Publications

Additive manufacturing (AM) technologies are expanding the boundaries of materials science and providing an exciting forum for interdisciplinary research. The ability to fabricate arbitrarily complex objects has made AM technologies indispensable in personalized healthcare, soft electronics, and renewable energy. At the intersection of AM technologies and materials chemistry are stimuli-responsive polymers, which change their chemical and physical properties in response to specific environmental cues. The responsiveness of these “smart” polymers makes them suitable for AM and provides functionality to the additively manufactured objects. Furthermore, the type and degree of stimulus response of smart polymers can be regulated through precise synthetic design or via incorporation of additives. Herein, we review recently reported stimuli-responsive polymers used in AM, with a focus on the design and chemistry of the polymers. The materials are broadly classified by type of printing, and more specifically classified by type of stimulus response. Finally, we briefly consider existing challenges that stimuli-responsive materials in AM can address in the future.

Production of objects with varied mechanical properties is challenging for current manufacturing methods. Additive manufacturing could make these multimaterial objects possible, but methods able to achieve multimaterial control along all three axes of printing are limited. Here we report a multi-wavelength method of vat photopolymerization that provides chemoselective wavelength-control over material composition utilizing multimaterial actinic spatial control (MASC) during additive manufacturing. The multicomponent photoresins include acrylate- and epoxide-based monomers with corresponding radical and cationic initiators. Under long wavelength (visible) irradiation, preferential curing of acrylate components is observed. Under short wavelength (UV) irradiation, a combination of acrylate and epoxide components are incorporated. This enables production of multimaterial parts containing stiff epoxide networks contrasted against soft hydrogels and organogels. Variation in MASC formulation drastically changes the mechanical properties of printed samples. Samples printed using different MASC formulations have spatially-controlled chemical heterogeneity, mechanical anisotropy, and spatially-controlled swelling that facilitates 4D printing.

Additive manufacturing, commonly referred to as 3D printing (3DP), has ushered in a new era of advanced manufacturing that is seemingly limited only by imagination. In actuality, the fullest potentials of 3DP can only be realized through innovative breakthroughs in printing technologies and build materials. Whereas equipment for 3DP has experienced considerable development, molecular-scale programming of function, adaptivity, and responsiveness in 3DP is burgeoning. This review aims to summarize the state-of-the-art in stimuli-responsive materials that are being explored in 3DP. First, we discuss stimuli-responsiveness as it is used to enable 3DP. This highlights the diverse ways in which molecular structure and reactivity dictate energy transduction that in turn enables 3D processability. Second, we summarize efforts that have demonstrated the use of 3DP to create materials, devices, and systems that are in their final stage stimuli-responsive. This section encourages the artistic license of advanced manufacturing to be applied toward leveraging, or enhancing, energy transduction to impart device function across multiple length scales.

New advancements in 3D printing enable manufacturing a solid part with spatially controlled and varying material properties; this research seeks to establish techniques for finding optimal designs that use this new technology for the greatest structural benefit. We describe the use of a sequential quadratic programming based optimization solver to find an optimal distribution of material properties that minimize strain energy gradients, as calculated using finite element analysis. This design method is applied to the case of a flat thin plate with a hole, and has been proven to successfully reduce strain energy gradients and therefore stress concentrations. The optimally designed plates are 3D printed using a novel technology that uses vat polymerization technology. The computational model is validated with experiments. Enabling design engineers to customize material properties around geometric discontinuities will provide greater flexibility in reducing stress concentrations without modifying geometry or adding additional supports.

A series of photoresins suitable for production of elastomeric objects via digital light processing additive manufacturing are reported. Notably, the printing procedure is readily accessible using only entry-level equipment under ambient conditions using visible light projection. The photoresin formulations were found to be modular in nature and straightforward adjustments to the resin components enabled access to a range of compositions and mechanical properties. Collectively, the series includes silicones, hydrogels, and hybrids thereof. Printed test specimens displayed maximum elongations of up to 472% under tensile load, tunable swelling behavior in water, and Shore A hardness values from 13.7 to 33.3. A combination of the resins was used to print a functional multi-material three-armed pneumatic gripper. These photoresins could be transformative to advanced prototyping applications such as simulated human tissues, stimuli-responsive materials, wearable devices, and soft robotics.