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 new 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 glea..., Nuclear Magnetic Resonance Spectroscopy: Solution state 1H nuclear magnetic resonance (NMR) spectra were recorded on a Varian 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm relative to residual protio-solvent in CDCl3 (7.26 ppm).
Size Exclusion Chromatography: Size-exclusion chromatography (SEC) was conducted on a Waters Alliance HPLC System, 2690 Separation Module using chloroform with 0.25% triethylamine as the eluent with a flow rate of 0.35 mL/min. Refractive index traces from a Waters 2410 Differential Refractometer detector were used for estimates of the molar mass and dispersity relative to linear polystyrene standards with a chloroform mobile phase.
Small Angle X-Ray Scattering: SAXS measurements of bulk samples were conducted using a custom-built high brilliance laboratory beamline for small and wide angle X-ray scattering (SAXS/WAXS) at the BioPACIFIC Materials Innovation Platform at UCSB. The instrument is constructed using a high brightness liquid metal jet X-..., , Accelerated Discovery and Mapping of Block Copolymer Phase Diagrams

Elizabeth A. Murphy,†,‡,# Stephen J. Skala,†,%,# Dimagi Kottage,†,‡ Phillip A. Kohl,†,# Youli Li,†,# Cheng Zhang,†,Ͱ Craig J. Hawker,,†,‡,%,# and Christopher M. Bates,,†,‡,§,%,#

†Materials Research Laboratory, ‡Department of Chemistry & Biochemistry, %Materials Department, §Department of Chemical Engineering, and #BioPACIFIC Materials Innovation Platform, University of California, Santa Barbara, California 93106, United States
Í°Australian Institute for Bioengineering and Nanotechnology and Centre for Advanced Imaging University of Queensland, Brisbane, Queensland 4072, Australia

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Data file names are labeled as Sample Name\_Characterization Technique and organized into folders corresponding to figure and table numbers in the manuscript.

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Data is acquired from the following analytical characterization techniques:

Nuclear Magnetic Resonance Spectroscopy: Solution state nuclear magnetic resonance (NMR) spe...