The disclosure herein relates to articles and related methods that utilize hybrid polysiloxane coatings to increase the strength of an armored substrate. In one embodiment, a hybrid polysiloxane coated armor substrate can comprise i) a hybrid polysiloxane coating which includes a polysiloxane epoxy polymer having 20% to 90% siloxane content by weight; and ii) an armor substrate coated with the hybrid polysiloxane coating. The hybrid polysiloxane includes chemical components, e.g., the polysiloxane epoxy polymer, that are covalently bonded to the armor substrate.