Crazing mechanism and physical aging of poly(lactide) toughened with poly(ethylene oxide)-block-poly(butylene oxide) diblock copolymers

Charles J. McCutcheon, Boran Zhao, Kailong Jin, Frank S. Bates, Christopher J. Ellison

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32 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)10163-10178
Number of pages16
Issue number22
StatePublished - Nov 24 2020

Bibliographical note

Funding Information:
This work was supported primarily by the farm families of Minnesota and their corn check-off investment, and in part by the National Science Foundation Center for Sustainable Polymers at the University of Minnesota, a Center for Chemical Innovation (CHE-1901635). SAXS experiments were conducted at the Advanced Photon Source (APS), Sector 5 (DuPont-Northwestern-Dow Collaborative Access Team, DND-CAT). DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under contract no. DE-AC02-06CH11357. SAXS data were collected using an instrument funded by the National Science Foundation under grant no. 0960140. Part of this work was carried out in the Characterization Facility at the University of Minnesota, which receives partial support from the NSF through the MRSEC program (DMR-2011401).

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