A desorption electrospray ionization mass spectrometry study of aging products of diphenylamine stabilizer in double-base propellants

Double-base propellants consisting of nitrocellulose, nitroglycerin and stabilizer undergo chemical and physical changes upon aging, leading to changes in ballistic power and presenting explosive hazards. During aging, PTFE seals of the glass ampoules used in the aging studies undergo a yellow discoloration. This report studies the discoloration of the liners using desorption electrospray ionization (DESI), a gentle surface analysis technique based on electrospray ionization. The color bodies in the PTFE liners were identified by DESI together with tandem mass spectrometry to be the nitrated derivatives of the diphenylamine stabilizer: dinitro-, trinitro-, and tetranitrodiphenylamine. While increased nitration decreases vapor pressure of the DPA species, an increase in solubility in the PTFE liners occurs. This may account for these species not previously being observed during early aging studies as they are preferentially absorbed into the liners, which were not extracted prior to high performance liquid-chromatography analysis.