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The rod-climbing or Weissenberg effect in which the free surface of a complex fluid climbs a thin rotating rod is a popular and convincing experiment demonstrating the existence of elasticity in polymeric fluids. The interface shape depends on the rotation rate, fluid elasticity, surface tension, and inertia. By solving the equations of motion in the low rotation rate limit for a second-order fluid, a mathematical relationship between the interface deflection and the fluid material functions, specifically the first and second normal stress differences, emerges. This relationship has been used in the past to measure the climbing constant, a combination of the first ($\Psi_{1,0}$) and second ($\Psi_{2,0}$) normal stress difference coefficients from experimental observations of rod-climbing in the low inertia limit. However, a quantitative reconciliation of such observations with the capabilities of modern-day torsional rheometers is lacking. To this end, we combine rod-climbing experiments with both small amplitude oscillatory shear flow measurements and steady shear measurements of the first normal stress difference from commercial rheometers to quantify the values of both normal stress differences for a series of polymer solutions. Furthermore, by retaining the oft-neglected inertial terms, we show that the climbing constant $\hat{\beta}=0.5\Psi_{1,0}+2\Psi_{2,0}$ can be measured even when the fluids, in fact, experience rod descending. A climbing condition derived by considering the competition between elasticity and inertial effects accurately predicts whether a fluid will undergo rod-climbing or rod-descending. The analysis and observations presented in this study establish rotating rod rheometry as a prime candidate for measuring normal stress differences in polymeric fluids at low shear rates that are often below commercial rheometers' sensitivity limits.

Biological organic-inorganic materials remain a popular source of inspiration for bioinspired materials design and engineering. Inspired by the self-assembling metal-reinforced mussel holdfast threads, we tested if metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization. Starting with aqueous solutions of polymers end-functionalized with metal-coordinating ligands of catechol or histidine, here we show that inter-molecular metal-ion coordination complexes can serve as mineral nucleation sites, whereby significant mechanical reinforcement is achieved upon nanoscale particle growth directly at the metal-coordinate network crosslink sites., Biological organic-inorganic materials, such as self-assembling metal-reinforced mussel holdfast threads, remain a popular source of inspiration for materials design and engineering. Here the authors show that metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization.

A general framework for Maxwell-Oldroyd type differential constitutive models is examined, in which an unspecified nonlinear function of the stress and rate-of-deformation tensors is incorporated into the well-known corotational version of the Jeffreys model discussed by Oldroyd. For medium amplitude simple shear deformations, the recently developed mathematical framework of medium amplitude parallel superposition (MAPS) rheology reveals that this generalized nonlinear Maxwell model can produce only a limited number of distinct signatures, which combine linearly in a well-posed basis expansion for the third order complex viscosity. This basis expansion represents a library of MAPS signatures for distinct constitutive models that are contained within the generalized nonlinear Maxwell model. We describe a framework for quantitative model identification using this basis expansion, and discuss its limitations in distinguishing distinct nonlinear features of the underlying constitutive models from medium amplitude shear stress data. The leading order contributions to the normal stress differences are also considered, revealing that only the second normal stress difference provides distinct information about the weakly nonlinear response space of the model. After briefly considering the conditions for time-strain separability within the generalized nonlinear Maxwell model, we apply the basis expansion of the third order complex viscosity to derive the medium amplitude signatures of the model in specific shear deformation protocols. Finally, we use these signatures for estimation of model parameters from rheological data obtained by these different deformation protocols, revealing that three-tone oscillatory shear deformations produce data that is readily able to distinguish all features of the medium amplitude, simple shear response space of this generalized class of constitutive models., 26 pages, 11 figures

An experimental protocol is developed to directly measure the new material functions revealed by medium amplitude parallel superposition (MAPS) rheology. This experimental protocol measures the medium amplitude response of a material to a simple shear deformation composed of three sine waves at different frequencies. Imposing this deformation and measuring the mechanical response reveals a rich data set consisting of up to 19 measurements of the third order complex modulus at distinct three-frequency coordinates. We discuss how the choice of the input frequencies influences the features of the MAPS domain studied by the experiment. A polynomial interpolation method for reducing the bias of measured values from spectral leakage and variance due to noise is discussed, including a derivation of the optimal range of amplitudes for the input signal. This leads to the conclusion that conducting the experiment in a stress-controlled fashion possesses a distinct advantage to the strain-controlled mode. The experimental protocol is demonstrated through measurements of the MAPS response of a model complex fluid: a surfactant solution of wormlike micelles. The resulting data set is indeed large and feature-rich, while still being acquired in a time comparable to similar medium amplitude oscillatory shear (MAOS) experiments. We demonstrate that the data represents measurements of an intrinsic material function by studying its internal consistency, its compatibility with low-frequency predictions for Coleman-Noll simple fluids, and its agreement with data obtained via MAOS amplitude sweeps. Finally, the data is compared to predictions from the corotational Maxwell model to demonstrate the power of MAPS rheology in determining whether a constitutive model is consistent with a material's time-dependent response., 31 pages, 18 figures

In many large-scale industrial applications dealing with particle-laden viscoelastic fluids, the ensemble-averaged behavior of the mixture is of most interest. The first step to parametrize this behavior is to develop an accurate expression to rapidly evaluate the drag coefficient over a broad range of kinematic parameters. The drag coefficient of a spherical particle translating in a viscoelastic matrix is strongly affected by the viscoelasticity of the fluid. In this study, we aim to parametrize the effects of fluid elasticity, especially the relaxation and retardation times, as well as inertia on the drag coefficient of a sphere translating in a viscoelastic fluid described by the Oldroyd-B model. To this end, we employed three-dimensional direct numerical simulations of viscoelastic flow past a stationary sphere. The accuracy of the numerical formulation is thoroughly tested against a number of benchmark problems consisting of steady flow past a sphere in a bounded circular or square domain filled with either a Newtonian or viscoelastic fluid. Initially, the numerical computations for the drag coefficient over a wide range of geometric and flow parameters are validated by comparison with existing data and drag correction models from the literature. The drag coefficient correction is then evaluated for unconfined flow past a sphere at different Reynolds number, Re, over a wide range of Deborah number, De < 9, and polymer viscosity ratio, 0 < ζ < 1. For small Deborah number (De < 1), the drag coefficient decreases with respect to the Stokes drag coefficient, whereas, at large Deborah number (De > 1), the drag is enhanced due to the large elastic stresses that develop on both the surface and wake of the sphere. These canonical behaviors, observed in the inertia-less flow regime (Re ≤ 1) are amplified as the polymer viscosity ratio approaches unity. At higher Reynolds numbers (Re > 1), the drag coefficient correction arising from viscoelasticity is found to be always bigger than unity, but sm, POFC - Programa Operacional Temático Factores de Competitividade (UID/CTM/50025/2019)

