This work concerns the effects of concurrent ball milling (BM) and octenyl succinic anhydride (OSA) modification on the starch microstructure and physicochemical properties (swelling, emulsifying, and rheological). Unlike normal OSA-modified starches, the BM/OSA-modified starch displayed new features such as reduced viscosity and rigidity but increased paste stability during shearing, heating and cooling, regardless of the substitution degree. More interestingly, while the physicochemical properties could be regulated by simply altering the BM treatment time, BM/OSA was more efficient and effective at modulating starch properties during the initial period (approx. 10h), as seen by the rapid evolutions in starch structural disruption and OSA esterification. Thus, the BM/OSA modification can serve as a viable and cost-effective approach for producing octenyl succinate starches where low viscosity (at relatively high concentrations) and high paste stability are desired.

Natural biopolymers, which are renewable, widely available, biodegradable, and biocompatible, have attracted huge interest in the development of biocomposite materials. Herein, formulation–property relationships for starch/agar composite films were investigated. First, rapid visco analysis was used to confirm the conditions needed for their gelation and to prepare filmogenic solutions. All the original crystalline and/or lamellar structures of starch and agar were destroyed, and films with cohesive and compact structures were formed, as shown by SEM, XRD, and SAXS. All the plasticized films were predominantly amorphous, and the polymorphs of the composite films were closer to that of the agar-only film. FTIR results suggest that the incorporation of agar restricted starch chain interaction and rearrangement. The addition of agar to starch increased both tensile strength and elongation at break, but the improvements were insignificant after the agar content was over 50 wt.%. Contact angle results indicate that compared with the other samples, the 4:6 (wt./wt.) starch/agar film was less hydrophilic. Thus, this work shows that agar dominates the structure and properties of starch/agar composites, and the best properties can be obtained with a certain starch/agar ratio. Such composite polysaccharide films with tailored mechanical properties and surface hydrophilicity could be useful in biodegradable packaging and biomedical applications (wound dressing and tissue scaffolding).