Effect of Pr-filling in binary skutterudites CoX3 (P,As and Sb) on structural,electronic, elastic and transport properties

ABSTRACT

We have studied the effect on the structural, electronic, elastic and transport properties of binary skutterudite CoX₃ (X?=?P, As, Sb) after filling void spaces by Pr atoms. All the calculations are carried out using the full-potential linearised augmented plane wave (FP-LAPW) method within the generalised gradient approximation (GGA) viz, PBE, and PBEsol. In case of binary skutterudites, equilibrium lattice parameters obtained using PBEsol functional are in good agreement with the theoretical and experimental results. The Hubbard parameter (U) has been used with PBEsol-GGA functional to see its effect on the band structures of binary and ternary compounds. Filling of Pr atoms at void positions in binary skutterudites creates the gap between the valence and conduction band. The obtained values of the elastic constants show that CoX₃, PrCo₄X₁₂ (X?=?P, As, Sb) are mechanically stable and brittle. Mechanically, PrCo₄P₁₂ and PrCo₄As₁₂ are anisotropic, but PrCo₄Sb₁₂ is isotropic. Obtained saturated Seeback coefficients are approximate ?60?μV/K (PrCo₄P₁₂), ?80?μV/K (PrCo₄As₁₂) and ?68?μV/K (PrCo₄Sb₁₂) in the spin-up channel while in the spin-down channel corresponding values are ?10, ?50 and ?120?μV/K at 800?K, respectively. These values are higher in magnitude than that in the corresponding binary compounds.     

Synthesis,physicochemical, and biological activities of novel N‐acyl tyrosine monomeric and Gemini surfactants in single and SDS/CTAB–mixed micellar system

A series of single‐chained N‐acyl tyrosine surfactants with varying chain lengths (C₁₀‐C₁₈) and degree of unsaturation, as well as an N‐acyl Gemini tyrosine surfactant with chain length C₁₂, were synthesized, and the structures were confirmed using spectral analysis. The effect of chain length and level of unsaturation on the physicochemical and antibacterial properties of the N‐acyl tyrosine surfactants was evaluated. The C₁₂ derivative displayed the optimum antibacterial activity among the single chain surfactants, and the presence of double bond in the oleoyl derivative enhanced the antibacterial activity over its saturated analogue. The N‐acyl Gemini surfactant displayed the highest antibacterial activity among the series and also showed greater micelle forming ability than its single chain analogue. Mixed micellar behavior of the N‐acyl Gemini surfactant with conventional cationic (CTAB) and anionic (SDS) surfactants in aqueous solution was studied. The negative value of the interaction parameter β₁₂ observed for the N‐acyl Gemini in binary mixture with CTAB surfactant indicated a synergistic interaction within the mixed micellar system. However, the binary mixture with SDS displayed antagonistic behavior. The binary mixture of N‐acyl Gemini surfactant with CTAB displayed better antibacterial activity and foaming properties than with SDS mixtures. Optimum antibacterial activity was observed for N‐acyl Gemini surfactant with mole ratio 0.4 to 0.6 in the CTAB binary mixture, at which the lowest ocular irritation index was observed. Overall, the study showed that the Gemini surfactant in combination with the conventional surfactant CTAB can be used as potential ingredients in detergent and pharmaceutical formulations.     

Modeling Sorption Behavior for Ethanol/Water Mixtures in a Cross-linked Polydimethylsiloxane Membrane Using the Flory-Huggins Equation

The sorption behaviors of aqueous ethanol solutions in a polydimethylsiloxane (PDMS) membrane at 25°C were investigated in this study. The sorption isotherms for the ethanol and water binary mixtures were experimentally determined. The water uptake reached a maximum at a concentration of 80 wt% ethanol, and the partial water uptakes were even higher than the pure water solubility for 10–95 wt% ethanol solutions in the PDMS membrane, which implies the presence of a strong synergistic effect due to the ethanol copermeant. The Flory-Huggins equation was utilized to predict the sorption levels at various ethanol/water compositions. The binary Flory-Huggins interaction parameters obtained from pure solvent sorption experiments (χ_iM ) and the ethanol/water vapor liquid equilibrium data (χ ₁₂) were used in the construction of the model for predicting the partial penetrant solubilities. Using constant χ_ij parameters could not render satisfactory predictions; therefore, concentration-dependent expressions for either χ ₁₂ or χ_iM were employed to improve the prediction power. We found that constant or concentration dependent χ ₁₂ parameters had little impact on the predicted sorption, whereas the modified concentration-dependent χ_iM values greatly improved the modeling precision.     

