Structural and lithium ion transport studies in sol-gel-prepared lithium silicophosphate glasses

Lithium silicophosphate glasses have been prepared by a sol-gel route over a wide range of compositions. Their structural and electrical properties have been investigated. Infrared spectroscopic studies show the presence of hydroxyl groups attached to Si and P. MAS NMR investigations provide evidence for the presence of different phosphatic units in the structure. The variations of de conductivities at 423 K and activation energies have been studied as a function of composition, and both exhibit an increasing trend with the ratio of nonbridging oxygen to bridging oxygen in the structure. Ac conductivity behavior shows that the power law exponent, s, is temperature dependent and exhibits a minimum. Relaxation behavior has been examined in detail using an electrical modulus formalism, and modulus data were fitted to Kohlraush-William-Watts stretched exponential function. A structural model has been proposed and the unusual properties exhibited by this unique system of glasses have been rationalized using this model. Ion transport in these glasses appears to be confined to unidimensional conduits defined by modified phosphate chains and interspersed with unmodified silica units.

Assembly of sol-gel-grown $Li _{(x)} CoO_{2}$ nanocrystals through electromagnetic irradiation

We report the fabrication of assembled nanostructures from the pre-synthesized nanocrystals building blocks through optical means of exciton formation and dissociation. We demonstrate that Li (x) CoO2 nanocrystals assemble to an acicular architecture, upon prolonged exposure to ultraviolet-visible radiation emitted from a 125 W mercury vapor lamp, through intermediate excitation of excitons. The results obtained in the present study clearly show how nanocrystals of various materials with band gaps appropriate for excitations of excitons at given optical wavelengths can be assembled to unusual nanoarchitectures through illumination with incoherent light sources. The disappearance of exciton bands due to Li (x) CoO2 phase in the optical spectrum of the irradiated film comprising acicular structure is consistent with the proposed mechanism of exciton dissociation in the observed light-induced assembly process. The assembly process occurs through attractive Coulomb interactions between charged dots created upon exciton dissociation. Our work presents a new type of nanocrystal assembly process that is driven by light and exciton directed.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively.

Some studies on TiO2 films deposited by sol-gel technique

TiO2 films are extensively used in various applications including optical multi-layers, sensors, photo catalysis, environmental purification, and solar cells etc. These are prepared by both vacuum and non-vacuum methods. In this paper, we present the results on TiO2 thin films prepared by a sol-gel spin coating process in non-aqueous solvent. Titanium isopropoxide is used as TiO2 precursor. The films were annealed at different temperatures up to 3000 C for 5 hours in air. The influence of the various deposition parameters like spinning speed, spinning time and annealing temperature on the thickness of the TiO2 films has been studied. The variation of film thickness with time in ambient atmosphere was also studied. The optical, structural and morphological characteristics were investigated by optical transmittance-reflectance measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM) respectively. The refractive index and extinction coefficient of the films were determined by envelope technique and spectroscopic ellipsometry. TiO2 films exhibited high transparency (92%) in the visible region with a refractive index of 2.04 at 650 nm. The extinction coefficient was found to be negligibly small. The X-ray diffraction analysis showed that the TiO2 film deposited on glass substrate changes from amorphous to crystalline (anatase) phase with annealing temperature above 2500 C. SEM results show that the deposited films are uniform and crack free.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively. (C) 2008 Elsevier B.V. All rights reserved.

Sol → gel transition with rings in a finite polycondensing system in solution

We report a theoretical formulation for the mean cluster size distribution in a finite polycondensing system. Expressions for the mean number of n-mers with j bonds ( nj) are developed. Numerical calculations show that while the non-cyclic molecules make the dominant contribution to the small clusters, the large clusters are dominated by cyclic structures. The number of particles in ringless chains, n n,n-1, decays monotonically with n at all extents of reaction, but n n becomes bimodal near the gel point. We also find that the solvent plays an important role in the cluster size distribution.

