The interaction in sorbitol-plasticized starch bionanocomposites via positron annihilation lifetime spectroscopy and small angle X-ray scattering
- Authors: Liu, Huihua , Chaudhary, Deeptangshu , Roberts, Jason , Weed, Ryan , Sullivan, James , Buckman, Stephen
- Date: 2012
- Type: Text , Journal article
- Relation: Carbohydrate Polymers Vol. 88, no. 4 (2012), p. 1172-1176
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- Description: We investigated the free volume variations (size and distribution) within sorbitol plasticized high amylose bionanocomposites of different formula where the interactions among sorbitol, amylose and hydrophilic montmorillonite nanoclay (MMT) modified the crystallinity and therefore, the free volume of the matrix. Positron Annihilation Lifetime Spectroscopy (PALS) is a useful technique to monitor the changes of free volume within the polymer matrix - due to polymer-plasticizer or polymer-polymer interactions. In a recent investigation (Liu et al.; Carbohydrate Polymer, 2011, 85(1), 97-104), we demonstrated that there exists a threshold plasticizer concentration - above which the matrix crystallinity and moisture content can be significantly altered. By investigating the relationship between the changes of free volume and the development of crystalline morphology, we presented evidence that, at the molecular level, the free volume changes due to amylose-MMT interactions were affected by the concentration of the sorbitol plasticizer. The free volume analysis revealed that when the concentration of sorbitol was low (5 wt%), the bionanocomposite showed a bimodal distribution for free volume pore-size. As the sorbitol concentration increased, these free volume pores coalesced. Further, due to sorbitol's hydrophilic nature, this study also presented the evidence of moisture 'lock-in' within the bionanocomposites matrix; only one pore size - was confirmed in the high moisture content samples; meaning that sorbitol was able to have binary interactions with the amylose and with the water molecules so that the free volume pore-size was relatively more uniform. © 2012 Elsevier Ltd. All rights reserved.
Investigations into the free-volume changes within starch/plasticizer/nanoclay systems using Positron Annihilation Lifetime Spectroscopy
- Authors: Liu, Huihua , Chaudhary, Deeptangshu , Campbell, Colin , Roberts, Jason , Buckman, Stephen , Sullivan, James
- Date: 2014
- Type: Text , Journal article
- Relation: Materials Chemistry and Physics Vol. 148, no. 1-2 (2014), p. 349-355
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- Description: 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.