First-principles study of lattice dynamics and thermodynamic properties of LiInX2 (X = S, Se, Te)

First-principles calculations of lattice dynamics and thermodynamic properties of orthorhombic LiInS₂ and LiInSe₂ and chalcopyrite LiInTe₂ have been performed within density functional perturbation theory using norm conserving pseudopotentials. Theoretical values of phonon mode frequencies are in good agreement with the experimental data available for these crystals obtained by methods of Raman spectroscopy and infrared one. In the whole frequency range a significant decrease of the vibrational frequencies is observed going from LiInS₂ to LiInSe₂ and LiInTe₂, which is a consequence of the anion radius increase. The lattice vibrations of In-X (X = S, Se, Te) bonds are mainly located in the low-frequency and mid-frequency ranges, and the Li-X bond vibrations are dominated in the higher frequency range. The mixed covalent-ionic nature of the three compounds is manifested by Born effective charge data. The vibration patterns of orthorhombic LiInS₂ and chalcopyrite LiInTe₂ were discussed in detail. The temperature dependences of thermodynamic quantities (including the internal energy, free energy, heat capacity, entropy and the Debye temperature Θ_D) of all the three compounds were also presented in this paper. It is proved that Debye stiffness increases from LiInTe₂ to LiInSe₂ and LiInS₂.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

Ba(Ti1 − xSnx)O3 (x = 0.13) nanomaterials produced by low-temperature aqueous synthesis

BaTi_0.87Sn_0.13O₃ (BTS₁₃) nanopowder was prepared by low-temperature aqueous synthesis (LTAS) method. The evolution of the structure and microstructure of the precursor precipitate, heated at temperatures up to 1000 °C was studied by TGA, FT-IR, SEM and XRD techniques. The dried precipitate showed a microstructure consisting of nano-sized grains (∼40 nm) with great tendency to agglomeration. BaTi_0.87Sn_0.13O₃ single phase was obtained at 800 °C. The ceramics prepared from as-obtained BTS₁₃ powders (60-70 nm) show good dielectric and ferroelectric characteristics. The dielectric constant was about 4800 and the dielectric loss (tan δ) was 0.229 at 1 kHz and at the Curie temperature (31 °C). The remanent polarization (P_r) and the coercive field (E_C) of Ba_0.97Ho_0.03TiO₃ ceramics, at 1 kHz, were P_r = 13 μC/cm² and E_C = 0.89 kV/cm. The ferroelectric parameters E_C and P_r decrease with increasing frequency in the domain 100 Hz to 10 kHz.     

MICROSCOPIC PHASE–FIELD METHOD SIMULATION FOR THE IN SITU TRANSFORMATION OF L10 PHASE AND L12 PHASE STRUCTURE

Ni₈₀Al₁₃Cr₇合金为研究对象, 采用描述单个格点位置原子占位的时间和空间演化为特征的微观相场法, 研究了Al和Cr原子在(100)和(200)面上的原子占位变化与时效早期Ni₃(Al, Cr)结构演化之间的关系. 研究表明, 在时效最初阶段, Al和Cr原子在(100)和(200)面上的成分序参数并不发生变化, 然而在两面上的长程序参数相等并随时间逐渐增大, 以等成分有序化的形式发生第一次原位转变, 形成低有序度的L1₀结构预析出相. 当有序度增大到一定值时, Al和Cr原子的成分序参数和长程序参数在(100)面上迅速增大, 而在(200)面上则迅速降低, 相结构发生第二次原位转变, L1₀结构逐渐向L1₂结构转化.     

First-principle study of magnetic,elastic and thermal properties of full Heusler Co2MnSi

In this work, first principles calculation of structural, electronic magnetic and elastic properties of the half-metallic ferromagnetic Heusler compound Co₂MnSi are presented. We have applied the full-potential linearized augmented plane waves plus local orbitals (FP-L/APW+lo) method based on the density functional theory (DFT). For the exchange and correlation potential generalized-gradient approximation (GGA) is used. The computed equilibrium lattice parameters agree well with the available theoretical and experimental data. Elastic constants and their pressure dependence are also calculated. The calculated total magnetization of 5 μ_B is in excellent agreement with recent experiments. We also presented the thermal effects using the quasi-harmonic Debye model, in which the lattice vibrations are taken into account. Temperature and pressure effects on the structural parameters, heat capacities, entropy, thermal expansion coefficient, and Debye temperatures are determined from the non-equilibrium Gibbs functions.     

