RESUMO Embora diferentes segmentos do mercado de filmes poliméricos possuam diferentes exigências de desempenho, as propriedades dos filmes dependem da arquitetura molecular, microestrutura, orientação molecular e cristalinidade, desenvolvidas em função do tipo de maquinário utilizado e das condições do processamento. Portanto, o conhecimento das microestruturas desenvolvidas é de grande interesse científico e tecnológico. Neste trabalho foi estudada a correlação entre orientação molecular, cristalinidade e propriedades de permeabilidade, ao vapor de água e ao oxigênio, de filmes biaxialmente orientados de polietileno linear de baixa densidade (PELBD), obtidos pelo processo de extrusão plana e estirados com diferentes razões de estiramento. O estudo da orientação molecular revelou a mudança da estrutura morfológica das cadeias da fração cristalina dos filmes submetidos a maiores graus de estiramento. Resultados do grau de cristalinidade dos filmes de PELBD evidenciaram uma tendência de aumento da cristalinidade com o aumento da orientação das cadeias poliméricas, devido ao estiramento. Resultados de propriedades de barreira mostraram que o aumento do grau de estiramento possui efeito moderado na diminuição da permeabilidade ao oxigênio e ao vapor de água dos filmes PELBD, e que esse comportamento está relacionado ao grau de estiramento e cristalinidade dos filmes.

ABSTRACT Although different polymeric film market segments have different performance requirements, the properties of the films depend upon the molecular architecture, microstructure, molecular orientation and crystallinity, developed according to the chosen processing tools and conditions. Therefore, knowledge of developed microstructure is of great scientific and technological interest. In this study, it was studied the correlation between molecular orientation, crystallinity and water vapor and oxygen permeability properties of biaxially oriented linear low-density polyethylene (LLDPE) films obtained by planar extrusion and stretched by different stretch rations. The molecular orientation study revealed morphological structure changing of chains in the crystalline fraction of the films submitted to higher degrees of stretching. Results of degree of crystallinity of LLDPE films evidenced a tendency to increase crystallinity with increasing orientation of the polymer chains, due to stretching. Results of barrier properties showed the increase of the degree of stretching has a moderate effect on the decrease of permeability to oxygen and water vapor of the LLDPE films, and that this behavior is related to the degree of stretching and crystallinity of the films.

RESUMO Neste estudo, a estabilidade térmica e as propriedades mecânicas da poliamida 6,6 (PA) e de seus nanocompósitos com nanofibras de celulose (NFC) foram investigadas. Objetivando a dispersão uniforme da NFC na PA e o processamento a altas temperaturas, os materiais foram inicialmente pré-misturados em solução e posteriormente processados por extrusão e moldagem por injeção. Os resultados obtidos por análise termogravimétrica confirmaram a maior estabilidade térmica das amostras sem NFC em relação as amostras com NFC. A pré-mistura e o processamento influenciaram na estabilidade térmica das amostras. Os resultados obtidos por ensaio de tração revelaram que a adição de 1% de NFC levou a um aumento médio de 16% no módulo elástico em relação a PA pura. A pré-mistura e a incorporação das NFC´s não prejudicaram o módulo elástico e a resistência máxima à tração, podendo indicar uma alternativa de uso para poliamida 6,6, dependendo da aplicação final do material.

ABSTRACT In this study, the thermal stability and mechanical properties of polyamide 6.6 (PA) and their nanocomposites with cellulose nanofibers (CNF) were investigated. In order to have uniform dispersion of CNF in the PA and the processing at high temperatures, the materials were initially premixed and further processed by extrusion and injection molding. The results obtained by thermogravimetric analysis confirmed the lower thermal stability of the samples without CNF in comparison to the samples with CNF. The premix and the processing influence on the thermal stability of the samples. The results obtained by tensile test showed the addition of 1% CNF leads to an average increase of 16% in the elastic modulus in comparison to the neat PA. The premix and the incorporation of CNF did not impair the elastic modulus and maximum tensile strength, and may indicate an alternative use for PA, depending on the final application of the material.

