Electronic structure,phase stability and elastic properties of ruthenium based four intermetallic compounds: Ab-initio study

The structural, electronic and elastic properties of four RuX (X = Sc, Ti, V and Zr) intermetallic compounds have been investigated by using density functional theory within full potential linearized augmented plane wave method and using generalized gradient approximations in the scheme of Perdew, Burke and Ernzrhof (PBE), Wu and Cohen (WC) and Perdew et al. (PBEsol) for the exchange correlation potential. The relative phase stability in terms of volume-energy and enthalpy-pressure for these compounds is presented for the first time in three different (B₁, B₂ and B₃) structures. The total energy is computed as a function of volume and fitted to Birch equation of states to find the ground state properties such as lattice constant (a₀), bulk modulus (B) and its pressure derivative (B′). It is found that the lattice parameters in B₂-phase agree well with the existing experimental and previous theoretical results. The second order elastic constants (SOECs) are also predicted for the above compounds. All the four compounds show ductile behavior. The ductility of these compounds has been analyzed using Pugh's rule. From the plots of electronic density of states (DOS), it can be concluded that these intermetallic compounds are metallic in nature.     

Theoretical prediction of the electronic structure,bonding behavior and elastic moduli of scandium intermetallics

We report the structural, electronic, bonding, elastic and mechanical properties of nine scandium intermetallic compounds, ScTM (TM = Co, Rh, Ir, Ni, Pd, Pt, Zn, Cd and Hg), using ab initio density functional theory with the generalized gradient approximation for exchange and correlation potentials. The calculated structural parameters, such as the lattice constant (a₀), bulk modulus (B) and its pressure derivative (B₀) and elastic constants, are calculated using the CsCl-(B₂ phase) structure. The electronic and bonding properties of the ScX compounds are quantitatively analyzed using band structures, DOS, Fermi surfaces and contour plots. The mechanical properties and ductile behaviors of these compounds are also predicted based on the calculated elastic constants.     

A first principles study of structural and mechanical properties of Ti2AlZr intermetallic

The present work describes the structural and mechanical behaviour of three phases namely B2, D0₁₉ and O phases of Ti₂AlZr intermetallic using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The equilibrium lattice constant values of B2, D0₁₉ and O phases are in good agreement with the experimental and theoretical data, respectively. Formation energy of O phase is minimum followed by D0₁₉ and B2. Bonding characteristics of these phases have been explained based on electronic density of states and charge density. All the three phases satisfy the Born stability criteria in terms of elastic constants and are associated with ductile behaviour based on G/B ratios. The B2 phase exhibits very high anisotropy in comparison to those of the D0₁₉ and O.     

Stability,elastic and electronic properties of the Rh–Zr compounds from first-principles calculations

A systematic investigation on structural, elastic and electronic properties of Rh–Zr intermetallic compounds is conducted using first-principles electronic structure total energy calculations. The equilibrium lattice parameters, enthalpies of formation (E_for), cohesive energies (E_coh) and elastic constants are presented. Of the eleven considered candidate structures, Rh₄Zr₃ is most stable with the lowest E_for. The two orthogonal-type, relative to the CsCl-type, are the competing ground-state structures of RhZr. The result is in agreement with the experimental reports in the literature. The analysis of E_for and mechanical stability excludes the presence of Rh₂Zr and RhZr₄ at low temperature mentioned by .Curtarolo et al. [Calphad 29, 163 (2005)]. It is found that the bulk modulus B increases monotonously with Rh concentration, whereas all other quantities (shear modulus G, Young's modulus E, Poisson's ratio σ and ductility measured by B/G) show nonmonotonic variation. RhZr₂ exhibits the smallest shear/Young's modulus, the largest Poisson's ratio and ductility. Our results also indicate that all the Rh–Zr compounds considered are ductile. Furthermore, the detailed electronic structure analysis is implemented to understand the essence of stability.     

