Simultaneous enhancement in thermal conductivity and flame retardancy of flexible film by introducing covalent bond connection

Abstract

Owing to the high interface thermal resistance and aggregation in polymer-based materials, the thermal conductivity of multi-walled carbon nanotubes (MWCNTs) has been severely decreased in practical applications. In this work, an amino-functionalized black phosphorene (BP–NH 2 ) fabricated by ball milling has been employed to react with carboxylated multi-wall carbon nanotubes (MWCNTs–COOH) via covalent bonds to prepare a nanofiller (BP–MWCNTs) with high thermal conductivity and excellent flame retardancy. When incorporating 20.0 wt% BP–MWCNTs into cellulose nanofiber (CNF), the CNF/BP–MWCNTs 20.0 shows an in-plane thermal conductivity of 22.38 ± 0.39 W m −1 K −1 and a cross-plane thermal conductivity of 0.36 ± 0.03 W m −1 K −1 , resulting in an anisotropy index of 62.17. The effective medium theory (EMT) calculation demonstrates the interface thermal resistance is reduced to 1/39 that of pure MWCNTs, which is ascribed to the covalent bond between BP–NH 2 and MWCNTs–COOH. Simultaneously, the CNF/BP–MWCNTs 20.0 can pass the testing of UL-94 V-0 grade and the limiting oxygen index (LOI) value can be increased from 18.1% to 29.9%. Its peak of heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), CO generated per second (COP) and CO 2 generated per second (CO 2 P) are decreased by 37.47%, 43.51%, 50.00%, 35.29%, 50.00% and 19.70%, respectively, which is due to the formation of an intumescent flame-retardant system rich in carbon source (MWCNTs), acid source (BP) and gas source (amino groups). This covalent linkage strategy offers a new thought for the preparation of flexible materials to enhance the thermal conductivity and fire resistance. • Aminated black phosphorene was successfully fabricated by ball milling. • Interface thermal resistance was significantly reduced. • Desirable thermal conductivity was obtained. • Efficient intumescent flame-retardant system was prepared.