Polyurethane adhesive and aluminum alloy were selected to make adhesive joints. Butt joints tested at different loading angles (0°, 45°, and 90°) using a modified Arcan fixture were selected to represent three stress states (normal stress, normal/shear combined stress, and shear stress, respectively). Firstly, the accelerated aging tests were carried out on the joints in a hygrothermal environment (80 °C/95% RH). The quasi-static tests were carried out at different temperatures (−40 °C, 20 °C, and 80 °C) for the joints after hygrothermal aging for different periods. The variation rules of the joints’ mechanical properties and failure modes with different aging levels were studied. The results show that the failure load of the joints was obviously affected by stress state and temperature. In the low-temperature test, the failure load of the joints decreased most obviously, and the BJ was the most sensitive to temperature, indicating that the failure load decreased more with the increase of the normal stress ratio in the joint. Through macroscopic and SEM analysis of the failure section, it was found that the hydrolysis reaction of polyurethane adhesive itself and the interface failure of the joints were the main reasons for the decrease of joint strength. The failure models were established to characterize the adhesive structure with different aging levels at service temperature.
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