Numerical study of the rutile band structure by the Hartree–Fock–Roothaan method in the CO LCAO approximation using the cyclic cluster model

The technique for calculatingmaterial characteristicswith the aid of theHartree–Fock–Roothaan method in the CO LCAO approximation using the cyclic clustermodel is considered. The results of the numerical study are verified for the TiO₂ system. The band gap minimum (2.9 eV) is calculated for the system under consideration.     

The calculation of active Raman modes of α-quartz crystal via density functional theory based on B3LYP Hamiltonian in 6–311+G(2d) basis set?

We obtained an approximation of the force field of ??-quartz crystal using a new idea of applying density functional theory [J Purton, R Jones, C R A Catlow and M Leslie, Phys. Chem. Minerals 19, 392 (1993)]. Our calculations were based on B3LYP Hamiltonian [A N Lazarev and A P Mirgorodsky, Phys. Chem. Minerals 18, 231 (1991)] in 6?311+G(2d) basis set for H₁₆Si₇O₆ cluster and included a unit cell of the lattice. The advantage of our method is the increase in the speed of calculations and the better adaption of simulation results with the experimental data.     

A comparative study on the nanocrystalline ZnO thin films prepared by ultrasonic spray and sol⿿gel method

Nanocrystalline ZnO thin films are deposited through two different chemical methods: (i) the films prepared by ultrasonic spray with 0.1 M and (ii) dip-coating from zinc acetate complex solutions with 0.5 M, the films obtained at different temperatures. The XRD analyses indicated that ZnO films have nanocrystalline hexagonal structure with (0 0 2) preferential orientation and the maximum crystallite size value of 103 nm measured from the films prepared by dip-coating. UV?vis measurement indicated that all films are transparency in the visible region. The optical band gap increased with decreasing of the Urbach tail energy indicating that the increase in the transition tail width and decrease of the defects, respectively.     

A comparative study on the effects of salt and filler on transport and structural properties of organic–inorganic hybrid electrolytes

Organic–inorganic hybrid electrolytes based on the reaction of tri-block copolymer poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), poly(ethylene glycol diglycidyl ether, and (3-glycidyloxypropyl)trimethoxysilane doped with LiClO₄ and SiO₂ nanoparticles were synthesized by a sol–gel process. The structural and dynamic properties of the materials thus obtained were systematically investigated by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, alternate current impedance, and ¹³C solid-state NMR measurements. A maximum ionic conductivity of 3.2?×?10^?5 S cm^?1 was obtained at 30 °C for the solid hybrid electrolyte with a [O]/[Li] ratio of 16 and 7 wt% of SiO₂ nanoparticles. A Vogel–Tamman–Fulcher-like temperature dependence of ionic conductivity was observed for the hybrid electrolytes, implying that the diffusion of charge carriers was assisted by the segmental motions of the polymer chains.     

A study on the early-stage decomposition in the Al–Mg–Si–Cu alloy AA6111 by electrical resistivity and three-dimensional atom probe

Electrical resistivity measurements and three-dimensional atom probe (3DAP) analysis were employed to investigate early-stage decomposition of the Al alloy AA6111 in the temperature range 60–180°C where electrical resistivity initially increased with ageing time. 3DAP measurements provided information on the shape, number density and solute content of the precipitates, as well as the solute concentration of the matrix, for the ageing conditions corresponding to the resistivity maxima. Using the 3DAP results, the precipitate size distributions for these ageing conditions were determined in terms of the measured number of solute atoms per precipitate. The number density and the Cu content of the precipitates decreased with increasing temperature, whereas the Mg/Si ratio increased. The size distribution of precipitates at the higher ageing temperatures showed the addition of larger size precipitates to the precipitate population. A modification to Matthiessen's law was employed to describe the anomalous resistivity increase by considering the effect of solutes and precipitates on the resistivity evolution. Using the 3DAP results in analysing the resistivity anomaly, it was found that the decrease in the resistivity maxima with increasing temperature was associated with the decrease in the number density of precipitates and not the scattering power of precipitates. The 3DAP results were further used to provide information on the mechanisms of early-stage decomposition and the temperature dependence of the nucleation rate. From this, the nucleation rate appeared to be controlled by the migration of solute atoms, which was assisted by quenched-in vacancies.     

