Syntheses, Crystal Structure, and Second Harmonic Generation Response of Four Novel Noncentrosymmetric Tellurites of Quaternary A/M/Te/O (A = Ba, Sr, Ca; M = V, Nb, Ta) System: BaTa4Te3O17, BaNb4Te3O17, SrTa4Te3O17, and CaV2TeO8.

Four new noncentrosymmetric tellurites of quaternary A/M/Te/O (A = Ba, Sr, Ca; M = V, Nb, Ta) system, namely, BaTa4Te3O17 (1), BaNb4Te3O17 (2), SrTa4Te3O17 (3), and CaV2TeO8 (4), were synthesized and characterized by single-crystal X-ray diffraction, thermal analysis, diffuse reflectance spectroscopy, and powder second harmonic generation (SHG) response measurements. The isostructural compounds 1-3 crystallize in the P212121 space group and have a three-dimensional (Ta4Te3O17)2-/(Nb4Te3O17)2- anionic framework, whereas the layered compound 4 crystallizes in the Ccc2 space group and has a [V2TeO8]2- anionic layer. The phase-matching compounds 1, 2, and 3 and the non-phase-matching compound 4 show powder SHG responses equivalent to ∼27, ∼13, ∼24, and ∼68% of that of LiNbO3, respectively.

Enhanced Dielectric Properties of LaNiO3/BaTiO3/PVDF: A Three-Phase Percolative Polymer Nanocrystal Composite.

Polymer (poly(vinylidene fluoride) (PVDF)) nanocrystal composites based on lanthanum nickelate (percolative oxide) and barium titanate were fabricated to obtain material systems with a high dielectric constant and low loss to be used for high-charge-storage applications. Lanthanum nickelate (LaNiO3) nanocrystallites were synthesized from a simple citrate-assisted sol-gel route that yielded agglomerated crystallites of an average size of 120 nm. The defective nature of the lanthanum nickelate nanocrystals was revealed by the transmission electron microscopy studies. Hot-pressing method was executed to fabricate the LaNiO3/PVDF nanocrystal composites, and their dielectric characteristics showed a low percolation threshold in the region of fLN (volume fraction of lanthanum nickelate) = 0.10. The percolative conductive filler-polymer nanocrystal composite at the percolation threshold exhibited a dielectric constant (εr) and loss ( D) of 55 and 0.263, respectively, at 10 kHz; the dielectric constant obtained was more than 5 times that of host matrix PVDF. To further improve upon the obtained dielectric properties from the two-phase composites, a high-dielectric-constant material, barium titanate (BaTiO3) nanocrystals, with an average size of 100 nm, was embedded in the polymer matrix as the third phase. The dielectric properties of the three-phase nanocrystal composites were measured as a function of the volume fraction of lanthanum nickelate (which was limited within the percolation threshold), and a dielectric constant as high as 90 and the associated loss of 0.13 at 10 kHz were achieved from fLN = 0.09 and fBT = 0.20. The obtained dielectric constant from this system is 9 times more than that of PVDF and 3 times that of a two-phase barium titanate/PVDF composite, which proves to be a promising material for charge-storage applications.

Syntheses and Characterization of AM2V2O11 (A = Ba, Sr, Pb; M = Nb, Ta) Vanadates with Centrosymmetric and Noncentrosymmetric Structures.

Five isomorphous AM2V2O11 vanadates of niobium and tantalum, namely, BaNb2V2O11, BaTa2V2O11, SrNb2V2O11, SrTa2V2O11, and PbTa2V2O11, were prepared by solid-state reactions and structurally characterized by single-crystal and powder X-ray diffraction techniques. Barium and strontium compounds, respectively, have centrosymmetric and noncentrosymmetric types of layered structure, wherein [M2V2O11]2- anionic layers are interleaved with A2+ cations. Both types of layered structure are found for lead compound. The strontium and lead compounds are type I phase-matching materials with second-harmonic-generating efficiencies of 33-50% of LiNbO3, and their dielectric properties were evaluated. A three-dimensional structural variant was also identified for strontium compounds, which crystallize in noncentrosymmetric orthorhombic space group C2221.

Structural and optical properties of (100-x)Li2B4O7·x(Ba5Li2Ti2Nb8O30) glasses and glass nanocrystal composites.

