Preparação de poliuretana à base de óleo de mamona

Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction

Teoria cinética não extensiva: efeitos físicos em gases e plasmas

The standard kinetic theory for a nonrelativistic diluted gas is generalized in the spirit of the nonextensive statistic distribution introduced by Tsallis. The new formalism depends on an arbitrary q parameter measuring the degree of nonextensivity. In the limit q = 1, the extensive Maxwell-Boltzmann theory is recovered. Starting from a purely kinetic deduction of the velocity q-distribution function, the Boltzmann H-teorem is generalized for including the possibility of nonextensive out of equilibrium effects. Based on this investigation, it is proved that Tsallis' distribution is the necessary and sufficient condition defining a thermodynamic equilibrium state in the nonextensive context. This result follows naturally from the generalized transport equation and also from the extended H-theorem. Two physical applications of the nonextensive effects have been considered. Closed analytic expressions were obtained for the Doppler broadening of spectral lines from an excited gas, as well as, for the dispersion relations describing the eletrostatic oscillations in a diluted electronic plasma. In the later case, a comparison with the experimental results strongly suggests a Tsallis distribution with the q parameter smaller than unity. A complementary study is related to the thermodynamic behavior of a relativistic imperfect simple fluid. Using nonequilibrium thermodynamics, we show how the basic primary variables, namely: the energy momentum tensor, the particle and entropy fluxes depend on the several dissipative processes present in the fluid. The temperature variation law for this moving imperfect fluid is also obtained, and the Eckart and Landau-Lifshitz formulations are recovered as particular cases

Síntese análise das propriedades magnéticas da ferrita de NiMg e características de absorção de radiação

It was synthesized different Ni1-xMgxFe2O4 (0,2 ≤ x ≤ 0,7) compositions by use of citrate precursor method. Initially, the precursory citrates of iron, nickel and magnesium were mixed and homogenized. The stoichiometric compositions were calcined from 350°C to 1200°C at ambient atmosphere or in argon atmosphere. The calcined powders were characterized by XRD, TGA/DTG, FTIR, magnetic measures and reflectivity using the wave guide method. I was observed pure magnetic phase formation between 350°C and 500°C, with formation of ferrite and hematite after 600°C at ambient atmosphere. The calcined powder at argon atmosphere formed pure ferromagnetic phase at 1100°C and 1200°C. The Rietveld analyses calculated the cations level occupation and the crystallite size. The analyses obtained nanometric crystals (11-66 nm), that at 900°C/3h presents micrometric sizes (0,45 - 0,70 Om). The better magnetization results were 54 Am2/Kg for x= 0,2 composition, calcined at 350°C/3h and 30 min, and 55,6 Am2/Kg for x= 0,2 1200°C, calcined in argon. The hysteresis shows characteristics of soft magnetic material. Two magnetization processes were considered, superparamagnetism at low temperature and the magnetic domains formation at high temperatures. The materials presented absorption less or equal the 50 % in ranges specific frequency. As for the 2,0 and 3,0 thickness (in 11,0 - 11,8 GHz), the reflectivity of the x= 0,3, 0,5 and 0,4 compositions, all calcined at 900°C/3h showed agreement with MS and O. Various factors contribute for the final radiation absortion effect, such as, the particle size, the magnetization and the polymer characteristics in the MARE composition. The samples that presented better magnetization does not obtaining high radiation absorption. It is not clear the interrelaction between the magnetization and the radiation absorption in the strip of frequencies studied (8,2 - 12,4 GHz)

Aplicação da espectroscopia de absorção de raios X no estudo do comportamento do íon Cu2+ em micelas inversas

This work deals with the application of X-Ray Absorption Spectroscopy on the study of the behavior of Cu2+ ions in inverse micelles. The formation of copper nanoparticles in water-in-oil microemulsions in pseudo-ternary systems of cetyl trimethylammonium Bromide (CTAB) surfactant, butanol co-surfactant, heptane as oil phase and aqueous solutions of CuSO4.5H2O, and NaBH4. The microemulsions were prepared with a fixed percentage (60 %) of oil phase and a variable water to tensoative proportion. It was observed an increase on Cu2+ reduction by the sodium borohydride in microemulsions with 13 % of aqueous phase, independent of the reaction time. For the microemulsions in which the aqueous phase is composed only by the CuSO4 solution, it was observed that the color of the solution depends on the water to surfactant ratio. These changes in color were attributed to a competition for the hidratation water between the polar head of the tensoative and Cu2+ ions with the eventual substitution of oxygen by bromine atoms in the first coordination shell of Cu2+ ions