Solvatochromic and Preferential Solvation Studies on Schiff Base 1,4-Bis(((2-Methylthio)Phenylimino)Methyl) Benzene in Binary Liquid Mixtures

The solvatochromic behavior of the 1,4-bis(((2-methylthio) phenylimino)methyl) benzene [BMTPMB] in single solvents and binary mixtures were investigated. Fluorescence spectra show the dual emission due to twisted intramolecular charge transfer (TICT) state. The preferential solvation parameters: local mole fraction, X₂^L, solvation index δ_s2, exchange constant K₁₂ were calculated for the binary mixtures, ACN+MEOH, DMSO+CCl₄ and CCl₄+1,2 DCE. The dipole moment ratios between ground and excited states were deduced using the solvatochromic shifts of absorption and fluorescence spectra as a function of dielectric constant (ε), refractive index (n) and it was found to be 1.25.     

Effect of the humidity on the uptake of NO<Subscript>3</Subscript> on coatings composed of MgCl<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and MgBr<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and mixtures thereof with NaCl

The reactive uptake of NO₃ radicals on the surface of wetted individual X salts and of wetted X-NaCl salts (X = MgCl₂ · 6H₂O and MgBr₂ · 6H₂O) at [H₂O] = 2 × 10¹²−2 × 10¹⁵ cm⁻³ and NO₃ (4.8 × 10¹² cm⁻³) was studied using a reactor with a movable insert covered with a salt coating in combination with a mass spectrometer for monitoring the initial reactant and products. The probabilities of NO₃ uptake γ on X-NaCl binary salts as functions of the content of doping salt were determined. A parametric approximation of the experimental data was proposed, which makes it possible to quantitatively predict the extent of surface enrichment of a wetted binary salt coating in doping salt and its dependence on the humidity and the content of this salt in the binary mixture. It was established that the relative surface density σ_X of X doping salt depends on its mole fraction μ_X in the X-NaCl binary salt as σ_X = aμ_X (a = 2.2 for MgBr₂ and 13.1 for MgCl₂) over the entire humidity range covered. The contributions of the X salts to the overall uptake of NO₃ at NO₃ concentration typical of the tropospheric conditions ([NO₃] ∼ 10⁷ cm⁻³ and relative humidities of RH ≤ 20%) were estimated.     

Excess properties of Lennard-Jones binary mixtures from computer simulation and theory

Monte Carlo simulation and theory are used to calculate the excess thermodynamic properties of binary mixtures of spherical Lennard-Jones molecules. We study the excess functions of three binary mixtures characterized by the following size and dispersive energy ratios: (1) (σ₂₂/σ₁₁)³ = 2 and ?₂₂/?₁₁ = 2; (2) (σ₂₂/σ₁₁)³ = 1 and ?₂₂/?₁₁ = 1/2 and (3) (σ₂₂/σ₁₁)³ = 1/2 and ?₂₂/?₁₁ = 2. In all cases, the unlike size parameter, σ₁₂, is kept constant and equal to the value given by the Lorentz combining rule (σ₁₂ = (σ₁₁ + σ₂₂)/2). However, different unlike dispersive energy parameter values are considered through the following combining rules: (a) ?₁₂ = (?₁₁?₂₂)^1/2 (Berthelot rule); (b) ?₁₂ = ?₁₁ (association); and (c) ?₁₂ = ?₂₂ (solvation). The pressure and temperature dependence of the excess volume and excess enthalpy is studied using the NpT Monte Carlo simulation technique for all the systems considered. Additionally, the simplest conformal solution theory is used to check the adequacy of this approach in predicting the excess properties in a wide range of thermodynamic conditions and variety of binary mixtures. In particular, we have applied the van der Waals one-fluid theory to describe Lennard-Jones binary mixtures through the use of the Johnson et al. [1993, Molec. Phys., 78, 591] Helmholtz free energy. Agreement between simulation results and theoretical predictions is excellent in all cases and thermodynamic conditions considered. This work confirms the applicability of the van der Waals one-fluid theory in predicting excess thermodynamic properties of mixtures of spherical molecules. Furthermore, since binary mixtures of spherical Lennard-Jones molecules constitute the reference fluid to be used in perturbation theories for complex fluids, such as the statistical association fluid theory (SAFT), this work shows clearly the applicability of the conformal solution theory within the framework of SAFT for predicting excess functions.     

