RESUMEN
The performance of polymer nanocomposites reinforced with cellulose nanocrystals (CNCs) is complicated by several factors, primarily CNC-polymer and polymer-polymer interactions. Our current work specifically seeks to address the effects of CNC geometry, CNC-polymer and polymer-polymer interactions on the structure and non-linear mechanical performance of nanocomposites prepared using two water-soluble polymers, polyethylene oxide (PEO) and polyvinyl alcohol (PVA), having different morphological and structural characteristics. PEO and PVA are chosen since they are compatible with CNCs, however, they interact quite differently with CNCs and result in different reinforcement mechanisms. PEO and PVA interact with CNCs via a nucleating effect and H-bonding, which influence the polymer structure in two opposite directions. The nucleating effect tends to lead the polymer chains to form more ordered structures, whereas H-bonding interactions restrict the mobility of the polymer chains. Since PEO has weaker interactions amongst molecular chains than PVA, the properties of PEO are more significantly influenced by CNCs.
RESUMEN
Bis(mexylamino)triazines have been identified as a family of compounds showing an exceptional propensity to form glassy phases as opposed to crystals. The particularities of this family of compounds are their ability to self-assemble through hydrogen bonding in well-defined patterns to form supramolecular aggregates which pack poorly and the wide range of glass transition temperatures (T(g)) that can be attained through minor structural modifications. Representative bis(mexylamino)triazines were studied by rheology to establish correlations between their rheological properties and their molecular structure, and all compounds were found to behave in a similar fashion except for the temperature at which glass transition takes place. FTIR and NMR spectroscopy experiments were performed on the molecular glasses studied herein; comparisons between the viscosity, T(g), hydrogen bonding, and association constant (K(a)) in CDCl3 solution have revealed a relationship between the rheological properties, the T(g) of the molecular glasses, and the extent and strength of hydrogen bonding present in the material.
RESUMEN
Polarization modulation infrared linear dichroism (PM-IRLD) is often used for measurements of molecular orientation with high sensitivity and good time resolution. However, PM-IRLD is unable to provide the structural absorbance spectrum because it does not measure separately the parallel and perpendicular spectra. Here we propose a new method, named polarization modulation infrared structural absorbance spectroscopy (PM-IRSAS), to overcome this limitation of PM-IRLD. PM-IRSAS measures the dichroic difference and structural absorbance spectra simultaneously and, therefore, allows quantitative analysis of molecular orientation and conformation with 200 ms time resolution. The PM-IRSAS method was first validated through comparison with conventional polarized FT-IR spectroscopy using drawn polymer films. Second, it was demonstrated that the PM-IRSAS method can provide a quantitative analysis of dynamic orientation and conformation changes in PET films during deformation and crystallization processes.
