Novel Electrochemically Responsive Porous Glass Matrix Composites from a Printable Silicone-Based Emulsion

The present study addresses the fabrication of porous gyroid architectures by additive manufacturing from preceramic polymer feedstocks. Photocurable emulsions were engineered by combining a silicone powder with acrylate monomers and dispersing an emulsified secondary phase of calcium nitrate. The formulations showed light-curing behaviour compatible with digital light processing vat photopolymerization (DLP-VPP), enabling high-fidelity replication of triply periodic minimal surface (TPMS) gyroids (designed porosity: 85 vol.%). After pyrolysis in nitrogen at 700 °C, the lattices converted into CaO–SiO2-derived amorphous matrices embedding an in situ turbostratic/pyrolytic carbon fraction, as suggested by the photothermal response and preliminary impedance behaviour, although the latter was measured in liquid electrolyte and therefore does not isolate electronic transport. To improve robustness during polymer-to-ceramic conversion, pharmaceutical borosilicate waste glass (BASG) was added as a passive filler (30–70 wt.%). The waste-glass phase acts as a passive filler that improves processing robustness and can mitigate shrinkage-induced damage during pyrolysis, while remaining electrically insulating (dielectric) and therefore not directly contributing to electronic conduction. The resulting structures combine high surface-to-volume ratio, controlled open porosity, and structural integrity with electrochemical responsiveness under the adopted test conditions, making them promising architected platforms for electrochemical components where interconnected porosity is advantageous.