Brownian Dynamics Simulations of Telechelic Polymers Transitioning between Hydrophobic Surfaces

Abstract

We use Brownian dynamics (BD) simulations resolved at the level of a Kuhn step to calculate the rate at which a telechelic polymer with surface-adhering endcaps transitions from a bridge between two flat surfaces to a loop on a single surface. We then use self-consistent field theory to obtain the equilibrium ratio of bridges to loops and apply the principle of detailed balance to obtain the slower loop-to-bridge times from the faster bridge-to-loop times. The bridge-to-loop transition time has two scaling regimes: one where it is approximately equal to the time for a lone hydrophobic particle to desorb from a surface, and the other where it is dominated by the retraction time of the polymer; approximate formulas for both times are given. The results are important for interpreting the dynamics and rheology of latex coating fluids, in which colloidal particles are dynamically bridged by telechelic rheology-modifying polymers.

Responsive Telechelic Block Copolymers for Enhancing the Elasticity of Nanoemulsions

“…First, the larger M n end blocks will result in stronger effective cross-links that enhance the network modulus . Second, the stronger partitioning should result in a higher fraction of bridging chains by slowing the kinetics of bridge-to-loop transitions. , …”

“…67 Second, the stronger partitioning should result in a higher fraction of bridging chains by slowing the kinetics of bridge-to-loop transitions. 68,69 Our finding that telechelic polymers with higher M n end blocks lead to more elastic emulsions is consistent with previous studies using telechelic polymers with oligomeric C18-end blocks. 70,71 These studies find that polymers with oligomeric end blocks significantly thicken a microemulsion suspension but fail to induce the same degree of elasticity observed in this study.…”

Experimental and modeling studies of IPDI‐based polyurea elastomers – The role of hard segment fraction

“…The dependence of τ c,2 on HSWF (Figure 10b) is likely the result of the "strengthening" of the hard phase as the average hard segment length is increased. Let us assume, in a somewhat simplistic fashion, that τ c,2 is related to the time corresponding to a pullout of a single chain out of the hard phase domain (again compare with the example of associating polymers in micelles or on nanoparticles 34,[64][65][66][67][68][69] ), that is, ln τ c,2…”

Understanding Interfacial Nanoparticle Organization through Simulation and Theory: A Review

“…58 The BD method has been applied to study dilute solutions containing macromolecules and colloidal particles in various biochemical and polymeric systems. 59,60 Self-Consistent Mean Field Theory (SCFT). Self-consistent field theory, based on the mean-field approximation theory, is another suitable approach for investigating the equilibrium morphologies of complex polymer and NP systems.…”

“…In Brownian dynamics (BD), solvent particles are implicit, leading to a dramatic reduction in the number of particles, greatly improving the simulation efficiency . The BD method has been applied to study dilute solutions containing macromolecules and colloidal particles in various biochemical and polymeric systems. , …”