Rubbers with olefinic double bonds, and rubber goods based on them, are destroyed by ozone. Crack formation can be retarded by adding antiozonants. The mechanism of the antiozonant effect has not yet been fully explained. The mechanism by which bis-(1,2,3,6-tetrahydrobenzaldehyde)-pentaerythrityl acetal (AFS), a nonstaining antiozonant, hinders the ozonation of polychloroprene has been described. AFS competes with the double bonds in the polymer for the available ozone. Additionally, the resulting ozonization products prevent the ozone from penetrating into the polymer matrix. This mechanism was corroborated by carrying out kinetic measurements of the competing reactions in solution and in the rubber. The findings were confirmed by studying model substances with basic structures identical to AFS but with modified active groups.

Intermittent stress relaxation is well suited for quantifying aging processes in rubber. For NR, the effects of different antioxidants can be measured by the rates at which the modulus falls. In synthetic rubbers (SBR, NBR, and CR), it can be measured through the modulus increases caused by oxygen crosslinking. Equal-value times, e.g., t0.75 for NR and t1.25 for SBR, NBR, and CR, are the times taken by the modulus to decrease or increase to a given percentage of its original level. They are better measures of aging than the modulus change after a given time. For NR, it has been shown that stress relaxation measurements at elevated temperatures and in pure oxygen correlate with the results of conventional aging methods. Thus the testing times can be drastically reduced—from up to 28 days to 1–8 hours. Discontinuous stress relaxation measurements are considerably more accurate and selective than conventional oxygen aging. For the repeatability of a single equal-value time measurement, we obtained a coefficient of variation (s/x) of 5–10% for stress relaxation measurement and about ±20% for oxygen aging. The degree of selectivity for oxygen aging and stress relaxation was found to be 3.6 and 18, respectively. The correlation between the results of stress relaxation measurements and those of the conventional oxygen and hot air aging tests was investigated for a large number of NR compounds and for some SBR, NBR, and CR compounds. The correlation is not very good, but it must be remembered that the equal-value times determined according to the two methods show relatively pronounced variability. With the conventional aging methods, the results also depend on what quantity is measured, e.g., the change in tensile strength or hardness, and on what equal-value time is chosen, e.g., the time taken by the property concerned to decrease to 90 or 75% of its original value. The conclusion of the investigations described above is that intermittent modulus measurement is an interesting high-speed method for the assessment of aging behavior. It will acquire a firm position in the arsenal of rubber testing methods, but will probably supplement, and not completely replace, the aging methods currently used.