Experimental and theoretical investigations on petroleum-based elastomers with two cross-linking systems of different lengths viewed as bimodal networks

A review with 36 references discussing the chemistry and the structure-property relationship of elastomers cured with two cross-linking systems of different chain lengths such as sulfur and the polymerization products of p-benzoquinone and viewed as bimodal networks. These exceptional networks have shown remarkable improvements in the overall mechanical properties which are anticipated to be due to the non-Gaussian effects known for bimodal networks and evident by the anomalous upturn in the modulus values in Mooney-Rivlin stress-strain data representations. Proton and ¹³C NMR as well as energy minimization calculations were used to study the chemical structures and single chain contributions of polyquinones. Nuclei bending of these oligomers have shown to be greatly influenced by the restricted torsional behavior due to the presence of the hydrogen bonds between the benzenoid nuclei. Intrinsic atomic-level forces for the networks were evaluated using molecular dynamics techniques and showed that while the forces acting on the junction points of the cross-linking segments and the elastomeric chains had no apparent change as a consequence of the networks' bimodal formation, forces acting on the short chains of the bimodal networks are of much higher values as compared to those of unimodal networks. The presence of the relatively long polyquinone chains in the bimodal networks has caused the short sulfur chains to stretch to its maximum extensibility and no longer can increase its end-to-end distance separation by simple rotations about its skeletal bonds. Limited chain extensibility of the short chains resulting from the deformation of the bond angles and bond lengths has lead to higher potential energies. Studies on the swollen bimodal networks have validated the above conclusions since swelling of the networks will prevent the elastomeric chains from undergoing possible strain-induced crystallization during the stress-strain experiments and any abnormalities in the mechanical behavior of these networks must be therefore the result of the limited extensibility of the short chains of the networks.