Structural and spectroscopic analysis of gamma-Al2O3 to alpha-Al2O3-CoAl2O4 phase transition

Co-doped alumina powders were synthesized by means of the polymeric precursor method to obtain ceramic pigments. The effect of different contents of Co2+ on phase transition gamma to alpha-Al2O3 and appearing of CoAl2O4 spinel were studied by means of X-ray diffraction. A partial phase diagram of the system CoAl2O3 was proposed from these data by means of determination of the percentages of these phases according to the calcining temperature. Critical particle size to phase transition was determined by means of calculations of crystallite size and determination of superficial area through the BET method. UV-vis spectroscopy of the samples allow to compare the band shift with the phase transition. Besides, a study of thermal stability and intensity of the blue coloration of the synthesized powders with the presence of cobalt in relation to the calcining temperature was accomplished and compared to the phase transition. The results show that the higher blue color intensity was obtained for the powders with Co-doped gamma-Al2O3 closest of phase transition to alpha-Al2O3 + CoAl2O4. (c) 2005 Elsevier B.V. All rights reserved.

Photoluminescence in disordered sm-doped PbTiO3: Experimental and theoretical approach

Sm-doped PbTiO3 powder was synthesized by the polymeric precursor method, and was heat treated at different temperatures. The x-ray diffraction, photoluminescence, and UV-visible were used as a probe for the structural order degree short-, intermediate-, and long-range orders. Sm-3+ ions were used as markers of these order-disorder transformations in the PbTiO3 system. From the Rietveld refinement of the Sm-doped PbTiO3 x-ray diffraction data, structural models were obtained and analyzed by periodic ab initio quantum mechanical calculations using the CRYSTAL 98 package within the framework of density functional theory at the B3LYP level. This program can yield important information regarding the structural and electronic properties of crystalline and disordered structures. The experimental and theoretical results indicate the presence of the localized states in the band gap, due to the symmetry break, which is responsible for visible photoluminescence at room temperature in the disordered structure. (c) 2006 American Institute of Physics.

Er3+ as marker for order-disorder determination in the PbTiO3 system

Er3+ ions were added to the PbTiO3 network using the polymeric precursor method to characterize the order-disorder transformation found in this material by means of experimental and theoretical approach. The disordered and ordered material structures were studied by photoluminescence measurements, X-ray diffraction (XRD) and U-V-visible spectroscopy. The Er3+ ions served as a marker to identify the structural short-range order beginning in the PbTiO3 matrix. From photoluminescence results it was concluded that disordered PbTiO3 powders have a certain short range order in the network that are undetected by XRD measurements. The electronic structures were calculated by the ab initio periodic method in DFT level with the non-local B3LYP hybrid approximation for the Ti atom site interpretation using density of states (DOS) results. This analysis enabled understanding that Ti atom sphere coordination can create possible states for radioactive return and trap of electron-holes pair. (c) 2007 Elsevier B.V. All rights reserved.

Preparation and characterization of spherical silica-porphyrin catalysts obtained by the sol-gel methodology

This work describes the synthesis of a first-generation iron porphyrin catalyst entrapped in a silica matrix by the sol-gel route, leading to spherical particles. The catalyst was synthesized by the method of Stober, through hydrolysis and condensation of the alkoxysilane TEOS in a mixture of alcohol, water and ammonia, in the presence of the iron porphyrin Fe(TPP)Cl. The relation between particle morphology and catalytic activity of the different Fe(TPP)-SiO2, obtained using different H2O/silane molar ratios and ammonia concentrations in the xerogel syntheses, was studied.The obtained catalysts were characterized by UV-vis spectroscopy, NMR Si-29. thermogravimetric analysis and transmission electron microscopy. Their ability to catalyze (Z)-cyclooctene epoxidation and cyclohexane oxidation was tested using iodosylbenzene as oxygen donor; the oxidation products were analyzed by gas chromatography and the catalysts obtained in a form of particles spherical and monodispersed showed to be a promising catalytic system for selective oxidation. (c) 2005 Elsevier B.V. All rights reserved.

