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Polybenzoxazine aerogels have gained much attention as a new type of polymeric aerogels in the field of flame resistant materials. Herein, a unique method for the preparation of fiber-reinforced PBa composite aerogels has been reported using polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) as dispersion carriers through freeze-drying for surface modified basalt fibers (Z@BF). Bisphenol-A type benzoxazine (Ba) monomer was used as the matrix, which infiltrated into the carrier for dispersed fibers to obtain a PBa composite gel by sol-gel method. Solvent exchange and ambient drying techniques were used to obtain the final composite aerogel samples. Z@BF formed a double-network structure with the aerogel matrix, which resulted in 55.43% increase in compressive strength, a low volumetric shrinkage (27.46%), and density (0.19–0.21 g cm 3) of the prepared aerogel. The addition of Z@BF increased the residual carbon content (59.6% at 800 °C) in the aerogel, while reducing the total heat release rate by 36.9% and the peak heat release rate by 60.61%. Besides, the aerogels possessed excellent self-extinguishing property, and the self-extinguishing time was only 1.31 s after flame burning at 1200 ℃ for 10 s. The composite aerogels obtained by this combination of atmospheric pressure drying and freeze-drying techniques not only possessed high mechanical strength and excellent flame retardant properties, but also provided a new idea for the preparation of fiber-reinforced PBa aerogels. This would further expand the potential use of PBa aerogels in flame retardant materials. [Display omitted] • A polybenzoxazine composite aerogels system capable of effectively dispersing fibers with flame retardant properties is designed. • Basalt fibers enhanced mechanical and flame retardant properties of polybenzoxazine composite aerogels are realized. • The polybenzoxazine composite aerogels have excellent self-extinguishing properties and low combustion shrinkage upon flame ignition (1200°C). • The polybenzoxazine composite aerogels have a low peak heat release rate of 115.5 kW/m2. [ABSTRACT FROM AUTHOR]

In this work, exfoliated α-zirconium phosphate (α-ZrP) and phosphated cellulose (PCF) were employed to synthesize poly(vinyl alcohol) composite aerogels (PVA/PCF/α-ZrP) with excellent flame retardancy through the multi-directional freezing method. The peak heat release rate (PHRR), total smoke release (TSR), and CO production (COP) of the (PVA/PCF10/α-ZrP10-3) composite aerogel were considerably decreased by 42.3%, 41.4%, and 34.7%, as compared to the pure PVA aerogel, respectively. Simultaneously, the limiting oxygen index (LOI) value was improved from 18.1% to 28.4%. The mechanistic study of flame retardancy showed evidence that PCF and α-ZrP promoted the crosslinking and carbonization of PVA chains to form a barrier, which not only served as insulation between the material and the air, but also significantly reduced the emissions of combustible toxic gases (CO2, CO). In addition, the multi-directional freezing method further improved the catalytic carbonization process. This mutually advantageous strategy offers a new strategy for the preparation of composite aerogels with enhanced fire resistance. [ABSTRACT FROM AUTHOR]