Investigation of Glasses and Glaze Coats of Composition R2O–RO–Fe2O3(FeO)–Al2O3–B2O3–SiO2 by the EPR Method

The valence state and the coordination environment of the paramagnetic centers of iron ions in glasses and vitreous coats of composition R₂O–RO–Fe₂O₃(FeO)–Al₂O₃–B₂O₃–SiO₂ have been investigated by the EPR method. The tetrahedral and octahedral coordinations of Fe³⁺ ions have been revealed. The character of change in the EPR spectra of the materials studied in the vitreous and vitrocrystalline state has been determined. It is shown that the coordination number of iron ions is dependent on the crystallization processes.     

Fedosov supermanifolds

We study the properties of the symplectic curvature tensor on supermanifolds. Using the method of normal coordinates, we establish higher-order relations between affine extensions of the curvature tensor and of the symplectic structure tensor. We find a generating function for higher-order relations. __________ Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 149, No. 2, pp. 202–227, November, 2006.     

Dielectric constant of polymer matrices containing isolated inclusions: Giant dielectric enhancement instead of collective resonance

A giant increase in the static dielectric constant and a giant dielectric relaxation are predicted for a heterogeneous medium consisting of matrix-isolated spheroids and described by the Maxwell-Garnett formula. The possibility of observing collective dielectric resonance in such a medium is also discussed.     

Nanoscale electrochemistry in a copper/aqueous/oil three-phase system: surface structure–activity-corrosion potential relationships

Practically important metal electrodes are usually polycrystalline, comprising surface grains of many different crystallographic orientations, as well as grain boundaries. In this study, scanning electrochemical cell microscopy (SECCM) is applied in tandem with co-located electron backscattered diffraction (EBSD) to give a holistic view of the relationship between the surface structure and the electrochemical activity and corrosion susceptibility of polycrystalline Cu. An unusual aqueous nanodroplet/oil (dodecane)/metal three-phase configuration is employed, which opens up new prospects for fundamental studies of multiphase electrochemical systems, and mimics the environment of corrosion in certain industrial and automotive applications. In this configuration, the nanodroplet formed at the end of the SECCM probe (nanopipette) is surrounded by dodecane, which acts as a reservoir for oil-soluble species (e.g., O₂) and can give rise to enhanced flux(es) across the immiscible liquid–liquid interface, as shown by finite element method (FEM) simulations. This unique three-phase configuration is used to fingerprint nanoscale corrosion in a nanodroplet cell, and to analyse the interrelationship between the Cu oxidation, Cu²⁺ deposition and oxygen reduction reaction (ORR) processes, together with nanoscale open circuit (corrosion) potential, in a grain-by-grain manner. Complex patterns of surface reactivity highlight the important role of grains of high-index orientation and microscopic surface defects (e.g., microscratches) in modulating the corrosion-properties of polycrystalline Cu. This work provides a roadmap for in-depth surface structure–function studies in (electro)materials science and highlights how small variations in surface structure (e.g., crystallographic orientation) can give rise to large differences in nanoscale reactivity.

Probing Cu corrosion in an aqueous nanodroplet/oil/metal three-phase environment revealed unique patterns of surface reactivity. The electrochemistry of high-index facets cannot be predicted simply from the low-index {001}, {011} and {111} responses.

