Disclosed herein are methods and formulations for the microencapsulation of aminosiloxanes, for example for use as an additive in protective material formulations such as those used in the protection and/or joining of metal substrates. The additives may be used in conjunction with a second reactant that may or may not be similarly microencapsulated for self-healing (and associated corrosion resistance) or delayed cure applications, or they may be used alone or in conjunction with other corrosion inhibitors for protective formulations with improved corrosion resistance on appropriate substrates.