Crazing Mechanism and Physical Aging of Poly(lactide) Toughened with Poly(ethylene oxide)-<i>block</i>-poly(butylene oxide) Diblock Copolymers
Charles J. McCutcheon, Boran Zhao, Kailong Jin, Frank S. Bates, Christopher J. Ellison
Abstract
Sustainable polymers are important alternatives to plastics and elastomers derived from petroleum resources. Poly(lactide) (PLA), a commercially available sustainable plastic, is a well-known success story. However, PLA lacks ductility and toughness, limiting the number of potential uses. In this study, small amounts of a liquid poly(ethylene oxide)-block-poly(butylene oxide) (PEO-PBO) diblock copolymer additive were blended with PLA to enhance its toughness and ductility. The incorporated PEO-PBO diblock copolymers generated a macrophase-separated morphology with particle diameters of 0.2–0.9 μm, and nearly matched refractive indices of PLA and PEO-PBO led to retention of optical transparency. Addition of just 1.8 wt % PEO-PBO into PLA led to a 20-fold increase in toughness, measured as the area under the stress–strain data in tension without affecting the bulk elastic modulus of the plastic. The micromechanical deformation process of the PEO-PBO/PLA blend was investigated via in situ small angle X-ray scattering during tensile testing. The total volume of the crazed material was proportional to the total surface area of the dispersed PEO-PBO particles, and both quantities increased with increasing PEO-PBO loading. Increasing the PEO-PBO loading also resulted in (A) an increase in particle size, causing a decrease in the craze initiation stress, and (B) an increase in fibril spacing, indicating a lower craze propagation stress. Furthermore, craze development was found to be independent of aging time. As a result, the PEO-PBO/PLA blend was able to remain ductile and tough for up to 114 days, exhibiting a 10-fold increase in elongation at break and toughness compared to neat PLA, which becomes brittle in less than 2 days. These results demonstrate that designing additives that promote deformation by crazing is an effective way to overcome the aging-induced embrittlement of glassy polymers.