3D-TEM study on the novel bicontinuous microdomain structure.

An ordered bicontinuous double-diamond (OBDD) morphology was found in polystyrene-block-(poly-4-vinylphenyldimethylvinylsilane-graft-polyisoprene), PS-b-(PVS-g-PI), block-graft copolymer. We obtained a 3D image of the microdomain structure formed in PS-b-(PVS-g-PI) using 3D-TEM. The 3D image shows that the polystyrene (PS) phase consists of two independent and interwoven networks. The structures of the two networks are identical and include tetrapod units that form planar six-membered rings. The features of the networks agree with those in the OBDD morphology, indicating that PS-b-(PVS-g-PI) exhibits ordered three-dimensional OBDD networks with the PS phase in the polyisoprene (PI) matrix phase. The grafted PI chains induce the frustration of the PS chains; thus, the effects of the specific interface are more dominant than those of packing frustration in the formation of the morphology, and the OBDD phase is stabilized.