title: Environmentally responsive self-assembly of mixed poly(tert-butyl acrylate)-polystyrene brush-grafted silica nanoparticles in selective polymer matrices.
abstract: Environmentally responsive self-assembly of nearly symmetric mixed poly(tert-butyl acrylate) (PtBA, 22.2 kDa)/polystyrene (PS, 23.4 kDa) brushes grafted onto 67 nm silica nanoparticles in selective homopolymer matrices [PtBA for the grafted PtBA chains and poly(cyclohexyl methacrylate) (PCHMA) for the grafted PS chains] was investigated using both conventional transmission electron microscopy (TEM) and electron tomography (i.e., 3D TEM). A variety of self-assembled phase morphologies were observed for the mixed brushes in selective polymer matrices with different molecular weights, and these can be explained by entropy-driven wet- and dry-brush theories. In a low molecular weight selective matrix, the wet-brush regime was formed with the miscible chains stretching out and the immiscible chains collapsing into isolated domains. In contrast, when the molecular weight of the selective matrix was higher than that of the compatible grafted polymer chains, the dry-brush regime was formed with the mixed brushes exhibiting the unperturbed morphology. In addition to the molecular weight, the size of nanoparticles (or the substrate curvature) was also observed to play an important role. For small particles (core size less than 50 nm), the wet brush-like morphology with a surface-tethered micellar structure was observed. Finally, the wet- and dry-brush regimes also significantly affected the dispersion of mixed brush particles in selective polymer matrices.
authors.affiliation: Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106-7202, USA. lxz121@case.edu.
authors.forename: Saide
authors.initials: S
authors.lastname: Tang
authors.forename: Tara L
authors.initials: TL
authors.lastname: Fox
authors.forename: Ting-Ya
authors.initials: TY
authors.lastname: Lo
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Horton
authors.forename: Rong-Ming
authors.initials: RM
authors.lastname: Ho
authors.forename: Bin
authors.initials: B
authors.lastname: Zhao
authors.forename: Phoebe L
authors.initials: PL
authors.lastname: Stewart
authors.forename: Lei
authors.initials: L
authors.lastname: Zhu
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D019277:Entropy; D008970:Molecular Weight; D053761:Nanocomposites / Q000737:chemistry* / Q000648:ultrastructure; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D010316:Particle Size; D058105:Polymerization; D011109:Polymethacrylic Acids / Q000737:chemistry; D011137:Polystyrenes / Q000138:chemical synthesis*; D017975:Ruthenium Compounds / Q000737:chemistry
chemical_list: D000179:Acrylates; D011109:Polymethacrylic Acids; D011137:Polystyrenes; D017975:Ruthenium Compounds; C532460:poly(tert-butyl acrylate); C027646:ruthenium tetraoxide