The Constrained Junction Model

More recent network models of rubber elasticity by Ronca and Allegra [11] and Hory and Erman [12] are based on the phantom network model but assume that the junction point fluctuations are restricted due to the presence of entanglements. The strength of the constraints is defined by a parameter 

Later refinements of the constrained junction model place the effects of the constraints on the centres of mass of the network chains [13] or consider distributing the constraints continuously along the chains [14]. 

---

The constrained-junction model was formulated in order to explain the decrease of the elastic moduli of networks upon stretching. It was first introduced by Ronca and Allegra [39], and Flory [40]. The model assumes that the fluctuations of junctions are diminished below those of the phantom network because of the presence of entanglements and that stretching increases the range of fluctuations back to those of the phantom network. As indicated by the second part of Equation (26), the fluctuations in a phantom network are substantial. For a tetrafunctional network, the mean-square fluctuations of junctions amount to as much as half of the mean-square end-to-end vector of the network chains. The strength of the constraints on these fluctuations is measured by a parameter k, defined as... 

The elastic free energy of the constrained-junction model is given by the expression... 

The elastic free energy of the constrained-junction model, similar to that of the slip-link model, is the sum of the phantom network free energy and that due to the constraints. Both the slip-link and the constrained-junction model free energies reduce to that of the phantom network model when the effect of entanglements diminishes to zero. One important difference between the two models, however, is that the constrained-junction model free energy equates to that of the affine network model in the limit of infinitely strong constraints, whereas the slip-link model free energy may exceed that for an affine deformation, as may be observed from Equation (41). 

According to the arguments based on the constrained-junction model, the term Gch should equate to the phantom network modulus onto which contributions from entanglements are added. 

This refinement of the constrained-junction model is based on re-examination of the constraint problem and evaluation of some neutron-scattering estimates of actual junction fluctuations [158, 159]. It was concluded that the suppression of the fluctuations was over-estimated in the theory, presumably because the entire effect of the inter-chain interactions was arbitrarily placed on the junctions. The theory was therefore revised to make it more realistic by placing the effects of the constraints along the network-chain contours, specifically at their mass centers [4, 160, 161]. This is illustrated in the second portion of Figure 2. Relocating the constraints in this more realistic way provided improved agreement between theory and experiment. 

The constraining potential represented by virtual chains must be set up so that the fluctuations of junction points are restricted, but the virtual chains must not store any stress. If the number of monomers in each virtual chain is independent of network deformation, these virtual chains would act as real chains and would store elastic energy when the network is deformed. A principal assumption of the constrained-junction model is that the constraining potential acting on junction points changes with network deformation. In the virtual chain representation of this con-... 

The constrained junction model has virtual chains (thin lines) connecting each network junction (circles) to the elastic background (at the crosses). 

The constrained-junction model relies on an additional parameter that determines the strength of the constraining potential, and can be thought of as the ratio of the number of monomers in real network strands and in wirtual chains NjnQ. If this ratio is small, the virtual-chain is relatively long... 

MORE ADVANCED MOLECULAR THEORIES 4.4.1 The Constrained Junction Model... 

Equation (4.39) shows that for nonzero values of the parameter k the shear modulus of the constrained-junction model is larger than the phantom network shear modulus. For the affine limit, k -t- oo, the shear modulus is... 

Experimental determination of the contributions above those predicted by the reference phantom network model has been controversial. Experiments of Oppermann and Rennar (1987) on endlinked poly(dimethylsiloxane) networks, represented by the dotted points in Figure 4.4, indicate that contributions from trapped entanglements are significant for low degrees of end-linking but are not important when the network chains are shorter. Experimental results of Erman and Wagner (1980) on randomly crosslinked poly(ethyl acrylate) networks fall on the solid line and indicate that the observed high deformation limit moduli are within the predictions of the constrained-junction model. 

The models presented in the previous section are of an elementary nature in the sense that they ignore contributions from intermolecular effects (such as entanglements that are permanently trapped on formation of the network). Among the theories that take account of the contribution of entanglements are (1) the treatment of Beam and Edwards [19] in terms of topological invariants, (2) the slip-link model [20, 21], (3) the constrained-]unction and constrained-chain models [22-27], and (4) the trapped entanglement model [11,28]. The slip-link, constrained-junction, and constrained-chain models can be studied under a common format as can be seen from the discussion by Erman and Mark [7]. For illustrative purposes we present the constrained-junction model in some detail here. We then discuss the trapped entanglement models. 

In real polymer network the effects of excluded volume and chain entanglements should be taken into account. In 1977 Hory [26] formulated the constrained junction model of real networks. According to this theory fluctuations of junctiOTs are affected by chains interpenetration, and as the result the elastic free energy is a sum of the elastic free energy of the phantom network AAph (given by Eq. (5.78)) and the free energy of constraints AA ... 

Sharaf, M. A. Kloczkowski, A. Mark, J. E., Networks Undergoing Strain-Induced Crystallization. Analysis in Terms of the Constrained-Junction Model. Comput. Polym. Sci. 1992,2,84-89. 

---