Primitive tube path

Figure 5.26. Running along the centre of the tube is a primitive chain. This is the shortest path down the tube. The deviations of the polymer chain from this path can be considered as defects. The motion of these kinks or defects in the chain away from the primitive path allows the chain to move within the tube. The polymer creeps through the tube, losing its original constraints and gradually creating a new portion of tube. This reptilian-like motion of the chain was named by de Gennes from the Latin reptare, to creep, hence reptation.

As in Sect. 2.1, Dj is the curvilinear centre-of-mass diffusion constant of the chain, and is given in terms of the monomeric friction constant by the Einstein relation Dj =kT/Nl. L is as before the length of the primitive path, or tube length of the chain, which is Finally, we need the initial condition on p(s,t), which... 

The chain tension arises in a physical way at timescales short enough for the tube constraints to be effectively permanent, each chain end is subject to random Brownian motion at the scale of an entanglement strand such that it may make a random choice of exploration of possible paths into the surrounding melt. One of these choices corresponds to retracing the chain back along its tube (thus shortening the primitive path), but far more choices correspond to extending the primitive path. The net effect is the chain tension sustained by the free ends. 

Motion within the tube is achieved by a random walk ( primitive path ) of unit steps of the order of the tube diameter, a. When a straight reptation tube is considered, for simplicity, reptation diffussional motion of the chain out of the tube is represented schematically in the steps depicted from Fig. 3.9(d)(i) to Fig. 3.9(d)(v). 

The tube itself is a random walk, each step of which has length a. This random walk is called the primitive path of the chain. The contour length of the tube, or the primitive path, is therefore Lj — aMfMg. For polymers of high molecular weight, the tube s contour length is much less than the contour length of the chain (see Fig. 3-24). Thus, the chain meanders about the primitive path. Some values for the tube diameter a for typical polymer melts are presented in Table 3-3. 

Despite these complications, there are now numerous evidences that the tube model is basically con-ect. The signatory mark that the chain is trapped in a tube is that the chain ends relax first, and the center of the chain remains unrelaxed until relaxation is almost over. Evidence that this occurs has been obtained in experiments with chains whose ends are labeled, either chemically or isotopically (Ylitalo et al. 1990 Russell et al. 1993). These studies show that the rate of relaxation of the chain ends is distinctively faster than the middle of the chain, in quantitative agreement with reptation theory. The special role of chain ends is also shown indirectly in studies of the relaxation of star polymers. Stars are polymers in which several branches radiate from a single branch point. The arms of the star cannot reptate because they are anchored at the branch point (de Gennes 1975). Relaxation must thus occur by the slower process of primitive-path fluctuations, which is found to slow down exponentially with increasing arm molecular weight, in agreement with predictions (Pearson and Helfand 1984). 

The Doi-Edwards model has been extended to allow processes of primitive-path fluctuations, constraint release, and tube stretching. These extensions of the theory allow accurate prediction of many steady-state and time-dependent phenomena, including shear thinning, stress overshoots, and so on. Predictions of strain localization and slip at walls... 

We may also obtain the mean-square tube radius by requiring that the mean-square end-to-end distance of the chain is given by a sum of independent contributions along the primitive path and between the chain ends and... 

Evans, in a numerical simulation exploring primitive paths for random walks which interpeiKtrate an obstade lattice, also found an expoi ntial distribution of surplus sequence lengths A term similar to Eq. 48 appears in tte Doi-Edwards expression for the distribution of chain along a tube defined by a quadratk confinii wtential (Eq. A. 6, Ref. 3). 

Each monomer is constrained to stay fairly close to the primitive path, but fluctuations driven by the thermal energy kT are allowed. Strand excursions in the quadratic potential are not likely to have free energies much more than kT above the minimum. Strand excursions that have free energy kT above the minimum at the primitive path define the width of the confining tube, called the tube diameter a (Fig. 7.10). In the classical affine -and phantom network models, the amplitude of the fluctuations of a... 

A chain or network strand (thick curve) is topologically constrained to a tube-like region by surrounding chains. The primitive path is shown as the dashed curve. The roughly quadratic potential defining the tube is also sketched. 

The average contour length (L) of the primitive path (the centre of the confining tube, see Fig. 7.10) is the product of the entanglement strand length a and the average number of entanglement strands per chain N/N. ... 

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