Accelerated discovery and mapping of block copolymer phase diagrams

Block copolymers are widely used in many applications due to their spontaneous self-assembly into a variety of nanoscale morphologies. However, a grand challenge in navigating this diverse and ever-growing array of possible structures is the accelerated discovery, design, and implementation of materials. Here, we report a versatile and efficient strategy to accelerate materials discovery by rapidly building expansive, high-quality, and detailed block copolymer libraries through a combination of controlled polymerization and chromatographic separation. To illustrate the potential of this approach, a family of 16 parent diblock copolymers was synthesized and separated, leading to over 300 distinct and well-defined samples at the multigram scale. The resulting materials span a wide range of compositions with exceptional resolution in volume fraction and domain spacing that allows for the impact of monomer design on polymer self-assembly to be elucidated. Phase behavior that can be gleaned from these libraries includes the precise location of order-order boundaries and the identification of morphologies with extremely narrow windows of stability. This user-friendly, scalable, and automated approach to discovery significantly increases the availability of well-defined block copolymers with tailored molecular weights, molar-mass dispersities, compositions, and segregation strengths, accelerating the study of structure-property relationships in advanced soft materials.