57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

Stabilization of valence fluctuations in the cerium solid by the time-dependent collision approach

The collision-generated hybridization which has been found responsible for the on-site mixing of the atomic-likef-state and the band-liked states in mixed valence solids has been studied for the cerium solid. A practical expression which depends on the lattice constant and temperature has been obtained for the collision-generated hybridization. Numerical calculations show that the valence varies continuously with lattice constant and that temperature makes the transition smoother. The collision-generated hybridization is found to be of significant strength in the intermediate valence regime; but over a wide range of the valence near 3.5 it varies rather slowly without preferring a particular valence. Factors which can assist the collision-generated hybridization in stabilizing the mixed valence phase at a particular lattice constant are discussed.     

Synthesis and characterization of some oxodiperoxo molybdenum(VI) complexes of Morpholinomethyl urea and related ligands

The oxodiperoxo complexes of Mo(VI) of the type [MoO(O₂)₂L], where L = Morpholinomethyl urea, morpholinomethyl thiourea, piperidinomethyl urea, piperidinomethyl thiourea, pyrrolidinomethyl urea, and pyrrolidinomethyl thiourea have been synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, and TGA/DTA techniques. It is shown that the ligands coordinate to the metal ion in a symmetrical bidentate fashion through heterocyclic nitrogen and carbonyl oxygen or thiocarbonyl sulfur. Thermal studies indicate continuous weight loss until a stable oxide is formed. The text was submitted by authors in English.     

Electrical breakdown of anodic aluminum oxide

Results are presented from a study of electrical breakdown of anodic aluminum oxide in a constant field with a platinum pressure electrode. Statistical breakdown parameters and their dependence on the magnitude and polarity of the applied voltage are obtained. Field and temperature dependences of breakdown delay time over the interval 10^–6–10³ sec are determined. It is shown that the experimental (E) curves can be rectified (in two segments) in the coordinates log E^–1. This indicates a possible contribution to the breakdown mechanism by both tunnel injection of electrons from the cathode and subsequent avalanche multiplication of electrons within the dielectric.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 25–29, April, 1990.In conclusion, the authors thank T. V. Shmidt and E. Ya. Khanin for assistance in the study.     

Kinetics and hydrothermal transformation of gibbsite

The transformation of gibbsite have been studied under hydrothermal influence. Results of the X-ray diffraction analysis of the samples heated at different temperatures from 170°C to 265°C are also discussed in detail. The percentage of the boehmite phase formed, due to the transformation of the gibbsite, have been determined by comparing the intensity of the most strongest reflection of the boehmite phase with a fully transformed sample. The activation energy value calculated form X-ray diffractograms is almost comparable with the value calculated from main DTA endotherm of gibbsite.Es wurde die Umwandlung von Gibbsit unter hydrothermalem Einfluß untersucht. Weiterhin werden auch Ergebnisse der Röntgendiffraktionsanalyse an den bei verschiedenen Temperaturen zwischen 170°C und 265°C erhitzten Proben besprochen. Durch Vergleich der Intensität der stärksten Reflexion der Böhmitphase mit einer vollständig umgewandelten Probe wurde der prozentuelle Anteil der während der Umwandlung von Gibbsit gebildeten Böhmitphase bestimmt. Der Wert für die Aktivierungsenergie, berechnet aus den Röntgendiffraktogrammen ist annähernd vergleichbar mit dem aus der DTA von Gibbsit berechneten Wert.

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RRL Contribution No. 2028.     

Mechanism of the formation of complexes of trimethylchlorosilane with some nitrogen donors in nitrobenzene

Reactions of trimethylchlorosilane (Me ₃SiCl) with some nitrogen donors viz. pyridine, 2-, 3- and 4-picolines, quinoline and isoquinoline in nitrobenzene have been studied conductometrically. The conductivities of the solutions during these reactions have been interpreted in terms of the formation of (Me ₃Si.D)⁺, (Me ₃SiCl₂)^? andMe ₃SiCl.D (D=N-donor molecule) species.