An in‐depth investigation on novel electro‐activated shape memory polymer composites (SMPCs) for digital light processing 3D‐Printing, consisting of a poly(ethylene glycol) diacrylate/poly(hydroxyethyl methacrylate) matrix embedding multi‐walled carbon nanotubes (CNTs), is reported here. The composition of the photocurable (meth)acrylate system is finely tuned to tailor the thermomechanical properties of the matrix, whereas the effect of CNTs on the photoreactivity and rheological properties of the formulations is investigated to assess the printability. Electrical measurements confirmed that the incorporation of CNT into the polymeric matrix enables the electrical conductivity and thus the possibility to remotely heat the nanocomposite using the Joule effect. The feasibility to drive a shape memory cycle via Joule heating is proved, given that the high shape fixity (R_f) and shape recovery (R_r) ratios achieved (R_f ≈ 100%,R_r > 95%) confirmed the significant electrically‐triggered responsiveness of such CNT/SMPCs. Finally, it is shown how to activate a modular and selective electro‐activated shape recovery, which may ultimately envisage the 4D‐Printing of remotely and selectively controllable smart devices.

Cyclodextrin with up to 10 bis(acyl)phosphanoxide functions serves as an initiator for highly cross-linked swellable hydrogels from mono-acrylates.

Emerging as a revolutionary strategy to fabricate dynamic three dimesional (3D) structures, 4D printing (4DP) mainly refers to printed materials capable of changing form over time when exposed to a predetermined stimulus. Nevertheless, the 4D concept can be extended beyond shape‐morphing, by including also changes in the properties and/or functionalities of printed materials over time. To this end, this work explores the 4DP of multifunctional nanocomposites that can adapt to different application scenarios exploiting the stimuli‐activable properties of two functional nanofillers embedded into the polymeric matrix. In particular, a photocurable system loaded with both Fe₃O₄ nanoparticles (NPs) and AgNO₃, as precursors for the in situ photo‐induced generation of Ag NPs, is used for the digital light processing of magnetic nanocomposites with integrated electrical and antibacterial functions. The composition of formulations is designed to both optimize their printability and maximize the magneto‐responsiveness and the electrical conductivity and/or antibacterial activity of the printed objects, given by Fe₃O₄ and Ag NPs, respectively. Finally, it is shown that the functional responses of the nanocomposites can be activated individually or in combination, which may be of particular interest for the fabrication of smart multifunctional devices with potential applications ranging from soft electronics to biomedicine.