ABSTRACT:The present work analyzed the possibility of obtaining and producing syndiotactic polystyrene (sPS)-based nanocomposites. The work first focused on possible technology to use for intercalation from solution and melt intercalation. Using a blend of sPS with atactic polystyrene (aPS) as the matrix was also considered. Thermal analysis techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), were used to study the thermal properties and stability of the nanocomposites obtained and to select the most appropriate nanocharges. The effect of the introduction of nanofillers on these properties also was evaluated. X-ray diffraction was used to investigate the degree of clay exfoliation. Finally, mechanical characterization of the nanocomposites obtained was performed and compared to that of the pure material. The tests demonstrated that nanodispersion of phyllosilicate layers improved the mechanical behavior of the polymers analyzed, especially the annealed sPS.
ABSTRACT:Montmorillonite nanocomposite systems obtained from epoxy cured using anhydride and the addition of a reacting flame retardant are studied in this paper. In particular, a thermokinetic analysis of the behavior of five different compounds was performed, using a differential scanning calorimeter. The isothermal tests showed double reaction peaks, due to the cure reactions of DGEBA/acid anhydride systems. The comparisons between dynamic thermograms (and between isothermal ones, too) for the different mixtures also showed that the addition of other active substances (such as a nanofiller or a flame retardant additive) does not change the mechanism of crosslinking from a qualitative point of view, but both the nanoreinforcement and the flame retardant seemed to exert an evident catalytic action on the cure reactions. A model describing the cure behavior of the aforementioned materials is proposed in this work. This model takes into account the fact that the reaction mechanism of each analyzed system is composed of a couple of parallel phenomena: the fast opening of anhydride ring (corresponding to a first exothermic peak and characterized by "n-th order" kinetics) and resin networking (corresponding to a second exothermic peak and characterized by an "auto-catalytic with zero initial velocity" behavior). The verification of the proposed model was performed by means of a comparison between experimental data (normalized curves derived from DSC thermograms) and theoretical data (derived from a numerical integration-using the second order Runge-Kutta method-of the model-representative equation) and provided very good results. This allows one to apply such a model to any engineering process problem concerning the cure of DGEBA/acid anhydride/ phyllosilicate nanocomposite systems.
Epoxy/amine/montmorillonite nanocomposite systems are studied in this article. Both a thermo2kinetic analysis (performed using a differential scanning calorimeter) and a chemorheological characterization were carried out. The comparison of DSC thermograms has shown that the addition the nanofiller does not change the mechanism of crosslinking from a qualitative standpoint, but the nanoreinforcement seemed to produce an evident hindrance on the molecular mobility, which in turn influences the cure reactions. As none of the kinetic models available in literature was able to describe the cure behavior of the aforementioned materials, a new phenomenological model is proposed in this work, which considers the activation energy of the networking process a function of the degree of cure (rising exponentially towards infinity when the system approaches vitrification). The effects of the presence of the clay on the chemorheology of the composites was resumed as follows: the viscosity of the nanocomposite was higher at any temperature, furthermore the composite viscosity showed an higher heating sensitivity before networking and gelation occurred at lower degrees of cure, thus determining a narrower shape of the chemoviscosity behavior. A modified version of the classical Williams-Landel-Ferry (WLF) equation that took into account the gelation and the effects of crosslinking was uses as chemorheological model. Once the characteristic parameters of both the neat resin and the nanocomposite were found, the chemoviscosity models were integrated using a numerical algorithm, to check their ability to foresee the behavior of the systems during a dynamic cure process. A very good correspondence between the results and the experimental data was obtained. POLYM.
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