REMAT Researchers Present at 2025 EFRC-Hub-CMS-CSS PI Meeting

 REMAT Presentation Team enjoying dinner in Rockville, MD.

Poster: EFRC for Regenerative Energy-Efficient Manufacturing of Thermoset Polymeric Materials

Presenters: Nancy Sottos and Leah Appelhans

Poster: Accelerating the Discovery of Sustainable Thermosets: High Throughput Testing and Data Management

Presenter: Ignacio Arretche and Sameh Tawfick

Poster: Using Chemical Inhibitors to Improve FROMP: From Stable Resins to Predictive Modeling Using Data Science Tools

Presenters: Pranav Krishnan and Samantha Sloane

Poster: Morphogneic Growth 3D Printing

Presenters: Yun Seong Kim and Brandon Clarke

Poster: Multigenerational Additive Manufacturing of pDCPD Thermosets

Presenter: Edgar Mejia

Poster: Morphogenic Patterning of Polymers by Frontal Polymerization

Presenters: Anna Cramblitt and Philippe Geubelle

Technical Talk: Efficient Manufacturing of Multigenerational Thermosets

Presenter: Jeremiah Johnson

Abstract: Polydicyclopentadiene (pDCPD) thermosets are valuable for high-performance structural applications, yet their permanent covalent network structures have historically precluded chemical recycling, which limits circularity and contributes to energy- and resource-intensive waste. Addressing these challenges, we introduce a suite of strategies that enable low-energy manufacturing and multi-cycle chemical recycling of pDCPD thermosets without compromising thermomechanical performance. Central to this approach is Frontal Ring-Opening Metathesis Polymerization (FROMP)—a self-propagating, energy-efficient curing process compatible with additive manufacturing workflows. We integrate cleavable additives, including cleavable comonomers (CCs) and strand-fusing cross-linkers (SFCs), with activatable repeat units to achieve deconstructability of pDCPD thermosets at minimal additive loadings. These functionalities allow for targeted bond cleavage and recovery of soluble oligomeric fragments. Through one-pot deconstruction-reactivation protocols, functional groups such as norbornenes and furans are retained or installed in situ, enabling reincorporation of recycled fragments into new thermoset formulations. Incorporation of 40–45 wt% recycled content per cycle has been demonstrated across three to five generations, with full retention of thermomechanical properties including glass transition temperature and stiffness. Overall, this material platform could significantly reduce energy demand during both manufacturing and end-of-life processing, contributing to decarbonization of industrial materials and promoting circular economy models. The combined advances in molecular design, energy-efficient curing, and chemical reusability establish a scalable pathway for next-generation thermosets that meet stringent performance requirements while improving sustainability metrics.

Technical Talk: Manufacturing Patterned Materials Using Frontal Polymerization Instabilities: A Multiscale Mechanism-Based Model

Presenters: Philippe Geubelle and Rafael Gomez-Bombarelli

Abstract: Materials with hierarchical architectures that combine soft and hard material domains with coalesced interfaces possess superior properties compared to their homogeneous counterparts. In REMAT, we harnessed frontal polymerization spin-mode dynamics to autonomously fabricate patterned stiff crystalline and soft amorphous domains in poly(cyclooctadiene) with multiscale organization (Paul et al., Nature 2024).  These front mode instabilities are associated with the processing conditions (e.g., initial temperature) and the chemistry (e.g., monomer-to-catalyst ratio) of the resin.  While some success was achieved in the modeling of this process using a reaction-diffusion model, the phenomenological nature of the thermo-chemical model used in that work prevented the unified capture of the impact on the FP-driven instabilities of the relative concentration of monomer, catalyst and inhibitor present in the resin.  We developed a multiscale mechanism-based 3-step model of FP that captures accurately the inhibition, initiation, and propagation steps of the ring-opening metathesis polymerization (ROMP) process and investigate the ability of the model to capture the effects of both the initial temperature and chemical composition of the resin on the thermo-chemical FP-driven instabilities (Bistri et al., JACS, 2024 & PNAS, 2025). While the propagation of the polymerization front is modeled at the continuum level by combining the reaction model with a thermal diffusion relation that incorporates the enthalpy of the exothermic polymerization reaction, some of the parameters entering the multiscale 3-step model are extracted from Density Functional Theory (DFT). The model is validated against experiments conducted with a resin system composed of cyclooctadiene, Grubbs initiator, and tributyl phosphite inhibitor.

Team Science Competition: Multimaterial 3D Printing with Frontally Polymerizable Resins

Presenters: Brandon Clarke, Pranav Krishnan, and Yun Seong Kim

Abstract: This work is part of the U.S. Department of Energy’s Energy Frontier Research Center (EFRC) for Regenerative Energy-Efficient Manufacturing of Thermoset Polymeric Materials (REMAT), a cross-institutional initiative aimed at revolutionizing the production, performance, and end-of-life management of thermoset polymers. This collaborative research unites experts in mechanical engineering, polymer chemistry, and polymer physics at Harvard University and the University of Illinois Urbana-Champaign to develop next-generation additive manufacturing (AM) materials and platforms.

This AM research is driven by the design and deployment of frontally polymerizable (FP) resins, particularly those incorporating dicyclopentadiene (DCPD) and cyclooctadiene (COD), which form low-energy, rapid-curing thermoset systems. These materials polymerize through self-sustaining reaction fronts which require a small thermal activation energy to initiate, significantly reducing cure energy consumption compared to traditional thermoset manufacturing. However, this resin system poses challenges for AM, including short working time and spontaneous polymerization. We address these hurdles through precise control of polymerization kinetics, catalyst/inhibitor ratios, and gelation behavior. Our team leverages copolymer chemistries to modulate network structure, achieving extended pot lives and printable gel states suitable for extrusion-based AM processes.

The copolymer resin systems have been utilized in three novel multi-material AM platforms: Rotational Direct Ink Writing (DIW), Active Mixing DIW, and Morphogenic Growth Printing (Figure 1a-c). These FP AM techniques are capable of efficiently forming complex geometries with orders of magnitude thermomechanical property tunability (e.g. glass transition temperature, Young’s modulus, and elongation at break) over multiple length scales through a single stream process. Multi-material FP AM offers a promising avenue for fabrication of functional, gradient-rich structures such as tendon-like hinges for soft robotic actuation and shape-memory components for biomedical devices, demonstrating performance tailored by design.

Art of Science Image Competition Display (REMAT images below)