Optical and structral properties of pure and Ce-doped nanocrystals of barium titanate

Nanocrystals barium titanate (nc-BT) and Ce-doped barium titanate were synthesized by an unusual hydrothermal process. X-ray diffraction and Raman spectroscopy were used to investigate their microstructures, as well as their lattice vibration and photoluminescence (PL) spectra. Particle sizes as small as 20 nm were measured by X-ray diffraction pattern via Scherer equation. The critical size relative to the cubic-tetragonal transition is about 48 nm in nc-BT below which ferroelectricity vanishes. The lattice parameter ratio c/a of is equal to 1.003, much smaller than 1.01 for that of the bulk crystal, leading to a weakening of ferroelectricity. Hydroxyl defects are observed in the Ce-doped nc-BT samples which show a vibrational band at 3300 em t. Good crystallization character and the lattice perfection were characterized by Raman spectra in the nanophase barium titanate. Strong PL spectra centered at 696 and 585 nm were observed in the pure and Ce-doped nc-BT, respectively. PL dependence on temperature and annealing time was examined. A molecule-like recombination and the charge transfer between Ce⁴⁺ and Ce ³⁺ are proposed to elucidate the luminescence process in the nc-BT and Cc-doped nc-BT system.     

In-situ size control and structural characterization of barium titanate nanocrystal prepared by crystallization of amorphous phase

We examined the influence of nanocrystalline particle size on the cubic-to-tetragonal phase transition of barium titanate (BaTiO₃). In-situ X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were used in combination with electron microscopy to study the evolution of lattice structure and phase-transformation behavior with heat treatment and particle growth for BaTiO₃. The lattice constants were obtained for various polycrystal orientations in the diameter size range 10–90 nm. In-situ XRD results during the crystallization of amorphous 4BaTiO₃-SiO₂ revealed a critical size of ∼25 nm for the cubic-to-tetragonal phase transition of BaTiO₃ at room temperature.     

Evolution of the structural and optical properties from cobalt cordierite glass to glass-ceramic based on spinel crystalline phase materials

Co²⁺-containing cordierite stoichiometric glasses have been prepared by melting colloidal gel precursors. After controlled thermal processing in the range of temperatures between 900 and 1300 °C different polycrystalline, almost single phase materials displaying μ-, α-, and β-cordierite crystalline forms were synthesized. In addition, spinel glass-ceramic materials were also prepared from the base glasses. All these materials were characterized by X-ray powder diffraction and infrared spectroscopy. Room temperature (RT) absorption and emission spectra of Co²⁺– cordierites and – spinel-glass material have allowed determining the local environment of the Co²⁺ in the crystalline structure of final materials. Results indicated that whereas in parent glasses and in the μ-cordierite forms there are a large fraction of Co²⁺ in octahedral coordination, in the low (β-) and high (α-) temperature crystalline forms the proportion of Co²⁺ in tetrahedral coordination increased. The final CoAl₂O₄-glass composite showed absorption and emission spectra very similar to the sol–gel CoAl₂O₄ spinel, both displaying pure Co²⁺ tetrahedral coordination.     

On the preparation and sintering behaviour of barium titanate

The present contribution reports on the preparation of BaTiO₃ powders in various ways including the characterization and the sintering behaviour. The powders were synthesized by using precursors like BaTiO(C₂O₄)₂ · 4 H₂O and BaTiO₂(O₂) · 3 H₂O, or by an alcoholate/hydroxide method, by a successive precipitation from solutions with following thermal treatment, or by the conventional route from BaCO₃ and TiO₂. The thermal decomposition of the precursors to BaTiO₃ is described. The different sintering behaviour of BaTiO₃ compacts is the consequence of granulometric properties and of their content of impurities. Possible sintering mechanisms are discussed.     

Synthesis,characterization and structural phase transition studies in trismethylammonium pentachloro barium dihydrate single crystals

Single crystals of trismethylammonium pentachlorobarium dihydrate were grown by slow evaporation method at ambient temperature. The crystals were characterized through powder XRD, thermal, infrared and NMR spectral studies. While the powder XRD pattern confirms the crystallinity of the title compound, the TG indicates the removal of occluded and adsorbed water molecules from the crystal when it is heated up to 86 °C. The TG study also confirms the presence of two water molecules of crystallization which are dehydrated on heating the crystal between 107 °C and 150 °C. The anhydrous compound is found to be stable at least up to 900 °C. The DTA curve shows two endothermic dips corresponding to weight losses observed in the TG curve. The low temperature DSC study shows thermal anomalies during the heating and cooling cycles indicating both first and second order phase transitions. The high temperature DSC shows the stepwise dehydration indicating phase transitions at temperatures 103 °C and 145 °C. The characteristic vibrational frequencies due to methylammonium ion, BaCl₅ and other groups are assigned based on FTIR spectra. The NMR spectrum confirms the presence of protons of the methyl group and water of crystallization in the compound. In this paper, an attempt is also made to understand the effect of methyl group on the phase transitions of the compound in comparison with a closely related compound, trisammoniumpentachloro barium dihydrate. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties of biocompatible polyaniline nano-composites