The aggregation of attractive colloids has been extensively studied from both theoretical and experimental perspectives as the fraction of solid particles is changed, and the range, type, and strength of attractive or repulsive forces between particles varies. The resulting gels, consisting of disordered assemblies of attractive colloidal particles, have also been investigated with regards to percolation, phase separation, and the mechanical characteristics of the resulting fractal networks. Despite tremendous progress in our understanding of the gelation process, and the exploration of different routes for arresting the dynamics of attractive colloids, the complex interplay between convective transport processes and many-body effects in such systems has limited our ability to drive the system toward a specific configuration. Here, we study a model attractive colloidal system over a wide range of particle characteristics and flow conditions undergoing aggregation far from equilibrium. The complex multiscale dynamics of the system can be understood using a time-rate-transformation diagram adapted from understanding of materials processing in block copolymers, supercooled liquids, and much stiffer glassy metals to direct targeted assembly of attractive colloidal particles. Keywords: Colloidal gels, Directed assembly, Rheology, Attractive colloids, Targeted-design of colloids

© 2020 American Chemical Society. Asphaltenes are heavy aromatic components of crude oil. Their complex chemical makeup - an aromatic core surrounded by aliphatic side chains - enables them to adhere to most surfaces. Their buildup in pipes can result in clogging and lead to interruption of production operations and expensive mechanical cleaning. We demonstrate the use of liquid-impregnated surfaces (LIS) to prevent asphaltene deposition and buildup on substrates. Indeed, these surfaces expose a liquid interface to the working fluid, which combines the benefits of a dynamic defect-free surface and tunable interfacial properties. In contrast to bulk additives that are typically mixed into the oil phase, the impregnating liquid also provides the great benefit of protecting the underlying solid surface with a stable and minimal layer of lubricant, thereby reducing costs and eliminating the need for subsequent downstream removal. We first select and confirm the thermodynamic stability of a suitable lubricant and its lack of interaction with asphaltenes. By using a carefully selected system composed of a textured and functionalized solid substrate in conjunction with a fluorinated lubricant, we show that asphaltene adsorption is prevented over long time scales. We further demonstrate the possibility of building such a system with representative industrial materials such as aluminum and expose the resulting substrate to an external shear flow to simulate pipe flow conditions.

International audience; Colloidal gels result from the aggregation of Brownian particles suspended in a solvent. Gelation is induced by attractive interactions between individual particles that drive the formation of clusters, which in turn aggregate to form a space-spanning structure. We study this process in aluminosilicate colloidal gels through time-resolved structural and mechanical spectroscopy. Using the time-connectivity superposition principle a series of rapidly-acquired linear viscoelastic spectra, measured throughout the gelation process by applying an exponential chirp protocol, are rescaled onto a universal master curve that spans over eight orders of magnitude in reduced frequency. This analysis reveals that the underlying relaxation time spectrum of the colloidal gel is symmetric in time with power-law tails characterized by a single exponent that is set at the gel point. The microstructural mechanical network has a dual character; at short length scales and fast times appearing glassy, whereas at longer times and larger scales it is gel-like. These results can be captured by a simple three-parameter constitutive model and demonstrate that the microstructure of a mature colloidal gel bears the residual skeleton of the original sample-spanning network that is created at the gel point. Our conclusions are confirmed by applying the same technique to another well-known colloidal gel system composed of attractive silica nanoparticles. The results illustrate the power of the time-connectivity superposition principle for this class of soft glassy materials and provide a new compact description for the dichotomous viscoelastic nature of weak colloidal gels

International audience; Dilute suspensions of repulsive particles exhibit a Newtonian response to flow that can be accurately predicted by the particle volume fraction and the viscosity of the suspending fluid. However, such a description fails when the particles are weakly attractive. In a simple shear flow, suspensions of attractive particles exhibit complex, anisotropic microstructures and flow instabilities that are poorly understood and plague industrial processes. One such phenomenon, the formation of log-rolling flocs, which is ubiquitously observed in suspensions of attractive particles that are sheared while confined between parallel plates, is an exemplar of this phenomenology. Combining experiments and discrete element simulations, we demonstrate that this shear-induced structuring is driven by hydrodynamic coupling between the flocs and the confining boundaries. Clusters of particles trigger the formation of viscous eddies that are spaced periodically and whose centers act as stable regions where particles aggregate to form flocs spanning the vorticity direction. Simulation results for the wavelength of the periodic pattern of stripes formed by the logs and for the log diameter are in quantitative agreement with experimental observations on both colloidal and noncolloidal suspensions. Numerical and experimental results are successfully combined by means of rescaling in terms of a Mason number that describes the strength of the shear flow relative to the rupture force between contacting particles in the flocs. The introduction of this dimensionless group leads to a universal stability diagram for the log-rolling structures and allows for application of shear-induced structuring as a tool for assembling and patterning suspensions of attractive particles.

