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Ultra‐small‐ and small‐angle neutron scattering techniques were employed to quantify thermally driven changes to the microstructure of the TATB‐based composite high explosive, PBX 9502. Samples of PBX 9502 were studied in‐situ at temperatures ranging from 25 to 220 °C and after re‐equilibration at ambient temperature. Significant changes to the void size and morphology within the PBX 9502 microstructure...