*Burak Erman and James E. Mark*

- Published in print:
- 1997
- Published Online:
- November 2020
- ISBN:
- 9780195082371
- eISBN:
- 9780197560433
- Item type:
- chapter

- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780195082371.003.0010
- Subject:
- Chemistry, Materials Chemistry

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 ...
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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.
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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.