Pearson-Helfand

It has been shown by Doi [11] that on the time scale of Tg contour length fluctuations may induce a rapid relaxation of chain ends, especially for moderately long chains. Indeed, wiggling motions involve forward and backward motions of the chain ends. Thus, chain length fluctuations in oriented materials lead to the creation of isotropic parts of tubes at each end. Their fractional length is roughly equal to 1.3(N e) > where N is the number of monomers per chain. An elaborate expression for the relaxation due to this mechanism, based on the Pearson-Helfand picture for star pol5uners [12], has been proposed by Viovy [13]. 

All these observed characteristics of viscoelasticity for star polymers are natural consequences of the tube model. As suggested by the sketch in Fig. 3.49, the presence of even one long branch would surely suppress reptation [53]. There is no longer any direction for the star to move freely into new positions and conformations, and accordingly relaxation and diffusion must occur by some other motion. The Pearson-Helfand theory for stars based on tube-length fluctuations alone [72]... 

Following the initial discovery [27] that rj0 depends on just arm molecular weight for star polymers with sufficiently high levels of branching, this type of dependence was confirmed by others both theoretically [32] and experimentally [33]. Pearson and Helfand [32] predicted that the zero shear viscosity of star polymers should scale with arm molecular weight (Afa) as... 

The spectroscopic data have been compared with the theoretical predictions of the Doi- Edwards model. In the time scale of our experiments, a quantitative agreement between experiment and theory is obtained if chain length fluctuations, retraction and reptation are taken into account. In the case of star polymers, the large scale fluctuation mechanism as proposed by Pearson and Helfand associated with the retraction process is accounting for... 

Pearson and Helfand [12] used a somewhat similar approach to determine the characteristic relaxation time for a branch to disentangle their calculation leads to a similar form, with a different exponent for the front factor ... 

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 predictions of the storage and loss moduli that are obtained from these relaxation processes are in excellent agreement with experiment (see Fig. 3-38). The predicted exponential dependences of the longest relaxation time and zero-shear viscosity on the arm molecular weight are also well-confirmed experimentally (Pearson and Helfand 1984 Fetters et al. 1993), as is the insensitivity of these quantities to the number of arms at fixed... 

L fluctuates in time as the chain (or snake) moves. A full description of chain dynamics requires knowledge of the probability distribution of the primitive path lengths. This problem has been solved exactly by Helfand and Pearson in 1983 for a lattice model of a chain in a regular array of... 

The basic idea, proposed by de Gennes [23], is that relaxation mechanism of linear pendant chains is governed by the reptation or snake-like motion of the chains retracting along their primitive path from the free end to the fixed one. This model proposed that the relaxation time of pendant chains should increase exponentially with the number of entanglements in which it is involved. Pendant chains must then contribute to viscoelastic properties for frequencies greater than the inverse of reptation times. Tsenoglou [26], Curro and Pincus [27], Pearson and Helfand [24] and Curro et al. [25] developed models for the relaxation of pendant chains in random cross-linked networks. 

Following Pearson and Helfand [24], the time necessary for reptation of a pendant chain is ... 

Pearson DS, Helfand E. Viscoelastic properties of star-shaped polymers. Macromolecules. 1984 17 888-95. 

---