crystals

Article
Crystal Structure and Mechanical Properties of ThBC2
Xinchun Zhou and Baobing Zheng *
College of Physics and Optoelectronic Technology & Advanced Titanium Alloys and Functional Coatings
Cooperative Innovation Center, Baoji University of Arts and Sciences, Baoji 721016, China
* Correspondence: zhengbaobing@bjwlxy.edu.cn; Tel.: +86-917-3364-258




Received: 6 July 2019; Accepted: 27 July 2019; Published: 29 July 2019


Abstract: Thorium borocarbide compounds have fascinating physical properties and diverse
structures, and hence have stimulated great interest. In this work, we determine the ground state
structure of ThBC2 by the unbiased structure prediction method based on first-principles calculations.
The dynamical and elastic stabilities of our proposed ThBC2 are verified by the calculations of phonon
spectrum and elastic constants. To study the mechanical properties fundamentally, we estimated the
elastic anisotropy of ThBC2 . The results show that the Young’s and shear moduli possess high degree
of anisotropy. The ideal strength calculations reveal that ThBC2 readily collapses upon applied stress
due to small ideal strengths. The cleavage fracture probably occurs along the [111] direction while slip
may easily appear along the [110] direction on the (111) plane for ThBC2 . In addition, we provide an
atomic explanation for the different characteristics of the strain–stress curves under different strains.

Keywords: ThBC2 ; crystal structure; anisotropic mechanical properties; ideal strength; first-principles
calculations

1. Introduction
Due to the potential application in fission fuel, actinoid-metal borocarbides are of great interest,
especially thorium borocarbide compounds [1–7]. Thorium borocarbide compounds have diversified
stoichiometric proportions with different crystal structures due to the flexible B–C framework.
Toth et al. [1] first investigated thorium borocarbide compounds, and observed four related compounds,
including ThBC, ThB2 C, ThBC2, and Th2 BC2 . The crystal structure of ThBC [2] shows a tetragonal
symmetry with the P41 22 space group, which contains tetrahedra and trigonal prisms of Th atoms,
and two boron and two carbon atoms form isolated zigzag chains. ThB2 C [3] crystallizes in the
rhombohedral space group (R3m) with slightly puckered Th-metal layers, and boron atoms form B6
hexagons connected by carbon atoms. Based on X-ray powder diffraction experiment, Rogl et al.
reported the crystal structures of Th3 B2 C3 [4] and Th2 B2 C3 [5]. The monoclinic Th3 B2 C3 belongs to the
space group of P2/m, in which Th atoms form octahedra, tetrahedra, and trigonal prisms with B and C
atoms occupying their centers, and non-metal atoms form isolated zigzag B–C chain fragments [4],
which are similar to the B–C chains in ThBC [2]. The crystal structure of Th2 B2 C3 consists of the infinite
branched B–C chains and triangular prisms of Th atoms. Therefore, the flexible B–C framework leads to
the complexity of the crystal structures for thorium borocarbide compounds. Consequently, the crystal
structure of ThBC2 , observed by Toth et al. long ago [1], remains an open question in the past years.
Actually, the determinations of crystal structures of ternary borocarbide compounds would
face many problems. First, the distributions of B and C atoms are so complex for a given crystal
framework that it is hard to determine the lowest energy phases of ternary borocarbide compounds,
which are called “coloring problems” in structural chemistry [8,9]. Second, from the point of view of
the experiment, ternary borocarbide compounds contain heavy metal atoms, which can be readily
distinguished by XRD or neutron-diffraction measurements. But for light B and C atoms, it is difficult

Crystals 2019, 9, 389; doi:10.3390/cryst9080389 www.mdpi.com/journal/crystals

Crystals 2019, 9, 389 2 of 10

to resolve their Wyckoff positions because the electronic and nuclear scattering cross-sections of B
and C atoms are very similar [10]. Therefore, it is challenging to solve their crystal structures in
experiments. To complement experiments, many crystal structure prediction techniques [11–14] based
on the first-principles density functional method have been proposed recently. In particular, the particle
swarm optimization (PSO) technique as implemented in the crystal structure analysis by particle
swarm optimization (CALYPSO) [11] has been suggested to be an efficient tool to resolve the ground
state of certain compound [15–17].
In the present work, we performed the PSO technique combined with first-principles calculations
to determine the ground state structure of ThBC2 . The stability of ThBC2 is verified by the phonon
spectrum and elastic constants. To show the mechanical properties, we have systematically studied
the elastic anisotropies of ThBC2. In addition, the failure modes under tensile and shear strains are
investigated by the ideal strength calculations.