Local zone wise elastic and plastic properties of electron beam welded Ti–6Al–4V alloy using digital image correlation technique: A comparative study between uniform stress and virtual fields method

Joining of materials using welding results in the formation of material zones with varying microstructure across the weld. Extraction of the mechanical properties of those individual heterogeneous zones are important in designing components and structures comprised of welds. In this study, the zone wise local extraction of the elastic and plastic properties of an electron beam welded Ti–6Al–4V titanium alloy has been carried out using both the uniform stress method (USM) and the virtual fields method (VFM) involving digital image correlation (DIC) technique. The surface strain field obtained using DIC technique from a transverse weld specimen tensile testing is used for extracting the zone wise strain evolution. Initially, using uniform stress assumption, zone wise full range stress–strain curves are extracted. In USM methodology, the elastic and plastic material models are fitted to the zone wise stress–strain curves and required parameters are extracted from it. But inherent disadvantage is lot of images need to be processed for the parameter extraction. Recently, VFM is gaining lot of popularity in characterization domain as it is robust, accurate and faster. VFM is based on the principle of virtual work where, the weak form of local equilibrium equations and kinematically admissible virtual displacement fields are utilized for parameter extraction. Hollomon׳s power law is used here as the hardening rule. Young׳s modulus, Poisson׳s ratio, yield stress, strength coefficient and strain hardening exponent are the parameters extracted zone wise using both USM and VFM. A Vicker׳s microhardness measurement is also conducted across the weld zone towards mapping the strength behavior. Fusion zone has reported higher yield strength, strength coefficient and Poisson׳s ratio. Young׳s modulus value is found decreasing from base metal towards the fusion zone. The trend observed in parameter variation across the weld zone obtained by both USM and VFM compares very well. Due to various advantages associated with VFM technique it is generally recommended for parameter extraction.     

A comparative study of different concentrations of pure Zn powder effects on synthesis,structure, magnetic and microwave-absorbing properties in mechanically-alloyed Ni–Zn ferrite

In this study, a powder mixture of Zn, Fe₂O₃ and NiO was used to produce different compositions of Ni_1−xZn_xFe₂O₄ (x=0.36, 0.5 and 0.64) nanopowders. High-energy ball milling with a subsequent heat treatment method was carried out. The XRD results indicated that for the content of Zn, x=0.64 a single phase of Ni–Zn ferrite was produced after 30 h milling while for the contents of Zn, x=0.36 and 0.5, the desired ferrite was formed after sintering the 30 h-milled powders at 500 °C. The average crystallite size decreased with increase in the Zn content. A DC electrical resistivity of the Ni–Zn ferrite, however, decreased with increase in the Zn content, its value was much higher than those samples prepared by the conventional ceramic route by using ZnO instead of Zn. This is attributed to smaller grains size which were obtained by using Zn. The FT-IR results suggested two absorption bands for octahedral and tetrahedral sites in the range of 350–700 cm⁻¹. The VSM results revealed that by increasing the Zn content from 0.36 to 0.5, a saturation magnetization reached its maximum value; afterwards, a decrease was observed for Zn with x=0.64. Finally, magnetic permeability and dielectric permittivity were studied by using vector network analyzer to explore microwave-absorbing properties in X-band frequency. The minimum reflection loss value obtained for Ni_0.5Zn_0.5Fe₂O₄ samples, about −34 dB at 9.7 GHz, making them the best candidates for high frequency applications.     

