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Two frontal polymerization (FP) mechanisms, frontal ring-opening metathesis polymerization (FROMP) of dicyclopentadiene and frontal radical polymerization (FRaP) of benzyl acrylate and hexanediol diacrylate, were combined for rapid manufacturing of welded thermoset materials. Leveraging the immiscibility of the two different FP resins, welded thermosets and gradient foams of varying composition were achieved by switching of FP mechanisms. The adhesion strength of the welded thermoset materials differed depending on the originating mechanism. Finally, welded thermoset foams of varying porosity and homogeneity were generated through initiation from the bottom of the two resins.

In this work, a simple method is reported for control over initiation in frontal ring-opening metathesis polymerization (FROMP). This noncontact approach uses 375 nm light to excite Grubbs' second-generation catalyst in the presence of a phosphite inhibitor. Photoinitiated FROMP of dicylcopentadiene (DCPD) displays a similar cure profile to that of its thermally initiated counterpart, yielding a robust polymer with high glass transition temperature. Furthermore, this system is applied to enhance reaction rates in conventional ring-closing metathesis reactions.

We report the design and characterization of a multiphase quadruple shape memory composite capable of switching between 4 programmed shapes, three temporary and one permanent. Our approach combined two previously reported fabrication methods by embedding an electrospun mat of PCL in a miscible blend of epoxy monomers and PMMA as a composite matrix. As epoxy polymerization occurred the matrix underwent phase separation between the epoxy and PMMA materials. This created a multiphase composite with PCL fibers and a two-phase matrix composed of phase-separated epoxy and PMMA. The resulting composite demonstrated three separate thermal transitions and amenability to mechanical programming of three separate temporary shapes in addition to one final, equilibrium shape. In addition, quadruple surface shape memory abilities are successfully demonstrated. The versatility of this approach offers a large degree of design flexibility for multi-shape memory materials.