Oxidation of anilinium ions intercalated in montmorillonite clay by electrochemical route

Resonance Raman, FTIR, X-ray diffraction, UV-vis-NIR, electron paramagnetic resonance, X-ray absorption at Si K-edge and electron microscopy were employed for characterizing the products formed through electrochemical oxidation of intercalated anilinium ions inside the cationic montmorillonite (MMT) clay. The layer silicate structure was not affected by the anilinium oxidation between the layers. The intercalated products present only an electronic absorption band at 400 nm, very low conductivity (ca. 10(-7) S cm(-1)) and their Raman spectrum displays bands, with high relative intensities, assigned to the benzidine dication, indicating that this product was formed in high amount. Nevertheless, bands that can be correlated to phenazine-like segments and 1,4-phenylenediamine repeat units (PANI like segments) are also observed. The very low EPR signal indicates that diamagnetic species are predominant. All results are compared to those obtained by anilinium-MMT chemically oxidized by persulfate and the differences are pointed out. (C) 2008 Elsevier B.V. All rights reserved.

Solvatochromism in Binary Mixtures: First Report on a Solvation Free Energy Relationship between Solvent Exchange Equilibrium Constants and the Properties of the Medium

We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromic indicators, hereafter designated as ""probes"", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr,, respectively. These can be divided into three pairs, each includes two probes of similar pK(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12 protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda(max) (of the probe intramolecular charge transfer) were converted into empirical polarity scales, E(T)(probe) in kcal/mol, whose values were correlated with the effective mole fraction of water in the medium, chi w(effective). This correlation furnished three equilibrium constants for the exchange of solvents in the probe solvation shell; phi(W/S) (W substitutes S): phi(S-W/W) (S-W substitutes W), and phi(S-W/S) (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi = constant + a alpha(BM) + b beta(BM) + s(pi*(BM) + d delta) + p log P(BM), where a, b, s, and p are regression coefficients alpha(BM), beta(BM), and pi*(BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors. In all cases, three descriptors gave satisfactory correlations; use of four parameters gave only a marginal increase of the goodness of fit. For phi(W/S), the most important descriptor was found to be the lipophilicity of the medium; for phi(S-W/W) and phi(S-W/S), solvent basicity is either statistically relevant or is the most important descriptor. These responses are different from those of E(T)(probe) of many solvatochromic indicators in pure solvents, where the importance of solvent basicity is usually marginal, and can be neglected.

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co-Solvent Mixtures

Co-solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non-polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co-solvents in cellulose chemistry could be advanced: Appropriate co-solvents should have EN T values (normalized empirical polarity) > 0.3, very low ``acidity`` (alpha < 0.5), and relatively high ""basicity`` (beta >= 0.4). Moreover, novel promising co-solvents and binary co-solvent mixtures were identified.

Bacterial cellulose-laponite clay nanocomposites

A novel material comprised of bacterial cellulose (BC) and Laponite clay with different inorganic organic ratios (m/m) was prepared by the contact of never-dried membranes of BC with a previous dispersion of clay particles in water. Field emission scanning electron microscopy (FE-SEM) data of composite materials revealed an effective adhesion of clay over the surface of BC membrane; inorganic particles also penetrate into the polymer bulk, with a significant change of the surface topography even at 5% of clay loading. As a consequence, the mechanical properties are deeply affected by the presence of clay, increasing the values of the Young modulus and the tensile strength. However the maximum strain is decreased when the clay content is increased in the composite in comparison to pristine BC. The main weight loss step of the composites is shifted towards higher temperatures compared to BC, indicating that the clay particles slightly protect the polymer from thermal and oxidative decomposition. (C) 2010 Elsevier Ltd. All rights reserved.

Aromatic nitro substitution reaction between 4-nitro-N-n-butyl-1,8-naphthalimide and n-heptanethiol in water-methanol binary mixtures

The second-order rate constants of thiolysis by n-heptanethiol on 4-nitro-N-n-butyl-1,8-naphthalimide (4NBN) are strongly affected by the water-methanol binary mixture composition reaching its maximum at around 50% mole fraction. In parallel solvent effects on 4NBN absorption molar extinction coefficient also shows a maximum at this composition region. From the spectroscopic study of reactant and product and the known H-bond capacity of the mixture a rationalization that involves specific solvent H-donor interaction with the nitro group is proposed to explain the kinetic data. Present findings also show a convenient methodology to obtain strongly fluorescent imides, valuable for peptide and analogs labeling as well as for thio-naphthalimide derivatives preparations. Copyright (C) 2008 John Wiley & Sons, Ltd.

