Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials

Significance 

Polymers are lightweight, durable, and easily processed into fabricated parts, features that promoted polymers to become the most relevant class of engineering materials by volume. However, recycling polymers is a challenge that materials scientists have been researching for decades. Copolymers are a special class of polymers that are made up of two different monomers and exhibit self-healing properties. The researchers found that when copolymers were added onto the surface of nanoparticles, new structures were formed that enhanced the polymer’s self-healing properties. This discovery is foundational to improving the recyclability of polymers.

An alternate route toward a more sustainable polymer industry is to increase the service lifetime of polymers. An intriguing new concept is to impart the ability to “self-heal” from structural damage. Michael Bockstaller, professor of materials science and engineering at Carnegie Mellon University Materials Science and Engineering, in collaboration with Krzysztof Matyjaszewski, professor of chemistry, has discovered that the binding of copolymers on the surface of nanoparticles that are already used in industrial manufacturing provides an economic and scalable route toward self-healing polymers with increased strength and toughness. This research was published in Macromolecules.

The properties of the resulting materials can be varied by controlling the interactions between nanoparticle building blocks. This concept opens up new possibilities to vary properties of engineering materials without having to change their chemical composition a feature that is highly beneficial in the context of recyclability. While working to make these particles more amenable to fabrication technologies like additive manufacturing, the authors experimented with putting copolymers at the surface of nanoparticles. The research work illustrates how controlling macromolecular architecture can dramatically enhance properties of various advanced materials.

The authors systematically evaluated the effect of BA/MMA composition in grafted random and gradient-type copolymer ligands on the deformation characteristics and thermomechanical properties of particle brush-based hybrid materials. The authors successfully developed a facile method to control copolymer architecture of brush materials based on the variation of the conversion ratio during surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, the thermomechanical properties of random and gradient brush systems were determined and compared with those of the linear copolymer analogues. Depending on the grafting density and composition, gradient polymer architectures exhibited heterogeneous microstructures with distinctively different properties as random copolymer analogues. The results thus highlight the importance of chain architecture as a “control parameter” for the design of functional materials based on copolymer brush particle-based hybrid materials. The authors will continue to explore strategies to maximize strength and toughness of copolymer-based self-healing materials and to make them available to scalable production methods.

Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials - Advances in Engineering

About the author

Professor Krzysztof Matyjaszewski
Carnegie Mellon University

He is the J.C. Warner Professor of the Natural Sciences at the Carnegie Mellon University. Matyjaszewski is best known for the discovery of atom transfer radical polymerization (ATRP), a novel method of polymer synthesis that has revolutionized the way macromolecules are made. Matyjaszewski was elected a member of the National Academy of Engineering in 2006 and the National Academy of Sciences in 2019.

About the author

Michael R. Bockstaller
Professor of Materials Science and Engineering
Carnegie Mellon University

Professor Bockstaller received his diploma in Chemistry from the Technical University of Karlsruhe (Germany) and his Ph.D. in Physical Chemistry from the Johannes Gutenberg University (Mainz, Germany). He came to Carnegie Mellon from the Technical University of Aachen (Germany) where he held a Habilitation position. He is a fellow of the Alexander von Humboldt foundation and Emmy Noether grant recipient of the German Science Foundation.

His research focus are Polymer morphology, polymer-based nanostructures; polymer-based nanoparticle assemblies; phase behavior and structure-property relations (optical/magnetic) of organic-inorganic heterogeneous materials; phase behavior of water-soluble polymers (synthetic and biological) under in-vivo conditions; field-responsive nanoparticles for drug delivery; X-ray and neutron scattering; Electron microscopy

Reference

Yuqi Zhao, Zongyu Wang, Chenxi Yu, Hanshu Wu, Mateusz Olszewski, Rongguan Yin, Yue Zhai, Tong Liu, Amy Coronado, Krzysztof Matyjaszewski*, and Michael R. Bockstaller. Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials. Macromolecules 2022, 55, 19, 8846–8856

Go To Macromolecules

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