R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb and Lu) and Lu3Mn3-3xCu2xVxO9: New noncentro symmetric oxides related to YMnO3

We report formation of new noncentrosymmetric oxides of the formula, R3Mn1.5CuV0.5O9 for R = Y, Ho, Er, Tm, Yb and Lu, possessing the hexagonal RMnO3 (space group P6(3)cm) structure. These oxides could be regarded as the x = 0.5 members of a general series R3Mn3-3xCu2xVxO9. Investigation of the Lu-Mn-Cu-V-O system reveals the existence of isostructural solid solution series, Lu3Mn3-3xCu2xVxO9 for 0 < x <= 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn3+, Cu2+ and V5+ atoms that preserve the noncentrosymmetric RMnO3 structure. (c) 2006 Elsevier Ltd. All rights reserved.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Phase behavior of concentrated aqueous solutions of cetyltrimethylammonium bromide (CTAB) and sodium hydroxy naphthoate (SHN)

We have characterized the phase behavior of mixtures of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the organic salt 3-sodium-2-hydroxy naphthoate (SHN) over a wide range of surfactant concentrations using polarizing optical microscopy and X-ray diffraction. A variety of liquid crystalline phases, such as hexagonal, lamellar with and without curvature defects, and nematic, are observed in these mixtures. At high temperatures the curvature defects in the lamellar phase are annealed gradually on decreasing the water content. However, at lower temperatures these two lamellar structures are separated by an intermediate phase, where the bilayer defects appear to order into a lattice. The ternary phase diagram shows a high degree of symmetry about the line corresponding to equimolar CTAB/SHN composition, as in the case of mixtures of cationic and anionic surfactants.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area. (c) 2005 Elsevier Inc. All rights reserved.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals,chalcogenides,and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area.

Composition of aqueous solutions in equilibrium with sulfides and oxides of iron at 3500°C

Solutions of potassium chloride (pH-buffered and 1-molat) equilibrated at 350°C with pyrrhotite, pyrite, and magnetite contained approximately 1 millimole of reduced sulfur and less than 0.1 millimole of oxidized sulfur per kilogram. Similar solutions equilibrated with pyrite, magnetite, and hematite contained approximately 1 millimole of reduced sulfur, but 3 to 6 millimoles of oxidized sulfur per kilogram. Both types of solutions contained less than 0.1 millimole of iron per kilogram at pH ≥ 6 and approximately 100 millimoles per kilogram at pH 2.

Unusual dielectric response in B-site size-disordered hexagonal transition metal oxides

We discover that hexagonal holmium copper titanate (Ho2CuTiO6), has a unique and highly desirable combination of high dielectric constant, low losses, very small temperature coefficient, and low frequency dependence. Our first-principles calculations indicate that these exceptional properties result from a size-difference at the Cu/Ti B-site that suppresses the expected ferroelectric transition, combined with the dominance of intermediate-frequency polar vibrational modes in the dielectric response. Our results suggest that the use of such B-site disorder in alloys of hexagonal transition-metal oxides should generally result in similar robust dielectrics.

Solvolytic disproportionation of non-stoichiometric oxides of praseodymium and terbiumstar, open

The solvolytic disproportionation of non-stoichiometric PrOχ and TbOχ in acid solutions to produce higher oxides has been investigated. Some new non-stoichiometric phases have been reported. A number of interesting features of the non-stoichiometric rare earth oxides have been discussed and the need for a satisfactory structural model has been pointed out.

Raman spectrum of sodium iodide

Raman spectrum of a single crystal of sodium iodide has been recorded for the first time using lambda 2537 excitation. The general features of the spectrum are discussed in the light of the existing theories on the dynamics of the alkali halides. The authors wish to thank Professor D.Y.Phadke of the Tata Institute of Fundamental Research, Bombay, for presenting the crystal of Nal used in the present investigation.