2. Computational Methods
The crystal structure of ThBC2 was predicted using the PSO technique as implemented in the
CALYPSO package [11]. To improve the prediction efficiency and avoid possible breakdown of
structure optimization, the initial minimum inter-atomic distance between different types of atoms are
0.6 times the length of the sum of atomic covalent radii for the random structures. The proportion of
the structures generated by PSO technique is set to 0.6. Other parameters are set as the default values of
the CALYPSO package. All the self-consistent field calculations and structural relaxations were carried
out within the framework of density functional theory using the Vienna ab initio simulation package
(VASP) [18]. The generalized gradient approximation (GGA) with the Perdew–Burke–Ernzerhof
functional was employed to describe exchange–correlation interaction [19]. The interactions between
electron and core were described by the frozen-core projector augmented wave (PAW) method [20],
where the 6s2 6p6 6d2 7s2 , 2s2 2p1 , and 2s2 2p2 are valence electrons for Th, B, and C atoms, respectively. The
PAW pseudo potential has been successfully used to study the compounds including Th atoms, such as
thorium dicarbide [21], thorium dioxide [22], thorium dihydride [23], and thorium mononitrides [24].
The cutoff energy of 600 eV for plane wave and the 9 × 9 × 9 k-point meshes with Monkhorst–Pack
method [25] were adopted, which can ensure that the total energy was converged to 1 meV per atom.
All the structures were relaxed until the forces on each atom are below 0.001 eV/Å. To verify the
dynamical stability, we performed the finite displacement method to calculate the phonon spectrum
of ThBC2 with 2 × 2 × 2 supercell of primitive cell and 4 × 4 × 4 k-point meshes as implemented
in PHONOPY package [26]. The elastic constants were estimated by the strain–stress method
described in our previous work [27], and a set of homogeneous strains with maximum strain value
of 0.1% is applied. The elastic moduli and Pugh’s ratio were calculated using the Voigt–Reuss–Hill
approximation [28]. To estimate the ideal tensile and shear strengths, the conventional cell of ThBC2
is deformed incrementally and continuously along the direction of the applied strain. Then, the
atomic basis vectors orthogonal to the applied strain and the positions of all atoms are relaxed
simultaneously. As a result, the strain–stress curves for deducing the ideal strength are obtained [29,30].
Considering that the spin-orbit coupling (SOC) plays an important role on the compounds including
heavy atoms [31], we tested the influence of SOC on the crystal structure and elastic constants of
ThBC2 . The calculated results [see the Supplementary Material (SM)] imply that SOC has little impact
on the structure and mechanical properties of ThBC2 . Therefore, we can ignore the SOC effect in the
following. For orthorhombic structure, the Young’s modulus E along the [hkl] direction is described by
the expression [32]

E−1 = s11 α4 + s22 β4 + s33 γ4 + (2s12 + s66 )α2 β2 + (2s23 + s44 )β2 γ2 + (2s13 + s55 )α2 γ2 , (1)
Crystals 2019, 9, 389 3 of 10
Crystals 2019, 9, x FOR PEER REVIEW 3 of 10

where ssijij are

where are the
the elastic
elastic compliance
compliance constants
constants of
of orthorhombic symmetry, α,
orthorhombic symmetry, α,β,β,and
andγγ denote
denote the
the
direction cosines of the [hkl] direction. The shear modulus G along the arbitrary [uvw] directions
direction cosines of the [hkl] direction. The shear modulus G along the arbitrary [uvw] directions on on the
(hkl) shearshear
the (hkl) planeplane
can becanwritten as [32].
be written as [32].

G−1 =G 4s=114αs2111αα221 +
α 24s+22 β 2 4s 4 sγ332γγ122γ + s12αα11α22 β1β2 + s2323ββ1 β1 β2γ21γγ12γ+28+ α113
αα2 γ11α
γ 22 γ1 γ2
−1 2 2 2 2 2 2
4 sβ222 β221 + + 33 2 +8s
812 +88s s138s
1 1 (2)
2 2 22 2 2 (2)
+s44+(βs 1 γ(2β+γ β+2 γβ1 )γ )+ +s55s (α(α
44 1 2 2 1 55
γ
1 2
α γ
1 γ2 + α2γ 1) + s 66
+ 2 1
) +66
s α
1
β
2
+ 2
α
(α β1 +2 α β2 ) 1,
( 1
β ) ,

