While the formation of (tri)block copolymer hydrogels has been extensively investigated, such studies mostly focused on equilibrium self-assembling whereas the use of preformed structures as building blocks such as out of equilibrium, quenched, nanofibrillar micelles is still a challenge. Here, we demonstrate that quenched, ultralong polystyrene-b-poly(ethylene oxide) (PS-b-PEO) micelles can be used as robust precursors of hydrogels. Two cross-linking strategies, (i) thermal fusion of micellar cores and (ii) chemical cross-linking of preformed micellar coronas were studied. The gelation process and the structure of the micellar networks were investigated by in situ rheological measurements, confocal microscopy and transmission electron microscopy. Direct observation of core fusion of preformed quenched micelles is provided validating this method as a robust gelation route. Using time sweep rheological experiments, it was found for both cross-linking methods that these 3D "mikado" gels are formed in three different stages, containing (1) initiation, (2) transition (growth), and (3) stabilization regimes.

A novel and facile approach to fabricating well-organized macroscopic 2D networks of cylindrical micelles is reported, based on transfer printing and thermal welding of aligned supramolecular micelles of block copolymers. This versatile approach provides a new strategy for fabricating functional 2D superstructures with a higher level of order.