Drying study of siloxane-PPG nanocomposites

This is a study of the structural transformations occurring in hybrid siloxane-polypropyleneglycol (PPG) nanocomposites, with different PPG molecular weight, along the drying process. The starting materials are wet gels obtained by the sol-gel procedure using as precursor the 3-(trietoxysilyl)propylisocyanate (IsoTrEOS) and polypropylenglycol bis(2-amino-propyl-ether) (NH2-PPG-NH2). The shrinkage and mass loss measurements were performed using a temperature-controlled chamber at 50 degreesC. The nanostructural evolution of samples during drying was studied in situ by small angle x-ray scattering (SAXS). The experimental results demonstrate that the drying process is highly dependent on the molecular weight of polymer. After the initial drying stage, the progressive emptying of pores leads to the formation of a irregular drying front in gels prepared from PPG of high molecular weight, like 4000 g/mol. As a consequence, an increase of the SAXS intensity due to the increase of electronic density contrast between siloxane clusters and polymeric matrix is observed. For hybrids containing PPG of low molecular weight, the pore emptying process is fast, leading to a regular drying front, without isolated nanopockets of solvents. SAXS intensity curves exhibit a maximum, which was associated to the existence of spatial correlation of the silica clusters embedded in the polymeric matrix. The spatial correlation is preserved during drying. These results also reveal that the structural transformation during drying is governed by capillary forces and depends on the entanglement of polymer chains.

EFFECT OF WATER POTENTIAL ON GERMINATION OF SEEDS OF STYLOSANTHES-GUIANENSIS (AUBL) SW

Effect of water potential on germination of seeds of Slylosanthes guianensis (Aubl.) Sw. To evaluate the water potential effect on germination of S. guianensis two experiments were performed.The first one used osmotic pre-treatment in the imbibition phase and after this period (14 h) the seeds were germinated on filter paper moistened with distilled water. In the second experiment, besides the imbibition phase, seeds were kept in a range of water potentials during all the process. The potentials ranged from 0 to -18 bars, with 3 bars increments, induced by mannitol or by polyethylene glycol. Each treatment was replicated 3 times with 100 seeds per replication. The seeds pre-treated during imbibition had high germination percentage, the highest being the ones in polhyetylene glycol. In the second experiment the polyethylene glycol solutions reduced dramatically the germination percentage in relation to mannitol. From -12 bars on germination ceased in the polyethylene glycol treatments, while in mannitol solution there was 52,67% of germination, in the same water potential.

Polymerization of photocurable commercial dental methacrylate-based composites - Photocalorimetry study

Due to their excellent aesthetics, photopolymers have been extensively used in several dentistry applications. However, several problems are reported, e.g. low mechanical and abrasion resistance, shrinkage during polymerization, etc. Properties of the final restorations are intrinsically related to the polymerization stage, which can be conveniently studied by photocalorimetry. In the present work the polymerization reaction and the filler content of different photocurable commercial dental methacrylate-based composites were studied by means of photocalorimetry and thermogravimetry, respectively. The results show that the values of curing rate, the heat of polymerization and the filler content vary significantly from one composite to another.

Effect of aging on the stability of ceramic foams prepared by thermostimulated sol-gel process

This work presents a new route of preparation of zirconium ceramic foams based on the thermostimulated sol-gel process. This method produces gelled bodies with up to 90% of porosity in the wet gel and can be used to make complex-shaped components. Unfortunately, the shrinkage during the drying step allows to a catastrophic reduction (50%) of the foam porosity. To improve the foam stability we carried out a systematic study of the effect of gel foam aging on the drying process. Samples were aged in closed vessel at 25 C during different time period (from 6 to 240 h). The shrinkage and the mass loss during drying at 50 C were measured in situ, using a non-contact technique performed with a special apparatus. The results show that the total linear shrinkage decreases from 46% to 8% as the aging period increase from 6 to 240 h. This behavior is followed by a small change of total mass loss, from 42 to 54%. It indicates that by aging the structural stiffness of the foams increases due to secondary condensation reactions. Thus, by controlling the aging period, the porosity can be increased from 67 to 75% and the average size of mesopores of dried foams can be screened from 0.3 to 0.9 mum. Finally, these results demonstrate that the thermostimulated sol-gel transition provides a potential route to ceramic foams manufacture.