L.L. Ferrás and A.M. Afonso acknowledge the Project PTDC/EMS-ENE/3362/2014-POCI010145-FEDER-016665—funded by FEDER funds through COMPETE2020—Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through FCT— Fundação para a Ciência e a Tecnologia; I.P. L.L. Ferrás would also like to thank the funding by FCT through the scholarship SFRH/BPD/100353/2014. M.L. Morgado would like to thank the funding by FCT through Project UID/MULTI/04621/2013 and M. Rebelo would also like to thank the funding by FCT through Project UID/MAT/00297/2013 (Centro de Matemática e Aplicações). In this chapter, we present a brief description of existing viscoelastic models, starting with the classical differential and integral models, and then focusing our attention on new models that take advantage of the enhanced properties of the Mittag-Leffler function (a generalization of the exponential function). The generalized models considered in this work are the fractional Kaye-Bernstein, Kearsley, Zapas (K-BKZ) integral model and the differential generalized exponential Phan-Thien and Tanner (PTT) model recently proposed by our research group. The integral model makes use of the relaxation function obtained from a step-strain applied to the fractional Maxwell model, and the differential model generalizes the familiar exponential Phan-Thien and Tanner constitutive equation by substituting the exponential function of the trace of the stress tensor by the MittagLeffler function. Since the differential model is based on local operators, it reduces the computational time needed to predict the flow behavior, and, it also allows a simpler description of complex fluids. Therefore, we explore the rheometric properties of this model and its ability (or limitations) in describing complex flows. publishersversion published

Cellulose nanocrystals (CNC) are naturally-derived nanostructures of growing importance for the production of composites having attractive mechanical properties, and offer improved sustainability over purely petroleum-based alternatives. Fabrication of CNC composites typically involves extrusion of CNC suspensions and gels in a variety of solvents, in the presence of additives such as polymers and curing agents. However, most studies so far have focused on aqueous CNC gels, yet the behavior of CNC-polymer gels in organic solvents is important to their wider processability. Here, we study the rheological behavior of composite polymer-CNC gels in dimethylformamide, which include additives for both UV and thermal crosslinking. Using rheometry coupled with in-situ infrared spectroscopy, we show that under external shear, CNC-polymer gels display progressive and irreversible failure of the hydrogen bond network that is responsible for their pronounced elastic properties. In the absence of cross-linking additives, the polymer-CNC gels show negligible recovery upon cessation of flow, while the presence of additives allows the gels to recover via van der Waals interactions. By exploring a broad range of shear history and CNC concentrations, we construct master curves for the temporal evolution of the viscoelastic properties of the polymer-CNC gels, illustrating universality of the observed dynamics with respect to gel composition and flow conditions. We therefore find that polymer-CNC composite gels display a number of the distinctive features of colloidal glasses and, strikingly, that their response to the flow conditions encountered during processing can be tuned by chemical additives. These findings have implications for processing of dense CNC-polymer composites in solvent casting, 3D printing, and other manufacturing techniques., 12 pages, 10 figures, Supplemental: 6 pages, 8 figures

This study reports the development of a direct simulation code for solid spheres moving through viscoelastic fluids with a range of different Theological behaviors. The numerical algorithm was implemented on an open source finite-volume solver coupled with an immersed boundary method, and is able to perform fully-resolved simulations, wherein all flow scales associated with the particle motion are resolved. The formulation employed exploits the log-conformation tensor to avoid high Weissenberg number issues when calculating the polymeric extra stress. A number of benchmark flows were simulated using this method, to assess the accuracy of the newly developed solver. First, the sedimentation of a sphere in a bounded domain surrounded by either Newtonian or viscoelastic fluid was computed, and the numerical results were verified by comparison with experimental and computational data from the literature. Additionally, the spatial and temporal accuracies of the algorithm were evaluated, and different transient and advection discretization schemes were investigated. Second, the rotation of a sphere in a homogeneous shear flow was studied, and again the numerical results obtained were compared to those from the literature. Good agreement is obtained for the variation in the particle rotation rate as a function of Weissenberg number, using both the newly implemented algorithm and an alternative fixed-mesh approach. Finally, the cross-stream migration of a neutrally buoyant sphere in a steady Poiseuille flow, consisting of either a Newtonian or viscoelastic suspending fluid was investigated. For the Newtonian fluid good agreement was obtained for the particle equilibrium position when compared to the well known Segre-Silberberg effect, and for the viscoelastic fluid the effect of the retardation ratio on the final particle equilibrium position was studied. Additionally, the newly-developed solver capabilities were tested to study the shear-induced particle alignment in wall-bounded Newtonian and viscoelastic fluids. The r, This work is funded by FEDER funds through the COMPETE 2020 Programme and National Funds through FCT - Portuguese Foundation for Science and Technology under the project UID/CTM/50025/2013 as well as by the MIT Portugal Program (MPP). The authors would like to acknowledge the Minho University cluster under the project Search-ON2: Revitalization of HPC infrastructure of UMinho (NORTE-07-0162-FEDER-000086), co-funded by the North Portugal Regional Operational Programme (ON.2-0 Novo Norte), under the National Strategic Reference Framework (NSRF), through the European Regional Development Fund (ERDF). Additionally, the authors would like to acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing HPC resources that have contributed to the research results reported within this paper. http://www.tacc.utexas.edu Finally, the authors thank Bruno Santos from FSD blueCAPE Lda for insightful comments regarding the usage of the TACC resources.

In this work we discuss the connection between classical and fractional viscoelastic Maxwell models, presenting the basic theory supporting these constitutive equations, and establishing some background on the admissibility of the fractional Maxwell model. We then develop a numerical method for the solution of two coupled fractional differential equations (one for the velocity and the other for the stress), that appear in the pure tangential annular flow of fractional viscoelastic fluids. The numerical method is based on finite differences, with the approximation of fractional derivatives of the velocity and stress being inspired by the method proposed by Sun and Wu (2006) for the fractional diffusion-wave equation [ Z.Z. Sun, X. Wu, A fully discrete difference scheme for a diffusion-wave system, Applied Numerical Mathematics 56 (2006) 193-209]. We prove solvability, study numerical convergence of the method, and also discuss the applicability of this method for simulating the rheological response of complex fluids in a real concentric cylinder rheometer. By imposing a torsional step-strain, we observe the different rates of stress relaxation obtained with different values of alpha and beta (the fractional order exponents that regulate the viscoelastic response of the complex fluids). (C) 2018 Elsevier Ltd. All rights reserved., L.L. Ferras and J.M. Nobrega would like to thank the funding by FEDER through the COMPETE 2020 Programme, the National Funds through FCT - Portuguese Foundation for Science and Technology under the project UID/CTM/50025/2013. L.L. Ferras would also like to thank the funding by FCT through the scholarship SFRH/BPD/100353/2014. M.L. Morgado would like to thank the funding by FCT through Project UID/MULTI/04621/2013 and M. Rebelo would also like to thank the funding by FCT through Project UID/MAT/00297/2013 (Centro de Matematica e Aplicacoes)., info:eu-repo/semantics/publishedVersion

