RESUMO Neste trabalho, membranas de polisulfona com adição de 3% em massa de argila montmorilonita natural, sódica e lítio, oriundas do estado da Paraíba, foram desenvolvidas pelo método de inversão de fases. Utilizou-se o N-metil-2 pirrolidona (NMP) como solvente na proporção de 80% e 20% de sólido. As argilas e membranas foram caracterizadas por difração de raios-X (DRX) e espectroscopia na região do infravermelho com transformada de Fourier (FTIR). Além disso, as membranas foram estudadas por microscopia eletrônica de varredura (MEV), porosidade e permeação a vapor d'água, a fim de se estudar seu comportamento para aplicação na separação de gás. Os DRX das argilas evidenciaram bandas de cristalinidade características de montmorilonita. Os difratogramas de DRX das membranas indicaram que possivelmente ocorreu a formação de uma estrutura intercalado/esfoliado devido à ausência das bandas referentes às argilas. Por FTIR das argilas foi visualizado as mesmas bandas características da montmorilonita, diferenciando pelos cátions que foram trocados na estrutura. O FTIR das membranas apresentaram bandas características da polisulfona, e para os híbridos estas bandas podem ser também das argilas por apresentarem as mesmas faixas de número de onda. As fotomicrografias de MEV evidenciaram a formação de uma camada densa na pele filtrante e na parte inferior foi observada uma estrutura de fingers que pode ter influenciado na permeação. O ensaio de porosidade indicou que a presença de argila na membrana reduziu a quantidade de poros e o ensaio de permeação a vapor d'água ilustrou que houve uma diminuição da permeação com a adição de argila em comparação com a membrana de polisulfona pura. A membrana aditivada de argila com lítio apresentou uma redução da permeação a vapor d'água em 53%, indicando melhores propriedades de barreira.

ABSTRACT In the present study, polysulfone membranes with addition of 3% by mass of natural montmorillonite clay, sodic and lithium, from the state of Paraiba, were developed by phase inversion method. The N-methyl-2-pyrrolidone (NMP) was used as a solvent in the proportion of 80% and 20% solid. The clays and membranes were also characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). In addition, the membranes were characterized by scanning electron microscope (SEM), porosity and vapor permeation of water in order to study their behavior in gas separation applications. The XRD of the clays showed peaks of crystallinity characteristic of montmorillonite. The XRD diffractograms of membranes showed that it has possibly occurred the formation of a structure intercalated/exfoliated due to the absence of peaks related clays. By FTIR of the clays were visualized the same bands characteristic of the montmorillonite, differentiating by the cations that were changed in the structure. The FTIR of the membranes presented bands characteristic of polysulfone, and for the hybrids these bands can also be of the clays because they present the same ranges of wave number. The SEM photomicrographs showed the formation of a dense layer on the filter skin and on the inferior surface was observed fingers structures that may have influenced the permeation. The porosity test indicated that the presence of clay in membranes reduced the amount of pores and the permeation test using water vapor showed that there was a decrease in the permeation by adding clay in comparison to pure polysulfone membrane. The membrane with additives of clay with lithium presented a 53% reduction of gas permeation, indicating better barrier properties.

Nanocomposites of polymer/clay have had much attention in recent years, particularly those developed with layered silicates due to the need of engineering materials more efficient than pure polymers for certain applications. The level of exfoliation of layered silicates in crystalline structure of polymer matrices has been studied and has been observed that it affects the crystalline behavior and the physical and mechanical properties. In this study, nanocomposites of polyamide 6 were obtained by the melt intercalation method, using a Brazilian bentonite modified with a quaternary ammonium salt. X-Ray Diffraction (XRD) results showed the incorporation of salt among the layers of clay, making it organophilic and that the nanocomposites presented exfoliated and/or partially exfoliated structures and confirmed by transmission electron microscopy (TEM). By thermogravimetry (TG), the results indicated that the presence of clay increased the thermal stability of polyamide 6. The impact properties of the nanocomposites showed inferior values in relation to the pure polyamide, in other words, decrease the toughness.

Recent interest in polymer/organoclays nanocomposites systems is motivated by the possibility of achieving enhanced properties and added functionality at lower clay loading as compared to conventional micron size fillers. By adding montmorillonite clay to polyamide 6 increases the Young modulus, yield strength and also improves barrier properties. In this work, nanocomposites of polyamide 6 with montmorillonite clay were obtained. The clay was chemically modified with three different quaternary ammonium salts such as: Dodigen, Genamin and Cetremide. In this case, a dispersion of Na-MMT was stirred and a salt equivalent to 1:1 of cation exchange capacity (CEC) of Na-MMT was added to the dispersion. The montmorillonite clay (untreated and treated by ammonium salts) and nanocomposites were characterized by X ray diffractions. Also the nanocomposites were characterized by transmission electron microscopy and mechanical properties. The results indicated that all the quaternary ammonium salts were intercalated between the layers of clay, leading to an expansion of the interlayer spacing. The obtained nanocomposites showed better mechanical properties when compared to polyamide 6. The clay acted as reinforcing filler, increasing the rigidity of nanocomposites and decreasing its ductility.