Structural stability of Fe-based topologically close-packed phases

Precipitates of topologically close-packed (TCP) phases play an important role in hardening mechanisms of high-performance steels. We analyze the influence of atomic size, electron count, magnetism and external stress on TCP phase stability in Fe-based binary transition metal alloys. Our density-functional theory calculations of structural stability are complemented by an analysis with an empirical structure map for TCP phases. The structural stability and lattice parameters of the Fe–Nb/Mo/V compounds are in good agreement with experiment. The average magnetic moments follow the Slater-Pauling relation to the average number of valence-electrons and can be rationalized in terms of the electronic density of states. The stabilizing effect of the magnetic energy, estimated by additional non-magnetic calculations, increases as the magnetic moment increases with band filling for the binary systems of Fe and early transition metals. For the case of Fe₂Nb, we demonstrate that the influence of magnetism and external stress is sufficiently large to alter the energetic ordering of the closely competing Laves phases C14, C15 and C36. We find that the A15 phase is not stabilized by atomic-size differences, while the stability of C14 is increasing with increasing difference in atomic size.     

Intrinsic brittleness of Mo5SiB2 and alloying effect on ductility studied by first-principles calculations

The ordered intermetallic Mo₅SiB₂ displays a ceramic-like brittleness at the ambient temperature. The state density, charge distribution and elastic parameters were calculated by first-principles, based on the density functional method. The results indicated that the two different kinds of covalent bonds were intricately woven into the refractory phase. The improved Peierls–Nabarro stress which is caused by this kind of distribution mode makes dislocations move difficultly, resulting in intrinsic brittleness. The effects of substitutional alloying on the ductility of Mo₅SiB₂ were also assessed by the calculations on the elastic properties and dislocation line energy. It was shown that the metal (Nb, Tc) alloying was not to enhance effectively its toughness, but to improve the brittle-to-ductile transition temperature.     

First-principle calculations of the electronic,elastic and thermoelectric properties of Ag doped CuGaTe2

To improve the performance of a thermoelectric material CuGaTe₂, element Ag is doped to replace element Ga and we investigate the electronic structure, phase stability, elastic and thermoelectric properties of CuGa_1−xAg_xTe₂ (x = 0, 0.25 and 0.5) via first-principles method. The phase stability of CuGa_1−xAg_xTe₂ is discussed by analyzing the formation energy, cohesive energy and elastic constants. The calculated sound velocities decrease with the increase of Ag content, which is favorable for reducing the lattice thermal conductivity. The analysis of band structures shows that the replacement of Ga by Ag makes CuGaTe₂ undergo a direct-indirect semiconductor transition. The Ag doping induces steep density of states in valence band edge, which is beneficial for increasing the carrier concentration and improving thermoelectric performance of CuGaTe₂.     

Structural and magnetic properties of Ni2CoSi: First-principles calculation and experimental realization

BCC Heusler phase Ni₂CoSi has been predicted to be a promising candidate to realize magnetic field induced martensitic transformation. We tried to prepare Ni₂CoSi single phase using different methods. Single phase Ni₂CoSi cannot be synthesized by arc-melting and annealing. Then we used mechanical alloying method to synthesize Ni₂CoSi. But a FCC phase rather than BCC was obtained after ball-milling. The lattice constant of FCC Ni₂CoSi is 3.52 Å and the Curie temperature is around 900 K. The saturation magnetization at 5 K is 2.44μ_B/f.u. This FCC phase is stable and no transition is observed when heating to 1173 K. The electronic structure and phase stability of the FCC and BCC Heusler phase have been investigated by first-principles calculations. The FCC Ni₂CoSi has lower total energy compared with BCC, agreeing with the experimental observation. But the calculated total moment is much smaller than the M_s at 5 K. This difference is related to the atomic disorder and was discussed by KKR-CPA calculation.     

Electronic and transport properties of Mg2Si under isotropic strains

Density functional theory and Boltzmann theory calculations of the electronic and thermoelectric properties of Mg₂Si subjected to isotropic strains have been performed. The electrical conductivity, the Seebeck coefficient and the power factor have been evaluated at two temperatures (300 K and 900 K) and two charge carrier concentrations (10¹⁸ cm⁻³ and 1.2 × 10²⁰ cm⁻³ electrons and holes). Up to 3% of both compressive and tensile strains have been applied to the material. From our results, we can highlight that a significant improvement of both the Seebeck coefficient (S) and the power factor (PF) is obtained at low temperature and moderate n-doping. The increase in S and PF amounts to 40% and 100%, respectively, compared to the unstrained Mg₂Si.     