Nanocomposites of an organic-modified montmorillonite (MMT) and polyamide 6 (PA6) with a residual monomer were produced by melt mixing in a torque rheometer. By wide angle X-rays diffraction (WAXD), intercalated/exfoliated structures were observed in the PA6/MMT nanocomposites with 3 and 5 wt. (%) of MMT; on the other hand, when 7 wt. (%) of MMT was added, a nanocomposite with exfoliated structures was obtained due to the predominant linking reactions between the residual monomer and the "nanoclays" organic surfactant. Solutions of these PA6/MMT nanocomposites at 15, 17 and 20 wt. (%) in formic acid were prepared. The 3 and 5 wt. (%) nanocomposites were successfully electrospun; however, electrospinning of the 7 wt. (%) nanocomposite was not possible. WAXD, scanning and transmission electron microscopy results showed that the 3 and 5 wt. (%) nanofibers with average diameter between 80-250 nm had exfoliated structures. These results indicate that the high elongational forces developed during the electrospinning process changed the initial intercalated/exfoliated structure of the nanocomposites to an exfoliated one.

Polyamide 66 (PA66) nanofibers of different molecular weights were obtained by electrospinning of formic acid solutions. An ionic salt, NaCl, was also added to the solutions to increase the conductivity. PA66 concentrations between 15-17 wt.(%)/v and electrical fields between 2.0 and 2.5 kV/cm were the best conditions to produce the smallest nanofibers; however, the addition of NaCl increased the fibers average diameters.The characterization of the fibers was done by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), wide angle X rays diffraction (WAXD) and Fourier Transformed Infrared (FTIR). As the molecular weight decreased, the nanofibers average diameters also decreased; however, critical number average and weight average molecular weights were necessary for electrospinning. As the amounts of carboxyl terminal groups (CTG) increased, the nanofibers average diameters decreased; however, above CTG's critical values of 8.7 x 10-5 mol.g-1 no electrospinning was possible. The addition of ionic salt increased the electrical conductivity of the solutions and increased the nanofibers' average diameters. By DSC, residual solvent in all the electrospun mats was found; two melting endotherms, one between 248 and 258 °C and the other one between 258 and 267 °C, depending on the sample were also observed. These endotherms were attributed to the melting, re-crystallization and re-melting of the PA66 α-phase. The nanofibers had low % of crystallinity compared to a textile fiber. By WAXS and FTIR, confirmation of the presence of α-phase crystals, of small dimensions and highly imperfect and of a very small amount of β and γ-phases crystals in the nanofibers structure was obtained.

The development of α and β-phases and the molecular orientation of injection molded disks of two isotactic polypropylene (i-PP) resins were studied by wide angle X-ray diffraction (WAXD) and pole figures. A nucleated (NPP) and non-nucleated (HPP) polymers were analyzed. The main proposal of this article was the comprehensive study of the interrelations between the processing conditions, phase contents and PP α-phase molecular orientation of injection molded PP resins. In both resins, it was observed that the α-phase was present in all regions along the thickness while the β-phase was present mainly in the external layers, decreasing from the surface to the core; however this last phase was present in a very small amount in the NPP resin. For both polymers, the orientation of the macromolecules c-axis was higher along the flow direction (RD) than along the transverse direction (TD). The b-axis of the PP α-phase molecules was oriented to the thickness direction (ND). The orientation of the c-axis along RD and b-axis along ND of the NPP samples was considerably higher than of the HPP samples, due to the NPP faster crystallization kinetics. For both polymers, the most influential processing parameters on the molecular orientation were the mold temperature and flow rate. The results indicate that, as the mold temperature increased, the characteristic molecular orientation of PP α-phase, with c-axis along RD and b-axis along ND, decreased. With increase in the flow rate an increase of the c-axis molecular orientation of the samples along RD was observed.