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The term “gel” has been used in a wide variety of contexts, and there have been difficulties in reaching an all-inclusive, workable definition for it. Perhaps the simplest way to proceed is to list some of its most important characteristics: It is a solidlike material that when deformed responds in the manner of a typical elastic body, but generally with a very small modulus. If it does show plastic flow, then this occurs above a threshold value of the stress, with full recoverability below this limit. It typically consists of two or more components: one a liquid in substantial quantity, and the other generally a polymeric network. One of the most direct ways of obtaining a gel is to place a network into a solvent known to be capable of dissolving the network chains in the absence of cross-links. In fact, a unique property of a highly extensible elastomer (resulting from a low degree of cross-linking) is its ability to swell greatly when exposed to a good solvent. A gel with less than 10-6 mol cm-3 of cross-links, for example, may increase its volume more than thousandfold when immersed in a suitable solvent. The extent to which such a network will swell depends specifically not only on the degree of cross-linking, but also on the interactions between the chains and the solvent. While the degree of cross-linking is established during the preparation of a network, the extent of the interaction of chains and solvent may be modified as desired, and therefore the degree of swelling may be controlled. A gel can be made to swell or shrink continuously by changing the quality of the solvent with which it is in contact. Alternatively, it may go through critical conditions and, in fact, can exhibit phase transitions, depending on the type of the polymer-solvent interaction and the extent of cross-linking. The discrete shrinkage of the gel, by changing the polymer-solvent interaction parameter, is a volume phase transition similar to the gas-liquid transition of a condensing gas. The possibility of such phase transitions was, notably, first discussed by Dusek and collaborators many years ago. Their treatment was confined to nonionic networks.

The classical theories of rubber elasticity presented in chapter 2 are based on a hypothetical chain which may pass freely through its neighbors as well as through itself. In a real chain, however, the volume of a segment is excluded to other segments belonging either to the same chain or to others in the network. Consequently, the uncrossability of chain contours by those occupying the same volume becomes an important factor. This chapter and the following one describe theoretical models treating departures from phantom-like behavior arising from the effect of entanglements, which result from this uncrossability of network chains. The chains in the un-cross-linked bulk polymer are highly entangled. These entanglements are permanently fixed once the chains are joined during formation of the network. The degree of entanglement, or degree of interpenetration, in a network is proportional to the number of chains sharing the volume occupied by a given chain. This is quite important, since the observed differences between experimental results on real networks and predictions of the phantom network theory may frequently be attributed to the effects of entanglements. The decrease in network modulus with increasing tensile strain or swelling is the best-known effect arising from deformation-dependent contributions from entanglements. The constrained-junction model presented in this chapter and the slip-link model presented in chapter 4 are both based on the postulate that, upon stretching, the space available to a chain along the direction of stretch is increased, thus resulting in an increase in the freedom of the chain to fluctuate. Similarly, swelling with a suitable diluent separates the chains from one another, decreasing their correlations with neighboring chains. Experimental data presented in figure 3.1 show that the modulus of a network does indeed decrease with both swelling and elongation, finally becoming independent of deformation, as should be the case for the modulus of a phantom network. Rigorous derivation of the modulus of a network from the elastic free energy for this case will be given in chapter 5. The starting point of the constrained-junction model presented in this chapter is the elastic free energy.

In the constrained-junction model presented in chapter 3, intermolecular correlations were assumed to suppress the fluctuations of junctions. According to this model, the elastic free energy of a network varies between the free energies of the phantom and the affine networks. In a second group of models, to be introduced here, there is a constraining action of entanglements along the chains that may further contribute to the elastic free energy, as if they were additional (albeit temporary) junctions. Consequently, the upper bound of the elastic free energy of such networks may exceed that of an affine network. Since the entanglements along the chain contour are explicitly taken into account in the models, they are referred to as the constrained-chain models. The idea of constrained-chain theories originates from the trapped-entanglement concept of Langley, and Graessley, stating that some fraction of the entanglements which are present in the bulk polymer before cross-linking become permanently trapped by the cross-linking and act as additional cross-links. These trapped entanglements, unlike the chemical cross-links, have some freedom, and the two chains forming the entanglement may slide relative to one other. The two chains may therefore be regarded as being attached to each other by means of a fictitious “slip-link,” as is illustrated schematically in figure 4.1. The entangled system of chains representing the real situation is shown in part (a), and the representation of two entangled chains in this system joined together by a sliplink is shown in part (b). The slip-link may move along the chains by a distance a, which is inversely proportional to the severity of the entanglements. A model based on this picture of slip-links was first proposed by Graessley, and a more rigorous treatment of the slip-link model was given by Ball et al. and subsequently simplified by Edwards and Vilgis; section 4.1 describes this latter treatment in detail. In section 4.2, we present the extension of the Flory constrained junction model to the constrained-chain model by including the effects of constraints along chains, following Erman and Monnerie. One of the newest approaches, the diffused-constraints model, is then described briefly in section 4.3.

The classical theories of rubber elasticity are based on the Gaussian chain model. The only molecular parameter that enters these theories is the mean-square end-to-end separation of the chains constituting the network. However, there are various areas of interest that require characterization of molecular quantities beyond the Gaussian description. Examples are segmental orientation, birefringence, rotational isomerization, and finite extensibility, and we will address these properties in the following chapters. One often needs a more realistic distribution function for the end-to-end vector, as well as for averages of the products of several vectorial quantities, as will be evident in these chapters. The foundations for such characterizations, and several examples of their applications, are given in this chapter. Several aspects of rubber elasticity (such as the dependence of the elastic free energy on network topology, number of effective junctions, and contributions from entanglements) are successfully explained by theories based on the freely jointed chain and the Gaussian approximation. Details of the real chemical structure are not required at the length scales describing these phenomena. On the other hand, studies of birefringence, thermoelasticity, rotational isomerization upon stretching, strain dichroism, local segmental orientation and mobility, and characterization of networks with short chains require the use of more realistic network chain models. In this section, properties of rotational isomeric state models for the chains are discussed. The notation is based largely on the Flory book, Statistical Mechanics of Chain Molecules. More recent information is readily found in the literature. Due to the simplicity of its structure, a polyethylene-like chain serves as a convenient model for discussing the statistical properties of real chains. This simplicity can be seen in figure 8.1, which shows the planar form of a small portion of a polyethylene chain. Bond lengths and bond angles may be regarded as fixed in the study of rubber elasticity because their rapid fluctuations are usually in the range of only ±0.05 A and ±5°, respectively. The chain changes its configuration only through torsional rotations about the backbone bonds, shown, for example, by the angle for the ith bond in figure 8.1.