Influência da densidade de carga e da massa molar da poliacrilamida na reologia de sistemas microemulsionados

The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60ºC in variations of 5ºC. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer

Aspectos da produtividade do feijão correlacionados com atributos físicos do solo sob elevado nível tecnológico de manejo

No ano agrícola de 2006/07, no município de Selvíria (MS), foi analisada a produtividade do feijão em função de alguns atributos físicos de um Latossolo Vermelho distroférrico, cultivado nas condições de elevado nível tecnológico de manejo pelo sistema plantio direto irrigado com pivô central. O objetivo foi selecionar, entre os atributos pesquisados do solo, aquele com a melhor representatividade para explicar a variabilidade da produtividade agrícola. Foi instalada a malha geoestatística, para a coleta de dados do solo e da planta, com 117 pontos amostrais, numa área de 2.025 m² e declive homogêneo de 0,055 m m-1. do ponto de vista linear e espacial, a produtividade de feijão foi explicada em função da densidade de partículas e da umidade gravimétrica do solo, respectivamente. Assim, os valores de densidade de partículas entre 1,95 e 2,20 kg dm-3 e de umidade gravimétrica entre 0,205 e 0,239 kg kg-1; ambas coletadas na camada intermediária, resultaram em sítios com as mais elevadas produtividades (2.200-2.600 kg ha-1). Entretanto, para as condições do elevado nível tecnológico de manejo empregado, a produtividade média do feijão não atingiu seu máximo potencial, uma vez que o agravado estado de compactação no qual o solo se encontrava proporcionou à produtividade redução de 26,6 %. Dessa forma, os valores médios da densidade do solo e da resistência do solo à penetração, respectivamente nas faixas de 1,36-1,41 kg dm-3 e de 1,56-3,24 MPa, típicos de solos argilosos compactados, atestaram a substancial queda da produtividade de grãos de feijão.

Densidade do solo e infiltração de água como indicadores da qualidade física de um Latossolo Vermelho distrófico em recuperação

A necessidade cada vez maior de alimentos, espaço e condições para sobrevivência faz com que as interferências antrópicas no ambiente sejam cada vez maiores. Solos intensivamente cultivados e de forma inadequada são degradados, assim como a construção de obras civis no meio rural sem atender à legislação pertinente tudo isso tem ocasionado problemas ao meio. Várias técnicas têm sido utilizadas para recuperar esses solos, sendo a principal delas a adição de MO. Contudo, informações sobre tempo para recuperação do solo, influência dos tipos de material orgânico e indicadores das alterações ainda são escassas. Este trabalho objetivou avaliar a recuperação das propriedades de um Latossolo Vermelho distrófico, de onde foi retirado material usado na terraplanagem e nas fundações da usina hidrelétrica de Ilha Solteira-SP, utilizando-se como indicadores de qualidade física a densidade do solo e a taxa de infiltração de água. A pesquisa foi feita em uma área onde se retirou uma camada de solo de 8,60 m. O delineamento experimental foi em blocos casualizados, com cinco repetições e cinco tratamentos: testemunha (solo exposto sem técnicas de recuperação); espécie arbórea gonçalo-alves (Astronium fraxinifolium Schott); gonçalo-alves + feijão-de-porco (Canavalia ensiformis); gonçalo-alves + nabo forrageiro (Raphanus sativus); e gonçalo-alves + gramínea (Brachiaria decumbens) + lodo de esgoto (60 Mg ha-1). A densidade do solo foi avaliada antes e 356 dias após a implantação dos tratamentos, e a infiltração de água no solo foi determinada 188 dias depois da instalação dos tratamentos. Concluiu-se que ocorrem melhorias na qualidade do solo quando efetuado o seu preparo e a adição de lodo de esgoto e adubos verdes. A densidade do solo e a infiltração de água do solo são bons indicadores na avaliação dessas melhorias. As diferentes fontes de MO adicionadas ao solo e a ação do preparo deste interagem de maneira semelhante na recuperação da sua qualidade, porém a combinação lodo de esgoto mais braquiária proporciona maior altura de planta da espécie gonçalo-alves.

Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

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

Produtividade do milho safrinha e modificações químicas de um latossolo em sistema plantio direto em função de espécies de cobertura após calagem superficial

Modern agriculture is undergoing profound changes, with demands for more efficient management practices in the production systems used in each area. The objectives of this study were: to evaluate the effect of different covering species on a no-tillage system; to find the results of lime application on soil surface after sowing those forage species; measure the effects on soil chemical properties and subsequent effect on corn yield; and to determine the dry matter produced by each species used. The experiment was conducted on November, 2002, in the town of Palotina, Parana State, Brazil. A randomized block design was used, with 4 repetitions, in a 2x6 factorial scheme -two depths of soil sampling (0-10 and 10-20 cm) and six types of forage covering on the soil (Mucuna deeringiana, Crotalaria juncea, Setaria incana, Pennisetum glancum and Eleusine gracilis, as well as a mix of all these species). 3 t ha(-1) of dolomitic limestone were applied in total surface area, without amending. The covering species associated with the surface limestone application showed improvement in soil fertility, mainly in the layer of 10-20 cm, with prominence to Elensine gracilis, Crotalaria juncea and Setaria incana. Eleusine gracilis and Crotalaria juncea featured the largest dry matter production; however, the great amount of straw of Eleusine gracilis damaged the productivity of corn. Grain and corn straw productivity was higher when previously cultivated along with Setaria incana and the mix of forage species covering.

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 das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers

Desempenho auditivo ao longo do tempo e satisfação dos usuários de implante coclear com perda auditiva pós-lingual

Most cochlear implant (CI) users, who suffer from post lingual hearing loss, are able to perceive sounds and comprehend speech after the implant. The prediction of maximal benefit over time, with the use of CI, can be useful for counseling patients about their expectations in using the new device. The measurement of satisfaction should be of primary interest in medical intervention, as the results may be used for intervention feedback. The purpose of this study is to analyze auditory performance of CI over time, as well as to evaluate users‟ satisfaction. Therefore two types of study designs were employed: a) retrospective cohort study with the analysis of medical records from 59 subjects about auditory performance before and after surgery. Results were submitted to the Kaplan -Meier estimator of cumulative probability and compared to prognostic factors of auditory performance using the logrank test. b) A sectional study design was conducted to evaluate the satisfaction of 51 subjects. The instrument consists of two specific questionnaires: Satisfaction with Amplification in Daily Life SADL and International Outcome Inventory Cochlear Implant IOI- CI. Results show statistical significant differences (p<0,001) in auditory performance before and after CI. The majority obtained satisfactory results of CI use during the first six months. Logrank tests does not indicate significant correlation between the analyzed covariates and the time in which adequate speech perception occurs. SADL e IOI-CI questionnaires indicate that most of the CI users are satisfied with their devices. The SADL detected a 27, 5% insatisfaction amongst CI users in relation to services and costs involved with the CI. The results of the IOI show 4% of insatisfaction with the use of CI and the social environment. In conclusion CI is capable to rehabilitate social auditory function in a short period of time and CI users demonstrate satisfaction with auditory, social and psychological gain offered through CI device

Qualidade e produtividade da cana planta e cana soca em função de doses e fontes de manganês

The crop of the sugarcane is stood out in the Brazilian agricultural scenery, due to the great demand of sugar, alcohol and by-products. The present work had as objective to evaluate the effect of five doses and three sources of manganese applied at planting furrow in sugarcane, in two cuts, in the Northwest area of São Paulo State, Brazil. The experiment was conducted at Fujimoto farm with coordinates 20 degrees 32 'S and 50 degrees 58' O, and altitude of 361 meters, area administered by Distillery Vale do Parana S/A Alcool and Acucar, in Suzanapolis county - São Paulo state. A randomizef blocks design in a factorial scheme 5x3, being 5 doses of manganese (0; 2.5; 5.0; 7.5 and 10.0 kg ha(-1)), and 3 sources (Quelate, FTE and manganese sulfate), applied at planting furrow, in 4 repetitions was used. The plots were constituted by 4 lines of 5 m length, spaced by 1.5 m. The RB 86-7515 variety was used. The sources of manganese did not influence in the technological quality and productivity of stems in none of the cuts of sugarcane. The application of doses of manganese resulted in increase on values of recoverable total sugar per ha and ton of pol per ha in plant cane, not influencing in the other variables analyzed on plant cane and ratoon cane.

