Hyperbranched polycarbosiloxanes and polysiloxanes with octafunctional polyhedral oligomeric silsesquioxane (POSS) branchpoints and curable alkoxysilane or silanol end-groups were formulated with linear polysiloxanes to fabricate transparent and robust nanostructured POSS-containing materials for use in a range of high performance space and solar applications. The effect of methyl vs. phenyl content, architecture and linear polysiloxane mass on transmission, thermal, physical, and proton, electron and UV radiation resistance properties was determined, and the physical properties of the nanomaterials were tailored to produce adhesives, or rigid or flexible coatings as desired. The methyl formulations showed superior electron resistance relative to a commercial space control material and to a POSS-free HB polymer control material, even when directly exposed to radiation in coating form, whereas the phenyl formulations were shown to have inferior electron and UV resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3849–3861, 2013
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