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With decreasing particle size the spacing decreases, and the two peaks gradually merge until only a single peak remains. The chemical shift of the single peak moves slightly towards lower field with the diminution of the particle size, reaching ultimately a limiting value, which depends on the % M. Andreis and J. L. Koenig 112 of DVB. With a degree of crosslinking of 11 mole % of DVB, separate signals of the internal and external water are observed at room temperature for particles with a diameter larger than lOu.

3 MHz for m-polybutadiene; linear PB (A) and samples with the following average number of repeat units between crosslinks: 140 (B), 44 (C) and 14 (D). Open symbols denote T2 measurements obtained by spin-echo technique (reprinted from Ref. 73) with permission) The dependence of T2 values on the molecular parameters is explained by a simple model for the chain with both ends fixed, and defined by the number of statistical segments, Z, in the chain between the crosslinks108) : Z = 1/ns (24) where n is the mole fraction of monomers bearing crosslinks and s is the number of monomers in one segment (thermodynamic rigidity).

Koenig 108 However, the Lorentzian form of the dipolar broadening function, which has the advantage of mathematical simplicity, is not suitable for an interpretation in terms of second moments; it is replaced with a Gaussian dipolar function S((a, AG), where the parameters AG correspond to the appropriate fractions of the square root of the intra-group rigid lattice second moments. With appropriate values for AG, calculated and experimental line shapes I((a) are found to be in a good agreement for crosslinked poly(ethylene oxide) swollen in chloroform 1U) .

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