Thermal degradation of composites of poly(methyl methacrylate) with alkoxysilane hydrolyzates

Organic-inorganic composites of poly(methyl methacrylate) with alkoxysilane hydrolyzates form transparent films. Their thermal and oxidative thermal degradation were studied by differential scanning calorimetry and thermogravimetric analysis.     

Thermochemical properties of new N,O-chelate Sc, Eu, and Tb complexes for OLED-devices

A new class of Sc, Eu, and Tb complexes with N,O-chelate ligands was synthesized for the first time. The mass spectra, thermogravimetric analysis, differential scanning calorimetry data, as well as the data on the saturated vapor pressure of the compounds were obtained. The main thermochemical parameters of the compounds were calculated.     

Electron density distribution in BaPb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> superconducting oxides studied by double nuclear magnetic resonance methods

The effect of charge disorder on the formation of an inhomogeneous state of the electron system in the conduction band in BaPb_{1 − x} Sb _x O₃ superconducting oxides is investigated experimentally by NMR methods. The NMR spectra of ¹⁷O are measured systematically, and the contributions from ¹⁷O atoms with different cation nearest surroundings are identified. It is found that microscopic regions with an elevated spin density of charge carriers are formed within two coordination spheres near antimony ions. Nuclei of the superconducting phase of the oxide (regions with an elevated antimony concentration) microscopically distributed over the sample are detected in compounds with x = 0.25 and 0.33. Experiments in which a double resonance signal of the spin echo of ¹⁷O-²⁰⁷Pb and ¹⁷O-¹²¹Sb are measured in the metal phase of BaPb_{1 − x} Sb _x O₃ oxides are carried out for the first time. The constants of indirect heteronuclear spin-spin ¹⁷O-²⁰⁷Pb interaction are determined as functions of the local Knight shift ₂₀₇ Ks. The estimates of the constants of the indirect interaction between the nuclei of the nearest neighbors (O-Pb and Pb-Pb atoms) and analysis of evolution of the NMR spectra of ¹⁷O upon a change in the antimony concentration are convincing evidence in favor of the development of a microscopically inhomogeneous state of the electron system in the metal phase of BaPb_{1 − x} Sb _x O₃ oxides.     

Thermodynamic properties of o-semiquinone complex of Co with Di-(2-pyridyl)amine in the temperature range T → 0 to 370 K

The heat capacity of di-(2-pyridyl)amine-bis-(4-methoxy-3,6-di-tert-butyl-o-benzosemiquinone)cobalt in the temperature range from 7 to 370 K was investigated by means of precise adiabatic vacuum calorimetry. It was established that the phase transition associated with the redox-isomeric transformation of the semiquinone-catecholate form of the complex into the bis-semiquinone form is observed above 260 K; this transition is not completed due to thermal destruction that begins at 367 K. The magnetic moment values in the temperature range from 5 to 350 K and the EPR spectra in the temperature range from 130 to 290 K, which confirm the nature of the phase transition, were obtained for the investigated complex. The standard thermodynamic functions C _p ^pO (T), H○(T)-H○(0), S○(T), and G○(T)-H○(0), were calculated from the data on heat capacity in the temperature range from T → 0 to 260 K. Analysis of the low temperature heat capacity on the basis of Debye’s theory of the heat capacity of solids and the multifractional model testifies to the chain-layered structural topology of the investigated complex.     

Study of thermochemical properties of diphenyl[dialkyl(alkyl)carbamoylmethyl]phosphine oxides

The synthesis and the studies of properties of diphenyl[dialkyl(alkyl)carbamoylmethyl]phosphine oxides by differential scanning calorimetry, mass spectrometry and Knudsen effusion method were performed. The thermodynamic parameters of melting and vaporization were calculated.     

Elastic waves and the Landau-Rumer mechanism of relaxation of quasi-transverse phonons in GaAs crystals

The dependences of the relaxation rate and the absorption coefficient of ultrasound in GaAs crystals on the direction of the wave vector of quasi-transverse phonons for the Landau-Rumer mechanism are analyzed in the framework of the anisotropic-continuum model. The calculations are performed with two sets of second-order and third-order elastic moduli experimentally measured by different authors. It is demonstrated that the angular dependences of the relaxation rates of quasi-transverse phonons and the ultrasonic absorption coefficients calculated from these data differ qualitatively. The correctness of the determination of the third-order elastic moduli available in the literature can be checked by measuring the ultrasonic absorption coefficients for GaAs crystals.     

Fe-containing nanoparticles used as effective catalysts of lignin reforming to syngas and hydrogen assisted by microwave irradiation

Active iron-containing nanosized components have been formed on the lignin surface. The metal was deposited on the lignin from an ethanol solution of Fe(acac)₃ and from a colloid solution of iron metal particles obtained beforehand by metal vapor synthesis. These active components are able to absorb microwave radiation and are suitable for microwave-assisted high-rate dehydrogenation and dry reforming of lignin without addition of a carbon adsorbent, as a supplementary radiation absorbing material, to the feedstock. The dependence of the solid lignin heating dynamics on the concentration of supported iron particles was investigated. The threshold Fe concentration equal to 0.5 wt.%, providing the highest rate of sample heating up to the reforming and plasma generation temperature was identified. The microstructure and magnetic properties of iron-containing nanoparticles supported on lignin were studied before and after the reforming. The Fe₃O₄ nanoparticles and also core-shell Fe₃O₄@γ-Fe-С nanostructures are formed during the reforming of lignin samples. The catalytic performance of iron-based nanoparticles toward the lignin conversion is manifested as increasing selectivity to hydrogen and syngas, which reaches 94% at the Fe concentration of 2 wt.%. It was found that with microwave irradiation under argon, hydrogen predominates in the gas. In the СО₂ atmosphere, dry reforming takes place to give syngas with the СО/Н₂ ratio of ~?0.9. In both cases, the degree of hydrogen recovery from lignin reaches 90–94%.

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Graphical abstract The microwave-supported deposition of iron on the lignin surface gives active well defined nanoparticles Fe₃O₄ and also core-shell Fe₃O₄@γ-Fe-С nanostructures. These nanocomponents provide for high-rate microwave-assisted dehydrogenation and dry reforming of lignin.

     

Magnetic properties of Li<Subscript>2</Subscript>RuO<Subscript>3</Subscript> as studied by NMR and LDA + DMFT calculations

We present results of the combined study of the magnetic properties of Li₂RuO₃ by means of nuclear magnetic resonance (NMR) spectroscopy and theoretical dynamical mean-field theory (LDA + DMFT) calculations. The NMR data clearly show the onset of a thermal activation process in the high temperature region, T > 560K, which is tentatively ascribed to the formation of the valence bond liquid. The LDA + DMFT calculations demonstrate that the magnetic response at these temperatures is mostly due to the xz/yz orbitals, while the xy orbitals of Ru still form molecular orbitals. Thus, Ru ions are in the orbital-selective state in the high temperature phase of Li₂RuO₃.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.