Accelerated discovery and mapping of block copolymer phase diagrams
Elizabeth A. Murphy, Stephen J. Skala, Dimagi Kottage, Phillip A. Kohl, Youli Li, Cheng Zhang, Craig J. Hawker, and Christopher M. Bates
Phys. Rev. Materials 2024
Abstract: 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.
