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Fabrication of macroporous polymers with functionally graded architecture or chemistry bears transformative potential in acoustic damping, energy storage materials, flexible electronics, and filtration but is hardly reachable with current processes. Here, we introduce thiol-ene chemistries in direct bubble writing, a recent technique for additive manufacturing of foams with locally controlled cell size, density, and macroscopic shape. Surfactant-free and solvent-free graded three-dimensional (3D) foams without drying-induced shrinkage were fabricated by direct bubble writing at an unparalleled ink viscosity of 410 cP (40 times higher than previous formulations). Functionalities including shape memory, high glass transition temperatures (&gt;25 °C), and chemical gradients were demonstrated. These results extend direct bubble writing from aqueous inks to nonaqueous formulations at high liquid flow rates (3 mL min -1 ). Altogether, direct bubble writing with thiol-ene inks promises rapid one-step fabrication of functional materials with locally controlled gradients in the chemical, mechanical, and architectural domains.

Programmable Porous Polymers via Direct Bubble Writing with Surfactant-Free Inks