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.     

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.     

First-principles investigation of phase stability,elastic and thermodynamic properties in L12 Co3(Al,Mo,Nb) phase

First-principles calculations have been performed to investigate the phase stability, elastic, and thermodynamic properties of Co₃(Al,Mo,Nb) with the L1₂ structure. Calculated elastic constants show that Co₃(Al,Mo,Nb) is mechanically stable and possesses intrinsic ductility. It is found that the shear and Young's moduli of Co₃(Al,Mo,Nb) are smaller than those of Co₃(Al,W). Calculated density of states indicate the existence of covalent-like bonding in Co₃(Al,Mo,Nb). Temperature-dependent thermodynamic properties of Co₃(Al,Mo,Nb) can be described satisfactorily using the Debye-Grüneisen approach, including entropy, enthalpy, heat capacity and linear thermal expansion coefficient, showing their significant temperature dependences. Furthermore the obtained data can be employed in the modeling of thermodynamic and mechanical properties of Co-based alloys to enable the design of high temperature alloys.     

Structural,elastic, electronic,and thermodynamic properties of intermetallic Zr2Cu: A first-principles study

Three competing structures (C11_b, C16 and E9₃) of intermetallic Zr₂Cu have been systematically investigated by first-principles calculations and quasi-harmonic Debye model. Both the calculated equation of states (EOS) and pressure–enthalpy results indicate a structural phase transition from C11_b to C16 phase at around 11–14 GPa. The calculated equilibrium crystal parameters and elastic constants are in consistence with available experimental or theoretical data. All three phases are mechanically stable according to the elastic stability criteria, and ductile according to Pugh's ratio, while the ambient-stable C11_b phase shows a higher elastic anisotropy. Furthermore, differences in the nature of bonding between three competing structures are uncovered by electron density topological analysis. C11_b Zr₂Cu possesses an intriguing pseudo BaFe₂As₂-type structure with the charge density maxima at Zr tetrahedral interstices serving as Fe-position pseudoatoms; C16 Zr₂Cu contains Zr-pair configurations bonded through bifurcated Zr–Zr bonding paths; while the E9₃ phase has only conventional straight bonding. Additionally, through quasi-harmonic Debye model, the pressure and temperature dependences of the bulk modulus, specific heat, Debye temperature, Grüneisen parameter and thermal expansion coefficient for three phases are obtained and discussed.     

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.     

First-principles study of the elastic and thermodynamic properties of HfB2 with AlB2 structure under high pressure

Elastic and thermodynamic properties of HfB₂ with AlB₂ structure under pressure are investigated by means of density functional theory method. The results at zero pressure are in good agreement with available theoretical and experimental values. The pressure dependence of elastic constants, bulk modulus and elastic anisotropy of HfB₂ has been investigated. Through quasi-harmonic Debye model, the variations of the Debye temperature, heat capacity and thermal expansion with pressure and temperature are successfully obtained and discussed.     

The first-principles calculations for the elastic properties of Zr2Al under compression

The first-principles calculations were applied to investigate the structural, elastic constants of Zr₂Al alloy with increasing pressure. These properties are based on the plane wave pseudopotential density functional theory (DFT) method within the generalized gradient approximation (GGA) for exchange and correlation. The result of the heat of formation of Zr₂Al crystal investigated is in excellent consistent with results from other study. The anisotropy, the shear modulus, and Young's modulus for the ideal polycrystalline Zr₂Al are also studied. It is found that (higher) pressure can significantly improve the ductility of Zr₂Al. Moreover, the elastic constants of Zr₂Al increase monotonically and the anisotropies decrease with the increasing pressure. Finally, it is observed that Zr d electrons are mainly contributed to the density of states at the Fermi level.     

Density functional study of the mechanical and phonon properties of Al12X (X = Mo,Tc, Ru,W, Re,and Os) compounds

By means of first principles calculations, we have studied the structural, elastic, and phonon properties of the Al₁₂X (X = Mo, Tc, Ru, W, Re, and Os) compounds in cubic structure. The elastic constants of these compounds are calculated, then bulk modulus, shear modulus, Young's modulus, Possion's ratio, Debye temperature, hardness, and anisotropy value of polycrystalline aggregates are derived and relevant mechanical properties are compared with the available theoretical ones. Furthermore, the phonon dispersion curves, mode Grüneisen parameters, and thermo-dynamical properties such as free energy, entropy and heat capacity are computed and the obtained results are discussed in detail.     

