First-principles study of electronic structure and elasticity of UAlx (x=1,2,3) system

A detailed theoretical study of structural, electronic, and elastic properties of cubic UAl_x (x=1,2,3) is presented employing the pseudopotential plane-wave method based on density-functional theory. The structure parameters of these three compounds have been calculated within generalized gradient approximation (GGA) and local density approximation (LDA). The calculated results were compared with the experimental data and previous research. With the GGA approximation, the elastic constants, shear modulus, Young's modulus, and Poisson's ratio of UAl_x (x=1,2,3) are derived. According to the generalized mechanical stability criteria for cubic crystals, our calculation suggested that C15 UAl₂ and L12 UAl₃ are stable substance under hydrostatic pressures, but B2 UAl might be expected as a metastable compound, which is not reported in previous literature, and future experimental confirmation is needed. Furthermore, the calculated energy band structure and density of state (DOS) are found to be in good agreement with the theoretical values. Additionally, the charge density of these compounds have also been worked out and analyzed.     

Al-Cr-Cu三元合金系相图的室温截面

本文用X射线粉末衍射法研究了Al-Cr-Cu三元合金系相图的室温截面。截面中出现了五个新相,称为ω₁,ω₂,ε_f,ε_x和γ_x,即共有19个单相区,41个双相区以及22个三相区。γ_x相属正交晶系,它可能是一个固定成分的化合物。 关键词：     

Valence instability of uranium in U(Al1−x Gex)3

The electronic structure of U and Ge in the solid solutions U(Al_1−x Ge_x)₃ is investigated by measuring x-ray line shifts. It is shown that uranium has the mixed valence U³⁺ [Rn](5f ³)-U⁴⁺ [Rn](5f ²) over the entire composition range (0⩽x⩽1) and that the population of the uranium 5f shell increases by ∼0.28 5f electrons/U atom from UAl₃ (x=0) to UGe₃ (x=1). The electronic structure of Ge is close to the electronic structure of Ge metal over the entire composition range 0<x⩽1. No variation of the population of the Ge 4p shell is detected to within the experimental error (∼0.1 4p electrons/Ge atom) as the composition varies from x=0.2 to 1. It is established that the delocalization of a U 5f electron occurs as a result of its transition to the s or d band of the same uranium atom. Fiz. Tverd. Tela (St. Petersburg) 39, 1505–1508 (September 1997)     

Anomalous hall effect in some uranium intermetallic compounds

We report Hall effect measurements on the uranium intermetallic compounds UAl₂, U_0.97La_0.03Al₂, U_0.93La_0.07Al₂, U_0.85La_0.15Al₂, UPt₃ and UPd₃. We find in all of these substances, a large positive Hall effect at high temperatures and maxima or minima at low temperatures. We have compared our data with the results of magnetic skew scattering theories and found qualitative agreement at high temperatures in the cases of U_1-xLa_xAl₂ and UPt₃, but not in the case of UPd₃.     

Application of transmission electron microscopy for studying phase relations in the bismuth-rich region of the Ba-Bi-O system

The crystal structure and cation composition of oxides of the Ba-Bi-O system in the composition range 80–100 mol % BiO_1.5 have been investigated by the methods of transmission electron microscopy. Ordered phases of the compositions Ba: Bi = 2: 9, 1: 6, and 1: 15 with a rhombohedral structure have been revealed. In the range of the compositions Ba: Bi from 1: 36 to 1: 46, phases with triclinic, monoclinic, and cubic structures have been found. The monoclinic and cubic phases have structures similar to the structures of the α and γ modifications of bismuth oxide Bi₂O₃, respectively. Phase formation was found to be dependent on the following parameters: annealing temperature, partial oxygen pressure, oxygen content in the initial pairs of reacting components (BaO₂-Bi₂O₃, Ba(NO₃)₂-Bi₂O₃, BaCO₃-Bi₂O₃), and crucible material (alundum or platinum).     

A method for determination of higher-order magnetic anisotropy constants — Importance of the cubic K3 and K4 for certain energy levels models

A method for determination of magnetocrystalline anisotropy constants of arbitrary order is proposed. The method is based on a least squares fitting of a phenomenological anisotropy energy for a given symmetry truncated at an arbitrary order term to a theoretical anisotropy energy computed exactly for a given energy level model. Several applications of the method to cubic systems are considered. The study reveals that the widely used expressions in the literature for the cubic constants K₁ and K₂ in terms of free energy for the three symmetry direction are of rather limitedvalidity only. The higher-order cubic constants K₃, K₄ and K₅ are determined besides the usual K₁ and K₂ in temperature range 0 to 300 K. The importance of the higher- order terms with respect to the first term in the cubic anisotropy energy is discussed. The results show that the cubic constants K₃ and K₄ cannot be neglected for most of the energy level models studied at certain temperatures.     