whereαα11, ,ββ
where 1 ,1,and
andγ1γare
1
thethe
are direction cosines
direction of the
cosines of[uvw] direction,
the [uvw] while αwhile
direction, 2 , β2 , and
α2, γβ22,are
andtheγdirection
2
are the
cosines of cosines
direction the normal direction
of the normalof the (hkl)ofshear
direction plane.
the (hkl) Theplane.
shear anisotropy of Young’sof
The anisotropy modulus
Young’sand shear
modulus
modulus are discussed based on above two expressions.
and shear modulus are discussed based on above two expressions.
3. Results and Discussion
3. Results and Discussion
To determine the ground state structure of ThBC2 , we performed the structural search by the
To determine the ground state structure of ThBC2, we performed the structural search by the
unbiased PSO technique [11] with the cell up to 8 formula units (f.u.). As a result, we obtained the
unbiased PSO technique [11] with the cell up to 8 formula units (f.u.). As a result, we obtained the
ground state structure of ThBC2 according to comparing their total energies. As shown in Figure 1a,b,
ground state structure of ThBC2 according to comparing their total energies. As shown in Figure 1a,b,
the predicted crystal structure of ThBC2 belong to the space group of Immm (no. 71) within orthorhombic
the predicted crystal structure of ThBC2 belong to the space group of Immm (no. 71) within
symmetry (16 atoms/cell), in which Th atoms occupy the 4e (0.26226, 0, 0) Wyckoff position, B atoms
orthorhombic symmetry (16 atoms/cell), in which Th atoms occupy the 4e (0.26226, 0, 0) Wyckoff
occupy 4j (1/2, 0, 0.36170) Wyckoff position, and C atoms occupy 8l (0, 0.17557, 0.26910) Wyckoff
position, B atoms occupy 4j (1/2, 0, 0.36170) Wyckoff position, and C atoms occupy 8l (0, 0.17557,
position, respectively. The optimized lattice constants of the conventional cell are a = 7.2403 Å,
0.26910) Wyckoff position, respectively. The optimized lattice constants of the conventional cell are a
b = 3.9978 Å, and c = 6.7686 Å. Clearly, we can see that the B and C atoms form the armchair-like
= 7.2403 Å, b = 3.9978 Å, and c = 6.7686 Å. Clearly, we can see that the B and C atoms form the
B–C chains along (010) direction (see Figure 1c). These armchair-like B–C chains are separated by the
armchair-like B–C chains along (010) direction (see Figure 2c). These armchair-like B–C chains are
adjacent Th atomic layers. Note that the armchair-like B–C chains had been uncovered in other thorium
separated by the adjacent Th atomic layers. Note that the armchair-like B–C chains had been
borocarbide compounds, such as ThBC [2,7]. One Th atom and four C atoms can constitute a square
uncovered in other thorium borocarbide compounds, such as ThBC [2,7]. One Th atom and four C
pyramid (see Figure 1d), which serves as a basic building-block of ThBC2 . The average B–C bond
atoms can constitute a square pyramid (see Figure 2d), which serves as a basic building-block of
length of ThBC2 is 1.57 Å, which is shorter than those of t-BC4 (1.66 Å) [27,33] and d-BC3 (1.61 Å) [34],
ThBC2. The average B–C bond length of ThBC2 is 1.57 Å, which is shorter than those of t-BC4 (1.66 Å)
but is slightly longer than those of ThBC (1.54 Å) [2] and ThB2 C (1.49 Å) [3]. The interatomic distance
[27,33] and d-BC3 (1.61 Å) [34], but is slightly longer than those of ThBC (1.54 Å) [2] and ThB2C (1.49
between adjacent B atoms is 1.87 Å, which is also larger than those of ThBC (1.77 Å) [2] and ThB2 C
Å) [3]. The interatomic distance between adjacent B atoms is 1.87 Å, which is also larger than those
(1.85 Å) [3]. In addition, to facilitate the possible experimental synthesis, we discuss the metastable
of ThBC (1.77 Å) [2] and ThB2C (1.85 Å) [3]. In addition, to facilitate the possible experimental
ThBC2 in the SM, and the crystal structures of the most stable form and other four predicted forms are
synthesis, we discuss the metastable ThBC2 in the SM, and the crystal structures of the most stable
available in the SM.
form and other four predicted forms are available in the SM.

