We analyze the evolution of the sensitivity of a TATB composition after thermal cycles at elevated temperatures. Sensitization due to thermal cycles is of variable magnitude depending on the kind of the second stimulus (mechanical or thermal). In order to investigate the possible mechanisms which govern these phenomena, we perform an extensive study of the evolution of the chemistry and microstructure of our composition and we determine the sensitivity of our explosive to various stimuli after various temperature/duration cycles. This first paper is devoted to the study of TATB chemical evolutions. We present the results obtained for explosive decomposition, furazan generation, gas analyses and solid residue characterization.