We present the results of a combined experimental and theoretical study of drop coalescence in the presence of an initial temperature difference 𝛥T[subscript 0] between a drop and a bath of the same liquid. We characterize experimentally the dependence of the residence time before coalescence on 𝛥T[subscript 0] for silicone oils with different viscosities. Delayed coalescence arises above a critical temperature difference 𝛥T[subscript c] that depends on the fluid viscosity: for 𝛥T[subscript 0] > 𝛥T[subscript c], the delay time increases 𝛥T[subscript 0] [superscript 2/3] as for all liquids examined. This observed dependence is rationalized theoretically through consideration of the thermocapillary flows generated within the drop, the bath and the intervening air layer., National Science Foundation (U.S.) (Grant CMMI-1727565), National Science Foundation (U.S.) (Grant DMS-1614043)

We introduce a novel apparatus designed for stress-controlled rheometers to perform simultaneous rheological and electrical measurements on strongly conductive complex fluids under shear. By means of a non-toxic liquid metal at room temperature, the electrical connection to the rotating shaft is completed with minimal additional mechanical friction, allowing for simultaneous stress measurements as low as 1 Pa. We use the capabilities of this design to perform an extensive set of rheo-electric experiments on gels formulated from attractive carbon black particles, at concentrations ranging from 4 to 15% wt. First, experiments on gels at rest prepared with different shear history show a robust power-law scaling between the elastic modulus $G'_0$ and the conductivity $\sigma_0$ of the gels, i.e. $G'_0 \sim \sigma_0^\alpha$, with $\alpha =1.65 \pm 0.04$ independently of the gel concentration. Second, conductivity measurements performed simultaneously with creep experiments reveal for the first time that plastic events take place in the bulk while the shear rate decreases as a weak power law of time in the early stage of the experiment. The subsequent evolution of the conductivity and shear rate allows us to propose a local yielding scenario that is in agreement with previous velocimetry measurements. Finally, we determine the constitutive rheological and electrical behavior of carbon black gels. Corrections first introduced for mechanical measurements are carefully extended to electrical measurements to accurately distinguish between bulk and surface contributions to the conductivity. As an illustrative example, we examine the constitutive rheo-electric properties of five carbon black gels of different grades, and demonstrate the relevance of the novel rheo-electric apparatus as a versatile characterization tool for strongly conductive complex fluids and their applications., Comment: 15 pages, 10 figures + supplemental material

Polymer gels behave as soft viscoelastic solids and exhibit a generic nonlinear mechanical response characterized by pronounced stiffening prior to irreversible failure, most often through macroscopic fractures. Here, we aim at capturing the latter scenario for a protein gel using a nonlinear integral constitutive equation built upon ($i$) the linear viscoelastic response of the gel, here well described by a power-law relaxation modulus, and ($ii$) the nonlinear viscoelastic properties of the gel, encoded into a "damping function". Such formalism predicts quantitatively the gel mechanical response to a shear start-up experiment, up to the onset of macroscopic failure. Moreover, as the gel failure involves the irreversible growth of macroscopic cracks, we couple the latter stress response with Bailey's durability criterion for brittle solids in order to predict the critical values of the stress $\sigma_c$ and strain $\gamma_c$ at the failure point, and how they scale with the applied shear rate. The excellent agreement between theory and experiments suggests that the crack growth in this soft viscoelastic gel is a Markovian process, and that Baileys' criterion extends well beyond hard materials such as metals, glasses, or minerals., Comment: 6 pages, 4 figures and 1 pages of supplemental materials

Since its invention in ancient times, relief printing, commonly called flexography, has been used to mass-produce artifacts ranging from decorative graphics to printed media. Now, higher-resolution flexography is essential to manufacturing low-cost, large-area printed electronics. However, because of contact-mediated liquid instabilities and spreading, the resolution of flexographic printing using elastomeric stamps is limited to tens of micrometers. We introduce engineered nanoporous microstructures, comprising polymer-coated aligned carbon nanotubes (CNTs), as a next-generation stamp material. We design and engineer the highly porous microstructures to be wetted by colloidal inks and to transfer a thin layer to a target substrate upon brief contact. We demonstrate printing of diverse micrometer-scale patterns of a variety of functional nanoparticle inks, including Ag, ZnO, WO[subscript 3], and CdSe/ZnS, onto both rigid and compliant substrates. The printed patterns have highly uniform nanoscale thickness (5 to 50 nm) and match the stamp features with high fidelity (edge roughness, ~0.2 μm). We derive conditions for uniform printing based on nanoscale contact mechanics, characterize printed Ag lines and transparent conductors, and achieve continuous printing at a speed of 0.2 m/s. The latter represents a combination of resolution and throughput that far surpasses industrial printing technologies., Massachusetts Institute of Technology. Department of Mechanical Engineering, National Science Foundation (U.S.) (Grant CMMI-1463181), United States. Air Force Office of Scientific Research. Young Investigator Program (Grant FA9550-11-1-0089), National Institutes of Health (U.S.) (Grant 1R21HL114011-01A1)

We investigate purely elastic flow instabilities in the almost ideal planar stagnation point elongational flow field generated by a microfluidic optimized-shape cross-slot extensional rheometer (OSCER). We use time-resolved flow velocimetry and full-field birefringence microscopy to study the behavior of a series of well-characterized viscoelastic polymer solutions under conditions of low fluid inertia and over a wide range of imposed deformation rates. At low deformation rates the flow is steady and symmetric and appears Newtonian-like, while at high deformation rates we observe the onset of a flow asymmetry resembling the purely elastic instabilities reported in standard-shaped cross-slot devices. However, for intermediate rates, we observe a new type of elastic instability characterized by a lateral displacement and time-dependent motion of the stagnation point. At the onset of this new instability, we evaluate a well-known dimensionless criterion M that predicts the onset of elastic instabilities based on geometric and rheological scaling parameters. The criterion yields maximum values of M which compare well with critical values of M for the onset of elastic instabilities in viscometric torsional flows. We conclude that the same mechanism of tension acting along curved streamlines governs the onset of elastic instabilities in both extensional (irrotational) and torsional (rotational) viscoelastic flows.