Figure 1. Side (a) and top (b) views of the crystal structure of ThBC2 , in which the purple (large),
Figure 1. Side (a) and top (b) views of the crystal structure of ThBC2, in which the purple (large), red
red (middle), and blue (small) spheres denote Th, C, and B atoms, respectively. (c) The infinite
(middle), and blue (small) spheres denote Th, C, and B atoms, respectively. (c) The infinite armchair-
armchair-like B–C chain along y-axis direction. (d) The square pyramid building block consisting of
like B–C chain along y-axis direction. (d) The square pyramid building block consisting of one Th and
one Th and four C atoms.
four C atoms.

To verify the stability, we first calculated the phonon spectrum of ThBC2. As shown in Figure
2a, it is found that there is no imaginary frequency in the Brillouin zone along the high-symmetry
Crystals 2019, 9, 389 4 of 10

To verify the stability, we first calculated the phonon spectrum of ThBC2 . As shown in Figure 2a,
Crystals 2019, 9, x FOR PEER REVIEW 4 of 10
it is found that there is no imaginary frequency in the Brillouin zone along the high-symmetry direction,
which indicates the dynamical stability of ThBC2 . Moreover, due to the large differences of atomic
direction, which indicates the dynamical stability of ThBC2. Moreover, due to the large differences of
masses among Th, B, and C atoms, the optical branches and acoustic branches of ThBC2 are separated
atomic masses among Th, B, and C atoms, the optical branches and acoustic branches of ThBC2 are
distinctly, leading to large acoustic-optical branch gap. Meanwhile, the high-frequency optical phonon
separated distinctly, leading to large acoustic-optical branch gap. Meanwhile, the high-frequency
bands are also discrete. The formation energy can reflect the relative stability of the compound and
optical phonon bands are also discrete. The formation energy can reflect the relative stability of the
whether the compound can be readily synthesized experimentally. Here, we choose the face-centered
compound and whether the compound can be readily synthesized experimentally. Here, we choose
cubic thorium, rhombohedral α-boron and graphite as the reference phases. Therefore, the formation
the face-centered cubic thorium, rhombohedral α-boron and graphite as the reference phases.
energy ∆E f of ThBC2 can be defined by
Therefore, the formation energy ΔE f of ThBC2 can be defined by

∆EΔf E= =EE((ThBC
ThBC 2 ) − E(Th) − E(B) − 2 × E(C), (3)
f 2 − E (Th) − E (B) − 2 × E (C)， (3)
where EE((ThBC
ThBC 22)) represents
representsthe
thetotal
totalenergy
energyofofThBC
ThBC , andE(Th
2 , 2and ), E,(BE),(B)
E (Th) and E(C)Edenote
, and the total
(C) denote the
energies of bulk thorium, α-boron, and graphite, respectively. The calculated
total energies of bulk thorium, α-boron, and graphite, respectively. The calculated formation energy formation energy of
ThBC
of ThBC −1.454
2 is2 is －1.454eV/f.u., suggesting
eV/f.u., suggestingthethethermodynamic
thermodynamic stability
stabilityand
andpossible
possiblesynthesis
synthesisofof ThBC
ThBC22
in experiment. In addition, the electronic band structure calculation reveals that
in experiment. In addition, the electronic band structure calculation reveals that ThBC2 is metallic, asThBC 2 is metallic,
as shown
shown in in Figure
Figure 2b,c.
2b,c. The
The density
density ofofstates
states(DOS)
(DOS)forforThBC
ThBC2 2implies
impliesthat
thatthetheTh
Thand
andCC atoms
atoms mainly
mainly
contribute
contribute to to the
the total
total density
density of
of states
states around
around thethe Fermi
Fermi level.
level.

Figure 2.
2. (a)
(a) Phonon spectrum of
Phonon spectrum of ThBC
ThBC2 along the high-symmetry lines. (b) Band structure of ThBC2
Figure 2 along the high-symmetry lines. (b) Band structure of ThBC2
along the high-symmetry lines. (c) DOS of ThBC22.. Here
along the high-symmetry lines. (c) DOS of ThBC Here the
the vertical
vertical blue
blue dashed
dashed lines represent the
lines represent the
positions of high-symmetry point in the Brillouin zone, and the horizontal blue dashed line denotes
positions of high-symmetry point in the Brillouin zone, and the horizontal blue dashed line denotes the
the Fermi
Fermi level.
level.

