


Vol 62, No 1 (2017)
- Year: 2017
- Articles: 21
- URL: https://journal-vniispk.ru/0036-0236/issue/view/10205
Synthesis and Properties of Inorganic Compounds
Formation and properties of composite coatings on aluminum alloys
Abstract
A study was made into the morphology, composition, and electrochemical and mechanical properties of protective composite coatings on various aluminum alloys, including those doped with Sc, Cu, and Ni. It was established that protective coatings significantly increase the corrosion resistance of the alloys in a 3% NaCl solution. Composite coatings produced by triple dip coating in an superdispersed polytetrafluoroethylene suspension have unique corrosion-resistance properties, reducing the corrosion current density for all the protected alloys to 3.1 × 10–11–4.0 × 10–12 A/cm2, which is more than three orders of magnitude lower than that for coatings formed by plasma electrolytic oxidation and five orders of magnitude lower than that for alloys without coating.



Double complex salts [Au(En)2][Ir(NO2)6] • nH2O (n = 0, 2), [Au(En)2][Ir(NO2)6]x[Rh(NO2)6]1–x • nH2O (x = 0.25, 0.5, 0.75): Synthesis, structure, thermal properties
Abstract
The double complex salts [Au(En)2][Ir(NO2)6] • 2H2O (I) and [Au(En)2][Ir(NO2)6] (II) and solid solutions [Au(En)2][Ir(NO2)6]x[Rh(NO2)6]1–x • nH2O, where x = 0.25, 0.5, 0.75, were prepared and characterized by powder X-ray diffraction, IR spectroscopy, elemental analysis, and DTA. The crystal structures were determined by X-ray diffraction. The thermal behavior of compounds under reducing atmosphere was studied. The final products of thermolysis were found to be two-phase mixtures consisting of nano-sized pure gold particles (~55 nm) and particles of Au–Ir–Rh solid solutions (~3 nm).



Effect of microwave exposure on the morphology of calcium hydroxyapatite nanocrystals synthesized from aqueous solutions
Abstract
The results of physicochemical examination (chemical analysis, XRD, IR spectroscopy) of the products synthesized in the Ca(OH)2–H3PO4–H2O system under microwave exposure are used to analyze the composition–synthesis conditions–structure–dispersion–properties relationships and to determine the effect of microwave irradiation on the size and morphology of the synthesized calcium hydroxyapatite (Ca10(PO4)6(OH)2) nanocrystals.



Crystal structure and properties of AHoCuS3 (A = Sr or Eu)
Abstract
The structures of complex sulfides AHoCuS3 (A = Sr or Eu) have been determined by X-ray powder diffraction. The crystals of the compounds belong to the orthorhombic crystal system; they are isostructural (space group, Pnma; structure type Eu2CuS3). The unit cell parameters for SrHoCuS3 and EuHoCuS3 are a = 10.1487(1) Å, b = 3.9332(1) Å, c = 12.9524(2) Å and a = 10.1484(2) Å, b = 3.9195(1) Å, c = 12.8499(2) Å, respectively. The temperatures and enthalpies of phase transformations of complex sulfides AHoCuS3 (A = Sr or Eu) have been determined.



Ammonolysis of magnesiothermic tantalum powders
Abstract
Tantalum nitrides are synthesized by ammonolysis of a mesoporous magnesiothermic tantalum powders. The effect of specific surface area of the powders and synthesis temperature on product composition is shown. Nitrogen content in the ammonolysis product of tantalum powder with a specific surface area of 56 m2 g–1 corresponds to oxynitride TaON exposed to 600°C for 1 h. The specific surface area of the oxynitride is 35 m2 g–1.