Produtividade e qualidade de sementes de soja em função de estádios de dessecação e herbicidas

O objetivo deste trabalho foi avaliar a melhor época de aplicação de dessecantes, de forma a permitir antecipação da colheita sem prejudicar a produtividade e qualidade de sementes de soja. O delineamento experimental foi de blocos ao acaso em esquema fatorial (3x3) + 1, com quatro repetições. Um dos fatores foi constituído pelos herbicidas dessecantes paraquat, glufosinato de amônio e glyphosate, nas doses de 400, 400 e 960 g i.a. ha-1, respectivamente. Outro fator constituiu-se de três estádios de aplicação dos herbicidas, via pulverização (R6, R7.2 e R8.1). Avaliaram-se a antecipação da colheita, massa de 100 sementes, produtividade, germinação e vigor das sementes. A utilização de herbicidas, aliada aos estádios fenológicos de aplicação, permitiu antecipar a colheita de um a seis dias. A dessecação de plantas de soja em pré-colheita com os herbicidas nos diferentes estádios fenológicos não afetou a produtividade. O herbicida glufosinato de amônio reduziu a germinação de sementes de soja quando aplicado no estádio R6. O herbicida glyphosate reduziu o vigor das sementes de soja quando aplicado nos estádios R6 e R7.2. O herbicida paraquat promoveu os melhores índices de germinação e vigor de sementes de soja quando utilizado nos estádios R6 e R7.2.

Produtividade e qualidade industrial do arroz de terras altas em função da disponibilidade hídrica e adubação

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

Análise econômica da produção de feijão em função de doses de nitrogênio e coberturas vegetais

O nitrogênio é o nutriente aplicado em maior quantidade à cultura do feijão, o mais limitante ao crescimento e desenvolvimento das plantas e o que mais onera o custo de produção. Uma boa opção para o produtor diminuir custos, com a utilização de fertilizantes nitrogenados, é a utilização de plantas de cobertura do solo, também conhecidas como adubos verdes. Assim, este trabalho objetivou avaliar os custos de produção e índices de lucratividade de diferentes tratamentos envolvendo coberturas vegetais e doses de nitrogênio em cobertura, na cultura do feijoeiro irrigado, em sistema plantio direto, nas safras de inverno de 2010 e 2011. O trabalho foi realizado em área experimental localizada no município de Selvíria (MS), em Latossolo Vermelho distrófico típico. Os tratamentos constituíram-se de seis coberturas vegetais (Crotalaria juncea, milheto, guandú, Crotalaria juncea + milheto, guandú + milheto e pousio) e quatro doses de N (0 kg ha-1, 30 kg ha-1, 60 kg ha-1 e 90 kg ha-1). Foram estimados o custo operacional total, receita bruta, lucro operacional, índice de lucratividade, produtividade de equilíbrio e o preço de equilíbrio. Concluiu-se que o uso da Crotalaria juncea, como cobertura vegetal do solo, proporcionou os maiores valores de custo operacional total e lucro operacional e os melhores índices de lucratividade, e que o incremento nas doses de nitrogênio aumentou o custo operacional total, com tendência de aumento na produtividade e, consequentemente, no preço de equilíbrio.

Desempenho agronômico de híbridos de milho, em função da aplicação foliar de fungicidas

The objective of the study was to evaluate the agronomic performance of corn hybrids (AG 8088, BG 7049, CD 327, CD 384, CD 351 and CD 321) at function of the foliar application of two fungicides (piraclostrobina + epoxiconazol and azoxistrobina + ciproconazol) at pre-tasseling of the culture. The experiment was conducted In Selviria - MS, in the experimental Farm of the Faculty of Engineering of Ilha Solteira - SP (UNESP), Brazil, during the harvest of 2008/09. The treatments were disposed in randomized complete block design in a factorial scheme 6 x 3 (corn hybrids x fungicides), with four replications. There was valued plant height and of insertion of the ear, number of rows of grains by ear and of grains by row, incidence of foliar diseases, weight of hundred grains and productivity. The results were submitted to the analysis of variance, and the hybrids and fungicides compared by Tukey test (P<0.05). For data analysis were used the software SISVAR. The foliar application of the fungicides piraclostrobina + epoxiconazol and azoxistrobina + ciproconazol in pre-tasseling of the culture the corn reduced the incidence of foliar diseases, nevertheless, was not sufficient to provoke growth of productivity. The hybrids CD 321, AG 8088 and CD 351 were highlighted by the higher yield obtained.

Qualidade fisiológica de sementes e crescimento de plântulas de feijoeiro, em função de aplicações de paraquat em pré-colheita

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