Sheets of branched poly(lactic acid) obtained by one-step reactive extrusion–calendering process: physical aging and fracture behavior

The architectural modifications of a linear poly(D,L-Lactide) acid (PD,L-LA) commercial grade were induced by a one-step reactive extrusion–calendering process using a styrene-glycidyl acrylate copolymer as reactive agent. The melt degradation was counteracted by chain extension and branching reactions, leading to a stabilization of the melt properties and an increase in the molecular weight. For such modified samples [poly(lactic acid) (PLA)-reactive extrusion (REX)], the rate of physical aging at 30 °C was investigated during 1 week in order to simulate industrial storage conditions. Fracture behavior of “de-aged” and “controlled aged” (1 week) samples was investigated using the essential work of fracture (EWF) methodology and the critical tip opening displacement at the crack propagation onset, respectively. These analyses were complemented by digital image correlation analysis and inspection of the fractured surfaces by scanning electronic microscopy. As a result of the architectural modifications, the entanglement network density was increased. Those accounted for a slight decrease in the physical aging rate. Under uniaxial loading, aged reactive extrusion (REX) samples exhibited multiple crazing, leading to a slight increase in strain at break. Nevertheless, as a result of a similar dynamic environment of the entangled polymer coils, de-aged REX samples disclosed similar mechanical properties as compared to their neat counterparts. Regarding de-aged samples, the EWF analysis revealed no changes in the work required for the onset of crack propagation. However, the energy consumed up to the onset of crack propagation of aged PLA-REX samples decreased due to an apparently decreased network extensibility, promoting a premature craze–crack transition.