Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

Effects of environrnental conditions on the radon daughters spatial distribution

The influence of environmental conditions on the indoor radon daughters spatial distribution is studied both theoretically and experimentally. Simple theoretical calculations indicate that ventilation and variation in the size distribution of aerosols should play an important role influencing the spatial distribution of indoor radon decay products, but experimental results indicate that these environmental factors have little influence on the spatial distribution of radon daughters near the walls of indoor environments. We have observed that the maximum effective range of the plate-out effect varies only between I and 3 cm in typical dwellings. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Calcium levels and limestone particle size in the diet of commercial layers at the end of the first production cycle

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Gap size measurement: the proposal of a new field method

In the tropical Atlantic Forest, 42 canopy gaps had their areas estimated using four different field methods of measurement: Runkle, Brokaw and Green [Runkle, J.R., 1981. Gap formation in some old-growth forests of the eastern United States. Ecology 62, 1041-1051; Brokaw, N.V.L., 1982. The definition of treefall gap and its effect on measures of forest dynamics. Biotropica 14, 158-160; Green, P.T., 1996. Canopy Gaps in rain forest on Christmas Island, Indian Ocean: size distribution and methods of measurement. J. Trop. Ecol. 12, 427-434] and a new method proposed in this work. It was found that within the same gap delimitation, average gap size varied from 56.0 up to 88.3 m(3) while total sum of gap area varied from 2351.3 to 3707.9 m(3) Differences among all methods and between pairs of method proved to be statistically significant. As a consequence, gap size-class distribution was also different between methods. When one method is held as a standard, deviation on average values of gap size ranged between 11.8 and 59.7% as deviations on single gap size can reach 172.8%. Implications on forest dynamics were expressed by the forest turnover rate that was 24% faster or 15% slower depending on the method adopted for gap measurement. Based on my results and on methods' evaluation, the use of a new method is proposed here for future research involving the measure of gap size in forest ecosystems. Finally, it is concluded that forest comparisons disregarding the influence of different methods of gap measurement should be reconsidered. (c) 2005 Elsevier B.V. All rights reserved.

Size distributions of fine silicate and other particles in Masaya's volcanic plume

Direct-sampling and remote-sensing measurements were made at the crater rim of Masaya volcano (Nicaragua) to sample the aerosol plume emanating from the active vent. We report the first measurements of the size distribution of fine silicate particles (d <10 mu m) in Masaya's plume, by automated scanning electron microscopy (QEMSCAN) analysis of a particle filter. The particle size distribution was approximately lognormal with modal d similar to 1.15 mu m. The majority of these particles were found to be spherical. These particles are interpreted to be droplets of quenched magma produced by a spattering process. Compositional analyses confirm earlier reports that the fine silicate particles show a range of compositions between that of the degassing magma and nearly pure silica and that the extent of compositional variability decreases with increasing particle size. These results indicate that fine silicate particles are altered owing to reactions with acidic droplets in the plume. The emission flux of fine silicate particles was estimated as similar to 10(11) s(-1), equivalent to similar to 55 kg d(-1). Sun photometry, aerosol spectrometry, and thermal precipitation were used to determine the overall particle size distribution of the plume (0.01 < d(mu m) < 10). Sun photometry and aerosol spectrometry measurements indicate the presence of a large number of particles (assumed to be aqueous) with d similar to 1 mu m. Aerosol spectrometry measurements further show an increase in particle size as the nighttime approached. The emission flux of particles from Masaya was estimated as similar to 10(17) s(-1), equivalent to similar to 5.5 Mg d(-1) where d < 4 mu m.

Composition-resolved size distributions of volcanic aerosols in the Mt. Etna plumes

Particle size distributions for soluble and insoluble species in Mt. Etna's summit plumes were measured across an extended size range (10 nm < d < 100 mu m) using a combination of techniques. Automated scanning electron microscopy (QEMSCAN) was used to chemically analyze many thousands of insoluble particles (collected on pumped filters) allowing the relationships between particle size, shape, and composition to be investigated. The size distribution of fine silicate particles (d < 10 mu m) was found to be lognormal, consistent with formation by bursting of gas bubbles at the surface of the magma. The compositions of fine silicate particles were found to vary between magmatic and nearly pure silica; this is consistent with depletion of metal ions by reactions in the acidic environment of the gas plume and vent. Measurements of the size, shape and composition of fine silicate particles may potentially offer insights into preemission, synemission, and postemission processes. The mass flux of fine silicate particles from Mt. Etna released during noneruptive volcanic degassing in 2004 and 2005 was estimated to be similar to 7000 kg d(-1). Analysis of particles in the range 0.1 < d/mu m < 100 by ion chromatography shows that there are persistent differences in the size distributions of sulfate aerosols between the two main summit plumes. Analysis of particles in the range 0.01 mu m < d < 0.1 mu m by scanning transmission electron microscopy (STEM) shows that there are significant levels of nanoparticles in the Mt. Etna plumes although their compositions remain uncertain.

Substâncias húmicas: sistema de fracionamento sequencial por ultrafiltração com base no tamanho molecular

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

Distribuição de Cr, Ni, Cu, Cd e Pb em frações húmicas de diferentes tamanhos moleculares extraídas de amostras de água e de sedimentos do reservatório de captação de água superficial Anhumas - Araraquara-SP

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

Different particle size silicas from water glass.