Effects of Ni vacancy,Ni antisite,Cr and Pt on the third-order elastic constants and mechanical properties of NiAl

Effects of Ni vacancy, Ni antisite in Al sublattice, Cr in Al sublattice, Pt in Ni sublattice on the second-order elastic constants (SOECs) and third-order elastic constants (TOECs) of the B2 NiAl have been investigated using the first-principles methods. Lattice constant and the SOECs of NiAl are in good agreement with the previous results. The brittle/ductile transition map based on Pugh ratio G/B and Cauchy pressure P_c shows that Ni antisite, Cr, Pt and pressure can improve the ductility of NiAl, respectively. Ni vacancy and lower pressure can enhance the Vickers hardness H_v of NiAl. The density of states (DOS) and the charge density difference are also used to analysis the effects of vacancy, Ni antisite, Cr and Pt on the mechanical properties of NiAl, and the results are in consistent with the transition map.     

First-principles study of mechanical and electronic properties of TiB compound under pressure

The effects of applied pressures on the structural, mechanical and electronic properties of TiB compound were studied using the first-principles method based on the density functional theory. The results showed the pressures have the significant effects on the mechanical properties and electronic properties of TiB phase. The calculated structural and mechanical parameters (i.e., bulk modulus, shear modulus, Young's modulus, Poisson's ratio and Debye temperature) were in good agreement both with the previously reported experimental and theoretical results at zero pressure. Additionally, all these parameters presented the linearly increasing dependences on the external pressure. The B/G ratios signified the TiB crystals should exhibit the brittle deformation behavior at 0–100 GPa. The universal anisotropic index indicated the TiB compound was elastically isotropic under zero pressure, and may become anisotropic at higher pressures. Further, the density of states and Mulliken charge of TiB were discussed. The bonding nature in TiB was a combination of metallic, ionic and covalent at zero pressure. The metallic component was derived from free-electron transfer from the Ti4s to Ti3d and Ti3p states. The ionic component was originated from the charge transfer from Ti to B atoms. The covalent component had two sources. One was from the B2s–B2p hybridization in the B atomic chains. The other one was from B2p–Ti3d bonding hybridization. Under higher pressures, the ionic and covalent bonds were both improved with the rising of pressures. This should be the fundamental reason for the enhanced mechanical properties in the TiB compound. At the same time, the metallic bond kept leveled to ensure the electric conductivity.     

Mechanical properties and bonding feature of the YAg,CeAg, HoCu,LaAg, LaZn,and LaMg rare-earth intermetallic compounds: An ab initio study

Full-potential linearized augmented plane wave (FLAPW) method has been employed within the generalized gradient approximation (GGA) to investigate structural and elastic properties of YAg, CeAg, HoCu, LaAg, LaZn, LaMg compounds. The calculated ground state properties such as lattice constants, bulk Modulus and elastic constants agree well with the experiment. The ductility or brittleness of these intermetallic compounds is predicted. The calculated results indicate that LaAg is the most ductile amongst the present compounds. For HoCu and LaZn compounds, the mechanical properties and Debye temperature are predicted from calculated elastic constants. In addition, chemical bonding of these compounds has been investigated in the light of topological analysis approach based on the theory of atoms in molecules.     

Structural stability of some CsCl structure HfTM (TM = Co, Rh, Ru, Fe) compounds

In order to investigate Hf-TM (TM = Fe, Co, Rh, Ru) phase diagrams in the region of 50:50% atomic ratio, we performed ab initio Full-Potential Linearized Augmented Plane Waves calculations of the most stable Hf and TM elemental phases and HfTM compounds of the CsCl and CuAu structure types. The obtained electronic structures, cohesive energies and enthalpies of formation are discussed and compared to some of the existing models and available experimental data. The non-existing compound HfFe is found to be at least metastable, and the reason for its absence from the phase diagram is discussed.     