Sintering of tin oxide using zinc oxide as a densification aid

The physicochemical electronic characteristics of SnO2 render it useful in many technical applications, including ceramic varistors, stable electrodes used in electric glass-melting furnaces and electrometallurgy of aluminum, transparent windows and chemical sensors. The use of ZnO as a sintering aid was explored in this study to obtain SnO2 as a dense ceramic. Compacts were obtained by mechanical mixing of oxides, isostatic pressing at 210 MPa and sintering in situ inside a dilatometer at heating rates of 10degreesC/min. The grain size and microstructure were investigated by scanning and transmission electron microscopy (SEM/TEM). The phases and chemical composition were analyzed by energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that ZnO acts as a densification aid for SnO2, improving its grain growth with additions of up to 2 mol%. ZnO forms a solid solution with SnO2 UP to 1 mol%, above which SnZnO3 precipitates in the grain boundary, potentially inhibiting shrinkage and grain growth. (C) 2004 Kluwer Academic Publishers

Densification and coarsening of SnO2-based materials containing manganese oxide

The present work presents results on natural sintering of tin dioxide ceramics, prepared by a chemical route or by conventional mixing and containing manganese (X-Mn = Mn/(Mn + Sn)(atomic) with 0 less than or equal to X(Mn)less than or equal to 0.15). This cation, which is practically insoluble in SnO2 network, stays at the grain surface. During thermal treatment (500 degrees C less than or equal to T-s less than or equal to 1400 degrees C), as long as the manganese surface concentration is lower than a critical value, equal to 5.10(-6) mol m(-2), no densification takes place. As soon as this value is reached, densification and grain growth occur simultaneously. The shrinkage kinetics is fast and high rho/rho(t) values can be obtained (for example. rho/rho(t)=0.95 for T-s=1300 degrees C and X-Mn=0.004). The dependence between manganese content, manganese distribution, grain size and sintering behaviour is also discussed. (C) 1998 Published by Elsevier B.V. Limited.

Sintering of ultrafine undoped SnO2 powder

The sintering process of nanometric undoped SnO2 powder was studied. No macroscopic shrinkage was observed during the sintening process. Grain growth kinetics investigation showed that surface diffusion is the dominant mechanism in the temperature range 500-1300 degreesC. For temperatures higher than 1300 degreesC, high weight loss was measured, suggesting evaporation-condensation as the dominant mass-transport mechanism. Thermogravimetric analysis (TG) and mass spectroscopy studies showed that the surface contamination of the SnO2 particles by chemical species like H2O, OH- and CO2, has a strong influence on the role of mass transport controlled by surface diffusion. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Whydration effects on DNA double helix stability modulates ligand binding to natural DNA in response to changes in water activity

In this work we present evidence that water molecules are actively involved on the control of binding affinity and binding site discrimination of a drug to natural DNA. In a previous study, the effect of water activity (a(w)) on the energetic parameters of actinomycin-D intercalation to natural DNA was determined using the osmotic stress method (39). This earlier study has shown evidence that water molecules act as an allosteric regulator of ligand binding to DNA via the effect of water activity on the long-range stability of the DNA secondary structure. In this work we have carried out DNA circularization experiments using the plasmid pUC18 in the absence of drugs and in the presence of different neutral solutes to evaluate the contribution of water activity to the energetics of DNA helix unwinding. The contribution of water to these independent reactions were made explicit by the description of how the changes in the free energy of ligand binding to DNA and in the free energy associated with DNA helix torsional deformation are linked to a(w) via changes in structural hydration. Taken together, the results of these studies reveal an extensive linkage between ligand binding affinity and site binding discrimination, and long range helix conformational changes and DNA hydration, This is strong evidence that water molecules work as a classical allosteric regulator of ligand binding to the DNA via its contribution to the stability of the double helix secondary structure, suggesting a possible mechanism by which the biochemical machinery of DNA processing takes advantage of the low activity of water into the cellular milieu.

