Web Release Date: December 15,
Patterning on Nonplanar Substrates: Flexible Honeycomb Films from a Range of Self-assembling Star Copolymers
and
Polymer Science Group, Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria, 3010, Australia, and Materials Research Laboratory and Departments of Materials, Chemistry and Biochemistry, University of California, Santa Barbara, California 93106
Received August 13, 2007
In Final Form: October 17, 2007
Abstract:
The effect of glass transition temperature, Tg, on the self-assembly of "honeycomb" microstructures on nonplanar
substrates was probed by the synthesis of a library of core cross-linked star polymers with different arm compositions.
Star polymers based on poly(dimethyl siloxane), poly(ethyl acrylate), poly(methyl acrylate), poly(tert-butyl acrylate),
and poly(methyl methacrylate) were synthesized by the "arm first" strategy using atom-transfer radical polymerization.
Reaction conditions were optimized, and a series of high molecular weight star polymers were prepared in high yield.
The glass transition temperature of the star polymers ranged from -123 to 100 
C which allowed the suitability for
the formation of porous honeycomb-like films via the "breath figure" technique on nonplanar surfaces to be investigated.
All star compositions successfully formed ordered films on flat surfaces. However, only star polymer compositions
with a Tg below 48 C could form homogeneous honeycomb coatings on the surface of nonplanar substrates.
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