RELATIONSHIPS BETWEEN THE PLASMA ENVIRONMENT AND THE COMPOSITION AND OPTICAL-PROPERTIES OF PLASMA-POLYMERIZED THIN-FILMS PRODUCED IN RF DISCHARGES OF C2H2-SF6 MIXTURES

Polymer films were grown in rf discharges containing different proportions of C2H2 and SF6. Quantitative optical emission spectrometry (actinometry) was used to follow the trends in the plasma concentrations of the species H and F, and more tentatively, of CH, CF, and CF2, as a function of the feed composition. Infrared spectroscopy revealed the density of CH and CF bonds in the deposited material. As the partial pressure of SF6 in the feed was increased, the degree of fluorination of the polymer also rose. The form of the dependency of the deposition rate on the proportion of SF6 in the feed was in good qualitative agreement with the activated growth model. From transmission ultraviolet visible spectroscopy data the refractive index and the absorption coefficient of the polymers were calculated as a function of the deposition parameters. Since the optical gap depended to some extent upon the degree of fluorination, it could, within limits, be determined by a suitable choice of the proportion of SF6 in the feed. A qualitative explanation of this relationship is given.

Characterization of the reversible photoinduced optical changes in Sb-based glasses

Changes occurring in absorption coefficients when glasses in the SbPO4-WO3 binary system were irradiated by light, at the edge of the absorption band, were measured in real time. These glasses present good thermal and optical properties and photoinduced changes in the absorption coefficients are reversible by heat treatment around 150 degrees C. Subsequent recording/erasing cycles could be made without sample degradation. The sensitivity of the induced optical changes was studied for different wavelengths, light powers and energy of light dose exposures, and for different compositions of the glasses. The changes in the absorption coefficients of the glass samples were accompanied by a color change from yellow to blue, and were also characterized by visible spectroscopy. The color changes occurred through the entire volume of the glass (similar to 2 mm thickness) for the Ar-ion laser lines at the edge of the absorption band. (c) 2006 Elsevier B.V. All rights reserved.

Thermal behaviour of intercalated 8-hydroxyquinoline (oxine) in montmorillonite clay

The composite montmorillonite-8-hydroxyquinoline (Swy-1-8-HQ) was prepared by two different processes and studied by using thermogravimetric analysis (TG/DTG and DSC), as well as helpful techniques as fluorescence in the UV-visible region and X-ray diffraction. The composites developed fluorescent appearance, however with quantum poor efficiency and they exhibited distinct TG and DSC thermal behavior. The fluorescence data of spectra associated to the TG/DT curves allowed to suggest that the 8-HQ was present in the composites in two different circumstances: 1 - intercalated in the interlayer spaces (Swy-1-8-HQ2), rigidly associated to the Substrate feasible as a monolayer with the aromatic rings parallel to the silica layer; and/or, 2 - adsorbed on the Surface (Swy-1-8-HQ1), either as a bilayer formation or tilting of the molecules to the silicate layer sheet. All results confirmed above are in agreement with X-ray diffraction patterns, once the interlayer space increases when 8-HQ is incorporated. The experimental results confirm the formation of the composites in agreement with the method used in the preparation.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Nanoscale processing of polyaniline and phthalocyanines for sensing applications

Nanostructured polyaniline-modified electrodes were fabricated via the electrostatic layer-by-layer (LbL) technique where polyaniline (PANI) was assembled with one of three tetrasulfonated metallic phthalocyanines, viz. iron (FeTsPc), nickel (NiTsPc) and copper (CuTsPc). The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the 800 run absorption band due to PANI. Infrared spectroscopy in the transmission mode suggested specific interactions between PANI and the phthalocyanines, such as those between SO3- groups from the phthalocyanines and the protonated NH group from PANI. The films were employed to detect dopamine (DA) using cyclic voltammetry. In the presence of dopamine the PANI-based LbL films showed additional redox peaks at ca. 230 and 190 mV the oxidation peak increased linearly with the concentration of DA in the electrolytic solution. Films comprising PANI/FeTsPc were able to distinguish between DA and ascorbic acid (AA), which acts as a natural interferent in biological fluids. (c) 2005 Elsevier B.V. All rights reserved.

