Forced reptation

SAN of 0.040 Jm-2. This small value of r(I) is probably related to the fact that separation of chains at low stress levels occurs in the most favourable sites, the polymer behaves like a visco-elastic fluid. As Fig. 12 shows, with increasing stress more such sites are activated and the scattering vector increases. On the other hand, annealing leads to a deactivation of such sites and to a coarser structure of the formed fibrils [62]. It must be concluded that in this regime no chain scission or forced reptation occur. 

The beauty of the reptation model is that it is able to make predictions about molecular flow both in solution and at fracture by assuming that the molecules undergo the same kind of motions in each case. For both self-diffusion in concentrated solutions and at fracture, the force to overcome in pulling the polymer molecule through the tube is assumed to be frictional. 

The earliest and simplest approach in this direction starts from Langevin equations with solutions comprising a spectrum of relaxation modes [1-4], Special features are the incorporation of entropic forces (Rouse model, [6]) which relax fluctuations of reduced entropy, and of hydrodynamic interactions (Zimm model, [7]) which couple segmental motions via long-range backflow fields in polymer solutions, and the inclusion of topological constraints or entanglements (reptation or tube model, [8-10]) which are mutually imposed within a dense ensemble of chains. 

The reptation model for polymer diffusion would predict that the thickness of the gel phase reflects the dynamics of disentanglement. The important factors here are chain length, solvent quality and temperature since they affect the dimensions of the polymer coils in the gel phase. The precursor phase, on the other hand, depends upon solvency and temperature only through the osmotic force it can generate in the system and the viscoelastic response of the system in the region of the front. These factors should be independent of the PMMA molecular weight. 

Figure 3.2 A mechanical force causes a loss of an entanglement in a covalent polymeric network by one of two major mechanisms process A, chain slippage via reptation process...

Figure 3.3 Entanglement response to a mechanical force in a supramolecular system process A, chain slippage via reptation process B, chain scission via breaking of the supramolecular bond.

Fig. 2.48 Self-diffusion of nearly symmetric diblock copolymers measured using forced Rayleigh scattering (Dalvi et al. 1993). (a) Diffusivities, D, for the lower molecular weight PS-PVP sample, which is disordered at these temperatures, have been scaled down by a factor of 0.48, assumming Rouse dynamics (b) D for the lower molecular weight symmetric PEP-PEE diblock copolymer have been scaled down by a factor of 0.40, assuming reptation dynamics. The solid line indicates a fit of the standard Williams-Landel-Ferry (WLF) temperature dependence to the data for the lower molecular weight sample. Values of M are in g mol1.

One of the most successful models for gel electrophoresis is the reptation theory of Lumpkin and Zimm for the migration of double-stranded DNA (Lumpkin, 1982). An in-depth discussion can be found in Zimm and Levene (1992) for a synopsis see Bloomfield et al. (2000). The velocity v of a charged particle in a solution with an electric field E depends on the electrical force Fei = ZqE, in which Z is the number of charges and q is the charge of a proton, and the frictional force l fr = —fv, in which/is the frictional coefficient. At steady state, these forces balance and the velocity is v = ZqE/f. The electrophoretic mobility fi is the velocity relative to the field strength, fi = vE = Zq/f. 

Extension of this theory can also be used for treating concentrated polymer solution response. In this case, the motion of, and drag on, a single bead is determined by the mean intermolecular force field. In either the dilute or concentrated solution cases, orientation distribution functions can be obtained that allow for the specification of the stress tensor field involved. For the concentrated spring-bead model, Bird et al. (46) point out that because of the proximity of the surrounding molecules (i.e., spring-beads), it is easier for the model molecule to move in the direction of the polymer chain backbone rather than perpendicular to it. In other words, the polymer finds itself executing a sort of a snake-like motion, called reptation (47), as shown in Fig. 3.8(b). 

These equations describe the reptation normal relaxation modes, which can be compared with the Rouse modes of the chain in a viscous liquid, described by equation (2.29). In contrast to equation (2.29) the stochastic forces (3.47) depend on the co-ordinates of particles, equation (3.48) describes anisotropic motion of beads along the contour of a macromolecule. 

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