Contribuição ao beneficiamento de finos de fosfatos

Foram estudadas as características de floculação da hidro-xiapatita, calcita e quartzo com poliacrilamidas aniônicas. Tanto as suspensões de hidroxiapatita como a calcita foram completamente floculadas enquanto que o quartzo foi refratário a floculação com esses polimeros. Entretanto, observou-se que a floculação da calcita foi impedida com a utilização de um poliacrilato de sódio, enquanto que a hidroxiapatita continuou a ser floculada pela poliacrilamida num intervalo de concentração de O a 1000 g/ton de poliacrilato. Estes resultados permitiram estabelecer condições para a floculação seletiva de hidroxiapatita em misturas sintéticas com quartzo e calcita. Nestes sistemas foram estudados diversos parâmetros operacionais, tais como tipo de separação, efeito do teor da alimentação, e influência da moagem. Onde a separação estagiada apresentou melhor resultado, uma moagem adicional no sistema não favoreceu a seletividade. Por outro lado, o teor de P205 no concentrado é proporcional ao teor presente na alimentação. A hidroxiapatita, em estudo, de alta pureza (de acordo com técnicas de análise química, espectrofotometria de infravermelho e difração de raios X) apresentou um parto de carga zero em pH 6,77 na presença de diversos eletrólitos. A aplicação do sistema de floculação seletiva a fraçoes ultrafinas industriais foi estudada em detalhe e comparada com processos de flotação e floco-flatação. 0s resultados obtidos mostraram que a floculação seletiva somente foi eficiente nos sistemas sintéticos. A flotação, embora o minério apresente uma granulometria muito fina, foi mais eficiente que a floculação seletiva e a floco-flotação nos sistemas reais, em termos de taxa de enriquecimento e percentual de rejeição de massa. Entretanto com a floco-flotação foi possivel obter altas recuperações(-90%) para os minérios de Araxá e Itataia. Para o minério de Tapira, um aumento do teor de P2O5 foi obtido com a flotação da fração seletivamente floculada. As taxas de enriquecimento obtidas foram baixas (entre 1,35 e 2,101 em função das associações entre a apatita do minério com óxido de ferro e argila, o que revelou a caracterização mineralógica. Conclue-se que a concentração de minerios fosfatados de baixo teor é uma operação onerosa, onde o fator predominante é a absorção seletiva de reagentes e atransferência não específica de material de ganga nos respectivos concentrados.

The implications of embodiment and Putty-Clay to economic development

In this paper we construct and analyze a growth model with the following three ingredients. (i) Technological progress is embodied. (ii) The production function of a firm is such that the firm makes both technology upgrade as well as capital and labor decisions. (iii) The firm’s production technology is putty-clay. We assume that there are disincentives to the accumulation of capital, resulting in a divergence between the social and the private cost of investment. We solve a single firm’s problem in this environment. Then we determine general equilibrium prices of capital goods of different vintages. Using these prices we aggregate firms’ decisions and construct the theoretical analogues of National Income statistics. This generates a relationship between disincentives and per capita incomes. We analyze this relationship and show the quantitative and qualitative roles of embodiment and putty-clay. We also show how the model is taken to data, quantified and used to determine to what extent income gaps across countries can be attributed to disincentives.

Otimização de uma metodologia para análise mineralógica racional de argilominerais

VARELA, M.L. et al. Otimização de uma metodologia para análise mineralógica racional de argilominerais. Cerâmica, São Paulo, n. 51, p. 387-391, 2005.

Aplicação da metodologia de planejamento de experimentos para formulação de massas cerâmicas para telhas

Rio Grande do Norte State stands out as one great producer of structural clay of the brazilian northeastern. The Valley Assu ceramic tiles production stands out obtained from ilitics ball clays that abound in the region under study. Ceramics formulation and the design of experiments with mixture approach, has been applied for researchers, come as an important aid to decrease the number of experiments necessary to the optimization. In this context, the objective of this work is to evaluate the effects of the formulation, temperature and heating rate in the physical-mechanical properties of the red ceramic body used for roofing tile fabrication of the Valley Assu, using design of mixture experiments. Four clays samples used in two ceramics industry of the region were use as raw material and characterized by X-ray diffraction, chemical composition, differential thermal analysis (DTA), thermogravimetric analysis (TGA), particle size distribution analysis and plasticity techniques. Afterwards, they were defined initial molded bodies and made specimens were then prepared by uniaxial pressing at 25 MPa before firing at 850, 950 and 1050 ºC in a laboratory furnace, with heating rate in the proportions of 5, 10 e 15 ºC/min. The following tecnologicals properties were evaluated: linear firing shrinkage, water absorption and flexural strength. Results show that the temperature 1050 ºC and heating rate of 5 ºC/min was the best condition, therefore presented significance in all physical-mechanical properties. The model was accepted as valid based of the production of three new formulations with fractions mass diferents of the initial molded bodies and heated with temperature at 1050 ºC and heating rate of 5 ºC/min. Considering the formulation, temperature and heating rate as variables of the equations, another model was suggested, where from the aplication of design of experiments with mixtures was possible to get a best formulation, whose experimental error is the minor in relation to the too much formulations

