Evaluation of elastic/mechanical properties of some glasses and nanocrystallized glass by cube resonance and nanoindentation methods

Elastic and mechanical properties of 10La₂O₃·30Bi₂O₃·60B₂O₃ (LaBiB) glass, 15K₂O·15Nb₂O₅·68TeO₂·2MoO₃ (KNbTeMo) glass and a transparent KNbTeMo nanocrystallized (particle size: ∼40 nm) glass were examined using cube resonance and nanoindentation methods. The values of Poisson’s ratio, Young’s modulus (E), Debye temperature (θ_D), fractal bond connectivity, Martens hardness, indentation hardness, indentation Young’s modulus, elastic recovery, Vickers hardness, fracture toughness (K_c) and brittleness for the samples were evaluated, and the relation with the structure and nanocrystallization were clarified. LaBiB glass containing high oxygen-coordinated La³⁺ ions and two-dimensional BO₃ structural units shows excellent properties of E=90.6 GPa, θ_D=404 K and K_c=0.72 MPa m^1/2 and a high resistance against deformation during Vickers indentation. KNbTeMo glass with the three-dimensional network structure and consisting of weak Te-O bonds has small values of E=51.4 GPa and K_c=0.29 MPa m^1/2. It was demonstrated that the elastic and mechanical properties of KNbTeMo precursor glass are largely improved by nanocrystallization, e.g., E=69.7 GPa and K_c=0.32 MPa m^1/2. The nanocrystallization also induces a high resistance against deformation during Vickers indentation.     

First-principles calculations of structural, electronic, and elastic properties of MgZrSi2O7

For the first time, the recently synthesized pyrochlore MgZrSi₂O₇ [J. Xu et al., Mater. Chem. Phys. 128 (2011) 410] has been analyzed using the first principles calculations. The electronic and elastic properties were predicted; in particular, the band gap is indirect and has the value of 6.75 eV. The bulk modulus equals to 186.51 ± 1.95 GPa. Anisotropy of elastic properties was analyzed by comparing the upper and lower estimates of the shear moduli. In addition, directional dependence of the Young's modulus was calculated and visualized; its value varies in the range from 249.7 GPa (along the a, b, c crystallographic axes) to 136.84 GPa (along the bisector direction in any of the ab, bc, ac planes).     

Specific heat, electrical resistivity and thermoelectric power of YbNi4Si

The studies of the specific heat, electrical resistivity and thermoelectric power of YbNi₄Si are reported. These studies are supported by magnetic susceptibility and X-ray photoemission spectroscopy (XPS) measurements. YbNi₄Si does not order magnetically down to 4 K. Nearly in the whole temperature range studied the magnetic susceptibility follows a Curie law with μ_eff = 4.15 μ_B/f.u. This effective magnetic moment is close to the value expected for the 4f¹³ configuration (4.54 μ_B). The Yb²⁺ and Yb³⁺ peaks observed by XPS in the valence band region confirm the domination of the Yb³⁺ valence state. Based on the specific heat measurements, the electronic specific heat coefficient γ = 25 mJ/mol/K² and the Debye temperature θ_D = 320 K were derived. A quadratic dependence of electrical resistivity at low temperatures has been observed. The Kadowaki-Woods ratio has been discussed. The thermoelectric power has been analyzed in the framework of the two band model.     

Optical properties of Cu(In,Ga)Se2 and Cu2ZnSn(S,Se)4

The optical properties of CuInSe₂, CuGaSe₂, Cu₂ZnSnS₄, and Cu₂ZnSnSe₄ are investigated using three different first-principles methods, namely the generalized gradient approximation by Perdew, Burke, and Ernzerhof (PBE), the hybrid Hartree-Fock-like functional by Heyd, Scuseria, and Ernzerhof (HSE), and a Green's function approach (GW). The density-of-states, the complex dielectric function ε(ω) = ε₁(ω) + iε₂(ω), and the optical absorption coefficient α(ω) are determined, providing fundamental understanding of these materials. We find that even though the PBE method generates fairly accurate effective crystal potentials, the HSE and GW methods improve considerably the band-gap energies E_g and also the localization of the semicore states, thereby describing the optical properties much better. Furthermore, we also present optimized convergence parameters for the self-consistent HSE calculation in order to reduce the computational time of this orbital-dependent method.     

