A[Bi3Ti4O13] and A[Bi3PbTi5O16] (A = K, Cs): New n=4 and n=5 members of the layered perovskite series, A[A ' n-1B nO3n+1], and their hydrates

We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi3Ti4O13] and A[Bi3PbTi5O16]for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'n-1BnO3n+1]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Angstrom and loses its doubling [for example, the tetragonal lattice parameters of K[Bi3Ti4O13] and its dihydrate are respectively a = 3900(1)Angstrom c 37.57(2) Angstrom; a 3.885(1) Angstrom, c = 20.82(4) Angstrom]; surprisingly, the cesium analogues do not show a similar change on hydration.

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.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.

Magnetoresistance of the metallic perovskite oxide LaNiO3-delta

We report a study of the magnetoresistance (MR) of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14), magnetic field (H less than or equal to 6 T) and temperature (1.5 K less than or equal to T less than or equal to 25 K). We find a strong dependence of the nature of the MR on the oxygen stoichiometry. The MR at low temperatures changes from positive to negative as the sample becomes more oxygen deficient (i.e. delta increases). Some of the samples, which are more resistive, show resistivity minima at T-min approximate to 20 K. We find that in these samples the MR is positive for T > T-min and negative for T < T-min. We conclude that in the absence of strong magnetic interaction, the negative MR in these oxides can arise from weak-localization effects.

Crystal structure and thermal and electrical properties of the perovskite solid solution Nd1-xSrxFeO3-delta (0 <= x <= 0.4)

The crystal structure, thermal expansion and electrical conductivity of strontium-doped neodymium ferrite (Nd1-xSrxFeO3-delta where 0less than or equal toxless than or equal to0.4) were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction. The orthorhombic distortion decreases with increasing Sr substitution. The pseudocubic lattice parameter shows a minimum at x=0.3. The thermal expansion curves for x=0.2-0.4 displayed rapid increase in slope at higher temperatures. The electrical conductivity increased with Sr content and temperature. The calculated activation energies for electrical conduction decreased with increasing x. The electrical conductivity can be described by the small polaron hopping mechanism. The charge compensation for divalent ion on the A-site is provided by the formation of Fe4+ ions on the B site and vacancies on the oxygen sublattice. The results indicate two defect domains: for low values of x, the predominant defect is Fe4+ ions, whereas for higher values of x, oxygen vacancies dominate. (C) 2002 Elsevier Science B.V. All rights reserved.

Spin-orbital ordering and mesoscopic phase separation in the double perovskite Ca2FeReO6

Neutron powder diffraction measurements on Ca2FeReO6 reveal that this double perovskite orders ferrimagnetically and shows anomalous lattice parameter behavior below T-C=521 K. Below similar to300 K and similar to160 K we observe that the high-T monoclinic crystal structure separates into two and three monoclinic phases, respectively. A magnetic field suppresses the additional phases at low T in favor of the highest-T phase. These manifestations of the orbital degree of freedom of Re 5d electrons indicate that these electrons are strongly correlated and the title compound is a Mott insulator, with competing spin-orbitally ordered states.

Microwave preparation and sintering of industrially important perovskite oxides: LaMO3 (M = Cr, Co, Ni)

Perovskite oxides LaMO3 (M = Cr, Co, Ni), have been successfully prepared using microwaves of 2.45 GHz. Microwave preparation is rapid, clean and energy efficient. Preparation of LaCrO3, LaCoO3 and LaNiO3 has been achieved in 3 min, 5 min and 10 min respectively. Direct reaction between component oxides is used for the preparation of LaCrO3 and LaCoO3, whereas nitrates are used as starting materials for LaNiO3 preparation. Products have been characterized using XRD, IR spectroscopy and SEM. Their dc electrical conductivity has also been studied and their fracture behaviour has been examined. All three microwave prepared oxide powders are of submicron size. These perovskite oxides have been sintered to very high densities using microwaves. Possible mechanisms of the microwave-material interaction both during preparation and during sintering have been discussed.

Novel ABO(3) oxides related to perovskite and YAlO3 structure types in the La-B-V-O (B = Ni, Cu) systems

The synthesis, structure and magnetic properties of mixed-metal oxides of ABO(3) composition in the La-B-V-O (B = Ni, Cu) systems are described in the present paper. While the B = Ni oxides adopt GdFeO3-like perovskite structure containing disordered nickel and vanadium at the octahedral B site, La3Cu2VO9 crystallizes in a YAlO3-type structure. A detailed investigation of the superstructure of nominal La3Cu2VO9 by WDS analysis and Rietveld refinement of powder XRD data reveal that the likely composition of the phase is La13Cu9V4O38.5, where the Cu and V atoms are ordered in a root13a(h) (a(h) = hexagonal a parameter of YAlO3-like subcell) superstructure. Magnetic susceptibility data support the proposed superstructure consisting of triangular Cu-3 clusters. At low temperatures, the magnetic moment corresponds to S = 1/2 per Cu-3 cluster, while at high temperatures the behavior is Curie-Weiss like, showing S = 1/2 per copper. The present work reveals the contrasting behavior of La-Cu-V-O and La-Ni-V-O systems: while a unique line-phase related to YAlO3 structure is formed around La3Cu2VO9 Composition in the copper system, a continuous series of perovskite-GdFeO3 solid solutions, LaNi1-xVxO3 for 0 less than or equal to x less than or equal to 1/3 seems to be obtained in the nickel system, where the oxidation state of nickel varies from 3+ to 2+.

