Volumetric Additive Manufacturing of Dicyclopentadiene by Solid-State Photopolymerization.

Polymerization in the solid state is generally infeasible due to restrictions on mobility. However, in this work, the solid-state photopolymerization of crystalline dicyclopentadiene is demonstrated via photoinitiated ring-opening metathesis polymerization. The source of mobility in the solid state is attributed to the plastic crystal nature of dicyclopentadiene, which yields local short-range mobility due to orientational degrees of freedom. Polymerization in the solid state enables photopatterning, volumetric additive manufacturing of free-standing structures, and fabrication with embedded components. Solid-state photopolymerization of dicyclopentadiene offers a new paradigm for advanced and freeform fabrication of high-performance thermosets.

4D Printing of Glass Fiber-Regulated Shape Shifting Structures with High Stiffness.

4D printing allows 3D printed structures to change their shapes overtime under external stimuli, finding a wide range of potential applications in actuators, soft robotics, active metamaterials, flexible electronics, and biomedical devices. However, most 4D printing uses soft polymers to accommodate large strain shape-changing capability at the price of low stiffness, which impedes their engineering applications. Here, we demonstrate an approach to design and manufacture self-morphing structures with large deformation and high modulus (∼4.8 GPa). The structures are printed by multimaterial direct ink writing (DIW) using composite inks that contain a high volume fraction of solvent, photocurable polymer resin, and short glass fibers as well as fumed silica. During printing, the glass fibers undergo shear-induced alignment through the nozzle, leading to highly anisotropic mechanical properties. The solvent is then evaporated, during which the aligned glass fibers enable anisotropic shrinkage in the parallel and perpendicular directions to the fiber alignment for shape shifting. A final postphotocuring step is applied to further increase the stiffness of the composite from ∼300 MPa to ∼4.8 GPa. A finite element analysis (FEA) model is developed to predict the influence of the solvent, fiber contents, and fiber orientation on the shape shifting. We demonstrate the anisotropic volume shrinkage of the structures can be used as active hinges to transform printed two-dimensional structures into complex three-dimensional structures with large shape-shifting and outstanding mechanical properties. This strategy for fabricating composite structures with programmable architectures and excellent mechanical properties shows potential applications in morphing lightweight structures with load-bearing capabilities.

3D Printing of Auxetic Metamaterials with Digitally Reprogrammable Shape.

Two-dimensional lattice structures with specific geometric features have been reported to have a negative Poisson's ratio, termed as auxetic metamaterials, that is, stretching-induced expansion in the transversal direction. In this paper, we designed a novel auxetic metamaterial; by utilizing the shape memory effect of the constituent materials, the in-plane moduli and Poisson's ratios can be continuously tailored. During deformation, the curved meshes ensure the rotation of the mesh joints to achieve auxetics. The rotations of these mesh joints are governed by the mesh curvature, which continuously changes during deformation. Because of the shape memory effect, the mesh curvature after printing can be programmed, which can be used to tune the rotation of the mesh joints and the mechanical properties of auxetic metamaterial structures, including Poisson's ratios, moduli, and fracture strains. Using the finite element method, the deformation of these auxetic meshes was analyzed. Finally, we designed and fabricated gradient/digital patterns and cylindrical shells and used the auxetics and shape memory effects to reshape the printed structures.