Using dual-cure architectures in HNBR: A detailed insight into their structure-property relationship

Hydrogenated acrylonitrile–butadiene rubber (HNBR) is widely used in automotive and sealing applications due to its oil resistance and mechanical durability; however, its long-term performance is significantly influenced by the curing chemistry. Sulfur vulcanization offers superior elasticity but restricted thermal stability, while peroxide curing improves heat resistance at the expense of flexibility. In this study, we investigate hybrid sulfur–peroxide curing to integrate these benefits. The hybrid pathway encompasses competitive and sequential processes, such as partial radical quenching and accelerator oxidation, resulting in a dual crosslink network. Dynamic mechanical, thermal, and temperature scanning stress relaxation (TSSR) evaluations demonstrate that hybrid systems provide precise modulation of the operational temperature–frequency range, broaden the glass-transition relaxation, and control stress dissipation. The coexistence of sulfur and C–C crosslinks results in a heterogeneous structure characterized by diverse crosslink densities and bond energies, leading to numerous relaxation modes and an optimal blend of elasticity, strength, and thermal stability. Microscopy confirms the absence of phase separation, indicating that hybrid vulcanization is a viable approach for producing robust, high-performance HNBR elastomers.