Rubbers ozone cracking

When diene rubbers are exposed to ozone under stressed conditions cracks develop which are perpendicular to the direction of stress. Whilst ozone must react with unstressed rubber no cracking occurs in such circumstances nor when such rubber is subsequently stressed after removal of the ozone environment. For many years such rubbers were protected by waxes which bloomed on to the surface of the rubber to form an impermeable film. This was satisfactory for static applications but where the rubber was operating under dynamic conditions the wax layer became broken and hence less effective. 

Ozone cracking is a physicochemical phenomenon. Ozone attack on olefinic double bonds causes chain scission and the formation of decomposition products. The first step in the reaction is the formation of a relatively unstable primary ozonide, which cleaves to an aldehyde or ketone and a carbonyl. Subsequent recombination of the aldehyde and the carbonyl groups produces a second ozonide [58]. Cross-linking products may also be formed, especially with rubbers containing disubstituted carbon-carbon double bonds (e.g. butyl rubber, styrene-butadiene rubber), due to the attack of the carbonyl groups (produced by cleavage of primary ozonides) on the rubber carbon-carbon double bonds. 

ISO 1431, Parts 1-3, Rubber, vulcanized or thermoplastic - Resistance to ozone cracking, 1989-2000. 

Standard method of test for accelerated ozone cracking of vulcanized rubber [Test method D-1149-64 (reapproved 1970)], pp. 554-560. In 1972 Annual Book of ASTM Standards. Part 28. Rubber Carbon Black Gaskets. Philadelphia American Society for Testing and Materials, 1972. 

Ozone attacks C=C in unsaturated compounds including olefins, cycloolefins, pinenes, aromatics, and polybutadienes (for example, causing rubber to crack). 

Haagen-Smit, A. J., M. F. Brunelle, and J. W. Haagen-Smit, Ozone Cracking in the Los Angeles Area, Rubber Chem. Technol., 32, 1134-1142(1959). 

Natural rubber is a polymer of isoprene- most often cis-l,4-polyiso-prene - with a molecular weight of 100,000 to 1,000,000. Typically, a few percent of other materials, such as proteins, fatty acids, resins and inorganic materials is found in natural rubber. Polyisoprene is also created synthetically, producing what is sometimes referred to as "synthetic natural rubber". Owing to the presence of a double bond in each and every repeat unit, natural rubber is sensitive to ozone cracking. Some natural rubber sources called gutta percha are composed of trans-1,4-poly isoprene, a structural isomer which has similar, but not identical properties. Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is vulcanized it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it shares properties of both, i.e., if it is heated and cooled, it is degraded but not destroyed. 

The ozone concentration in the atmosphere is only a few pphm. In certain chemical plants as in electrolytic mercury cell houses in the chloralkali industry, the ozone concentration is higher. Although the atmospheric ozone level is low, it reacts with rubber double bonds rapidly and causes cracking of rubber products. Especially when rubber is under stress (stretching and bending as in the case of flexible cell covers), the crack development is faster. Neoprene products resist thousands of parts per hundred million of ozone for hours without surface cracking. This nature of neoprene is quite suitable for cell house application in chlor-alkali industries. Natural rubber will crack within minutes when subjected to ozone concentration of only 50 pphm. 

Vulcanized rubber was ozonized as follows. Natural rubber was compounded with the ingredients shown in Table III and cured at 141 °C. for 13 minutes. The vulcanizates were cut off from the sheets with JIS No. 1 dumbbell cutter to obtain the specimens for the ozone crack test. The test pieces were exposed to an oxygen atmosphere containing 0.01% ozone under an elongation of 50%, and a time, t0, required for the initial crack formation was measured. 

The above units are randomly arranged in emulsion copolymers, but in solution the polymers may occur in uniform blocks of varying length. These block copolymers are resilient and rubber-like at room temperature, but are thermoplastic at higher temperatures. SBRs are similar to natural rubber, in that they are susceptible to atmospheric oxidation and ozone cracking when stretched in air. They are swollen and weakened by hydrocarbons and halogenated hydrocarbons. However, their resistance to abrasion and ageing is superior to natural rubber. 

Butyl rubber like Hypalon, Neoprene or nitrile rubber is a speciality polymer which can be compounded for a soft, deformable elastic vulcanisate similar to the other elastomers, but having certain distinctive characteristics, like low permeability to all gases and resistance to ageing and ozone cracking. Butyl has poor oil resistance and medium low temperature flexibility. 

Butyl rubber consists mostly of isobutylene (95-98%) and about 2-5% isoprene units. 1 The isoprene unit is halogenated by either chlorine or bromine to obtain the corresponding halobutyl rubbers. Despite the superior elastomeric properties of halobutyl, the elastomer can easily undergo dehydrohalogenation leading to crosslinfang, and the isoprene unsaturation is subject to ozone cracking. To remedy these problems and to improve the halobutyl properties, a new class of elastomer poly(isobutylene-co-p-methylstyrene) [poly (IB-PMS)] was developed. Unlike butyl rubber, it contains no double bonds and therefore cannot be crosslinked unless otherwise functionalized. The chemical structures of butyl rubber and poly (IB-PMS) copolymers are shown below. 

Stress rupture tests on test pieces are very important under conditions where, in addition to the stress, the atmosphere is chosen to accelerate failure. The best known t> pe of test is a test of the so-called environmental. stress cracking of plastics, where the aggressis e atmosphere is a chemical that causes cracking when the material is in a strained state. These tests are usually considered as a form of chemical resistance test and are cosered in Chapter 14. Ozone cracking of rubber, also an environmental resi.stance test, is another example. 

Rubbers having main chain unsaturation can undergo ozone cracking when test pieces are exposed to atmospheric traces of ozone at an elongation above a characteristic threshold strain [63]. For most diene rubbers this strain is typically around 5% in the absence of any protective agent, although under dynamic strain conditions it can be reduced to less than 1%. Antiozonant materials are added to rise the threshold strain above the maximum strain encountered in service life or alternatively, as is usually the case in dynamically strained applications, to reduce the rate of crack growth. 

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