CONTRIBUTION TO THE STUDY OF ZIRCONIUM AND HAFNIUM ALPHA-HYDROXYCARBOXYLATES

A study of both zirconium and hafnium alpha-hydroxycarboxylates for analytical applications is presented, These compounds are studied by infrared spectroscopy, thermal analysis and X-ray diffractometry. dl-Mandelic, dl-p-bromomandelic and dl-2-naphthylglycolic acids are the more adequate reagents for gravimetric determinations of zirconium and hafnium, the ligands dl-2-hydroxyhexanoic and dl-2-hydroxydodecanoic acids were used for the first time and the results showed that they are also adequate reagents for the same purpose.

Solid-state chelates of ethylenediamine-tetraacetate with alkali earth metals

Solid-state M-EDTA chelates, where M represents the divalent ions Mg(II), Ca(II), Sr(II) or Ba(II) and EDTA is ethylenediaminetetraacetate anion, were synthesized. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC) and X-ray diffraction powder patterns have been used to characterize and to study the thermal behaviour of these chelates. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition.

TG studies of a composite solid rocket propellant based on HTPB-binder

Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E-a (activation energy) and A (pre-exponential factor) and the compensation parameter (S-p) were determined. The apparent activation energies obtained from different methods showed a very good agreement.

Structural characterization of blends containing both PVDF and natural rubber latex

Films containing different volumes of latex of natural rubber (NR) in a fixed mass of poly (vinylidene fluoride) (PVDF) powder were fabricated by compressing under annealing a mixture of both materials without using any solvent. This is an important issue keeping in mind that these films have to be used in the future as biomaterials in different applications once the solvents that are used to dissolve the PVDF become toxic to human. The films with different percentage of latex in PVDF were characterized using microRaman scattering and Fourier transform infrared absorption (FTIR) spectroscopies, thermomechanical techniques using thermogravimetry (TG), differential scanning calorimetry (DSC), dynamical-mechanical analysis (DMA) and scanning electron microscopy (SEM). The results showed that the latex of NR and PVDF do not interact chemically, leading to the formation of a polymeric blend with high thermal stability and mechanical properties suitable for applications involving bone (prostheses, for instance). Besides, the results recorded using the micro-Raman technique revealed that for a fixed amount of PVDF the higher the amount of latex in the blend, the better the miscibility between both materials. Copyright (c) 2005 John Wiley & Sons, Ltd.

Synthesis and characterization of solid molybdenum(VI) complexes with glycolic, mandelic and tartaric acids. Photochemistry behaviour of the glycolate molybdenum complex

The complexes (NH4)(2)[ MoO2( C2H2O3)(2)]center dot H2O, (NH4)(2)[MoO2(C8H6O3)(2)] and (NH4)(2) [MoO3(C4H4O6)]center dot H2O were prepared by reaction of MoO3 with glycolic, mandelic and tartaric acids, respectively. The complexes were characterized by elemental and thermal analysis, IR spectroscopy and X- ray diffraction. Crystals of the glycolate and tartarate complexes are orthorhombic and the mandelate complex is monoclinic. Elemental and thermal analysis data showed that the glycolate and tartarate complexes are monohydrated. Hydration water is not present in the structure of the mandelate complex. IR spectra showed COO- is involved in coordination as well as the oxygen atom of the deprotonated hydroxyl group of the alpha-carbon. The glycolate molybdenum complexes with general formula M-2[MoO2(C2H2O3)(2)]center dot nH(2)O, where M is an alkali metal and n=1 or 1/2, were also prepared and characterized. Aqueous solutions of the glycolate complex become blue and mandelate and tartarate complexes change to yellow or brown when exposed to UV- radiation.

Non-isothermal kinetic of oxidation of tungsten carbide

Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant atmosphere. The oxidation of WC to WO3 tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal condition, could be evaluated to the oxidation of WC to heating rate below 15 degrees C min(-1) or low flow of air (10 mL min(-1)). The reaction is governed by nucleation and growth at 5 to 10 degrees C min(-1) then the tendency is to be autocatalytic, JMA and SB, respectively.

Preparation of Pb(Zr,Ti)O-3 thin films by soft chemical route

Lead zirconate titanate, Pb(Zr0.3Ti0.7)O-3 (PZT) thin films were prepared with success by the polymeric precursor method. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), Micro-Raman spectroscopy and X-ray diffraction (XRD) were used to investigate the formation of the PZT perovskite phase. X-ray diffraction revealed that the film showed good crystallinity and no presence of secondary phases was identified. This indicates that the PZT thin films were crystallized in a single phase. PZT thin films showed a well-developed dense grain structure with uniform distribution, without the presence of rosette structure. The Raman spectra undoubtedly revealed these thin films in the tetragonal phase. For the thin films annealed at the 500-700 degreesC range, the vibration modes of the oxygen sublattice of the PZT perovskite phase were confirmed by FT-IR. The room temperature dielectric constant and dielectric loss of the PZT films, measured at 1 kHz were 646 and 0.090, respectively, for thin film with 365 nm thickness annealed at 700 degreesC for 2 h. A typical P-E hysteresis loop was observed and the measured values of P-s, P-r and E-c were 68 muC/cm(2), 44 muC/cm(2) and 123 kV/cm, respectively. The leakage current density was about 4.8 x 10(-7) A/cm(2) at 1.5 V. (C) 2003 Elsevier Ltd. All rights reserved.

