Vol 62, No 5 (2017)

Simple crystal forms are analyzed as the orbits of noncrystallographic point symmetry groups on a set of smooth or structured (“hatched”) planes of crystal space. Polyhedra with symmetrically equivalent faces, obtained using noncrystallographic point symmetry groups, are considered. All possible versions of simple forms for all noncrystallographic groups are listed in a unified table.

A combinatorial and topological modeling of 1D, 2D, and 3D packings of symmetrically linked A₄ tetrahedra has been performed. Three types of 1D chains with tetrahedra connectivities of 4, 6, and 8 were used to model 2D layers L-1, L-2, and L-3 and 3D frameworks FR-1, FR-2, FR-3, and FR-4. A family of tetrahedral structures with FR-1, FR-2, and FR-3 frameworks has been selected among the intermetallic compounds with chemical compositions of A₃B, A₂B₂, AB₃, A₂BC, AB₂C, and ABCD; this family includes more than 1900 compounds (TOPOS program package). It is found that the topological models of tetrahedral 3D frameworks are in correspondence with all types of the crystal structures formed in Au–Cu binary systems (FR-1 for Cu₃Au (auricupride), Cu₂Au₂ (tetraauricupride), and CuAu₃ (bogdanovite)), in the Mg–Cd system (FR-3 for Mg₃Cd, Mg₂Cd₂, and MgCd₃), in the Li–Hg system (FR-2 for Li₃Hg and Li₂Hg₂ and FR-3 for LiHg₃), in the Li–Ag–Al ternary system (FR-2 for LiAg₂Al and Li₂AgAl), and in the Li–Mg–Pd–Sn quaternary system (FR-2 for LiMgPdSn). Framework FR-4 has been established in ternary intermetallic compounds A(Li₂Sn₂); A = Cu, Ag, Au.

A complex study of the structure of β-boron single crystal grown by the floating-zone method, with sizes significantly exceeding the analogs known in the literature, has been performed. The study includes X-ray diffraction analysis and X-ray diffractometry (measurement of pole figures and rocking curves), performed on both laboratory and synchrotron sources; atomic-resolution scanning transmission electron microscopy with spherical aberration correction; and energy-dispersive microanalysis. X-ray diffraction analysis using synchrotron radiation has been used to refine the β-boron structure and find impurity Si atoms. The relative variations in the unit-cell parameters a and c for the crystal bulk are found to be δa/a ≈ 0.4 and δc/c ≈ 0.1%. X-ray diffractometry has revealed that the single-crystal growth axis coincides with the [\(2\bar 2013\)] crystallographic axis and makes an angle of 21.12° with the [0001] threefold axis. Electron microscopy data have confirmed that the sample under study is a β-boron crystal, which may contain 0.3–0.4 at % Si as an impurity. Planar defects (stacking faults and dislocations) are found. The results of additional measurements of the temperature dependence of the thermal conductivity of the crystal in the range of 50–300 K are indicative of its high structural quality.

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α_V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.

The possibilities of low-voltage scanning electron microscopy for visualization of specific features of the microstructure in internal layers of multilayer polymer films are demonstrated by the example of “chitosan–polyelectrolyte complex–alginic acid” composite. The process of electron beam interaction with a sample at low electron energies is considered. The key parameters of low-voltage electron microscopy, which make it possible to increase the resolution of SEM images of polymer systems, are discussed.

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [U^VIO₂(C₃H₇NO)₅](ClO₄)₂ (I) and [U^IV(C₃H₈N₂O)₄(Н₂О)₄](ClO₄)₄ (II), where C₃H₇NO is N,N-dimethylformamide (Dmfa) and C₃H₈N₂O is N,N-dimethylcarbamide (a-Dmur), were studied by X-ray diffraction. Complex II and the complex U^IV(s-Dmur)₄(Н₂О)₄(ClO₄)₄ (III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO₂(Dmfa)₅]²⁺ and [U(Dmur)₄(Н₂О)₄]⁴⁺ groups as uranium-containing structural units belonging to the crystal-chemical groups AМ₇¹ (А = U^VI, М¹ = O^2– and Dmfa) and AМ₈¹ (А = U^IV, М¹ = Dmur and Н₂О) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

Cobalt nanotubes have been synthesized by electrochemical deposition in pores of ion track membranes. The structures obtained have been studied by scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction analysis, and gas permeability method. The influence of electron irradiation on the cobalt nanotube structure has been investigated. It is shown that an increase in the irradiation dose leads to the transformation of the sample crystal structure. This fact can be explained by the simultaneous reduction of the β-Co metastable phase and relaxation of the microstress formed by the fcc phase in the lattice. The degree of sample texturing along the [100] direction increases under electron irradiation. The dependences of the resistive and magnetic properties of cobalt nanotubes on the irradiation dose have been analyzed.

