Effect of Strain-Induced Crystallization on the Elastomeric Properties of Cis-1,4-Polybutadiene Networks

Abstract Polymer networks, when studied at very high elongations, frequency show anomalous stress-strain isotherms in that they exhibit values of the modulus or “reduced force” [ƒ*] which increase markedly with increasing elongation. Such isotherms depart appreciably from the form predicted by the molecular theories of rubberlike elasticity and from the Mooney—Rivlin representation adopted from phenomenological arguments as well. For this reason, the interpretation of the increase in [ƒ*] at high elongations has been of great interest for a considerable period of time. For several decades now, this behavior has generally been attributed to the limited extensibility of the network chains. Critical examination of various published results pertinent to this question, in conjunction with more definitive experimental studies reported recently, however, support the alternative suggestion that such atypical isotherms are due to strain-induced crystallization. One experiment particularly relevant to this issue is the study of the stress-strain isotherms of a polymer network as a function of temperature. Such experiments have been carried out on natural rubber, but the relatively poor thermal stability of this polymer and the extent to which its melting point is increased by elongation make it essentially impossible to study the high elongation stress-strain relationships for this polymer at a temperature sufficiently high to ensure complete suppression of strain-induced crystallinity. Similar experiments carried out on networks of a more suitable polymer, polyisobutylene, gave stress-strain isotherms showing the upturn in the reduced force at low temperature, but not at higher temperatures, thus strongly implicating strain-induced crystallization as the origin of this anomalous behavior. These experiments, however, suffered somewhat from the one shortcoming that the increase in temperature required to suppress the upturn in [ƒ*] also decreased the maximum extensibility of the network to below the elongation at which the upturn occurred at the lower temperatures.