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Transition Pathway between Gyroid and Cylindrical Morphology in Linear Triblock Terpolymer Thin Films

Guliyeva, Aynur; Vayer, Marylène; Warmont, Fabienne; Takano, Atsushi; Matsushita, Yushu; Sinturel, Christophe

By 27 January 2020No Comments

Macromolecules, 2019, vol 52, 17, pp. 6641-6648



A new transition between alternating gyroid (GA) structure and cylindrical morphology was observed in thin films for a poly(isoprene-block-styrene-block-(2-vinylpyridine)) (ISP) triblock terpolymer (I/S/P volume fraction = 0.20:0.66:0.14) exhibiting in bulk a Q214 (space group I4132) morphology. Thin films were organized using solvent vapor annealing (SVA) and characterized by atomic force microscopy, transmission electron microscopy, and grazing-incidence small-angle X-ray scattering, coupled with several selective revealing methods adapted to the ISP system. After a short SVA time, the bulk morphology was reproduced with the (011) plane parallel to the surface. With a longer annealing time, a P2mm structure with cylindrical polyisoprene (PI) and poly(2-vinylpyridine) (P2VP) domains was obtained. Evidence of domains in transition between gyroid and cylinders was found, suggesting an epitaxial relationship between these two structures. In contrast to the well-known double gyroid (GD) to hexagonal (HEX) transition where {121} planes of the GD structure are epitaxially related to the {100} planes of the HEX phase and cylinders grow along the ?111? direction, we showed that the {011} planes of the GA phase become the {001} planes of the cylindrical structure (P2mm) and the cylinders grow along the ?010? direction of the GA, parallel to the substrate. This was directly related to the three-dimensional topology of the PI and P2VP networks.

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