Segmental Dynamics and Cooperativity Length of PMMA/SAN Miscible Blend Intercalated in Organically Modified Nanoclay

The effect of nanoconfinement on the segmental dynamics of a poly(methyl methacrylate) (PMMA)/poly(styrene-ran-acrylonitrile) (SAN) miscible blend, intercalated into the interlayer spacing of the organically modified nanoclay (OMNC), was investigated using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) methods. We reported an unusual phenomenon in which the weak interfacial interactions between the polymer chains and OMNCs was responsible for increase in segmental mobility at the glass-transition temperature (Tg). Remarkably, we found a positive correlation between dynamic fragility and thermodynamic fragility, in which both fragilities decreased under nanoconfinement. The cooperative length of segmental motions, or length of cooperatively rearranging regions, ξCRR, decreased from 2.64 nm for the PMMA/SAN blend to 1.86 nm for the PMMA/SAN/OMNC nanocomposite. The segmental mobility of the PMMA/SAN/OMNC model was also studied using the molecular dynamics simulations. The simulation results showed the increased segmental mobility of the PMMA/SAN chains in the presence of OMNCs, which is in agreement with the DMA and DSC results.