Embedded Direct Ink Writing of Thermoset and Elastomeric Polymers via Frontal Polymerization

TL;DR

This paper introduces an embedded 3D printing method for frontal polymerization that enables complex thermoset and elastomeric structures with tunable properties, overcoming previous rheological and feature size limitations.

Contribution

It develops a novel embedded printing technique with delayed solidification, allowing low-viscosity inks and complex architectures in frontal polymerization.

Findings

Supports complex, mechanically interlinked structures

Enables a broad range of formulations and properties

Achieves finer feature sizes with delayed solidification

Abstract

Direct ink writing (DIW) using frontal ring-opening metathesis polymerization (FROMP) offers a compelling route to the rapid and energy-efficient fabrication of thermoset and elastomeric polymer architectures, leveraging a self-propagating exothermic curing reaction. While FP-DIW excels at freestanding path printing due to the rapid solidification, it is constrained by stringent rheological requirements, a lower bound on achievable feature size due to quenching, and the need for the reaction front to closely follow the nozzle during printing. Here, we overcome these constraints by leveraging embedded 3D printing to implement FP-DIW with delayed solidification, thereby decoupling shape retention and solidification from ink chemistry and rheology. The use of a yield-stress support medium enables extrusion of low-viscosity inks by suppressing gravitational and capillary instabilities, mitigating front quenching at small diameters, and allowing time-delayed solidification to fuse complex, overlapping, and mechanically interlinked features after deposition. Two complementary thermal initiation strategies are introduced:\ volumetric dielectric heating via microwaves and surface heating at the boundary of the support bath. Formulations based on dicyclopentadiene (DCPD), cyclooctadiene (COD), and mixtures thereof, result in tunable final mechanical properties with glass transition temperatures spanning $-50$ to $160 $$^\text{o}$C. The versatility of this approach is demonstrated through the fabrication of lattices, springs, mechanically interlocked, and multimaterial architectures. Compared to printing in air, this embedded approach introduces a substantially broader range of possible formulations, material properties, feature sizes, and architectures.