Isothermal structural evolution of SnO2 monolithic porous xerogels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Titanium(IV)-EDTA complex - Kinetics of thermal decomposition by non-isothermal procedures

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)-ethylenediaminetetraacetate complex. Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E=172.4 +/- 9.7 and 205.3 +/- 12.8 kJ mol(-1), and pre-exponential factor: logA = 16.38 +/- 0.84 and 18.96 +/- 1.21 min(-1) at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively.From E and logA values, Dollimore and Malek methods could be applied suggesting PT (Prout-Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.

Tin(II)-EDTA complex: kinetic of thermal decomposition by non-isothermal procedures

Tin on the oxide form, alone or doped with others metals, has been extensively used as gas sensor, thus, this work reports on the preparation and kinetic parameters regarding the thermal decomposition of Sn(II)-ethylenediaminetetraacetate as precursor to SnO2. Thus, the acquaintance with the kinetic model regarding the thermal decomposition of the tin complex may leave the door open to foresee, whether it is possible to get thin film of SnO2 using Sn(II)-EDTA as precursor besides the influence of dopants added.The Sn(II)-EDTA soluble complex was prepared in aqueous medium by adding of tin(II) chloride acid solution to equimolar amount of ammonium salt from EDTA under N-2 atmosphere and temperature of 50degreesC arising the pH similar to 4. The compound was crystallized in ethanol at low-temperature and filtered to eliminate the chloride ions, obtaining the heptacoordinated chelate with the composition H2SnH2O(CH2N(CH2COO)(2))(2).0.5H(2)O.Results from TG, DTG and DSC curves under inert and oxidizing atmospheres indicate the presence of water coordinated to the metal and that the ethylenediamine fraction is thermally more stable than carboxylate groups. The final residue from thermal decomposition was the SnO2 characterized by X-ray as a tetragonal rutile phase.Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E-a = 183.7 +/- 12.7 and 218.9 +/- 2.1 kJ mol(-1), and pre-exponential factor: log A = 18.85 +/- 0.27 and 19.10 +/- 0.27 min(-1), at 95% confidence level, could be obtained, regarding the loss of coordinated water and thermal decomposition of the carboxylate groups, respectively. The E-a and logA also could be obtained applying isoconventional Wall-Flynn method on the TG curves.From E-a and log A values, Dollimore and Malek procedures could be applied suggesting R3 (contracting volume) and SB (two-parameter model) as the kinetic model to the loss of coordinated water (177-244degreesC) and thermal decomposition of the carboxylate groups (283-315degreesC), respectively. Simulated and experimental normalized DTG and DSC curves besides analysis of residuals check these kinetic models. (C) 2003 Elsevier B.V. All rights reserved.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

Non-isothermal study of the devitrification kinetics of fluoroindate glasses

The understanding of the kinetics of devitrification of a glass is important for anticipating its stability in a particular purpose, such as fiber-drawing processes. The crystallization kinetics of (BaF2)16(ZnF2)20(SrF 2)20(NaF)2 (GaF3)5(InF3)36(GdF 3)1 glass prepared by quenching were studied by differential scanning calorimetry (DSC). Avrami's exponent (n) obtained by a non-isothermal method was 4.3 for a solid and 2.4 for a powdered sample. According to the classical interpretation of n, these magnitudes correspond to an interface-controlled crystal growth and a diffusion-controlled crystal growth, respectively. The activation energies for crystallization (E) was 62 ± 1 kJ/mol for solid glass and 245 ± 2 kJ/mol for powdered glass. These results are discussed in terms of glass particle size. © 2000 Elsevier Science B.V. All rights reserved.

Non isothermal study of the devitrification kinetics of fluoroindate glasses

The kinetics of crystallization in an indium fluoride-based glass was studied by a non-isothermal method using differential scanning calorimetry. The experiments led to an Avrami's exponent of 4.6 for solid glass and 2.2 for a powdered sample. The apparent activation energy for crystallization was found to be 130 kJ/mol for solid glass and 354 kJ/mol for the powder. These results express the profound effect of glass particle size on those kinetic parameters, as different crystallization mechanisms take place during sample heating.

