One-Pot Printing of Robust Multimaterial Devices

Polymer 3D printing is a broad set of manufacturing methods that permit the fabrication of complex architectures, and, as a result, numerous efforts focus on formulating processible chemistries that produce desirable material behavior in printed parts. However, current resin chemistries typically result in a single fixed set of properties once fully polymerized, a fact that poses significant engineering challenges to obtaining multimaterial devices. As an alternative to single-property materials, we introduce a ternary sequential reaction scheme that exhibits diverse multimaterial properties by profoundly altering the polymer microstructure from within a single resin composition. In this system, the photodosage during 3D printing sets both the shape and extent of conversion for each subsequent reaction. This different polymerization mechanisms of the subsequent stages yield disparate crosslink densities and viscoelastic properties. As a result, our materials possess Young's Moduli spanning over three orders of magnitude (400 kPa < E < 1.6 GPa) with smooth transitions between soft and stiff regions. We successfully pattern a 500x change in modulus in under a millimeter while the sequential assembly of our polymer networks ensures robust interfaces and enhances toughness by 10x compared to the single property materials. Most importantly, the final objects remain stable to UV and thermal aging, a key limitation to applications of previous multimaterial chemistries. We demonstrate the ability to 3D print intricate multimaterial architectures by fabricating a soft, wearable braille display.