Efeitos de surfatantes sobre a tensão superficial e a área de molhamento de soluções de glyphosate sobre folhas de tiririca

Com o objetivo de avaliar a eficiência da agregação de surfatantes ao herbicida glyphosate analisou-se a tensão superficial de diferentes soluções de pulverização contendo o hebicida e o surfatante, e a área de molhamento destas soluções nas folhas de Cyperus rotundus L.. Foram desenvolvidos métodos para avaliação da tensão superficial e da área de molhamento. Para analisar a tensão fez-se pesagens das gotas formadas na extremidade de uma bureta, com os seguintes tratamentos combinados de forma fatorial (3 x 5 x 11): 3 surfatantes (Extravon, Aterbane e Silwet L-77), 5 concentrações do herbicida, produto comercial Roundup (0; 1; 2; 3,5 e 5 %) e 11 concentrações de cada surfatantes (0; 0,005; 0,01; 0,02; 0,05; 0,1; 0,2; 0,5; 1; 2 e 3,5 %), num total de 165 tratamentos. Para avaliar a área de molhamento nas folhas de tiririca aplicou-se gotas de 0,48 .l. Os dados foram ajustados pelo modelo de Mitscherlich e, observou-se que para o surfatante Extravon que a eficiência decrescia gradativamente a medida em que aumentava a concentração do herbicida; para o Aterbane a eficiência foi reduzida apenas em baixas concentrações; já o surfatante Silwet L-77 apresentou eficiência bem superior aos demais e sua eficiência foi pouco alterada com a adição herbicida. Houve uma correlação positiva entre área de molhamento e tensão superficial. Concluiu-se, ainda, que não basta um surfatante reduzir a tensão superficial da água destilada, para que possa ser recomendado seu uso agrícola, assim, o surfatante deve ser submetido a testes preliminares com os defensivos em que serão conjugados para posterior recomendação.

Murcha por Ceratocystis em eucalipto: avaliação de resistência e análise epidemiológica

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

Alteração de atributos físicos em latossolo com aplicação superficial de escória de aciaria, lama cal, lodos de esgoto e calcário

Os resíduos industriais e urbanos podem atuar como condicionadores do solo, pois possuem a capacidade de alterar suas propriedades físicas. Contudo, não há referência para os atributos físicos do solo quando esses resíduos são aplicados sobre a superfície do solo no sistema plantio direto. O objetivo deste trabalho foi avaliar o efeito da aplicação superficial de escória de aciaria, lama cal, lodos de esgoto e calcário nos atributos físicos de um Latossolo Vermelho distrófico sob sistema plantio direto. Os tratamentos foram constituídos por quatro resíduos: lodos de esgoto centrifugado - LC e de biodigestor - LB, escória de aciaria - E, e lama cal - Lcal, interagindo com quatro doses (0, 2, 4 e 8 t ha-1, aplicadas na forma seca) mais uma testemunha (controle), constituída da aplicação de 2 t ha-1 de calcário. O delineamento experimental foi em blocos casualizados no esquema fatorial 4 x 4 + 1, com quatro repetições. A presença de Ca na composição de lama cal, lodo de esgoto centrifugado, escória de aciaria e calcário permite o aumento da agregação das partículas, diâmetro médio ponderado, índice de estabilidade de agregados, porosidade e retenção de água, sendo essas alterações distintas para cada fonte, dose e profundidade de reação no solo. A aplicação superficial da lama cal na dose de 8 t ha-1, após 27 meses de reação, proporcionou a maior agregação das partículas no solo, desde a superfície até 40 cm de profundidade.

Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Síntese, caracterização e estudo cinético da degradação de quitosana impregnada em SBA-15

O recente interesse em se obter materiais nanoporosos funcionalizados para aplicações como calisadores heterogêneos e adsorção de CO2, tem aumentado no meio industrial e cientifico. Nesta última aplicação, a introdução de grupos aminas, como os presentes em quitosana, em materiais nanoporosos do tipo SBA-15 para gerar interações específicas com o CO2 tem ganhado importância. Assim, neste trabalho foram realizadas a síntese do SBA-15 e posterior impregnação da CS no suporte mesoporoso através do método de impregnação por via úmida. Os materiais obtidos foram caracterizados por meio DRX, TG, DSC, MEV, FTIR e adsorção/dessorção de N2. Os resultados de DRX indicaram que a estrutura ordenada do suporte SBA-15 foi preservada após a impregnação e os cálculos mostraram que o diâmetro médio do poro e/ou a espessura média da parede (wt) foram alterados devido a introdução da quitosana nas amostras funcionalizadas. As curvas de TG e de DSC,corroboraram com os dados de DRX, indicando a presença da quitosana na estrutura mesoporosa do SBA-15, assim como as micrografias das amostras funcionalizadas, que possibilitou visualizar o estado de agregação do material obtido. As bandas características de absorção da CS na região IV foram identificadas e interpretadas nas amostras funcionalizadas confirmando as outras caracterizações. Foi visto também que a área superficial diminuiu nas amostras funcionalizadas, indicando a sucessiva incorporação do polímero no suporte mesoporoso. A energia de ativação do processo de degradação térmica da quitosana impregnada no suporte foi determinada por meio do método de cinética livre de Viazovkin e pelo método de Ozawa-Flay-Wall com os resultados indicando que o aumento da quitosana diminui em aproximadamente 10% a energia de ativação para sua degradação.

