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Article Dans Une Revue Macromolecules Année : 2019

Cooperativity Scaling and Free Volume in Plasticized Polylactide

Résumé

The experimental evidence of the increase of activation energy associated with the super Arrhenius behavior governing amorphous polylactide by free volume variations has been obtained through a combination of calorimetric, dielectric, and positron annihilation lifetime measurements. The amount of free volume in polylactide was controlled by the amount of acetyltributylcitrate plasticizer in the composition. Plasticization is shown to decrease both the fragility index and the scale of cooperative motions at the glass transition. The calculations of volume and energetic components of kinetic fragility reveal that the fragility drop is governed by the change in the size of cooperative rearranging region. As a result, direct correlation has been established between cooperativity and activation energy for the entire plasticized polylactide series. It is also shown that cooperativity variations with both temperature and plasticizer content can be simplified as a master curve with free volume.
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Dates et versions

hal-02277312 , version 1 (30-10-2020)

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Steven Araujo, Nicolas Delpouve, Sandra Domenek, Alain Guinault, Roman Golovchak, et al.. Cooperativity Scaling and Free Volume in Plasticized Polylactide. Macromolecules, 2019, 52 (16), pp.6107-6115. ⟨10.1021/acs.macromol.9b00464⟩. ⟨hal-02277312⟩
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