Spontaneous Patterning during Frontal Polymerization.

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.

Rapid synchronized fabrication of vascularized thermosets and composites.

Bioinspired vascular networks transport heat and mass in hydrogels, microfluidic devices, self-healing and self-cooling structures, filters, and flow batteries. Lengthy, multistep fabrication processes involving solvents, external heat, and vacuum hinder large-scale application of vascular networks in structural materials. Here, we report the rapid (seconds to minutes), scalable, and synchronized fabrication of vascular thermosets and fiber-reinforced composites under ambient conditions. The exothermic frontal polymerization (FP) of a liquid or gelled resin facilitates coordinated depolymerization of an embedded sacrificial template to create host structures with high-fidelity interconnected microchannels. The chemical energy released during matrix polymerization eliminates the need for a sustained external heat source and greatly reduces external energy consumption for processing. Programming the rate of depolymerization of the sacrificial thermoplastic to match the kinetics of FP has the potential to significantly expedite the fabrication of vascular structures with extended lifetimes, microreactors, and imaging phantoms for understanding capillary flow in biological systems.

Rapid Synthesis of Elastomers and Thermosets with Tunable Thermomechanical Properties.

Rapid, solvent-free synthesis of poly(1,4-butadiene) in ambient conditions is demonstrated by frontal ring-opening metathesis polymerization (FROMP) of 1,5-cyclooctadiene (COD). Furthermore, cross-linked copolymers with a wide range of tunable properties are readily prepared by FROMP of mixtures of COD and dicyclopentadiene (DCPD). Specifically, glass transition temperature and tensile modulus are varied from -90 to 114 °C and 3.1 MPa to 1.9 GPa, respectively, by controlling the comonomer ratio. Copolymers with subambient glass transition temperature exhibit robust elastomeric behavior, with the ability to repeatedly recover from large elastic deformations. As a demonstration of the capability of this manufacturing strategy, gradient materials are fabricated in less than a minute with spatially controlled properties for multistage shape memory actuation. This simple yet powerful manufacturing strategy enables rapid synthesis of copolymers ranging from elastomers to thermosets with precise control over thermomechanical properties.

Enhanced Mixing of Microvascular Self-Healing Reagents Using Segmented Gas-Liquid Flow.

Microvascular self-healing systems have previously been demonstrated to restore large-scale damage and achieve repeated healing of multiple damage events in polymers. However, the healing performance of these systems is often limited because the laminar nature of flow in microchannels  results in poor mixing of two-part self-healing reagents. In this paper, we introduce segmented gas-liquid flow (SGLF) to enhance the mixing of reagents in microvascular self-healing systems. In SGLF, discrete liquid slugs containing self-healing reagents are separated by gas bubbles while flowing through a single microchannel. Recirculating streamlines within the liquid slugs can enhance the mixing of miscible liquids such as healing reagents. We investigate the effect of SGLF on mixing and healing for a two-stage chemistry used to restore large-scale damage in thermoset polymers. Additionally, we employ SGLF to deliver an epoxy-thiol chemistry, enabling the repeated recovery of fracture toughness in glass fiber-reinforced composites. In both systems, the mixing of healing agents delivered by SGLF is enhanced compared to alternative microvascular delivery strategies. For the two-stage chemistry, SGLF increases the maximum damage size that can be healed by 25% compared to laminar single-phase flow. Furthermore, there are concomitant increases in the extent of polymerization and the mechanical properties of the restored material, including a fivefold increase in the peak load sustained during a push-out test. For the epoxy-thiol chemistry, SGLF enables multiple healing cycles with healing efficiency above 100%. On the basis of these results, we envision that SGLF could improve performance for a variety of microvascular self-healing systems with different host materials, damage modes, and healing chemistries.

Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization.

Thermoset polymers and composite materials are integral to today's aerospace, automotive, marine and energy industries and will be vital to the next generation of lightweight, energy-efficient structures in these enterprises, owing to their excellent specific stiffness and strength, thermal stability and chemical resistance1-5. The manufacture of high-performance thermoset components requires the monomer to be cured at high temperatures (around 180 °C) for several hours, under a combined external pressure and internal vacuum 6 . Curing is generally accomplished using large autoclaves or ovens that scale in size with the component. Hence this traditional curing approach is slow, requires a large amount of energy and involves substantial capital investment6,7. Frontal polymerization is a promising alternative curing strategy, in which a self-propagating exothermic reaction wave transforms liquid monomers to fully cured polymers. We report here the frontal polymerization of a high-performance thermoset polymer that allows the rapid fabrication of parts with microscale features, three-dimensional printed structures and carbon-fibre-reinforced polymer composites. Precise control of the polymerization kinetics at both ambient and elevated temperatures allows stable monomer solutions to transform into fully cured polymers within seconds, reducing energy requirements and cure times by several orders of magnitude compared with conventional oven or autoclave curing approaches. The resulting polymer and composite parts possess similar mechanical properties to those cured conventionally. This curing strategy greatly improves the efficiency of manufacturing of high-performance polymers and composites, and is widely applicable to many industries.

Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life.

Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.

Polarity-switching top coats enable orientation of sub-10-nm block copolymer domains.

Block copolymers (BCPs) must necessarily have high interaction parameters (χ), a fundamental measure of block incompatibility, to self-assemble into sub-10-nanometer features. Unfortunately, a high χ often results from blocks that have disparate interfacial energies, which makes the formation of useful thin-film domain orientations challenging. To mitigate interfacial forces, polymers composed of maleic anhydride and two other components have been designed as top coats that can be spin-coated from basic aqueous solution in the ring-opened, acid salt form. When baked, the anhydride reforms and switches polarity to create a neutral layer enabling BCP feature alignment not possible by thermal annealing alone. Top coats were applied to the lamella-forming block copolymers poly(styrene-block-trimethylsilylstyrene-block-styrene) and poly(trimethylsilylstyrene-block-lactide), which were thermally annealed to produce perpendicular features with linewidths of 15 and 9 nanometers, respectively.