Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate

The excessive use and disposal of plastic products have become a severe threat to the environment, animal welfare, and human health. Naturally synthesized, marine-degradable polyhydroxybutyrate (PHB) represents a viable green substitute for conventional plastics. However, the inherent brittleness of...

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Main Authors: Hou, Xunan, Sun, Wen, Liu, Zhibang, Liu, Siqi, Yeo, Jayven Chee Chuan, Lu, Xuehong, He, Chaobin
Other Authors: School of Materials Science and Engineering
Format: Article
Language:English
Published: 2023
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Online Access:https://hdl.handle.net/10356/164045
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1640452023-01-03T06:41:14Z Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate Hou, Xunan Sun, Wen Liu, Zhibang Liu, Siqi Yeo, Jayven Chee Chuan Lu, Xuehong He, Chaobin School of Materials Science and Engineering Engineering::Materials Blends Polyhydroxyalkanoates The excessive use and disposal of plastic products have become a severe threat to the environment, animal welfare, and human health. Naturally synthesized, marine-degradable polyhydroxybutyrate (PHB) represents a viable green substitute for conventional plastics. However, the inherent brittleness of PHB remains a major challenge due to undesirable large spherulites and secondary crystallization. Herein, we report PHB-based (up to 70 wt %) ductile and flexible materials by facile physical blending with edible poly(vinyl acetate) (PVAc). Theoretical and experimental analyses show that entropy rather than enthalpy drives the high miscibility between two polymers. Entropic mixing turns fragile PHB spherulitic crystals (>70 μm) into myriads of ultrafine domains (<2 μm). Interfacial entanglements between PVAc and PHB further prevent secondary crystal formation of the rigid amorphous phase. The resultant biopolymer blends demonstrate mechanical properties similar to commercial polyethylene plastics, such as high ductility (elongation >500%), toughness (∼62 MJ m-3), flexibility, and shape recovery under repeated bending (180°) or twisting (360°). Under controlled composting conditions, the food-safe bioblends exhibit ∼2.4 times weight loss of virgin PHB. The proposed strategy proves applicable to other crystalline/amorphous polymeric mixtures. This discovery sheds new light on the rational design of green plastics for future sustainable electronics, agriculture, and biomedicine. X.H. would like to thank the National University of Singapore (NUS) for providing NUS Research Scholarship. 2023-01-03T06:41:14Z 2023-01-03T06:41:14Z 2022 Journal Article Hou, X., Sun, W., Liu, Z., Liu, S., Yeo, J. C. C., Lu, X. & He, C. (2022). Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate. Macromolecules, 55(13), 5527-5534. https://dx.doi.org/10.1021/acs.macromol.2c00832 0024-9297 https://hdl.handle.net/10356/164045 10.1021/acs.macromol.2c00832 2-s2.0-85134514570 13 55 5527 5534 en Macromolecules © 2022 American Chemical Society. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Materials
Blends
Polyhydroxyalkanoates
spellingShingle Engineering::Materials
Blends
Polyhydroxyalkanoates
Hou, Xunan
Sun, Wen
Liu, Zhibang
Liu, Siqi
Yeo, Jayven Chee Chuan
Lu, Xuehong
He, Chaobin
Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
description The excessive use and disposal of plastic products have become a severe threat to the environment, animal welfare, and human health. Naturally synthesized, marine-degradable polyhydroxybutyrate (PHB) represents a viable green substitute for conventional plastics. However, the inherent brittleness of PHB remains a major challenge due to undesirable large spherulites and secondary crystallization. Herein, we report PHB-based (up to 70 wt %) ductile and flexible materials by facile physical blending with edible poly(vinyl acetate) (PVAc). Theoretical and experimental analyses show that entropy rather than enthalpy drives the high miscibility between two polymers. Entropic mixing turns fragile PHB spherulitic crystals (>70 μm) into myriads of ultrafine domains (<2 μm). Interfacial entanglements between PVAc and PHB further prevent secondary crystal formation of the rigid amorphous phase. The resultant biopolymer blends demonstrate mechanical properties similar to commercial polyethylene plastics, such as high ductility (elongation >500%), toughness (∼62 MJ m-3), flexibility, and shape recovery under repeated bending (180°) or twisting (360°). Under controlled composting conditions, the food-safe bioblends exhibit ∼2.4 times weight loss of virgin PHB. The proposed strategy proves applicable to other crystalline/amorphous polymeric mixtures. This discovery sheds new light on the rational design of green plastics for future sustainable electronics, agriculture, and biomedicine.
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Hou, Xunan
Sun, Wen
Liu, Zhibang
Liu, Siqi
Yeo, Jayven Chee Chuan
Lu, Xuehong
He, Chaobin
format Article
author Hou, Xunan
Sun, Wen
Liu, Zhibang
Liu, Siqi
Yeo, Jayven Chee Chuan
Lu, Xuehong
He, Chaobin
author_sort Hou, Xunan
title Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
title_short Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
title_full Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
title_fullStr Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
title_full_unstemmed Tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
title_sort tailoring crystalline morphology via entropy-driven miscibility: toward ultratough, biodegradable, and durable polyhydroxybutyrate
publishDate 2023
url https://hdl.handle.net/10356/164045
_version_ 1754611261307355136