Advances in Thermoset Polymer Networks: From Cure Kinetics to Structure and Performance

Thermoset polymers underpin many high-performance applications because covalent cross-linking yields stability, chemical resistance, and robust mechanics. Yet it remains hard to predict thermoset performance from first principles because the “true” network structure - connectivity, topology, defects, and spatial heterogeneity - is difficult to quantify, and it often forms under non-equilibrium conditions. This gap grows as thermosets move into dynamic processing and additive manufacturing, where flow, thermal gradients, light transport, and layer-by-layer interfaces can imprint anisotropy and interfacial heterogeneities. Recent in situ/operando tools, especially synchrotron X-ray scattering and diffraction, now enable time- and space-resolved views of cure, morphology evolution, and (in hybrid systems) crystallization, offering new pathways to link processing history to structure and properties.This Research Topic aims to advance structure–processing–property relationships in covalently cross-linked polymer networks by connecting network formation kinetics, evolving soft matter morphology, and final macroscopic performance. A central objective is to understand how network architecture (cross-link density distributions, branch placement effects, loop/dangling-chain defects, trapped entanglements) and mesoscale structure (phase separation, interfaces, hierarchical microstructure) emerge during realistic processing, including additive manufacturing and photopolymerization. We particularly encourage studies that use in situ/operando synchrotron approaches (e.g., SAXS/WAXS, diffraction, imaging) combined with complementary spectroscopy, rheology, and calorimetry to track structure development during cure and printing. Contributions that pair experiments with polymer theory, kinetic modeling, and simulations are welcome, especially when they deliver predictive descriptors that guide resin design, process windows, and performance in demanding environments.We welcome original research, reviews, and mini-reviews on thermosets and related cross-linked networks, spanning experimental, theoretical, and computational approaches. Topics include: - Network topology and defects (e.g., loops, dangling chains, trapped entanglements, connectivity distributions)- Cross-link heterogeneity and processing-induced spatial gradients (e.g., conversion, cross-link density, thermal/light gradients)- Phase separation and cure-driven evolution, including gelation/vitrification, cure shrinkage, and interfacial heterogeneity- Photopolymerization and reaction/network design, including thiol–ene, dual-cure strategies, covalent adaptable networks, and recyclable/degradable thermosets- Additive manufacturing of soft and high-performance polymers, linking print parameters to crystallization kinetics (for hybrid/semi-crystalline systems) and hierarchical microstructure controlTopic Coordinator Dr. Chase Thompson is employed by Leidos. Topic Editor Dr. Alexa Alexa Kuenstler has received fundings from industry. The other Topic Editor declare no competing interests with regard to the Research Topic subject. Topic editors: Alexa Kuenstler, Brian Ree Source: https://www.frontiersin.org/research-topics/77445/advances-in-thermoset-polymer-networks-from-cure-kinetics-to-structure-and-performance