1,4 Polybutadiene rubber failure

A base polymer particularly interesting for studying the effect of the aforementioned mechanisms on rubber failure is polybutadiene. In fact, polybutadiene microstructure can be changed in an extremely wide range, by making use of the host of catalyst systems. developed by the ingenuity of chemists, just starting with the same monomer. 

Although elastomers are usually amorphous, strain-induced crystallization occurs in rubbers such as cA-l,4-polybutadiene, butyl rubber, and NR. Crystallization under stress, discovered 200 years ago [239], increases the modulus and most failure properties of rubber and is essential to performance in many... 

Hanson, D. E. Martin, R. L., How Ear Can a Rubber Molecule Stretch Before Breaking Ah Initio Study of Tensile Elasticity and Failure in Single-Molecule Polyisoprene and Polybutadiene. J. Chem. Phys. 2009,130, 064903. 

The cross-link density of the polymer network, as well as its properties, depend on the functionality, the length and the chemical nature of the polyene (R ) and thiol (R) prepolymer chains, and it can thus be tailored as desired. Low-modulus polymers suitable for adhesive applications were obtained by using aliphatic prepolymer chains, in particular with polybutadiene-based elastomers which were cross-linked very efficiently by UV-irradiation in the presence of a tri- or tetrathiol [45-48]. As only a few cross-links need to be formed between the polymer chains to make the rubber insoluble, low concentrations of thiol (2 wt%) proved to be sufficient to achieve an effective and fast cross-finking. Hardening was found to hardly occur upon UV-curing (increase of the Persoz hardness from 40 to 55 s), which is essential to ensure outstanding adhesion. At the same time, the shear adhesion failure temperature (SAFT) increased from 80 to 160°C, due to the formation of the chemical network (Fig. 4). 

Cohesive failure was found to be the predominant mode of failure for each rubber compound containing Saret 633 (Figure 8.7). Therefore, it would be expected that as the Saret 633 concentration is increased, the rubber compound would become stronger due to additional crosslinking, which would result in an increase in adhesive strength at the interface between rubber and substrate. This proved to be the case and is shown in Figure 8.8 for EPDM bonded to untreated steel. As the Saret 633 concentration was increased from 0 to 20 phr, the shear adhesion increased from approximately 0.55 MPa for the control to over 11.0 MPa. Cohesive failure was the predominant mode of failure at each concentration. Similar performance was observed for other rubbers, such as nitrile, natural, polybutadiene, silicone and hydrogenated nitrile. 

The question now arises which fracture processes, if any, are strongly affected by the local chemical structure Two examples are considered below tearing and crack growth, and abrasive wear. Under certain conditions these failure processes are found to depend upon particular features of the elastomer molecule and they are therefore distinctly different, even for closely-related chemical structures. Natural rubber can usefully be compared with cis 1, 4-polybutadiene in this respect, because, although their chemical structures are superficially similar, large differences are observed in their resistance to tearing and in the mechanism of wear. 

We have discussed above the uncured properties of a synthetic rubber which are similar to those of NR. A major difference between the rubbers is that the synthetic SBR has better thermal oxidative resistance than NR. Under oxidative ageing conditions, 1,4-polybutadiene structure tends to crosslink to a greater extent relative to undergoing chain scission. The reverse is the case for NR (cw-l,4-polyisoprene structure). The greater resistance to oxidative degradation of HTSBR vulcanizates is indicated by a comparison of plots of flex life (cycles to failure) of HTSBR and NR versus strain amplitude, shown in Fig. 34. 

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