Dynamical study of ZnO nanocrystal and Zn-HDS layered basic zinc acetate formation from sol-gel route

We have pointed out that zinc based particles obtained from ethanolic solution of a zinc acetate derivative (zinc oxy-acetate, Zn4O(Ac)(6)) are a mixture of nanometer sized ZnO, zinc oxy-acetate, and zinc hydroxide double salt (Zn-HDS). The knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, and the evolution of Zn species in reaction medium was monitored in situ during 14 h by simultaneous measurements of UV-vis absorption and extended X-ray absorption fine structures (EXAFS) spectra. This spectroscopic monitoring was initialized just after the addition of an ethanolic lithium hydroxide solution ([LiOH]/[Zn] = 0. 1) to the reaction medium kept under controlled temperature (40 degrees C). This study points out the first direct evidence of the reaction between ZnO nanoparticles and unreacted zinc oxy-acetate to form a Zn-HDS phase. The dissolution of ZnO and the reprecipitation of Zn-HDS are induced by the gradual release of water mainly produced by ethanol esterification well evidenced by gas chromatography coupled to mass spectroscopy and FT-IR measurements.

SAXS study of the kinetics of formation of ZnO colloidal suspensions

We have investigated, by in situ small-angle X-ray scattering (SAXS), the kinetics of formation of zinc oxide colloidal suspensions obtained after refluxing alcoholic solution of zinc acetate and catalysed by lithium hydroxide. The experimental results demonstrate that the suspensions are composed of colloidal spheroidal particles with a multimodal size distribution. The average radius of the main mode, approximately 2 nm, is invariant but the number of these basic particles continuously increases for increasing hydrolysis reaction time. The other two modes correspond to particles with average radii close to 6 and 10 nm, respectively. The larger particles are formed by coagulation of the smaller ones. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Upconversion fluorescence spectroscopy of Er3+/Yb3+-doped heavy metal Bi2O3-Na2O-Nb2O5-GeO2 glass

Upconversion fluorescence emission of Er3+/Yb3+-doped Bi2O3-Na2O-Nb2O5-GeO2 heavy metal glass samples excited at 1.06 mu m is experimentally investigated. The results reveal the existence of intense emission bands centered around 520, 545, and 655 nm. The germano-niobate based host glass presents high transparency in the region of 400-2700 nm, the capability of incorporating high dopant concentrations, high melting temperature, and large resistance to atmospheric moisture. The observed intensity of the green fluorescence emission, suggested that the niobium based host glass material plays an important role in the efficiency of the upconversion process. Emission lines centered at 425, 483, 503, 608, and 628 nm were also observed. (C) 1997 American Institute of Physics.

Voltage responsivity of pyroelectric sensor

Composites polymer-ceramic using castor oil-based polyurethane (PU) as non-ferroelectric matrix and Lead Zirconate Titanate (PZT) as ceramic powder have been prepared at thin films form by spin coating. The samples are poled by appropriated electric field to show piezo and pyroelectric activity. The pyroelectric coefficient p(T) at 343 K is obtained to be equal 5.8 X 10(-5) C m(-2) K-1 for a composite with 32 vol.% of ceramic. The figure of merit of this composite is six times higher than of PZT ceramic. The voltage responsivity of the pyroelectric is reduced when the thickness of the sample increases. It was used modulated white light as radiation source to excite the sensor film. The electric signal of the sensor decreases with the light modulation frequency by 1/f. (C) 1999 Elsevier B.V. S.A. All rights reserved.

Quantitative structural analysis of the transition from LT-LixCoO2 to HT-LixCoO2 using the rietveld method: correlation between structure and electrochemical performance

A quantitative phase analysis was made of LiXCoO2 powders obtained by two distinct chemical methodologies at different temperatures (from 400 to 700degreesC). A phase analysis was made using Rietveld refinements based on X-ray diffraction data, considering the LiXCoO2 powders as a multiphase system that simultaneously contained two main phases with distinct, layered and spinel-type structures. The sults showed the coexistence of both structures in LiXCoO2 obtained at low temperature (400 and 500degreesC), although only the layered structure was detected at higher temperatures (600 and 700degreesC, regardless of the chemical powder process employed. The electrochemical performance, evaluated mainly by the cycling reversibility of LiXCoO2 in the form of cathode insertion electrodes, revealed that there is a close correlation between structural features and the electrochemical response, with one of the redox processes (3.3 v/3.9 v) associated only with the presence of the spinel-type structure. (C) 2003 Elsevier B.V. All rights reserved.

