Ozone Cracking - Ozonolysis

Ozonolysis

The reaction occurring between double bonds and ozone is known as ozonolysis when one molecule of the gas reacts with the double bond:

The immediate result is formation of an ozonide, which then decomposes rapidly so that the double bond is cleaved. This is the critical step in chain breakage when polymers are attacked. The strength of polymers depends on the chain molecular weight or degree of polymerization, the higher the chain length, the greater the mechanical strength (such as tensile strength). By cleaving the chain, the molecular weight drops rapidly and there comes a point when it has little strength whatsoever, and a crack forms. Further attack occurs in the freshly exposed crack surfaces and the crack grows steadily until it completes a circuit and the product separates or fails. In the case of a seal or a tube, failure occurs when the wall of the device is penetrated.

The carbonyl end groups which are formed are usually aldehydes or ketones, which can oxidise further to carboxylic acids. The net result is a high concentration of elemental oxygen on the crack surfaces, which can be detected using Energy-dispersive X-ray spectroscopy in the environmental SEM, or ESEM. The spectrum at left shows the high oxygen peak compared with a constant sulfur peak. The spectrum at right shows the unaffected elastomer surface spectrum, with a relatively low oxygen peak compared with the sulfur peak.