Butyl and bromobutyl inner tubes, specified by the Aerospace Standard AS50141 for military aircraft, were thermally aged from 40 to 120 °C for varying lengths of time and then their hardness and mechanical properties were measured. 1H double quantum nuclear magnetic resonance (DQ NMR) was used to elucidate crosslink density and distribution changes. Time–temperature superposition of the aged data coupled with the Arrhenius approach was used to determine an approximate shelf life. High (80–120 °C) and low (40–80 °C) temperature oxidation processes were occurring for both rubbers. Below 80 °C, an increase in crosslink density, hardening, stiffening, and loss of elongation was observed. Plasticizer and volatile loss contributes to compound stiffening. Sulfur crosslink network modifications during thermal aging can explain ultimate property loss and stiffness increase. Diffusion limited oxidation was taking place above 80 °C, with the development of a thin oxidized layer composed of ionic crosslinking that affected both hardness and mechanical properties. For butyl rubber, the hardness rise stabilizes as do the ultimate properties, likely due to the proliferation of chain scission reactions, whereas crosslinking reactions prevailed over chain scission events for bromobutyl rubber. Crosslink density and defect fractions B and C as measured through DQ NMR were in agreement with the physical property testing results. The degree of heterogeneity of the network as perceived visually through DQ NMR regularization increases upon exposure to higher temperatures and longer aging times due to the broadening of the crosslink density distribution. Similar Arrhenius activation energies were calculated for the low and high temperature oxidation process for butyl and bromobutyl rubbers. The projected shelf life for the butyl and bromobutyl inner tubes was 10 and 20 yr, respectively. For the first time, DQ NMR testing results (crosslink density and its distribution, defect level) have been successfully applied to support a shelf life determination.

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