First-principle calculations of structural,elastic and thermodynamic properties of Fe–B compounds

The structural, elastic and thermodynamic properties of FeB, Fe₂B, orthorhombic and tetrahedral Fe₃B, FeB₂ and FeB₄ iron borides are investigated by first-principle calculations. The elastic constants and polycrystalline elastic moduli of Fe–B compounds are usually large especially for FeB₂ and FeB₄, whose maximum elastic constant exceeds 700 GPa. All of the six compounds are mechanically stable. The Vickers hardness of FeB₂ is estimated to be 31.4 GPa. Fe₂B and FeB₂ are almost isotropic, while the other four compounds have certain degree of anisotropy. Thermodynamic properties of Fe–B compounds can be accurately predicted through quasi-harmonic approximation by taking the vibrational and electronic contributions into account. Orthorhombic Fe₃B is more stable than tetrahedral one and the phase transition pressure is estimated to be 8.3 GPa.     

Elasticity and thermodynamic properties of α-Ta4AlC3 under pressure

First-principles calculations of the crystal structure and the elastic properties of α-Ta₄AlC₃ have been carried out with the plane-wave pseudopotential density functional theory method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The pressure dependence of the elastic constants c_ij, the aggregate elastic moduli (B, G, E), the Poisson's ratio, and the elastic anisotropy has been investigated. Using the quasi-harmonic Debye model considering the phonon effects, the temperature and pressure dependencies of isothermal bulk modulus, and the thermal expansions, and Grüneisen parameters, as well as Debye temperatures are investigated systematically in the ranges of 0–60 GPa and 0–1500 K as well as compared to available data.     

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.     

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.     

Comparison of mechanical properties of Ni3Al thin films in disordered FCC and ordered L12 phases

We report the results of several experiments isolating the effect of long-range order on mechanical properties of intermetallic compounds. Kinetically disordered FCC Ni₃Al (Ni 76%) thin films were produced by rapid solidification following pulsed laser melting. For comparison, compositionally and microstructurally identical films with ordered L1₂ structure were produced by subsequent annealing at 550°C for 2 h. These FCC and L1₂ Ni₃Al thin films were tested by nanoindentation for hardness and Young's modulus, and the critical strain to fracture was measured by straining the substrate under four-point bending. Ni₃Al thin films in the disordered phase were found to have nearly twice the critical strain to fracture, more than three times the fracture toughness, and about 20% lower hardness than in the ordered counterpart. Blunter crack tips and crack bridging observed in the disordered phase also illustrate increased ductility. The increased plasticity of Ni₃Al due to chemical disorder is manifested both within the grains and at the grain boundaries. Young's moduli of the ordered and disordered materials were found to be indistinguishable.     

Theoretical prediction of temperature dependent shear modulus of bulk metallic glasses

A model of temperature dependent shear modulus and Young's modulus in bulk metallic glasses is established. The inherent relationship between the glass transition temperatures, the Debye temperature and shear modulus of bulk metallic glasses is revealed. The temperature dependent shear modulus can be predicted by our model without any fitting parameter. The model is presented based on a critical energy density criterion for plastic yielding which is derived from fundamental thermodynamics. This critical energy density consists of two parts: the heat added to the system and the input of mechanical energy, which are not completely equivalent. The agreement between theoretical results and experimental results is striking. And it is found that the temperature dependent Young's modulus could also be predicted pretty well by our model.     

高压高温下Re 2 N的弹性和热力学性能

采用基于密度泛函理论的第一性原理计算方法,系统研究高压高温下Re2N的晶体参数、力学性能和热力学性能。结果表明：在高压下Re2N具有明显的弹性各向异性,与弹性常数C12、C13、C44相比,C11和C33的变化随着压力的变化非常明显。此外,首次计算Re2N的体弹模量B、弹性模量E和剪切模量G沿不同晶轴的分布。弹性模量在一些主要晶轴方向上的大小分布趋势如下：[0001][1211][1010][1011]EEEE〉〉〉。计算结果还表明：在（0001）晶面,Re2N的抗剪切能力是最低的,从而极大地减小对大剪切变形的阻力。基于准简谐德拜模型,在0~50GPa压力和0~1600K温度下得到德拜温度、格林艾森参数、热传导以及热扩散系数的变化行为。     

First-principles investigation of electronic,mechanical and thermodynamic properties of L12 ordered Co3(M,W) (M = Al,Ge, Ga) phases

Studies were carried out on the equilibrium structural, temperature-dependent mechanical and thermodynamic properties of the Co₃(M, W) (M = Al, Ge, Ga) phases in terms of first-principles calculations. The results of the ground-state elastic constants revealed that Co₃(M, W) phases are mechanically stable and possess intrinsic ductility. It was found that the elastic heat-resistant properties of Co₃(Ge, W) phase are inferior to those of Co₃(Al, W) and Co₃(Ga, W). Analyzing the charge density difference provides the explanation that the sharp decrease in mechanical properties is mainly due to the weakening of Co–Ge bonding at elevated temperatures for Co₃(Ge, W). The elastic anisotropy as a function of temperature is discussed using a universal index. It is observed that Co₃(M, W) phases show a high degree of elastic anisotropy. The degree of elastic anisotropy could be significantly decreased by an increase in temperature for Co₃(M, W). The lattice vibration is treated with the quasiharmonic phonon approach, considering both the vibrational and thermal electronic contributions. The thermodynamic properties as a function of temperature are computed without any adjustable parameters, including heat capacity, entropy, enthalpy and thermal expansion coefficient.     

