Block Copolymers: Emerging Building Blocks for Additive Manufacturing

ABSTRACT 3D printing (3DP) is leveraged in cutting‐edge research across disparate disciplines, with block copolymers (BCPs) frequently playing key roles in state‐of‐the‐art techniques. Here we review basic block copolymer physics and properties, highlighting the applications they have enabled across many 3DP subfields. We emphasize promising areas for optical, mechanical, electronic, templating, and bioengineering advancements in applications of BCPs in 3DP. We envision these advancements will largely be enabled through using 3DP to direct self‐assembly of these nanostructured materials in 3D to enable hierarchical structural control, ultimately using BCPs either as templates for further functionalization or as inherently anisotropic materials. This review examines established and emerging applications of block copolymers in 3DP. Block copolymers are widely utilized in inks for extrusion‐based 3DP and as support matrices and sacrificial inks for embedded 3DP. New methods are being actively developed to facilitate printing of BCPs via vat photopolymerization, electric‐field‐driven deposition techniques, and other emerging techniques. We highlight the subset of BCP 3DP studies which move beyond rheological and interfacial modification to leverage the functionality of these inherently nanostructured materials. We focus on the potential to couple bottom‐up BCP self‐assembly with top‐down patterning via 3DP to achieve on‐the‐fly tunability of BCP material structure and function.