On secondary loops in LAOS via self-intersection of Lissajous–Bowditch curves

When the shear stress measured in large amplitude oscillatory shear (LAOS) deformation is represented as a 2-D Lissajous–Bowditch curve, the corresponding trajectory can appear to self-intersect and form secondary loops. This self-intersection is a general consequence of a strongly nonlinear material response to the imposed oscillatory forcing and can be observed for various material systems and constitutive models. We derive the mathematical criteria for the formation of secondary loops, quantify the location of the apparent intersection, and furthermore suggest a qualitative physical understanding for the associated nonlinear material behavior. We show that when secondary loops appear in the viscous projection of the stress response (the 2-D plot of stress vs. strain rate), they are best interpreted by understanding the corresponding elastic response (the 2-D projection of stress vs. strain). The analysis shows clearly that sufficiently strong elastic nonlinearity is required to observe secondary loops on the conjugate viscous projection. Such a strong elastic nonlinearity physically corresponds to a nonlinear viscoelastic shear stress overshoot in which existing stress is unloaded more quickly than new deformation is accumulated. This general understanding of secondary loops in LAOS flows can be applied to various molecular configurations and microstructures such as polymer solutions, polymer melts, soft glassy materials, and other structured fluids

Power-law rheology in the bulk and at the interface: quasi-properties and fractional constitutive equations

Consumer products, such as foods, contain numerous polymeric and particulate additives that play critical roles in maintaining their stability, quality and function. The resulting materials exhibit complex bulk and interfacial rheological responses, and often display a distinctive power-law response under standard rheometric deformations. These power laws are not conveniently described using conventional rheological models, without the introduction of a large number of relaxation modes. We present a constitutive framework using fractional derivatives to model the power-law responses often observed experimentally. We first revisit the concept of quasi-properties and their connection to the fractional Maxwell model (FMM). Using Scott-Blair's original data, we demonstrate the ability of the FMM to capture the power-law response of ‘highly anomalous’ materials. We extend the FMM to describe the viscoelastic interfaces formed by bovine serum albumin and solutions of a common food stabilizer, Acacia gum. Fractional calculus allows us to model and compactly describe the measured frequency response of these interfaces in terms of their quasi-properties. Finally, we demonstrate the predictive ability of the FMM to quantitatively capture the behaviour of complex viscoelastic interfaces by combining the measured quasi-properties with the equation of motion for a complex fluid interface to describe the damped inertio-elastic oscillations that are observed experimentally.United States. National Aeronautics and Space Administration (Microgravity Fluid Sciences (Code UG) for support of this research under grant no. NNX09AV99G

Wet Adhesion and Adhesive Locomotion of Snails on Anti-Adhesive Non-Wetting Surfaces

Creating surfaces capable of resisting liquid-mediated adhesion is extremely difficult due to the strong capillary forces that exist between surfaces. Land snails use this to adhere to and traverse across almost any type of solid surface of any orientation (horizontal, vertical or inverted), texture (smooth, rough or granular) or wetting property (hydrophilic or hydrophobic) via a layer of mucus. However, the wetting properties that enable snails to generate strong temporary attachment and the effectiveness of this adhesive locomotion on modern super-slippy superhydrophobic surfaces are unclear. Here we report that snail adhesion overcomes a wide range of these microscale and nanoscale topographically structured non-stick surfaces. For the one surface which we found to be snail resistant, we show that the effect is correlated with the wetting response of the surface to a weak surfactant. Our results elucidate some critical wetting factors for the design of anti-adhesive and bio-adhesion resistant surfaces

Formulation, characterisation and flexographic printing of novel Boger fluids to assess the effects of ink elasticity on print uniformity

Model elastic inks were formulated, rheologically characterised in shear and extension, and printed via flexography to assess the impact of ink elasticity on print uniformity. Flexography is a roll-to-roll printing process with great potential in the mass production of printed electronics for which understanding layer uniformity and the influence of rheology is of critical importance. A new set of flexo-printable Boger fluids was formulated by blending polyvinyl alcohol and high molecular weight polyacrylamide to provide inks of varying elasticity. During print trials, the phenomenon of viscous fingering was observed in all prints, with those of the Newtonian ink exhibiting a continuous striping in the printing direction. Increasing elasticity significantly influenced this continuity, disrupting it and leading to a quantifiable decrease in the overall relative size of the printed finger features. As such, ink elasticity was seen to have a profound effect on flexographic printing uniformity, showing the rheological tuning of inks may be a route to obtaining specific printed features

