Ozone cracking

Cracks can be formed in many different elastomers by ozone attack, and the characteristic form of attack of vulnerable rubbers is known as ozone cracking. The problem was formerly very common, especially in tires, but is now rarely seen in those products owing to preventive measures.

However, it does occur in many other safety-critical items such as fuel lines and rubber seals, such as gaskets and O-rings, where ozone attack is considered unlikely. Only a trace amount of the gas is needed to initiate cracking, and so these items can also succumb to the problem.

Susceptible elastomers

Tiny traces of ozone in the air will attack double bonds in rubber chains, with natural rubber, polybutadiene, styrene-butadiene rubber and nitrile rubber being most sensitive to degradation. Every repeat unit in the first three materials has a double bond, so every unit can be degraded by ozone. Nitrile rubber is a copolymer of butadiene and acrylonitrile units, but the proportion of acrylonitrile is usually lower than butadiene, so attack occurs. Butyl rubber is more resistant but still has a small number of double bonds in its chains, so attack is possible. Exposed surfaces are attacked first, the density of cracks varying with ozone gas concentration. The higher the concentration, the greater the number of cracks formed.