Coil to extended coil transition in polygalacturonic acid: Conductometric titration and monte carlo simulations

The conformational transition from coil to extended coil for polygalacturonic acid has been studied by conductometric titrations and Monte Carlo simulations. The results of conductometric titrations at different polymer concentrations have been analyzed using the model proposed by Manning,1 which describes the conductivity of polyelectrolitic solutions. This experimental approach provides the transport factor and the average distance between charged groups at different degrees of ionization (α). The mean distances between charged groups have been compared with the values obtained by Monte Carlo simulations. In these simulations the polymer chain is modeled as a self-avoiding random walk in a cubic lattice. The monomers interact through the unscreened Coulombic potential. The ratio between the end-to-end distance and the number of ionized beads provides the average distance between charged monomers. The experimental and theoretical values are in good agreement for the whole range of ionization degrees accessed by conductometric titrations. These results suggest that the electrostatic interactions seem to be the major contribution for the coil to extended coil conformational change. The small deviations for α ≤ 0.5 suggests that the stiffness of the chain, associated with local interactions, becomes increasingly significant as the fraction of charged groups is decreased. © 2000 American Chemical Society.

Non-aqueous Titration of Gatifloxacin in Pharmaceutical Formulations using Perchloric Acid

An inexpensive, simple, precise and rapid method for the determination of fluoroquinolone gatifloxacin in tablets is described. The procedure is based on the use of volumetric dosage in a non-aqueous medium in glacial acetic acid with 0.1 M perchloric acid. The method validation yielded good results and included the precision, recovery and accuracy. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Entropy variation in isothermal fluid flow considering real gas effects

The present paper concerns on the estimative of the pressure loss and entropy variation in an isothermal fluid flow, considering real gas effects. The 1D formulation is based on the isothermal compressibility module and on the thermal expansion coefficient in order to be applicable for both gas and liquid as pure substances. It is emphasized on the simple methodology description, which establishes a relationship between the formulation adopted for ideal gas and another considering real gas effects. A computational procedure has been developed, which can be used to determine the flow properties in duct with a variable area, where real gas behavior is significant. In order to obtain quantitative results, three virial coefficients for Helium equation of state are employed to determine the percentage difference in pressure and entropy obtained from different formulations. Results are presented graphically in the form of real gas correction factors, which can be applied to perfect gas calculations.

Development of a Loop-Mediated Isothermal Amplification Method for Detection of Histoplasma capsulatum DNA in Clinical Samples

Improved methods for the detection of Histoplasma capsulatum are needed in regions with limited resources in which the organism is endemic, where delayed diagnosis of progressive disseminated histoplasmosis (PDH) results in high mortality rates. We have investigated the use of a loop-mediated isothermal amplification (LAMP) assay to facilitate rapid inexpensive molecular diagnosis of this disease. Primers for LAMP were designed to amplify the Hcp100 locus of H. capsulatum. The sensitivity and limit of detection were evaluated using DNA extracted from 91 clinical isolates of known geographic subspecies, while the assay specificity was determined using DNA extracted from 50 other fungi and Mycobacterium tuberculosis. Urine specimens (n = 6) collected from HIV-positive individuals with culture- and antigen-proven histoplasmosis were evaluated using the LAMP assay. Specimens from healthy persons (n = 10) without evidence of histoplasmosis were used as assay controls. The Hcp100 LAMP assay was 100% sensitive and specific when tested with DNA extracted from culture isolates. The median limit of detection was <= 6 genomes (range, 1 to 300 genomes) for all except one geographic subspecies. The LAMP assay detected Hcp100 in 67% of antigen-positive urine specimens (4/6 specimens), and results were negative for Hcp100 in all healthy control urine specimens. We have shown that the Hcp100 LAMP assay is a rapid affordable assay that can be used to expedite culture confirmation of H. capsulatum in regions in which PDH is endemic. Further, our results indicate proof of the concept that the assay can be used to detect Histoplasma DNA in urine. Further evaluation of this assay using body fluid samples from a larger patient population is warranted.