Study of the factors affecting the formation of copper–chromium/aluminum oxide compounds with a spinel structure
Abstract
The effect of the Cr3+/Al3+ ratio on the crystallization temperature of mixed oxide compounds with a spinel structure and their structural features and morphological characteristics have been studied using a combination of physicochemical methods: thermal analysis, IR spectroscopy, X-ray powder diffraction, and electron microscopy. The role of temperature of synthesis and drying of Cu–Cr/Al hydroxy precursors in the formation of copper-containing spinels CuCrxAl2–xO4, where x = 0–2, has been elucidated. The results are of interest for selection of the optimal composition and conditions of synthesis and formation of copper-containing spinels for their practical use.



Coordination Compounds
Structure of glutarate-containing uranyl coordination polymers with organic amides
Abstract
Three new uranyl complexes [UO2(C5H6O4)(Meur)] (I), [UO2(C5H6O4)(Aa)] (II), and [(UO2)2(C5H6O4)2(Tmur)2(H2O)] • H2O (III), where C5H6O42− is glutarate anion, Meur is methylcarmamide, Aa is acetamide, and Tmur is tetramethylcarbamide, have been synthesized and characterized by X-ray diffraction. 1D uranyl-glutarate complexes have been found in the structures of all compounds; in I and II their composition is [UO2(C5H6O4)(L)] and crystallographic formula is AQ21M1 (where A = UO22+, Q21 = C5H6O42-, and M1 = L = Meur or Aa). In crystals III, chain complexes have the composition [(UO2)2(C5H6O4)2(Tmur)2(H2O)] and crystallographic formula A2Q202M31 (where A = UO22+, Q02 = C5H4O62-, and M1 = Tmur or H2O). All compounds were characterized by IR spectroscopy. Structural features of all known complexes of uranyl glutarate with neutral ligands have been discussed.



Triphenylantimony dioximates Ph3Sb(ON=CHR)2 (R = C6H4NO2-2, C6H4NO2-3, C6H4Br-2, C6H4Br-3, or C4H2ONO2-5): Synthesis and structure
Abstract
Triphenylantimony dioximates Ph3Sb(ON=CHR)2 (R = C6H4NO2-2 (I), C6H4NO2-3 (II), C6H4Br-2 (III), C6H4Br-3 (IV), and C4H2ONO2-5 (V)) have been synthesized by the reaction between triphenylantimony and oximes in diethyl ether in the presence of tert-butylhydroperoxide (1: 2: 1 mol/mol/mol). The antimony atoms in I–V have a distorted trigonal bipyramidal coordination. The axial ОSbO angles are 174.8(3)°, 174.4(3)° (Ia, Ib), 175.02(19)° (II), 175.62(9)° (III), 176.34(5)° (IV), and 172.0(4)° (V). The Sb–O and Sb–C bond lengths are 2.046(7)–2.088(6) and 2.075(9)–2.185(8) Å in Ia, Ib, 2.079(5), 2.090(7), and 2.090(7)–2.115(7) Å in II, 2.0712(19), 2.0744(19), and 2.096(3)–2.109(3) Å in III, 2.065(4), 2.083(3), and 2.089(5)–2.140(5) Å in IV, and 2.088(7) and 2.110(10)–2.116(14) Å in V. The Sb···N intramolecular distances (2.779(10)–2.900(9) Å) are ~1 Å shorter than the antimony and nitrogen van der Waals radii in sum.



Effect of different temperature on the N-[(3-pyridine)-sulfonyl]aspartate polymers synthesis: Crystal structure and fluorescence
Abstract
The title coordination polymers of Zn(II), Cd(II), Pb(II) based on H2L (H2L = N-[(3-pyridine)-sulfonyl]aspartate) had been synthesized in the same material ratio, under different synthesis temperature. The results show that the polymer 1 is a three-dimensional structure and synthesized under room temperature condition; the polymers 2–4 are two-dimensional structure and synthesized under hydrothermal synthesis conditions. A structural comparison of these polymers suggests that different reaction temperatures play important role in the construction of resulting architectures for 1–4. Fluorescence properties of these polymers showed blue shift occurred.



