Confinement in extruded nanocomposites based on pcl and mesoporous silicas: Effect of pore sizes and their influence in ultimate mechanical response

In this study, nanocomposites based on polycaprolactone (PCL) and two types of mesoporous silicas, MCM-41 and SBA-15, were attained by melt extrusion. The effect of the silica incorporated within the PCL matrix was observed, firstly, in the morphological characteristics and degradation behavior of the resultant composites. DSC experiments provided information on the existence of confinement in the PCL¿SBA-15 materials through the appearance of an additional small endotherm, located at about 25¿50¿C, and attributed to the melting of constrained crystallites. Displacement to a slightly lower temperature of this endothermic event was observed in the first heating run of PCL¿MCM-41 composites, attributed to the inferior pore size in the MCM-41 particles. Thus, this indicates variations in the inclusion of PCL chains within these two mesostructures with different pore sizes. Real-time variable-temperature small-angle X-ray scattering (SAXS) experiments with synchrotron radiation were crucial to confirm the presence of PCL within MCM-41 and SBA-15 pores. Accurate information was also deduced from these measurements regarding the influence of these two mesoporous MCM-41 and SBA-15 silicas on PCL long spacing. The differences found in these morphological and structural features were responsible for the ultimate mechanical response exhibited by the two sets of PCL nanocomposites, with a considerably higher increase of mechanical parameters in the SBA-15 family.This work was supported by the Agencia Estatal de Investigación (AEI, Spain) together with the European Regional Development Fund (FEDER, UE) (grant numbers MAT2016-79869-C2-1-P and PID2020-114930GB-I00), by CSIC (grant number 2020AEP129) and ALBA Synchrotron Light Facility. TMDR is also grateful for her pre-doctoral funding (contract number BES-2017-082284).Peer reviewe