The flow of generalized Newtonian fluids with a rate-dependent viscosity through fibrous media is studied with a focus on developing relationships for evaluating the effective fluid mobility. Three different methods have been used here: i) a numerical solution of the Cauchy momentum equation with the Carreau or power-law constitutive equations for pressure-driven flow in a fiber bed consisting of a periodic array of cylindrical fibers, ii) an analytical solution for a unit cell model representing the flow characteristics of a periodic fibrous medium, and iii) a scaling analysis of characteristic bulk parameters such as the effective shear rate, the effective viscosity, geometrical parameters of the system, and the fluid rheology. Our scaling analysis yields simple expressions for evaluating the transverse mobility functions for each model, which can be used for a wide range of medium porosity and fluid rheological parameters. While the dimensionless mobility is, in general, a function of the Carreau number and the medium porosity, our results show that for porosities less than $\varepsilon\simeq0.65$, the dimensionless mobility becomes independent of the Carreau number and the mobility function exhibits power-law characteristics as a result of high shear rates at the pore scale. We derive a suitable criterion for determining the flow regime and the transition from a constant viscosity Newtonian response to a power-law regime in terms of a new Carreau number rescaled with a dimensionless function which incorporates the medium porosity and the arrangement of fibers.

The migration of a sphere in the pressure-driven channel flow of a viscoelastic fluid is studied numerically. The effects of inertia, elasticity, shear-thinning viscosity, secondary flows and the blockage ratio are considered by conducting fully resolved direct numerical simulations over a wide range of parameters. In a Newtonian fluid in the presence of inertial effects, the particle moves away from the channel centreline. The elastic effects, however, drive the particle towards the channel centreline. The equilibrium position depends on the interplay between the elastic and inertial effects. Particle focusing at the centreline occurs in flows with strong elasticity and weak inertia. Both shear-thinning effects and secondary flows tend to move the particle away from the channel centreline. The effect is more pronounced as inertia and elasticity effects increase. A scaling analysis is used to explain these different effects. Besides the particle migration, particle-induced fluid transport and particle migration during flow start-up are also considered. Inertial effects, shear-thinning behaviour, and secondary flows are all found to enhance the effective fluid transport normal to the flow direction. Due to the oscillation in fluid velocity and strong normal stress differences that develop during flow start-up, the particle has a larger transient migration velocity, which may be potentially used to accelerate the particle focusing., National Science Foundation (U.S.) (grant no. CBET-1445955-CAREER)

Biphasic electrode suspensions composed of well-dispersed electrochemically active particles and weakly attractive electronically conductive particles are created. They exhibit high energy density, fast charge transport, and low viscous dissipation during flow., United States. Department of Energy. Office of Science, Basic Energy Sciences, Argonne National Laboratory (Contract No. DE-AC02–06CH11357)

We provide an overview of transient extensional rheometry techniques for wheat flour doughs in which the deformation and material response is well defined. The behavior of a range of model doughs was explored with a Filament Stretching Extensional Rheometer (FISER). The measurements were also compared to data obtained with a new wind-up extensional rheometer; the SER universal testing platform. A simple empirical constitutive equation, which allows characterization of the experimental results with a small number of parameters, is presented to describe the resulting measurements. To characterize the relaxation modulus of the doughs, small amplitude oscillatory tests were performed on samples that have been shear-mixed in a mixograph for varying lengths of time. The linear viscoelastic properties were found to exhibit a broad power-law dependence on the imposed oscillatory frequency that is very reminiscent of that exhibited by a critical gel. The critical gel model of Winter-Chambon [1, 2] was used as the basis for constructing a non-linear constitutive equation for the material stress by combining the relaxation modulus for the critical gel with a Lodge rubber-like liquid form for the kinematics. Transient uniaxial extensional data recorded from the FISER and SER instruments were then compared to the predictions of the constitutive equation. The model captures the initial power-law response and subsequent strain-hardening; however additional physics is required to describe the rheological phenomena at very large Hencky strains, including finite extensibility effects and filament rupture in extensional flows. Zusammenfassung: Wir geben eine Ubersicht uber Techniken der transienten Dehnrheometrie fur Weizenmehlteig, bei denen die Deformation und die Antwort des Materials wohl definiert sind. Das Verhalten einer Serie von Weizenmehlteigmodellsubstanzen wurde mit dem sog. Filament Stretching Extensional Rheometer (FISER) untersucht. Die Messungen wurden auch mit Daten verglichen, die mit einem sog. Wind-Up-Rheometer erhalten wurden, der SER Universal Testing Platform. Eine einfache empirische Konstitutivgleichung wurde entwickelt, um die Messresultate zu beschreiben, die die Charakterisierung der experimentellen Resultate mit Hilfe von wenigen Parametern erlaubt. Um den Relaxationsmodul von Weizenmehlteig zu charakterisieren, wurden Oszillationsmessungen bei kleiner Amplitude mit Weizenmehlteig durchgefuhrt, der bei unterschiedlicher Dauer in einem Mixograph durch Scherung gemischt worden war. Die linear-viskoelastischen Eigenschaften zeigten eine breite Potenzgesetzabhangigkeit als Funktion der Frequenz, die ahnlich dem Verhalten eines kritischen Gels ist. Das Modell des kritischen Gels von Winter-Chambon [1, 2] wurde als Grundlage genutzt, um eine nichtlineare Konstitutivgleichung fur die Materialspannung zu erhalten durch die Kombination des Relaxationsmoduls des kritischen Gels mit einer Lodge-Gummi-Flussigkeit-Gleichung fur die Kinematik. Transiente uniaxiale Dehndaten des FISER und des SER wurden dann mit den Vorhersagen der Konstitutivgleichung verglichen. Das Modell beschreibt die anfangliche Potenzgesetz-Antwort und die nachfolgende Dehnverfestigung. Jedoch ist zusatzliche Physik notwendig, um die Phanomene bei grossen Dehnungen zu beschreiben einschliesslich der Effekte basierend auf der endlichen Verstreckbarkeit und des Reissens des Filaments in der Dehnstromung. Resume