The new model of thresholdless distortion of the orientational structure in a homeotropic layer of nematic liquid crystal with free ends in ultrasonic field has been experimentally substantiated for the first time. The model is constructed within the concepts of nonequilibrium thermodynamics and statistical hydrodynamics of liquid crystals for the frequency range in which the elastic and viscous wavelengths are, respectively, longer and shorter than the layer thickness. The main regularities of the phenomenon, which relate the conditional effect threshold to the ultrasonic frequency and layer thickness, have been established based on the experimental data for (20–150)-μm-thick layers in the frequency range of 0.1–9 MHz. These data are compared with the results of numerical calculations, performed taking into account two mechanisms of liquid crystal structure distortion (convective and nonlinear relaxation ones).

A complex study of the (001) cleavage surface of a V₂O₅ single crystal annealed in vacuum at 450 and 550°C has been performed. Tunnel microscopy of the sample surface annealed in vacuum at 550°C showed the formation of a plane with a corundum structure, reconstructed according to the V₂O₃ (0001)-(1/√3 × 1/√3)R30° type, on the surface. X-ray photoelectron spectroscopy revealed a significant modification of interatomic bonds in the surface layers of V₂O₅ single crystal after vacuum annealing at 550°C, which is related to the partial reduction of V⁵⁺ ions and formation of lower vanadium oxides. These modifications lead to a decrease in the electrical resistivity of V₂O₅ and the occurrence of bending at a temperature of 61.5°С in the temperature dependence of the sample resistance, which is indicative of phase transition.

Thin Ga₂Se₃ layers deposited on silicon substrates with the (100), (111), and (123) orientations are studied by transmission electron microscopy and X-ray microanalysis. Some features and regularities of the stoichiometric gallium vacancy ordering at different substrate orientations are discussed. The Ga₃Se₄(100)с(2 × 2) and Ga₂Se₃(111)(√3 × √3)-R30° ordered structures are formed on the Si(100) and Si(111) surfaces, respectively.

Nanocomposites based on butadienenitrile rubber (butadiene copolymer with 28% acrylonitrile) with functional titania nanoparticles of different nature have been obtained, and their complex study by X-ray diffractometry, small-angle X-ray scattering, scanning electron microscopy, electron probe X-ray microanalysis, and X-ray energy-dispersive spectroscopy has been performed. Differences in the morphology and composition of the surface and transverse cuts of nanocomposites in dependence of nanoparticle characteristics are established. It is found that the nanocomposites with the largest crystallite sizes have the lowest viscosity. It is also revealed that the nature of titania nanoparticles barely affects the vulcanization kinetics, and that the optimal vulcanization time for the composites is 25 min. Uniaxial extension tests have shown that nanocomposites with the best properties can be fabricated by introducing amorphous titania into the polymer (butadienenitrile rubber).

Specific features of the crystallization of calcium oxalates (CaC₂O₄) in the presence of amino acids have been established based on thermodynamic and experimental modeling. Phase formation in the Ca²⁺–C₂O₄^2-–H₂O–amino acid system in a wide range of variation in the component concentrations and solution pH have been theoretically investigated. The influence of pH on the thermodynamic stability of crystallizing compounds is considered. The effect of amino acids of different structures on the formation of the CaC₂O₄ solid phase in a prototype of physiological solution is analyzed. The kinetic crystallization parameters (induction period and rate constant) and crystallite growth are determined.

Huber-5042 diffractometer with a closed-cycle Displex DE-202 helium cryostat is a unique scientific instrument for carrying out X-ray diffraction experiments when studying the single crystal structure in the temperature range of 20–300 K. To make the service life longer and develop new experimental techniques, the diffractometer control is transferred to a new hardware and software platform. To this end, a modern computer; a new detector reader unit; and new control interfaces for stepper motors, temperature controller, and cryostat vacuum pumping system are used. The system for cooling the X-ray tube, the high-voltage generator, and the helium compressor and pump for maintaining the desired vacuum in the cryostat are replaced. The system for controlling the primary beam shutter is upgraded. A biological shielding is installed. The new program tools, which use the Linux Ubuntu operating system and SPEC constructor, include a set of drivers for control units through the aforementioned interfaces. A program for searching reflections from a sample using fast continuous scanning and a priori information about crystal is written. Thus, the software package for carrying out the complete cycle of precise diffraction experiment (from determining the crystal unit cell to calculating the integral reflection intensities) is upgraded. High quality of the experimental data obtained on this equipment is confirmed in a number of studies in the temperature range from 20 to 300 K.

The efficiency of the synthesis and application of metal/nonmetal particles several nanometers in size, prepared in solutions and stabilized with polymers, can be increased by applying a reliable statistical analysis and determining particle-size distributions for different systems. A new method for processing electron microscopy images of nanoparticles ≤10 nm in size and the program Analyzer of Nanoparticles designed for rapid recognition and measurements are presented. The program combines two approaches: threshold image processing for particle recognition and fitting the model of the particles with neighborhood background to the real experimental images.