The anharmonic force field and equilibrium structure of methane

The anharmonic force field of methane has been refined to fit spectroscopic data from the isotopic species ¹²CH₄, ¹³CH₄, ¹²CH₄, ¹²CH₃D, ¹²CHD₃ and ¹²CH₂D₂. Six of the thirteen cubic force constants have been determined experimentally, the remaining cubic constants being fixed at values derived from ab initio calculations. The quartic force field is very crude, in that only f_rrrr has been refined. It is concluded however that the cubic and quartic force fields, even though they are subject to limitations, provide a considerable improvement in the experimental determination of the r _e structure and the quadratic force field. The equilibrium bond length is found to be r _e(CH) = 1·085₈ ± 0·001 Å.     

Structural transformation in Mg2NiH4

X-Ray diffraction measurements show that on heating Mg₂NiH₄ in a 1 atm pressure H₂ atmosphere, above ～250°C it transforms into a cubic structure, metal atoms in CaF₂ arrangement, a = 6.525 Å. It is concluded that the H atoms are in tetrahedral clusters, and that the structure is only weakly ionic. This conclusion is also supported by NMR measurements. The 20°C structure of Mg₂NiH₄ is shown to be describable primarily as a slight monoclinic distortion of the cubic unit cell; a = 6.594 Å, b = 6.412 Å, c = 6.490 Å and β = 93.1°. However, weak small angle lines show that a longer range order exists and that the true unit cell, which we have not determined, must be very large. To what extent the cubic phase should be considered a high temperature and/or low concentration (Mg₂NiH_4??) phase is not resolved.     

Crystal and Magnetic Structures of Granular Powder Spinel Mn–Zn and Ni–Zn Ferrites

Some specific features of the crystal and magnetic structures of granular powder spinel-like ferrites Mn_0.160Mg_0.404Zn_0.448Fe₂O₄, Mn_0.676Zn_0.227Fe_0.09Fe₂O₄, Mn_0.5792Zn_0.2597Fe_0.1612Fe₂O₄, and Ni_0.32Zn_0.68Fe₂O₄ have been studied by neutron diffraction. It has been established that the crystal structure of all the studied compounds has a cubic symmetry with space group Fd\(\bar 3\)m. Ferrimagnetic ordering is observed in all the studied structures. Based on the experimental data, the unit cell parameters and interatomic bond lengths of the studied compounds are determined alongside with the distribution of cations between octahedral and tetrahedral crystallographic positions in their cubic crystal structure. Corresponding average magnetic moments are calculated for different positions in their cubic structure. Some structural mechanisms of the formation of magnetic properties depending on the level of doping and the size of powder grains are discussed.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Mössbauer Study of Ferrite-garnets as Matrixes for Disposal of Highly Radioactive Waste Products

Mössbauer study of synthesized ferrite-garnet samples containing Zr, Th, Ce and Gd of the following composition: 1C – Ca_{2, 5} Ce_{0, 5} Zr₂ Fe₃ O₁₂, 2C – Ca_{1, 5} GdCe_{0, 5} ZrFeFe₃ O₁₂, 1T – Ca_{2, 5} Th_{0, 5}Zr₂ Fe₃ O₁₂ and 2T – Ca_{1, 5} GdTh_{0, 5} ZrFeFe₃ O₁₂ are carried out. As a result of ⁵⁷Fe Mössbauer study it is found that iron atoms in all investigated samples of garnets are in a trivalent state. The analysis of experimental Mössbauer spectra definitely specifies a various structural state of iron atoms in two investigated groups of samples: 1T, 1C and 2T, 2C. X-ray study have shown that 1T and 1C garnet samples crystallize in tetragonal space group I4₁/acd, but 2T and 2C samples crystallize in cubic space group Ia3d.     