Thin films of bilayer poly(divinyl benzene) p(DVB)/poly(perfluorodecylacrylate) (p-PFDA) are synthesized via iCVD on steel and silicon substrates. Nanomechanical measurements reveal that the elastic modulus and hardness of the films are enhanced through the bilayer structure and that the adhesion of the films to the substrate is improved via in situ grafting mechanism. The strength of ice adhesion to the treated surfaces is reduced more than six-fold when the substrates are coated with these bilayer polymer networks., Chevron-MIT Energy Initiative

Cellulose derivatives containing associating hydrophobic groups along their hydrophilic backbone are used as rheology modifiers in the formulation of water-based spray paints, medicinal sprays, cosmetics and printable inks. Jetting and spraying applications of these materials involve progressive thinning and break-up of a fluid column or sheet into drops. Strong extensional kinematics develop in the thinning fluid neck. In viscous Newtonian fluids, inertial and viscous stresses oppose the surface tension-driven instability. In aqueous solutions of polymers such as Ethyl Hydroxy-Ethyl Cellulose (EHEC), chain elongation provides additional elastic stresses that can delay the capillary-driven pinch-off, influencing the sprayability or jettability of the complex fluid. In this study, we quantify the transient response of thinning filaments of cellulose ether solutions to extensional flows in a Capillary Break-up Extensional Rheometer (CaBER) and in a forced jet undergoing break-up using Rayleigh Ohnesorge Jetting Extensional Rheometry (ROJER). We also characterize the steady state molecular deformations using measurements of the flow-induced birefringence and excess pressure drop in an extensional stagnation point flow using a Cross-Slot Extensional Rheometer (CSER). We show that under the high extension rates encountered in jetting and spraying, the semi-dilute solutions of hydrophobically modified ethyl hydroxy-ethyl cellulose (hmEHEC) exhibit extensional thinning, while the unmodified bare chains of EHEC display an increase in extensional viscosity, up to a plateau value. For both EHEC and hmEHEC dispersions, the low extensibility of the cellulose derivatives limits the Trouton ratio observed at the highest extension rates attained (close to 10[superscript 5] s[superscript −1]) to around 10–20. The reduction in extensional viscosity with increasing extension rate for the hydrophobically modified cellulose ether is primarily caused by the disruption of a transient elastic network that is initially formed by intermolecular association of hydrophobic stickers. This extensional thinning behavior, in conjunction with the low extensibility of the hydrophobically modified cellulose ether additives, makes these rheology modifiers ideal for controlling the extensional rheology in formulations that require jetting or spraying, with minimal residual stringiness or stranding., Akzo Nobel (Firm), United States. National Aeronautics and Space Administration (Microgravity Fluid Sciences (Code UG) Grant NNX09AV99G), European Commission. Marie Curie Actions (FP7-PEOPLE-2011-IIF Grant 298220), Okinawa Institute of Science and Technology Graduate University (OIST)

The relaxation processes of a wide variety of soft materials frequently contain one or more broad regions of power-law like or stretched exponential relaxation in time and frequency. Fractional constitutive equations have been shown to be excellent models for capturing the linear viscoelastic behavior of such materials, and their relaxation modulus can be quantitatively described very generally in terms of a Mittag–Leffler function. However, these fractional constitutive models cannot describe the nonlinear behavior of such power-law materials. We use the example of Xanthan gum to show how predictions of nonlinear viscometric properties, such as shear-thinning in the viscosity and in the first normal stress coefficient, can be quantitatively described in terms a nonlinear fractional constitutive model. We adopt an integral K-BKZ framework and suitably modify it for power-law materials exhibiting Mittag–Leffler type relaxation dynamics at small strains. Only one additional parameter is needed to predict nonlinear rheology, which is introduced through an experimentally measured damping function. Empirical rules such as the Cox–Merz rule and Gleissle mirror relations are frequently used to estimate the nonlinear response of complex fluids from linear rheological data. We use the fractional model framework to assess the performance of such heuristic rules and quantify the systematic offsets, or shift factors, that can be observed between experimental data and the predicted nonlinear response. We also demonstrate how an appropriate choice of fractional constitutive model and damping function results in a nonlinear viscoelastic constitutive model that predicts a flow curve identical to the elastic Herschel-Bulkley model. This new constitutive equation satisfies the Rutgers-Delaware rule, which is appropriate for yielding materials. This K-BKZ framework can be used to generate canonical three-element mechanical models that provide nonlinear viscoelastic generalizations of other empirical inelastic models such as the Cross model. In addition to describing nonlinear viscometric responses, we are also able to provide accurate expressions for the linear viscoelastic behavior of complex materials that exhibit strongly shear-thinning Cross-type or Carreau-type flow curves. The findings in this work provide a coherent and quantitative way of translating between the linear and nonlinear rheology of multiscale materials, using a constitutive modeling approach that involves only a few material parameters.

We develop new criteria that describe the minimum concentration limits controlling the spinnability of dilute and semi-dilute flexible polymer solutions with high molecular weight and varying polydispersity. By asserting that the finite and bounded extensional viscosity of the solution is the key material property determining the stability of a filament during spinning, we propose a new scaling relating the minimum necessary concentration of a polymer c[subscript spin] to its molecular weight M and the quality of the solvent (through the excluded volume exponent ν ) of the form c[subscript spin]∼M−(ν+1). This new scaling differs from the classical interpretation of the coil overlap concentration c[superscript ∗] or entanglement concentration c[subscript e] as the minimum concentration required to increase the viscosity of the spinning dope, and rationalizes the surprising spinnability of high molecular weight polymers at concentrations much lower than c[subscript e]. Furthermore, we introduce the concept of an extensibility average molecular weight M[subscript L] as the appropriate average for the description of polydisperse solutions undergoing an extension-dominated spinning process. In particular it is shown that this extensibility average measure, and thus the solution spinnability, is primarily determined by the extensibility of the highest molecular weight fractions. For highly polydisperse systems this leads to an effective lowering of the minimum required concentration for successful fibre spinning (in comparison to narrowly distributed polymer solutions of similar weight average molecular weights). These predictions are validated with experimental observations of the electrospinnablity of mono- and polydisperse poly(methyl methacrylate) (PMMA) solutions as well as a model bimodal blend, and through comparison to published literature data on the minimum spinnable polymer concentration for a variety of flexible long chain polymers over a range of molecular weights., United States. Air Force Research Laboratory, United States. Army. Natick Soldier Systems Center

