Abstract

The transient rheological behavior of several thermotropic nematic side-chain liquid crystal polysiloxanes is investigated. A homopolymer with a low-temperature smectic phase and two random copolymers, one consisting of smectogenic and non-smectogenic mesogens, the other one containing two spacers of different lengths, are studied. All systems are of tumbling type and exhibit oscillations in transient shear stress and first normal stress difference. Only the copolymer with mixed spacers shows a temperature-dependent transition from tumbling to flow-aligning within the nematic phase. The rheological response is slightly different for each polymer. The reactive parameter λ was calculated from the period of the oscillations and compared with rheo-NMR results. For all polymers, λ increases with increasing temperature. The sign of λ, obtained from NMR experiments, is positive for the copolymer with mixed spacers and negative for the other two systems, indicating a prolate shape of the first system and oblate shapes of the other two.

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