By adding minute concentrations of a high molecular weight polymer, liquid jets or bridges collapsing under the action of surface tension develop a characteristic shape of uniform threads connecting spherical fluid drops. In this paper, high-precision measurements of this beads-on-string structure are combined with a theoretical analysis of the limiting case of large polymer relaxation times, for which the evolution can be divided into two distinct regimes. This excludes the very late stages of the evolution, for which the polymers have become fully stretched. For times smaller than the polymer relaxation time, over which the beads-on-string structure develops, we give a simplified local description, which still contains the full complexity of the problem. At times much larger than the relaxation time, we show that the solution consists of exponentially thinning threads connecting almost spherical drops. Both experiment and theoretical analysis of a one-dimensional model equation reveal a self-similar structure of the corner where a thread is attached to the neighbouring drops.
We investigate the concentration-dependence of the characteristic relaxation time of dilute polymer solutions in transient uniaxial elongational flow. A series of monodisperse polystyrene solutions of five different molecular weights (1.8×10 6 ≤ M ≤ 8.3×10 6 g/mol) with concentrations spanning five orders of magnitude were dissolved in two solvents of differing solvent quality (diethyl phthalate and oligomeric styrene). Optical measurements of the rate of filament thinning and the time to break-up in each fluid are used to determine the characteristic relaxation time. A lower sensitivity limit for the measurements was determined experimentally and confirmed by comparison to numerical calculations. Above this sensitivity limit we show that the effective relaxation time of moderately dilute solutions (0.01 ≤ c/c* ≤ 1) in transient extensional flow rises substantially above the fitted value of the relaxation time extracted from small amplitude oscillatory shear flow and above the Zimm relaxation time computed from kinetic theory and intrinsic viscosity measurements. This effective relaxation time exhibits a power-law scaling with the reduced concentration (c/c*) and the magnitude of the exponent varies with the thermodynamic quality of the solvent.
The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.
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