Abstract Stiff‐chain polymers are preponderant in biology as structural components of tissue and living cells. Hence, understanding their solution behavior under different flow histories is fundamental. Here, the extensional flow under capillary breakup of isotropic semidilute solutions of stiff‐chain poly‐n‐butyl isocyanate (PBIC) and hydroxypropyl cellulose (HPC) has been studied. PBIC‐chloroform and HPC‐water were studied as the polymer‐solvent interaction tunes the molecular conformation (Romo‐Uribe, J. Appl. Polym. Sci. 2021, 138, e49712). PBIC in chloroform exhibits a rod‐like conformation, and capillary breakup at constant concentration and temperature initially showed an exponential decay of filament diameter D(t) followed by a sudden decrease of D, and finally slow filament thinning. Increasing the molecular weight by threefold increased the breakup time τb by twofold. HPC in water adopts a semiflexible conformation and the filament thinning also exhibited three stages, however the breakup time was shorter than PBIC. Hence, the extensional viscosity as a function of strain of PBIC and HPC solutions exhibited three regimes, where initial constant extensional viscosity ηE was followed by strain hardening and finally a sudden decrease of extensional viscosity as strain increased. It was found that the filament breakup time τb is a function of the radius of gyration Rg.
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