Photoluminescence investigations of cubic boron nitride doped with neodymium during high-pressure synthesis

Micropowders of cubic boron nitride doped with neodymium are prepared under high-pressure and high-temperature conditions. The phase composition of the micropowders is studied using X-ray diffractometry and X-ray fluorescence analysis. The photoluminescence, photoluminescence excitation spectra, and the life-time of the ⁴ F _3/2 excited state of Nd ions introduced into cubic boron nitride are investigated. In photoluminescence spectra of the micropowders, structured bands are recorded in the range of the ⁴ F _3/2 → ⁴ I _9/2 and ⁴ F _3/2 → ⁴ I _11/2 electronic transitions. A higher intensity of the first structured band indicates that the corresponding photoluminescence in cubic boron nitride doped with neodymium is excited by the “three-level scheme.” It is demonstrated that an increase in the concentration of the neodymium compound in the growth batch leads to the formation of two luminescence centers Nd1 and Nd2 formed by neodymium ions located in different low-symmetry crystal fields in the micropowders. This is confirmed by X-ray diffraction investigations and the study of the photoluminescence decay curves. The ⁴ F _3/2 short-lived state is assigned to the Nd ions forming the Nd1 centers, and the long-lived state is attributed to the Nd ions forming the Nd2 centers.     

Investigation of hyperfine quadrupole interactions in UGe<Subscript>2</Subscript> and UAl<Subscript>2</Subscript> compounds on <Superscript>111</Superscript>Cd probe nuclei by the perturbed angular correlation method

The parameters of nuclear quadrupole hyperfine interaction in intermetallic UGe₂ and UAl₂ compounds have been measured in a temperature range of 100–300 K using the perturbed angular γγ correlation method on ¹¹¹Cd probe nuclei. The results obtained for UGe₂ indicate a pronounced anisotropic character in the distribution of f electrons in agreement with the calculation of the electronic structure of this compound. The hybridization degree between f electrons of U and p electrons of Al in UAl₂ is lower than the hybridization degree between f electrons of U and p electrons of Ge in UGe₂.     

Mechanical properties,anisotropy and hardness of group IVA ternary spinel nitrides

In this work, new ternary cubic spinel structures are designed by the substitutional method. The structures, elasticity properties, intrinsic hardness and Debye temperature of the cubic ternary spinel nitrides are studied by first principles based on the density-functional theory. The results show that γ-CSn₂N₄, γ-SiC₂N₄, γ-GeC₂N₄ and γ-SnC₂N₄ are not mechanically stable. The elastic constants C_ij of these cubic spinel structures are obtained using the stress–strain method. Derived elastic constants, such as bulk modulus, shear modulus, Young's modulus, Poisson coefficient and brittle/ductile behaviour are estimated using Voigt–Reuss–Hill theories. The B/G value, the Poisson's ratio and anisotropic factor are calculated for eight ternary stable crystals. Based on the microscopic hardness model, we further estimate the Vickers hardness of all the stable crystals. From the calculated hardness of the stable group IVA ternary spinel nitrides by Gao's and Jiang's methods, it is observed that the stable group IVA ternary spinel nitrides are not superhard materials except for γ-CSi₂N₄. Furthermore, the Debye temperature for the eight stable crystals is also estimated.     

Spontaneous Polarization and Its Effect on the Physical Characteristics of Isomorphic KDP-Crystals

KDP ferroelectrics are isomorphic crystals of potassium, rubidium, cesium dihydrogen phosphates and arsenates: KH₂PO₄, RbH₂PO₄, CsH₂PO₄,KH₂AsO₄, RbH₂AsO₄, CsH₂AsO₄ and their deuterated (partially or fully) analogs. The substitution of protium by deuterium leaves the regularities of their physical properties unaffected. The study of KDP-crystals is of obvious interest. These crystals are widely used in laser technology. Their physical properties are described in [1–5], where a thermodynamical theory of ferroelectrics of various structures is also discussed. The results of the statistical theory of KDP-crystals are discussed on the basis of molecular-kinetic representations which account for and substantiate their physical properties. It is found that the phase transition from a para- to a ferrophase is the transition of the ordering type [1–5] since the crystals undergo dipole and deformation ordering. An early statistical theory of dipole ordering was developed for crystals possessing cubic structures [9] of the perovskite BaTiO₃ (or Fe₃AIC) type and those of the ReO₃ (or Cu₃N) type [6–8].     

Characterization of Ni–Cu mixed spinel ferrite

Crystal structure, X-ray density, porosity, compressive strength of Ni_1−xCu_xFe₂O₄ have been investigated along with scanning electron microscopy (SEM) to study the effect of composition and microstructure on the magnetic and electrical properties. The formation of single-phase ferrite is confirmed by the X-ray diffraction. Tetragonal deformation is observed for the sample of composition x=1, i.e. for pure CuFe₂O₄ Crystal structure for samples of other compositions are face centered cubic (FCC). SEM micrographs exhibit increase in grain size with the increase of copper content. Compressive strength decreases with the increase of Cu. Initial magnetic permeability and saturation magnetization is maximum for the composition of x=0.2, i.e. for Ni_0.8Cu_0.2Fe₂O₄, which can be attributed to the maximum sintered density obtained for this composition. Resistivity decreases with the increase of Cu content.     

