Self-motion Stars

The Vlasov-Newton equation has many steady solutions describing a self-gravitating cluster. This is easy to show in the spherically symmetric case (the situation we shall restrict in this work, except for a few remarks at the end of this section). If one assumes a given r(r) in the steady state, the general steady solution of Eq. (4) is a somewhat arbitrary function of the constants of the motion of a single mass in this given external held, namely a funchon/(E, I ) where niE is the total energy of a star in a potenhal (r) such that r(r) = —(r/r) [d r)/dr] and where — (r.v) is the square of the... 

For both linear and star polymers, the above-described theories assume the motion of a single molecule in a frozen system. In polymers melts, it has been shown, essentially from the study of binary blends, that a self-consistent treatment of the relaxation is required. This leads to the concepts of "constraint release" whereby a loss of segmental orientation is permitted by the motion of surrounding species. Retraction (for linear and star polymers) as well as reptation may induce constraint release [16,17,18]. In the homopol5mier case, the main effect is to decrease the relaxation times by roughly a factor of 1.5 (xb) or 2 (xq). In the case of star polymers, the factor v is also decreased [15]. These effects are extensively discussed in other chapters of this book especially for binary mixtures. In our work, we have assumed that their influence would be of second order compared to the relaxation processes themselves. However, they may contribute to an unexpected relaxation of parts of macromolecules which are assumed not to be reached by relaxation motions (central parts of linear chains or branch point in star polymers). 

The result is that diffusion in branched-chain polymers is much slower than in linear chains. For rings, diffusion is even more sluggish, because the ring is forced to collapse into a quasihnear conformation in order to have center-of-mass motion. Since many commercial polymers are branched or star-shaped, the self-diffusion of the polymer is correspondingly decreased, and the melt viscosity increased. 

In the case of star polymers as test chains, the more the number of arms, the smaller the possibility for stars to be detached from the matrix once they are attached to the matrix over much longer periods. Even though star test chains are smaller, their motions are still hindered by other entangled polymer coils. If most star test chains participate in the entanglement, the amount of "free" stars is too small to be detected. So the CONTIN analysis did not show two modes for LPS84, but we do not want to deny the possible existence of self-diffusion of star test chains because I I of LPS84 evidently deviated from the single exponential decay. 

Finally, we remark that the idea of self-consistent dynamic dilution was applied first by Marrucci [20] to the case of monodisperse linear polymers, and was then adapted by BaU and McLeish [11] to monodisperse stars. We also note that theories combining reptation, primitive path fluctuations, and constraint release by dynamic dilution have been applied successfully by Milner and McLeish and coworkers to monodisperse linear polymers [21], monodisperse stars [13], bimodal star/star blends [22], and star/linear blends [23], as well as H-branched polymers [24], and combs [25]. The approach taken for all these cases is similar at early times after a small step strain, the star arms and the tips of linear molecules relax by primitive path fluctuations and dynamic dilution. At some later time, if there are linear chains that reach their reptation time, there is a rapid relaxation of these linear chains. This produces a dilation of the effective tubes that surround any remaining unrelaxed star arms by constraint-release Rouse motion (see Section 7.3). Finally, after dilation has finished, the primitive path fluctuations of remaining portions of star arms begin again, in the dilated tube. We refer to this set of theories for stars, linears, and mixtures thereof as the Milner-McLeish theory . The details of the Milner-McLeish theory are beyond the scope of this work, but the interested reader can learn more from the original articles as well as from McLeish and Milner [26], McLeish [14], Park and Larson [27], and by Watanabe [19]. 

---