearly from 0.75 (Fe3C)
to 0.80 states/(eV atom) (Fe3B) due primarily to the
contributions from the Fe 3d↓ states.
The calculations performed allow us to interpret the
Mössbauer data [12, 13], according to which, upon sub-
stitution of boron for carbon in the composition of the
Fe3C compound, the isomer shift at the iron nuclei in
the Fe3C1 – xBx system weakly depends on the boron
concentration. As is known, the isomer shift is deter-
mined by the density of s electrons at the nucleus and
depends on the populations of both the 3d and 4s
valence states due to the screening effect. However, the
variations in these populations affect the isomer shift in
different ways. A decrease in the population of the 3d
states (q3d) leads to a decrease in the isomer shift, while
a decrease in the population of the 4s states (q4s), on the
contrary, results in an increase in the isomer shift. The
obtained averaged populations of the Fe 3d states
decrease linearly as the boron concentration x
increases, and the difference between the populations
for the Fe3B and Fe3C compounds, according to our
data, is equal to ∆q3d = –0.057 e/atom for the 3d states
and ∆q4s = +0.018 e/atom for the 4s states. Taking into
account the strong screening effect of the 4s electrons,
the constancy of the isomer shift [12, 13] can be
explained by the compensating effect, which is caused
by an increase in the population of the 4s states.
3.3. Stability and Chemical Bonding
in Borocementites
The relative stability of the Fe3C and Fe3B com-
pounds and the Fe3C1 – xBx solid solutions was esti-
mated from the changes in the enthalpies of their for-
mation (∆H), which were calculated from the total
energies (Etot) of the cementite-like phases Etot(Fe3C,
Fe3B, Fe3C1 – xBx), bcc iron Etot(Fe), graphite Etot(C),
and α-boron Etot(B) as follows:
Fe 3 C, Fe 3 B
∆H
= E tot ( Fe 3 C, B ) – { 3E tot ( Fe ) + E tot ( C, B ) },
Fe 3 C 1 – x, B x
∆H = E tot ( Fe 3 C 1 – x, B x )
– { 3E tot ( Fe ) + ( 1 – x )E tot ( C ) + xE tot ( B ) }.
It can be seen from Table 2 that the change in the
enthalpy of formation of the Fe3C compound is positive
Fe 3 C
in sign ( ∆H > 0), which is in good agreement with
the observed metastable behavior of Fe3C under normal
conditions [14]. For the composition of borocementite
Fe3C0.75B0.25, the enthalpy of formation becomes nega-
tive, and a further increase in the boron concentration x
leads to an increase in the absolute value of
Fe 3 C 1 – x B x
∆H , which takes the maximum value for Fe3B
Fe 3 B
( ∆H = –0.87 eV/form.unit). It is known [15] that,
in contrast to boron carbide, the Fe3B boride is a stable
phase. According to our calculations, the dependence
∆H(x) is linear and the quantity ∆H changes sign at a
boron concentration x = 20%.
The established concentration change in ∆H for
borocementites can be explained with allowance made
for the specific features revealed in the interatomic
interactions in the series Fe3C Fe3C1 – xBx
Fe3B. From the charge density maps presented in
Fig. 2, it can be seen that the covalent Fe–B bonds are
stronger than the Fe–C bonds. Since an increase in the
boron concentration is accompanied by an increase in
the unit cell volume and a weakening of the Fe–Fe
bonds weaken, the total stabilization of the boroce-
mentites with increasing boron content is caused by an
increase in the number of strong covalent Fe–B bonds.
This conclusion also follows from the analysis of the
calculated densities of states (Fig. 1), which demon-
strates an increase in the density of states in the energy

PHYSICS OF THE SOLID STATE Vol. 49 No. 12 2007

 SIMULATION OF THE STRUCTURAL, ELECTRONIC, AND MAGNETIC PROPERTIES
(‡)
Feg
C C
(b)
Feg
B C
(c)
Feg
B
B
Fig. 2. Charge density maps in the C(B)–Feg–C(B) plane
for the compounds (a) Fe3C, (b) Fe3C0.75B0.25, and
(c) Fe3B.
range from –3.5 to –2.5 eV in the series Fe3C
Fe3C1 – xBx Fe3B. This fact indicates an enhance-
ment of the d–p hybridization.