Influência espaço-temporal e fisiológica na absorção de nutrientes e elementos tóxicos por Eichhornia crassipes visando o uso adequado da sua biomassa: o caso do Rio Apodi/Mossoró - RN

This study aims to determine the amount of nutrients and toxic elements in aquatic macrophytes of species Eichhornia crassipes present in River Apodi/Mossoró - RN and check some of the possibilities of using the biomass produced, based on the influence of space - temporal and physiological absorption of nutrients by plants. For this, was determined: Leaf area, Leaf wet mass, Leaf dry mass, Real humidity, Apparent humidity, Ash, Total nitrogen, Crude protein, Calcium, Magnesium, Potassium, Total phosphorus, Sodium, Iron, Copper, Manganese, Zinc, Nickel, Cobalt, Aluminum, Cadmium, Lead and Total chromium at different times, 2 sampling points and 2 parts of plants (leaves and roots). The results show that the levels of nutrients, protein and toxic elements present in plant tissue of Eichhornia crassipes are influenced by spatial, temporal and physiological variability. In general, because the maximum values in the dry matter for total nitrogen (4.4088 g/100g), crude protein (27.5549 g/100g), total phosphorus (0.642 g/100 g), calcium (1.444 g/100g), magnesium (0.732 g/100 g), potassium (7.51 g/100 g), copper (4.4279 mg/100g), manganese (322.668 mg/100g), sodium (1.39 g/100g), iron (194.169 mg/100g) and zinc (3.5836 mg/100g), there was the possibility of using biomass of Eichhornia crassipes for various purposes such as in food animal, products production for human consumption, organic fertilizers, fabrication of brick low cost, and crafts. For all these applications requires a control of the levels of substances in plant tissue. Based on the levels of nutrients and crude protein, the younger plants (0 Month) would be best to have their biomass used. Moreover, one factor that contributes to the use of larger plants (6 Months), the levels of toxic elements which have significantly small or below the detection limit. Therefore, further studies quantifying the biomass produced/m2 at 0 and 6 months are needed for a more correct choice for the best time of harvest

Avaliação da influência da matéria orgânica, na determinação quantitativa de metais em amostras de sedimento, por espectrometria de absorção atômica e análise de metais traços por fluorescência de raios-X

The proposal of this work is to evaluate the influence of the organic matter on the results of the analyses of the metals (Zn, Pb, Al, Cu, Cr, Fe, Cd e Ni) for Atomic Absorption Spectrometry (AAS), so much in the extraction stage as in the reading using for that the chemometrics. They were used for this study sample of bottom sediment collected in river Jundiaí in the vicinity of the city of Macaíba-RN, commercial humus and water of the station of treatment of sewer of UFRN. Through the analyses accomplished by EAA it was verified that the interference of the organic matter happens in the extraction stage and not in the reading. With relationship to the technique of X Ray Fluorescence Spectrometry (XRFS), the present work has as intended to evaluate the viability of this technique for quantitative analysis of trace metals (Cr, Ni, Cu, Zn, Rb, Sr and Pb) in having leached obtained starting from the extraction with acqua regia for an aqueous solution. The used samples constitute the fine fraction (<0.063 mm) of sediments of swamp of the river Jundiaí. The preparation of tablets pressed starting from the dry residue of those leached it allowed your analysis in the solid form. This preliminary study shows that, in the case of the digestion chemistry partially of the fine fractions of bottom sediments used for environmental studies, the technique of applied EFRX to the analysis of dry residues starting from having leached with acqua regia, compared her it analyzes of the leached with ICP-OES, it presents relative mistakes for Cu, Pb, Sr and Zn below 10%

