Gelation of siloxane-poly(oxypropylene) composites

The viscoelastic properties of siloxane-poly(oxypropylene) (PPO) nanocomposites prepared by the sol-gel process has been analyzed during gelation by dynamic rheological measurements. The changes of storage and loss moduli, complex viscosity and phase angle has been measured as a function of time showing the newtonian viscosity of the sol in the initial step of gelation, and its progressive transformation to a viscoelastic gel. The rheologic properties have been correlated to mass fractal, nearly linear growth models and percolation theory. This study, completed by quasi-elastic light scattering and Si-29 solid state nuclear magnetic resonance measurements, shows that the mechanisms of gelation of siloxane-PPO hybrids depend on the molecular weight of the polymer and on the pH of the hybrid sol. For hybrids prepared in acid medium, a polymerization involving silicon reactive species located at the extremity of the polymer chains and presenting a functionality f = 2 occurs, forming a fractal structure during the first stage of sol-gel transition. For samples prepared under neutral pH, the fractal growth is only observed for hybrids containing short polymer chains (M-w similar to 130 gmol(-1)). The fractal dimensionality determined from the change in the rheological properties, indicates that the fractal growth mechanism changes from reaction-limited to diffusion-limited aggregation when the molecular weight of the PPO increases from 130 to 4000 gmol(-1) and as catalyst conditions change from acidic to neutral. Near the gel point, these hybrid gels have the typical scaling behavior expected from percolation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.

Spectroscopic properties of polycarbonate and poly(methyl methacrylate) blends doped with Europium(III) acetylacetonate

Spectroscopic properties of blends formed by bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) doped with Europium (III) acetylacetonate [Eu(acac)(3)], have been studied by photoacoustic spectroscopy (PAS) and photoluminescent (PL) spectroscopy. Emission and excitation spectra, excited state decay times, and quantum efficiency have been evaluated as well. PAS studies evidenced chemical interactions between the Europium complex and the PC/PMMA blend, which presented typical percolation threshold behavior regarding the Eu3+ content. PL spectra evidenced the photoluminescence of the Eu3+ incorporated into the blend. Photoluminescence property enhancement was observed for the composite in comparison with the precursor compound. Optimized emission quantum efficiency was observed for the 60/40 blend doped with 2% and 4% Europium (III) acetylacetonate. (c) 2005 Elsevier B.V. All rights reserved.

Sol-gel transition in SnO2 colloidal suspensions: viscoelastic properties

This paper describes particle aggregation process during gelation of SnO2 hydrosols. The effect of the concentration of SnO2 colloidal particles on the kinetics of gelation of hydrosols containing PVA (poly(vinyl alcohol)) was analysed by dynamic rheological measurements. The complex viscosity and the storage and loss moduli have been measured during the sol-gel transition and the results correlated to mass fractal growth, nearly linear growth models, and scalar percolation theory. The analysis of the experimental results shows that a linear aggregation occurs in the initial step of the gelation followed by a fractal growth to form a three-dimensional network. Near the gel point this physical gel exhibits the typical scaling expected from an electrical percolation analogy. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Non-stationary frequency analysis of extreme daily rainfall in São Paulo, Brazil

This work is an assessment of frequency of extreme values (EVs) of daily rainfall in the city of São Paulo. Brazil, over the period 1933-2005, based on the peaks-over-threshold (POT) and Generalized Pareto Distribution (GPD) approach. Usually. a GPD model is fitted to a sample of POT Values Selected With a constant threshold. However. in this work we use time-dependent thresholds, composed of relatively large p quantities (for example p of 0.97) of daily rainfall amounts computed from all available data. Samples of POT values were extracted with several Values of p. Four different GPD models (GPD-1, GPD-2, GPD-3. and GDP-4) were fitted to each one of these samples by the maximum likelihood (ML) method. The shape parameter was assumed constant for the four models, but time-varying covariates were incorporated into scale parameter of GPD-2. GPD-3, and GPD-4, describing annual cycle in GPD-2. linear trend in GPD-3, and both annual cycle and linear trend in GPD-4. The GPD-1 with constant scale and shape parameters is the simplest model. For identification of the best model among the four models WC used rescaled Akaike Information Criterion (AIC) with second-order bias correction. This criterion isolates GPD-3 as the best model, i.e. the one with positive linear trend in the scale parameter. The slope of this trend is significant compared to the null hypothesis of no trend, for about 98% confidence level. The non-parametric Mann-Kendall test also showed presence of positive trend in the annual frequency of excess over high thresholds. with p-value being virtually zero. Therefore. there is strong evidence that high quantiles of daily rainfall in the city of São Paulo have been increasing in magnitude and frequency over time. For example. 0.99 quantiles of daily rainfall amount have increased by about 40 mm between 1933 and 2005. Copyright (C) 2008 Royal Meteorological Society

