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Stabilizing a Double Gyroid Network Phase with 2 nm Feature Size by Blending of Lamellar and Cylindrical Forming Block Oligomers.

ABSTRACT: Molecular dynamics simulations are used to study binary blends of an AB-type diblock and an AB₂-type miktoarm triblock amphiphiles (also known as high-χ block oligomers) consisting of sugar-based (A) and hydrocarbon (B) blocks. In their pure form, the AB diblock and AB₂ triblock amphiphiles self-assemble into ordered lamellar (LAM) and cylindrical (CYL) structures, respectively. At intermediate compositions, however, the AB₂-rich blend (0.2 ≤ x _AB ≤ 0.4) forms a double gyroid (DG) network, whereas perforated lamellae (PL) are observed in the AB-rich blend (0.5 ≤ x _AB ≤ 0.8). All of the ordered mesophases present domain pitches under 3 nm, with 1 nm feature sizes for the polar domains. Structural analyses reveal that the nonuniform interfacial curvatures of DG and PL structures are supported by local composition variations of the LAM- and CYL-forming amphiphiles. Self-consistent mean field theory calculations for blends of related AB and AB₂ block polymers also show the DG network at intermediate compositions, when A is the minority block, but PL is not stable. This work provides molecular-level insights into how blending of shape-filling molecular architectures enables network phase formation with extremely small feature sizes over a wide composition range.

SUBMITTER: Shen Z

PROVIDER: S-EPMC9241014 | biostudies-literature |

REPOSITORIES: biostudies-literature

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