Influence of milling time on mechanically assisted synthesis of Pb0.91Ca0.1TiO3 powders

Pb0.91Ca0.1TiO3 powders (PCT) were prepared by mechanochemical synthesis from high-energy ball milling process. The influence of milling time on the phase formation, crystal structure, specific surface area, density and powder morphology was observed. We adopted the Rietveld refinement technique to investigate the crystal structure of the PCT powders. Scanning electron microscopy (SEM) analysis revealed that PCT powders milled for 5 h showed a wide distribution of particle agglomerates while milled for 35 h showed a decrease in agglomerates size. Further prolongation of milling time resulted in the agglomerates growth. (C) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Synthesis and characterization of Li2ZnTi3O8 spinel using the modified polymeric precursor method

In this work we report the synthesis procedure, crystallographic, structural and magnetic properties of the Li2ZnTi3O8 spinel obtained using a modified polymeric precursor method. This synthesis method generates very reactive and property-controlled nanoparticles. The samples were characterized using X-ray powder diffraction (XRD) associated to the Rietveld refinement method, thermogravimetric analysis (TG), specific surface area, scanning electron microscopy (SEM) and magnetic susceptibility measurements.The phase formation temperature of the lithium zinc titanate spinel was observed to decrease due to the homogeneity and highly controlled nanometric particle size. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Sol-gel prepared Pt-modified oxide layers: Synthesis, characterization, and electrocatalytic activity

Thin films of pure RuO2 and IrO2 and mixed Ru0.5Ir0.5O2 oxide modified with Pt particles were prepared by a sol-gel method in the form of thin films of similar to 2 mu m thickness on Ti substrates. Surface morphology of these Pt- modified oxides was examined by scanning electron microscopy and was found to exhibit a significant influence of the chemical composition of the oxide matrix. Element mapping showed homogeneous distribution of the metals. X- ray diffraction and X- ray photoelectron spectroscopy analyses showed that these films consist of metallic Pt particles dispersed in an oxide matrix. Cyclic voltammetry in acid solutions showed that the sol- gel prepared layers have relatively high Pt surface areas. The electrocatalytic activity of these materials toward the anodic oxidation of formaldehyde and methanol was compared in terms of onset potential and current density and was found to follow the sequence: Pt- Ru0.5Ir0.5O2/ Ti > Pt- RuO2/ Ti > Pt- IrO2/ Ti.

Characterization of bismuth titanate ceramics derived by mechanochemical synthesis

Bismuth titanate, Bi(4)Ti(3)O(12) (BIT) nanosized powders have been successfully synthesized via high energy mechanochemical activation. The phase formation of BIT, crystal structure, microstructure, crystallite size and specific surface area were followed by XRD, scanning electron microscopy (SEM) and the BET specific surface area measurements. The BIT milled 2 h shows the orthorhombic crystalline structure with small amount of amorphous phase. The microstructure of Bi(4)Ti(3)O(12) ceramics sintered at 1000 degrees C for 12h exhibit plate-like grain structure.

Correlation between the surface morphology and structure and the photoluminescence of amorphous PbTiO3 thin films obtained by the chemical route

A polymeric precursor method was used to synthesis PbTiO3 amorphous thin film processed at low temperature. The luminescence spectra of PbTiO3 amorphous thin films at room temperature revealed an intense single-emission band in the visible region, the visible emission band was found to be dependent on the thermal treatment history, Photoluminescence properties Versus different annealing temperatures were investigated. The experimental results (XRD, AFM, FL) indicate that the nature of photoluminescence (PL) must be related to the disordered structure of PbTiO3 amorphous thin films, Copyright (C) 2000 John Wiley & Sons, Ltd.

Improvement of the Mo/TiO2-Al2O3 catalyst by the control of the sol-gel synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al2O3 promoted by nickel and phosphorous. Several studies have shown that TiO2-Al2O3 mixed oxides are excellent supports for the active phases. Results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N-2 Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m(2).g(-1)) and minimal (127 m(2).g(-1)) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS2 active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.

pH at the micellar interface: Synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of' the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl Sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate- 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate-, 2-hydroxy-5-(2-diniethylhexadecylammoniumundecanoyl)betizoate; 2-hydroxy-5-acetylbenzoic acids and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pKap. The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of' the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pKap's of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis. (c) 2005 Elsevier B.V. All rights reserved.

