Single-vat single-cure grayscale digital light processing 3D printing of materials with large property difference and high stretchability.

Multimaterial additive manufacturing has important applications in various emerging fields. However, it is very challenging due to material and printing technology limitations. Here, we present a resin design strategy that can be used for single-vat single-cure grayscale digital light processing (g-DLP) 3D printing where light intensity can locally control the conversion of monomers to form from a highly stretchable soft organogel to a stiff thermoset within in a single layer of printing. The high modulus contrast and high stretchability can be realized simultaneously in a monolithic structure at a high printing speed (z-direction height 1 mm/min). We further demonstrate that the capability can enable previously unachievable or hard-to-achieve 3D printed structures for biomimetic designs, inflatable soft robots and actuators, and soft stretchable electronics. This resin design strategy thus provides a material solution in multimaterial additive manufacture for a variety of emerging applications.

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.

Sequential Self-Folding Structures by 3D Printed Digital Shape Memory Polymers.

Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.

Effects of oxygen on light activation in covalent adaptable network polymers.

Light activated polymers are a novel group of active materials that deform when irradiated with light at specific wavelengths. This paper focuses on the understanding and evaluation of light activated covalent adaptable networks formed by radical polymerization reactions, which have potential applications as novel actuators, surface patterning, and light-induced bending and folding. In these polymer networks, free radicals are generated upon light irradiation and lead to evolution of the polymer network structure through bond exchange reactions. It is well known that oxygen is an important inhibitor in radical-based chemistry as oxygen reacts with free radicals and renders them as inactive species towards further propagation and reaction. However, it is unclear how radical depletion by oxygen may affect the light-induced actuation. This paper studies the effects of oxygen on both stress relaxation and bending actuation. Light induced stress relaxation experiments are conducted in an environmental chamber where the concentration of oxygen is controlled by the nitrogen flow. A constitutive model that considers oxygen diffusion, radical termination due to oxygen, and the polymer network evolution is developed and used to study the stress relaxation and bending, and the model predictions agree well with experiments. Parametric studies are conducted to identify the situations where the effects of oxygen are negligible and other conditions where they must be considered.