Complex patterns integral to the structure and function of biological materials arise spontaneously during morphogenesis. In contrast, functional patterns in synthetic materials are typically created through multistep manufacturing processes, limiting accessibility to spatially varying materials systems. Here, we harness rapid reaction-thermal transport during frontal polymerization to drive the emergence of spatially varying patterns during the synthesis of engineering polymers. Tuning of the reaction kinetics and thermal transport enables internal feedback control over thermal gradients to spontaneously pattern morphological, chemical, optical, and mechanical properties of structural materials. We achieve patterned regions with two orders of magnitude change in modulus in poly­(cyclooctadiene) and 20 °C change in glass transition temperature in poly­(dicyclopentadiene). Our results suggest a facile route to patterned structural materials with complex microstructures without the need for masks, molds, or printers utilized in conventional manufacturing. Moreover, we envision that more sophisticated control of reaction-transport driven fronts may enable spontaneous growth of structures and patterns in synthetic materials, inaccessible by traditional manufacturing approaches.

The synthesis and processing of most thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization is an attractive, scalable alternative due to its exploitation of polymerization heat that is generally wasted and unutilized. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully cured thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat-or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Numerous applications of frontally generated materials exist, ranging from porous substrate reinforcement to fabrication of patterned composites. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

Motivated by the use of frontal polymerization for the manufacturing of thin layers with thickness down to ∼100 μm, we numerically and experimentally investigate the interplay between the exothermic polymerization and the heat losses to the substrate. The results show how the reaction–diffusion power balance affects the velocity and temperature of the polymerization front. The lower thickness limit of the thin layer depends on the cure kinetics of the resin and the thermal properties of the substrate and is described by a scaling law. Concurrently, thin-layer frontal polymerization experiments confirm the effects of front–substrate interaction on the front propagation and the limiting thickness of the polymerized layer. The present study offers a fundamental understanding of the resin–substrate interplay in thin-layer frontal polymerization and provides a quantitative description of the limiting thickness of the layer in the fabrication of functional thin polymeric parts and resin coatings.

Frontal polymerization provides a rapid, economic, and environmentally friendly methodology to manufacture thermoset polymers and composites. Despite its efficiency and reduced environmental impact, the manufacturing method is underutilized due to the limited fundamental understanding of its dynamic control. This work reports the control and patterning of the front propagation in a dicyclopentadiene resin by immersion of phase‐changing polycaprolactone particles. Predictive and designed patterning is enabled by multiphysical numerical analyses, which reveal that the interplay between endothermic phase transition, exothermic chemical reaction, and heat exchange govern the temperature, velocity, and propagation path of the front via two different interaction regimes. To pattern the front, one can vary the size and spacing between the particles and increase the number of propagating fronts, resulting in tunable physical patterns formed due to front separation and merging near the particles. Both single‐ and double‐frontal polymerization experiments in an open mold are performed. The results confirm the front–particle interaction mechanisms and the shapes of the patterns explored numerically. The present study offers a fundamental understanding of frontal polymerization in the presence of heat‐absorbing second‐phase materials and proposes a potential one‐step manufacturing method for precisely patterned polymeric and composite materials without masks, molds, or printers.

Recently presented as a rapid and eco-friendly manufacturing method for thermoset polymers and composites, frontal polymerization (FP) experiences thermo-chemical instabilities under certain conditions, leading to visible patterns and spatially dependent material properties. Through numerical analyses and experiments, we demonstrate how the front velocity, temperature, and instability in the frontal polymerization of cyclooctadiene are affected by the presence of poly(caprolactone) microparticles homogeneously mixed with the resin. The phase transformation associated with the melting of the microparticles absorbs some of the exothermic reaction energy generated by the FP, reduces the amplitude and order of the thermal instabilities, and suppresses the front velocity and temperatures. Experimental measurements validate predictions of the dependence of the front velocity and temperature on the microparticle volume fraction provided by the proposed homogenized reaction−diffusion model.