Entanglement in Cross-linked Systems

Analysis of networks in terms of molecular structure relies heavily on the kinetic theory of rubber elasticity. Although the theory is very well established in broad outline, there remain some troublesome questions that plague its use in quantitative applications of the kind required here. The following section reviews these problems as they relate to the subject of entanglement. 

The kinetic theory of rubber elasticity is so well known and exhaustively discussed (17, 27, 256-257, 267) that the remarks here will be confined to questions which relate only to its application in determining the concentration of elastically effective strands. In principle, both network swelling properties and elasticity measurements can provide information on network characteristics. However, swelling measurements require the evaluation of an additional parameter, the polymer-solvent interaction coefficient. They also involve examining the network in two states, one of which differs from its as-formed state. This raises some theoretical difficulties which will be discussed later. Questions on local non-uniformity in swelling (17) also complicate the interpretation. The results described here will therefore concern elasticity measurements alone. 

If no volume or internal energy changes accompany deformation, the network is neo-Hookean (258), obeying the constitutive equation 

The proportionality factor G is the equilibrium shear modulus of the network, given by 

The front factor g as defined above5 is unity in all the earlier theories (17). Recently Duiser and Staverman (233) have obtained g = j and Imai and Gordon (259) g — 0.54 with Rouse model theories which make no a priori assumptions about the junction point locations after deformation. Edwards (260) also arrives at and Freed (261) deduces that g= 1 is an upper bound by similar approaches. The front factor usually assumed in the shifted relaxation theory of the plateau modulus is g = 1, although Chompff and Duiser (232) obtain g = j through their extension of the Duiser-Staverman result to entanglement networks. The physical reasons for the different values of g in different treatments are not clear at present. 

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Contents Chain Configuration in Amorphous Polymer Systems. Material Properties of Viscoelastic Liquids. Molecular Models in Polymer Rheology. Experimental Results on Linear Viscoelastic Behavior. Molecular Entan-lement Theories of Linear iscoelastic Behavior. Entanglement in Cross-linked Systems. Non-linear Viscoelastic-Properties. 

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