Corrosion has long been studied, as a significant concern and a costly issue (ca. 3% of the GDP of industrialised countries) for the modern world.^1,2 For metals, in particular, electrochemical techniques, allied to complementary analytical and microscopy methods, play a central role in unveiling corrosion and corrosion protection mechanisms.^3–7 However, a limitation of many experimental approaches is that the electrochemical perturbation (and measurement) is applied globally at a macroscopic electrode immersed in a bulk solution,⁸ but most corrosion processes are initiated and perpetuated at (sub)microscopic surface sites (e.g., grain boundaries, inclusions, microscratches etc.).^9–14 Mismatch between the scale of key corrosion phenomena and conventional electrochemical methods makes it difficult to unambiguously identify the key anodic/cathodic sites driving corrosion. This issue is compounded for the case of atmospheric corrosion,¹⁵ or corrosion in certain automotive/industrial environments (vide infra),^16,17 which take place due to the action of small droplets on the surface in a confined system. Corrosion science needs electrochemical techniques that operate at the (sub)microscale, and allow activity and surface structure to be correlated commensurately at this scale.Among the limited library of electrochemical techniques that can routinely operate at the (sub)microscale,^18,19 scanning electrochemical cell microscopy (SECCM) is attracting significant attention.^20–22 SECCM maps electrochemistry locally and directly via a nanoscale electrochemical meniscus cell (formed at the end of a fluidic probe) that makes measurements over an array of points (typically thousands of discrete areas) on an electrode (or other) surface. For polycrystalline surfaces, SECCM measurements are powerfully combined with co-located electron backscattered diffraction (EBSD), to elucidate nanoscale structure–activity, as exemplified by studies of various electrochemical processes at a range of polycrystalline materials, including Pt,^23–26 Au,²⁷ Pd,²⁸ low carbon steel,^29–31 Zn³² and boron-doped diamond.³³In addition to its high spatiotemporal resolution, the meniscus cell configuration of SECCM facilitates rapid reactant/product exchange with the surrounding environment, mimicking a gas diffusion electrode, with an enhanced flux of gases into the meniscus cell (i.e., at the three-phase boundary).^24,27,34 When operated in air, SECCM emulates the configuration of atmospheric corrosion, with gas exchange (e.g., oxygen, O₂) taking place across the liquid/gas interface of the meniscus in contact with a surface of interest. As recently reported, and expanded upon herein, SECCM can also be operated under oil immersion,^32,35 which not only aids in confinement of the meniscus cell during prolonged measurements,³⁵ but also opens up the possibility of studying the effect of oil-soluble species (e.g., corrosion inhibitors, organic contaminants, redox mediators etc.) on local reactions at the solid/liquid/liquid interface with high spatial-resolution. This configuration is regaining interest for fundamental studies,^36,37 as well as being of great practical importance (e.g., phase-transfer reactions in industrial chemical processes, biology etc.).³⁸A key attribute of SECCM is that a number of conventional dynamic electrochemistry techniques (e.g., potentiometry, amperometry and voltammetry) can be translated readily to the confines of the meniscus cell.^20,22,39 Herein, the versatility of chronopotentiometry for local corrosion and electrochemical measurements is demonstrated. First, it is possible to make meniscus contact at zero applied current, corresponding to open circuit potential (OCP), which is measured. This corresponds to the corrosion (mixed) potential, where the rate of anodic dissolution of the metal (forming metal ions) and the rate of reduction of oxygen are balanced. Surface ion release under this condition is then analysed by subsequent “electrochemical titration” of a portion of the released metal ions, by applying a cathodic current and recording the resulting chronopotentiometric curve.⁴⁰ This allows the evaluation of intrinsic corrosion susceptibility, in situ, with high spatial-resolution, for the entire range of crystallographic orientations of a polycrystalline metal (i.e., revealed through co-located EBSD analysis). Chronopotentiometry measurements with and without O₂ present, and the use of an anodic pulse to induce the anodic dissolution (as well as the cathodic measurements mentioned) allow all of the key electrochemical processes underpinning localised corrosion to be studied. The patterns of surface reactivity establish the intimate link between corrosion susceptibility, electrochemical kinetics and surface structure at the nanoscale.     

A study of the composition of polyacrylamide-polyaluminum chloride polymer-colloid complexes

The behavior of aqueous solutions of polymer-colloid complexes based on polyacrylamide (M ～ 5.2 × 10⁵) and colloid particles of polyaluminum chloride depending on the initial component ratio and the concentration of a low-molecular-mass electrolyte (NaCl) was studied by means of viscometry and turbidimetry. It was suggested that the composition of polymer-colloid complexes, ? (the number of colloid particles attached to one macromolecule), depends on the component ratio. At ? > 1, the polymer-colloid complexes take on the polyelectrolyte properties, namely, repulsion in the case of overlap of the diffuse layers of counterions of colloid particles bound to the polymer chain leads to unfolding of macromolecular coils. Correspondingly, as the concentration of a low-molecular-mass salt increases, the coil size diminishes and the solubility of the complex drops. At ? = 1, the concentration of low-molecular-mass salt has no effect on the solubility of the complex and the viscosity of its solution.     

Reaction of Hypoxanthine and Its Analogs with Acrylonitrile in Liquid Ammonia

Russian Journal of General Chemistry -     

Solid-State Flexural–Vibrational Low-Frequency Magnetic Field Sensor Based on the Piezoelectric Effect

Technical Physics - Optimal geometrical and electrophysical parameters are calculated theoretically; the effective response of a solid-state hybrid...     

Polyethylenimine complexes with silver ions in aqueous solutions as precursors for synthesis of monodisperse silver iodide particles

The conditions of formation and composition of polyethylenimine complexes with silver ions in aqueous solutions are found. The complex is formed according to the model of a uniform distribution of ions throughout the macromolecule, and the composition of the complex may vary depending on pH of the medium. The size parameters are determined and the volume fractions of polyethylenimine macromolecular coils in solution are calculated. The synthesis of silver iodide particles is carried out under conditions where the silver ions are bound in the complex with polyethylenimine macromolecules and are distributed homogeneously over the volume of solution. The use of the polyethyleneimine complex with silver ions as a precursor of silver iodide allows the preparation of particles 1.2 nm in diameter with a narrow size distribution.     

Approximation by maps with nonnegative Jacobian

The problem of approximating continuous maps by smooth maps with nonnegative Jacobian is considered.