Strength of Elastomers. A Perspective

The strength and extensibility of an elastomer depend on its overall viscoelastic properties, as reflected in the time and temperature dependence of stress-strain curves, and also on those discrete processes, including crack formation and growth, that culminate in high-speed crack propagation. The discrete processes determine the lifetime of a specimen; the viscoelastic characteristics affect the dependence of stress on deformation. The interplay between these effects causes strength and extensibility to depend strongly on test conditions. An elastomeric network composed solely of highly mobile chains is very weak indeed and fractures at a low elongation. This characteristic differs diametrically from that expected of an idealized network of mobile chains. If such a network were stretched, stress concentrations and unbalanced forces at the molecular level, which can result from short chains, entanglements, and network imperfections, would be vitiated rapidly by stress-biased segmental diffusion, especially at the elevated temperature. Therefore the network should be able to withstand a high elongation and thus a high stress. Hence, the low strength always exhibited by a single-phase non-crystallizable elastomer at elevated temperatures is incompatible with the characteristics ascribed to a network in the molecular theory of rubber elasticity. A network of mobile chains is weak for two reasons. First, microcracks develop readily in a stretched specimen. Their formation is usually attributed to stress concentrations near heterogeneties either within or on the surface of a specimen. Second, and most importantly, a microcrack—once it forms—encounters little resistance to growth because the chains are highly mobile. High strength results not because microcracks do not develop but because their growth is impeded. Unless processes that impede growth come into play, a microcrack enlarges rapidly and catastrophic propagation soon follows. When chain mobility is relatively low, the dissipation of energy through viscoelastic processes near the tip of a slowly growing crack retards its progressive growth. But this source of strength is rather ineffective except within narrow ranges of temperature and extension rate, or time scale more generally. Thus, high strength and toughness result from other mechanisms that impede crack growth. Effective mechanisms usually come into play and impart toughness if colloidal particulate fillers or plastic domains are present, except at low concentration.