3.4. Magnetic Properties
Table 2 presents the magnetic moments of the car-
bon, boron, and iron atoms in nonequivalent positions
and the total magnetization of the Fe3C1 – xBx solid solu-
tion. It can be seen that the carbon and boron atoms
have small values of the induced magnetic moments,
which appear because of the polarization of the 2p
states owing to the Fe–C(B) covalent bonds. In this
PHYSICS OF THE SOLID STATE Vol. 49 No. 12
2301
case, the magnetic moments of the boron atoms turn out
to be higher than the magnetic moments of the carbon
atoms because of the stronger orbital hybridization of
the B–Fe bond as compared to the C–Fe bond. An
increase in the boron concentration is attended by an
increase in the magnetic moments of the iron atoms,
and a more significant increase in the magnetic
moments is observed for the Fes atoms rather than for
the Feg atoms. As can be seen from Table 2, the total
magnetization of the borocementites in the series
Fe3C Fe3C1 – xBx Fe3B increases linearly. The
calculation performed have demonstrated that there are
two factors responsible for the observed increase in the
magnetic moments and the magnetization with an
increase in the boron concentration x; namely, a
decrease in the populations of the Fe 3d states (a
decrease in the density of states in the range from –2 eV
to the energy at the Fermi level EF) and an increase in
the unit cell volume of the cementite.
4. CONCLUSIONS
Thus, the results of the calculations performed have
demonstrated that, in the series of borocementites
Fe3C Fe3C1 – xBx Fe3B, the unit cell volume
increases at the expense of the increase in the lattice
parameter a, whereas the lattice parameters b and c
decrease. The main variations in the electronic spec-
trum occur in the region of the bottom of the valence
band and result from the redistribution of the contribu-
tions of the C 2p–B 2p states to the region of the band
of the Fe 3d states, whereas the density of states at the
Fermi level changes insignificantly. It has been estab-
lished that the constancy of the isomer shift for differ-
ent boron concentrations is determined by the compen-
sation of the contributions due to a decrease in the pop-
ulation of the Fe 3d states and an increase in the
population of the Fe 4s state. An increase in the boron
concentration is accompanied by the stabilization of the
borocementites and the enthalpy of formation changes
sign in the vicinity of the composition Fe3C0.80B0.20.
The magnetic moments of the iron atoms and the total
magnetization increase with an increase in the boron
concentration, and the induced magnetic moments of
the boron atoms are larger than those at the carbon
atoms due to the stronger orbital p–d hybridization.
ACKNOWLEDGMENTS
This study was supported by the Russian Founda-
tion for Basic Research (project no. 05-03-32021), the
OAO MMK Foundation, ITTs Ausferr, and FNiO Intels
(project no. 41-06-01).
REFERENCES
1. M. E. Nicholson, Trans. Am. Inst. Min., Metall. Pet. Eng.
209, 1 (1957).
2007
2302 MEDVEDEVA et al.
2. I. S. Koifman, V. A. Egorshina, and G. V. Laskova, Met.
Sci. Heat Treat. 2, 141 (1969).
3. G. Kresse and D. Joubert, Phys. Rev. B: Condens. Matter
59, 1758 (1999).
4. E. J. Fasiska and G. A. Jeffry, Acta Crystallogr. 19, 463
(1965).
5. I. G. Wood, L. Vocadlo, K. S. Knight, D. P. Dobson,
W. G. Marshall, G. D. Price, and J. Brodholt, J. Appl.
Crystallogr. 37, 82 (2004).
6. S. Nagakura, J. Phys. Soc. Jpn. 16, 1213 (1961).
7. W. C. Chiou and E. A. Carter, Surf. Sci. 530, 87 (2003).
8. N. I. Medvedeva, L. E. Kar’kina, and A. L. Ivanovskii,
Fiz. Met. Metalloved. 96 (5), 16 (2003) [Phys. Met. Met-
allogr. 96 (5), 452 (2003)].
9. I. R. Shein, N. I. Medvedeva, and A. L. Ivanovskii, Phys-
ica B (Amsterdam) 371, 126 (2006).
PHYSICS OF THE SOLID STATE
10. N. I. Medvedeva, L. E. Kar’kina, and A. L. Ivanovskiœ,
Fiz. Tverd. Tela (St. Petersburg) 48 (1), 17 (2006) [Phys.
Solid State 48 (1), 15 (2006)].
11. N. I. Medvedeva, L. E. Kar’kina, and A. L. Ivanovskii,
Fiz. Met. Metalloved. 101 (5), 479 (2006) [Phys. Met.
Metallogr. 101 (5), 440 (2006)].
12. H. Bernas, I. A. Campbell, and R. Fruchart, J. Phys.
Chem. Solids 28, 17 (1967).
13. H. Bernas and I. A. Campbell, Phys. Lett. A 24, 74
(1967).
14. M. Umemoto, Y. Todaka, T. Takahashi, P. Tokumiya, and
K. Tsuchiya, Mater. Sci. Eng., A 375–377, 894 (2004).
15. G. V. Samsonov and N. M. Vinnitskii, Handbook of
Refractory Compounds (Metallurgiya, Moscow, 1976;
Plenum, New York, 1980).
Translated by N. Korovin
Vol. 49 No. 12 2007