The present paper relies on the original idea to design multifunctional coatings, and in particular highly efficient intumescent flame retardant coatings, based on the diffusion of polyphosphates (PSPs) in exponentially growing "layer-by-layer" films made from montmorillonite (MMT) and poly(allylamine) (PAH). Here, we used polyphosphates as an acid source, polyallylamine as both a carbon source and a swelling agent, and finally clays to reinforce the intumescent char strength and also for their oxygen barrier property. The coatings made from the alternated deposition of n = 60 layer pairs of PAH and MMT reach a considerable thickness of ∼18 μm with well-defined ordering of the MMT in the direction parallel to the substrate. Structural, morphological, mechanical, gas barrier, and fire resistance properties of these films have been studied. Excellent oxygen barrier properties and extraordinary fire resistance properties are demonstrated based on the basis of a strong increase of the time to ignition and on a decrease of the heat release rate of polylactide substrates during mass loss calorimeter tests. This new and innovative intumescent flame retardant system based on (PAH-MMT)(n)-PSP coatings is a promising universal treatment for current polymeric materials.
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