Chemical trends of the band gaps of idealized crystal of semiconducting silicon clathrates, M8Si38A8 (M = Na, K, Rb, Cs; A = Ga, Al, In), predicted by first-principle pseudopotential calculations

We have calculated the band structures of Si clathrate, M₈Si₃₈Ga₈ (M = Na, K, Rb, and Cs), using the density-functional theory under the generalized gradient corrected local density approximation, where M is the encapsulated guest alkali atom. They are found to be indirect semiconductors with the calculated gaps (E_g) from 0.45 to 0.89 eV, which should be compared to the calculated gap of 0.65 eV of crystalline Si with the diamond structure. The gaps become wider with the promotion to the heavier guest alkali atoms and the reasons of gap widening are discussed using the calculated dependence of E_g on the cell-volume of guest-free silicon clathrate (Si₄₆). Effect of the substitutional elements in the clathrate framework (Al and In in place of Ga) was also discussed.     

Thermal vibrations and polymorphic β → γ transition in cerium

Method of neutron diffraction was used to determine the temperature dependence of the Debye-Waller factor and the related thermal atomic displacements for two polymorphic modifications of cerium, namely, for β-Ce with a double hexagonal closed-packed (dhcp) structure and for γ-Ce with a face-centered cubic (fcc) structure. It has been shown that the phase transition does not lead to substantial changes in the root-mean-square thermal atomic displacements and that the Debye temperatures of the two modifications are close: 131 K for β-Ce and 127 K for γ-Ce. However, the relative (with respect to the lattice parameters) displacements along the axes change considerably. The transition from the anisotropic hexagonal to the isotropic cubic modification leads, because of a redistribution of thermal atomic displacements along the crystallographic axes, to a decrease in the maximum values of these quantities and to a weakening of their temperature dependence. It has also been shown that a change in the thermal atomic vibrations and in the vibrational contribution to the entropy of the polymorphic transformations is connected with the sign of the volume effect of the transformation (stronger upon a positive effect and weaker, upon a negative one). The reasons for this behavior are discussed.     

Magnetomechanical properties of epoxy-bonded Sm1−xNdxFe1.55 (0 ≤ x ≤ 0.56) pseudo-1-3 magnetostrictive particulate composites

Pseudo-1-3 magnetostrictive particulate composites consisting of light rare earth (Sm and Nd)-based magnetostrictive Sm_1−xNd_xFe_1.55 particles with the Nd content x of 0-0.56 and randomly distributed sizes of 10-180 μm embedded and aligned in a passive epoxy matrix are fabricated using the particulate volume fraction of 0.5. The quasistatic magnetomechanical properties of the composites are investigated and the results are compared with their monolithic alloys for various x. The composites exhibit similar qualitative trends in properties with the alloys for all x. The Sm_0.92Nd_0.08Fe_1.55 composite shows a large unsaturated magnetostriction λ of −530 ppm at 500 kA/m and a high piezomagnetic coefficient d₃₃ of −2.0 nm/A at 100 kA/m as a result of the magnetocrystalline anisotropy compensation between Sm³⁺ and Nd³⁺ ions in the Sm_0.92Nd_0.08Fe_1.55 alloy.     

Preparation and electrical properties of perovskite ceramics in the system BaBi1−xSbxO3 (0 ≤ x ≤ 0.5)

The effect of the composition on the electrical properties of BaBi_1−xSb_xO₃ (0 ≤ x ≤ 0.5) negative temperature coefficient (NTC) thermistors was studied. Major phases present in the sintered bodies of BaBi_1−xSb_xO₃ (0 < x < 0.5) ceramics were BaBi_0.5Sb_0.5O₃ compounds with a rhombohedral structure and BaBiO₃ compounds with a monoclinal structure. Most pores were located in the grains of BaBiO₃ and BaBi_0.5Sb_0.5O₃ ceramics. It was apparent that the ρ₂₅ and B_25/85 constant of the thermistors increased with increasing Sb content.     

