Article Type : Research Article
Authors : Yu AY
Keywords : Superhard materials; Mechanical properties; First-principles calculation; Electron localization function (ELF)
The structural,
electronic and mechanical properties of RuBx (x=1, 2, 3) are investigated by
performing ?rst principles calculations using density functional theory (DFT).
The calculated lattice constants agree well with the available results. The
chemical bonding is interpreted by calculating the electron localization
function (ELF). The covalent Ru-B bond and B-B bond become stronger with the
increase of boron’s concentrations, which can help improve the hardness of RuBx
system. Moreover, RuB has the highest bulk modulus, which means more prominent
volume-compression resistance. RuB2 has a certain elastic anisotropy and RuB3
has the best toughness.
Because of the superior property of high hardness,
superhard materials have played a vital role in industrial production,
including many applications in abrasives, cutting tool materials as well as
wear-resistant coatings, etc [1,2]. A recent perspective has reached to the
conclusion that diamond remains the hardest known material under normal
conditions [3]. In the past decades, many efforts have been devoted into
fabricating or designing new type of superhard and ultrahard materials [4-10].
A very important route of synthesizing novel superhard materials is the
alloying between low-mass element and transient metal element [11-13]. In a
previous research, it was found that RuB2 has high elastic anisotropy [14].
Additionally, the flexibility of RuB2 can be improved with the increase of
pressure and temperature can have an obvious impact on the mechanical
properties of RuB2 [15]. Modern computational techniques allow the
computationally prediction of novel superhard materials with superior
properties, which can be promising for practical applications. Computational
discovery of hard and superhard materials is a booming field of science, which
help predict novel materials with enhanced physical properties [16]. In spite
of some experimental advances, a systematic research about physical properties
of RuBx (x=1, 2, 3) compounds is still lacking and new computational work is
needed strongly. In this paper, the crystal structures, electronic structure as
well as mechanical properties of RuBx (x=1, 2, 3) have been reported.
The density-functional theoretical method (DFT) has
witnessed a great success in the computation of the electronic structure of
solids. As one of the most accurate methods used for the present work, the
structures of RuBx (x=1, 2, 3) are optimized by adopting projector augmented
wave (PAW) approach [17]. Exchange and correlation effects are treated by the
generalized-gradient approximation (GGA) [18]. The total energy and charge
density are integrated in the Brilorine zone by means of Monkhorst-Pack scheme
[19]. A suitable plane wave cutting kinetic energy should be selected in order
to ensure the accuracy of results. With a test, an energy cutoff of 330 eV is
enough for the expansion of plane wave basis set.
The structural model of Ru-Bx (x=1, 2, 3) system is illustrated in (Figure 1). It can be seen that all these compounds have layered geometry. For RuB (P-6m2), the Ru atomic layer and B atomic layer are in alternating stack arrangement in the form of Ru-B-Ru along the c-axis direction. Each boron atom is located at the center of a triangular columnar formed by six Ru atoms.Table 1: lists the optimized lattice constants of RuBx(x=1, 2, 3) in the most stable state, with the reference values denoted in brackets.
Lattice constants Materials |
a(nm) |
C(nm) |
RuB (P-6m2) |
0.288
(0.285[12]) |
0.287(0.286[12]) |
RuB2 (Pmmn) |
0.467
(0.465[12,13]) |
0.406(0.405[12,13]) |
RuB3 (P-6m2) |
0.290 |
0.457 |
In order to determine the chemical bonding of title
materials, the electron localization function (ELF) is calculated and analyzed
in the present work [20]. Actually, ELF can help us judge the chemical bonding
of a given system. There will be the perfect localization of electron or strong
covalent bonding when ELF is adjacent to 1. On the contrary, there will be no
electrons in a specific area if ELF=0. ELF of RuBx (x=1, 2, 3) has been
presented in (Figure 2). It should be noted that chemical bonding of title
materials could be predicted more reasonable after combing ELF with the crystal
structure. ELF of RuB shows that Ru layer and B layer are packed in turn along
c axis and there is no direct B-B contact or bonding in RuB. As for RuB2, there
is strong Ru-B covalent bonding along the direction of c-axis, which means that
this type of material possesses good incompressibility along c-axis. Compared
with RuB2, there is stronger B-B covalent bonding in RuB3, which means that the
hardness of RuB3 has been improved greatly. Additionally, there is strong Ru-B
covalent bonding along the direction of c-axis, which has also improved the
hardness of RuB3.
Elastic constants (Cij) are often used to describe a given material’s rigidity resulting from the external strain. The elastic constants (Cij), bulk modulus (B), shear modulus (G), Young’s modulus (E) and Poisson’s ratio (? ) of RuBx (x=1,2,3) have been calculated and results are listed in. The bulk modulus and listed in. The bulk modulus and shear modulus are calculated through the Voigt-Reuss-Hill approximation [21-23]. According to these elastic constants (Cij) and the judgment of mechanical stable conditions, all these compounds (RuB, RuB2 and RuB3) are mechanically stable [24]. It can also be found that C33 value is the largest among all these RuBx compounds, which indicates that there is larger incompressibility for RuBx along c-axis direction.
Table 2: Calculated elastic
constants and the elastic parameters (B, G, E, B/G, ? ) for RuBx (x=1,2,3) at
GGA level.
Elastic
properties Materials |
Elastic
constants |
Elastic
parameters |
RuB
(P-6m2) |
C11=527; C33=718; C44=157; C12=190; C13=165 |
B=312; G=179;
B/G=1.74; E=449;
?
=0.26 |
RuB2
(Pmmn) |
C11=526; C22=451;
C33=702; C44=109; C55=209; C66=177; C12=191; C13=158;
C23=129 |
B=288; G=181;
B/G=1.59; E=448;
?
=0.24 |
RuB3
(P-6m2) |
C11=436; C33=713; C44=174; C12=182; C13=186 |
B=293; G=161;
B/G=1.82; E=407;
?
=0.27 |
Additionally, it can be predicted that orthogonal
RuB2 has a certain elastic anisotropy. It has also been shown in that RuB has
the largest bulk modulus, shear modulus and Young’s modulus (Table 2). The bulk
modulus of RuB is about 332Gpa, which is slightly lower than cubic boron
nitride (379Pa) [25]. Therefore, we can predict that RuB has very good volume-compression
resistance. According to Pugh model, it is reasonable to adopt B/G or Poisson’s
ratio (?) to evaluate the toughness or brittleness of a given material [26].
Usually, lower B/G and ? values mean that the material is more brittle and
harder. On the contrary, very high B/G and ? values mean that the material is
tough and soft. We can see that B/G and ? values of RuB3 are the largest among
RuBx (x=1, 2, 3). Therefore, we can confirm that RuB3 is a type of material
that has good toughness.
In this systematic study, the crystal structure,
electronic structure as well as mechanical properties of RuBx (x=1, 2, 3)
compounds have been investigated based on first-principles method. We can draw
some conclusions as follows:
·
The covalent Ru-B bond
and B-B bond become stronger with the increase of boron’s concentrations, which
can help improve the hardness of RuBx system.
·
RuB has the highest
bulk modulus, which means more prominent volume-compression resistance. RuB2
has a certain elastic anisotropy and RuB3 has the best toughness.