Estudo da formação de micelas reversas do copolímero tribloco (EO13PO30EO13) em p-xileno: efeito da adição de solução salina

• Autor(a) principal: Rocha, Júlio Cézar Barbosa
• Data de Publicação: 2012
• Tipo de documento: Dissertação
• Idioma: por
• Título da fonte: LOCUS Repositório Institucional da UFV
• Texto Completo: http://locus.ufv.br/handle/123456789/4254
• topic: Micelas reversas; Coloides; Copolímeros; Reverse micelles; Colloids; Copolymer; CNPQ::CIENCIAS EXATAS E DA TERRA::FISICA::FISICA DA MATERIA CONDENSADA

Triblock copolymer (EO13PO30EO13) in p-xylene and small amounts of water forms various self-organized structures, one of which are the reverse micelles. Reverse micelles are a type of self-organized system that forms in solutions and interfaces. Reverse micelles can be used in the extraction of amino acids or as nanoreactors for the synthesis of nanoparticles. In this work, reverse micelles were produced by (EO13PO30EO13) the triblock copolymer in p-xylene at concentration of 15% w/w in the presence of water or 0.1 M aqueous solutions of cadmium chloride, sodium nitroprusside, sodium sulfide, sodium hydroxide, lithium sulfate and tetra methyl ammonium chloride. We evaluated the scattered intensity and hydrodynamic diameter in different amounts of water or salts by the techniques of static and dynamic light scattering, respectively. There was an increase in the hydrodynamic diameter in the presence of all salts in comparison with that of water. The scattered intensity also increased for all salts, except for the micelles with tetra methyl ammonium chloride. We measured the variation of the refractive index of solution of 15% w/w (EO13PO30EO13) in p-xylene with different amounts of water or aqueous solutions and compared to with solution of 15% w/w (EO13PO30EO13) without amounts of water or aqueous solutions. The variation of refractive index indicated the point of formation of reverse micelles for some salts, which was not possible to determine using light scattering, and the transition point in the form of reverse micelles from spherical to ellipsoidal. In addition to the scattering experiments, microcalorimetric measurements of the reverse micelles systems were carried out using the Isothermal Titration Calorimetry technique. The results showed that the enthalpy of mixing has changed from exothermic (micelles with water) to endothermic (micelles with salt) for very low water content. In addition, reverse micelles with tetra methyl ammonium chloride and sodium hydroxide showed enthalpy of mixing much smaller in magnitude than the reverse micelles with other salts or water. For the low aqueous solution content inside the reverse micelles the endothermic enthalpy of mixing indicates that the process of desolvation of salts by molecules of water and the interaction of salts and water with the EO segments happens with cost of energy. Nuclear magnetic resonance spectra of hydrogen of the molecules of water showed the formation of free water and bound water inside the reverse micelles. The chemical shift curves increased slightly in the presence of all salts. The relaxation spin-spin of hydrogens of groups CH3 decrease with the increase of water or aqueous solution content. This was interpreted as the passage of molecules of (EO13PO30EO13) from the form of free chain to the form of reverse micelles. The value of relaxation of groups CH2 did not show significant change with the increase of water or aqueous solution content. Measurements of the relaxation of the water molecules inside the reverse micelles were made and it was determined the relaxation constant T2 of the molecule of water in the macroscopic water phase and inside the reverse micelles. The value of T2 decreases from 3.2 seconds in the macroscopic phase to a few microseconds in the inside of reverse micelles. The presence of salt in the inside of reverse micelles induced a more significant decrease in the value of T2 of molecules of water than when there was only water inside the reverse micelles.