First-principles study of electronic structure and magnetic properties of orthorhombic CrGa2Sb2 and MnGa2Sb2

By the first-principles calculations, we present the results of electronic structure and magnetic properties on bulk CrGa₂Sb₂ and MnGa₂Sb₂ in an orthorhombic structure with the linear chains of transition-metal Cr and Mn atoms, using four different exchange correlation potentials: the local density approximation (LDA), the generalized gradient approximation (GGA), GGA + U, and the Tran-Blaha modified Becke-Johnson functional (mBJ). The electronic structure calculations from four exchange correlation potentials show that CrGa₂Sb₂ is a pseudogap (negative gap) material with very small density of states (DOS) at the Fermi level, while MnGa₂Sb₂ has notably higher DOS at the Fermi level compared to CrGa₂Sb₂, exhibiting stronger metallic conductivity, although the mBJ potential obtains lower DOS at the Fermi level than LDA and GGA for both CrGa₂Sb₂ and MnGa₂Sb₂. The GGA + U method with a small value (1 eV) of the on-site Coulomb interaction parameter U obtains lower DOS at the Fermi level compared to the large value of U. In agreement with the measurement data, the total energy calculations reveal that both CrGa₂Sb₂ and MnGa₂Sb₂ have a stable ferromagnetic ground state with lower energies relative to antiferromagnetic state. Based on the Heisenberg model, the magnetic exchange constants between the nearest-neighbor Cr–Cr and Mn–Mn along transition-metal linear chains are calculated to be 48.6 meV and 27.5 meV for CrGa₂Sb₂ and MnGa₂Sb₂, respectively. By the mean-field approximation method, we calculated the Curie temperature of two compounds to be above room-temperature.     

Ab initio based study of finite-temperature structural,elastic and thermodynamic properties of FeTi

We employ density functional theory (DFT) to calculate pressure dependences of selected thermodynamic, structural and elastic properties as well as electronic structure characteristics of equiatomic B2 FeTi. We predict ground-state single-crystalline Young's modulus and its two-dimensional counterpart, the area modulus, together with homogenized polycrystalline elastic parameters. Regarding the electronic structure of FeTi, we analyze the band structure and electronic density of states. Employing (i) an analytical dynamical matrix parametrized in terms of elastic constants and lattice parameters in combination with (ii) the quasiharmonic approximation we then obtained free energies, the thermal expansion coefficient, heat capacities at constant pressure and volume, as well as isothermal bulk moduli at finite temperatures. Experimental measurements of thermal expansion coefficient complement our theoretical investigation and confirm our theoretical predictions. It is worth mentioning that, as often detected in other intermetallics, some materials properties of FeTi strongly differ from the average of the corresponding values found in elemental Fe and Ti. These findings can have important implications for future materials design of new intermetallic materials.     

Temperature-dependent mechanical properties of alpha-/beta-Nb5Si3 phases from first-principles calculations

The temperature-dependent structural properties and anisotropic thermal expansion coefficients of α-/β-Nb₅Si₃ phases have been determined by minimizing the non-equilibrium Gibbs free energy as functions of crystallographic deformations. The results indicate that the crystal anisotropy of α-Nb₅Si₃ phase is much more temperature dependence than that of β-Nb₅Si₃ phase. The total/partial density of states of α-/β-Nb₅Si₃ phases are discussed in detail to analyze their electronic hybridizations. It is demonstrated that the bonding of the two phases is mainly contributed from the hybridization between Nb-4d and Si-3p electronic states. The temperature-dependent mechanical properties of α-/β-Nb₅Si₃ phases are further investigated via the quasi-harmonic approximation method in coupling with continuum elasticity theory. The calculated single-crystalline and polycrystalline elasticity shows that both phases are mechanically stable and exhibit the intrinsic brittleness. The results also suggest that α-Nb₅Si₃ phase possesses a superior ability of compression resistance but an inferior ability of high-temperature resistance of mechanical properties than those of β-Nb₅Si₃ phase. The bonding features of α-/β-Nb₅Si₃ phases are discussed by means of charge density difference analysis in order to explain the difference of the temperature-dependent mechanical properties between the two phases.     