Polyaniline (PANI) is an electro-active polymer of great interest thanks to its outstanding physical and chemical properties which make it suitable for various applications in optics, bioelectronics, biosensors, diagnostics and therapeutic devices. Unfortunately, PANI is infusible and insoluble in most common solvents and, thus, very difficult to process. In the attempt of improving processability, yet preserving its interesting properties, PANI has been synthesized in the form of particles and dispersed into a hydrogel matrix. The synthesis of PANI–hydrogel composites proceeds via γ-irradiation of PANI dispersions as obtained by ‘in situ’ polymerization of aniline in the presence of water-soluble, polymeric stabilizers. The chosen stabilizers are able to undergo to chemical cross-linking when exposed to ionizing radiations, so forming the highly hydrophilic network that entrap PANI particles. The presence of a hydrogel matrix induces biocompatibility to the final composite material which, in a typical bottom-up approach, may become suitable for the development of biocompatible, optoelectronic devices. Some morphological and optical features of these novel soft, functional nano-composites are here presented.     

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Physical structure of P(VDF-TrFE)/barium titanate submicron composites

Dynamic Dielectric Spectroscopy and Thermo Stimulated Current were used to investigate of the dielectric relaxation of hybrid Poly(vinylidene-fluoride-trifluoroethylene)/barium titanate 700 nm composites with 0–3 connectivity. The results obtained by this method allow us to describe the physical structure of these composites in the glassy state at a nanometric scale. The decrease of the activation enthalpies and activation entropies involved in the dynamics of the α relaxation is attributed to: the decrease of Cooperative Rearranging Region sizes and an increase of intra/inter macromolecular interactions in the amorphous phase with the volume fraction.     

Influence of alternating electric fields on the crystallization of barium titanate glasses

The paper is concerned with the question as to how far low-frequency electric fields exert an influence on the crystallization process. The results for a glass of the composition 75 mol.% BaO---TiO₂, 19 mol.% SiO₂, 6 mol.% Al₂O₃ show that the samples which are influenced by electric fields have a higher degree of crystallization than the electrically uninfluenced samples under well-defined annealing conditions.     

Growth and optical property characterization of textured barium titanate thin films for photonic applications

We have investigated the growth of barium titanate thin films on bulk crystalline and amorphous substrates utilizing biaxially oriented template layers. Ion beam-assisted deposition was used to grow thin, biaxially textured, magnesium oxide template layers on amorphous and silicon substrates. Growth of highly oriented barium titanate films on these template layers was achieved by molecular beam epitaxy using a layer-by-layer growth process. Barium titanate thin films were grown in molecular oxygen and in the presence of oxygen radicals produced by a 300 W radio frequency plasma. We used X-ray and in situ reflection high-energy electron diffraction (RHEED) to analyze the structural properties and show the predominantly c-oriented grains in the films. Variable angle spectroscopic ellipsometry was used to analyze and compare the optical properties of the thin films grown with and without oxygen plasma. We have shown that optical quality barium titanate thin films, which show bulk crystal-like properties, can be grown on any substrate through the use of biaxially oriented magnesium oxide template layers.     

Synthesis and characterization of magnesium doped lead titanate

Magnesium (Mg) doped lead titanate powders (PT: Mg) ceramics, with various Mg contents (0, 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, and 30 mole %), are prepared by the sol‐gel method and characterized by X‐Ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. XRD results show that the magnesium diminishes the lattice tetragonality of PT:Mg. The average particle size and morphology were studied by SEM. The investigations done by Raman spectroscopy allow the analyzis of the substitution mechanism behavior related to the Mg incorporation into PT structure. A concentration threshold appears around 10% of Mg corresponding in a change of the compensation process with Mg²⁺ ions replacing Pb²⁺ ions below and both Pb²⁺ and Ti⁴⁺ above. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,growth, morphology and characterization of ferroelectric glycine phosphite single crystals