Antinociceptive effects of epidural buprenorphine or medetomidine, or the combination, in conscious cats

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

The effects of sildenafil on rectal sensitivity and tone in patients with the irritable bowel syndrome

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Antinociceptive effects of tramadol and acepromazine in cats

Effects of tramadol and acepromazine on pressure and thermal thresholds were examined in eight cats. After baseline measurements, subcutaneous (SC) tramadol 1 mg/kg, acepromazine 0.1 mg/kg, tramadol 1 mg/kg with acepromazine 0.1 mg/kg, or saline 0.3 ml were given. Serial measurements were made for 24 h. Mean thermal thresholds did not change significantly [analysis of variance (ANOVA)] from baseline. The maximum thermal threshold increase above baseline was 2.8 +/- 2.8 degrees C at 6 h (P > 0.05) after tramadol; it was above the 95% confidence interval (0) at 0.75, 3 and 6 h. Pressure thresholds increased above baseline from 0.25 to 2 h after acepromazine (P < 0.05) and from 0.5 to 3 h after the combination (P < 0.05), with a maximum increase of 132 +/- 156 mmHg 0.25 h after acepromazine and 197 129 mmHg 0.5 h after the combination. Pressure thresholds were above the 95% Cl from 0.25 to 2 h after acepromazine and from 0.5 to 3 h after the combination. SC tramadol at 1 mg/kg in cats had limited effect on thermal and pressure nociception, but this was enhanced by acepromazine. Acepromazine alone had pressure antinociceptive effects. (c) 2007 ESFM and AAFR Published by Elsevier Ltd. All rights reserved.

In vitro Anthelmintic effect of Melia azedarach L. and Triclinia claussenii C. against sheep gastrointestinal nematodes

The control of parasitic diseases in small ruminants is mainly done with the use of synthetic anthelmintics. However, incorrect and indiscriminate use of these products has caused the emergence of parasite resistance. Plants with anthelmintic activity are used in folk veterinary medicine, but it is necessary to investigate and scientifically validate low-cost phytotherapeutic alternatives for future use to control gastrointestinal nematodes in small ruminants by family farmers. Thus, the aim of this study was to evaluate the in vitro anthelmintic effect of plant extracts from Melia azedarach and Trichilia claussenii by the egg hatch test (EHT) and larval development test (LDT) against sheep gastrointestinal nematodes. The hexane extract of M. azedarach fruits was extracted through cold percolation and the methanol extract of T. claussenii leaves was obtained by extraction at room temperature in solvents in order of increasing polarity. The efficacy results were analyzed using the Probit program of SAS. The M. azedarach extract showed a LC50 of 572.2 mu g/mL and LC99 of 1137.8 mu g/mL in the EHT, and LC50 of 0.7 mu g/mL and LC99 of 60.81 mu g/mL in the LDT. In turn, the T. claussenii extract presented a LC50 of 263.8 mu g/mL and LC99 of 522.5 mu g/mL in the EHTand LC50 of 1.11 mu g/mL and LC99 of 26.4 mu g/mL in the LDT. Comparing the extracts of the species from the Meliaceae family, T. claussenii showed greater anti-parasite potential in vitro than M. azedarach. However, studies on the isolated compounds, toxicity and administration forms to animals are also needed to validate low-cost alternative herbal remedies for use to control gastrointestinal nematodes by family farmers. (C) 2011 Elsevier B.V. All rights reserved.

Bacterial leaching of uranium ore from Figueira-PR, Brazil, at laboratory and pilot scale

A bacterial leaching program was carried out in order to evaluate the potential of applying this process to leach uranium from the ore of Figueira-PR, Brazil. The experiments were carried out in shake flasks, column percolation (laboratory and semipilot scale) and in heap leaching. In shake flasks and in column percolation experiments at laboratory scale, bacterial activity on the ore was confirmed: approximately 60% of uranium was leached, against around 30% in sterilized controls. Column percolation experiments at semipilot scale and heap leaching (850 tons of ore) showed uranium extractions of approximately 50%. In both experiments, a complementary sulfuric acid attack, after the bacterial leaching phase, was necessary to reach this level of uranium extraction.