Theoretical Inorganic Chemistry
Structure and donor–acceptor properties of Au12M (M = Hf, Ta, W, Re, and Os) intermetallic clusters
Abstract
Evolution of three-dimensional configurations, electronic properties, and energies of attachment of donor and acceptor ligands to Au12M (M = Hf, Ta, W, Re, and Os) intermetallic clusters were studied by quantum-chemical methods. The attachment of F to clusters Au12Re and Au12Os and the attachment of H to clusters Au12Ta and Au12Hf are found to give rise to more symmetric structures. The energies of attachment of F to >18-electron Au12M clusters and the energies of attachment of H to <18-electron clusters exceed the energies of attachment of the same atoms to 18-electron cluster Au12W and to cluster Au12.



Physical Methods of Investigation
Heat capacity and thermodynamic functions of La(VO4)1–x(PO4)x solid solutions at low temperatures
Abstract
Continuous monazite solid solutions La(VO4)1–х(PO4)х were prepared by ceramic technology. Heat capacities of three samples (х = 0.25, 0.50, and 0.75) were measured by adiabatic calorimetry at low temperatures (5–350 K). Thermodynamic functions were calculated in the range of temperatures studied.



Thermal and thermomechanical properties of trialkylammonium dodecahydro-closo-dodecaborates (R3NH)2[B12H12] (R = Et, Вu)
Abstract
This work is devoted to specific features of the thermal and thermomechanical properties of trialkylammonium salts of the [B12H12]2– anion (R3NH)2 [B12H12], where R = Et, Вu, and is of fundamental importance for the development of composite materials with an increased boron content. The results are given in comparison with similar data for (Et3NH)2[B10H10].



Hall effect, electrical and magnetic resistance in Cd3As2 + MnAs (30%) composite at high pressures
Abstract
Electrical resistivity ρ, Hall factor RH, magnetic resistance (Rm–R0)/R0, and magnetic-field-dependent resistances were measured in 70 mol % Cd3As2 + 30 mol % MnAs composite at fixed values of high hydrostatic pressures (up to p ≤ 9 GPa). The ρ, RH, and (Rm–R0)/R0 versus pressure curves feature a phase transition at p = 4–4.3 GPa. Field-dependent magnetic resistance features a negative pressure-induced trend.



Production of carbon nano- and microfibers by methane pyrolysis on zirconia
Abstract
The production of carbon nano- and microfibers by pyrolysis of methane (mains gas) on three ZrO2 samples prepared by different methods, at 400–700°C, methane flow rates of 175–1050 mL/min, and process times up to 4 h was studied. Comparatively long carbon bamboo-like microfibers having diameters of 0.24–0.31 μm were found to form on ZrO2, their weights and linear growth rates were assessed, and the process was shown to not slow down over time. The electrical conductivities of the fibers were measured.



Synthesis and magnetic properties of solid solutions In1–xGaxSb〈Mn〉
Abstract
Manganese-doped solid solutions In1–xGaxSb (x = 0.05, 0.1, 0.5, 0.9, 0.95) were synthesized. It was found that, in samples of the compositions In0.95Ga0.05Sb〈Mn〉 and In0.05Ga0.95Sb〈Mn〉, a homogeneous substitutional solid solution forms, into which manganese-containing clusters are incorporated. The clusters are mainly located at crystal lattice defects—grain boundaries and dislocations. The ferromagnetic properties of the obtained samples at room temperature and higher are caused by clusters Mn1+xSb, the effective size of which is about 180–300 nm.



