Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

Rheological study of the thermoreversible sol-gel transition of sulfate modified zirconyl chloride aqueous sol

The sols prepared by mixing a ZrOCl2 acidified solution to a hot H2SO4 aqueous solutions were studied in order to clarify the mechanism of thermoreversible sol-gel transition observed in this system. The viscoelastic properties of these suspensions were analyzed during the sol-gel transition by dynamic rheological measurements and quasi-elastic light scattering. The rheological properties were correlated to mass fractal and nearly linear growth models, and percolation theory. The results evidence that the thermoreversible sol-gel transition in this system is due to the formation of a network of physically linked aggregates having fractal structure. The decrease of the SO42- contents in the initial solution leads to the decrease of the fractal dimensionality from 2.3 to 1.8, indicating a change of the kinetic mechanism of aggregate growth. Near the gel point these samples have the typical scaling expected from percolation theory. (C) 2004 Elsevier B.V. All rights reserved.

Dehydromonocrotaline inhibits mitochondrial complex 1. A potential mechanism accounting for hepatotoxicity of monocrotaline

Monocrotaline is a pyrrolizidine alkaloid present in plants of the Crotalaria species, which causes cytotoxicity and genotoxicity, including hepatotoxicity in animals and humans. It is metabolized by cytochrome P-450 in the liver to the alkylating agent dehydromonocrotaline. We evaluated the effects of monocrotaline and its metabolite on respiration, membrane potential and ATP levels in isolated rat liver mitochondria, and on respiratory chain complex I NADH oxidase activity in submitochondrial particles. Dehydromonocrotaline, but not the parent compound, showed a concentration-dependent inhibition of glutamate/malate-supported state 3 respiration (respiratory chain complex 1), but did not affect succinate-supported respiration (complex II). Only dehydromonocrotaline dissipated mitochondrial membrane potential, depleted ATP, and inhibited complex I NADH oxidase activity (IC50 = 62.06 mu M) through a non-competitive type of inhibition (K-I = 8.1 mu M). Therefore, dehydromonocrotaline is an inhibitor of the activity of respiratory chain complex I NADH oxidase, an action potentially accounting for the well-documented monocrotaline's hepatotoxicity to animals and humans. The mechanism probably involves change of the complex I conformation resulting from modification of cysteine thiol groups by the metabolite. (c) 2007 Elsevier Ltd. All rights reserved.

Temperature and wavelength dependence of the thermo-optical properties of tellurite and chalcogenide glasses

The refractive index and the temperature coefficient of the optical path length change of tellurite (80TeO(2):20Li(2)O) and chalcogenide glasses (72.5Ga(2)S(3):27.5La(2)O(3)) were determined as a function of temperature (up to 150 degrees C) and wavelength (in the range between 454 and 632.8 nm). The tellurite glass exhibits the usual refractive index dispersion in the wavelength range analyzed, while anomalous refractive index dispersion was observed for the chalcogenide glass between 454 and 530 nm. The dispersion parameters were determined by means of the single-effective oscillator model. In addition, a strong dependence of the temperature coefficient of the optical path length on the photon energy and temperature was found for the chalcogenide glass. The latter was correlated to the shift of the optical band gap (or electronic edge) with temperature, which was interpreted by the electron-phonon interaction model. (C) 2007 American Institute of Physics.

Effect of an iron mouthrinse on enamel and dentine erosion subjected or not to abrasion: An in situ/ex vivo study

Objectives: This in situ/ex vivo study evaluated whether a rinse with an iron solution could reduce wear and the percentage of microhardness change of human enamel and dentine submitted to erosion followed by brushing after 1 or 30 min.Design: During 2 experimental 5-day crossover phases (wash-out period of 10 days), 10 volunteers wore intraoral palatal devices, with 12 specimens (6 of enamel and 6 of dentine) arranged in 3 horizontal rows (4 specimens each). In one phase, the volunteers immersed the device for 5 min in 150 mL of cola drink, 4 times a day. Immediately after immersion, no treatment was performed in one row. The other row was brushed after 1 min using a fluoride dentifrice and the device was replaced into mouth. After 30 min, the remaining row was brushed. In the other phase, the procedures were repeated, but after immersion the volunteers rinsed for 1 min with 10 mL of a 10 mM ferrous sulphate solution. Changes in surface microhardness (%SMH) and wear (profilometry) of enamel and dentine were measured. Data were tested using ANOVA and Tukey's tests (p < 0.05).Results: the enamel presented more wear than dentine, under all experimental conditions. The iron solution caused a significant reduction on the %SMH in enamel, and a significant reduction on the wear in dentine, regardless the other conditions.Conclusions: Rinsing with an iron solution after an erosive attack, followed or not by an abrasive episode, may be a viable alternative to reduce the loss of dental structure. (c) 2006 Elsevier Ltd. All rights reserved.