On the temperature dependence of the intensity of the induced absorption of oxygen in a region of the Herzberg photodissociation continuum in binary mixtures of oxygen with argon and nitrogen

Values of the binary absorption coefficient μ₁₂ in the induced Herzberg III band of oxygen for O₂-Ar and O₂-N₂ pairs have been obtained for the first time in the range 200–215 nm and in the temperature interval 295–120 K. It has been found that, as the temperature decreases, the binary absorption coefficient increases continuously: for O₂-Ar pairs, a marked increase in μ₁₂ starts immediately from room temperature, and, for O₂-N₂ pairs, it begins at temperatures below 180 K. As the temperature decreases from room temperature to 120 K, μ₁₂ increases roughly by 40 and 35% for O₂-Ar and O₂-N₂ pairs, respectively. For each type of pairs, the dependence μ₁₂(T) has been calculated with the use of the dipole moment function of the induced transition, taking into account both short-and long-range interactions, as well as the multiparametric isotropic potential of intermolecular interactions. It is shown that it is possible to select such parameters of the dipole moment function of the transition that the theoretical curve μ₁₂(T) describes satisfactorily the experimental data on the temperature dependence of μ₁₂ in the Herzberg III band for O₂-Ar and O₂-N₂ pairs in the whole temperature range under study.     

Static and vibrational properties of equiatomic Na-based binary alloys

The computations of the static and vibrational properties of four equiatomic Na-based binary alloys viz. Na_0.5Li_0.5, Na_0.5K_0.5, Na_0.5Rb_0.5 and Na_0.5Cs_0.5, to second order in local model potential is discussed in terms of real-space sum of Born von Karman central force constants. The local field correlation functions due to Hartree (H), Ichimaru-Utsumi (IU) and Sarkar et al. (S) are used to investigate the influence of the screening effects on the aforesaid properties. Results for the lattice constants C₁₁, C₁₂, C₄₄, C₁₂-C₄₄, C₁₂/C₄₄ and bulk modulus B obtained using the H-local field correction function have higher values in comparison with the results obtained for the same properties using IU- and S-local field correction functions. The results for the Shear modulus (C′), deviation from Cauchy's relation, Poisson's ratio σ, Young modulus Y, propagation velocity of elastic waves, phonon dispersion curves and degree of anisotropy A are highly appreciable for the four equiatomic Na-based binary alloys.     

Transport properties of a binary mixture of CO2ben N2 from the pair potential energy functions based on a semi-empirical inversion method

The potential energy surface of a CO₂-N₂ mixture is determined by using an inversion method, together with a new collision integral correlation [J. Phys. Chem. Ref. Data 19 1179 (1990)]. With the new invert potential, the transport properties of CO₂-N₂ mixture are presented in a temperature range from 273.15 K to 3273.15 K at low density by employing the Chapman-Enskog scheme and the Wang Chang-Uhlenbeck-de Boer theory, consisting of a viscosity coefficient, a thermal conductivity coefficient, a binary diffusion coefficient, and a thermal diffusion factor. The accuracy of the predicted results is estimated to be 2% for viscosity, 5% for thermal conductivity, and 10% for binary diffusion coefficient.     

Theory of the liquid-vapour interface of a binary mixture of Lennard-Jones fluids

We present results of calculations of the equilibrium surface tension and density profiles for the liquid-vapour interface of a binary mixture of Lennard-Jones 12-6 fluids. The calculations are based on a density-functional theory for the Helmholtz free energy of the inhomogeneous mixture. This is a ‘microscopic’ generalization of the van der Waals-Cahn-Hilliard theory for the interface of a binary mixture.

Our calculations cover the full range of liquid-vapour coexistence and the whole range of concentration. We find a correlation between the excess surface tension of the mixture and the surface segregation (adsorption) of the species with the lower surface tension. The ways in which segregation and excess surface tension depend on the Lennard-Jones parameters of the pure components are briefly discussed. Our results for the excess surface tension of mixtures of Ar and N₂ and Ar and CH₄ are compared with experiment; the agreement is reasonable.     

