Sebastian Bindgen

Molecular dynamics (MD) simulations represent a powerful investigation tool in the field of soft matter. By using shear flows, one can probe the bulk rheology of complex fluids, also beyond the linear response regime, in a way that imitates laboratory experiments. One solution to impose a shear flow in particle-based simulations is the Lees–Edwards technique, which ensures that particles experience shear by imposing rules for motion and interactions across the boundary in the direction of the shear plane. Despite their presentation in 1972, a readily available public implementation of Lees–Edwards boundary conditions has been missing from MD simulation codes. In this article, we present our implementation of the Lees–Edwards technique and discuss the relevant technical choices. We used ESPResSo, the extensible simulation package for research on soft matter, for molecular dynamics simulations which can be used as a reference for other implementers. We illustrate our implementation using bulk dissipative particle dynamics fluids, compare different viscosity measurement techniques, and observe the anomalous diffusion in our samples during continuous and oscillatory shear, in good comparison with theoretical estimates.

We introduce graph theory measures and demonstrate how transitions in microstructural conformations can be quantified and correlated to the rheology.

We have investigated the uniaxial elongation behavior of six different wormlike micelle systems covering a broad range of surfactant concentrations cs and salt/surfactant ratios R using the capillary breakup elongational rheometry (CaBER). In the fast-breaking limit (high cs and R), filament lifetime tfil is controlled by the equilibrium shear modulus G0 and the breakage time λbr obtained from small oscillatory shear according to tfil/G0∝λbr2/3 and relaxation time ratios λe/λs≈1 are found. When reptation dominates (high cs, low R) λe/λs<1 is observed similar as for solutions of covalently bound polymers. In this concentration regime, the micellar structure seems not to be affected by the strong elongational flow. In contrast, high filament lifetimes up to 1000 s and λe/λs values up to 10 are observed at low cs irrespective of R. This indicates the formation of elongation-induced structures (EISs). A minimum viscosity and a minimum initial diameter are required for creating EIS. Additional filament stretching experiments indicate that a critical total deformation has to be exceeded for structure build-up. Finally, our experiments reveal a distinct difference regarding the dependence between solutions of linear and branched micelles of filament lifetime on viscosity suggesting that CaBER is a versatile means to distinguish between these structures.