Microwave frequency electromagnetic properties are critical for understanding and predicting the heating and ignition behavior of explosives subjected to microwave irradiation. In this work we report relative complex permittivity measurements in the X‐band (8–12 GHz) for 13 neat explosives measured by the circular cavity technique. This data set was then used in conjunction with COMSOL 4.3 Multiphysics® finite element analysis software to design and simulate a low power (100 W), high electric field X‐band microwave applicator. The role of the sample holder on our ability to directly study the response of explosives to electromagnetic energy is examined and shown to be critical. Times to ignition were predicted for PETN, TATB, and HMX and indicate that for the proposed applicator and considered properties ignition may occur in less than one second exposure. These predictions show that explosives can be effectively heated in short time scales through direct microwave heating without absorptive binders or inclusions.

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