Structural Diversity and Phase Behavior of Brush Block Copolymer Nanocomposites

Brush block copolymers (BBCPs) exhibit attractive features for use as templates for functional hybrid nanomaterials including rapid ordering dynamics and access, to broad ranges of domain sizes; however, there are relatively few studies of the morphology of the BBCPs as a function of their structural variables and fewer still studies of BBCP composite systems. Here we report the structural diversity and phase behavior of one class of BBCP nanocomposites as a function of the volume fractions of their components and the side chain symmetry of the BBCPs. We conducted a systematic investigation of gold nanoparticle (NP) (similar to 2 nm) assembly in a series of poly(tert-butyl acrylate)-block-poly(ethylene oxide) (PtBA-b-PEO) BBCPs with a fixed side chain length of PtBA (M-n = 8.2 kg/mol) but with different PEO brush lengths (M-n = 5.0, 2.0, or 0.75 kg/mol) as well as volume fractions (f(PEO) = 0.200-0.484). The gold NPs are selectively incorporated within the PEO domain via hydrogen bond interactions between the 4-mercaptophenol ligands of the gold NPs and the PEO side chains. A number of morphological transitions were observed and were dependent on the total volume fraction (f(NP/PEO)) of NPs and PEO domain. Symmetric or asymmetric lamellar morphologies of NP arrays were readily created through simple variation of f(NP/PEO). Interestingly, a lamellar structure was obtained at a small f(NP/PEO) of only 0.248 for nanocomposites based on BBCPs with comparable side chain lengths (MWPEO/MWPtBA = 0.63). In contrast, NP morphological transitions from wormlike through cylindrical to lamellar structures were observed with the increase of f(NP/PEO) for nanocomposites based on BBCPs with a large difference in side chain length (MWPEO/MWPtBA = 0.09). Highly deformed cylinders were observed in the cylindrical morphology as clearly identified by high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) tomography. This work represents a starting point for understanding BBCP composite phase behavior, and it provides new insight toward strategies for control over the microstructure of NP arrays assembled in BBCP templates, which is essential for functional. materials design.