A comprehensive study of the synergistic flame retardant mechanisms of halloysite in intumescent polypropylene

This work aims to evaluate the efficiency of halloysite as synergistic agent in an intumescent PP system based on a coated ammonium polyphosphate (IFR). The first part of the study analyses the thermal stability and fire performance of PP when using the intumescent formulation alone or in combination with the aluminosilicate nanotubes (HNTs). Cone calorimetry reveals that partial substitution of IFR by HNTs (3 wt.%) imparts substantial improvement in flame retardancy with reduced heat release rate and longer burning times. Additionally, a shift from V-1 to V-0 classification is achieved at the UL-94 test with only 1.5 wt.% HNTs. The second part provides a better understanding of the physical and chemical mechanisms of action of HNTs in the intumescent systems. The chemical evolution of the condensed phase during combustion is described by solid state NMR, and in particular using 2D NMR. Results indicate that halloysite speeds up the development of the intumescent shield, but also enhances its mechanical properties by physical reinforcement (i.e. aluminosilicate "skeleton-frame" for the phosphocarbonaceous structure) and/or by chemical interactions with IFR yielding to aluminophosphates. These new chemical species allow thermal stabilization of the char at high temperatures and provide good macro- and micro-structural properties. Both effects increase the mechanical strength of the protective layer during burning ensuring excellent heat and mass transfer limitations between gas and condensed phases. (C) 2013 Elsevier Ltd. All rights reserved.