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Jayaraman, Ashish
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Publications (5/5 displayed)
- 2022Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymerscitations
- 2021Quasicrystals and Their Approximants in a Crystalline–Amorphous Diblock Copolymercitations
- 2021Dodecagonal quasicrystals of oil-swollen ionic surfactant micellescitations
- 2020Emergence of a C15 Laves Phase in Diblock Polymer/Homopolymer Blendscitations
- 2019Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomercitations
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article
Emergence of a C15 Laves Phase in Diblock Polymer/Homopolymer Blends
Abstract
<p>The observation of complex, Frank-Kasper (FK) particle packings in diblock polymer melts has until recently been limited to low molecular weight, conformationally asymmetric polymers. We report temperature-dependent small-angle X-ray scattering (SAXS) studies of blends of a sphere-forming poly(styrene-block-1,4-butadiene) (SB) diblock polymer (M<sub>n</sub> = 33.3 kg/mol, Ð = M<sub>w</sub>/M<sub>n</sub> = 1.08, f<sub>B</sub> = 0.18) with two different poly(1,4-butadiene) (B) homopolymer additives. When the B additive M<sub>n</sub> is the same as that of the diblock core-forming B segment, these blends remarkably form tetrahedrally close-packed FK s and Laves C14 and C15 phases with increasing B content. However, binary blends in which the B additive M<sub>n</sub> is 60% of that of the diblock B segment form only the canonical body-centered cubic (BCC) particle packing and hexagonally-packed cylinders (HEXc). The observed phase behavior is rationalized in terms of "wet" and "dry" brush blending, whereby higher B M<sub>n</sub> drives stronger localization of the homopolymer in the particle cores while preserving the interfacial area per SB diblock chain. The consequent packing constraints in these blends destabilize the BCC packing, and FK phases emerge as optimal minimal surface solutions to filling space at constant density while maximizing local particle sphericity.</p>