Toughening mechanisms in poly(lactic) acid reinforced with TEMPO-oxidized cellulose

The mechanical properties of poly(lactic) acid (PLA) were modified by the addition of small amounts of cellulose, prepared from the mechanical disintegration of birch Kraft pulp following oxidation of the primary alcohol groups mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO). The TEMPO-fibrillated cellulose (TOFC) was subsequently acetylated in acetic anhydride to degrees of substitution (DS) of 0.4 and 0.6 to enhance the compatibility between the polar cellulose and the non-polar polymer. The fracture behaviour of tensile specimens prepared from PLA film containing weight fractions of 1, 2 and 5 % of TOFC was considerably altered. The strain-to-failure of PLA modified by the incorporation of 1 wt% TOFC acetylated to a DS of 0.6 increased approximately 25-fold and the work of fracture by order of magnitude. The increase in the fracture properties were, nevertheless, accompanied by a reduction in Young's modulus of around 60 % at both DS levels. At the higher TOFC addition levels, no toughening was observed, with the strains-to-failure and works of fracture both decreasing compared to pure PLA film. On the other hand, the Young's modulus and tensile strength of films prepared from PLA incorporating TOFC esterified to a DS of 0.6 was found to be greater than that of pure PLA film. Possible mechanisms explaining the increase in toughness at 1 wt% are postulated.