Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Synthesis, structure and IR absorption studies of LnBaCuCoO(5) (Ln equal earth) oxides

A series of oxides LnBaCuCoO(5) (Ln = Pr, Nd, Sm, Dy, Gd, Ho and Er) have been synthesized by ceramic method. The oxides crystallize in a tetragonal structure, isostructural to YBaCuCoO5. All the oxides in the series are semiconducting. IR spectra of these oxides show distinct absorption bands at 630 cm(-1), 550 cm(-1) and 330 cm(-1) which are assigned to E, A(2) and A(1) modes respectively. Doping of holes in these oxides, by calcium substitution in Er1-xCaxBaCuCoO5-x (up to x similar or equal to 0.3) was done but, these oxides did not show metallic behaviour.

The crystal structure of hydrated barium copper oxalate

BaCu(C2O4)(2) . 6H2O is triclinic, P (1) over bar, with a = 6.5405(9), b = 9.202(3), c = 10.939(1) Angstrom, alpha = 85.46(2), beta = 79.22(1), gamma = 80.45(2), V = 636.99(1) Angstrom(3), Z = 2, D-0 = 2.14, D-c = 2.465 g . cm(-3), R = 0.074, wR = 0.0746 for 2219 significant reflections \F-0\ greater than or equal to 6.0 sigma F-0. The barium has eleven coordinations and the coordination polyhedra is a capped antiprism. Six water oxygen atoms are coordinated whereas the other five are coming from the oxalate group. In the unit cell the molecule's form a polymeric network. One lattice water molecule belongs to the coordinating water. The barium oxygen distances vary from 2.75 Angstrom to 3.15 Angstrom.

ChemInform Abstract: Slicing the Perovskite Structure into Layers: Synthesis of Novel Three- Dimensional and Layered Perovskite Oxides, ALaSrNb2M(II)O9 (A: Na, Cs)

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Study of the reactions of pyridinium poly(hydrogen fluoride) with some ternary oxides

The products of the reaction of pyridinium poly(hydrogen fluoride), PPHF, with KIO3, Na2SnO3, NaBiO3, K2CrO4, Na2MoO4 and Na2WO4 were KIO2F2; Na2SnF6; NaHF2, BiF3; K3CrF6, KHF2, (PyH)(3)CrF6; NaHF2, (PyH)(2)MoO2F4.2NaHF(2); and (PyH)(2)WO2F4.2NaHF(2), respectively, while KClO3, KBrO3 and KlO(4) react with complete decomposition to form KHF2 as the fluorinated product. This differential reactivity and mode of reaction has been discussed in terms of the oxidation state of the central atom, the nature and strength of the bonds and the complex behaviour of the formed intermediate or fluorinated products that undergo complexation or solvation with pyridine and/or hydrogen fluoride.

Low temperature H-1 NMR relaxation studies of phase transitions in dicalcium barium propionate

The two low-temperature phase transitions in dicalcium barium propionate have been investigated by H-1 NMR relaxation (T-1,T-2,T-1 rho) studies carried out at a Larmor frequency of 300 MHz. The T-1 and T-1 rho results indicate the presence of C2H5 dynamics near these two transitions. We infer from the T-1 rho results that the slow motions of the C2H5 groups are responsible for the II-III transition.

Metal-insulator transition in perovskite oxides: Tunneling experiments

In this paper we have investigated the composition-driven metal-insulator (MI) transitions in two ABO3 classes of perovskite oxides (LaNixCo1-xO3 and NaxTayW1-yO3) in the composition range close to the critical region by using the tunneling technique. Two types of junctions (point-contact and planar) have been used for the investigation covering the temperature range 0.4 K

Metastable phase relations and europium(II) luminescence of barium hexa-aluminates prepared by gel to crystallite conversion

Wet chemical reaction of hydrated alumina gels, Al2O3.yH(2)O(80

Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Preparation and dielectric properties of zinc and cadmium doped barium tantalates, Ba3Zn1?xCdxTa2O9

Members of the Ba2Zn1-xCdxTa2O9 (0 less than or equal to x less than or equal to 1) series have been synthesized by solid state reactions at 1473K. Powder x-ray diffraction studies show a cubic perovskite cell with a similar to 4.1 Angstrom which increases with increase in x. Electron diffraction studies show the presence of hexagonal ordered perovskite structure in addition to the cubic structure seen by x-rays, the x = 0.5 composition showing more ordered crystallites. These samples show high dielectric constants with a maximum (epsilon(r) = 30 at 1 kHz) for the x = 0.5 member. The dielectric loss increases with increase in x at all the frequencies under study.

Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition

Thin films of barium strontium titanate (BST) including BaTiO3 and SrTiO3 end members were deposited using the metallo-organic decomposition (MOD) technique. Processing parameters such as nonstoichiometry, annealing temperature and time, film thickness and doping concentration were correlated with the structural and electrical properties of the films. A random polycrystalline structure was observed for all MOD films under the processing conditions in this study. The microstructures of the films showed multi-grains structure through the film thickness. A dielectric constant of 563 was observed for (Ba0.7Sr0.3)TiO3 films rapid thermal annealed at 750 degrees C for 60 s. The dielectric constant increased with annealing temperature and film thickness, while the dielectric constant could reach the bulk values for thicknesses as thin as similar to 0.3 mu m. Nonstoichiometry and doping in the films resulted in a lowering of the dielectric constant. For near-stoichiometric films, a small dielectric dispersion obeying the Curie-von Schweidler type dielectric response was observed. This behavior may be attributed to the presence of the high density of disordered grain boundaries. All MOD processed films showed trap-distributed space-charge limited conduction (SCLC) behavior with slope of similar to 7.5-10 regardless of the chemistry and processing parameter due to the presence of main boundaries through the film thickness. The grain boundaries masked the effect of donor-doping, so that all films showed distributed-trap SCLC behavior without discrete-traps. Donor-doping could significantly improve the time-dependent dielectric breakdown behavior of BST thin films, mostly likely due to the lower oxygen vacancy concentration resulted from donor-doping. From the results of charge storage density, leakage current and time-dependent dielectric breakdown behavior, BST thin films are found to be promising candidates for 64 and 256Mb ULSI DRAM applications. (C) 1997 Elsevier Science S.A.

Investigation of valence states in the perovskite oxides, LaAFeNbO(6) (A = Ca, Sr)

Compounds of the type, LaAFeNbO(6) (A = Ca Sr) have been synthesized to study the electrical and magnetic properties and to examine valence degeneracy. The results show that valence degeneracy is not operative and the compounds are insulating. Magnetic susceptibility data show that part of the Fe is in Fs(2+) state, thus oxidizing part of Nb4+ to Nb5+ by an internal redox mechanism. The presence of mixed valent Fe is confirmed by Mossbauer spectra. (C) 1999 Elsevier Science B.V. All rights reserved.

Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD

Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams'' have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1: 3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for low-pressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis ( and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.