Mechanical and electrical driving field induced high-frequency dielectric anomalies in ferroelectric systems

Polycrystalline or single-crystal ferroelectric materials present dielectric dispersion in the frequency range 100 MHz-1 GHz that has been attributed to a dispersive ( relaxation-like) mechanism as well as a resonant mechanism. Particularly in 'normal' ferroelectric materials, a dielectric response that is indistinguishable from dispersion or a resonance has been reported. Nevertheless, the reported results are not conclusive enough to distinguish each mechanism clearly. A detailed study of the dielectric dispersion phenomenon has been carried out in PbTiO3-based ferroelectric ceramics, with the composition Pb1-xLaxTiO3 (x = 0.15), over a wide range of temperatures and frequencies, including microwave frequencies. The dielectric response of La-modified lead titanate ferroelectric ceramics, in 'virgin' and poled states, has been investigated in the temperature and frequency ranges 300-450 K and 1 kHz-2 GHz, respectively. The results revealed that the frequency dependence of the dielectric anomalies, depending on the measuring direction with respect to the orientation of the macroscopic polarization, may be described as a general mechanism related to an 'over-damped' resonant process. Applying either a uniaxial stress along the measurement field direction or a poling electric field parallel and/or perpendicular to the measuring direction, a resonant response of the real and imaginary components of the dielectric constant is observed, in contrast to the dispersion behavior obtained in the absence of the stress, for the 'virgin' samples. Both results, resonance and/or dispersion, can be explained by considering a common mechanism involving a resonant response (damped and/or over-damped) which is strongly affected by a ferroelastic-ferroelectric coupling, contributing to the low-field dielectric constant.

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

Silica-PEG hybrid ormolytes: structure and properties

The effect of lithium salt doping on the structure and ionic conduction properties of silica-polyethyleneglycol composites is reported. These materials, so called ormolytes (organically modified electrolytes), were obtained by the sol-gel process. They have chemical stability due to the covalent bonds between the inorganic (silica) and organic (polymer) phase. The structure of these hybrid materials was investigated by small-angle X-ray scattering (SAXS) as a function of lithium concentration [O]/[Li] (O being the oxygens of the ether type). The spectra have a well-defined peak attributed to the existence of a liquid-like spatial correlation of silica clusters. The ionic conductivity was studied by AC impedance spectroscopy and is maximum for [O]/[Li] = 15. This result is consistent with SAXS and thermo-mechanical analysis measurements and is due to the formation of cross-linking between the polymer chains for the larger lithium concentrations. These materials are solid, transparent, flexible and have an ionic conductivity up to 10(-4) S/cm. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Thermal properties of fluoride glasses and their gel precursors

Xerogels were prepared from zirconium, barium, aluminum, lanthanum and lithium acetates, corresponding to a Li containing ZBLA composition. The study of their thermal properties (DSC, TG/DTG, FT-IR) showed that they might be used as chemically stable precursors in the preparation of fluoride glasses. Hydrofluoric acid in solution was chosen as a mild fluorinating agent. This newly proposed technique of fluorinating allowed to obtain high quality ZBLALi glass which presents the advantage of higher thermal stability and homogeneity in comparison with the glass obtained using individual commercial fluorides.

Effect of thermal treatment temperature on the crystallinity and morphology of LiTaO3 thin films prepared from polymeric precursor method

Lithium tantalate thin films (LiTaO3) with (50:50) stoichiometry were prepared by spin coating method using a polymeric organic solution. The films were deposited on silicon (100) substrates with 4 layers. The substrates were previously cleaned and then the solution of lithium tantalate was deposited by adjusting the speed at 5000 rpm. The thin films deposited were thermally treated from 350 to 600degreesC for 3 hours in order to study the influence of the thermal treatment temperature on the crystallinity, microstructure, grain size and roughness of the final film. X-ray diffraction (XRD) results showed that the films are polycrystalline and secondary phases free. The thickness of films was observed by scanning electron microscopy (SEM). The atomic force microscopy (AFM) studies showed that the grain size and roughness are strongly influenced by thermal treatment.