FP-LAPW study of the fundamental properties of the cubic spinel CdAl2O4

We have investigated the structural, elastic, electronic, optical and thermodynamic properties of the cubic spinel CdAl₂O₄ using accurate ab initio calculations. Computed equilibrium structural parameters are in good agreement with the available experimental data. Single-crystals elastic parameters are calculated for pressure up to 30 GPa using a conserving-volume total energy-strain method. Isotropic elastic parameters for ideal polycrystalline CdAl₂O₄ aggregates are computed in the framework of the Voigt-Reuss-Hill approximation. Result for band structure using the Engel-Vosko scheme of the GGA shows a significant improvement over the common GGA functionals. Optical spectra have been calculated for the energy range 0-30 eV. The peaks and structures in the optical spectra are assigned to interband transitions. Pressure dependence of the band gaps, static dielectric constant and static refractive index are also investigated. Pressure and thermal effects on some macroscopic properties are predicted using the quasi-harmonic Debye model.     

Theoretical prediction of the structural, electronic and optical properties of SnB2O4 (B = Mg, Zn, Cd)

The structural, electronic and optical properties of the cubic spinels SnB₂O₄, with B = Mg, Zn and Cd, were studied by means of the full-potential (linear) augmented plane wave plus local orbitals method within the local density and generalized gradient approximations for the exchange-correlation potential. The Engel-Vosko form of the generalized gradient approximation (EV-GGA), which better optimizes the potential for the band structures, was also used. The results of bulk properties, including lattice constants, internal parameters, bulk moduli and their pressure derivatives are in good agreement with the literature data. The band structures show a direct band gap (Γ-Γ) for the three compounds. The computed band gaps using the EV-GGA show a significant improvement over the more common GGA. All the calculated band gaps increase with increasing pressure and fit well to a quadratic function. Analysis of the density of states revealed that the lowering of the direct gap (Γ-Γ) from SnMg₂O₄ to SnZn₂O₄ to SnCd₂O₄ can be attributed to the p-d mixing in the upper valence band of SnZn₂O₄ and SnCd₂O₄. We present calculations of the frequency-dependent complex dielectric function ?(ω). We find that the values of zero-frequency limit ?₁(0) increase with decreasing the energy band gap. The origin of the peaks and structures in the optical spectra is determined in terms of the calculated energy band structures.     

Structural, elastic, electronic, chemical bonding and thermodynamic properties of CaMg2N2 and SrMg2N2: First-principles calculations

We report first-principles density functional theory calculations of the structural, elastic, electronic, chemical bonding and thermodynamic properties of the ternary alkaline earth metal nitrides CaMg₂N₂ and SrMg₂N₂. The calculated equilibrium structural parameters agree well with the experimental findings. Single-crystal and polycrystalline elastic constants and some related properties under pressure effect have been predicted. Both compounds exhibit a striking elastic anisotropy and a ductile behavior. Electronic properties and chemical bonding nature have been studied throughout the band structure, density of states and charge distribution analyses. It is found that these two materials have a direct band gap (Γ-Γ) and a transition to an indirect gap (Γ-M) occurs at about 8.63 and 5.16 GPa in CaMg₂N₂ and SrMg₂N₂, respectively. The chemical bonding has a mixture covalent-ionic character. Thermal effects on some macroscopic properties are predicted using the quasi-harmonic Debye model.     