Glass transitions for freeze-dried and air-dried tomato

Glass transition temperatures of freeze-dried tomato conditioned at various water activities at 25 C were determined by differential scanning calorimetry (DSC). Air-dried tomato with and without osmotic pre-treatment in sucrose/NaCl solutions was also analyzed. Thermograms corresponding to the low water activity domain (0.11 less than or equal to a(w) less than or equal to 0.75) revealed the existence of two glass transitions, which were attributed to separated phases formed by sugars and water and other natural macromolecules present in the vegetable. Both transitions were plasticized by water and experimental data could be well correlated by the Gordon-Taylor equation in the low-temperature domain, and by the Kwei model in the high-temperature domain. For higher water activities, the low-temperature glass transition curve exhibited a discontinuity, with suddenly increased glass transition temperatures approaching a constant value that corresponds to the T-g of the maximally freeze-concentrated amorphous matrix. The unfreezable water content was determined through the melting enthalpy dependence on the moisture content. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Effect of chemical pretreatment on the physical properties of dehydrated grapes

The effects of chemical pretreatment and air drying temperature on drying kinetics, shrinkage, density and rehydration ratio of grapes were determined at various moisture contents. It was observed that the chemical pretreatment employed - a solution of 2% CaCO3 with 0 to 3% ethyl oleate - increased considerably the drying rate. It was established that the shrinkage increased with drying temperature between 40 to 80 degrees C and decreased with increasing concentration of ethyl oleate in the chemical pretreatment solution.

Sintering of ZnO doped SnO2

Dense SnO2 ceramics were obtained by doping with ZnO concentrations varies from 0.5 to 5.0 mel. The obtained powder was isostaticaly pressed to 210MPa in cylindrical shape and sintered from ambient to 1.500 degrees C using constant heating rate of 10 degrees C/min. Densities above 97% were obtained depending on the ZnO doping concentration. A maximum density was reached with the addition of 2 mol%. It can be concluded from shrinkage data and the observed microstructure obtained by SEM that the solid solution limit for ZnO in SnO2 is about 1.0 mol%. Above this concentration the formation of a second ceramic phase is observed.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

ESTIVATION IN SOUTH-AMERICAN AMPHIBIANS AND REPTILES

A number of amphibians and reptiles have cyclic behavior, becoming inactive with the coming of the dry season. In South America this pattern of activity is common, particularly in savannah-like vegetation. During the dry season amphibians burrow into the mud or soil, and either form a cocoon or increase the osmotic concentration of body fluids to reduce evaporative water loss. Some phyllomedusid tree frogs coat their body surface with skin secretion and excrete uric acid to minimize water loss. Reptiles also retreat into shelter deep enough to avoid temperature fluctuation during estivation or reduce metabolic response to temperature. Reduction of temperature sensitivity of the metabolism seems to be a strategy common to estivating amphibians and reptiles. Despite seasonal change of the environment, some species of reptiles are active all year round.

Effect of ceria content on the sintering of ZrO2 based ceramics synthesized from a polymeric precursor

Zirconia-ceria powders with ceria concentration varying from 0 to 12 mol% were synthesized using a polymeric precursor route based on the Pechini process. Powder characteristics were evaluated with regard to the crystallite size, BET surface area, phase distribution, nitrogen adsorption/desorption behavior, and agglomeration state. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. It was demonstrated that the synthesis method is effective to prepare nanosized powders of tetragonal zirconia single-phase. Sinterability mainly depended on the agglomeration state of powders and the monoclinic phase content, fully tetragonal zirconia ceramic, with grain size of 2.4 mu m, was obtained after addition of at least 9 mol% ceria and sintering at 1500 degrees C for 4 h. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

A nonisothermal study of the kinetics of the nanoporosity elimination in sonogels-derived silica xerogels

A nonisothermal study of the kinetics of the nanoporosity elimination in monolithic silica xerogels, prepared from acid and ultrasound catalyzed hydrolysis of tetraethylortosilicate (TEOS), has been carried out by means of in situ linear shrinkage measurements performed with different heating rates. The study could be applied up to almost alpha similar to 0.6 of the volume fraction alpha of eliminated pores. The activation energy was found increasing from about 3.2 x 10(2) kJ/mol for alpha similar to 0.06 up to about 4.4 x 10(2) kJ/mol for alpha. similar to 0.44. The sintering process accompanying the nanopore elimination in this set of xerogels is in agreement with a viscous flux sintering process with the hydroxyl content diminishing with the volume fraction of eliminated pores. All the volume fraction of eliminated pores versus temperature (T) curves can be matched onto a unique curve with an appropriate rescaling of the T axis, independent of the heating rate. This scaling property suggests that the path of sintering seems the same, regardless of the heating rate; the difference is that the rate is faster at higher temperature.