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Segmental diffusion local melting

The other important physical assumption is that the friction is local (hydro-dynamic interactions are screened in the melt [2]) so that D -(N /N)D with the diffusion constant in the melt of an unentangled chain of segments. Now the characteristic relaxation (Rouse) time of an entanglement segment % is just a /D. so that... [Pg.205]

Abstract The discussion of relaxation and diffusion of macromolecules in very concentrated solutions and melts of polymers showed that the basic equations of macromolecular dynamics reflect the linear behaviour of a macromolecule among the other macromolecules, so that one can proceed further. Considering the non-linear effects of viscoelasticity, one have to take into account the local anisotropy of mobility of every particle of the chains, introduced in the basic dynamic equations of a macromolecule in Chapter 3, and induced anisotropy of the surrounding, which will be introduced in this chapter. In the spirit of mesoscopic theory we assume that the anisotropy is connected with the averaged orientation of segments of macromolecules, so that the equation of dynamics of the macromolecule retains its form. Eventually, the non-linear relaxation equations for two sets of internal variables are formulated. The first set of variables describes the form of the macromolecular coil - the conformational variables, the second one describes the internal stresses connected mainly with the orientation of segments. [Pg.135]

The principle of the NMR approach to semi-local properties of polymeric melts is considered in Section 2 it is shown how the existence of a temporary network structure is detected from the relaxation of the transverse magnetisation of protons attached to chains. The observation of segmental motions from the longitudinal relaxation of proton magnetisation is described in Section 3 it is also shown how local motions in concentrated polymeric solutions can be probed from the diffusion process of small molecules. Section 4 is devoted to the analysis of the effect of entanglement relaxation on NMR properties. [Pg.19]

For the most part, the timescales for the aforementioned kinetic processes are well beyond the accessible timescale for fuUy atomistic MD simulations. Local dynamics such as rotation of a methyl group or a polymer side chain can certainly be explored. For example, in a polymer melt at a temperature of lOOK above the T, the timescale for methyl-group rotations is about Ips and approximately 1-lOns for segmental a-relaxation in a polymer [4b]. Diffusion for even a small molecule such as water in... [Pg.333]


See other pages where Segmental diffusion local melting is mentioned: [Pg.200]    [Pg.99]    [Pg.225]    [Pg.26]    [Pg.88]    [Pg.101]    [Pg.179]    [Pg.56]    [Pg.261]    [Pg.300]    [Pg.111]    [Pg.746]    [Pg.326]    [Pg.272]    [Pg.158]    [Pg.136]    [Pg.738]    [Pg.482]    [Pg.195]   
See also in sourсe #XX -- [ Pg.117 ]




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