Structural studies of annealed neodymia-silica composite synthesized by solgel technique

Nd₂O₃-SiO₂ binary oxide was prepared by solgel technique using tetra-ethoxysilane and neodymium nitrate as precursor materials and HCl as a catalyst. The prepared samples were subjected to heat treatment in the temperature range from 600 to 1100 °C for different time duration. Characterization of heat treated samples was carried out by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The effect of sintering temperature and time on structural changes of Nd-doped silica has been discussed. The sample sintered at 1100 °C for 12 h shows the formation of monoclinic Nd₂O₃ nanocrystallites in silica matrix with average grain size ∼18 nm.     

A simulation study of rapid solidification and crystal configuration of Cu70Ni30 alloy

A molecular dynamics (MD) simulation study has been performed for the rapid solidification of Cu₇₀Ni₃₀ adopting the quantum Sutton-Chen many-body potentials. By analyzing the bond-types and the relation of atomic average energy versus temperature, it was demonstrated that as cooling rate being 2×10¹² K/s, the Cu₇₀Ni₃₀ formed fcc crystal structures and freezing point was found. In addition, having analyzed the transformation of microstructures and the detail of crystal growth by using atomic trace and visual method, not only could the formation of binary disordered solid solution be showed, but also the solidification of liquid metals and the crystal growth processes could be, further understood.     

Novel fabrication route for carbon-free and dense CuInSe2 (CIS) thin films via a non-vacuum process for solar cell application

Carbon-free CuInSe₂ (CIS) thin film with a dense microstructure has been prepared using a novel non-vacuum based fabrication route. Cu_xS_y and In₂Se₃ binary nanoparticles, approximately 10 nm in size, were synthesized by a low temperature colloidal process. The precursor film was deposited using the coating ink formulated with the binary nanoparticles and pyridine, and then annealed in the rapid thermal annealing (RTA) chamber at 540 °C for 15 min under selenium (Se) atmosphere. Scanning electron micrographs, X-ray diffraction patterns and Raman spectra showed a phase pure carbon-free and dense CIS thin film was prepared in this method. A solar cell device fabricated using this CIS thin film showed the following photovoltaic characteristics: V_OC = 350 mV, J_SC = 24.72 mA cm⁻², FF = 38.73% and η = 3.36% under standard AM 1.5 condition.     

Short-range order and pair correlations in a binary solid solution with a square lattice

Using the example of a disordered A _y B _{1 ? y} solid solution whose atoms are distributed over squarelattice sites, it is shown that correlations in the first coordination shell inevitably cause correlations in the second and more distant coordination shells. These induced correlations decay with distance extending to the ninth coordination shell in a square lattice. The induced correlations are calculated as a function of the correlation in the first coordination shell for binary solid solutions with various compositions. This dependence is described by a third-degree polynomial in the first-shell correlation to within the computational accuracy. The coefficients of the polynomial calculated in this paper using computer simulation can be useful in developing short-range order theory and in calculating the phase diagrams of binary solid solutions.     

A simulation study of rapid solidification and crystal configuration of Cu<Subscript>70</Subscript>Ni<Subscript>30</Subscript> alloy

A molecular dynamics (MD) simulation study has been performed for the rapid solidification of Cu₇₀Ni₃₀ adopting the quantum Sutton-Chen many-body potentials. By analyzing the bond-types and the relation of atomic average energy versus temperature, it was demonstrated that as cooling rate being 2×10¹² K/s, the Cu₇₀Ni₃₀ formed fcc crystal structures and freezing point was found. In addition, having analyzed the transformation of microstructures and the detail of crystal growth by using atomic trace and visual method, not only could the formation of binary disordered solid solution be showed, but also the solidification of liquid metals and the crystal growth processes could be, further understood.     

