AbstractWhatever the state of the iron compounds as smoke suppressant during the combustion of poly(vinyl chloride), they lead rapidly to native αFe2O3in the char residue left after dehydrochlorination. It causes incandescence of the char residue and catalyzes its oxidation into carbon monoxide and carbon dioxide that contributes to decreasing the amount of available carbon for the soot formation after self‐ignition. FeCl2and FeCl3are the precursors of αFe2O3, which is the true compound as smoke suppressant. Nevertheless, as intermediate, iron chlorides are able to modify the degradation processes, and they favor the formation of light tars instead of heavy tars. For that reason the iron compounds cause the formation of smoke at lower temperature than for pure PVC, but, as αFe2O3is formed, the smoke production levels off and then decreases. The higher the ease of the iron compounds to give chlorides through reaction with HCI and further native αFe2O3, the higher the ease of the additive to cause the oxidation of the char residue sooner and in consequence to decrease the smoke level. In the PVC combustion three main steps may be distinguised: dehydrochlorination step between 200–300°C; tars aerosols formation from the char residue between 300°C and self‐ignition; at temperature higher than self‐ignition, formation of soot from the previous tars
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