PLA nanocomposites were prepared by adding organically modified montmorillonite clay (Viscogel B8) and a homoionic clay (NT25), as well as unmodified silica (A200) and modified organic silica (R972). All nanocomposites were obtained by the solution intercalation method using chloroform as a solvent. The materials obtained were essentially characterized by X-ray diffraction and low-field nuclear magnetic resonance relaxometry, through the measurement of proton spin-lattice relaxation time (LF-NMR). Both clays and silicas used to obtain the polymeric nanocomposites showed good dispersion in the polymeric matrix. The relaxation times were distinct for each type of nanoparticle used. The nanocomposite formed with homoionic clay, NT25, presented an increase in the relaxation data, indicating formation of intercalated nanocomposites, contrary to the action of the organoclay Viscogel B8, which preferentially formed an exfoliated nanocomposite. When unmodified and organo-modified silica were added to PLA, an increase in the relaxation time of the polymer matrix was observed. According to the relaxation data, the organosilica R972 dispersed better in the polymeric matrix and consequently interacted better than the A200.

a b s t r a c tStarch and PLA were used alone and in blends to prepare nanostructured materials using both hydrophilic and organophilic clays, and PVA. All nanostructured materials were obtained by the solution intercalation method using water and chloroform as solvents. These systems were characterized by using conventional X-ray diffraction (XRD), conventional NMR and the non-conventional fast field cycling (FFC) NMR technique. The spin-lattice relaxation times were measured as a function of the Larmor frequency. The FFC results showed that the starch has only one relaxation time related to the amorphous region. PLA hybrids presented two distinct spin-lattice relaxation times. The blends of the two polymers also showed two relaxation times. The renormalized Rouse formalism was applied to describe the polymer molecular dynamics behavior in the studied systems containing starch. By adding clay or PVA, differences could be observed in relaxation time corresponding to the more amorphous region, indicating that, when adding clay and PVA, the effect that each has on the dynamics of the mixture is cancelled out.

Blends formed by starch and poly(lactic acid) (PLA) are very promising from environmental and economic standpoints, because starch is an abundant and cheap natural polymer and PLA is a biodegradable polymer that has good mechanical properties. In this study, starch-PLA blends were prepared by solution casting, employing chloroform and distilled water as a solvent pair. Then, dispersions containing 1, 3 and 5% montmorillonite clay and a dispersion containing 0.1% silica were added to the starch-PLA blends. The new materials obtained were characterized by X-ray diffraction, thermal analysis and, especially, nuclear low-field nuclear magnetic resonance (LF-NMR) relaxometry to measure the proton spin-lattice relaxation. All blends composed of starch and PLA showed significant increase in relaxation time due to the homogenous mixing of both polymers as a consequence of strong intermolecular interaction between them. Addition of clays caused substantial modification of the material and a large unique domain was observed. As a consequence, the domains corresponding to pure polymers were not observed. With the addition of the clay NT25, intermediate degradation temperatures were observed at concentrations of 3 and 5%, compared to the degradation temperatures of pure polymers. The X-ray diffraction results indicated the formation of an intercalated nanocomposite. There was an increase in the organization of the material compared to previous results observed for polymeric material, indicating the formation of an intercalated structure.

Resumo: Nanocompósitos de amido de batata foram preparados pelo método de intercalação por solução, com a adição de argilas montmorilonita: organicamente modificada (Viscogel B8) e não modificada argila sódica (NT25) e de sílicas: modificada (R972) e não modificada (A200). Os nanocompósitos foram caracterizados pelas técnicas convencionais de difratometria de raios X e análise termogravimétrica. Foram caracterizados também por uma técnica denominada como não convencional, a ressonância magnética nuclear (RMN) de baixo campo, que é alternativa e efetiva na caracterização de nanocompósitos. Com ela, pode-se investigar a dispersão das nanocargas pelo grau de intercalação e/ou esfoliação, além de verificar a distribuição e modificações da mobilidade molecular da matriz polimérica. Os materiais nanoestruturados obtidos com as argilas apresentaram boa dispersão e formação de nanomateriais mistos, com diferentes graus de intercalação e esfoliação. Ao adicionar as sílicas na matriz de amido pode-se observar uma diminuição da mobilidade do material, este efeito foi observado para ambas às sílicas utilizadas. Utilizando a técnica de TGA verificou-se um ligeiro aumento na estabilidade térmica do material produzido em relação ao amido. Palavras-chave: Amido, nanocompósitos, RMN de baixo campo. Development of Nanocomposites Based on Potato StarchAbstract: Nanocomposites of potato starch were prepared by the solution intercalation method with the addition of organically modified montmorillonite clay (Viscogel B and unmodified sodic clay (NT25) as well as modified and unmodified silica (R972 and A200, respectively), using water as the solvent. The nanocomposites were characterized by conventional techniques of X-ray diffraction and thermogravimetric analysis. They were also characterized using the non-conventional low-field nuclear magnetic resonance, which is an effective alternative technique for characterizing nanocompósitos. This technique allows one to investigate dispersion of nanofillers by the degree of intercalation and/ or exfoliation, in addition to determine the distribution of nanoparticles in the polymer matrix and modifications of the molecular mobility of these fillers. The nanostructured materials obtained with the clays presented good dispersion and formation of mixed nanomaterials, with different degrees of intercalation and exfoliation. The mobility of the material decreased upon adding silica in the starch matrix, which applied to both types of silica. From the TGA technique, a slight increase in thermal stability of the nanocomposite was noted in relation to the starch matrix. Keywords: Starch, nanocomposites, low-field NMR. IntroduçãoProdutos plásticos preparados a partir de polímeros sintéticos são amplamente utilizados em diversas áreas. Estes materiais não são facilmente degradáveis e causam sérios problemas ambientais. Nos últimos anos, os bioplásticos tiveram um grande interesse devido ao aumento da consciência em relação ao desenvolvimento sustentável [1][2][3][4][5] . O amido, um dos polímeros nat...