Non-crystalline silica was obtained with different particle sizes. Samples were prepared from soluble sodium silicate (water glass) and sulfuric acid solutions. Dialysis was performed for sodium sulfate elimination. Products were dried in a microwave oven, milled and characterized by X-ray powder diffraction, infrared spectrum and sedigraphic analysis. Products milled for more than 120 minutes showed uniform particle size distribution with average silica particle size of 4.5 mu m.

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal-humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubatao city in São Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. C-13-NMR and H-1-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F-1 (> 100 kDa).

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Some structural and physicochemical characteristics of tuber and root starches

Starches from six different species (cassava, arrowroot, sweet potato, yam, canna and ginger) were isolated and some structural and physicochemical characteristics analysed and correlated. Phosphorous and amylose contents were determined using a colorimetric method and measuring iodine affinity, respectively. Molecular weight distributions of starches were analysed by Sepharose CL 2B. Granular shape and size distribution were performed using an image analyser system attached to a light microscope. Swelling power was determined at 60, 70, 80 and 90 degrees C. Pasting and thermal properties were measured using a rapid viscoanalyser, and a differential scanning calorimeter, respectively. Phosphorous content varied from 0.007 to 0.031% for cassava and canna starches, respectively. Yam, canna and ginger starches displayed higher amylose contents (32.6, 31.7 and 26.5%, respectively) than cassava, arrowroot and sweet potato starches (19.8, 20.8 and 22.6%, respectively). These last three starches displayed amylose molecules of higher molecular weight than those shown for yam, canna and ginger starches. Canna starch showed higher proportions of longer branch chains of amylopectin than others starches. The size and shape of granules were quite variable among all starches and the average size of granules varied from 13.9 to 42.3 mu m for sweet potato and canna, respectively. Swelling power, pasting, and thermal properties were affected by structural characteristics of the starches.

Multifractal characterization of saprolite particle-size distributions after topsoil removal

Multifractal analysis is now increasingly used to characterize soil properties as it may provide more information than a single fractal model. During the building of a large reservoir on the Parana River (Brazil), a highly weathered soil profile was excavated to a depth between 5 and 8 m. Excavation resulted in an abandoned area with saprolite materials and, in this area, an experimental field was established to assess the effectiveness of different soil rehabilitation treatments. The experimental design consisted of randomized blocks. The aim of this work was to characterize particle-size distributions of the saprolite material and use the information obtained to assess between-block variability. Particle-size distributions of the experimental plots were characterized by multifractal techniques. Ninety-six soil samples were analyzed routinely for particle-size distribution by laser diffractometry in a range of scales, varying from 0.390 to 2000 mu m. Six different textural classes (USDA) were identified with a clay content ranging from 16.9% to 58.4%. Multifractal models described reasonably well the scaling properties of particle-size distributions of the saprolite material. This material exhibits a high entropy dimension, D-1. Parameters derived from the left side (q > 0) of the f(alpha) spectra, D-1, the correlation dimension (D-2) and the range (alpha(0)-alpha(q+)), as well as the total width of the spectra (alpha(max) - alpha(min)) all showed dependence on the clay content. Sand, silt and clay contents were significantly different among treatments as a consequence of soil intrinsic variability. The D, and the Holder exponent of order zero, alpha(0), were not significantly different between treatments; in contrast, D-2 and several fractal attributes describing the width of the f(alpha) spectra were significantly different between treatments. The only parameter showing significant differences between sampling depths was (alpha(0) - alpha(q+)). Scale independent fractal attributes may be useful for characterizing intrinsic particle-size distribution variability. (c) 2006 Elsevier B.V. All rights reserved.

Characterization of PLGA microparticles as a drug carrier for 3-ethoxycarbonyl-2H-benzofuro[3,2-f]-1-benzopyran-2-one. Ultrastructural study of cellular uptake and intracellular distribution

Here we describe the application of microparticles (MPs) for the delivery and release of the drug a benzopsoralen. We also evaluated the intracellular distribution and cellular uptake of the drug by using an encapsulation technique for therapeutic optimization. MPs containing the compound 3-ethoxycarbonyl-2H-benzofuro[3,2-f]-1-benzopyran-2-one (psoralen A) were prepared by the solvent evaporation technique, and parameters such as particle size, drug encapsulation efficiency, effect of the encapsulation process on the drug's photochemistry, zeta potential, external morphology, and < i > in vitro release behavior were evaluated. The intracellular distribution of MPs as well as their uptake by tissues were monitored. Size distribution studies using dynamic ligh scattering and scanning electron microscopy revealed that the MPs are spherical in shape with a diameter of 1.4 mu m. They present low tendency toward aggregation, as confirmed by their zeta potential (+10.6 mV). The loading efficiency obtained was 75%. As a consequence of the extremely low diffusivity of the drug in aqueous medium, the drug release profile of the MPs in saline phosphate buffer (pH 7.4) was much slower than that obtained in the biological environment. Among the population of peritoneal phagocytic cells, only macrophages were able to phagocytose poly-d,l-lactic-co-glycolic acid (PLGA) MP. The use of psoralen A in association with ultraviolet light (360 nm) revealed morphological characteristics of cell damage such as cytoplasmic vesiculation, mitochondria condensation, and swelling of both the granular endoplasmatic reticulum and the nuclear membrane. These results indicate that PLGA MP could be a promising delivery system for psoralen in connection with ultraviolet irradiation therapy (PUVA).