Vol 61, No 2 (2016)

An empirical formula is derived to describe the quasi-periodic structure of a layer of porous aluminum oxide obtained by anodization. The formula accounts for two mechanisms of the transition from the ordered state (2D crystal) to the amorphous state. The first mechanism infers that vacancy-type defects arise, but the crystal lattice remains undestroyed. The second mechanism describes the lattice destruction. The radial distribution function of the pores in porous aluminum oxide is obtained using the Bessel transform. Comparison with a real sample is performed.

The W–Al₂O₃ system at T = 2400 K and standard pressure (controlled Ar + H₂ atmosphere) has been calculated by stochastic simulation. It is shown that the presence of hydrogen leads to the formation of aluminum hydrides, hydrogen oxides, and aluminum hydroxides; the compounds from the two latter groups (except for water) can interact directly with tungsten. The main chemical reactions occurring in the system are determined, based on which a conclusion about the cyclic character of the processes is drawn. Some recommendations on the composition and pressure of controlled atmosphere for growing sapphire crystals are given.

A comprehensive analysis of the evolution of the structural and superconducting properties of FeSe crystals stored in air for several years has been performed. It is established that the structure and phase composition of the samples remained invariable, while the superconducting parameters significantly degraded. These changes may be due to the stress relaxation or redistribution of defects in the samples.

Mathematical modeling of the distribution of Ga and Sb impurities in homogeneous (with respect to the content of the main components) single crystals of Ge–Si alloys, grown by double feeding of the melt, has been performed in the Pfann approximation. It is shown that the axial gradient of impurity concentration in Ge–Si crystals can be controlled in wide limits by changing the ratio of crystallization rate and the rates of feeding of the melt by silicon and germanium rods. The conditions for growing alloy single crystals, homogeneous both with respect to the content of the main components and to the impurity concentration distribution, have been determined.

The role of glide planes in the organization of structures is shown based on a crystallographic analysis of the monoclinic structures of TlAs₃S₅ and Tl₂(As,Sb)₃S₁₃ sulfides. In the first structure, cations and anions form systems (with identical geometries) of two face-centered sublattices, linked by the c plane, with the effect of unified “two-dimensional” (2D) ordering. The second structure, exhibiting signs of order–disorder (OD) type, is interpreted as a superposition of two noncentrosymmetric components with independent cation and anion sublattices, which, however, also form a regular 2D order due to the n plane. The stabilizing role of Tl cations in the geometry of cation matrices is indicated.

A method of tuning (scanning) X-ray beam wavelength based on modulation of the lattice parameter of X-ray optical crystal by an ultrasonic standing wave excited in it has been proposed and experimentally implemented. The double-crystal antiparallel scheme of X-ray diffraction, in which an ultrasonic wave is excited in the second crystal, is used in the experiment. The profile of characteristic line k_α1 of an X-ray tube with a molybdenum anode is recorded using both the proposed tuning scheme and conventional mechanical rotation of crystal. The results obtained by both techniques are in good agreement.

The unit-cell parameters of dodecaboride LuB₁₂, which undergoes a transition to the cage-glass phase, have been determined for the first time in the temperature range of 50–75 K by X-ray diffraction, and the single-crystal structure of this compound is established at 50 K. Nonlinear changes in the unit-cell parameters correspond to anomalies in the physical properties near the glass-transition temperature T* ~ 50–70 K. This compound has cubic symmetry at room temperature, and it is reduced to tetragonal symmetry at lower temperatures. Based on the X-ray diffraction data and relying on the physical properties of the crystals, the structure model, in which a small part (~15%) of Lu atoms are displaced from the 2a sites at the centers of the B₂₄ cuboctahedra to the 16n sites of sp. gr. I4/mmm, seems preferable.

The single-crystal structure of cooperite, a natural platinum sulfide PtS, is studied by X-ray diffraction supported by high-resolution scanning transmission electron microscopy and X-ray spectrum microanalysis. It is found that, in addition to the main reflections corresponding to the known tetragonal cell (a = 3.47 and c = 6.11 Å; space group P4₂/mmc), many weak reflections with intensities I ≤ 60σ(I) are clearly observed. These reflections fit the tetragonal cell (space group I4/mmm) with doubled parameters. In structures with small (P4₂/mmc) and large (I4/mmm) cells, the S atoms occupy statistically two special positions. It is shown that the chemical composition of the cooperite crystals deviates from the stoichiometric composition: sulfur-deficient specimens predominate.

The synthesis and X-ray diffraction study of compound {[Ag₂Ge(НCit)₂(H₂O)₂] ∙ 2H₂O}_n, where H₄Cit is the citric acid, are performed. In the polymeric structure, the НCit^3– ligand fulfils the tetradentate chelate–μ₄-bridging (3Ag, Ge) function (tridentate with respect to Ge and Ag atoms). The Ge atom is octahedrally coordinated by six O atoms of two HCit^3–ligands. The coordination polyhedron of the Ag atom is an irregular five-vertex polyhedron [four O atoms of four HCit^3– ligands and the О(Н₂О) atom]. An extended system of О–Н···О hydrogen bonds connects complex molecules into a supramolecular 3D-framework.

Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato) aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H₂O)₃N(CH₂PO₃H)₃] is composed of linear coordination polymers and belongs to sp. gr. P2₁/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na₄[Ni(H₂O)N(CH₂PO₃)₃] ∙ 11H₂O has an island dimeric chelate structure and belongs to sp. gr. С2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond.

