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• W1978702308 abstract "Pulsed NMR studies of proton spin relaxation are used to investigate both radiation-induced crosslinking and entanglements in three high molecular weight linear polydimethylsiloxanes (Mw = 26,000, 63,000 and 110,000). Particular emphasis is placed on the spin-spin relaxation since this is determined by the slower relative traslational motions of the polymer chains and hence is profoundly affected by the presence of intermolecular couplings such as crosslinks or entanglements. The spin-lattice relaxation times, T1, are determined by the fast anisotropic chain rotations and are The spin-lattice relaxation times, T1, are determined by the fast anisotropic chain rotations and are rather insensitive to such intermolecular couplings. The spin-spin relaxation in these materials is represented by a double exponential decay involving two time constants, T2S and T2L. The shorter component, T2S, is attributed to network material, which may be either of a dynamic form arising from temporary entanglements or of a permanent nature due to crosslinks. The concentration of entanglements depends on the initial molecular weight of the sample whereas the concentration of crosslinks is a function of the radiation dose. The longer component, T2L, is attributed to the non-network molecules. On the time scale of the NMR measurements the entanglements are shown to act in the same way as crosslinks. The variation of the relative proportions of network and no-network material with dose is shown to be accounted for by using standard gelation theory when allowance is made for the initial effective crosslink density due to entanglements. Our analysis provides a value for the average molecular weight per entanglement point of 27,000 ± 1000 which is consistent with the critical molecular weight for entanglements of 29,000. The dependences of T2S and T2L on dose and molecular weight are also discussed in terms of the molecular motion." @default.
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• W1978702308 title "Pulsed NMR studies of crosslinking and entanglements in high molecular weight linear polydimethylsiloxanes" @default.
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• W1978702308 doi "https://doi.org/10.1016/0146-5724(77)90059-0" @default.
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