Controlled patterning of crystalline domains by frontal polymerization

Journal Article · Wed Sep 18 00:00:00 EDT 2024 · Nature (London)

DOI:https://doi.org/10.1038/s41586-024-07951-7· OSTI ID:2475368

Paul, Justine E. ^[1]; Gao, Yuan ^[2]; Go, Yoo Kyung ^[1]; Rodriguez Koett, Luis E. ^[1]; Sharma, Anisha ^[1]; Chen, Manxin ^[1]; Lessard, Jacob J. ^[1]; Topkaya, Tolga ^[3]; Leal, Cecilia ^[1]; Moore, Jeffrey S. ^[1]; Geubelle, Philippe H. ^[1]; Sottos, Nancy R. ^[1]

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1. University of Illinois Urbana-Champaign, IL (United States)
2. University of Illinois Urbana-Champaign, IL (United States); Huazhong University of Science and Technology, Wuhan (China)
3. University of Illinois Urbana-Champaign, IL (United States); Batman University (Turkey)

Materials with hierarchical architectures that combine soft and hard material domains with coalesced interfaces possess superior properties compared with their homogeneous counterparts. These architectures in synthetic materials have been achieved through deterministic manufacturing strategies such as 3D printing, which require an a priori design and active intervention throughout the process to achieve architectures spanning multiple length scales. Here we harness frontal polymerization spin mode dynamics to autonomously fabricate patterned crystalline domains in poly(cyclooctadiene) with multiscale organization. This rapid, dissipative processing method leads to the formation of amorphous and semi-crystalline domains emerging from the internal interfaces generated between the solid polymer and the propagating cure front. The size, spacing and arrangement of the domains are controlled by the interplay between the reaction kinetics, thermochemistry and boundary conditions. Small perturbations in the fabrication conditions reproducibly lead to remarkable changes in the patterned microstructure and the resulting strength, elastic modulus and toughness of the polymer. Furthermore, this ability to control mechanical properties and performance solely through the initial conditions and the mode of front propagation represents a marked advancement in the design and manufacturing of advanced multiscale materials. Drawing inspiration from biological systems in which structural complexity develops through dissipative reaction–diffusion processes, this study explores a transformative synthetic manufacturing strategy aimed at harnessing the principles underpinning morphogenic growth, unlocking new avenues for advanced materials design and fabrication. Synthetic coupled reaction-transport processes offer a versatile yet relatively underexplored method to manipulate the spatial attributes of synthetic materials10. Here we introduce an innovative manufacturing approach based on frontal ring-opening metathesis polymerization (FROMP) that draws parallels with morphogenic growth and development, enabling the formation of patterned microstructures within polymeric materials.

• Research Organization: University of Illinois Urbana-Champaign, IL (United States)
• Sponsoring Organization: National Science Foundation (NSF); Scientific and Technological Research Council of Turkey (TUBITAK); USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: AC02-06CH11357; SC0023457
• OSTI ID: 2475368
• Journal Information: Nature (London), Journal Name: Nature (London) Journal Issue: 8032 Vol. 634; ISSN 0028-0836
• Publisher: Nature Publishing Group
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
Mechanical properties
Polymers