Different characteristic effects of ageing on starch-based films plasticised by 1-ethyl-3-methylimidazolium acetate and by glycerol. (1st August 2016)

• Record Type: Journal Article
• Authors: Zhang, Binjia; Xie, Fengwei; Zhang, Tianlong; Chen, Ling; Li, Xiaoxi; Truss, Rowan W.; Halley, Peter J.; Shamshina, Julia L.; McNally, Tony; Rogers, Robin D.
• Is Part Of: Carbohydrate polymers. Volume 146(2016)
• Page Start: 67
• Page End: 79
• Publication Date: 2016-08-01
• Subjects: Starch (PubChem CID: 24836924) -- Water (PubChem CID: 962) -- Glycerol (PubChem CID: 753) -- 1-Ethyl-3-methylimidazolium acetate (PubChem CID: 11658353); Starch-based materials -- Ionic liquid -- 1-Ethyl-3-methylimidazolium acetate -- Plasticizer -- Relative humidity -- Ageing; Polysaccharides -- Periodicals; Polysaccharides -- Periodicals; Polysaccharides -- Périodiques; Electronic journals; 547.78
• DOI: 10.1016/j.carbpol.2016.03.056
• Languages: English
• ISSNs: 0144-8617

Abstract

Graphical abstract: Highlights: Plasticised starch films were prepared by a simple compression moulding process. [C2 mim][OAc] suppressed densification in amorphous starch during ageing. [C2 mim][OAc] stabilised starch structure on the nano-scale during ageing. [C2 mim][OAc]-plasticised starch had stabilised structure and mechanical properties. Abstract: The focus of this study was on the effects of plasticisers (the ionic liquid 1-ethyl-3-methylimidazolium acetate, or [Emim][OAc]; and glycerol) on the changes of starch structure on multiple length scales, and the variation in properties of plasticised starch-based films, during ageing. The films were prepared by a simple melt compression moulding process, followed by storage at different relative humidity (RH) environments. Compared with glycerol, [Emim][OAc] could result in greater homogeneity in [Emim][OAc]-plasticised starch-based films (no gel-like aggregates and less molecular order (crystallites) on the nano-scale). Besides, much weaker starch–starch interactions but stronger starch-[Emim][OAc] interactions at the molecular level led to reduced strength and stiffness but increased flexibility of the films. More importantly, [Emim][OAc] (especially at high content) was revealed to more effectively maintain the plasticised state during ageing than glycerol: the densification (especially in the amorphous regions) was suppressed; and the structural characteristics especially on the nano-scale were stabilised (especially at a high RH), presumably due to the suppressed starch molecular interactions by [Emim][OAc] as confirmed by Raman spectroscopy. Such behaviour contributed to stabilised mechanical properties. Nonetheless, the crystallinity and thermal stability of starch-based films with both plasticisers were much less affected by ageing and moisture uptake during storage (42 days), but mostly depended on the plasticiser type and content. As starch is a typical semi-crystalline bio-polymer containing abundant hydroxyl groups and strong hydrogen bonding, the findings here could also be significant in creating materials from other similar biopolymers with tailored sensitivity and properties to the environment.