Variation of microstructure and composition of the Cr2AlC coating prepared by sputtering at 370 and 500 °C

Cr₂AlC coating was deposited at 370 and 500 °C by D.C. magnetron sputtering from an as-synthesized bulk Cr₂AlC target. The phase composition and preferential orientation of the coating were investigated using XRD, and the microstructure of the coating was characterized by TEM. Results indicated that Cr₂AlC coating with a strong (110) preferential orientation could be obtained. The coating microstructure was clearly affected by the deposition temperature. At 370 °C, the deposited coating possessed a triple-layered structure with an α-(Cr, Al)₂O₃ inner layer, an amorphous intermediate layer and a crystalline Cr₂AlC outer layer. However, the coating deposited at 500 °C had a single-layered structure consisting of crystalline Cr₂AlC layer. The growth mechanism of the Cr₂AlC coating at different deposition temperatures is discussed.     

Hot corrosion and oxidation behavior of a novel Pt + Hf-modified γ′-Ni3Al + γ-Ni-based coating

A new type of Pt + Hf-modified γ′-Ni₃Al + γ-Ni-based coating has been developed in which deposition involves Pt electroplating followed by combined aluminizing and hafnizing using a pack cementation process. Cyclic oxidation testing of both Pt + Hf-modified γ′ + γ and Pt-modified β-NiAl coatings at 1150 °C (2102 °F), in air, resulted in the formation of a continuous and adherent α-Al₂O₃ scale; however, the latter developed unwanted surface undulations after thermal cycling. Type I (i.e. 900 °C/1652 °F) and Type II (i.e. 705 °C/1300 °F) hot corrosion behavior of the Pt + Hf-modified γ′ + γ coating were studied and compared to Pt-modified β and γ + β-CoCrAlY coatings. Both types of hot corrosion conditions were simulated by depositing Na₂SO₄ salt on the coated samples and then exposing the samples to a laboratory-based furnace rig. It was found that the Pt + Hf-modified γ′ + γ and Pt-modified β coatings exhibited superior Type II hot corrosion resistance compared to the γ + β-CoCrAlY coating; while the Pt + Hf-modified γ′ + γ and γ + β-CoCrAlY coatings showed improved Type I hot corrosion performance than the Pt-modified β.     

Internal friction, dilatometric and calorimetric study of anelasticity in Fe-13 at.% Ga and Fe-8 at.% Al-3 at.% Ga alloys

This paper investigates the structural transitions associated with different cooling rates from a high temperature disordered state and the effect of substitution of Ga atoms by Al atoms in Fe-Ga binary alloys on the ordering processes. Two iron-based low carbon (about 0.04 at.% C) alloys Fe-13 at.% Ga and Fe-8 at.% Al-3 at.% Ga are studied. Internal friction, dilatometric and calorimetric tests are carried out to check ordering in these alloys and contribution of structural defects to relaxation spectrum. Several thermally activated internal friction peaks have been observed and their activation parameters evaluated by means of temperature and frequency dependent internal friction tests using forced vibration. For most of these peaks physical mechanisms are proposed. Apart from these thermally activated relaxation peaks, a structural, frequency independent relaxation takes place at 250-300 °C. Dilatometric and DSC curves show the appearance of a contraction effect in the same temperature range. This effect was studied in alloys cooled down with different cooling rates. We believe that the frequency independent internal friction peak (denoted as the P3 peak in this paper) and peaks at dilatometric and DSC curves are controlled by the same structural mechanism and therefore the activation energy for this anelastic mechanism is derived from DSC data.     

Electronic structure of antiferromagnetic PbCrO3 (0 0 1) surfaces

Surfaces of cubic perovksite PbCrO₃ in (0 0 1) plane are investigated through density functional theory. The plane wave pseudopotential method is applied with generalized gradient approximation scheme. Hubbard U correction (GGA + U) is included in all calculations in order to simulate on-site Coulomb interactions between Cr-d states. Two types of terminations, namely, PbO- and CrO₂-terminations are considered in construction of the surfaces. Surfaces of both terminations show convergence at 9-layer slab geometry. The density of states calculations on the converged slab geometry yield a metallic behavior for both PbO- and CrO₂-terminations. Both metal atoms, Pb and Cr, in the uppermost layer of the respective terminations, have inward atomic relaxations much larger in magnitude than the oxygen atoms of the respective layer. However, Cr atoms which are labeled as up and down according to their spin orientation show different relaxations. The interlayer distance between the uppermost layer and the first one next to it decreases in both PbO- and CrO₂-terminated surface geometries. The calculations of the relative movement of the oxygen atom with respect to the Pb or Cr atom in each terminations give a positive rumpling in the uppermost layer.     