Rheo-PIV of a shear-banding wormlike micellar solution under large amplitude oscillatory shear

We explore the behavior of a wormlike micellar solution under both steady and large amplitude oscillatory shear (LAOS) in a cone–plate geometry through simultaneous bulk rheometry and localized velocimetric measurements. First, particle image velocimetry is used to show that the shear-banded profiles observed in steady shear are in qualitative agreement with previous results for flow in the cone–plate geometry. Then under LAOS, we observe the onset of shear-banded flow in the fluid as it is progressively deformed into the non-linear regime—this onset closely coincides with the appearance of higher harmonics in the periodic stress signal measured by the rheometer. These harmonics are quantified using the higher-order elastic and viscous Chebyshev coefficients e [subscript n] and v [subscript n] , which are shown to grow as the banding behavior becomes more pronounced. The high resolution of the velocimetric imaging system enables spatiotemporal variations in the structure of the banded flow to be observed in great detail. Specifically, we observe that at large strain amplitudes (γ [subscript 0] ≥ 1), the fluid exhibits a three-banded velocity profile with a high shear rate band located in-between two lower shear rate bands adjacent to each wall. This band persists over the full cycle of the oscillation, resulting in no phase lag being observed between the appearance of the band and the driving strain amplitude. In addition to the kinematic measurements of shear banding, the methods used to prevent wall slip and edge irregularities are discussed in detail, and these methods are shown to have a measurable effect on the stability boundaries of the shear-banded flow.Spain. Ministerio de Educación y Ciencia (MEC) (Project FIS2010-21924-C02-02

Effect of the environmental humidity on the bulk, interfacial and nanoconfined properties of an ionic liquid

With reference to our previous surface-force study on 1-hexyl-3-methylimidazolium ethylsulfate ([HMIM] EtSO4) using an extended surface forces apparatus, which showed an ordered structure within the nanoconfined dry ionic liquid (IL) between mica surfaces that extended up to ∼60 nm from the surface, this work focuses on the influence of the environmental humidity on the bulk, interfacial and nanoconfined structure of [HMIM] EtSO4. Infrared spectroscopy and rheometry reflect the changes in chemical and physical properties of the bulk IL due to the uptake of water when exposed to ambient humidity, while wide-angle X-ray scattering shows a mild swelling of the bulk nanostructure, and the AFM sharp tip reveals an additional surface layer at the mica–IL interface. When the water-containing [HMIM] EtSO4 is nanoconfined between two mica surfaces, no long-range order is detected, in contrast to the results obtained for the dry IL, which demonstrates that the presence of water can prevent the liquid-to-solid transformation of this IL. A combination of techniques and the calculated Bjerrum length indicate that water molecules weaken interionic electrostatic and hydrogen-bonding interactions, which lessens ion–ion correlations. Our work shows that the solid-like behavior of the nanoconfined IL strongly depends on the presence of absorbed water and hence, it has implications with regard to the correct interpretation of laboratory studies and their extension to real applications in lubricatio

Large amplitude oscillatory shear of pseudoplastic and elastoviscoplastic materials

We explore the utility of strain-controlled large amplitude oscillatory shear (LAOS) deformation for identifying and characterizing apparent yield stress responses in elastoviscoplastic materials. Our approach emphasizes the visual representation of the LAOS stress response within the framework of Lissajous curves with strain, strain-rate, and stress as the coordinate axes, in conjunction with quantitative analysis of the corresponding limit cycle behavior. This approach enables us to explore how the material properties characterizing the yielding response depend on both strain amplitude and frequency of deformation. Canonical constitutive models (including the purely viscous Carreau model and the elastic Bingham model) are used to illustrate the characteristic features of pseudoplastic and elastoplastic material responses under large amplitude oscillatory shear. A new parameter, the perfect plastic dissipation ratio, is introduced for uniquely identifying plastic behavior. Experimental results are presented for two complex fluids, a pseudoplastic shear-thinning xanthan gum solution and an elastoviscoplastic invert-emulsion drilling fluid. The LAOS test protocols and the associated material measures provide a rheological fingerprint of the yielding behavior of a complex fluid that can be compactly represented within the domain of a Pipkin diagram defined by the amplitude and timescale of deformation.National Science Foundation (U.S.) (Graduate Research Fellowship)United States. Defense Advanced Research Projects Agency (DARPA) (Chemical Robots program