Ultrahigh thermoresistant polybenzimidazole films with uniform pores and hard craters on the surface were prepared by a silica template method. The pore and crater formation enhanced elongation and Young's modulus.

Polybenzimidazoles are one of the most thermally and chemically stable polymers due to their rigid chemical structure with π-π stacking and conjugated bonding. Poly(2,5-benzimidazole) (ABPBI), the simplest structure of polybenzimidazole, was synthesized, but the cast film was not homogeneous and featured thick brown areas, which limited their further application. Silica nanospheres were adapted as porogen to generate nanopores in the ABPBI film by successive etching with hydrofluoric acid. As a result of air-composite formation, the ABPBI film became homogeneous and its surface roughness was reduced from 10.0 to 2.5 nm. The obtained air-composite ABPBI film had more favorable mechanical properties than the original film. An air-composite film prepared with 50 wt % silica content had a tensile strength of 128 MPa and an elongation at break of 23%, both of which values were approximately twice as high as the corresponding values of the original film.

Transitions seen in the electric properties of water-absorbable poly(2,5-benzimidazole) (ABPBI) films were confirmed by electric conductivity, dielectric constant, and time-domain nuclear magnetic resonance (NMR) measurements. The electric resistance of the films was measured at room temperature using a high-resistance meter, and the dielectric constant at room temperature was measured using an LCR meter in the frequency range of 90 Hz to 8 MHz. The water absorption ratio at equilibrium absorption for the films was 37%, which corresponded to a volume fraction of water of 0.33. The electric conductivity of the films without water absorption was ~1014 S·cm−1, and it increased to ~1010 S·cm−1 with increasing volume fraction, showing a percolation threshold at a volume fraction of 0.025, and remarkable transitions at volume fractions of 0.075 and 0.135. The dielectric constant of the films without water absorption was 3.4, and it increased to 8.1 with increasing volume fraction, showing a transition only at a volume fraction of 0.135. Above a volume fraction of 0.075, where a transition in conductivity was observed, there were two relaxation times at 18–31 μs and 20–93 μs, as determined from the time-domain NMR, and these relaxation times increased with increasing volume fraction. The longer relaxation time increased significantly at a volume fraction of 0.072, which was close to the volume fraction of the transition seen in conductivity. The relationship between the chain mobility of ABPBI and the deterioration in electric insulating properties is discussed.

Polybenzimidazole (PBI) is a high-performance polymer known for its excellent thermal stability, mechanical strength, and chemical resistance, attributes that are derived from its unique structure comprising repeated benzene and imidazole rings. However, limitations such as relatively low thermal stability and moisture sensitivity restrict its application as a super engineering plastic. In this study, amide groups are incorporated into the PBI backbone to synthesize the copolymer poly(BI-co-A), effecting a structural modification at the molecular level. Additionally, silica nanospheres were composited into the poly(BI-co-A) film to further enhance its thermal performance. The resulting composite films exhibited remarkable thermal stability, with the temperature for 10% weight loss reaching as high as 761 °C. To address increased water absorption due to the high hydrophilicity of hydroxyl groups on the silica nanospheres’ surface, a dehydration treatment was applied in an electric furnace. This treatment produced a highly thermoresistant poly(BI-co-A) nanocomposite film with reduced wettability, making it suitable for applications in humid environments.