Effect of ternary addition on bonding properties of Rh3V

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Journal of Chemical and Pharmaceutical Research, 2015, 7(1):329-332
Research Article
ISSN : 0975-7384
Effect of ternary addition on bonding properties of Rh3V intermetallics:
A theoretical study
M. Manjula* and M. Sundareswari
Department of Physics, Sathyabama University, Tamilnadu, India
Structural, Elastic and Electronic properties of Rh3V and Rh3Vx(Ni)1-x are studied by Full Potential Linearized
Augmented Plane Wave(FP-LAPW) method. The basic physical parameter such as lattice constants, elastic
constants, bulk modulus, shear modulus, Young’s modulus and Poisson’s ratio are reported. Furthermore, the
chemical bonding properties of Rh3V and Rh3Vx(Ni)1-x discussed using Cauchy’s Pressure, Poisson’s Ratio, Pugh
Rule and charge density plot. A strong directional bonding is seen between V-Rh-V atoms in Rh3V compound
whereas no such directional bonding is seen in Rh3Vx(Ni)1-x compound.
Keywords: Ternary alloying, Intermetallics, Interatomic bonding, Electronic band structure.
Platinum metal base alloys, such as Ir and Rh- base alloys are base elements for ultra-high temperature applications
owing to their high-melting temperatures, good oxidation resistance and good high temperature strengths[1-4].
Among platinum group metals, Rh- base alloys are more promising materials for ultra-high temperature gas turbine
applications, due to its high thermal conductivity, lower thermal expansion coefficient, low density and better
oxidation resistance[5]. In addition, Rh- based alloys can be prepared with a microstructure similar to that of nickel
based alloys with enhanced ductility and workability[6], which is our reason for studying on these compounds. The
ductile/brittle nature of Rh- based intermetallic compounds with ternary addition by Rh3Tix(V, Hf, Al)1-x is
reported[7]. In this present study we have considered the more brittle material Rh3V[20] and for the first time the
bonding mechanism and elastic properties of Rh3V87.5Ni12.5 has been analyzed and computed.
In the present paper, all calculations have been carried out using Full Potential Linearized Augmented Plane Wave
(FP-LAPW) method implemented in the WIEN2K code[8]. Generalized Gradient Approximation(PBE-GGA) based
on Perdew et al [9] has been used to determine the exchange and correlation energy. The plane wave expansion is
taken as Kmax x Rmax equal to 7.0 and lmax=10.. For K-space summation the 14x14x14 for Rh3V and 10x10x10
for Rh3V87.5Ni12.5 Monkhorst and Pack grid of k-points have been used[17]. The self-consistent calculations are
carried out to an accuracy of 0.0001ev for energy and 0.001 for charge.
The optimized lattice parameters for Rh3V Rh3V87.5Ni12.5are presented in the Table1. The calculated lattice
constant for Rh3V correlate very well with the experimental value. For Rh3V, the percentage error between the
calculated and the experimental lattice constant is 0.3.
M. Manjula and M. Sundareswari
J. Chem. Pharm. Res., 2015, 7(1):329-332
The calculated values of Bulk modulus(B), Shear modulus(G), Young’s modulus (E), Cauchy pressur(C12-C44), G/B,
Poisson’s ration(ν) and Hv for Rh3V and Rh3V87.5Ni12.5 are reported in table1. From Table.1, it can be noted that for
Rh3V the computed B,G, E and C44 values are 258.646GPa, 165.719GPa, 409.664GPa and 204.005GPa
respectively, which are quantitatively higher than the Rh3V87.5Ni12.5 values viz., 252.553GPa, 145.805GPa,
366.823GPa and 168.46GPa1 respectively.