Influence of viscoelastic characteristics of the colloidal suspensions on the formation of SnO2 supported membranes

SnO2 supported membranes have been prepared by sol-casting on alumina tubular substrate, using aqueous colloidal suspensions prepared by sol-gel route. The viscoelastic behaviour during sol ageing was analyzed by dinamic rheologial measurements. The complex viscosity and the storage and loss moduli have been followed during the sol-gel transition and the results have been correlated with the linear aggregates growth and the scalar percolation models. The scanning electron microscopy has evidenced that the homogeneity and thickness of the membrane depend on the sol ageing time. Crack-free and homogeneous membranes have been obtained for coated layers of 0.5μm thickness. © 1997 Trans Tech Publications.

Evolution of the viscoelastic properties of SnO2 colloidal suspensions during the sol-gel transition

This paper describes the effect of the concentration of electrolyte and pH on the kinetics of aggregation and gelation processes of SnO2 colloidal suspensions. Creep, creep-recovery, and oscillatory rheological experiments have been done in situ during aggregation and gelation. A phenomenological description of the structure of the colloidal system is given from the time evolution of rheological parameters. The dependence of the equilibrium steady-state shear compliance on the terminal region of clusters or aggregates seems to be a way to determine the beginning of interconnection of aggregates and the gel point. We propose that at this point the equilibrium steady-state compliance is a minimum. The steady-state viscosity determined from creep experiment can be fit with a power law with the extent of the transformation, giving critical exponent s = 0.7 ± 0.1. The value of the critical exponent Δ = 0.78 ± 0.05 was determined from oscillatory experiment. These results indicate that gelation of SnO2 colloidal suspension exhibits the typical scale expected from the scalar percolation theory. © 2000 Elsevier Science B.V. All rights reserved.

Effect of temperature on development and population growth of Acarophenax lacunatus (Cross and Krantz) (Prostigmata: Acarophenacidae) on Rhyzopertha dominica (F.) (Coleoptera: Bostrichidae)

The parasitic mite Acarophenax lacunatus kills the eggs upon which it feeds and seems to have potential as a biological control agent of stored grain pests. The lack of biological studies on this mite species led to the present study carried out in laboratory conditions at eight different temperatures (ranging from 20 to 41°C) and 60% relative humidity using Rhyzopertha dominica as host. The higher the temperature, the faster: (1) the attachment of female mites to the host egg (varying from 1 to 5 h); (2) the increase in body size of physogastric females (about twice faster at 40°C than at 20°C); and (3) the generation time (ranging from 40 to 220 h). In addition, the higher the temperature, the shorter the maximum female longevity (ranging from about 75 to 300 h). The two estimated temperature thresholds for development of A. lacunatus on R. dominica were 18 and 40°C. The average number of female and male offspring per gravid mite were 12.8 and 1.0, respectively, with sex ratios (females/total) ranging from 0.91 to 0.94 (maximum at 30°C). The net reproductive rate and intrinsic rate of increase also presented maximum values at 30°C (12.1 and 0.04, respectively).

Effect of lithium doping on the evolution of rheological and structural properties during gelation of siloxane-poly(oxypropylene) nanocomposites

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

Comparação entre limiar anaeróbio determinado por variáveis ventilatórias e pela resposta do lactato sanguíneo em ciclistas

Many investigations have shown that the coincidence between the ventilatory thresholds and those thresholds using the lactate response does not happen all of the time, suggesting that there is no relationship between the cause-effect between these phenomena. Thus, the present study had as main purpose to compare and correlate the Oxygen consumption (V̇O 2), the power (W), and the heart rate (HR) values attained using protocols to determine the Ventilatory Threshold (VT) and the Individual Anaerobic Threshold (IAT). The sampling was constituted by eight State and National level cyclists (age: 27.88 ± 8.77 years; body mass: 65.19 ± 4.40 kg; height: 169.31 ± 5,77 cm). The IAT was determined starting from a three minutes 50 W warm up with progressive increases of 50 W.3min -1 up to achieving the voluntary exhaustion, when the blood was collected in the last 20 seconds of each phase, and during the recovering period. In order to determine the VT, it was used the same protocol used to determine the IAT, but without performing the blood collection. The VT was identified through the changes in the pulmonary ventilation, as well as of the ventilatory equivalent of the O 2 and CO 2. The t-Student test showed no significant statistical difference in any of the attained variables. The associations found were high and significant. The V̇O 2 (ml.kg -1.min. -1), P (W), and HR (bpm) corresponding to the VT and IAT, as well as the associations between variables were respectively: 48.00 ± 3.82 vs. 48.08 ± 3.71 (r = 0.90); 256.25 ± 32.04 vs. 246.88 ± 33.91 (r = 0.84); 173.75 ± 9.18 vs. 171.25 ± 12.02 (r = 0.97). According to the results attained, it can be concluded that the IAT and the VT produce similar V̇O 2, W, and HR values, favoring the adoption of the VT because it is a non-invasive method to determine the anaerobic threshold in cyclists.