further confirm
To further confirm thethe stability
stability and
and assess
assess the
the mechanical
mechanical properties, we have calculated the
elastic moduli
elastic constants and elastic moduli ofof ThBC
ThBC22. The orthorhombic ThBC22 has nine independent elastic
constants, which areCC1111= =
which are 315 GPa,
315 GPa, = 146
C12C=12146 GPa,GPa,
C13 =C40 = 40 C
13 GPa, 23 = 67
GPa, C23 = 67
GPa, C22GPa, 22 = 286
= 286CGPa, C33 =GPa,
576
C 33 = C
GPa, 44 =GPa,
576 C44 =
40 GPa, C5540= GPa,
49 GPa, = 49CGPa,
C55 and 66 = 117 C66 =
andGPa. Clearly, these
117 GPa. elasticthese
Clearly, constants
elasticsatisfy the satisfy
constants elastic
stability criteria for a stable orthorhombic structure, that is, C11 > 0, C44 > 0, C55 > 0, C66 > 0, C11C22 > C122,
C11C22C33+2C12C13C23－ C11C232－ C22C132－ C33C122 > 0 [35]. The estimated bulk modulus (B) and shear
modulus (G) of ThBC2 are 184 and 86 GPa, which are larger than the bulk modulus (123 GPa) and
shear modulus (61 GPa) of tetragonal ThBC [7]. That is to say, our predicted orthorhombic ThBC2 has
Crystals 2019, 9, 389 5 of 10

the elastic stability criteria for a stable orthorhombic structure, that is, C11 > 0, C44 > 0, C55 > 0, C66 > 0,
C11 C22 > C12 2 , C11 C22 C33 + 2C12 C13 C23 − C11 C23 2 − C22 C13 2 − C33 C12 2 > 0 [35]. The estimated bulk
modulus (B) and shear modulus (G) of ThBC2 are 184 and 86 GPa, which are larger than the bulk
modulus (123 GPa) and shear modulus (61 GPa) of tetragonal ThBC [7]. That is to say, our predicted
orthorhombic ThBC2 has better ability to resist the tensile and shear deformations than that of ThBC.
Accordingly, we can obtain the Pugh’s modulus ratio B/G, which is an indicator for determining
whether material is ductile or brittle; if Pugh’s ratio is larger than 1.75, a material will tend to be ductile,
otherwise brittle [36,37]. The calculated Pugh’s ratio of 2.13 implies that our predicted ThBC2 tends to
be ductile.
The elastic anisotropy refers to the directional dependence of mechanical properties, which is
closely related with plastic deformation and crack behavior of materials. To get a comprehensive
understanding of elastic anisotropy, we calculated the Young’s modulus E as a function of the directions
based on their analytical expressions discussed above, in which the elastic compliance constants can
be deduced by the elastic constants. As shown in Figure 3a,b, the Young’s moduli of ThBC2 along
Crystals 2019, 9, x FOR PEER REVIEW 5 of 10
different orientations present a high degree of anisotropy. In particular, we can clearly see that the
maximum Young’s
better ability modulus
to resist is along
the tensile andtheshear
[001]deformations
direction, which thanis significantly
that of ThBC. larger than the Young’s
Accordingly, we can
modulus along other directions. This can be ascribed to the fact that there
obtain the Pugh's modulus ratio B/G, which is an indicator for determining whether material exist a number of strongis
covalent B–C bonds along the [001] direction, which facilitates ThBC
ductile or brittle; if Pugh's ratio is larger than 1.75, a material will tend 2 to resist tensile deformation and
to be ductile, otherwise brittle
results
[36,37].inThe
largest Young’s
calculated modulus
Pugh's ratioalong this
of 2.13 direction.
implies that our predicted ThBC2 tends to be ductile.

Figure 3. 3D plots of Young’s modulus (a) and its plane projections (b) as the function of the directions,
Figure 3. 3D plots of Young’s modulus (a) and its plane projections (b) as the function of the
in which the distances between the origin and the surface are the values of Young’s moduli along
directions, in which
corresponding the distances
directions. between
Orientation the originof
dependence and the surface
Young’s are the
modulus (c)values of Young’s
and shear moduli
modulus (d),
along corresponding directions. Orientation dependence of Young’s modulus (c) and shear modulus
in which the principal crystal orientations [110], [101], and [011] are marked by arrows with different color.
(d), in which the principal crystal orientations [110], [101], and [011] are marked by arrows with
different color.

