Alginates (nickel alginate, NiA; copper alginate, CuA; zinc alginate, ZnA) and 3-aminopropyltriethoxysilane (APTES) were alternately deposited on a magnesium hydroxide (MH) surface by the spray-drying-assisted layer-by-layer assembly technique, fabricating some efficient and environmentally benign flame retardants (M-FR, including Ni-FR, Cu-FR, and Zn-FR). The morphology, chemical compositions, and structures of M-FR were investigated. With 50 wt % loading, compared with EVA28+MH, the peak heat release rate, smoke production rate, and CO production rate of EVA28+Ni-FR decreased by 50.78%, 61.76%, and 66.67%, respectively. The metals or metal oxide nanoparticles arising from alginates could catalyze the pyrolysis intermediates of EVA into graphene and amorphous carbon, which could bind the inorganic compounds (the decomposition products of MH and APTES) together and form some more protective barriers. For each M-FR, the flame retardant and smoke suppression efficiency were different, which were caused by the diverse carbonization and graphitization behaviors of three alginates. ZnA generated some ZnO aggregations and could not catalyze the graphitization of intermediates. For CuA, the catalytic graphitization was limited by the tightly binding graphene layer. As for NiA, the configuration of the Ni atom could not provide strong binding of Ni substrate and carbon. The liquid-like Ni nanoparticles could restructure and get out from firm graphene shells, so the catalytic graphitization of NiA was efficient and sustainable. This work displayed the catalytic graphitization mechanism of alginates while exploring a simple and novel strategy for fabricating efficient green flame retardants.
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