Partial purification and characterization of pectin methylesterase from orange (Citrus sinensis) cv. Pera-rio

The enzyme pectin methylesterase (PME) from orange was extracted and partially purified by filtration on Sephadex G-100. The extraction buffer for orange PME was borate-acetate containing 0.4 M NaCl. Orange PME showed optimum pH at 8.0 and optimum temperature at 50C. The PME enzyme was completely inactivated after 1 min of incubation at 90C. The specific activity increased in the presence of 0.15 M NaCl or 0.025 M Na2SO4, 0.10 M KCl, 0.025 M K2SO4, 0.05 and 0.1 M NH4Cl. Lithium chloride and Li(2)SO(4)inhibited the enzymatic activity at all concentrations studied. The K-m and V(max)value of PME were 0.36 mg/mL and 5.26 mu mol/mL-mg protein, respectively.

Transparent and conductive ZnO : Al thin films prepared by sol-gel dip-coating

Aluminum doped zinc oxide polycrystalline thin films (AZO) were prepared by sol-gel dip-coating process. The sol was prepared from an ethanolic solution of zinc acetate using lithium hydroxide or succinic acid as hydrolytic catalyst. The quantity of aluminum in the sol was varied from 1 to 10 mol%. The structural characteristics studied by X-ray diffractometry were complemented by resistivity measurements and UV-Vis-NIR spectroscopy. The films are transparent from the near ultraviolet to the near infrared, presenting an absorption cut-off at almost 290 nm, irrespective of the nature of the catalyst and doping level. The best conductors were obtained for the AZO films containing 3 mol% of aluminum, prepared under acidic and basic catalysis and sintered at 450 degreesC. Their optical band-gap of 4.4 eV calculated from the absorption cut-off is larger than the values for band-gap widening predicted by the standard model for polar semiconductors. These polycrystalline films are textured with preferential orientation of grains along the wurtzite c-axis or the (100) direction. (C) 2003 Elsevier Ltd. All rights reserved.

Effect of preannealing on the morphology of LiTaO3 thin films prepared from the polymeric precursor method

Lithium tantalate (LiTaO3) thin films with 50:50 stoichiometry were deposited on silicon (100) substrates with two layers by the spin coating method using a polymeric organic solution. In order to study the influence of preannealing on the crystallinity, microstructure, grain size and roughness of the final film, two annealing procedures, slow preannealing and fast preannealing, were used. X-ray diffraction (XRD) results showed that LiTaO3 thin films are polycrystalline. It was observed by scanning electron microscopy (SEM) that the thin film, which had been thermally treated using slow preannealing, was characterized by a dense and homogeneous surface. The atomic force microscopy (AFM) studies showed that the roughness is strongly influenced by preannealing temperature. (C) 2003 Elsevier B.V. All rights reserved.

Effect of oxygen atmosphere on the morphology of LiTaO3 thin films prepared from polymeric precursor method

Lithium tantalate (LiTaO3) thin films with (50:50) stoichiometry were prepared using polymeric organic solution. The 5-layered films were deposited on silicon (100) substrates by spin coating method. The coated substrates were thermally treated at 500degreesC for 3 h under several oxygen atmospheres in order to study the influence of oxygen flow on the crystallinity, microstructure, grain size and roughness of the final film. X-ray diffraction results showed that an oxygen flow of 100 cm(3)/min leads to LiTaO3 thin films with higher crystallinity, without preferential orientation. It was observed by scanning electron microscopy (SEM) that the thickness of thin films decreases when the oxygen flow increases. The atomic force microscopy (AFM) studies showed that the grain size and roughness are strongly influenced by oxygen flow.

Structure of weakly bonded PPG-silica nanocomposites

The structure of silica-polypropyleneglycol (PPG) nanocomposites with weak physical bonds between the organic (PPG) and inorganic (silica) phase, prepared by the sol-gel process, was investigated by small angle X-ray scattering (SAXS). These nanocomposite materials are transparent, flexible, have good chemical stability and exhibit high ionic conductivity when doped with lithium salt. Their structure was studied as a function of silica weight fraction x (0.06 less than or equal to x less than or equal to 0.29) and [O]/[Li] ratio (oxygens being of ether-type). The shape of the experimental SAXS curves agrees with that expected for scattering intensity produced by fractal aggregates sized between 30 and 90 Angstrom. This result suggests that the structure of the studied hybrids consists of silica fractal aggregates embedded in a matrix of PPG. The correlation length of the fractal aggregates decreases and the fractal dimension increases for increasing silica content. The variations in structural parameters for increasing Li+ doping indicate that lithium ions favor the growth of fractal silica aggregates without modifying their internal structure and promote the densification of the oligomeric PPG matrix.