Chain segment ordering

Figure 15.7 Variation of the splitting A in an elongated PDMS model network containing a small amount (9%) of free PDMS chains, as a function of (A2-A 1), with X the elongation ratio. A pair of identical network/free chains systems are used A deuterated network chains (Mn = 10500 g.mol 1) o deuterated free chains (M = 10500 g.mol"1). S is the chain segment order parameter...

LEONCIO GARRIDO, JEROME L, ACKERMAN AND JAMES E, MARK Chain Segment Ordering in Strained Rubbers 367... 

This relation also applies to any portion of the chain segments as long as the number of segments in the portion is sufficient. Therefore, if one proceeds segmental steps, starting from a point in the interior of the chain, the resulting average displacement is of the order of. Conversely, the number of monomers contained in a sphere of... 

In otlier words, tire micelle surface is not densely packed witli headgroups, but also comprises intennediate and end of chain segments of tire tailgroups. Such segments reasonably interact witli water, consistent witli dynamical measurements. Given tliat tire lifetime of individual surfactants in micelles is of tire order of microseconds and tliat of micelles is of tire order of milliseconds, it is clear tliat tire dynamical equilibria associated witli micellar stmctures is one tliat brings most segments of surfactant into contact witli water. The core of nonnal micelles probably remains fairly dry , however. 

The above results proved the potential viability of the adsorbed hydrophilic macromolecules as bonded phases in chromatography of biopolymers but it must be admitted that additional crosslinking of previously adsorbed macromolecules is usually needed in order to obtain stable composites. The cross-linked bonded polymeric phases, however, may suffer from the restricted flexibility of the chain segment and their steric repellency may be diminished. Moreover, the conformational adaptivity of cross-linked chains for binding with solutes is poorer than that of grafted or chemically bound macromolecules. 

The parameters indexed with a are connected with the nucleation step or other effects occurring only once per triple helix. Parameters denoted by s are related with the equilibrium constants of the propagation steps and are ordered to be independent of the position of the reacting chain segment. This implies that end effects are neglected. Since the same dependences are valid for AH° and AS, with the help of their chain length dependence we can determine AG by extrapolation up to 3 n - 2 = 0, and thus, a can be estimated it depends neither on temperature nor on the chain length. 

Besides crystalline order and structure, the chain conformation and segment orientation of polymer molecules in the vicinity of the surface are also expected to be modified due to the specific interaction and boundary condition at the surface between polymers and air (Fig. 1 a). According to detailed computer simulations [127, 128], the chain conformation at the free polymer surface is disturbed over a distance corresponding approximately to the radius of gyration of one chain. The chain segments in the outermost layers are expected to be oriented parallel to the surface and chain ends will be enriched at the surface. Experiments on the chain conformation in this region are not available, but might be feasible with evanescent wave techniques described previously. Surface structure on a micrometer scale is observed with IR-ATR techniques [129],... 

Nucleation can occur either homogeneously or heterogeneously. Homogeneous nucleation occurs when random molecular motion in the molten state results in the alignment of a sufficient number of chain segments to form a stable ordered phase, known as a nucleus. The minimum number of unit cells required to form a stable nucleus decreases as the temperature falls. Thus, the rate of nucleation increases as the temperature of the polymer decreases. The rate of homogeneous nucleation also increases as molecular orientation in the molten polymer increases. This is because the entropy difference between the molten and crystalline states diminishes as molecular alignment in the molten state increases. 

By application of proton multiple quantum (MQ) NMR experiments, information about the segmental order parameter, which is directly related to the restrictions on chain motion (cross-links) formed upon gelation of PVA, is obtained.103The quantitative study of rigid phase... 

The case of isotactic polypropylene (iPP) presents some differences with respect to those just discussed. While both sPP and PET adopt in their mesophases disordered, extended, essentially non-helical conformations, iPP is characterized by a unique, relatively well ordered, stable chain structure with three-fold helical symmetry [18,19,36]. More accurately we can state that an iPP chain segment can exist in the mesophase either as a left handed or as the enantiomeric right-handed three-fold helix. The two are isoener-getic and will be able to interconvert only through a rather complex, cooperative process. From a morphological point of view Geil has reported that thin films of mesomorphic iPP quenched from the melt to 0 °C consist of... 

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