Thermal analysis of the Bi2O3-Er2O3-Zro2 pigments

The synthesis of new compounds based on Bi₂O₃ is investigated because they can be used as new ecological inorganic pigments. Chemical compounds of the Bi_2−xEr_x/2Zr_3x/8O₃ type were synthetized. The host lattice of these pigments is Bi₂O₃ that is doped by Er³⁺ and Zr⁴⁺ ions. The incorporation of doped ions provides interesting colours and contributes to a growth of the thermal stability of these compounds. The simultaneous TG-DTA measurements were used for determination of the temperature region of the pigment formation and thermal stability of pigments. This paper also contains the results of the pigment characterization by X-ray powder diffraction and their colour properties.     

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO3 as a Model Material

The kinetics of stoichiometry change of an oxide--a prototype of a simple solid-state reaction and a process of substantial technological relevance--is studied and analyzed in great detail. Oxygen incorporation into strontium titanate was chosen as a model process. The complete reaction can be phenomenologically and mechanistically understood beginning with the surface reaction and ending with the transport in the perovskite. Key elements are a detailed knowledge of the defect chemistry of the perovskite as well as the application of a variety of experimental and theoretical tools, many of them evolving from this study. The importance of the reaction and transport steps for (electro)chemical applications is emphasized.     

Surface Structure and Catalytic Performance of CuCl/SiO2-Al2O3 Catalysts for Methanol Oxidative Carbonylation

Aluminum was doped into amorphous silica gel to modify its surface structure. The obtained SiO₂-Al₂O₃ support was used to prepare the CuCl/SiO₂-Al₂O₃ catalyst by solid-state ion exchange, and the catalyst activity for liquid-phase oxidative carbonylation of methanol to dimethyl carbonate was investigated. The results showed that the prepared SiO₂-Al₂O₃ support kept the amorphous structure of the silica gel. The BET specific surface area of the silica gel was decreased to 200 m²/g, and the surface acid sites (including Brønsted acid sites) were increased. In the CuCl/SiO₂-Al₂O₃ catalyst, CuCl was not only dispersed on surface but also was ion exchanged with surface Brønsted acid sites of the SiO₂-Al₂O₃ support to form Cu⁺ species, which resulted in a decrease in BET specific surface area to 148 m²/g. These two kinds of Cu⁺ species on the catalyst surface were both active centers for the oxidative carbonylation of methanol to dimethyl carbonate. When the catalyst was prepared with Si/Al molar ratio of 5 and was calcined at 500 °C, the selectivity and space-time yield of dimethyl carbonate reached 74% and 1.27 g/(g·h), respectively.     

New Transition and Actinide Metal Complexes of 2‐Carboxy‐phenylhydrazo‐Benzoylacetone Ligand: Synthesis,Characterization and Biological Study

A new series of binary mononuclear complexes were prepared from the reaction of the hydrazone ligand, 2-carboxyphenylhydrazo-benzoylacetone (H2L), with the metal ions, Cd(II), Cu(II), Ni(II), Co(II), Th(IV) and UO2(VI). The binary Cu(II) complex of H2L was reacted with the ligands 1,10-phenanthroline or 2-aminopyridine to form mixed-ligand complexes. The binary complexes of Cu(II) and Ni(II) are suggested to have octahedral configurations. The Cd(II) and Co(II) complexes are suggested to have tetrahedral and/or square-planar geometries, respectively. The Th(IV) and UO2(VI) complexes are suggested to have octahedral and dodecahedral geometries, respectively. The mixed-ligand complexes have octahedral configurations. The structures of all complexes and the corresponding thermal products were elucidated by elemental analyses, conductance, IR and electronic absorption spectra, magnetic moments, 1H NMR and TG-DSC measurements as well as by mass spectroscopy. The ligand and some of the metal complexes were found to activate the enzyme pectinlyase.     

Uniform grid approximation of nonsmooth solutions to the mixed boundary value problem for a singularly perturbed reaction-diffusion equation in a rectangle

A mixed boundary value problem for a singularly perturbed reaction-diffusion equation in a square is considered. A Neumann condition is specified on one side of the square, and a Dirichlet condition is set on the other three. It is assumed that the coefficient of the equation, its right-hand side, and the boundary values of the desired solution or its normal derivative on the sides of the square are smooth enough to ensure the required smoothness of the solution in a closed domain outside the neighborhoods of the corner points. No compatibility conditions are assumed to hold at the corner points. Under these assumptions, the desired solution in the entire closed domain is of limited smoothness: it belongs only to the Hölder class C ^μ, where μ ∈ (0, 1) is arbitrary. In the domain, a nonuniform rectangular mesh is introduced that is refined in the boundary domain and depends on a small parameter. The numerical solution to the problem is based on the classical five-point approximation of the equation and a four-point approximation of the Neumann boundary condition. A mesh refinement rule is described under which the approximate solution converges to the exact one uniformly with respect to the small parameter in the L _∞ ^h norm. The convergence rate is O(N ^?2ln² N), where N is the number of mesh nodes in each coordinate direction. The parameter-uniform convergence of difference schemes for mixed problems without compatibility conditions at corner points was not previously analyzed.     

Small deviations of series of independent positive random variables with weights close to exponential

Let ξ, ξ₀, ξ₁, ... be independent identically distributed (i.i.d.) positive random variables. The present paper is a continuation of the article [1] in which the asymptotics of probabilities of small deviations of series S = Σ _j=0 ^∞ a(j)ξ _j was studied under different assumptions on the rate of decrease of the probability ?(ξ < x) as x → 0, as well as of the coefficients a(j) ≥ 0 as j → ∞. We study the asymptotics of ?(S < x) as x → 0 under the condition that the coefficients a(j) are close to exponential. In the case when the coefficients a(j) are exponential and ?(ξ < x) ～ bx ^α as x → 0, b > 0, a > 0, the asymptotics ?(S < x) is obtained in an explicit form up to the factor x ^o(1). Originality of the approach of the present paper consists in employing the theory of delayed differential equations. This approach differs significantly from that in [1].