Re-exchange of Fe and Cu at the interface in sintered Nd–Fe–B magnets: A method to eliminate Fe precipitation at grain boundaries

According to the decoupling hypothesis for magnetic grains, the coercivity in sintered Nd–Fe–B magnets is increased after Cu doping, which is due to the formation of non-magnetic grain boundaries. However, this method partially fails, and ferromagnetic Fe-segregation occurs at the grain boundary. We discovered both experimentally and through calculation that the Fe content at the grain boundaries can be tuned across a wide range by introducing another element of Ag. Segregated Fe at high temperature at the grain boundary re-dissolves into Nd₂Fe₁₄B grains during annealing at low temperature. Both configurable and magnetic entropies contribute a large driving force for the formation of nonmagnetic grain boundaries. Almost zero Fe content could be achieved at the grain boundaries of sintered Nd–Fe–B magnet.     

A study of the influence of chemical environment on the Li (i = 1–3) subshell X-ray intensity ratios and the L3 absorption-edge energy for some compounds of 66Dy using synchrotron radiation

In the present work, the X-ray intensity ratios, I_Lk/I_Lα (k = l, β, γ_1,5, γ₂,₃, γ₄), have been measured for different compounds of ₆₆Dy, namely, Dy₂O₃, Dy₂(CO₃)₃, Dy₂(SO₄)₃.8H₂O, DyI₂, and the ₆₆Dy metallic foil by tuning the incident photon energies across its L_i (i = 1–3) absorption-edge energies covering the region 7.8–10 keV in order to investigate the influence of chemical effects on these intensity ratios in the presence of the many-body effects, which become significant at photon energies in proximity to the L_i absorption-edge energies. The present measured intensity ratios I_Lk/I_Lα have been compared with two sets of values calculated using the nonrelativistic Hartree–Fock–Slater model-based L_i (i = 1–3) subshell photoionization cross sections, the Dirac–Fock model-based X-ray emission rates, and two sets of the fluorescence and Coster–Kronig yields. The L₃ absorption-edge energy of ₆₆Dy in its different compounds and metallic foil has been deduced from the XANES spectra recorded in the present work. The L₃ absorption-edge energy shifts obtained from these absorption-edge energies are found to increase linearly with the partial charge on the metal atom (₆₆Dy).     

A comparative study of cationic distribution in the systems Li1+5XM1−XO3 and Li1+XM1−XM′ XO3 (M=Nb,M′=Ti; M=Ta,M′=Ti,Zr, Sn)

Abstract

A comparative ferroelectric and NMR studies of the systems Li_1+5X M_1?XO₃ and Li_1+XM_1?XM^′ _XO₃ (M=Nb, M′=Ti M = Ta; M′=Ti, Zr, Sn) have indicated that plot of T_C versus composition can be qualitatively explained on the basis of cationic distribution. The strong drop of T_C has been found in systems with all cations in octahedral sites, whereas little change of T_C was observed along the solid solutions with Li-ions in interstitial tetrahedral sites.     

Effect of electron-donating and electron-withdrawing atoms on the C–H…Y hydrogen bond in model X3CH…YZ (X = B,F; YZ = BF,CO, N2) complexes

A computational study of model complexes X₃CH…YZ (X = B, F; YZ = BF, CO, N₂) was undertaken to assess the effect of electron-donating and electron-withdrawing X atoms on the properties of the C–H…Y hydrogen bond. Sequential substitution of the B atoms in B₃CH by F atoms to produce F₃CH allowed for the elucidation of interesting trends in the corresponding hydrogen-bonded complexes. The dipole moments and the dipole moment derivative with respect to C–H bond displacement for the proton donors and the chemical hardness of the Y atom of the proton acceptor YZ were found to be useful parameters for understanding these trends. It was found that a positive dipole derivative favours red-shifted hydrogen bonds, whereas a negative dipole derivative favours blue-shifted hydrogen bonds. However, decreasing hardness of Y (which correlates with increasing intermolecular attraction) modifies the interaction such that either greater C–H bond extensions/red shifts or smaller C–H bond compressions/blue shifts are obtained.