Ab-initio study of the structural,electronic, elastic and vibrational properties of the intermetallic Pd3V and Pt3V alloys in the L12 phase

Pseudopotential plane-wave method based on density functional theory within the generalized gradient approximation for the exchange-correlation potential has been applied to study the structural, electronic, elastic and vibrational properties of the binary intermetallic Pd₃V and Pt₃V in the L1₂ phase. The optimized lattice constant, bulk modulus and its pressure derivative, independent single-crystal elastic constants and elastic wave velocities in three different directions are evaluated and compared with the available experimental and theoretical data. The polycrystalline elastic parameters, hardness coefficient, elastic anisotropy, Debye temperature are estimated. The electronic band structure, electronic total and partial densities of states, and total magnetic moment of the Pd₃V and Pt₃V alloys are computed and analyzed in comparison with the existing theoretical and experimental findings. Phonon-dispersion curves and their corresponding total and projected densities of states were obtained for the first time using a linear-response in the framework of the density functional perturbation theory.     

Thermoelectric properties of Cu1−xPtxFeO2 (0.0 ≤ x ≤ 0.05) delafossite-type transition oxide

The samples of Cu_1−xPt_xFeO₂ (0 ≤ x ≤ 0.05) delafossite were synthesized by solid state reaction method for studying thermoelectric properties. The properties of Seebeck coefficient, electrical conductivity and thermal conductivity were measured in the high temperature ranging from 300 to 960 K. The results of Seebeck coefficient, electrical conductivity and power factor were increased with increasing Pt substitution and temperature. The thermal conductivity was decreased from 5.8 to 3.5 W/mK with increasing the temperature from 300 to 960 K. An important results, the highest value of power factor and ZT is 2.0 × 10⁻⁴ W/mK² and 0.05, respectively, for x = 0.05 at 960 K.     

Characterization of sol-gel synthesised lead-free (1 − x)Na0.5Bi0.5TiO3-xBaTiO3-based ceramics

The crystal structure, microstructure, dielectric and ferroelectric properties of (1 − x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics with x = 0, 0.03, 0.05, 0.07 and 0.1 are investigated. A structural variation according to the system composition was investigated by X-ray diffraction (XRD) analyses. The results revealed that the synthesis temperature for pure perovskite phase powder prepared by the present sol-gel process is much lower (800 °C), and a rhombohedral-tetragonal morphotropic phase boundary (MPB) is found for x = 0.07 composition which showing the highest remanent polarization value and the smallest coercive field. The optimum dielectric and piezoelectric properties were found with the 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃ composition. The piezoelectric constant d₃₃ is 120 pC/N and good polarization behaviour was observed with remanent polarization (P_r) of 12.18 pC/cm², coercive field (E_c) of 2.11 kV/mm, and enhanced dielectric properties ?_r > 1500 at room temperature. The 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃-based ceramic is a promising lead-free piezoelectric candidate for applications in different devices.     

Strong correlation between structural, magnetic and transport properties of non-stoichiometric Sr2FexMo2−xO6 (0.8 ≤ x ≤ 1.5) double perovskites

Sr₂Fe_xMo_2−xO₆ (x = 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 and 1.5 wt.%) (SFMO) double perovskite oxides of different compositions have been prepared by sol-gel method. These materials were subjected to X-ray diffraction and found that crystal structure changes from tetragonal to cubic around x = 1.2 wt.%. Lattice parameters and unit cell volume have been calculated using X-ray diffraction data. Magnetization studies have been carried out using Vibrating Sample Magnetometer ranging from −15 kOe to +15 kOe and saturation magnetization (M_s) has been determined. Electrical resistivity and magnetoresistance studies have been carried out in the magnetic field range of −40 kOe to +40 kOe keeping the temperature constant at 5, 150 and 300 K using standard four-probe method. Resistivity studies have also been carried out in the temperature ranging from 5 to 300 K keeping the magnetic field constant at 0, 10, 20 and 40 kOe. Maximum degree of Fe/Mo ordering (η_max) of SFMO has been calculated and compared with magnetic and transport properties. It has been found that there is a strong correlation between 3 parameters η_max, M_s and MR (%), i.e. all of them show a maximum at x = 1.0 wt.% and decreases as x deviates from 1.0 in SFMO. It has been also found that there is a different resistivity behavior between x ≤ 1.2 wt.% and x > 1.2 wt.% samples of SFMO. Semiconductor metal transition temperature was found to be maximum at x = 1.0 wt.%.     