Estudo do equilíbrio e cinética de adsorção de um corante aniônico em quitosana

The phenomenon of adsorption is of fundamental importance for the treatment of textile effluents and removal of dyes. Chitosan is characterized as an excellent adsorbent material, not only for its adsorption capacity but also the low cost production. Equilibrium and kinetic studies were developed in this study to describe the mechanism of adsorption of the anionic azo dye Orange G in chitosan, with the isotherms obtained from the variation of the concentration of dye in the continuous phase. The kinetics of the process was analyzed based on models involving the adsorption of molecules of the dye in nonpolar and polar sites. Adsorption experiments were carried out in water and in saline media with different NaCl concentrations, both for the determination of the equilibrium time as isotherms for making kinetic curves in which the amount of dye adsorbed measured indirectly varied with time. The experiments revealed the opening of the biopolymer structure with increasing concentration of Orange G, accompanied by high pH values and change on the type of interaction between the dye and the adsorbent surface, suggesting behavior advocated by the Langmuir equation in a certain range of concentration of the adsorbate and following the Henry's Law at higher concentrations, from the increased number of sites available for adsorption. The studies conducted showed that the saline medium reduces the chitosan s adsorption capacity according to a certain concentration, the occurrence of the cooperative adsorption process steps kinetic mechanism suggested as a new alternative for the interpretation of the phenomenon

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

Caracterização estrutural de Perovskitas Lax-1AxCoO3 (x=0 e 0,2) ,dopadas com cálcio e bario, por espectroscopia de absorção de raios X (XAS).

In this work, the structures of LaCoO3, La0,8Ba0,2CoO3 and La0,8Ca0,2CoO3 perovskites were characterized as a function of temperature (LaCoO3 structure being analyzed only at room temperature). The characterization of these materials were made by X-Ray Absorption Spectroscopy (XAS), in the cobalt K-edge, taking into account the correlated Einstein model X-ray absorption fine structure (EXAFS). The first part of the absorption spectrum corresponded the X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). These materials were prepared by the combustion method. The combustion products were calcinated at 900 0C, for 6 hours in air. Noted that the sample LaCoO3 at room temperature and samples doped with Calcium and Barium in the temperature range of 50 K to 298 K showed greater distortion to monoclinic symmetry with space group I2/a. However, the sample doped with barium at the temperatures 50 K, 220 K, and 260 K showed a slight distortion to rhombohedral symmetry with space group R-3c. The La0,8Ca0, 2CoO3 structure was few sensitive to temperature variation, showing a higher local distortion in the octahedron and a higher local thermal disorder. These interpretations were in agreement with the information electronic structural on the XANES region and geometric in the EXAFS region

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Estratégias de Produção in vitro de Bioinseticida Viral: influências do Isolado, da Cinética e do Modo de operação

Societal concerns about environmental sustainability has lead to the development of ecologically-friendly alternatives to chemical insecticides for crop protection. One such alternative is biological pest control. In particular, baculoviruses are well suited as insect biopesticides due to their narrow host specificity and relative ease of propagation. In Brazil, the baculovirus Anticarsia gemmatalis nucleopolyhedrovirus (AgMNPV) is the main biological control agent employed for the soybean pest, Anticarsia gemmatalis. This baculovirus biopesticide is currently produced using caterpillars, but increasing market demand for the product has encouraged the development of an in vitro manufacturing process, which can be scaled up to much higher virus productivities. In this study, three wild-type AgMNPV isolates (AgMNPV-2D, AgMNPV-MP2 and AgMNPV-MP5) and a recombinant form (vAgEGT-LacZ) were characterised in terms of occlusion body (OB) production and infection kinetics, to enable future optimisation of the in vitro production process. These viruses were propagated using a Spodoptera frugiperda (IPLB-SF21) insect cell line grown in shaker-flask batch cultures. Among the virus isolates tested, AgMNPV-MP5 was found to be the best producer, yielding (5.3±0.85)x108 OB/mL after 8 days post infection. The characterisation of vAgEGT-LacZ propagation in suspension cell cultures has not been previously reported in the literature; hence it became the main focus for this thesis. In particular, it was carried out a study on the effect of the multiplicity of infection (MOI) on OB production. Five successive batches were performed getting a final production (8.9±1.42)x1014 occlusion bodies, considering that production is related for a bioreactor with final volume of 10m3. A low MOI associated with a fed-batch process for vAgEGT-LacZ production was found to support a 3-fold higher OB yield when compared to the default batch process (1.8x107 and 5.3x107 OB/mL, respectively). This yield is competitive with regards to the production process.

