The Elasticity of Rubber
Abstract Rubbers, natural and synthetic, are unique in being highly extensible and in retracting forcibly and quickly to substantially their original dimensions when released. It has been found that the stress-strain curves for extension and compression of most of the simplest vulcanizates of natural rubber and the three most important synthetic rubbers are similar in shape. The relationship is expressed by the equation F/M=(L−1−L−2) exp A(L−L−1) where F is the stress, L the ratio of stretched to unstretched length, and M and A are constants. The constant M depends on the nature of the rubber, the extent of vulcanization, and the time of creep. The constant A has a value of about 0.38. By a study of stress-temperature relations it is found that the most important factor in the retraction of stretched rubber is the tendency of long chain flexible molecules to return to a configuration which is statistically more probable than the one which the stretching has forced them to assume. Calculations of entropy changes arising from stretching can be made from probability considerations, and a strain energy function deduced from the entropy changes. Stresses calculated from the strain energy function agree with those observed in compression but are greater than those observed in extension by almost 50 per cent at L=3. A phenomenological approach shows that the strain energy should be expressible as a function of certain quantities called strain invariants, calculable from the deformations. The simplest behavior is found in the region of compression (L less than 1), where the strain energy is merely the first invariant times a constant calculable from the entropy changes. For values of L between 1.5 and 3 a different constant and an added term involving the second strain invariant are required. The explanation of this behavior in molecular terms is one of the most important current problems of rubber elasticity.