Abstract
A general formula for the high-frequency limiting viscosity of dilute solution of polymers is derived.N beads successively connected withN-1 bonds are employed as the model of a polymer chain and the viscosity is calculated from the sum of frictional loss of each beads, assuming that the chain is free-draining, the internal rotation of the bonds is frozen and the beads move by the hydrodynamic force under some geometrical constraints. The derived formula proves to be equivalent to the frequency-independent term in theErpenbeck-Kirkwood theory on the viscosity for the same model. The formula is applied to a freely jointed chain and it is shown that the intrinsic limiting viscosity of the chain is 2.51 times as large as that of the individual segment which consists of a single bond with two half beads at each ends. This result is compared with existing experimental values of the high-frequency viscosity of poly(L-glutamic acid) in the broken helix state and polystyrene in a highly viscous solvent.
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