Thermal aging of hydroxy-terminated polybutadiene/isophorone diisocyanate (HTPB/IPDI)-based polyurethane was studied as a function of NCO/OH ratio (1.0 and 0.85). Samples were aged in air ovens at ...50, 60, 65, and 70 degree C for periods of time from 1 to 34 weeks. Changes in chemical (swelling testing and FT-IR spectroscopy) and mechanical (tension testing and hardness) properties were evaluated throughout the aging assays. Correlation between equilibrium swelling ratio and clastic modulus, coupled with changes in FT-IR spectra, indicated oxidative cross-linking as the dominant mechanism for both molar ratios investigated. However, determination of Arrhenius activation energy resulted in values of (82 plus or minus 10) kJ.mol super(-1) and (156 plus or minus 30) kJ.mol super(-1) for 1.0 and 0.85 NCO/OH ratios, respectively, thus revealing faster oxidative degradation kinetics for higher urethane linkage networks.
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