Rare earths in UAl2: quenching of spin fluctuations?

Experimental results involving the substitution of U atoms by Gd and Dy in the spin fluctuation system UAl₂ are studied in terms of the theory proposed by Doniach and Wohlfarth. Besides the intraband f-f Coulomb interaction, the model contains the Zener coupling between localized 4f spins and itinerant 5f states. The induced effective f-f interaction increases the proximity to a magnetic instability.     

On the existence of a homologous series of BamCum+nOy oxides with the cubic structure of the BaCuO2 oxide

Phase relations have been studied in the BaO–CuO_x system in the range of 42.0–83.0 mol.% CuO at P(O₂) = 21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis (TGA), chemical analysis (CA), and electron diffraction (ED) with simultaneous elemental analysis (EA) in a transmission electron microscope (TEM). The existence of discrete crystallization fields of barium–copper oxides of cation compositions Ba₄Cu₅O_y, Ba₅Cu₆O_y, Ba₇Cu₈O_y, Ba₁₂Cu₁₃O_y, and Ba₂₄Cu₂₅O_y, which have the cubic structure of the BaCuO₂ oxide, is revealed in the studied region of the system. The oxides may be represented as members of a Ba_mCu_m+nO_y homologous series. The BaCuO₂ oxide does not exist in the subsolidus region and does not have its own crystallization field. The oxygen-deficient oxide BaCuO_1.78 of the cation composition (Ba:Cu) 1:1 with the BaCuO₂ cubic structure is found in melted samples of the 50.0 mol.% CuO composition quenched at 1020–1060 °С.     

Weak segregation theory and non-conventional morphologies in the ternary ABC triblock copolymers

The statistical theory of microphase separation in the ternary ABC triblock copolymers is presented and the corresponding phase diagrams are built both for the linear and miktoarm copolymers. For this purpose the Leibler weak segregation theory in molten diblock copolymers is generalized to multi-component monodisperse block copolymers with due regard for the 2nd shell harmonics contributions defined in the paper. The Hildebrand approximation for the χ-parameters is used. The physical meaning of this and alternative choices for the χ-parameters is discussed. The symmetric A_fB_1-2fC_f copolymers with the middle block non-selective with respect to the side ones are shown to undergo the continuous ODT not only into the lamellar phase but also, instead, into various non-conventional cubic phases (depending on the middle block composition it could be the simple cubic, face-centered cubic or non-centrosymmetric phase, which reveals the symmetry of I4₁ 32 space group No. 214 first predicted to appear in molten block copolymers). For asymmetric linear ABC copolymers a region of compositions is found where the weakly segregated gyroid (double gyroid) phase exists between the planar hexagonal and lamellar or one of the non-conventional cubic phases up to the very critical point. In contrast, the miktoarm (star) ABC block copolymers with one of its arm non-selective with respect to the two others are shown to reveal a pronounced tendency towards strong segregation, which is preceded by increase of stability of the conventional BCC phase and a peculiar weakly segregated BCC phase (BCC₃), where the dominant harmonics belong to the 3rd coordination sphere of the reciprocal lattice. The validity region of the developed theory is discussed and outlined in the composition triangles both for linear and miktoarm copolymers. We present also the list of the 2nd shell harmonics (SAXS reflections) allowed and prohibited in some of the non-conventional morphologies due to the weak segregation considerations and comparison of our results with the preceding SCFT treatment of the ABC copolymers by Matsen.     

Crystal structure analysis of novel complex hydrides formed by the combination of LiBH4 and LiNH2

Combination of LiBH₄ and LiNH₂ by ball milling forms the series of novel complex hydrides Li₂BNH₆, Li₃BN₂H₈ and Li₄BN₃H₁₀, depending on the combination ratios. The crystal structure of Li₄BN₃H₁₀ analyzed by synchrotron X-raydiffraction measurements is determined to be a cubic system (space group: I2₁3) with the lattice constant of a=10.673(2)Å. It should be emphasized that Li₄BN₃H₁₀ is an ionic crystal which is composed of a lithium cation Li⁺ and two different kinds of the complex anion [BH₄]^- and [NH₂]^-. These anions are located in the vertex and face-center of the cubic sub-lattice, and the lithium cation Li⁺ in the interstitial site between the anions, respectively. The other series of complex hydrides, Li₂BNH₆ and Li₃BN₂H₈, are also predicted to possess similar structures composed of a lithium cation Li⁺ and two different kinds of the complex anion [BH₄]^- and [NH₂]^-.