The covalent/ionic nature of the compounds could be predicted by Cauchy pressure (C12-C44), Poisson’s ratio(ν),
Young’s modulus(E) and Pugh criterion G/B. According to Pettifor[10] and Johnson[11], for metallic bonding,
Cauchy pressure(C12-C44) is positive; whereas for directional bonding the Cauchy pressure is negative. From
Table.1 one can observe that the Rh3V compound having negative Cauchy pressure(-26.363GPa) represents more
directional characteristics and Rh3V87.5Ni12.5 having positive Cauchy pressure(5.773) represents metallic nondirectional bonding. For covalent materials, the value of Poisson’s ratio is small (ν=0.1), whereas for ionic materials
the value of ν is 0.25[12,13]. In the present case, the Rh3V87.5Ni12.5 has the largest Poisson’s ratio(0.26) represents
ionic contributions to the atomic bonding are dominant and the Rh3V has the ν value (0.23) which is less than 0.25
represents covalent contribution in inter-atomic bonding are dominant.
Young’s modulus(E) is used to provide a measure of the stiffness of the solid and when the value of E is large, the
material is stiff. If the value of Young’s modulus(E) increases, the covalent nature of the material also increase[12].
From Table.1, it is observed that the value of E, for Rh3V is 409.664GPa and for Rh3V87.5Ni12.5 is 366.823GPa. Due
to the higher value of Young’s modulus, Rh3V is stiffer than Rh3V87.5Ni12.5 and having higher covalent nature.
In covalent and ionic materials, the brittle/ductile behavior are G ~ 1.1B and G ~ 0.6B respectively[12,13].
According to the Pugh criterion[14], if G/B > 0.57, the material behaves in a brittle manner and the stronger the
directional bonding character. This ratio for Rh3V is 0.64 and for Rh3V87.5Ni12.5 is 0.57. Hence Rh3V will behave as
brittle manner(covalent nature) and Rh3V87.5Ni12.5 behave as ductile manner(ionic nature).
Based on charge density plots also we can study the covalent/ionic nature of the materials. Figure 1a&1b and 2a&2b
shows that the X-CRYSDEN and charge density plot of cubic Rh3V and Rh3V87.5Ni12.5 compounds respectively.
From Fig. 1a&2a, one can observe that the charge locate between V-Rh-V atoms, suggesting strong covalent bonds
between them[15]. One can note that the absence of such charge density contours in Fig.1b&2b. Hence it can be
concluded that
Rh3V having higher covalent nature in inter-atomic bonding whereas Rh3V87.5Ni12.5 having ionic
nature in inter-atomic bonding.
Figure 3a & 3b represents DOS curves of Rh3V & Rh3V87.5Ni12.5. In fig.3a, one can notice a pseudogap in Rh3V
intermetallic compound and in fig.3b, there is no noticeable pseudogap in Rh3V87.5Ni12.5 compound. Hence, we
conclude that the presence of pseudogap in intermetallic compound Rh3V is originating from V-Rh-V bond as
shown in fig. 1a&2a[16].
FIGURE 1a. X-CRYSDEN plot of (001) plane FIGURE 1b. X-CRYSDEN plot of (001)
of cubic Rh3V compound
plane Rh3V87.5Ni12.5 compound.
M. Manjula and M. Sundareswari
J. Chem. Pharm. Res., 2015, 7(1):329-332
FIGURE 2a&2b. charge density plot of (001)plane of cubic Rh3V & Rh3V87.5Ni12.5
TABLE 1. The optimized lattice parameter, elastic constants and elastic properties of Rh3Vx(Ni)(1-x) intermetallic compounds
Lattice Constant (a.u.)
acal =7.2014
Other studya
acal =7.2432
Cauchy Pressure(C12-C44)
Bulk Modulus(B) GPa
at -0.003 GPa
Shear Modulus(G) GPa
Young’s Modulus(E) GPa
Poisson’s Ratio(ν)
a Ref.[5]
at -0.938 GPa
FIGURE 3a&3b. DOS histogram of cubic Rh3V & Rh3V87.5Ni12.5
From this study, we concluded that the covalent contribution in inter-atomic bonding are dominant in Rh3V
compound and the ionic contributions to the atomic bonding are dominant in Rh3V87.5Ni12.5 compound.
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