Constrained network chains

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... 

Figure 2. Types of constraint in the molecular theories. In the earliest such constraint theoiy (uppermost portion of the figure) the total effects of the constraints were placed on the cross-links themselves. In the subsequent constrained-chains theory, they were placed at the mass centers of the network chains and, in the diffused-constraints theory, along the entire network chains. The lowermost portion of the figure shows how additional experimental information could suggest a more refined placement of the constraints.

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. 

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 simplest case is that of high crosslink density or small coil interpenetration (Np 1). In this case, the restrictions on the configurations of network chains caused by the crosslinks dominate, and the constraints acting on the constraining chains may be omitted in the course of the calculation of the constraining potential. With the assumption of an affine displacement of the crosslink positions with the deformation of the sample, Eq. (12) was obtained with... 

A number of theoretical models use a single-chain approach to simulate topological constraints in real polymer networks. The basic idea is that one starts from the statistical mechanics of a single network chain which is subjected to a spatial domain of constraints. The constraining potential is introduced in a heuristic manner and cannot be calculated within the frame of the chosen model self-consistently. Hence, the strength of the topological interaction must be characterized by best-fit parameters of the model. 

Here k is a parameter which measures the strength of the constraints. For k = 0 we obtain the phantom network limit, and for infinitely strong constraints (k = oo) the affine limit is obtained. Erman and Monnerie [27] developed the constrained chain model, where constraints effect fluctuations of the centers of the mass of chains in the network. Kloczkowski, Mark, and Erman [28] proposed a diffused-constraint theory with continuous placement of constraints along the network chains. 

In Eq. (29.23) W 0) is the distribution of constraints among different points along the network chain and 0 = i/n is the position of the /th segment of the chain as a fraction of the contour length between two crosslinks. If the distribution is uniform, then W 0) = 1 inside the integrand of Eq. (29.23). In the case when constraints are assumed to affect only fluctuations of junctions (as in the constrained-junction theory), 0 is limited to 0 = 0 or 0 = 1 only. [95] It is important to note that this theory does not reduce identically to the constrained-chain theory, because the latter characterizes the deformation-dependent fluctuations of the centers of mass of the chains and not the deformation-independent fluctuations of the midpoints [95]. 

In summary, the common feature of all constrained chain models is that they impose only limited constraints on chain fluctuations. [101] The constrained-junction fluctuation model restricts fluctuations of junctions and of the center of mass of network chains. The diffused constraint model restricts fluctuations of a single randomly chosen monomer for each network strand. Consequently, all these models can only represent the crossover between the phantom and afflne limits. [101] The phantom limit corresponds to a weak constraining case, while the affine limit corresponds to a very strong constraining potential. 

Biodegradable shape-memory polymer networks with single POSS moieties located in the center of the network chains would promote POSS crystallization even within a constraining network structure. Successful synthesis of POSS initiated poly(e-caprolactone) (PCL) telechelic diols, utilizing a POSS diol as initiator, was reported by Lee et al. [116]. The POSS-PCL diols were terminated with acrylate groups and photocured in the presence of a tetrathiol crosslinker. Scheme 1 shows the chemical reaction for the synthesis of POSS-PCL network. 

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 theory successfully describes most of the features of numerous investigations that have been made on stress-strain relationships involving a variety of t5rpes of deformations (1-3,13,220,249-252). Specifically, the decrease in modulus f ] with the increase in elongation is viewed as the deformations becoming more nonaffine as the stretching of the network chains... 

The deformation of polymer chains in stretched and swollen networks can be investigated by SANS, A few such studies have been carried out, and some theoretical results based on Gaussian models of networks have been presented. The possible defects in network formation may invalidate an otherwise well planned experiment, and because of this uncertainty, conclusions based on current experiments must be viewed as tentative. It is also true that theoretical calculations have been restricted thus far to only a few simple models of an elastomeric network. An appropriate method of calculation for trapped entanglements has not been constructed, nor has any calculation of the SANS pattern of a network which is constrained according to the reptation models of de Gennes (24) or Doi-Edwards (25,26) appeared. 

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