This work reports a direct surface analysis of ozonization of vulcanized NR compounds by ATR. On ozonization of a vulcanized NR compound without clay filler or AO a degraded rubber layer, which contains ozonides and carbonyl compounds, is formed on the surface. This reaction is considerably slower than that of raw NR. When clay filler is added, the first effect is a decrease of rubber on the surface and a corresponding increase in the surface concentration of clay. With further ozone exposure, ozonides and carbonyl compounds appear. When a compound containing N,N′-dioctyl-p-phenylenediamine AO is ozonized, a film is seen, which has an ATR spectrum essentially identical to that of the ozonized liquid AO. There is no evidence of ozonized NR products, or of complex reaction products between AO and ozonized NR. These results are consistent with a scavenger or protection-layer mechanism for antiozonant protection.
This work reports a direct surface analysis of ozonization of carbon black loaded NR compounds by ATR and SEM. On ozonization of raw NR or NR containing carbon black, a thick layer builds up consisting of ozonides and carbonyl compounds. It is suggested that this layer is composed principally of the reaction products of ozone with unsaturated fatty acids and unsaturated fatty acid esters found in NR. On ozonization of cured and uncured carbon black loaded NR compounds containing curatives, the NR is attacked causing a decrease of rubber on the surface and a corresponding increase in the surface concentration of carbon black. The thick ozonide/carbonyl layer did not form, probably due to the coordination of the fatty acids and esters with ZnO, which was added with the curatives. On ozonization of carbon black-loaded NR compounds containing N,N′-dioctyl-p-phenylenediamine antiozonant, a continuous film is seen by SEM which has an ATR spectrum essentially identical to ozonized antiozonant. There is no evidence of ozonized NR products, or of complex reaction products between antiozonant and ozonized NR. These results are consistent with a dual scavenger and protective layer mechanism for antiozonant protection.
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