Structural,half-metallic and elastic properties of the half-Heusler compounds NiMnM (M = Sb,As and Si) and IrMnAs from first-principles calculations

The structural, half-metallic and elastic properties of the half-Heusler compounds NiMnM (M = Sb, As and Si) and IrMnAs were investigated using first-principles calculations within the generalized gradient approximation (GGA) based on density function theory (DFT). The most stable lattice configurations about site occupancy are (Ni)_4a(Mn)_4c(Sb)_4d, (Ni)_4a(Mn)_4c(As)_4d, (Ni)_4a(Mn)_4c(Si)_4d and (Ir)_4a(Mn)_4c(As)_4d, respectively, and the exchange of elements in Wyckoff position 4c and 4d results in an identical (symmetry-related) phase. The half-Heusler compounds show half-metallic ferromagnetism with a half-metallic gap of 0.168 eV, 0.298 eV, 0.302 eV and 0.109 eV, respectively, and the total magnetic moments (M_tot) are 4.00 μ_B, 4.00 μ_B, 3.00 μ_B and 3.00 μ_B per formula unit, respectively, which agree well with the Slater–Pauling rule based on the relationship of valence electrons. The compound (Ir)_4a(Mn)_4c(As)_4d with half-metallic ferromagnetic character was reported for the first time. The individual elastic constants, shear modulus, Young's moduli, ratio B/G and Poisson's ratio were also calculated. The compounds are ductile based on the ratio B/G. The Debye temperatures derived from the average sound velocity (ν_m) are 327 K, 332 K, 434 K and 255 K, respectively. The predicted Debye temperature for NiMnSb agrees well with the available experimental value, and the Debye temperatures for the rest three compounds were reported for the first time.     

Effect of compositional modification on Young's modulus of Ti2AlNb-based alloy

The Young's moduli of three Ti₂AlNb-based alloys were investigated. When they were heat treated to have a B2 single-phase structure, their Young's moduli were identical. In an O+B2 structure, the Young's modulus of O phase changed with alloy, and showed a correlation with the lattice parameter rate a/b.     

Formation of AB2-intermetallics by diffusion in the Au–Sb–Bi system

Binary diffusion couples, in which one single-phased product layer is growing between pure elements, were employed to study the diffusion properties of Au₂Bi- and AuSb₂-intermetallics at 230 and 330 °C. The position of the Kirkendall-marker plane inside the reaction zones revealed that in this temperature range the minority element is the faster diffuser in the Laves-phase Au₂Bi as well as in AuSb₂. The concept of integrated diffusion coefficient is used to describe the growth kinetics of the intermetallic compounds. The integrated diffusion coefficient in an intermetallic is related to the tracer diffusivities of the components and the thermodynamic stability of the phases involved in the interaction. The tracer diffusion coefficients were deduced from the interdiffusion experiments. The isothermal cross-section through the ternary phase diagram Au–Sb–Bi at 230 °C was constructed by means of the diffusion couple technique. No ternary phases are found in this system. Both intermetallic compounds Au₂Bi and AuSb₂ are in equilibrium with the (Sb,Bi)-solid solution. The solubility of Sb in the Laves-phase Au₂Bi was found to be negligible. Up to about 10.5 at.% of Bi can be dissolved in the AuSb₂-phase, the Bi-atoms substituting Sb in the cubic lattice of AuSb₂.     

A new semiconductor Al2Fe3Si3 with complex crystal structure

Al₂Fe₃Si₃, a new semiconductor with complex triclinic structure was synthesized by arc melting and spark plasma sintering, followed by heat treatment. The nominal compositions of samples have been changed to compensate Al evaporation during synthesis process, and single Al₂Fe₃Si₃ phase has been obtained with the nominal composition of Al: Fe: Si = 26: 37: 37 (6 at.% Al excess against stoichiometry). In this study, we measured the sound velocity, thermal expansion coefficient, Vickers hardness, fracture toughness, electrical conductivity, Seebeck coefficient, and thermal conductivity of the new semiconductor Al₂Fe₃Si₃. The Al₂Fe₃Si₃ sample displayed positive Seebeck coefficient from 300 to 850 K, with a maximum Seebeck coefficient of 110 μV/K at 430 K. The Debye temperature of Al₂Fe₃Si₃ was 640 K, which was similar to or higher than those of other Al, Fe, Si based thermoelectric materials, but the lattice thermal conductivity was lower, 4–5 W/mK, due to the complex crystal structure of Al₂Fe₃Si₃. The maximum ZT value was 0.06 at 580 K.