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Kirkensgaard, Jacob J. K.; Evans, Myfanwy E.; de Campo, Liliana; Hyde, Stephen T.
Proceedings of the National Academy of Sciences - PNAS, 01/2014, Letnik: 111, Številka: 4Journal Article
Numerical simulations reveal a family of hierarchical and chiral multicontinuous network structures self-assembled from a melt blend of Y-shaped ABC and ABD three-miktoarm star terpolymers, constrained to have equal-sized A/B and C/D chains, respectively. The C and D majority domains within these patterns form a pair of chiral enantiomeric gyroid labyrinths (srs nets) over a broad range of compositions. The minority A and B components together define a hyperbolic film whose midsurface follows the gyroid minimal surface. A second level of assembly is found within the film, with the minority components also forming labyrinthine domains whose geometry and topology changes systematically as a function of composition. These smaller labyrinths are well described by a family of patterns that tile the hyperbolic plane by regular degree-three trees mapped onto the gyroid. The labyrinths within the gyroid film are densely packed and contain either graphitic hcb nets (chicken wire) or srs nets, forming convoluted intergrowths of multiple nets. Furthermore, each net is ideally a single chiral enantiomer, induced by the gyroid architecture. However, the numerical simulations result in defect-ridden achiral patterns, containing domains of either hand, due to the achiral terpolymeric starting molecules. These mesostructures are among the most topologically complex morphologies identified to date and represent an example of hierarchical ordering within a hyperbolic pattern, a unique mode of soft-matter self-assembly.
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