Glycine phosphite (NH₃CH₂COO.H₃PO₃), a potential ferroelectric material, was grown as single crystals from aqueous solutions by slow evaporation and slow cooling methods. Laboratory synthesized title compound was purified by recrystallization method and confirmed by Fourier transform infrared and Laser Raman studies. Temperature dependent solubility in double distilled water in the range between 288 and 328 K was determined by gravimetric method. Morphological importance of various growth faces were studied by optical goniometry. Powder x‐ray diffraction study performed on the grown crystals confirms the crystal system and lattice parameters of the unit cell. Optical transparency of the grown crystals in the ultraviolet–visible ‐near infrared region was studied by spectroscopic method. Thermal stability of the grown crystals in the temperature region above ambient until melting was studied using differential scanning calorimetry. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural relaxation and optical properties in transparent nanocrystalline β-quartz glass-ceramic

We studied structural relaxation in a nanocrystalline β-quartz solid solution (s.s.) glass-ceramic through density measurement, and the effect of structural relaxation on its optical properties. The density of the glass-ceramic changed as structural relaxation proceeded in the glass phase. It was found that the glass-ceramic whose glass phase has a high fictive temperature shows a high optical transmittance because of less optical scattering. We also demonstrated that the refractive index difference between the crystal and glass phases can be calculated from the scattering coefficients of the specimens with different fictive temperatures. The calculated refractive index of the crystalline phase was in fair agreement with the indices of a high-quartz crystal.     

Optical properties of zinc barium silicate glasses

A serial of glasses samples with the higher ZnO concentration from 30 mol% to 45 mol% were prepared and their optical absorption and photoluminescence properties were investigated. It is shown that the composition of glass strongly affects the position of the absorption edge and emission band where a fairly big red-shift was observed with increasing of ZnO concentration. It is most likely attributed to the reduced quantum confinement effect due to increased aggregation degree of ZnO in the glass matrix. The introduction of F^? into zinc barium silicate glasses leads to a notable red-shift of the absorption spectra, as well as the enhanced UV emission and distinctive visible emissions.     

Rheological properties of potassium barium borate glasses

Several series of potassium barium borate glasses have been investigated as to their rheological properties.It has been found, that all these glasses show deviations from ‘Newtonian’ behaviour below temperatures corresponding to viscosities of 10¹⁰ poises. The activation energies of viscous flow are linear in both the potassium and barium mole percentages.For the ternary systems the pre-exponential factors of the viscosities do not decrease considerably with increasing metal ion content, contratry to what has been found in binary systems.     

Structural and optical properties of lithium barium bismuthate glasses

Structural and optical properties of some ion-conducting lithium barium bismuthate glasses have been studied. The structure of these glasses has been explored from the compositional variation of the density, the molar volume and the glass transition temperature. The density and the molar volume decrease with the increase of lithium ion content in these glasses keeping the barium content fixed. The optical studies in the ultraviolet–visible (UV–VIS) and infrared (IR) regions for all these glasses show a sharp cut-off and a large transmitting window, which make them appealing candidates for the different spectral devices.     

Electrical,structural and optical properties of amorphous carbon

The planar and transverse electrical resistivity of amorphous carbon (a-C) films getter-sputtered at low temperature (77–95 K) is well-fitted by the expression $\text{? = ?}{}_0\text{exp}\text{(T}{}_0\text{/T)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$ The exponent T₀ being approximately the same in both cases (≈ 7 × 10⁷ K) suggests that the amorphous films are isotropic. Films thinner than 600 Å display a two-dimensional hopping conductivity from which one deduces a density of states N(E_F) at the Fermi level of 10¹⁸ eV^?1 cm^?3 and a radius of the localized wave functions (a) of 12 Å. Tunneling experiments and optical absorption measurements are consistent with a pseudogap of approximately 0.8 eV. Electron diffraction experiments indicate that a-C films consist of a mixture of diamond and graphite bonds; this fact taken in the light of the other experiments would suggest that the graphite bonds act as the localized conduction states.     

Structural,ferroelectric and magnetic properties of Bi0.85Sm0.15FeO3 perovskite

Room temperature crystal structure, ferroelectric and magnetic properties of polycrystalline Bi_0.85Sm_0.15FeO₃ samples were investigated. X‐ray diffraction study shows that the compound possesses a dominant PbZrO₃‐like orthorhombic structure with √2a ×2√2a ×2a superlattice (a is the parameter of the cubic perovskite subcell). In contrast to piezoresponse force microscopy data demonstrating some features characteristic of ferroelectrics, polarization vs. electric field measurements reveal the behavior expected for nonpolar materials. Investigation of magnetic properties confirms that 15% samarium substitution suppresses the spin modulation typical of BiFeO₃ and induces the appearance of spontaneous magnetization. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)