The elastic anisotropy refers to the directional dependence of mechanical properties, which is
closely related with plastic deformation and crack behavior of materials. To get a comprehensive
Crystals 2019, 9, 389 6 of 10

To further study the mechanical anisotropy, we estimated the orientation dependence of Young’s
modulus and shear modulus as the tensile or shear strain is within the (001), (100), and (010) planes.
For instance, when the tensile strain is within the (001) plane, the tensile direction can be denoted as
[hk0], and we refer to the angle between the [hk0] and [100] direction as θ. As a result, the direction
cosines of the [hk0] can be obtained as α = cos θ, β = sin θ, and γ = 0. Thus, Equation (1) translates into

E−1 = s11 cos4 θ + s22 sin4 θ + (2s12 + s66 ) cos2 θsin2 θ, (4)

in which the Young’s modulus is dependent with the defined orientation θ. The other orientation
dependence of Young’s modulus and shear modulus can be obtained using similar method, and the
detailed results can be found in Ref. [32]. Based on the above approach, the calculated results are shown
in Figure 3c,d. The maximum Young’s modulus is found along the [001] direction (E[001] = 560 GPa),
which shows excellent consistency with the three-dimensional (3D) plots of Young’s modulus. It is
found that Young’s modulus along principal crystal directions possess the sequence of E[101] < E[011]
< E[010] < E[100] < E[110] < E[001] . To measure the ability of resisting shear deformation for ThBC2 ,
the dependences of shear moduli on the directions are illustrated in Figure 3d. We can see that
the largest shear modulus (G = 117 GPa) appears along the [001] direction on the (100) shear plane.
Meanwhile, the obtained smallest shear modulus is along the [100] direction on the (001) shear plane,
i.e., G(001)[100] = 40 GPa, which is equal to the elastic constant of C44 .
The ideal strength of a material is the upper limit of mechanical strength that it can sustain. If the
stress upon material is larger than ideal strength, it will collapse. In particular, the ideal tensile and shear
strengths are intimately related with the failure mode of material, and thus can be employed to uncover
when the cleavage fracture and slip will appear for certain compounds. Therefore, we next study
the ideal tensile and shear strengths of ThBC2 to further explore its mechanical property. The tensile
and shear strains are continuously applied upon ThBC2 to obtain the strain–stress relationships, and
consequently the ideal strength can be deduced. The calculated strain–stress relationships are shown
in Figure 4. It is found that the largest ideal tensile strength is σ = 59 GPa along the [010] direction.
The main reason is that the armchair-like B–C chains are along [010] direction, which can form strong
covalent B–C against the tensile deformation. The lowest ideal tensile strength appears in the [111]
direction, i.e., σ[001] = 7 GPa, suggesting that the cleavage fracture can easily occur along this direction.
An inspection of the Th-C bond length suggests that the distance between the Th4 and C6 increases
from 2.66 Å to 3.01 Å when the [111] tensile strain increases from 0 to 0.07. This fact implies these Th-C
bonds are the main load bearing component along the [111] direction. Therefore, the weak Th-C bonds
along the [111] direction is responsible for this low tensile strength. Besides the [111] direction, the
[011] and [110] tensile deformation also easily stretch the weak Th-C bonds and result in small ideal
tensile strength along these directions. It is worth noting that the ideal shear strengths of ThBC2 on
different shear planes are all very small, which is the inevitable consequence of the layered structure of
ThBC2 . We can see that the highest ideal shear strength is along the [100] direction on the (001) plane,
i.e., τ(001)[100] = 18 GPa, and the obtained lowest ideal shear strength occurs within the [110] direction
on the (111) plane, indicating that ThBC2 can readily slip under shear along this direction.
It is found that Young’s modulus along principal crystal directions possess the sequence of E[101] <
E[011] < E[010] < E[100] < E[110] < E[001]. To measure the ability of resisting shear deformation for ThBC2, the
dependences of shear moduli on the directions are illustrated in Figure 3d. We can see that the largest
shear modulus (G = 117 GPa) appears along the [001] direction on the (100) shear plane. Meanwhile,
the obtained
Crystals smallest shear modulus is along the [100] direction on the (001) shear plane, i.e., G(001)[100]
2019, 9, 389 7 of 10
= 40 GPa, which is equal to the elastic constant of C44.

Figure 4.
Figure 4. The
The stress
stress as
as the
the function
function of
of tensile
tensile (a)
(a) and
and shear
shear (b)
(b) strains
strains along
along different tensile and
different tensile and shear
shear
strain directions.
strain directions.