Avaliação da argila atapulgita para potencial uso como excipiente farmacêutico em formas sólidas

Clays are natural materials that have great potential for use as excipients for solid dosage forms. Palygorskite is a type of clay that has hydrophilic properties as well as a large surface area, which could contribute to the dissolution of drugs. Thus, the present study aims to evaluate the use of palygorskite clay, from Piaui (Northeast region of Brazil), as a pharmaceutical excipient for solid dosage forms, using rifampicin and isoniazid as the model drugs. The former is a poorly soluble drug often associated with isoniazid for tuberculosis treatment. Palygorskite was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and specific surface area (BET). The rheological and technological properties of palygorskite were determined and compared to those of talc, magnesium stearate and Aersosil 200. Mixtures between drugs and palygorskite were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) combined with thermal analysis (DTA) and Fourier Transform Infrared Spectroscopy (FT-IR), where the results were compared with those of the individual compounds. In addition, dissolution studies of solid dispersions and capsules containing the drugs, mixed with either palygorskite or a mixture of talc and magnesium stearate, were performed. The results showed that palygorskite has small particles with a high surface area. Its rheological characteristics were better than those of others commonly used glidants and lubricants. There was no interaction between palygorskite and the drugs (rifampicin and isoniazid). Among the dispersions studied, the mixture with palygorskite (5%) showed the highest drug dissolution when compared to other excipients. The dissolution of the rifampicin capsules containing palygosrkite was faster in higher concentrations. However, these differences were statistically different only in the first minutes of the dissolution experiment. The dissolution profile of isoniazid was also statistically different on the initial part of the experiment. The formulations prepared with isoniazid and palygorskite showed higher drug dissolution, but it was in descending order of concentration. According to these results, the palygorskite clay used in this study has great potential for application as an excipient for solid dosage forms

Mineralogy of the clay fraction of Alfisols in two slope curvatures: III - spatial variability

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

Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

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

Hillslope curvature, clay mineralogy, and phosphorus adsorption in an Alfisol cultivated with sugarcane

As curvaturas do relevo promovem pedoambientes específicos que condicionam os atributos químicos e mineralógicos do solo e podem auxiliar na definição de zonas específicas de manejo. O fósforo (P) é um dos principais elementos limitantes ao desenvolvimento e longevidade do canavial. O teor e a constituição mineralógica da fração argila assumem papel importante na disponibilidade do P, sendo que a gibbsita (Gb), quando presente em altas proporções no solo, pode ser a principal responsável pela sua adsorção e indisponibilidade. Investigaram-se as relações e a variabilidade espacial da adsorção de P e a ocorrência de caulinita (Ct) e gibbsita na fração argila de um Argissolo Vermelho-Amarelo eutrófico originado de rochas areníticas sob diferentes curvaturas do relevo em área sob cultivo de cana-de-açúcar. Duas malhas de 1 ha foram delimitadas numa área côncava e outra área convexa. Foram coletadas 121 amostras em cada área para realização das análises granulométricas, químicas e mineralógicas. A capacidade máxima de adsorção de P foi obtida em seis amostras escolhidas ao acaso em cada área. Os resultados foram submetidos às análises estatísticas descritiva e geoestatística. Os menores valores médios de P disponível encontraram-se na área convexa. Nesta área, a proporção de gibbsita, expressa pelos valores da razão [Gb/(Gb+Ct)] e os valores de capacidade máxima de adsorção de fósforo foram maiores do que na área côncava.

Incorporação de cinzas da casca de café na produção de placas cerâmicas para revestimento

Brazil is the world s leading coffee producer. In 2008, 45.99 million of 60 kg bags of benefited coffee were produced. In the process of improvement 50% is grain and 50% is husk, thus, 1.38 million tons of coffee husk are produced annually. The husk is used as combustible in the drying and improvement ovens in the coffee farms, generating ash as residue. These ashes contain a high concentration of alkaline metals and earth metals, mainly K2O and CaO. This work studies the use of this residue in the ceramic tiles industry, as fluxing agents in substitution to the feldspar. Ten mixtures with equal ratios of clay and kaolin, proceeding from Bahia and the residue (varying from 30 to 5%) were defined and produced in uniaxial tool die of 60x20mm with approximately 5 mm of thickness and 45MPa compacting pressure. The samples were fired in four different temperatures: 1100 °C, 1150 °C, 1185 °C and 1200 °C during 60 minutes and characterized by means of X-ray fluorescence, X-ray diffraction, gravimetric thermal analysis and differential thermal analysis. The results of water absorption, apparent porosity, linear shrinkage, XRD, dilatometry, flexural strength and SEM were also analysed. The test specimen with addition of 10% of ash fired in 1200 °C resulted in 0.18% water absorption and 40.77 MPa flexural strength, being classified as porcelain stoneware tiles according to ABNT, UNI and ISO norms