Overview and Some Fundamental Information

Abstract

This chapter is a brief overview of the topics treated in the book. It is aimed, in particular, at providing some qualitative information on rubber elasticity theories and their relationships to experimental studies, and at putting this material into context. The following chapter describes in detail the classical theories of rubber elasticity, that is, the phantom and affine network theories. The network chains in the phantom model are assumed not to experience the effects of the surrounding chains and entanglements, and thus to move as “phantoms.” Although this seems to be a very severe approximation, many experimental results are not in startling disagreement with theories based on this highly idealized assumption. These theories associate the total Helmholtz free energy of a deformed network with the sum of the free energies of the individual chains—an important assumption adopted throughout the book. They treat the single chain in its maximum simplicity, as a Gaussian chain, which is a type of “structureless” chain (where the only chemical constitution specified is the number of bonds in the network chain). In this respect, the classical theories focus on ideal networks and, in fact, are also referred to as “kinetic” theories because of their resemblance to ideal gas theories. Chain flexibility and mobility are the essential features of these models, according to which the network chains can experience all possible conformations or spatial arrangements subject to the network’s connectivity. One of the predictions of the classical theories is that the elastic modulus of the network is independent of strain. This results from the assumption that only the entropy at the chain level contributes to the Helmholtz free energy. Experimental evidence, on the other hand, indicates that the modulus decreases significantly with increasing tension or compression, implicating interchain interactions, such as entanglements of some type or other. This has led to the more modern theories of rubber elasticity, such as the constrained-junction or the slip-link theories, which go beyond the single-chain length scale and introduce additional entropy to the Helmholtz free energy at the subchain level.