Síntese, caracterização e estudo cinético da degradação de quitosana impregnada em SBA-15

The recent interest in obtaining functionalized nanoporous materials for applications such as heterogeneous catalysts and adsorption of CO2 has increased today. In the latter application, the introduction of amino groups such as present in the chitosan (CS), in the nanoporous materials like SBA-15 to generate specific interactions with CO2 has gained importance. In this work were performed to hydrothermal synthesis of SBA-15 and subsequent impregnation of the CS in the support mesoporous by the method of the wet impregnation. The materials were characterized by TG/DTG, DSC, XRD, SEM, FTIR and adsorption / desorption of N2. The XRD showed that the ordered structure of the support SBA-15 was preserved after the impregnation and calculations have shown that the average pore diameter (Dp) and / or the average wall thickness (wt) have been changed due to introduction of the CS in the samples functionalized. The curves of TG and DSC data corroborates the XRD, indicating the presence of CS in the nanoporous structure of SBA-15, as well as micrographs of samples, which allowed the display state of aggregation of the material obtained. The characteristics of bands absorption in the region of the CS in the FTIR were identified and interpreted in the samples functionalized, confirming the further characterization. Measurements showed that the BET surface area decreases in the functionalized samples, indicating the successive incorporation of the polymer in the nanoporous support. The activation energy apparent (Ea) for the process of thermal degradation of CS in the impregnated support was determined by the methods of kinetic freedom Vyazovkin and Ozawa-Flynn-Wall with the results indicating that the sample functionalized CS/SBA-15 2,5 % was decrease of the Ea in their degradation of about 10% compared to 1,0 % CS/SBA-15 sample

Síntese e caracterização de poliacrilamidas modificadas para utilização na indústria do petróleo

Modified polyacrylamides with ≅ 0.2 mol % of N,N-dihexylacrylamide and hydrolysis degree from 0 to 25 % were synthesized by micellar copolymerization. The hydrophobic monomer was obtained by the reaction between acryloyl chloride and N,Ndihexylamine and characterized by infrared (IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The polymer molecular structures were determined through 1H and 13C NMR spectroscopy and the polymers were studied in dilute and semi-dilute regimes by viscometry, rheometry, static light scattering and photon correlation spectroscopy, at the temperature range from 25 to 55 ºC. The data obtained by viscometry showed that the intrinsic viscosity from the hydrolyzed polymers is larger than the precursor polymers at the same ionic strength. The comparison between the charged polymers showed that the polymer with higher hydrolysis degree has a more compact structure in formation water (AFS). The increase of temperature led to an enhanced reduced viscosity to the polymers in Milli-Q water (AMQ), although, in brine, only the unhydrolyzed polymer had an increase in the reduced viscosity with the temperature, and the hydrolyzed derivatives had a decrease in the reduced viscosity. The static light scattering (SLS) analyses in salt solutions evidenced a decrease of weight-average molecular weight (⎯Mw) with the increase of the hydrolysis degree, due to the reduction of the thermodynamic interactions between polymer and solvent, which was evidenced by the decrease of the second virial coefficient (A2). The polymers showed more than one relaxation mode in solution, when analyzed by photon correlation spectroscopy, and these modes were attributed to isolated coils and aggregates of several sizes. The aggregation behavior depended strongly on the ionic strength, and also on the temperature, although in a lower extension. The polymers showed large aggregates in all studied conditions, however, their solutions did not displayed a good increase in water viscosity to be used in enhanced oil recovery (EOR) processes

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

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

Avaliação econômica dos incentivos fiscais e financeiros: uma análise das empresas industriais têxteis localizadas no Rio Grande do Norte, no período de 1999 a 2003

This study has as main objective to verify the effect of the tax and financial incentives granted by the brazilian states, specially in the reduction of ICMS on the investment decision of the entities, which in the last years led to the companies to decide new projects in based on the region that presented the better infrastructure beyond lesser tributary expense. For in such was made an economic valuation of the companies with focus in the beneficiary s optics using an adaptation of the Discounted Cash Flow method to measure the impact of the tax incentives in the value of the companies, this study selected the textile industry segment located in the State of Rio Grande do Norte, Brazil. The results indicated that such incentives created addition in the value of the companies, however the inexistence of incentives would not be enough to a negative decision of investment in the Rio Grande do Norte. The smallest difference between the value with and without incentive observed was 8.9%, and the biggest 31.7%, and the average of value aggregation with the tax incentives represented 18.9%