Insight into Phase Transition,Electronic, Magnetic,Mechanical, and Thermodynamic Properties of TbTe: a DFT Investigation

Theoretical investigation on TbTe for its structural, electronic, magnetic, and thermodynamic stuffs has been carried within density functional theory (DFT) as implemented in WIEN2K code. TbTe was found stable in ferromagnetic phase. The calculated ground-state parameters were found in a good agreement with the experimental data. The compound was found to have a structural stability in cubic B1 (NaCl-type structure) phase, but under the application of high pressure (at 27 GPa), it undergone to B2 (CsCl-type structure) phase of pressure. The second-order elastic constants and mechanical properties like Young’s modulus, Shear modulus, Poisson ratio, Cauchy pressure (C₁₂–C₄₄), and Pugh’s ratio (B/G) were calculated. The present calculations confirmed the ductile nature of TbTe. Further, the thermodynamic investigations have been carried using quasi-harmonic Debye approximation. We have calculated the pressure and temperature dependence of Debye temperature (??_D), bulk modulus (B), thermal expansion (α), heat capacities (C_V), and entropy (S) in the temperature range of 0 to 1000 K and pressure range of 0 to 25 GPa.     

Sintering, microstructure and microwave dielectric properties of rare earth orthophosphates, RePO4 (Re = La, Ce, Nd, Sm, Tb, Dy, Y, Yb)

Various rare earth orthophosphates, such as monazite and xenotime RePO₄ (Re = La, Ce, Nd, Sm, Tb, Dy, Y, Yb) were prepared by a conventional solid-state reaction method. The crystal structure and microstructure of the sintered ceramics were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), respectively. The dielectric properties were measured in the microwave region using a network analyzer. It was found that the monazite RePO₄ could be sintered near 1400 °C, although the xenotime RePO₄, which had a smaller Re³⁺ ionic radius, could be sintered above 1600 °C. The permittivity (?_r) of the monazite structures was higher than that of the xenotime structures. This difference was explained by the differences in ionic polarizability and bond strength. Both monazite and xenotime rare earth orthophosphates, however, exhibited a high quality factor (Q × f), where Q = 1/tan δ and f is the measuring frequency, of greater than 60,000 GHz. The temperature coefficient of resonant frequency (τ_f) was a negative value, ranging between −17 and −56 ppm/°C.     

Theoretical investigations of optical properties of l-arginine trifluoroacetate crystal

In order to determine the molecular dipole moment (μ), polarizability (α), and first hyperpolarizability (β) of l-arginine trifluoroacetate (LATF) crystals, a series of basis sets including polarized and diffuse functions have been employed at the framework of Hartree–Fock and second order Möller–Plesset perturbation theory methods. The MP2/6-311++G(d,p) model predicts for the converged value of in-crystal dipole moment, polarizability and first hyperpolarizability are 21.2 D, 20.0 × 10⁻²⁴ esu and 50.0 × 10⁻³¹ esu, respectively. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Electronic excitation properties are discussed within the framework of the two-level model on the basis of an orbital analysis. The coupled perturbed Hartree–Fock (CPHF) procedure yields information on the dispersion behavior of first hyperpolarizability terms. The magnitudes of the various hyperpolarizability terms which describe the various second-order nonlinear processes show the following trend: β(−2ω;ω,ω) > β(0;ω,−ω) > β(0,0,0). By using the molecular structures and the molecular first hyperpolarizability, the components of second harmonic tensor coefficient d of the crystals were evaluated by the oriented-gas model.     

Anomaly diffuse and dielectric relaxation in strontium doped lanthanum molybdate

The dielectric properties of the La_2−xSr_xMo₂O_9−δ (x = 0-0.2) ceramics were investigated in the temperature range of 300-800 K. Dielectric measurement reveals that two dielectric anomalies, associated with the oxygen ion diffusion, exist in frequency spectrum with x = 0.5. The broad dielectric peaks in tan δ(ω) can be well fitted by a modified Cole-Cole approach. When x = 0.1, only one dielectric relaxation peak is observed, corresponding to different oxygen ion diffusion processes, as distinct from the only relaxation peak in the pure La₂Mo₂O₉. The relaxation parameters τ₀, the dielectric relaxation strength Δ, and the activation energy E_a were obtained. The result of this work shows that, the conductivity change caused by doping between the two phases is due to the combination of the dipolar effects and motion of ions.     