First-principles investigations on structural,elastic, thermodynamic and electronic properties of Ni3X (X = Al,Ga and Ge) under pressure

The structural, elastic, thermodynamic and electronic properties of L1₂-ordered intermetallic compounds Ni₃X (X = Al, Ga and Ge) under pressure range from 0 to 50 GPa with a step of 10 GPa have been investigated using first-principles method based on density functional theory (DFT). The calculated structural parameters of Ni₃X at zero pressure and zero temperature are consistent with the experimental data. The results of bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio v, anisotropy index A^U and Debye temperature Θ_D increase with the increase of external pressure. In addition, the Debye temperature of these compounds gradually reduce as the order of Ni₃Al > Ni₃Ga > Ni₃Ge. The ratio of shear modulus to bulk modulus G/B shows that the three binary compounds are ductile materials, and the ductility of Ni₃Al and Ni₃Ga can be improved with pressure going up, while Ni₃Ge is opposite. Finally, the pressure-dependent behavior of density of states, Mulliken charge and bond length are analyzed to explore the physical origin of the pressure effect on the structural, elastic and thermodynamic properties of Ni₃X.     

Competition of XA and L21B ordering in Heusler alloys Mn2CoZ (Z = Al,Ga, Si,Ge and Sb) and its influence on electronic structure

Competition between the highly-ordered XA structure and disordered L2₁B structure in Heusler alloys Mn₂CoZ (Z = Al, Ga, Si, Ge, Sb) has been investigated. The relative stability of the two structures strongly depends on the main group element Z. When Z belongs to Al or Ga, the XA structure is stabler, but when Z belongs to Si, Ge or Sb, the L2₁B structure gains stability and is lower in energy. This is related to the different number of valence electrons in main group element Z, which influences the DOS structure near the Fermi level and changes N(E_F). The energy difference ΔE between the XA and L2₁B structures may be used to estimate the tendency to form L2₁B structure in different Heusler alloys qualitatively. A large negative ΔE is preferable to retard the A-C site disorder and retain the highly-ordered XA structure. That is just the case in Mn₂CoAl. A robust half-metallicity is observed in Mn₂CoSi, Mn₂CoGe and Mn₂CoSb, they are always half-metallic under either XA or L2₁B structure. But in Mn₂CoAl and Mn₂CoGa, their spin gapless semiconducting character will be destroyed and replaced by a half-metallic state if L2₁B disorder occurs. Finally, these results suggest that the L2₁B structure should be considered together with XA structure when discussing the electronic structure of “inverse” Heusler alloys.     

Structural,electronic, elastic,mechanical and thermal behavior of RESn3(RE = Y,La and Ce) compounds: A first principles study

The structural, electronic, elastic, mechanical and thermal properties of the isostructural and isoelectronic nonmagnetic RESn₃ (RE = Y, La and Ce) compounds, which crystallize in AuCu₃-type structure, are studied using first principles density functional theory based on full potential linearized augmented plane wave (FP-LAPW) method. The calculations are carried out within PBE-GGA, WC-GGA and PBE-sol GGA for the exchange correlation potential. Our calculated ground state properties such as lattice constant (a₀), bulk modulus (B) and its pressure derivative (B′) are in good agreement with the experimental and other available theoretical results. We first time predict the elastic constants for these compounds using different approximations of GGA. All these RESn₃ compounds are found to be ductile in nature in accordance with Pugh's criteria. The computed electronic band structures and density of states show metallic character of these compounds. The elastic properties including Poisson's ratio (σ), Young's modulus (E), shear modulus (G_H) and anisotropy factor (A) are also determined using the Voigt–Reuss–Hill (VRH) averaging scheme. The average sound velocities (v_m), density (ρ) and Debye temperature (θ_D) of these RESn₃ compounds are also estimated from the elastic constants. We first time report the variation of elastic constants, elastic moduli, Cauchy's pressure, sound velocities and Debye temperatures of these compounds as a function of pressure.     

Synergistic effect of co-alloying elements on site preferences and elastic properties of Ni3Al: A first-principles study

The site preferences of co-alloying elements (Mo–Ta, Mo–Re, Mo–Cr) in Ni₃Al are studied using first-principles calculations, and the effects of these alloying elements on the elastic properties of Ni₃Al are evaluated by elastic property calculations. The results show that the Mo–Ta, Mo–Re and Mo–Cr atom pairs all prefer Al–Al sites and the spatial neighbor relation of substitution sites almost has no influence on the site preference results. Furthermore, the Young's modulus of Ni₃Al increases much higher by substituting Al–Al sites with co-alloying atoms, among which Mo–Re has the best strengthening effect. The enhanced chemical bondings between alloying atoms and their neighbor host atoms are considered to be the main strengthening mechanism of the alloying elements in Ni₃Al.