Solid propellant systems include a main propellant and a secondary propellant in contact with the first propellant that exhibits autoignition temperatures of at least about 100° F. lower than the autoignition temperature of the main propellant. The secondary propellant of the present invention is most advantageously employed with conventional AP-containing solid propellant formulations as the main propellant, especially formulations containing both AP, an energetic solid, and a binder. In especially preferred forms, the secondary propellant will include a nitramine which is at least one selected from nitroguanidine (NQ), cyclotrimethylene trinitramine (RDX) and cyclotetramethylenetetranitramine (HMX), and a binder which is at least one selected from HTPB, HTPE or glycidyl azide polymer (GAP). Most preferably, the secondary propellant will include a combination of nitramines which includes NQ and one of RDX or HMX.