Dielectric properties of Na1-xLixNbO3 ceramics from powders obtained by chemical synthesis

Ultra-fine powders of Na1-xLixNbO3 (x=0; 0.06; 0.09; 0.12) were synthesized by the Polymeric Precursors Method. Such powders had their orthorhombic structures determined by X-ray diffraction and their surface area determined by BET isotherms (less than 10 m(2) g(-1)). Densification was followed by dilatometric study. The powders, calcined at 700 degrees C for 5 h, were sintered at 1290 degrees C during 2 h under ambient atmosphere with no application of extra pressure. The samples with relative densities higher than 95% were analyzed by impedance spectroscopy at room temperature, under a signal amplitude of 1 V-rms. Dielectric constants of about 180 and dielectric loss factor of about 0.03 were measured showing small dependence with frequency. The electrical properties were similar to those obtained for samples sintered by hot pressing. (C) 1999 Elsevier B.V. Limited and Techna S.r.l. All rights reserved.

Synthesis by the polymeric precursor method and characterization of undoped and Sn, Cr and V-doped ZrTiO4

In this work, zirconium titanate doped with 0. 1, 0.2, and 0.4 mole% of tin, chromium and vanadium was synthesized by the polymeric precursors method and characterized by thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen adsorption and scanning electronic microscopy (SEM). The powder presented two mass losses attributed to the exit of water and to the pyrolysis of the organic material. The surface area reduction observed from 500 degrees C indicates the beginning of the sintering process. All the dopants led to changes in the lattice parameters and to the decrease of both crystallite size and particle size. (c) 2005 Elsevier B.V. All rights reserved.

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Mechanochemical synthesis of PZT powders

PZT ceramic powders were successfully prepared from the mixture of PbO, ZrO2 and TiO2 by mechanochemical synthesis in a planetary ball mill, under different milling conditions. Phase evolution during synthesis was monitored by X-ray diffraction analysis. Intensive milling resulted in formation of the nanocrystalline, perovskite PZT powders after 1 h of milling. This is a significant improvement in comparison to milling conditions reported by other authors. Depending on milling parameters the presence of some other phases, such as unreacted ZrO2, was also detected in some samples. The changes in powder size and morphology due to intensive milling, were determined by SEM and TEM, while BET analysis was used to determine specific surface area of the powders. Conclusions about processes taking place during mechanochemical synthesis of PZT powders were made based on the results of characterization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Microwave synthesis of calcium bismuth niobate thin films obtained by the polymeric precursor method

The crystal structure, surface morphology and electrical properties of layered perovskite calcium bismuth niobate thin films (CaBi2Nb2O9-CBN) deposited on platinum coated silicon substrates by the polymeric precursor method have been investigated. The films were crystallized in a domestic microwave and in a conventional furnace. X-ray diffraction and atomic force microscopy analysis confirms that the crystallinity and morphology of the films are affected by the different annealing routes. Ferroelectric properties of the films were determined with remanent polarization P-r and a drive voltage V-c of 4.2 mu C/cm(2) and 1.7 V for the film annealed in the conventional furnace and 1.0 mu C/cm(2) and 4.0 V for the film annealed in microwave furnace, respectively. A slight decay after 10(8) polarization cycles was observed for the films annealed in the microwave furnace indicating a reduction of the domain wall mobility after interaction of the microwave energy with the bottom electrode. (C) 2006 Elsevier Ltd. All rights reserved.

Synthesis, characterization and electropolymerization of a new polypyrrole iron(II) Schiff-base complex

This work presents the synthesis of the complex [Fe(L)(2)](PF6)(2) (.) H2O (L = 2,6-bis[1-(3-pyrrol-1-yl-propylimino)ethyl]pyridine (Fig. 1) and its characterization through elemental and thermal analysis, X-ray diffraction and UV-Vis, IR and H-1 NMR spectra. The use of this compound in the preparation of modified electrodes is also described. The best electrochemical parameters to achieve optimum film formation have been established and the effects of both the upper-limit of the applied scanning potential (E-aul) and the number of scans on the efficiency of film formation have been investigated. Film surface morphology has been characterized by atomic force microscopy. (C) 2004 Elsevier Ltd. All rights reserved.