Optical, magnetic and electronic properties of Ln2O2Te (Ln = La, Sm and Gd)

The synthesis, the optical and magnetic properties and the electronic structure of the rare-earth oxytellurides of formula Ln₂O₂Te (Ln = La, Sm and Gd) are reported. The magnetic measurements show that La₂O₂Te exhibit a diamagnetic behavior. The value of the magnetization M of Gd₂TeO₂ at our highest available field (50 kOe) is about 5.5μ_B, well below the expected value for two independent Gd ions (2gJ = 14μ_B) confirming the antiferromagnetic character of this compound. The magnetic properties of Sm₂TeO₂ reveal that Sm is in its 3+ oxidation state with a large Van Vleck contribution. The electronic structure calculations, studied by means of a first principles DFT approach, are consistent with the optical measurements and suggest an indirect band gap semiconductor behavior.     

Elastic properties and Vickers hardness of optically transparent glass-ceramics with fresnoite Ba2TiSi2O8 nanocrystals

Optically transparent glass-ceramics (40BaO-20TiO₂-40SiO₂ (mol%)) consisting of nonlinear optical fresnoite Ba₂TiSi₂O₈ (BTS) nanocrystals (diameter: 100-200 nm) are fabricated, and their elastic properties and deformation behavior are examined as a function of the volume fraction (f) of BTS nanocrystals using cube resonance and Vickers indentation techniques. The elastic properties such as Young's modulus (E) increases linearly with increasing the volume fraction of nanocrystals, e.g., E = 84 GPa for f = 0% (glass) to E = 107 GPa for f = 54.5%. The Vickers hardness (H_v) and indentation fracture toughness (K_c) increase from 5.0 to 6.0 GPa for H_v and 0.48 to 1.05 MPa m^−1/2 for K_c with increasing the volume fraction (from f = 0% to f = 54.5%), but they do not change linearly against the volume fraction of nanocrystals. It is suggested that BTS nanocrystals themselves induce a high resistance against deformation during Vickers indenter loadings.     

First-principles calculations of mechanical and thermodynamic properties of YAlO3

First-principles calculations are performed to investigate the crystal structure, electronic properties, the elastic properties, hardness and thermodynamic properties of YAlO₃. The calculated ground-state quantities such as lattice parameter, bulk modulus and its pressure derivative, the band structure and densities of states were in favorable agreement with previous works and the existing experimental data. The elastic constants C_ij, the aggregate elastic moduli (B, G, E), the Poisson’s ratio, and the elastic anisotropy have been investigated. YAlO₃ exhibits a slight elastic anisotropy according to the universal elastic anisotropy index A^U = 0.24. The estimated hardness for YAlO₃ is consistent with the experimental value, and Al–O bond in AlO₆ octahedra plays an important role in the high hardness. The Y–O bonds in YO₁₂ polyhedra exhibit different characteristic. Using the quasi-harmonic Debye model considering the phonon effects, the temperature and pressure dependencies of bulk modulus, heat capacity and thermal expansion coefficient are investigated systematically in the ranges of 0–20 GPa and 0–1300 K.     

Synthesis and study of Sr-substituted misfit layer sulfides

Two series of [(Ln_1/3Sr_2/3S)_1.5]_1.15NbS₂ (1.5Q/1H) and (Ln_1−xSr_xS)_1+yNbS₂ (1Q/1H) misfit layer sulfides have been synthesised and studied by X-ray powder and single crystal diffraction, EDX-analysis and magnetic measurements. For the early lanthanides (Ln = La, Ce) only the (Ln_1−xSr_xS)_1+yNbS₂ (x < 0.40-0.45, y = 0.15-0.17) compounds were formed whereas for late lanthanides (Ln = Pr, Nd, Sm, Gd-Er, Yb, Lu), and yttrium, both types of phases can be obtained. The crystal structure of (Pr_0.55Sr_0.45S)_1.15NbS₂ has been refined on the basis of X-ray single crystal data using the superspace approach. It consists of double layers [Pr_0.55Sr_0.45S] of NaCl-type (Q-part: a = 5.799(3) Å, b = 5.810(2) Å, c = 23.331(9) Å, z = 4) and NbS₂-sandwiches (H-part: a = 3.332(3) Å), z = 8, yielding a q-vector q = (α 0 0), α = 0.74) alternating along the c-direction. The superspace group pair is Fm2m (α 0 0):Fm2m (α 0 0) (No. 42.7). The refinement converged to R_w(obs) = 0.069. According to the structure refinement and EDX-analysis data in the [Pr_0.55Sr_0.45S]-slab almost half of the Pr-atoms are randomly replaced by Sr. The minimal formal value of charge transfer from the Q- to the H-part of the structure necessary to stabilise the misfit Nb-based layer sulfides has been estimated as about 0.6 ē per Nb atom.     