Preparation specifics and properties of AMn3V4O12 (А = Ca, Ce, and Sm) high-pressure phases
Abstract
Perovskite-like phases AMn3V4O12 (A = Ca, Ce, and Sm) were prepared under borothermic conditions (p = 7.0–9.0 GPa, T = 700–1100°C). Their X-ray diffraction structure (space group Im\(\bar 3\) , Z = 2) was determined, and unit cell parameters were calculated: for CaMn3V4O12: а = 7.40824(3) Å, for SmMn3V4O12: а = 7.45280(8) Å, and for CeMn3V4O12: а = 7.46965(4) Å. The temperature-dependent electrical resistivity (10–300 K) and magnetic susceptibility (2–300 K) of the prepared phases were studied.



Physicochemical Analysis of Inorganic Systems
Phase equilibria in the ternary system NaF–KF–CsF
Abstract
The ternary eutectic system CsF–KF–NaF was studied by differential thermal analysis. The melting point and composition of the ternary eutectic were determined, and so was the boundary of the region of limited series of solid solutions within the composition triangle. The compositions of crystallizing phases were confirmed by X-ray powder diffraction analysis. The specific enthalpy of melting of the ternary eutectic was experimentally found.



Phase equilibria in the cutting elements LiF–KCl–Li2WO4 and LiF–KCl–LiKWO4 of the quaternary reciprocal system Li, K‖F, Cl, WO4
Abstract
The quaternary reciprocal system comprising fluorides, chlorides, and tungstates of lithium and potassium was partitioned into simplexes using graph theory, and a phase tree of the system was constructed. In the cutting triangles LiF–KCl–Li2WO4 and LiF–KCl–LiKWO4 by differential thermal analysis, the melting points and compositions of ternary eutectics were determined, and the crystallization fields of phases are delineated. For each element of the state diagram, phase reactions were described. The compositions of crystallizing phases in the cutting triangles LiF–KCl–Li2WO4 and LiF–KCl–LiKWO4 were confirmed by X-ray powder diffraction analysis.



Physical Chemistry of Solutions
Coordination properties of molecular and anionic forms of 5,10,15,20,21-pentaphenyl-2,3,7,8,12,13,17,18-octaethylporphyrin in acetonitrile
Abstract
Acid and coordination properties of 5,10,15,20,21-pentaphenyl-2,3,7,8,12,13,17,18-octaethylporphine in 1,8-diazabicyclo[5.4.0]undec-7-ene–acetonitrile system at 298 K have been studied by spectrophotometric titration. It has been found that titration causes deprotonation of nitrogen atom of the pyrrole ring to produce monodeprotonated form. Acid dissociation constant of the compound in 1,8-diazabicyclo[5.4.0]undec-7-ene–acetonitrile system at 298 K has been determined. Complexation of molecular and deprotonated forms of the ligand with silver nitrate has been studied, kinetic parameters of the corresponding reactions have been obtained. Kinetics of silver complexation with the studied ligand by ionic and molecular mechanism has been analyzed.



Radiation of multicomponent aqueous salt solutions in the millimeter-wave spectral region
Abstract
The low-intensity radiation and radiobrightness contrasts of multicomponent aqueous solutions of alkali metal chlorides have been studied at a frequency of 61.2 GHz. An additive character of changes in radiobrightness contrasts relative to initial binary systems (component ratio, 1: 1) is shown. The concentration dependence for solutions of potassium and lithium chlorides shows that initial different-sign radiation effects are eliminated. The radiation of mixed solutions proves to be close to the radiation of pure water (up to 4 m solutions).



Synthesis and luminescence of lead(II)-activated cadmium sulfide in poly(methyl methacrylate)
Abstract
Optically transparent polymeric materials PMMA: Cd(Pb)S have been synthesized by polymerization of methyl methacrylate, which concurrently acts as a reaction medium for synthesis of metal sulfides, dispersion medium for the resulting colloidal solution forming during synthesis, and the base of compositions. Dependences of cadmium sulfide luminescence on the concentrations, concentration ratios of the initial compounds, reaction medium composition, and temperature have been established. The observed changes in the spectra are related to the introduction of lead(II) into compositions, complex formation on the surface of colloidal particles, and the effect of polar acetonitrile.


