Kinetics of force-mediated chemical reactions of end-tethered polymers with varying chain length N in varying shear rate flow γ̇ are explored via coarse-grained Brownian dynamics simulations. At fixed γ̇, force F along a polymer increases linearly with N as previously predicted; however, contrary to existing theory, the F(N) slope increases for N above a transition length that exhibits minimal dependence on γ̇. Force profiles are used in a stochastic model of a force-mediated reaction to compute the time for x percent of a polymer population to experience a reaction, tx. Observations are insensitive to the selected value of x in that tx data for varying N and γ̇ can be consistently collapsed onto a single curve via appropriate scaling, with one master curve for systems below the transition N (small N) and another for those above (large N). Different force scaling for small and large N results in orders of magnitude difference in force-mediated reaction kinetics as represented by the population response time. Data presented illustrate the possibility of designing mechano-reactive polymer populations with highly controlled response to flow across a range in γ̇.
© 2023 Author(s). Published under an exclusive license by AIP Publishing.