Re-examination of one-point methods of liquid limit determination

This Paper deals with the analysis of liquid limit of soils, an inferential parameter of universal acceptance. It has been undertaken primarily to re-examine one-point methods of determination of liquid limit water contents. It has been shown by basic characteristics of soils and associated physico-chemical factors that critical shear strengths at liquid limit water contents arise out of force field equilibrium and are independent of soil type. This leads to the formation of a scientific base for liquid limit determination by one-point methods, which hitherto was formulated purely on statistical analysis of data. Available methods (Norman, 1959; Karlsson, 1961; Clayton & Jukes, 1978) of one-point liquid limit determination have been critically re-examined. A simple one-point cone penetrometer method of computing liquid limit has been suggested and compared with other methods. Experimental data of Sherwood & Ryley (1970) have been employed for comparison of different cone penetration methods. Results indicate that, apart from mere statistical considerations, one-point methods have a strong scientific base on the uniqueness of modified flow line irrespective of soil type. Normalized flow line is obtained by normalization of water contents by liquid limit values thereby nullifying the effects of surface areas and associated physico-chemical factors that are otherwise reflected in different responses at macrolevel.Cet article traite de l'analyse de la limite de liquidité des sols, paramètre déductif universellement accepté. Cette analyse a été entreprise en premier lieu pour ré-examiner les méthodes à un point destinées à la détermination de la teneur en eau à la limite de liquidité. Il a été démontré par les caractéristiques fondamentales de sols et par des facteurs physico-chimiques associés que les résistances critiques à la rupture au cisaillement pour des teneurs en eau à la limite de liquidité résultent de l'équilibre des champs de forces et sont indépendantes du type de sol concerné. On peut donc constituer une base scientifique pour la détermination de la limite de liquidité par des méthodes à un point lesquelles, jusqu'alors, n'avaient été formulées que sur la base d'une analyse statistique des données. Les méthodes dont on dispose (Norman, 1959; Karlsson, 1961; Clayton & Jukes, 1978) pour la détermination de la limite de liquidité à un point font l'objet d'un ré-examen critique. Une simple méthode d'analyse à un point à l'aide d'un pénétromètre à cône pour le calcul de la limite de liquidité a été suggérée et comparée à d'autres méthodes. Les données expérimentales de Sherwood & Ryley (1970) ont été utilisées en vue de comparer différentes méthodes de pénétration par cône. En plus de considérations d'ordre purement statistque, les résultats montrent que les méthodes de détermination à un point constituent une base scientifique solide en raison du caractère unique de la ligne de courant modifiée, quel que soit le type de sol La ligne de courant normalisée est obtenue par la normalisation de la teneur en eau en faisant appel à des valeurs de limite de liquidité pour, de cette manière, annuler les effets des surfaces et des facteurs physico-chimiques associés qui sans cela se manifesteraient dans les différentes réponses au niveau macro.

Hybrid Sol-Gel Combustion Synthesis of Nanoporous Anatase

Nanoporous anatase with a thin interconnected filmlike morphology has been synthesized in a single step by coupling a nonhydrolytic condensation reaction of a Ti precursor with a hybrid sol-gel combustion reaction. The method combines the advantages of a conventional sol-gel method for the formation of porous structures with the high crystallinity of the products obtained by combustion methods to yield highly crystalline, phase-pure nanoporous anatase. The generation of pores is initiated by the formation of reverse micelles in a polymeric polycondensation product, which expand during heating, leading to larger pores. A reaction scheme involving a complex formation and nonhydrolytic polycondensation reaction with ester elimination leads to the formation of ail extended Ti-O-Ti network. The effect of process parameters, such as temperature and relative ratio of cosurfactants, on phase formation has been studied. The possibility of band gap engineering by controlled doping during synthesis and the possibility of attachment of molecular/nanoparticle sensitizers provide opportunities for easy preparation of photoanodes for solar cell applications.

Optical, dielectric and morphological studies of sol-gel derived nanocrystalline TiO2 films

Nanocrystalline TiO2 films have been synthesized on glass and silicon substrates by sol-gel technique. The films have been characterized with optical reflectance/transmittance in the wavelength range 300-1000nm and the optical constants (n, k) were estimated by using envelope technique as well as spectroscopic ellipsometry. Morphological studies have been carried Out using atomic force microscope (AFM). Metal-Oxide-Silicon (MOS) capacitor was fabricated using conducting coating on TiO2 film deposited on silicon. The C-V measurements show that the film annealed at 300 degrees C has a dielectric constant of 19.80. The high percentage of transmittance, low surface roughness and high dielectric constant suggests that it can be used as an efficient anti-reflection coating on silicon and other optical coating applications and also as a MOS capacitor.

