Polyimide Aerogels with Excellent Thermal Insulation, Hydrophobicity, Machinability, and Strength Evolution at Extreme Conditions

High performance polyimide aerogels (PIA) are highly desirable as a part of thermal protection systems for aircraft. However, the large drying shrinkage and insufficient thermal insulation of PIA limit their practical applications in the aerospace field. Herein, the strategy of two-step prepolymerization and polycondensation route was proposed to fabricate PIA with ultralow drying shrinkage, outstanding thermal insulation, hydrophobicity, machinability, compressive strength in cryogenic/high-temperature atmospheres, flame resistance, and fantastic dimensional stability. In more detail, the drying shrinkage rate of PIA series can be lowered to 1.84%, mainly owing to the strengthened skeletons by chemical bond formation and physical entanglement of molecular chains. Excellent thermal insulation is reflected upon keeping an ink drop state as long as 265 s despite placing it on a cold surface with a temperature of −196 °C. PIA-O2B2 are imparted with hydrophobic properties (with water contact angle of 135°) depending on the hydrogen-bonding interaction between polyimide networking chains and 1H,1H,2H,2H-perfluorodecyltriethoxysilane that was introduced. In addition, the exceptional flame retardant is endowed completely, which is attributed to the evidence of the presence of aromatic ring structures in constructing the aerogel. The high-temperature shrinkage rate of PIA series is as low as 4.81% due to the relative small free volume of the molecular chains. Our study would provide a method for designing ultralow drying shrinkage and superb thermal insulation in cryogenic conditions for PIA in aerospace uses.