Highly elastic silicone foams, especially those with tunable properties and multifunctionality, are of great interest in numerous fields. However, the liquid nature of silicone precursors and the complicated foaming process hinder the realization of its three-dimensional (3D) printability. Herein, a series of silicone foams with outstanding performance with regards to elasticity, wetting and sensing properties, multifunctionality, and tunability is generated by direct ink writing. Viscoelastic inks are achieved from direct dispersion of sodium chloride in a unique silicone precursor solution. The 3D-architectured silicone rubber exhibits open-celled trimodal porosity, which offers ultraelasticity with hyper compressibility/cycling endurance (near-zero stress/strain loss under 90% compression or 1000 compression cycles), excellent stretchability (210% strain), and superhydrophobicity. The resulting foam is demonstrated to be multifunctional, such that it can work as an oil sorbent with super capacity (1320%) and customizable soft sensor after absorption of carbon nanotubes on the foam surface. The strategy enables tunability of mechanical strength, elasticity, stretchability, and absorbing capacity, while printing different materials together offers property gradients as an extra dimension of tunability. The first 3D printed silicone foam, which serves an important step toward its application expansion, is achieved.

An unprecedented four-dimensional (4D) printing process allowing high-performance and shape memory thermoset to be printed, for the first time, by fused deposition modeling (FDM) with isotropic properties has been achieved. Bisphenol A-based epoxy and benzoxazine were formulated to a low-temperature thermoplastic and high-temperature thermoset resin, which is melt-extrudable and can be postcured into covalently cross-linked material. Carbon nanotube (CNT) was added in the resin to work as both mechanical enhancement filler and rheology modifier to prevent shape deformation during postcuring process. The cross-layer reaction fuses individual layers into an integrity, thus eliminating layer delamination induced by FDM, offering isotropic mechanical properties regardless of the printing orientations. The highly cross-linked network provides outstanding mechanical strength and superb thermal stability. The excellent shape memory performance with fast recovery rate and large recovery degree is also obtained in the three-dimensional (3D) printed composites.

Bisphenol A-based epoxies are much used in a wide range of composite and coating applications due to their excellent thermomechanical properties. However, their 3D printability remains a challenge with most reported materials suffering from high brittleness and low toughness. Here, we have described especially modified epoxy resins that enable 3D printing with both fast and slow curing rates. These materials exhibit greatly enhanced toughness, tunable thermomechanical properties, and excellent shape memory behavior. Two different printing systems, including a two-part static mixing printhead and a single extrusion printhead, were developed for fast-and slow-curing epoxies, respectively. The rheology of inks in both systems has been modified into printable thixotropic fluids with the aid of silica nanoparticles and other additives. Epoxide-functionalized telechelic polybutadiene was added into the resins, which are then introduced inside the epoxy network after cross-linking. The addition of polybutadiene rubber significantly improves the toughness (over 135%), fracture strain (over 200%), and shape memory behavior. By adding different amounts of the rubber telechelic, thermomechanical properties, including modulus, elongation, and T g of epoxy, can be well controlled in a wide range to satisfy different applications.

Surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain transfer (SI-PET-RAFT) polymerization has been preferentially used for preparing thin polymeric film coatings due to its simple execution under ambient conditions (e.g., in air) and visible light requirement. Herein, we demonstrate the preparation of polymer brushes by SI-PET-RAFT polymerization on a thin macroinitiator film electrodeposited on electrically conductive indium tin oxide and gold surfaces. An electrochemically active carbazole-containing chain transfer agent as macroinitiator was shown to be not only effective in mediating SI-PET-RAFT polymerization for various monomers but also capable of forming block copolymers. Additionally, the fabricated polymer brush films were able to encapsulate colloidal gold nanoparticles, thereby demonstrating potential use for biomedical and sensing applications.