Free energy of mixing of divalent basic oxides with silica

An expression derived for the free energy of mixing of a divalent basic oxide (MO) with SiO2 based on a model of silicate structure, takes into account the distribution of O2- (from MO) into the silica network, the mixing of silicate ions with O2- and the enthalpy of mixing. The resulting expression is ΔGmix=RT{N11n (2N1-N)2/4N1(1-N)+N21n N 2-N/1-N}, where N={(β+N1)-√(β+N 1)2-8βN1N2}/2β β=characteristic constant for the system N1=mol fraction of silica N2=mol fraction of MO. For the proper choice of β, calculated values of the activity of MO for the system PbO-SiO2, MnO-SiO2, FeO-SiO2 and CaO-SiO2 are in good agreement with experiment. The model predicts that the activity of the basic oxide decreases with increase in temperature.

Colorimetric determination of 2,4-dinitrophenylamino groups by sodium borohydride reduction

When sodium borohydride is added to aqueous solutions of 2,4-dinitrophenylamino acids and related derivatives, an intense red color is formed. Measurement of the red color, with a 420 filter, permits the determination of such compounds in concentrations of 0.01 to 0.06 μmole per ml. with a precision to 2%. The reaction is highly specific-while 2,4-dinitroaniline will react to the test, o-, m-, and p-nitroanilines, 2,4-dinitrophenyl aryl or alkyl ethers, and 2,4-dinitrophenyl-imidazole and pyrrolidine derivatives will not. Heretofore aromatic nitro groups have been considered resistant to attack by sodium borohydride. The method, as developed, is applicable to the evaluation of the degree of substitution of protein amino groups by fluorodinitrobenzene.

Polarisation studies on the Raman spectra of cubic crystals - Part I. Sodium chlorate

neral expressions have been derived for the intensities of the three classes of Raman lines namely totally symmetric A, doubly degenerate E and triply degenerate F, in the case of cubic crystals under the following conditions. The direction of the incident beam which is polarised with its electric vector inclined at an angle α to the normal to the scattering plane makes an angle Θ with one of the cubic axes of the crystal. The transversely scattered light is analysed by a double image prism with its principal axes inclined at angle β to the normal to the scattering plane, which is horizontal. For incident unpolarised light and Θ=22 1/2°, and the scattered light being analysed by a double image prism rotated through 45° from the position when its principal axes are vertical and horizontal ρ{variant} for A lines is equal to one, for E lines >1 and for F lines <1. This gives a method of classifying the Raman lines of a cubic crystal in a single setting. The results have been experimentally verified in sodium chlorate.

Dielectric properties of some MM′O4 and MTiM′O6 (M=Cr, Fe, Ga; M′=Nb, Ta, Sb) rutile-type oxides

We describe an investigation of the structure and dielectric properties of MM'O-4 and MTiM'O-6 rutile-type oxides for M = Cr, Fe, Ga and M' = Nb. Ta and Sb. All the oxides adopt a disordered rutile structure (P4(2)/mnm) at ambient temperature. A partial ordered trirutile-type structure is confirmed for FeTaO4 from the low temperature (17 K) neutron diffraction studies While both the MM'O-4 oxides (CrTaO4 and FeTaO4) investigated show a normal dielectric property MTiM'O-6 oxides for M = Fe, Cr and M' = Nb/Ta/Sb display a distinct relaxor/relaxor-like response. Significantly the corresponding gallium analogs, GaTiNbO6 and GaTiTaO6, do not show a relaxor response at T<500K (C) 2010 Elsevier Inc All rights reserved

Pressure dependence of chlorine nuclear quadrupole resonance in sodium chlorate

The pressure dependence of the chlorine NQR frequency in NaClo3 has been investigated up to 20 k bar hydrostatic pressure. A distinct break in slope in the pressure dependence of the resonance frequency is observed near 11 k bar. This is attributed to a phase transition reported earlier by Bridgman in this pressure region.