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• great reactivity of montmorillonite (oMMT) in presence of phosphates. • formation of different Al-O-P and Si-O-P compounds. • mechanism of fire behaviour occurred in the condensed phase. • formation of a charred structure that reduced the fuel production. In the first part of this work, novel elastomeric panels with paraffin for thermal energy storage applications were developed. Ethylene-Propylene Diene Monomer (EPDM) rubber filled with a shape-stabilized paraffin, as phase change material with a melting temperature of 28 °C, was covered with a nitrile-butadiene rubber (NBR) envelope. In order to improve the fire resistance, two selected flame retardants (FRs) were dispersed both in the EPDM core and in the NBR envelope. In this work, the combustion residues from cone calorimeter tests were analysed by various techniques to explain the combustion mechanisms and the interaction of FRs. Nuclear magnetic resonance (NMR) evidenced the complexity of the system, characterized by the formation of char, by the reactivity of organomodified montmorillonite (oMMT) in presence of phosphates and structural rearrangements of the inorganic components. The use of a flame retardant based on ammonium polyphosphate and synergistic agents (based on phosphorus) led to formation of different Al-O-P and Si-O-P compounds. The X-ray diffraction (XRD) analysis highlighted that the formation of silicon phosphate, from the reaction of ammonium polyphosphate and oMMT, was possible only at high phosphorus contents. From the phosphorus content detected through energy dispersive X-ray spectroscopy (EDX) it was possible to indicate that the phosphorus remained in the condensed phase during the combustion. [ABSTRACT FROM AUTHOR]

• Fly ash (FA) and flame retardants were evaluated to fire retard polylactide. • Partial substitution of FR systems by FA allowed to improve the fire performance. • Interactions between flame retardants and FA were observed and new components are identified by XRD and NMR. For a long time, fly ash has been considered as pure waste of coal power plants. Nevertheless, unique properties and compositions that vary with the material's origin make fly ash appealing as an engineering material in various applications. Thus, the opportunity to reduce the environmental footprint of polylactide through the incorporation of fly ash as a component of flame retardant systems has been investigated. Combinations of fly ash with ammonium polyphosphate and/or melamine polyphosphate were made for a global loading of 25 wt% with various rates of substitution of the flame retardants. Fire performance has been studied from cone calorimeter experiments as well as the use of pyrolysis combustion flow calorimeter (PCFC) and the UL94V test. The interpretation of the fire retardant mechanisms has been performed through the examination of cone calorimeter residues by scanning electronic microscopy, X-ray microanalysis, X-ray diffraction (XRD) and multinuclear solid-state NMR. It can be shown that fly ash is mainly composed of spherical particles which are thermally stable at cone calorimeter tests when used alone in PLA. Conversely, fly ash behaves as a reactive component with both flame retardants, leading to the formation of new crystalline and amorphous compounds as shown by XRD and NMR. Synergistic effects in fire performance resulting from the reactive behavior of fly ash can be highlighted and are ascribed to fire retardant mechanisms acting in the condensed phase, and corresponding to the conservation of high phosphorus contents in the condensed phase. [ABSTRACT FROM AUTHOR]