Laser surface alloying of aluminium with WC + Co + NiCr for improved wear resistance

In the present study, laser surface alloying of aluminium with WC + Co + NiCr (in the ratio of 70:15:15) has been conducted using a 5 kW continuous wave (CW) Nd:YAG laser (at a beam diameter of 0.003 m), with the output power ranging from 3 to 3.5 kW and scan speed from 0.012 m/s to 0.04 m/s by simultaneous feeding of precursor powder (at a flow rate of 1 × 10^− 5 kg/s) and using He shroud at a gas flow rate of 3 × 10^− 6 m³/s. The effect of laser power and scan speed on the characteristics (microstructures, phases and composition) and properties (wear and corrosion resistance) of the surface alloyed layer have been investigated in details. Laser surface alloying leads to development of fine grained aluminium with the dispersion of WC, W₂C, Al₄C₃, Al₉Co₂, Al₃Ni, Cr₂₃C₆, and Co₆W₆C. The microhardness of the alloyed zone is significantly improved to a maximum value of 650 VHN as compared to 22 VHN of the as-received aluminium substrate. The mechanism of microhardness enhancement has been established. The fretting wear behavior of the alloyed zone was evaluated against WC by Ball-on-disc wear testing unit and the mechanism of wear was established.     

Isothermal section of the Ho-Co-Fe system at 773 K

The 773 K isothermal section of the phase diagram of the Ho-Co-Fe ternary system was investigated by using X-ray diffraction technique, metallographic analysis and scanning electron microscopy with energy dispersive analysis. The isothermal section of the ternary system consists of 6 three-phase regions, 16 two-phase regions and 11 single-phase regions. Three pairs of corresponding compounds of Ho-Co and Ho-Fe systems, i.e., Ho₂Co₁₇ and Ho₂Fe₁₇, HoCo₃ and HoFe₃, HoCo₂ and HoFe₂, form a continuous series of solid solution. At 773 K the compound Ho₆Fe_23−xCo_x was found to have a wide homogeneity range from 0 to 29 at.% Co. The maximum solid solubilities of Fe in Co, Ho₂Co₇, Ho₁₂Co₇ and Ho₃Co were determined to be about 10, 9, 2 and 5 at.% Fe, respectively. The maximum solid solubility of Co in Fe is found to be 78 at.% Co.     

Microwave dielectric properties of (1 − x)ZnMoO4-xTiO2 composite ceramics

(1 − x)ZnMoO₄-xTiO₂ (x = 0.0, 0.05, 0.158, 0.25, and 0.35) composite ceramics were synthesized by the conventional solid state reaction process. The sintering behavior, phase composition, chemical compatibility with silver, and microwave dielectric properties were investigated. All the specimens can be well densified below 950 °C. From the X-ray diffraction analysis, it indicates that the triclinic wolframite ZnMoO₄ phase coexists with the tetragonal rutile TiO₂ phase, and it is easy for silver to react with ZnMoO₄ to form Ag₂Zn₂(MoO₄)₃ phase and hard to react with TiO₂. When the volume fraction of TiO₂ (x value) increasing from 0 to 0.35, the microwave dielectric permittivity of the (1 − x)ZnMoO₄-xTiO₂ composite ceramics increases from 8.0 to 25.2, the Q_f value changes in the range of 32,300-43,300 GHz, and the temperature coefficient τ_f value varies from −128.9 to 157.4 ppm/°C. At x = 0.158, the mixture exhibits good microwave dielectric properties with a ?_r = 13.9, a Q_f = 40,400 GHz, and a τ_f = +2.0 ppm/°C.