Probing the Curing Reaction of HTPB Propellant with Low-Field NMR

Hydroxyl-terminated polybutadiene (HTPB) propellants are widely used in aerospace applications owing to their excellent mechanical performance and storage stability, which are primarily governed by the crosslinked network formed during curing. Understanding the evolution of this network is therefore essential for optimizing propellant formulations and curing parameters. In this work, the curing behaviors of HTPB-based propellant slurries employing two representative curing agents, toluene diisocyanate (TDI) and isophorone diisocyanate (IPDI), were systematically investigated under isothermal conditions at 60 °C using low-field nuclear magnetic resonance (LF-NMR), combined with infrared spectroscopy, dynamic mechanical analysis, and macroscopic mechanical testing. The curing time and crosslink density of both propellant systems were quantitatively determined by LF-NMR crosslink densitometry, while transverse relaxation time measurements were used to monitor the mobility evolution of different molecular segments during curing. The results show that with increasing curing time, the crosslink density and crosslinked chain content progressively increased, whereas the free chain content decreased, accompanied by a transient increase and subsequent decrease in dangling chains. The curing endpoints of the HTPB/TDI and HTPB/IPDI propellants were determined to be approximately 1.25 days and 5.5 days, with corresponding final crosslink densities of 2.438 × 10⁻⁴ and 2.007 × 10⁻⁴ mol mL⁻¹, respectively. Excellent agreement between LF-NMR results and complementary characterization techniques confirms LF-NMR as an effective tool for studying curing reaction and network evolution in complex solid propellant systems.