Sol-Gel Template Synthesis, Structural Characterization and Growth Mechanism of Barium Zirconate Nanotubes

In this paper, we report the synthesis of barium zirconate, BaZrO3, (BZ) nanotubes fabricated by the modified sol-gel method within the nanochannels of anodic aluminum oxide (AAO) templates. The morphology, structure, and composition of as prepared nanotubes were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), selected-area electron diffraction ( SAED), high resolution TEM (HRTEM) and energy-dispersive X-ray spectroscopy (EDX). The results of XRD and SAED indicated that postannealed (at 650 degrees C for 1 h) BZ nanotubes (BZNTs) exhibited a polycrystalline cubic perovskite crystal structure. SEM and TEM analysis revealed that BZNTs possessed a uniform length and diameter (similar to 200 nm) and the thickness of the wall of the BZNTs was about 20 nm. Y-junctions, multiple branching and typical T-junctions were also observed in some BZNTs. EDX analysis demonstrated that stoichiometric BaZrO3 was formed. HRTEM image confirmed that the obtained BZNTs were composed of nanoparticles in the range of 5-10 nm. The possible formation mechanism of BZNTs was discussed.

Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol-gel route

Sol-gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn1-xLixO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400-500 degrees C. Ferroelectricity in Zn0.85Li0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C-V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P-s) and coercive field were 0.15 mu C/cm(2) and 20 kV/cm, respectively, confirming the presence of ferroelectricity.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO2 thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO2 films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO2 films was estimated by Tauc's method at different annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

Slim P‐E hysteresis loop and anomalous dielectric response in sol-gel derived antiferroelectric PbZrO3 thin films

Sol-gel derived PbZrO3 (PZ) thin films have been deposited on Pt(111)/Ti/SiO2/Si substrate and according to the pseudotetragonal symmetry of PZ, the relatively preferred (110)t oriented phase formation has been noticed. The room temperature P‐E hysteresis loops have been observed to be slim by nature. The slim hysteresis loops are attributed to the [110]t directional antiparallel lattice motion of Pb ions and by the directionality of the applied electric field. Pure PZ formation has been characterized by the dielectric phase transition at 235 °C and antiferroelectric P‐E hysteresis loops at room temperature. Dielectric response has been characterized within a frequency domain of 100 Hz–1 MHz at various temperatures ranging from 40 to 350 °C. Though frequency dispersion of dielectric behaves like a Maxwell–Wagner type of relaxation, ω2 dependency of ac conductivity indicates that there must be G‐C equivalent circuit dominance at high frequency. The presence of trap charges in PZ has been determined by Arrhenius plots of ac conductivity. The temperature dependent n (calculated from the universal power law of ac conductivity) values indicate an anomalous behavior of the trapped charges. This anomaly has been explained by strongly and weakly correlated potential wells of trapped charges and their behavior on thermal activation. The dominance of circuit∕circuits resembling Maxwell–Wagner type has been investigated by logarithmic Nyquist plots at various temperatures and it has been justified that the dielectric dispersion is not from the actual Maxwell–Wagner-type response.

Template-Assisted Sol-Gel Synthesis of Nanocrystalline BaTiO3

Nanocrystalline perovskite barium titanate with an average particle size less than similar to 10 nm is produced using sol-gel route involving ligand-assisted templating. BaTiO3 is obtained by the controlled hydrolysis and condensation reaction of barium acetate (Ba(CH3COO)(2)) with titanium tetra chloride (TiCl4) in the reverse micelles of dodecylamine (DDA) which is used as the template. Our attempts to produce mesoporous BaTiO3 have resulted in the formation of nanocrystalline BaTiO3. The synthesis of nanostructured BaTiO3 is carried out using the ligand-assisted templating approach which proceeds through the sol-gel route. Dodecylamine is used as the template. The sol-gel process in general presents inherent advantages because the nanostructure of the desired materials can be controlled together with their porous structure. Ligand-assisted templating approach involves the formation of covalent bond between the inorganic analogue and the template. Ba(CH3COO)(2) and TiCl4 are used as barium-source and titanium-source respectively. The reaction between Ba(CH3COO)(2) and TiCl4 is found to take place deliberately on the pre-assembled species which acts as the template or occurring with in them which in turn will lead to the generation of the desired nanoscale structure (nanopores or nanoparticles).