Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer

Small-angle X-ray scattering analyses reveal that the hydrated diblock oligomer n-C₁₆H₂₃(OCH₂CH₂)₂₀-OH (C₁₆E₂₀ or Brij 58) forms lyotropic liquid crystals (LLCs) exhibiting face-centered cubic (FCC), body-centered cubic (BCC), Frank-Kasper (FK) A15, and cylindrical (H_I) morphologies over the concentration range 30-65 wt % amphiphile. Heating LLCs comprising 54-59 wt % C₁₆E₂₀ drives the temperature-dependent phase transition sequence: A15 → BCC → H_I. However, rapidly quenching the resulting H_I phase from 70 to 25 °C initially forms a BCC phase that isothermally transforms into a complex, tetragonal FK σ phase comprising 30 quasispherical micelles. The metastability of this micellar σ phase is shown to depend on the sample cooling rate, thermal quench depth, and isothermal annealing temperature. We rationalize the preference for the A15 structure at 25 °C in terms of minimizing unfavorable water/hydrophobic contacts, while maximizing local particle sphericity. The symmetry breaking transition kinetics in these micellar LLCs apparently stem from the temperature-dependent activation barriers for phase nucleation and growth, which are intimately coupled to the time scales for micelle reconfiguration by amphiphile chain exchange and their spatial rearrangement. These findings highlight how thermal processing influences nucleation and growth of the self-assembled morphologies of intrinsically reconfigurable, soft spherical particles.