Highly mobile systems melts

Polymer melts mark the effective boundary of this chapter. It may be necessary to record the decay of the transverse magnetisation under some sort of echo sequence designed to compensate for magnet inhomogeneities if T2 is long. 

It has been known for some time that the FIDs of such systems often decay in a way that is well represented for the most part by a Weibullian [60,61]. Arguments based on consideration of correlation functions suggested that the FID of high molecular weight polydimethyl siloxane in the melt should decay for the most part with a Weibullian power of between 1.25 and 1.5 [62], and the existence of residual static dipolar interactions in these systems was confirmed by the existence of the pseudo-solid echo [63]. This reference forms part of a much larger body of work on such systems by Cohen-Addad and co-workers which it is beyond the scope of this chapter to cover in any detail, but interested readers are directed to literature such as [64] and [65]. 

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Kakiage M, Uehara H, Yamanobe T. Novel in situ NMR Measurement System for Evaluating Molecular Mobility during Drawing from Highly Entangled Polyethylene Melts. Macromol Rapid Commun 2008 29 1571. 

PDMS consist of -Si-O- sequences that exhibit a very low variation of the potential energy of the system with respect to internal rotation angles. This means that the chains exhibit high mobility even at low temperature (Tg = — 120°C). This property combined with the low density of their cohesive energy (S = 14.9 MPa / ) favors their use as elastomeric materials. The regularity of the molecular structure induces a certain crystallinity which appears by stretching and corresponds to a melting zone observed at about —38°C. For low temperature applications, the crystallinity can be suppressed by introduction of side branches by copolymerization. 

Diffusion of ions can be observed in multicomponent systems where concentration gradients can arise. In individnal melts, self-diffnsion of ions can be studied with the aid of radiotracers. Whereas the mobilities of ions are lower in melts, the diffusion coefficients are of the same order of magnitude as in aqueous solutions (i.e., about 10 cmVs). Thus, for melts the Nemst relation (4.6) is not applicable. This can be explained in terms of an appreciable contribntion of ion pairs to diffusional transport since these pairs are nncharged, they do not carry cnrrent, so that values of ionic mobility calculated from diffusion coefficients will be high. 

Every ionic crystal can formally be regarded as a mutually interconnected composite of two distinct structures cationic sublattice and anionic sublattice, which may or may not have identical symmetry. Silver iodide exhibits two structures thermodynamically stable below 146°C sphalerite (below 137°C) and wurtzite (137-146°C), with a plane-centred I- sublattice. This changes into a body-centred one at 146°C, and it persists up to the melting point of Agl (555°C). On the other hand, the Ag+ sub-lattice is much less stable it collapses at the phase transition temperature (146°C) into a highly disordered, liquid-like system, in which the Ag+ ions are easily mobile over all the 42 theoretically available interstitial sites in the I-sub-lattice. This system shows an Ag+ conductivity of 1.31 S/cm at 146°C (the regular wurtzite modification of Agl has an ionic conductivity of about 10-3 S/cm at this temperature). 

Lipid nanodispersions (SLN and NLC) are complex, thermodynamically unstable systems. The colloidal size of the particles alters physical features (e.g., increasing solubihty and the tendency to form supercooled melts). The complex structured lipid matrix may include hquid phases and various lipid modifications that differ in the capacity to incorporate drugs. Lipid molecules of variant modifications may differ in their mobility. Moreover, the high amount of emulsifier used may result in liposome or micelle formation in addition to the nanoparticles. 

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