Dinâmica e estrutura de redes complexas no modelo de afinidade

In this work we elaborate and discuss a Complex Network model which presents connectivity scale free probability distribution (power-law degree distribution). In order to do that, we modify the rule of the preferential attachment of the Bianconi-Barabasi model, including a factor which represents the similarity of the sites. The term that corresponds to this similarity is called the affinity, and is obtained by the modulus of the difference between the fitness (or quality) of the sites. This variation in the preferential attachment generates very interesting results, by instance the time evolution of the connectivity, which follows a power-law distribution ki / ( t t0 )fi, where fi indicates the rate to the site gain connections. Certainly this depends on the affinity with other sites. Besides, we will show by numerical simulations results for the average path length and for the clustering coefficient

Contribuição ao estudo das redes complexas: extensão do modelo de afinidade

Neste trabalho, elaboramos e discutimos uma rede complexa sem escala, ou seja, uma rede cuja distribuição de conectividade segue uma lei de distribuição de potência. Nosso trabalho pode ser resumido da seguinte forma: Para efeito de didática vamos começar com redes aleatórias que estão relacionados com situações reais e artificiais, e depois comentar as redes livres de escala, como proposto por Barabási-Albert (BA). Depois disso, discutimos uma extensão deste modelo, onde Barabasi e Bianconi (BB) incluem a qualidade. Discutimos também o modelo de afinidade, ou seja, (Ver Almeida et al). Finalmente vamos mostrar o nosso modelo, uma extensão do modelo de afinidade dada por e apresentar os resultados correspondentes. Para realizar tal tarefa modificamos a regra de ligação preferencial do modelo de BB colocando um fator que apresenta o grau de probabilidade entre os sítios da rede. Esta quantidade é feita pela diferença entre a qualidade do novo sítio e a qualidade dos anteriores. Este novo parâmetro produz novos resultados interessantes: a distribuição que segue uma lei de especial de potência, expoente apropriado. A evolução temporal da conectividade do sítio também é calculada . Além disso, mostramos também, os resultados que foram obtidos, via simulação numérica, para o menor caminho médio e o coeficiente de agregação da rede gerada pelo nosso modelo, isto é, pelo modelo de afinidade.

Física estatística aplicada a sistemas sociais através do estudo de redes complexas

In this work a study of social networks based on analysis of family names is presented. A basic approach to the mathematical formalism of graphs is developed and then main theoretical models for complex networks are presented aiming to support the analysis of surnames networks models. These, in turn, are worked so as to be drawn leading quantities, such as aggregation coefficient, minimum average path length and connectivity distribution. Based on these quantities, it can be stated that surnames networks are an example of complex network, showing important features such as preferential attachment and small-world character

Gagueira desenvolvimental persistente familial: perspectivas genéticas

A gagueira é uma desordem da comunicação oral que tem uma característica multidimensional. A predisposição biológica no desenvolvimento da gagueira ainda não é bem compreendida, mas contribuições genéticas para esta predisposição são reforçadas tanto por referências à agregação familial da gagueira, quanto à gagueira familial, que têm aparecido na literatura há mais de 70 anos. Assim, procuramos estabelecer uma revisão quanto aos prováveis fatores genéticos envolvidos com a manifestação da gagueira desenvolvimental persistente familial. A identificação de genes relacionados à gagueira, bem como de alterações em suas estruturas (por exemplo, mutações), contribuem significativamente para sua compreensão. O modelo exato de transmissão da herança genética para a gagueira ainda não está claramente definida e, provavelmente pode ser diferente entre diferentes famílias e populações. As análises genômicas demonstram, concomitantemente, a relevância dos componentes genéticos envolvidos e sua complexidade, sugerindo assim tratar-se de uma doença poligênica, na qual diversos genes de efeitos variados podem estar envolvidos com o aumento da susceptibilidade de ocorrência da gagueira. O clínico deverá estar alerta ao fato de que uma criança com histórico familial positivo para gagueira poderá ter uma forte tendência a desenvolver o distúrbio de forma crônica. É importante que o clínico esteja atento, de modo a fornecer às famílias orientações precisas sobre o distúrbio. As avaliações objetivas e os tratamentos controlados têm um papel muito importante para o domínio da evolução do distúrbio.

Behaviour of dispersion indices in pattern detection of a population of angico, Anadenanthera peregrina (Leguminosae)

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