A series of cubic network phases was obtained from the self-assembly of a single-composition lamellae (L)-forming block copolymer (BCP) polystyrene-block-polydimethylsiloxane (PS-b-PDMS) through solution casting using a PS-selective solvent. An unusual network phase in diblock copolymers, double-primitive phase (DP) with space group of [Formula: see text], can be observed. With the reduction of solvent evaporation rate for solution casting, a double-diamond phase (DD) with space group of [Formula: see text] can be formed. By taking advantage of thermal annealing, order-order transitions from the DP and DD phases to a double-gyroid phase (DG) with space group of [Formula: see text] can be identified. The order-order transitions from DP (hexapod network) to DD (tetrapod network), and finally to DG (trigonal planar network) are attributed to the reduction of the degree of packing frustration within the junction (node), different from the predicted Bonnet transformation from DD to DG, and finally to DP based on enthalpic consideration only. This discovery suggests a new methodology to acquire various network phases from a simple diblock system by kinetically controlling self-assembling process.
Keywords: double diamond; double gyroid; double-primitive network; order–order transitions; self-assembly.