The flow interception efficiency, which provides a measure of the fraction of streamlines that intercept a porous collector, is an important parameter in applications such as particle capture, filtration, and sedimentation. In this work, flow permeation through a porous circular cylinder located symmetrically between two impermeable parallel plates is investigated numerically under different flow and geometrical conditions. A flow interception efficiency is defined and calculated based on the flow permeation rate for a wide range of system parameters. The dependencies on all physical variables can be captured in three dimensionless numbers: the Reynolds number, the Darcy number (ratio of permeability to the square of cylinder diameter), and the plate separation relative to the cylinder size. The flow interception efficiency is very low in the limit of unbounded cylinders but significantly increases by restricting the flow domain. The fluid permeation rate through the porous cylinder varies nonlinearly with the relative plate/cylinder spacing ratio, especially when the gap between the cylinder and the confining plates is small compared to the cylinder size. In general, the effects of the Reynolds number, the Darcy number, and confinement on the flow interception efficiency are coupled; however, for most practical cases it is possible to factorize these effects. For practical ranges of the Darcy number (Da, National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762), Massachusetts Institute of Technology. Department of Mechanical Engineering (Rohsenow Fellowship)

Birds in the cormorant (Phalacrocoracidae) family dive tens of metres into water to prey on fish while entraining a thin layer of air (a plastron film) within the microstructures of their feathers. In addition, many species within the family spread their wings for long periods of time upon emerging from water. To investigate whether wetting and wing-spreading are related to feather structure, microscopy and photographic studies have previously been used to extract structural parameters for barbs and barbules. In this work, we describe a systematic methodology to characterize the quasi-hierarchical topography of bird feathers that is based on contact angle measurements using a set of polar and non-polar probing liquids. Contact angle measurements on dip-coated feathers of six aquatic bird species (including three from the Phalacrocoracidae family) are used to extract two distinguishing structural parameters, a dimensionless spacing ratio of the barbule (D*) and a characteristic length scale corresponding to the spacing of defect sites. The dimensionless spacing parameter can be used in conjunction with a model for the surface topography to enable us to predicta priorithe apparent contact angles of water droplets on feathers as well as the water breakthrough pressure required for the disruption of the plastron on the feather barbules. The predicted values of breakthrough depths in water (1–4 m) are towards the lower end of typical diving depths for the aquatic bird species examined here, and therefore a representative feather is expected to be fully wetted in a typical deep dive. However, thermodynamic surface energy analysis based on a simple one-dimensional cylindrical model of the feathers using parameters extracted from the goniometric analysis reveals that for water droplets on feathers of all six species under consideration, the non-wetting ‘Cassie–Baxter’ composite state represents the global energy minimum of the system. By contrast, for other wetting liquids, such as alkanes and common oils, the global energy minimum corresponds to a fully wetted or Wenzel state. For diving birds, individual feathers therefore spontaneously dewet once the bird emerges out of water, and the ‘wing-spreading’ posture might assist in overcoming kinetic barriers associated with pinning of liquid droplets that retard the rate of drying of the wet plumage of diving birds.

A multifunctional surface that enables control of wetting, optical reflectivity and mechanical damage of nanostructured interfaces is presented. Our approach is based on imprinting a periodic array of nanosized cones into a UV-curable polyurethane acrylate (PUA), resulting in a self-reinforcing egg-crate topography evenly distributed over large areas up to several cm[superscript 2] in size. The resulting surfaces can be either superhydrophilic or superhydrophobic (through subsequent application of an appropriate chemical coating), they minimize optical reflection losses over a broad range of wavelengths and a wide range of angles of incidence, and they also have enhanced mechanical resilience due to greatly improved redistribution of the normal and shearing mechanical loads. The transmissivity and wetting characteristics of the nanoscale egg-crate structure, as well as its resistance to mechanical deformation are analyzed theoretically. Experiments show that the optical performance together with self-cleaning or anti-fogging behavior of the inverted nanocone topography is comparable to earlier designs that have used periodic arrays of nanocones to control reflection and wetting. However the egg-crate structures are far superior in terms of mechanical robustness, and the ability to replicate this topography through several generations is promising for large-scale commercial applications where multifunctionality is important., Massachusetts Institute of Technology. Institute for Soldier Nanotechnologies, Singapore-MIT Alliance for Research and Technology (Singapore. National Research Foundation), Samsung (Firm), Kwanjeong Educational Foundation (Korea) (Scholarship)

Using self-designed particle visualization instrumentation, startup shear and step-strain tests were conducted under a series of systematically varied rheological and geometrical conditions, and the velocity profiles in three different well-entangled polybutadiene/oligomer solutions were obtained. For startup shear tests, in the regime of entanglement densities up to 89 and nominal reptation Weissenberg numbers up to 18.6, we generally observe either wall slip and a linear velocity/strain profile or simply the linear profile with no wall slip unless a massive edge fracture or instability has occurred in the sample. Meanwhile, step-strain tests conducted at similar and higher step Weissenberg numbers revealed little particle motion upon cessation. These results lead us to a conclusion that there is no compelling evidence of shear banding or nonquiescent relaxation in the range of entanglement density and Wi investigated; we interpret the results to imply that any observed banding probably correlates with edge effects., National Science Foundation (U.S.) (Grant DMR-0934305)

