Complex interfaces stabilized by proteins, polymers or nanoparticles, have a much richer dynamics than those stabilized by simple surfactants. By subjecting fluid-fluid interfaces to step extension-compression deformations, we show that in general these complex interfaces have dynamic heterogeneity in their relaxation response that is well described by a Kohlrausch-Williams-Watts function, with stretch exponent β between 0.4–0.6 for extension, and 0.6–1.0 for compression. The difference in β between expansion and compression points to an asymmetry in the dynamics. Using atomic force microscopy and simulations we prove that the dynamic heterogeneity is intimately related to interfacial structural heterogeneity and show that the dominant mode for stretched exponential relaxation is momentum transfer between bulk and interface, a mechanism which has so far largely been ignored in experimental surface rheology. We describe how its rate constant can be determined using molecular dynamics simulations. These interfaces clearly behave like disordered viscoelastic solids and need to be described substantially different from the 2d homogeneous viscoelastic fluids typically formed by simple surfactants.
We investigate nanoparticle (NP) dispersion, polymer conformations, entanglements and dynamics in ionic nanocomposites. To this end, we study nanocomposite systems with various spherical NP loadings, three different molecular weights, two different Bjerrum lengths, and two types of charge-sequenced polymers by means of molecular dynamics simulations. NP dispersion can be achieved in either oligomeric or entangled polymeric matrices due to the presence of electrostatic interactions. We show that the overall conformations of ionic oligomer chains, as characterized by their radii of gyration, are affected by the presence and the amount of charged NPs, while the dimensions of charged entangled polymers remain unperturbed. Both the dynamical behavior of polymers and NPs, and the lifetime and amount of temporary crosslinks, are found to depend on the ratio between the Bjerrum length and characteristic distance between charged monomers. Polymer–polymer entanglements start to decrease beyond a certain NP loading. The dynamics of ionic NPs and polymers is very different compared with their non-ionic counterparts. Specifically, ionic NP dynamics is getting enhanced in entangled matrices and also accelerates with the increase of NP loading.
We here propose a multiscale approach that allows the gas–liquid expanded phase equilibrium of a Langmuir monolayer to be studied efficiently by coarse-grained two-dimensional simulations and density functional theory.
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