Pressure dependence of the mutual diffusion coefficients of the binary systems N2 + Ar, N2 + O2, O2 + Ar and Ar + Kr at 300 and 323 K

The Loschmidt technique has been used to measure the pressure dependence at two temperatures of the binary diffusion coefficients of the systems N₂-Ar, N₂-O₂, O₂-Ar and Ar-Kr; gas mixtures were analysed with a mass spectrometer. The results for the first three systems indicate that the first term of the Thorne-Enskog theory for moderately dense gases is not adequate to describe binary diffusion in these systems. Because the quantity (n$\text{D}$₁₂) is a linear function of the number density in all cases, higher order terms need not be considered.     

Microwave absorption investigation on the formation of YBa2Cu3O7−σ by a binary metal oxide route involving interaction of BaCuO2 and Y2Cu2O5

Low-field microwave absorption has been used to discriminate between the YBa₂Cu₃O_7?σ high temperature superconductor synthesized by reacting the binary metal oxides, BaCuO₂ and Y₂Cu₂O₅, versus synthesis with a single metal oxide route. This discrimination is more clearly seen by microwave absorption than by resistance measurements. Supplementary data was obtained by electron spin resonance in the g=2 region, scanning electron microscopy, thermal analysis and x-ray diffraction techniques. The scanning electron micrographs indicate a more separated granular structure for the material synthesized from the binary oxides. The low field non-resonant microwave absorption, which is characteristic of the superconducting phase, is twice as intense for the binary metal oxide preparation as compared to the single metal oxide preparation. Also, the superconducting transition temperature seems to be several degrees higher for the binary oxide preparation.     

A comparative study of non-polar solvents effect on dielectric relaxation and dipole moment of binary mixtures of mono alkyl ethers of ethylene glycol and of diethylene glycol with ethyl alcohol

Dielectric relaxation and dipole moment of binary mixtures of homologous series of mono alkyl ethers of ethylene glycol and of diethylene glycol, i.e., mono methyl, mono ethyl and mono butyl ethers of ethylene glycol (ROCH₂CH₂OH) and mono methyl, mono ethyl and mono butyl ethers of diethylene glycol (ROCH₂CH₂OCH₂CH₂OH) with ethyl alcohol (C₂H₅OH) of different concentrations were studied in dilute solutions of benzene, dioxane and carbon tetrachloride at 35 °C. Permittivity (ε′) and loss (ε″) at 10.1 GHz, static dielectric constant ε_o at 1 MHz and high frequency limiting dielectric constant ε_∞ = n_D² at optical frequency of these molecules and their binary mixtures at different concentration were measured in dilute solutions of non-polar solvents. The average relaxation time τ_o, relaxation times corresponding to overall molecular reorientation τ₁ and group rotations τ₂ were determined using Higasi's single frequency measurement equations for dilute solutions. The evaluated values of relaxation times and free energy of activation ΔF were used to explore the solvent effect on molecular dynamics of these polar binary systems in non-polar solvents. The excess inverse relaxation time and excess free energy of activation were determined to confirm the existence of hydrogen-bonded heterogeneous cooperative domains of the ethers and alcohol molecules at different concentration their binary mixtures in non-polar solvents. The dipole moment of the binary mixtures was evaluated using Higasi's and Guggenheim's equation for dilute solutions. The evaluated values of dipole moments and computed dipole moment values using a simple mixing equation of the polar molecules binary mixture were used to explore the effect of non-polar solvent environment on heterogeneous molecular interactions between ethers and alcohol molecules. The effect of number of carbon atoms in the molecular structure of these homologous series molecules was also considered for the interpretation of various evaluated dielectric parameters.     

Calculation of distribution functions for two-component rigid-sphere molecules of a fluid

Analytical expressions are derived and a computational algorithm and program for calculating distribution functions of rigid spheres g _ij (r) necessary for calculations of the thermodynamic parameters of a binary fluid mixture are developed in the context of perturbation theory using the procedure based on the inversion of the Laplace transform for functions rg _ij (r) obtained from the Percus–Yevick equation.     

非晶态FeCoSiB,FeSiB和FeB的微观结构X射线衍射分析

用X射线衍射方法分析非晶态合金Fe₅Co₇₀Si₁₅B₁₀,Fe₇₈Si_1OB₁₂和Fe₈₀B₂₀的结构,由测得的衍射强度数据计算了这些合金的结构因子和径向分布函数(RDF)。为得到二元非晶合金Fe₈₀B₂₀的部分径向分布函数(PRDF),用两个高斯型函数之和弥合Fe 关键词：