Mechanistic origins of multi-scale reinforcements in segmented polyurethane-clay nanocomposites

The objective of the present work is to get insights into the mechanistic origin of the reinforcement effects of nanoclay on a segmented polybutadiene polyurethane-urea system. To this end, a convergent analysis of the hard domain morphology and conformational state of soft segment in the nanocomposites was carried out by using a combination of complementary characterization techniques, namely, Fourier transform infrared spectroscopy, small angle neutron scattering, transmission electron microscopy, modulated differential scanning calorimetry and dynamic mechanical analysis. Analysis of small angle neutron scattering data by a combination of Percus–Yevick hard sphere and Zernike-Ornstein model coupled with direct visualization of the dispersed hard domain morphology from transmission electron microscopy provided insight on clay induced changes in the hard domain morphology. A monotonic decrease in the domain size as well as the average interdomain distance was observed with increasing nanoclay content in the polymer matrix. Analysis of the carbonyl stretching region from FTIR showed increased degree of hydrogen bonding for the urethane carbonyl groups of the nanocomposites compared to the neat matrix. A combination of calorimetric and dynamic mechanical analysis revealed the existence of a constrained amorphous region; quantified to be ≈ 16% at the highest clay content experimented. The manifestation of these morphological and conformational changes on the nano-, micro- and macro scale reinforcements in the nanocomposites was investigated by mechanical properties at these length scales using nanoindentation, DMA and tensile testing, respectively.