Accelerated discovery and mapping of block copolymer phase diagrams
Data files
Sep 26, 2023 version files 180.18 MB
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Murphy-Accelerated_Discovery.zip
180.17 MB
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README.md
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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 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 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.
README
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
ͰAustralian Institute for Bioengineering and Nanotechnology and Centre for Advanced Imaging University of Queensland, Brisbane, Queensland 4072, Australia
Data file names are labeled as Sample Name_Characterization Technique and organized into folders corresponding to figure and table numbers in the manuscript.
Data is acquired from the following analytical characterization techniques:
Nuclear Magnetic Resonance Spectroscopy: Solution state 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). 1H, 13C, and 19F data has been collected. Data is shown as x: chemical shift (ppm) and y: intensity (a.u.).
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. Data is shown as x: retention time (min) and y: differential refractive index intensity (a.u.).
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 University of California, Santa Barbara. The instrument is constructed using a high brightness liquid metal jet X-ray source (D2+ 70 kV from Excillum), a low background scatterless slit beam collimation system developed in house, and a 4-megapixel hybrid photon counting area detector (Eiger2 R 4M from Dectris) housed inside a 3 meter-long vacuum vessel. Data is shown as x: scattering q vector (A-1), y: intensity (a.u.), and z: error.
Differential Scanning Calorimetry: Differential scanning calorimetry (DSC) was performed using a TA Instruments DSC Q2000 from –90 to 55 °C at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in a sealed Tzero aluminum pan. Data is shown as x: time (min), y: temperature (ºC), and z: heat flow (W/g).
Data shown in the main text of the manuscript is located in the folder "Main text":
Figure 2: NMR spectroscopy data (1H) of representative D-1F, D-5F, D-9F, and D-12F parent diblock copolymers.
Figure 3: SEC chromatograms of representative D-1F, D-5F, D-9F, and D-12F parent diblock copolymers and their corresponding homopolymers. Folders organized by sections Figure 3a, 3b, 3c, 3d.
Figure 4: NMR spectroscopy data (1H) of D-1F,-57% D-5F-28%, D-9F-36%, and D-12F-39% parent diblock copolymers and fractions derived therefrom. Folders organized by sections Figure 4a, 4b, 4c, 4d with D-1F,-57% D-5F-28%, D-9F-36%, and D-12F-39% data respectively.
Figure 5: SAXS and NMR spectroscopy data (1H) for D-1F, D-5F, D-9F, and D-12F phase diagrams. Folders organized by phase diagram with subfolders of characterization technique (NMR and SAXS).
Figure 6: SAXS data of D-12F-31% parent diblock copolymer and fractions derived therefrom.
Figure 7: SAXS data of D-5F-67% parent diblock copolymer and fractions derived therefrom.
Data shown in the supporting information of the manuscript is located in the folder "Supporting Information":
Figure S1: NMR spectroscopy data (1H) of 2-fluoroethyl acrylate monomer.
Figure S2: NMR spectroscopy data (13C) of 2-fluoroethyl acrylate monomer.
Figure S3: NMR spectroscopy data (19F) of 2-fluoroethyl acrylate monomer.
Figure S4: NMR spectroscopy data (1H) of representative D homopolymer.
Figure S5: NMR spectroscopy data (1H) of 1F homopolymer.
Figure S6: NMR spectroscopy data (19F) of 1F homopolymer.
Figure S7: NMR spectroscopy data (1H) of 5F homopolymer.
Figure S8: NMR spectroscopy data (19F) of 5F homopolymer.
Figure S9: NMR spectroscopy data (1H) of 9F homopolymer.
Figure S10: NMR spectroscopy data (19F) of 9F homopolymer.
Figure S11: NMR spectroscopy data (1H) of 12F homopolymer.
Figure S12: NMR spectroscopy data (19F) of 12F homopolymer.
Figure S13: NMR spectroscopy data (1H) of a representative D-1F diblock copolymer.
Figure S14: NMR spectroscopy data (19F) of a representative D-1F diblock copolymer.
Figure S15: NMR spectroscopy data (1H) of a representative D-5F diblock copolymer.
Figure S16: NMR spectroscopy data (19F) of a representative D-5F diblock copolymer.
Figure S17: NMR spectroscopy data (1H) of a representative D-9F diblock copolymer.
Figure S18: NMR spectroscopy data (19F) of a representative D-9F diblock copolymer.
Figure S19: NMR spectroscopy data (1H) of a representative D-12F diblock copolymer.
Figure S20: NMR spectroscopy data (19F) of a representative D-12F diblock copolymer.
Figure S21: DSC thermogram of 1F homopolymer.
Figure S22: DSC thermogram of 5F homopolymer.
Figure S23: DSC thermogram of 9F homopolymer.
Figure S24: DSC thermogram of 12F homopolymer.
Table S1: SEC chromatograms of 1F, 5F, 9F, and 12F homopolymers. NMR spectroscopy data (1H) for 1F, 5F, 9F, and 12F homopolymers shown in Figures S5, S7, S9, S11, respectively.
Table S3: SEC chromatograms of D-1F-16%, D-1F-27%, D-1F-36%, D-1F-57% parent diblock copolymers. NMR spectroscopy data (1H) for and SAXS data shown in Figure 5, D-1F phase diagram and not duplicated in the supporting information folder.
Tables S4, S5, S6, S7: NMR spectroscopy data (1H) and SAXS data shown in Figure 5, D-1F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Table S8: SEC chromatograms of D-5F-14%, D-5F-27%, D-5F-28%, D-5F-40%, D-5F-67% parent diblock copolymers. NMR spectroscopy data (1H) for and SAXS data shown in Figure 5, D-5F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Tables S9, S10, S11, S12, S13: NMR spectroscopy data (1H) and SAXS data shown in Figure 5, D-5F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Table S14: SEC chromatograms of D-9F-27%, D-9F-36%, D-9F-50% parent diblock copolymers. NMR spectroscopy data (1H) for and SAXS data shown in Figure 5, D-9F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Tables S15, S16, S17: NMR spectroscopy data (1H) and SAXS data shown in Figure 5, D-9F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Table S18: SEC chromatograms of D-12F-31%, D-12F-32%, D-12F-39%, D-12F-68% parent diblock copolymers. NMR spectroscopy data (1H) for and SAXS data shown in Figure 5, D-12F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Tables S19, S20, S21, S22: NMR spectroscopy data (1H) and SAXS data shown in Figure 5, D-9F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a tabulated form in the supporting information.
Figures S27, S28, S29, S30: SAXS data shown in Figure 5, D-1F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a plotted form in the supporting information.
Figures S31, S32, S33, S34, S35: SAXS data shown in Figure 5, D-5F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a plotted form in the supporting information.
Figures S36, S37, S38 : SAXS data shown in Figure 5, D-9F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a plotted form in the supporting information.
Figures S39, S40, S41, S42 : SAXS data shown in Figure 5, D-12F phase diagram and not duplicated in the supporting information folder as this is the same data but shown in a plotted form in the supporting information.
Figure S43: SEC chromatograms of D-5F-27% parent diblock copolymer with A15 structure and fraction 60 derived therefrom with sigma structure.
Methods
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-ray source (D2+ 70 kV from Excillum), a low background scatterless slit beam collimation system developed in house, and a 4-megapixel hybrid photon counting area detector (Eiger2 R 4M from Dectris) housed inside a 3 meter-long vacuum vessel.
Differential Scanning Calorimetry: Differential scanning calorimetry (DSC) was performed using a TA Instruments DSC Q2000 from –90 to 55 °C at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in a sealed Tzero aluminum pan.