A primer includes a layered thermite coating comprising alternating layers of metal oxide and reducing metal (thermite) deposited upon a substrate. The layered thermite coating may include a primary ignition portion adjacent to the substrate, and a secondary ignition portion deposited on the primary ignition portion. The alternating thermite layers may be thinner within the primary ignition portion than in the secondary ignition portion. The primary ignition portion is structured for sensitivity to a firing pin strike to the opposite side of the substrate. The secondary ignition portion is structured to burn at a rate that will ignite smokeless powder or other ignitable substances used in munitions.