Fundamentação cinética da estatística não gaussiana : efeitos em politrópicas

Considering a non-relativistic ideal gas, the standard foundations of kinetic theory are investigated in the context of non-gaussian statistical mechanics introduced by Kaniadakis. The new formalism is based on the generalization of the Boltzmann H-theorem and the deduction of Maxwells statistical distribution. The calculated power law distribution is parameterized through a parameter measuring the degree of non-gaussianity. In the limit = 0, the theory of gaussian Maxwell-Boltzmann distribution is recovered. Two physical applications of the non-gaussian effects have been considered. The first one, the -Doppler broadening of spectral lines from an excited gas is obtained from analytical expressions. The second one, a mathematical relationship between the entropic index and the stellar polytropic index is shown by using the thermodynamic formulation for self-gravitational systems

Influência da absorção de umidade no comportamento mecânico nos compósitos poliméricos híbridos Kevlar/vidro quando imerso em água do mar e petróleo

The polymer matrix composite materials are being used on a large scale in the most different industrial fields such as aerospace, automotive, oil, among others, since the industrial perspectives is currently working with materials which have a good mechanical performance at high service life and cost / benefit. Thus, the determination of the mechanical properties is indispensable for the characterization of waste resulting in greater expansion of this type of material. Thus, this work will be obtained three plates laminated with tereftálica polymeric matrix reinforced by a bidirectional woven E-glass and kevlar both industrially made, where the plates are manufactured by manual lamination process (hand lay-up), all laminates have five enhancement layers, the first hybrid laminate will consist of bidirectional woven E-glass fiber, kevlar fiber interspersed with layers, is formed by the second bidirectional woven kevlar fiber at the ends of the laminate (two layers), and in the center the glass fiber fabric (three layers), the third plate is composed of only the bidirectional woven E-glass fiber. Then were prepared specimens (CP) by standard, to determine the mechanical properties of tensile and bending in three points. After fabrication of the specimens, they were immersed in oil and seawater. After that, there was a comparison of the mechanical properties for the test condition in the dry state. Showing that there was a considerable increase in the properties studied because the effect of hybridization in laminates.

Desempenho de uma lagoa de infiltração na absorção de cheias e na recarga de aquífero

A type of macro drainage solution widely used in urban areas with predomi-nance of closed catchments (basins without outlet) is the implementation of detention and infiltration reservoirs (DIR). This type of solution has the main function of storing surface runoff and to promote soil infiltration and, consequently, aquifer recharge. The practice is to avoid floods in the drainage basin low-lying areas. The catchment waterproofing reduces the distributed groundwater recharge in urban areas, as is the case of Natal city, RN. However, the advantage of DIR is to concentrate the runoff and to promote aquifer recharge to an amount that can surpass the distributed natu-ral recharge. In this paper, we proposed studying a small urban drainage catchment, named Experimental Mirassol Watershed (EMW) in Natal, RN, whose outlet is a DIR. The rainfall-runoff transformation processes, water accumulation in DIR and the pro-cess of infiltration and percolation in the soil profile until the free aquifer were mod-eled and, from rainfall event observations, water levels in DIR and free aquifer water level measurements, and also, parameter values determination, it is was enabled to calibrate and modeling these combined processes. The mathematical modeling was carried out from two numerical models. We used the rainfall-runoff model developed by RIGHETTO (2014), and besides, we developed a one-dimensional model to simu-late the soil infiltration, percolation, redistribution soil water and groundwater in a combined system to the reservoir water balance. Continuous simulation was run over a period of eighteen months in time intervals of one minute. The drainage basin was discretized in blocks units as well as street reaches and the soil profile in vertical cells of 2 cm deep to a total depth of 30 m. The generated hydrographs were transformed into inlet volumes to the DIR and then, it was carried out water balance in these time intervals, considering infiltration and percolation of water in the soil profile. As a re-sult, we get to evaluate the storage water process in DIR as well as the infiltration of water, redistribution into the soil and the groundwater aquifer recharge, in continuous temporal simulation. We found that the DIR has good performance to storage excess water drainage and to contribute to the local aquifer recharge process (Aquifer Dunas / Barreiras).