Optical conductivity of perovskite manganites

We calculate the optical conductivity sigma(omega) for doped rare-earth manganites based on the recently proposed microscopic ``two fluid'' l-b model. We study the temperature dependence of sigma(omega) for La(0.825)Sr(0.175)MnO(3), which has a metallic ground state. At low temperatures, the calculated sigma(omega) shows a ``two-peak'' structure consisting of a far-infrared coherent Drude peak and a broad mid-infrared ``polaron'' peak, as observed in experiments. Upon heating, the Drude peak rapidly loses spectral weight, and sigma(omega) crosses over to having just a single broad mid-infrared peak. The temperature dependence of the mid-infrared peak and the spectral weight transfer between the two peaks are also in agreement with experimental findings. We also study the doping dependence of sigma(omega) for the same compound. The integrated spectral weight under the Drude peak increases rapidly as the doping level is increased from an underdoped, insulating state (x = 0.1) to a highly doped, metallic state (x = 0.3), again in agreement with trends seen experimentally.

Casting of titanium and titanium alloys

Titaniuni and its alloys have many applications in aerospace, marine and other engineering industries. Titanium requires special melting techniques because of its high reactivity at elevated temperatures and needs special mould materials and methods for castings. This paper reviews the development of titanium casting technology.

Evaluation of the reactivity of titanium with mould materials during casting

A methodology for evaluating the reactivity of titanium with mould materials during casting has been developed. Microhardness profiles and analysis of oxygen contamination have provided an index for evaluation of the reactivity of titanium. Microhardness profile delineates two distinct regions, one of which is characterised by a low value of hardness which is invariant with distance. The reaction products are uniformly distributed in the metal in this region. The second is characterised by a sharp decrease in microhardness with distance from the metal-mould interface. It represents a diffusion zone for solutes that dissolve into titanium from the mould. The qualitative profiles for contaminants determined by scanning electron probe microanalyser and secondary ion mass spectroscopy in the as-cast titanium were found to be similar to that of microhardness, implying that microhardness can be considered as an index of the contamination resulting from metal-mould reaction.

Metal mould reactions during casting of titanium in zircon sand moulds

Metal-mold reaction during Ti casting in zircon sand molds has been studied using scanning electron microscope, energy and wave length dispersive analysis of X-rays, X-ray diffraction, microhardness measurements, and chemical analysis. Experimental results suggest that oxides from the mold are not fully leached out by liquid Ti, but oxygen is preferentially transferred to liquid Ti, leaving behind metallic constituents in the mold as lower oxides or intermetallics of Ti. The electron microprobe analysis has revealed the depth profile of contaminants from the mold into the cast Ti metal. The elements Si, Zr and O were found to have diffused to a considerable distance within the Ti metals. A possible mechanism has now been evolved in regard to the reactions that occur during casting of Ti in zircon sand molds.

Griffiths phase-like behavior and spin-phonon coupling in double perovskite Tb(2)NiMnO(6)

The Griffiths phase-like features and the spin-phonon coupling effects observed in Tb(2)NiMnO(6) are reported. The double perovskite compound crystallizes in monoclinic P2(1)/n space group and exhibits a magnetic phase transition at T(c) similar to 111 K as an abrupt change in magnetization. A negative deviation from ideal Curie-Weiss law exhibited by 1/chi(T) curves and less-than-unity susceptibility exponents from the power-law analysis of inverse susceptibility are reminiscent of Griffiths phase-like features. Arrott plots derived from magnetization isotherms support the inhomogeneous nature of magnetism in this material. The observed effects originate from antiferromagnetic interactions that arise from inherent disorder in the system. Raman scattering experiments display no magnetic-order-induced phonon renormalization below Tc in Tb(2)NiMnO(6), which is different from the results observed in other double perovskites and is correlated to the smaller size of the rare earth. The temperature evolution of full-width-at-half-maximum for the stretching mode at 645 cm(-1) presents an anomaly that coincides with the magnetic transition temperature and signals a close connection between magnetism and lattice in this material. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3671674]

Perovskite phase transformation in 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) nanoparticles derived by sol-gel

Fabrication of 0.65Pb(Mg1/3Nb2./3)O-3-0.35PbTiO(3) (PMN-PT) nanoparticles with an average size of about 40 nm and their phase transformation behavior from pyrochlore to perovskite phase is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PMN-PT which was dried and partially calcined at 450 degrees C for 1 h to decompose organics and bring down the free energy barrier for perovskite crystallization and then finally annealed in the temperature range 600 to 700 degrees C. Annealed at around 700 degrees C for 1 h, PMN-PT gel powder exhibited nanocrystalline morphology with perovskite phase as confirmed by the transmission electron microscopy and X-ray diffraction techniques. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3677974]