Optically clear glasses of various compositions in the system (100-x)(Li2B4O7)·x(Ba5Li2Ti2Nb8O30) (5 ≤ x ≤ 20, in molar ratio) were fabricated by splat quenching technique. Controlled heat-treatment of the as-quenched glasses at 500 °C for 8 h yielded nanocrystallites embedded in the glass matrix. High Resolution Transmission Electron Microscopy (HRTEM) of these samples established the composition of the nano-crystallites to be that of Ba5Li2Ti2Nb8O30. ¹¹B NMR studies revealed the transformation of BO4 structural units into BO3 units owing to the increase in TiO6 and NbO6 structural units as the composition of Ba5Li2Ti2Nb8O30 increased in the glass. This, in turn, resulted in an increase in the density of the glasses. The influence of the nominal composition of the glasses and glass nanocrystal composites on optical band gap (E(opt)), Urbach energy (ΔE), refractive index (n), molar refraction (R(m)), optical polarizability (α(m)) and third order non-linear optical susceptibility (χ³) were studied.

Optical properties of nanocrystalline potassium lithium niobate in the glass system (100-x) TeO2-x(1.5K2O-Li2O-2.5Nb2O5).

Optically clear glasses of various compositions in the system (100-x) TeO2-x(1.5K2O-Li2O-2.5Nb2O5) (2 < or = x < or = 12, in molar ratio) were prepared by the melt-quenching technique. The glassy nature of the as-quenched samples was established via differential scanning calorimetry (DSC). The amorphous and the crystalline nature of the as-quenched and heat-treated samples were confirmed by the X-ray powder diffraction and transmission electron microscopic (TEM) studies. Transparent glasses comprising potassium lithium niobate (K3Li2Nb5O15) microcrystallites on the surface and nanocrystallites within the glass were obtained by controlled heat-treatment of the as-quenched glasses just above the glass transition temperature (T(g)). The optical transmission spectra of these glasses and glass-crystal composites of various compositions were recorded in the 200-2500 nm wavelength range. Various optical parameters such as optical band gap, Urbach energy, refractive index were determined. Second order optical non-linearity was established in the heat-treated samples by employing the Maker-Fringe method.

Synthesis, structural characterization and formation mechanism of ferroelectric bismuth vanadate nanotubes.

We report the synthesis and structural characterization of ferroelectric bismuth vanadate (Bi2VO5.5) (BVO) nanotubes within the nanoporous anodic aluminum oxide (AAO) templates via sol-gel method. The as-prepared BVO nanotubes were characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), High-Resolution Transmission Electron Microscope (HRTEM) and the stoichiometry of the nanotubes was established by energy-dispersive X-ray spectroscopy (EDX). Postannealed (675 degrees C for 1 h), BVO nanotubes were a polycrystalline and the XRD studies confirmed the crystal structure to be orthorhombic. The uniformity in diameter and length of the nanotubes as reveled by the TEM and SEM suggested that these were influenced to a guest extent by the thickness and pore diameter of the nanoporous AAO template. EDX analysis demonstrated the formation of stoichiometric Bi2VO5.5 phase. HRTEM confirmed that the obtained BVO nanotubes were made up of nanoparticles of 5-9 nm range. The possible formation mechanism of nanotubes was elucidated.

Hydrogen-bonded sheets in 2-(2-aminophenyl)-1H-benzimidazol-3-ium dihydrogen phosphate.

The title salt, C(13)H(12)N(3)(+).H(2)PO(4)(-), contains a nonplanar 2-(2-aminophenyl)-1H-benzimidazol-3-ium cation and two different dihydrogen phosphate anions, both situated on twofold rotation axes in the space group C2. The anions are linked by O-H...O hydrogen bonds into chains of R(2)(2)(8) rings. The anion chains are linked by the cations, via hydrogen-bonding complementarities and electrostatic interactions, giving rise to a sheet structure with alternating rows of organic cations and inorganic anions. Comparison of this structure with that of the pure amine reveals that the two compounds generate characteristically different sheet structures. The anion-anion chain serves as a template for the assembly of the cations, suggesting a possible application in the design of solid-state materials.

Molten salt synthesis of nanocrystalline phase of high dielectric constant material CaCu3Ti4O12.

