The basic technology for forming crosslinked elastomers by the end linking of low molecular weight hydroxyl-terminated poly(dimethylsiloxane) (PDMS) with tetraethoxysilane (TEOS) was modified to make it suitable for preparing coatings for controlled drug release. The requirements for this application included establishing conditions for the end linking that did not require the usual toxic tin or platinum catalysts; preparation of emulsions of small PDMS network particles that had extensive shelf-lives and that could be coalesced into cohesive thin films or coatings; and the determination of the conditions to make such coatings pinhole free, mechanically robust, and of sufficient thermal stability for coating procedures at elevated temperatures. The approach taken consisted of preparing water-based emulsions of the PDMS with sodium lauryl sulfate and restriction of the pH of the system to the acidic range with HCl. Evaporation of water from the emulsions resulted in elastomeric free-standing films of the PDMS that were characterized using stress-strain isotherms in elongation and equilibrium swelling in toluene, both at room temperature. The mechanical properties of the films were found to improve with an increasing molar ratio of HCl/TEOS and an increase in the amount of TEOS (giving increased degrees of crosslinking). Conditions for the optimization of the thermal stabilities as gauged by thermogravimetic analysis were established, including beneficial effects from the introduction of the crosslinks. Scanning electron microscopy showed that the predominant morphology was void-free films with very small, homogeneously dispersed silica particles from the hydrolysis of some of the TEOS. Additional work should be facilitated by the mechanisms for the crosslinking suggested by the experimental results. (C) 2003 Wiley Periodicals, Inc.