Commercial applications of magnetorheological (MR) fluids often require operation at elevated temperatures as a result of surrounding environmental conditions or intense localized viscous heating. Previous experimental investigations of thermal effects on MR fluids have reported significant reductions in the magnetorheological stress with increasing temperature, exceeding the predictions made by considering the thermal variations in the individual physical properties of the fluid and solid constituents of a typical MR fluid. In the low-flux regime, designers of MR fluid actuators can alleviate this thermal reduction in stress by increasing the applied magnetic field strength. However, this is not possible in the high-flux regime because of magnetic saturation, and it becomes necessary to explore and understand the intrinsic limitations of the fluid at elevated temperature. We describe a new magnetorheological fixture, which was designed as an accessory to a commercial torsional shear rheometer, capable of applying magnetic flux densities up to 1 T and controlling the sample temperature up to 150°C. During the design of the instrument, close attention was given to the uniformity of the magnetic field applied to the sample by using numerical simulations. Incorporation of a custom-built magnetic flux sensor which matches the environmental capabilities of the fixture enables in situ measurement of the local magnetic field at each temperature. The numerical results are also validated by spatially resolved measurements of the local magnetic field. Finally, we explore the ability of a shift factor between fluid magnetization and yield strength to describe the measured variation in the MR fluid response at elevated temperatures.

Switchable polymer multilayer coatings consisting of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) were prepared via Layer-by-Layer (LbL) assembly and post-functionalized with poly(ethylene glycol methyl ether) (PEG). This resulted in a soft polar coating that reversibly and repeatedly rearranges from hydrophobic to hydrophilic (or vice versa) when contacted with water (or air). Goniometry is used to quantify the forward surface rearrangement in the form of transient measurements of the water contact angle. By examining the time evolution of the water contact angle at various temperatures, the apparent activation energy for the forward surface rearrangement (E[subscript a,f]) can be determined. Further insight can be gained into the kinetics of this surface reconstruction process by utilizing dynamic tensiometry to measure the evolution in the contact angle of a liquid meniscus at several rates and temperatures as it advances or recedes over the multilayer films. A simple first-order thermally-activated rate process is shown to describe the forward and reverse surface reconstruction and enables the shape of the measured tensiometric force curves during repeated immersion and emersion to be predicted quantitatively. Using this model we show that the character of this switchable surface coating can appear to be hydrophobic or hydrophilic depending on a single dimensionless parameter which incorporates the characteristic time-scale for temperature-dependent surface rearrangement, the speed of immersion and the capillary length of the liquid meniscus., Air Force Research Laboratory (Wright-Patterson Air Force Base, Ohio). Propulsion Directorate, United States. Air Force Office of Scientific Research, United States. Army Research Office (Contract W911NF-07-D-0004), National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762)

Enhanced knowledge of the transient behavior and characteristics of electrorheological (ER) fluids subject to time dependent electric fields offers the potential to advance the design of fast actuated hydraulic devices. In this study, the dynamic response of electrorheological fluid flows in rectilinear microchannels was investigated experimentally. Using high-speed microscopic imaging, the evolution of particle aggregates in ER fluids subjected to temporally stepwise electric fields was visualized. Nonuniform growth of the particle structures in the channel was observed and correlated to field strength and flow rate. Two competing time scales for structure growth were identified. Guided by experimental observations, we developed a phenomenological model to quantitatively describe and predict the evolution of microscale structures and the concomitant induced pressure gradient., United States. Defense Advanced Research Projects Agency. Maximum Mobility and Manipulation (M3) Program

Non-wetting surfaces containing micro/nanotextures impregnated with lubricating liquids have recently been shown to exhibit superior non-wetting performance compared to superhydrophobic surfaces that rely on stable air–liquid interfaces. Here we examine the fundamental physico-chemical hydrodynamics that arise when droplets, immiscible with the lubricant, are placed on and allowed to move along these surfaces. We find that these four-phase systems show novel contact line morphology comprising a finite annular ridge of the lubricant pulled above the surface texture and consequently as many as three distinct 3-phase contact lines. We show that these distinct morphologies not only govern the contact line pinning that controls droplets' initial resistance to movement but also the level of viscous dissipation and hence their sliding velocity once the droplets begin to move., United States. Defense Advanced Research Projects Agency. Young Faculty Award, Massachusetts Institute of Technology. Energy Initiative, National Science Foundation (U.S.). CAREER Award (0952564)

In the past twenty years, shear-banding flows have been probed by various techniques, such as rheometry, velocimetry and flow birefringence. In micellar solutions, many of the data collected exhibit unexplained spatiotemporal fluctuations. Recently, it has been suggested that those fluctuations originate from a purely elastic instability of the shear-banding flow. In cylindrical Couette geometry, the instability is reminiscent of the Taylor-like instability observed in viscoelastic polymer solutions. The criterion for purely elastic Taylor–Couette instability adapted to shear-banding flows suggested three categories of shear-banding depending on their stability. In the present study, we report on a large set of experimental data which demonstrates the existence of the three categories of shear-banding flows in various surfactant solutions. Consistent with theoretical predictions, increases in the surfactant concentration or in the curvature of the geometry destabilize the flow, whereas an increase in temperature stabilizes the flow. However, experiments also exhibit some interesting behaviors going beyond the purely elastic instability criterion., National Science Foundation (U.S.). Graduate Research Fellowship Program

Large amplitude oscillatory shear (LAOS) is used as a tool to probe the nonlinear rheological response of a model elasto-viscoplastic material (a Carbopol microgel). In contrast to most recent studies, these large amplitude measurements are carried out in a stress-controlled manner. We outline a descriptive framework of characterization measures for nonlinear rheology under stress-controlled LAOS, and this is contrasted experimentally to the strain-controlled framework that is more commonly used. We show that this stress-controlled methodology allows for a physically intuitive interpretation of the yielding behavior of elasto-viscoplastic materials. The insight gained into the material behavior through these nonlinear measures is then used to develop two constitutive models that prescribe the rheological response of the Carbopol microgel. We show that these two successively more sophisticated constitutive models, which are based on the idea of strain decomposition, capture in a compact manner the important features of the nonlinear rheology of the microgel. The second constitutive model, which incorporates the concept of kinematic hardening, embodies all of the essential behaviors exhibited by Carbopol. These include elasto-viscoplastic creep and time-dependent viscosity plateaus below a critical stress, a viscosity bifurcation at the critical stress, and Herschel–Bulkley flow behavior at large stresses.