Phase Behavior of Charged Star Block Copolymers at Fluids Interface

Chen, Zhan; Ribbe, Alexander E.; Steinmetz, Christian; Coughlin, E. Bryan; Hu, Mingqiu; Gan, Xuchen; Russell, Thomas P.

doi:10.1002/anie.202400127

Phase Behavior of Charged Star Block Copolymers at Fluids Interface

Journal Article · Wed Jan 10 23:00:00 EST 2024 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202400127· OSTI ID:2429591

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Univ. of Massachusetts, Amherst, MA (United States)
Univ. of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

The phase behavior of block copolymers (BCPs) at the water-oil interface is influenced by the segmental interaction parameter (χ) and chain architecture. We synthesized a series of star block copolymers (s-BCPs) having polystyrene (PS) as core and poly(2-vinylpyridine) (P2VP) as corona. The interaction parameters of block-block (χ _PS-P2VP) and block-solvent (χ _P2VP-solvent) were varied by adjusting the pH of the aqueous solution. Lowering pH increased the fraction of quaternized-P2VP (Q-P2VP) with enhanced hydrophilicity. By transferring the equilibrated interfacial assemblies, morphologies ranging from bicontinuous films at pH of 7 and 3.1 to nanoporous and nanotubular structure at pH of 0.65 were observed. The nanoporous films formed hexagonally packed pores in s-BCP matrix, while nanotubes comprised Q-P2VP as corona and PS as core. Control over pore size, d-spacing between pores, and nanotube diameters was achieved by varying polymer concentration, molecular weight, volume fraction and arm number of s-BCPs. Large-scale nanoporous films were obtained by freeze-drying emulsions. Remarkably, the morphologies of linear BCPs were inverted, forming hexagonal-packed rigid spherical micelles with Q-P2VP as core and PS as corona in multilayer. Here, this work provides insights of phase behaviors of BCP at fluids interface and offer a facile approach to prepare nanoporous film with well-controlled pore structure.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2429591

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 11 Vol. 63; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Phase Behavior of Charged Star Block Copolymers at Fluids Interface

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