Rift to post-rift evolution of a passive continental margin: the Ponta Grossa Arch, SE Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aging reduces complexity of heart rate variability assessed by conditional entropy and symbolic analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Methods to estimate the number of surface nucleation sites on glass particles

Based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, we propose two new models to describe the crystallisation kinetics of glass particles and use them to determine the density of nucleation sites, N(s), on glass powders. We tested these models with sintered compacts of diopside glass particles using sinter-crystallisation treatments at 825 degrees C (T(g)similar to 727 degrees C), that covered from null to almost 100% crystallised volume time fraction. We measured and compared the evolution of the crystallised volume fractions by optical microscopy and x-ray diffraction. Then we fit our expressions to experimental data using Ns and R (the average particle radius) as adjustable parameters. For comparison, we also fit to our data existing expressions that describe the crystallised volume fraction in glass powders. We demonstrate that all the methods allow one to estimate N(s) with reasonable accuracy. For our ground and water washed diopside glass powder, N(s) is between 10(10)-10(11) sites.m(-2). The reasonable agreement between experimental and adjusted R confirms the consistency of all five models tested. However, one of our equations does not require taking into account the change of crystallisation mode from 3-dimensional to 1-dimensional, and this is advantageous.

Sedimentation rates of tripton in Jurumirim Reservoir (São Paulo, Brazil)

Sedimentation rates of particulate material and some physicochemical parameters of water were determined in October, January, April and July 1990-91 at seven stations in the Jurumirim Reservoir (São Paulo, Brazil), three located in the Paranapanema arm, three in the Taquari arm and one near the dam. Higher sedimentation rates of tripton were found in the Paranapanema arm, followed by those from the Taquari arm and the dam. Suspended matter (2.5-48.7 mg · 1-1) and chlorophyll-a (0.7-8.1 mg · m-3) concentrations in the Paranapanema arm were in general higher resulting in lower water transparency (0.3-1.7m) than in the Taquari arm. Temporal and spatial variations in the tripton sedimentation rates were mainly influenced by allochthonous input at the stations near the river mouth. The settling fluxes at station near the dam of the reservoir were affected rather by a small autochthonous production (65 g C ass m-2 ;yr-1), indicated by a higher organic content (64-87%). Therefore, sedimentation rates measured by bottom traps were affected by sediment ressuspension especially at isothermal conditions. With respect to sedimentation, the riverine, the transition and the lacustrine zones commonly found in reservoires could be distinguished. The extent of the riverine zone in each arm of the Jurumirim Reservoir depends on the seasonal change of allochthonous input.

Unrestricted linear dimensional changes of two hard chairside reline resins and one heat-curing acrylic resin

The selection and use of hard chairside reline resins must be made with regard to dimensional stability, which will influence the accuracy of fit of the denture base. This study compared the dimensional change of two hard chairside reline resins (Duraliner II and Kooliner) and one heat-curing denture base resin (Lucitone 550). A stainless steel mold with reference dimensions (AB, CD) was used to obtain the samples. The materials were processed according to the manufacturer's recommendations. Measurements of the dimensions were made after processing and after the samples had been stored in distilled water at 37° C for eight different periods of time. The data were recorded and then analyzed with analysis of variance. All materials showed shrinkage immediately after processing (p < 0.05). The only resin that exhibited shrinkage after 60 days of storage in water was Duraliner II; these changes could be clinically significant in regard of tissue fit.