Nanocrystalline powders of giant dielectric constant material, CaCu3Ti4O12 (CCTO), have been prepared successfully by the molten salt synthesis (MSS) using KCl at 750 degrees C/10 h, which is significantly lower than the calcination temperature (approximately 1000 degrees C) that is employed to obtain phase pure CCTO in the conventional solid-state reaction route. The water washed molten salt synthesized powder, characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) confirmed to be a phase pure CCTO associated with approximately 150 nm sized crystallites of nearly spherical shape. The decrease in the formation temperature/duration of CCTO in MSS method was attributed to an increase in the diffusion rate or a decrease in the diffusion length of reacting ions in the molten salt medium. As a consequence of liquid phase sintering, pellets of as-synthesized KCl containing CCTO powder exhibited higher sinterability and grain size than that of KCl free CCTO samples prepared by both MSS method and conventional solid-state reaction route. The grain size and the dielectric constant of KCl containing CCTO ceramics increased with increasing sintering temperature (900 degrees C-1050 degrees C). Indeed the dielectric constants of these ceramics were higher than that of KCl free CCTO samples prepared by both MSS method and those obtained via the solid-state reaction route and sintered at the same temperature. Internal barrier layer capacitance (IBLC) model was invoked to correlate the observed dielectric constant with the grain size in these samples.

Thermal, structural, optical, and dielectric properties of (100 - x)Li2B4O7 - x(BaO-Bi2O3-Nb2O5) glasses and glass-nanocrystal composites.

Transparent glasses in the system (100 - x)Li2B4O7 - x(BaO-Bi2O3-Nb2O5) (x = 10, 20, and 30) were fabricated via the conventional melt-quenching technique. The amorphous and glassy characteristics of the as-quenched samples were established by the differential thermal analyses (DTA) and X-ray powder diffraction (XRD) studies. Glass-nanocrystal composites (GNCs) i.e., the glasses embedded with BaBi2Nb2O9 (BBN) nanocrystals (10-50 nm) were produced by heat-treating the as-quenched glasses at temperatures higher than 500 degrees C. Perovskite BBN phase formation through an intermediate fluorite-like phase in the glass matrix was confirmed via XRD and transmission electron microscopic (TEM) studies. The optical transmission properties of these GNCs were found to have a strong compositional (BBN content) dependence. The refractive index (n = 1.90) and optical polarizability (alphao = 15.3 x 10(-24) cm3) of the GNC (x = 30) were larger than those of as-quenched glasses. The temperature dependent dielectric constant (epsilonr) and loss factor (D) for the glasses and GNCs were determined in the 100-40 MHz frequency range. The epsilonr was found to increase with increase in heat-treatment temperatures, while the loss of the glass-nanocomposites was less than that of as-quenched glasses. The sample heat-treated at 620 degrees C/1 h (x = 30) exhibited relaxor behavior associated with a dielectric anomaly in the 150-250 degrees C temperature range. The frequency dependence of the dielectric maximum temperature was found to obey the Vogel-Fulcher relation (Ea = 0.32 eV and Tf = 201 K).

Nanocrystallization of ferroelectric strontium bismuth vanadium niobate in lithium tetraborate glasses.

Transparent glass samples in (100-3x) (Li2O-2B2O3)-x(SrO-Bi2O3-0.7Nb2O5-0.3V2O5) (10 < or = x < or = 60, in molar ratio) system have been fabricated via conventional melt-quenching technique. The as-quenched samples, of all the compositions under study have been confirmed to be amorphous, by X-ray powder diffraction (XRD) studies. Differential thermal analysis (DTA) was employed to confirm the glassy nature of the as-quenched glasses. Glass composites comprising vanadium doped strontium bismuth niobate nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. Perovskite SrBi2(Nb0.7VO3)2O9-delta phase formation was found to be preceded by an intermediate fluorite phase which was established via XRD and transmission electron microscopy (TEM). The dielectric constants (epsilonr) of the as-quenched glasses as well as the glass nanocrystal composites decreased with increase in frequency (100 Hz-10 kHz) at 300 K. Interestingly, the dielectric constant of the glass nanocrystal composite (heat-treated at 783 K/6 h) undergoes a maximum in the vicinity of the crystallization temperature of the host glass (Li2B4O7) reaching an anomalously high value (approximately 10(6)) at 800 K. Different dielectric mixture formulae were employed to rationalize the dielectric properties of the glass nanocrystal composite. The optical transmission properties of these glass nanocrystal composites were found to have strong compositional dependence.