Effect of the modifier ion on the properties of MgFe2O4 and ZnFe2O4 pigments

Magnesium and zinc ferrites have been prepared by the polymeric precursor method. The organic material decomposition was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The variation of crystalline phases and particle morphology with calcination temperature were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM), respectively. The colors of the ferrites were evaluated using colorimetry. Magnesium ferrite crystallizes above 800 degrees C, presenting a yellow-orange color with a reflectance peak at the 600-650 nm range, while zinc ferrite crystallizes at 600 degrees C, with a reflectance peak between 650-700 nm, corresponding to the red-brick color.

Influence of pH and precipitation temperature on the structural characteristics of aluminium hydroxides prepared form nitrate aqueous solutions

Aluminium Hydroxides were precipitated from Aluminium Nitrate and Ammonium Hydroxide, at the temperatures 64 degrees C (hot) and 25 degrees C (cold), under the pH conditions 5, 7 and 9. The samples were characterized by X-Ray Diffraction (XRD) and Differential Thermal Analysis (DTA). The hydroxide precipitated at pH 9 and 64 degrees C is built up by pseudoboehmite and a minor share of others apparently amorphous hydroxides. The crystallinity of the hot yielded pseudoboehmite diminishes with the pH. The crystallite size was evaluated as about 40 Angstrom for the best crystallized sample. The cold precipitated product is apparently composed by amorphous or very poorly crystallized hydroxides. Upon heating, the cold precipitated hydroxides, and the low pH and hot precipitated hydroxide, release their structural water before the occurrence, about 430 degrees C, of the transition of the pseudoboehmite to gamma-alumina, and exhibit a shifting (towards low temperature side) and a broadening in the peak of the transition to alpha-alumina, which occurs at 1200 degrees C in the pseudoboehmite pattern. The yielded pseudo-boehmite peptized by HNO3, addition and gelified by evaporation in a critical concentration approximately 0.17 gcm(-3).

Nucleation and growth of mullite whiskers from lanthanum-doped aluminosilicate melts

Nucleation and growth of mullite whiskers in the La2O3-Al2O3-SiO2 system were investigated in the 1500degrees-1700degreesC temperature range. A differential thermal analysis (DTA) showed that the mullitization temperature decreases from 1350degreesC to 1240degreesC as a result of lanthania doping. In the temperature range of 1250-1500degreesC, most of the mullite grains have an Al2O3/SiO2 = 1.5 composition throughout the ceramic body; however, from 1400degreesC upward, the number of anisotropic grains with the Al2O3/SiO2 = 1.3 composition begins to increase. The concentration of alumina in the composition of the grain-boundary phase decreases as firing temperatures increase. At temperatures > 1500degreesC, alumina grains and whiskers grow on the internal and external surfaces of the ceramic body with the characteristic Al2O3/SiO2 = 1.3 composition. Removal of the mullite whisker layer by acid attack revealed an alumina-rich, rosace-like patterned microstructure correlated with the process of whisker nucleation and growth. In the early stages, whisker growth rates were found to be near 60 mum/h. Experimental evidence pointed to nucleation inside the thin glass layer on the external surface.

SiO2-PbF2-CdF2 glasses and glass ceramics

Lead-Cadmium fluorosilicate stable glasses were prepared and the vitreous domain region determined in the composition diagram. Characteristic temperatures were obtained from thermal analysis and the structural studies performed illustrate clearly the role played by lead atoms in the glasses crystallization behavior and the glass-forming ability of cadmium atoms. The occurrence of either a cubic lead fluoride or a lead-cadmium fluoride solid solution in crystallizing samples was found to be dependent on Er3+ doping. The optically active ions were found to concentrate in the crystalline phase and in fact play the role of nucleating agent as suggested from X-ray diffraction and EXAFS measurements. (C) 2002 Elsevier B.V. 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.

An ultra stable glass system for optical fiber devices

In this paper a modified chalcogenide glass was studied by X-ray powder diffraction, differential thermal analysis, infrared and Raman scattering spectroscopies. The study of this new matrix opens new perspectives to fabricate Pr3+-doped fibers to operate as an optical amplifier in the 1.3 mum telecommunications window. The Pr3+-doped 70Ga(2)S(3)-30La(2)S(3) glass was modified through the substitution of La2S3 by La2O3, which improves the thermal stability of these glasses without any modification of phonon energy. The possibility to pull a fiber from this glass system without any devitrification is easily achieved.

Kinetic parameters of polymer degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

Glasses in the SbPO4-WO3 system

Glasses in the binary system (100 - x)SbPO4-xWO3 (20 <= x <= 60, x in mol%) have been prepared and characterized. Differential thermal analysis (DTA) shows that the glass transition temperature, T-g increases from 412 degrees C, for samples containing 20 mol% of WO3 to 481 degrees C observed for glass containing 60 mol%. Sample containing 40 mol% in WO3 were observed to be the most stable against devitrification. The structural organization of the glasses has been studied by using Fourier transform infra-red (FTIR), Raman, P-31 Magic angle spinning (MAS) and spin echo nuclear magnetic resonance (NMR) spectroscopies. Results suggest two distinct networks comprising the glass structure, one with high SbPO4 content and the other characteristic of the highest WO3 content samples. The glasses present photochromic properties. Colour changes are observed for samples after exposure to ultraviolet or visible laser light. XANES, at L-1 absorption edge of tungsten, suggests partial reduction from W6+ to W5+ species during the laser irradiation. The photochromic effects and the colour changes, promoted by laser excitation, are reversible and easily removed by heat for during 1 h at 150 degrees C. Subsequent 'write/erase' cycles can be done without degradation of the glasses. (C) 2007 Elsevier B.V. All rights reserved.