The crystalline domain changes and lamellar structure observations of sorbitol-plasticized starch nanocomposite had been investigated via synchrotron. Strong interactions were found between amylose-sorbitol, resulting in reduced inter-helix spacing of the starch polymer. Achievable dspacing of nanoclay was confirmed to be correlated to the moisture content (mc) within the nanocomposites. SAXS diffraction patterns changed from circular (high mc samples) to elliptical (low mc samples), indicating the formation of long periodic structure and increased heterogeneities of the electron density within the samples. Two different domains sized at around 90 Ã… and 350 Ã… were found for the low mc samples. However, only the ~90 Ã… domain was observed in high mc samples. Formation of the 380 Ã… domain is attributed to the retrogradation behaviour in the absence of water molecules. Meanwhile, the nucleation effect of nanoclay is another factor leading to the emergence of the larger crystalline domain.
The free-volume of a matrix is a fundamental parameter that relates to its molecular and bulk characteristics, such as crystalline change and glass transition behavior. In starch-based bionanocomposite, we investigated the effect of the addition of montmorillonite nanoclay (MMT) and food plasticizers (glycerol and sorbitol) on changes of molecular pore size (including pore volume and pore distribution) using the Positron Annihilation Lifetime Spectroscopy (PALS) method. The results demonstrated counter-intuitive impact of MMT on the total free-volume where the total free-volume increased within the polymeric matrix. When compared to the pure matrix free-volume, the addition of MMT also resulted in the appearance of a broader distribution of the void sizes. The plasticizers, on the other hand, apparently occupied the void spaces, and therefore decreased the free-volume of the matrix. Further, together with the small angle X-ray scattering (SAXS) analysis, we concluded that this is a result of interplay between the plasticizer-plasticizer interactions and the polymer-plasticizer interactions. For example, in the starch/glycerol/MMT system, the pore radii slightly decrease upon the increasing of glycerol amount (OG210 = O.27 nm and OG220 = 0.26 nm), but the relative weight did increase with the increasing glycerol concentration. However, increasing the sorbitol amount increased the pore size from 0.23 nm(OS210) to 0.28 nm(OS220). Furthermore, the addition MMT in the OS010 system, promote the emergence of a new dateable pore radius(0.90 nm), and the total weight significantly increased from 13.70 (OS010) to 19.5% (OS210). We suggest that the pore variation (size and distribution) due to the MMT and plasticizers are reflected in the polymer glass transition and crystallinity because ultimately, the, total free-volume is a reflection of level of interactions existing within the bulk of these nanocomposites.