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Simulation-guided analysis of resonant soft X-ray scattering for determining the microstructure of triblock copolymers

Resonant soft X-ray scattering (RSoXS) probes structure with chemical sensitivity that is useful for determining the morphology of multiblock copolymers. However, the hyperspectral scattering data produced by this technique can be challenging to interpret. Here, in this study, we use computational scattering simulations to extract the microstructure of a model triblock copolymer from the energy-dependent scattering from RSoXS. An ABC triblock terpolymer formed from poly(4-methylcaprolactone) (P4MCL), poly(2,2,2-trifluoroethylacrylate) (PTFEA), and poly (dodecylacrylate) (PDDA), P4MCL-block-PTFEA-block-PDDA, was synthesized as the model triblock system. Through quantitative evaluation of simulated scattering data from a physics-informed set of candidate structure models against experimental RSoXS data, we find the best agreement with hexagonally packed core–shell cylinders. This result is also consistent with electron-density reconstruction from hard X-ray scattering data evaluated against electron-density maps generated with the same model set. These results demonstrate the utility of simulation-guided scattering analysis to study complex microstructures that are challenging to image by microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable and unstable tiling patterns formed by ABC miktoarm star triblock terpolymers of symmetric interactions

Several discrepancies exist among previous self-consistent field calculations of symmetrically interacting ABC miktoarm star triblock terpolymer melts. Here we address this issue by including all known tiling patterns, as well as several lamellar-type phases known to bound the regions in the parameter space occupied by these patterns. After carefully studying the effect of numerical parameters on the free-energy accuracy, the central region of the phase diagram is constructed in detail; both the (3.4.6.4) pattern and the three-dimensional phase of hierarchical-hexagonal lamellae are found to be stable for the first time. The energetic and entropic contributions to the free-energy density of several phases are analyzed and compared in detail to reveal their stability mechanisms, including the important ( 3 2 .4.3.4) pattern. Comparisons to previous studies of the same model system are present throughout, with our results resolving the aforementioned discrepancies and providing a sound basis for future work to build upon. Published by the American Physical Society 2024

Materials Science↗