Kinetics of the polarization reversal process in a non-constant applied electric field and the generalized superposition principle

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electric and magnetic properties of polymer electrolyte/carbon black composites

Measurements of 1H Nuclear Magnetic Resonance (NMR) relaxation times, Electron Paramagnetic Resonance (EPR) and AC Impedance Spectroscopy (IS) are reported for composites based on PEO8:LiClO4 and carbon black (CB), prepared by two methods: solvent and fusion processing. Three nuclear relaxation processes were identified for 1H nuclei: (i) belonging to the polymer chains in the amorphous phase, loosely bound to the CB particles, whose dynamics is almost the same as for unfilled polymer, (ii) belonging to the polymer chains which are tightly attached to the CB particles, and (iii) belonging to the crystalline phase in the loose polymer chain. The paramagnetic electronic susceptibility of the composite samples, measured by EPR, was interpreted by assuming a contribution of localized spin states that follow a Curie law, and a Pauli-like contribution of delocalized spins. A significant change of the EPR linewidth was observed at 40 K, which is the temperature where the Curie and Pauli susceptibilities equally contribute to the paramagnetic electronic susceptibility. The electrical properties are very sensitive to the preparation methods of the composites, which conditions the interaction between carbon particle-carbon particle and carbon particle-polymer chain. Classical statistic models to describe the conductivity in these media were not satisfactory. © 1998 Published by Elsevier Science B.V. All rights reserved.

Study of a hybrid solid oxide fuel cell: Energetic analysis and sankey diagram

In this paper a hybrid solid oxide fuel cell (SOFC) system is analyzed. This system applies a combined cycle utilizing gas turbine associated to a SOFC for rational decentralized energy production. Initially the relative concepts about the fuel cell are presented, followed by some chemical and technical informations such as the change of Gibbs free energy in isothermal fuel oxidation (or combustion) directly into electricity. This represents a very high fraction of the lower heating value (LHV) of a hydrocarbon fuel. In the next step a methodology for the study of SOFC associated with a gas turbine system is developed, considering the electricity and steam production for a hospital, as regard to the Brazilian conditions. This methodology is applied to energetic analysis. Natural gas is considered as a fuel. In conclusion, it is shown by a Sankey Diagram that the hybrid SOFC system may be an excellent opportunity to strengthen the decentralized energy production in Brazil. It is necessary to consider that the cogeneration in this version also is a sensible alternative from the technical point of view, demanding special methods of design, equipment selection and mainly of the contractual deals associated to electricity and fuel supply.

The synergistic effects of Nb/Mn and Sb/Mn on the microstructure and electrical characteristics of BaTiO3 based ceramics

The microstructure and dielectric properties of Nb-Mn or Sb-Mn codoped BaTiO3 compositions were investigated. Starting ceramics powders were prepared by Pechini method. The composites were sintered at 1310°C and 1330°C in an air atmosphere for two hours. The microstructure and compositional investigations were done with SEM equipped with EDS. Two distinguish microstructure regions are observed in Nb/0.05Mn doped BaTiO 3 ceramics sintered at low temperature. The first, large one, with grain sizes from 5-40 μm and the second region with small grain sizes from 1 to 5 μm. Sintering at higher temperature, independent of Mn content, enables to achieve a uniform microstructure with grains less than 6 μm. In Sb/Mn doped ceramics, for both sintering temperatures, bimodal microstructures with fine grained matrix and grains up to 10 μm is formed. The highest value of permittivity at room temperature and the greatest change of permittivity in function of temperature are observed in Nb/0.01Mn doped ceramics compared to the same ones in Sb/Mn doped ceramics. The greatest shift of Curie temperature towards lower temperature has been noticed in Sb/Mn BaTiO3 ceramics compared to others samples. In all investigated samples the dielectric loss after initially large values at low frequency maintains a constant value for f>3 kHz.

Densification of Mn-doped tin oxide films by conventional heating and microwave heating treatment

Mn(II) doped SnO2 thin films used for shielding fluoride glasses against corrosion were investigated by x-ray absorption spectroscopy (EXAFS and XANE)S at the Sn and Mn K-edges. The effect of firing treatment on the densification of the films was studied. It has been evidenced a partial change of Mn valence from 2.3 to 2.6 upon heating which is attributed to a change of ratios of two Mn sites: grafted divalent Mn ions at the surface of SnO 2 nanocrystallites and trivalent Mn ions embedded into a substitutional solid solution with Sn. © Physica Scripta 2005.