The ideal strength

Interestingly, of a materialcurves
the strain–stress is the upper
underlimit tensile of mechanical strength that exhibit
and shear deformation it can sustain.
different If
the stress upon
characteristic material
along variousis directions.
larger thanFor ideal strength,
instance, theitstress
will collapse.
along the In particular,
[010] directionthe ideal
drops tensile
abruptly
and shear
under tensilestrengths are intimately
deformation, while along related
the [111] with the failure
direction mode
the stress of material,
decreases graduallyand rather
thus can thanbe a
employed
sharp to uncover
decrease when limit.
past the elastic the cleavage
To get deeperfracture and slip
insights into will appear forcharacteristic,
this interesting certain compounds.
we next
Therefore,
analyze we bondings
atomic next study andthe ideal localization
electron tensile andfunction shear strengths of ThBC
(ELF) to clarify to further
this2 point. Figure explore
5a shows its
mechanical
the property.
bond lengths of ourThe tensile
chosen and Th-C,
typical shear B–C,strainsC–C,areTh-B,
continuously applied
and B–B bonds asupon ThBCof
a function 2 to
theobtain
[010]
the strain–stress
tensile relationships,
strain. Clearly, we can see and consequently
that the distancethe ideal strength
between the B3 and canC8 be atoms
deduced. The calculated
increases abruptly
strain–stress
when relationships
the tensile are shown
strain exceeds in Figure
the critical 4. It of
value is found that the
0.17, while largest
other bondsidealshowtensile strength
small changesis σ
= 59 GPa along
compared theB–C
with the [010] direction.
bonds. The main
Therefore, reason is of
the alignment that the armchair-like
strong covalent B–C B–C bonds chains
alongarethealong
[010]
[010] direction,
direction whichload
is the main canbearing
form strong covalentwhich
component, B–C against
leads tothe thetensile
largestdeformation.
ideal tensile The lowest
strength 59 ideal
GPa.
tensile strength
Nevertheless, appears
once in thestrain
the tensile [111]isdirection,
larger than i.e.,
theσ[001] = 7 GPa,
critical valuesuggesting
of 0.17, as showthat the cleavage
in Figure 4, afracture
sudden
can easily
“hard” occur along
breaking of thethis direction.
strong covalent AnB–C inspection
bonds of the Th-C
occurs, whichbond length suggests
accounts for the sharpthat the distance
decrease of
between
the stressthe Th4this
along anddirection.
C6 increases from 2.66
To further Å to this
confirm 3.01 bond-breaking
Å when the [111] tensilethe
pattern, strain increases from
three-dimensional
0 to 0.07. This
isosurfaces fact implies
of ELF with anthese Th-Cofbonds
isovalue are theand
0.75 before main load
after thebearing
criticalcomponent
tensile strains alongarethe [111]
plotted
direction.
in Therefore,
Figure 5b,c. the weak
Generally, the Th-C
large bonds
ELF value alongcorresponds
the [111] directionto highiselectron
responsible for this low
localization andtensile
is the
strength. Besidesofthe
characterization [111] direction,
covalent bondings. theAs [011]
shownand in [110] tensile
Figure 5b,c,deformation also easily stretch
the charge distribution localizedthe
weak
in Th-C B3–C8
between bonds and
bondresult in small
exhibits a sharpideal tensile strength
decrease when thealong tensilethese directions.
strain changes Itfrom is worth noting
0.15 to 0.18,
that thesuggesting
further ideal shear thestrengths
bond-breakingof ThBC 2 on different
of strong covalentshear B–C bondplanes are all
under the very
[010] small,
tensile which is the
deformation.
inevitable for
However, consequence of thedeformation,
the [111] tensile layered structureas shown of ThBC 2. We
in Figure 5d,can
thesee
bond that the highest
lengths of B–C,ideal
C–C, shear
Th-B,
and B–B bonds nearly keep invariant with the increase of tensile strain, while the Th-C bond increases
gradually as the tensile loading increases, even though beyond the critical strain 0.06. Therefore,
the stress under this tensile mode change gradually beyond the critical strain, corresponding to the
softer bond-deformation behavior. In a word, the ‘hard” breaking of B–C bonds correspond to the
sharp decrease of the stress in the strain–stress curve, while the weak Th-C bonds result in softer
bond-deformation behavior as characterized by a gradual decrease of the stress.
Crystals 2019, 9, x FOR PEER REVIEW 7 of 10

strength is along the [100] direction on the (001) plane, i.e., τ(001)[100] = 18 GPa, and the obtained lowest
ideal shear
Crystals 2019, 9,strength
389 occurs within the [ 110 ] direction on the (111) plane, indicating that ThBC82ofcan
10
readily slip under shear along this direction.