Fabrication and mechanical properties of monolithic MoSi2 by spark plasma sintering

Fine MoSi₂ powders containing a small amount of Mo₅Si₃ have been prepared by self-propagating high-temperature synthesis (SHS), followed by spark plasma sintering (SPS) for 10 min at 1200-1500°C and 30 MPa. Dense MoSi₂ materials, in which the grain size is ∼7.5 μm, have been fabricated at 1300°C. They exhibit excellent mechanical properties: Vicker’s hardness H_v (10.6 GPa), fracture toughness K_IC (4.5 MPa m^1/2), and bending strength σ_b (560 MPa). The strength of 325 MPa can be retained up to 1000°C.     

Influence of mixed alkali on the spectral properties of vanadyl ions doped xNa2O-(30 − x)K2O-60B2O3 glasses—an EPR and optical study

Electron paramagnetic resonance (EPR) and optical investigations have been performed in the mixed alkali borate xNa₂O-(30 − x)K₂O-60B₂O₃ (5 ≤ x ≤ 25) glasses doped with 10 mol% of vanadyl ions in order to look for the effect of ‘mixed alkalis’ on the spectral properties of the glasses. The observed EPR spectra have structures for x > 5 mol% which are characteristic of a hyperfine interaction arising from an unpaired electron with the ⁵¹V nucleus and it builds up in intensity as x increases. It is observed that the mixed alkali play a significant role in accommodating the vanadyl ions in these mixed alkali glasses and for x > 5 mol%, shows a well resolved hyperfine structure typical for isolated VO²⁺ ions. The spin-Hamiltonian parameters (g and A), the dipolar hyperfine coupling parameter (P) and Fermi contact interaction parameter (k) have been evaluated. It is observed that the spin-Hamiltonian parameters do not vary much with the change in composition. It is observed that with increase of x, an increase occurs in tetragonal distortion for VO²⁺. The number of spins (N) participating in resonance and the paramagnetic susceptibility (χ) have been calculated. It is observed that N and χ increase with x. The optical bandgap energies evaluated for these glasses slightly increase with x and reach a maximum around x = 20 and thereafter decrease showing the mixed alkali effect. Optical band gap energies obtained in the present work vary from 2.73 to 3.10 eV for both the direct and indirect transitions. The physical parameters of the glasses are also determined with respect to the composition.     

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

Synthesis and characterisation of the double perovskite Ba2(Zn0.5Ti0.5X)O6 (X = Nb, Ta) ceramics

Ba₂(Zn_0.5Ti_0.5X)O₆ compounds from the general ABO₃ perovskite family were synthesized by the classical solid-state route for X = Nb and Ta with various A/B ratios (1.005, 1 and 0.995). After the calcination step at 1100 °C, both compounds (X = Nb and Ta) contain mainly the cubic disordered ‘Ba₂(Zn_0.5Ti_0.5X)O₆’ phase but traces of BaTiO₃ and secondary phases are often detectable. Nevertheless, after the sintering stage at higher temperature (from 1300 to 1500 °C) and for all A/B ratios investigated, Ti enters into the cubic perovskite structure, resulting in the formation of a unique ‘Ba₂(Zn_0.5Ti_0.5X)O₆’ phase. Attractive dielectric properties have been measured on the tantalum-based compound for A/B = 0.995 (Q ∼2000 at 7.4 GHz and ? = 39.6) as well as on the niobium-based phase for A/B = 1.005 (Q ∼2200 at 6.1 GHz and ? = 54.8). All these characteristics were confirmed at 1 MHz and a linear dependence of the permittivity versus temperature from −60 to 180 °C has also been evidenced for both formulations. Sinterability, dielectric properties and microstructure of such compounds are discussed with respect to the stoichiometry.