Templating of cylindrical and spherical block copolymer microdomains by layered silicates

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Abstract
The influence of a highly anisotropic layered silicate (organically modified montmorillonite) in directing the mesoscopic self-assembly of a block copolymer blend is studied as a model for the development and tailoring of templated inorganic–organic hybrid materials. The potential for nanometer thick layers to induce large-scale mesoscopic ordering of cylindrical and spherical microdomains in asymmetric block copolymers is studied using a combination of rheology, electron microscopy, and small angle neutron scattering. Spherical microdomains arranged on a bcc lattice are templated by the anisotropic layered silicate and the kinetics of their growth are dramatically accelerated by the presence of even 0.1 wt.% (0.04 vol.%) of the filler. However, for cylindrical microdomain ordering, the kinetics are essentially unaffected by the addition of layered silicates and the development of three-dimensional mesoscopic order is possibly even disrupted. These results suggest that for the development of three-dimensional well-ordered nanostructures, the surface defining the pattern has to be significantly larger than the leading dimension of the structure being templated.