The title compound, 2-(thiophen-2-yl)-1-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)ethenyl] benzamide:N,N-dimethylformamide (1: 1), (C₁₅H₁₁N₃O₂S₂ · C₃H₇NO), was synthesized, and its structure was established by spectral analysis and X-ray diffraction studies. The compound crystallizes in the monoclinic space group P2₁/n with a = 10.8714(7), b = 9.0497(5), c = 19.8347(13) Å, β = 91.093(5)°, Z = 4. The crystal structure is stabilized by N–H···S, C–H···O and N–H···O hydrogen bonds. The π···π interactions are also observed between the rings.

The crystal structure of the title compound, C₁₄H₁₂N₂O₃, was recently determined as a mixture of its neutral (OH containing) and zwitterionic (NH containing) forms, in a 0.60 (4): 0.40 (4) ratio using the X-ray determination. In this study, the title compound has been characterized by FT-IR and X-ray diffraction. The redetermination showed that the title compound has only enol (OH) form because of lack of the NH stretching vibration in FT-IR spectrum. In addition, the molecular structure and tautomerism of the title compound have been discussed.

Purine nucleoside phosphorylases (PNPs) catalyze the reversible phosphorolysis of nucleosides and are key enzymes involved in nucleotide metabolism. They are essential for normal cell function and can catalyze the transglycosylation. Crystals of E. coli PNP were grown in microgravity by the capillary counterdiffusion method through a gel layer. The three-dimensional structure of the enzyme was determined by the molecular-replacement method at 0.99 Å resolution. The structural features are considered, and the structure of E. coli PNP is compared with the structures of the free enzyme and its complexes with purine base derivatives established earlier. A comparison of the environment of the purine base in the complex of PNP with formycin A and of the pyrimidine base in the complex of uridine phosphorylase with thymidine revealed the main structural features of the base-binding sites. Coordinates of the atomic model determined with high accuracy were deposited in the Protein Data Bank (PDB_ID: 4RJ2).

The bidomain structures produced by light external heating in z-cut lithium niobate and lithium tantalate single crystals are formed and studied. Interdomain regions about 200 and 40 μm wide in, respectively, LiNbO₃ and LiTaO₃ bidomain crystals are visualized and studied by optical microscopy and piezoresponse force microscopy. Extended chains and lines of domains in the form of thin layers with a width less than 10 μm in volume, which penetrate the interdomain region and spread over distances of up to 1 mm, are found.

Experimental samples of solid solutions of the (1–x)BiFeO_3–xPbFe_0.5Nb_0.5O₃ (0.00 ≤ x ≤ 1.00, Δx = 0.025–0.05) system have been prepared according to the conventional ceramic technology. Their structural and dielectric characteristics have been studied. A phase diagram of the system at room temperature has been plotted taking into account the crystallochemical specificity, spatial inhomogeneity, and structural imperfection of the samples. This diagram is characterized by the presence of solid substitutional and interstitial solutions; the formation of concentration ranges with a dominant role of BiFeO₃ and PbFe_0.5Nb_0.5O₃; the presence of five single-phase regions, two regions of coexistence of phase states, and three morphotropic regions; and the formation of six regions with a constant experimental unit-cell volume. Correlations between the structural characteristics and dielectric properties of the ceramics under study have been established.

Electrical conductivity σ of ScF₃ single crystals (sp. gr. \(Pm\overline 3 m\), ReO₃ structure type) has been studied by impedance spectroscopy and compared with the electrical conductivity of rare earth HoF₃ (β-YF₃ type) and LaF₃ (tysonite type) trifluorides. ScF₃ crystals obtained by Bridgman directional solidification have ionic conductivity σ = 4 × 10^–8 S/cm at 673 K. It is smaller than the σ values for LaF₃ (sp. gr. \(P\overline 3 c1\)) and HoF₃ (sp. gr. Pnma) single crystals by a factor of 10⁴–10⁵. The low conductivity of ScF₃ crystals is due to the weak coordinating ability (coordination number CN = 6) and low electronic polarizability (α_cat = 1.1 ų) of Sc³⁺ ions. Mobile V_F⁺ vacancies and less mobile interstitial V_i^- ions (defects are formed according to the Frenkel mechanism) are involved in the ion transport. HoF₃ and LaF₃ single crystals have a high coordinating ability (CN = 9 for Ho³⁺ and CN = 11 for La³⁺) and a high electronic polarizability of cations (α_cat = 1.6–1.9 ų for Ho³⁺ and α_cat = 2.2 ų for La³⁺). Only mobile V_F⁺ vacancies (defects are formed according to the Schottky mechanism) are involved in ion transport.

Nanocomposites based on a thermoplastic elastomer (TPE) (low-density polyethylene (LDPE) and 1,2-polybutadiene in a ratio of 60/40) with functional titanium dioxide nanoparticles of different nature, TiO₂/TPE, have been prepared and investigated by a complex of methods (X-ray diffraction analysis using X-ray and synchrotron radiation beams, scanning electron microscopy, transmission electron microscopy, and X-ray energy-dispersive spectroscopy). The morphology of the composites is found to be somewhat different, depending on the TiO₂ characteristics. It is revealed that nanocomposites with cellular or porous structures containing nano-TiO₂ aggregates with a large specific surface and large sizes of crystallites and nanoparticles exhibit the best deformation‒strength and fatigue properties and stability to the effect of active media under conditions of ozone and vapor‒air aging.