Figure 5.
Figure 5. Bond
Bond lengths
lengths as
as aa function
function ofof strain
strain under
under the
the [010]
[010](a)
(a) and
and[111]
[111](d)
(d)tensile
tensilemodes.
modes. The
The ELF
ELF
for ThBC
for ThBC22 before
before (b)
(b) and
and after
after (c)
(c) the
the critical
critical [010]
[010] tensile
tensile strain.
strain.

4. Conclusions
Interestingly, the strain–stress curves under tensile and shear deformation exhibit different
characteristic
In summary, along various directions.
we predicted For instance,
the crystal structure of ThBCthe2 and
stress along the
calculated the [010] direction
mechanical drops
properties
abruptly under tensile deformation, while along the [111] direction the
of ThBC2 . Our predicted ThBC2 consists of the Th atomic layers and the armchair-like B–C chains stress decreases gradually
rather
in thanwith
parallel a sharp decrease
Th atomic pastBased
layers. the elastic
on the limit.
phonon To spectra
get deeper insights
and elastic into thiswe
constants, interesting
verified
characteristic, we next analyze atomic bondings and electron localization
the stability of ThBC2 . We also calculated the anisotropy of Young’s modulus and shear modulus function (ELF) to clarify
this point. Figure 5a shows the bond lengths of our chosen typical Th-C,
for ThBC2 . The obtained results show that ThBC2 exhibits significant anisotropy. The calculated B–C, C–C, Th-B, and B–B
bonds as a function
strain–stress of the [010]
curves suggest ThBC tensile strain. Clearly, we can see that the distance between the B3
2 has low ideal strengths, implying that the cleavage fracture and
and C8 atoms increases abruptly when
slip can easily occur in ThBC2 . We expect that the tensile strain exceeds
our findings the the
can favor critical value of 0.17,
identification while other
of structure for
bonds show small changes compared with the B–C bonds. Therefore,
ThBC2 , and provide insight understanding into the mechanical properties of ThBC2 . the alignment of strong covalent
B–C bonds along the [010] direction is the main load bearing component, which leads to the largest
Supplementary Materials:
ideal tensile strength The following
59 GPa. are available
Nevertheless, once the online at http://www.mdpi.com/2073-4352/9/8/389/s1,
tensile strain is larger than the critical value of
Figure S1: Crystal structure and phonon spectrum of Pmmm ThBC2 , Figure S2: Crystal structure and phonon
0.17, as show in Figure 4, a sudden ‘‘hard’’ breaking of the strong covalent B–C bonds occurs, which
spectrum of C2/m ThBC2 , Figure S3: Crystal structure and phonon spectrum of I4m2 ThBC2 , Figure S4: Crystal
accountsand
structure forphonon
the sharp decrease
spectrum of the
of Amm2 ThBCstress along this direction. To further confirm this bond-
2 , Table S1: Lattice parameters, atomic positions and the total
breaking
energies pattern,
per atom ofthe
fourthree-dimensional isosurfaces
metastable ThBC2 , Table of ELF elastic
S2: Calculated with an isovalue
constants Cij of
of 0.75 before
the most stableand after
ThBC 2
without
the critical tensile strains are plotted in Figure 5b,c. Generally, the large ELF value corresponds of
and with SOC, most stable structure.cif (The most stable structure of ThBC 2 ), no.47.cif (Crystal structure to
Pmmm ThBC2 ), no.12.cif
high electron (Crystal
localization andstructure of C2/m ThBC2 ), no.119.cif
is the characterization of covalent(Crystal structure
bondings. Asofshown
I4m2 ThBC 2 ), no.38.cif
in Figure 5b,c,
(Crystal structure of Amm2 ThBC2 ).
the charge distribution localized in between B3–C8 bond exhibits a sharp decrease when the tensile
Author Contributions: Formal analysis, X.Z. and B.Z.; Investigation, X.Z.; Writing—original draft, X.Z. and B.Z.
strain changes from 0.15 to 0.18, further suggesting the bond-breaking of strong covalent B–C bond
under theThis
Funding: work
[010] is supported
tensile by the Natural
deformation. However, Science
for Foundation of China
the [111] tensile (Grant No. 11647007),
deformation, as shownthe inNatural
Figure
Science Basic Research plan in Shaanxi Province of China (Grant Nos. 2018JQ1083), the Baoji University of Arts
5d, the bond lengths of B–C, C–C, Th-B, and B–B bonds nearly keep invariant with the increase of
and Sciences Key Research (Grant No. ZK2017009), and the National Undergraduate Innovative Training Program
(Grant No. 201610721017).
Crystals 2019, 9, 389 9 of 10

Conflicts of Interest: The authors declare no conflict of interest.

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