AN ACTINOMETRIC STUDY OF C2H2 PLASMA POLYMERIZATION AND FILM PROPERTIES

Thin polymer films were grown in radio frequency discharges containing C2H2. Actinometry revealed the trend in the plasma concentration of the CH species as a function of the operating pressure. The C-H bond density in the films, revealed by infrared analysis, was found to increase with the pressure of C2H2 in a similar way to that of the concentration of the CH species in the discharge. From transmission ultraviolet-visible spectroscopy data, optical parameters of the polymers, namely, the refractive index and the optical gap, were calculated. For the range of pressure studied, the refractive index decreased from 1.73 to 1.63 and the optical gap increased from 2.4 to 3.3 eV. Finally, measurements of the residual stress of the polymer films were carried out by the bending beam method, using a He-Ne laser, yielding values from 0.05 to 0.3 GPa. (C) 1995 American Vacuum Society.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Sol-gel entrapped cobalt complex

This work describes optimized conditions for preparation of a cobalt complex entrapped in alumina amorphous materials in the form of powder. The hybrid materials, CoNHG, were obtained by a nonhydrolytic sol-gel route through condensation of aluminum chloride with diisopropylether in the presence of cobalt chloride. The materials were calcined at various temperatures. The presence of cobalt entrapped in the alumina matrix is confirmed by ultraviolet visible spectroscopy. The materials have been characterized by X-ray diffraction (XRD), surface area analysis, thermogravimetric analysis (TGA), differential thermal analyses (DTA) and transmission electron microscopy (TEM). The prepared alumina matrix materials are amorphous, even after heat treatment up to 750 degreesC. The XRD, TGA/DTA and TEM data support the increase of sample crystallization with increasing temperature. The specific surface area, pore size and pore diameter changed as a function of the heat treatment temperature employed. Different heat treatment temperatures result in materials with different compositions and structures, and influence their catalytic activity. The entrapped cobalt materials calcined at 750 degreesC efficiently catalyzed the epoxidation of (Z)-cyclooctene using iodozylbenzene as the oxygen donor. (C) 2003 Elsevier B.V. All rights reserved.

In situ and simultaneous nanostructural and spectroscopic studies of ZnO nanoparticle and Zn-HDS formations from hydrolysis of ethanolic zinc acetate solutions induced by water

The simultaneous formation of nanometer sized zinc oxide (ZnO), and acetate zinc hydroxide double salt (Zn-HDS) is described. These phases, obtained using the sol-gel synthesis route based on zinc acetate salt in alcoholic media, were identified by direct characterization of the reaction products in solution using complementary techniques: nephelometry, in situ Small-Angle X-ray Scattering (SAXS), UV-Vis spectroscopy and Extended X-ray Absorption Fine Structures (EXAFS). In particular, the hydrolytic pathway of ethanolic zinc acetate precursor solutions promoted by addition of water with the molar ratio N = [H2O]/[Zn2+] = 0.05 was investigated in this paper. The aim was to understand the formation mechanism of ZnO colloidal suspension and to reveal the factors responsible for the formation of Zn-HDS in the final precipitates. The growth mechanism of ZnO nanoparticles is based on primary particle (radius approximate to 1.5 nm) rotation inside the primary aggregate (radius < 3.5 nm) giving rise to an epitaxial attachment of particles and then subsequent coalescence. The growth of second ZnO aggregates is not associated with the Otswald ripening, and could be associated with changes in equilibrium between solute species induced by the superficial etching of Zn-HDS particles at the advanced stage of kinetic.

Zeta potential and doping in polyaniline dispersions

Polyaniline (PAni) has been classified as an intractable polymer, particularly in its conducting form, the emeraldine salt (ES). Therefore one can consider the mixture of water and PAni as a suspension. The conducting form of PAni can be obtained by a doping process known as acid doping, in which a strong acid turns PAni from its insulating form, the emeraldine base (EB), into the conducting form, the emeraldine salt. With the objective of establishing a correlation between the doping level and the zeta potential of polyaniline dispersions, polyaniline + HCl aqueous suspensions were prepared. Positive zeta potential values for the various suspensions of PAni showed that it acquired positive charges after the doping process. It was also observed an increase in zeta potential values as HCl concentration increased, which could be correlated to UV-visible spectra of PAni suspensions.