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We demonstrate a method to address the problem of spectral overlap in multidimensional vibrational spectroscopy and use it to investigate supercooled aqueous sorbitol solutions. The absence of crystallization in these solutions has been attributed to “soft” confinement of water in subnanometer voids in the sorbitol matrix, but the details of the hydrogen-bond structure are still largely unknown. 2D-IR spectroscopy of the OH-stretch mode is an excellent tool to investigate hydrogen bonding, but in this case it seems difficult because of the overlapping water and sorbitol contributions to the 2D-IR spectrum. Using the difference in OH-stretch lifetimes of water and sorbitol we can cleanly separate these contributions. Surprisingly, the separated 2D-IR spectra show that the hydrogen-bond disorder of soft-confined water is independent of temperature and decoupled from its orientational order. We believe the approach we use to separate overlapping 2D-IR spectra will enhance the applicability of 2D-IR spectroscopy to study multicomponent systems.

Deposits from evaporating drops have been shown to take a variety of shapes, depending on the physicochemical properties of both solute and solvent. Classically, the evaporation of drops of colloidal suspensions leads to the so-called coffee ring effect, caused by radially outward flows. Here we investigate deposits from evaporating drops containing living motile microalgae (Chlamydomonas reinhardtii), which are capable of resisting these flows. We show that utilizing their light-sensitivity allows control of the final pattern: adjusting the wavelength and incident angle of the light source enables forcing the formation, completely suppressing and even directing the spatial structure of algal coffee rings.

Background When spraying simple liquids through a hydraulic nozzle, the mechanisms that affect breakup into droplets have recently been described. However, it is unknown how the droplet size distribution changes when surfactant‐based adjuvants are added to the spray. Results When spraying different surfactant‐based solutions containing commercial adjuvants, the breakup of the different liquids behaves in the same way as for water‐only sprays, but the droplet sizes are smaller. By replacing the equilibrium surface tension with the dynamic surface tension at a surface age of ~20 ms, the volume mean droplet size variation with the Weber number, flow rate and nozzle geometry follows the predictions established for pure water sprays. When we rescale the droplet size distribution with the mean droplet size, all distributions collapse onto a single curve and can be described by a compound Gamma function. Conclusion Addition of a number of surfactant‐based adjuvants to an agricultural spray is observed to lead to a slight decrease in the volume mean droplet size. We show that the effects of these adjuvants on the drop size can be understood by taking into account the nozzle geometry, the flow rate, the liquid and air densities and the dynamic surface tension of the surfactant solutions at a surface age of approximately 20 ms. © 2020 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry., Surfactant additives are often used for agricultural sprays; we show that this leads to smaller droplets due to the dynamic surface tension. © 2020 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

When two objects are in contact, the force necessary for one to start sliding over the other is larger than the force necessary to keep the sliding motion going. This difference between static and dynamic friction is thought to result from a reduction in the area of real contact upon the onset of slip. Here, we resolve the structure in the area of contact on the molecular scale by means of environment-sensitive molecular rotors using (super-resolution) fluorescence microscopy and fluorescence lifetime imaging. We demonstrate that the macroscopic friction force is not only controlled by the area of real contact but also controlled by the ``quality'' of that area of real contact, which determines the friction per unit contact area. We show that the latter is affected by the local density of the contacting surfaces, a parameter that can be expected to change in time at any interface that involves glassy, amorphous materials.

Controlling and predicting friction is a significant scientific and technological issue. It is our everyday experience that two smooth surfaces slide more easily over each other than two rough ones, due to interlocking of the rough surfaces. However, the interpretation of such friction forces is difficult since other contributions arise from e.g. adhesion forces, that are harder to control. Here, we demonstrate that designer macroscopic roughness can be used to control, dynamically tune and quantitatively predict friction. We show that the roughness allows to tune the friction coefficient by more than an order of magnitude, which can be explained completely by a simple Coulombic friction model. A kirigami metamaterial surface with externally tunable roughness allows us to show that this understanding of geometrical friction can be used to control on-the-fly the friction in a single system by dynamically controlling its roughness.

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm−1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.

The running-in wear of a multi-asperity silicon carbide sphere-on-silicon flat interface is investigated at the micro- and nanoscale in relation to the friction behaviour of an unlubricated macroscale tribological system sliding in a unidirectional mode. Experiments and contact simulations indicated that the macroscale friction behaviour during running-in was governed by the wear behaviour of roughness asperities on the sphere and their influence on the interfacial contact pressure. Specific ploughing tracks on the flat corresponded to individual asperities on the sphere which, when worn-off, led to lower, more stable friction behaviour and mild wear at an atomic attrition-like rate. It was also found that single asperity contact simulations are unable to reliably predict multi-asperity friction and wear behaviour for this system.

ConspectusThe ice premelt, often called the quasi-liquid layer (QLL), is key for the lubrication of ice, gas uptake by ice, and growth of aerosols. Despite its apparent importance, in-depth understanding of the ice premelt from the microscopic to the macroscopic scale has not been gained. By reviewing data obtained using molecular dynamics (MD) simulations, sum-frequency generation (SFG) spectroscopy, and laser confocal differential interference contrast microscopy (LCM-DIM), we provide a unified view of the experimentally observed variation in quasi-liquid (QL) states. In particular, we disentangle three distinct types of QL states of disordered layers, QL-droplet, and QL-film and discuss their nature.The topmost ice layer is energetically unstable, as the topmost interfacial H2O molecules lose a hydrogen bonding partner, generating a disordered layer at the ice-air interface. This disordered layer is homogeneously distributed over the ice surface. The nature of the disordered layer changes over a wide temperature range from -90 °C to the bulk melting point. Combined MD simulations and SFG measurements reveal that the topmost ice surface starts to be disordered around -90 °C through a process that the topmost water molecules with three hydrogen bonds convert to a doubly hydrogen-bonded species. When the temperature is further increased, the second layer starts to become disordered at around -16 °C. This disordering occurs not in a gradual manner, but in a bilayer-by-bilayer manner.When the temperature reaches -2 °C, more complicated structures, QL-droplet and QL-film, emerge on the top of the ice surface. These QL-droplets and QL-films are inhomogeneously distributed, in contrast to the disordered layer. We show that these QL-droplet and QL-film emerge only under supersaturated/undersaturated vapor pressure conditions, as partial and pseudopartial wetting states, respectively. Experiments with precisely controlled pressure show that, near the water vapor pressure at the vapor-ice equilibrium condition, no QL-droplet and QL-film can be observed, implying that the QL-droplet and QL-film emerge exclusively under nonequilibrium conditions, as opposed to the disordered layers formed under equilibrium conditions.These findings are connected with many phenomena related to the ice surface. For example, we explain how the disordering of the topmost ice surface governs the slipperiness of the ice surface, allowing for ice skating. Further focus is on the gas uptake mechanism on the ice surface. Finally, we note the unresolved questions and future challenges regarding the ice premelt.

Normal stresses in complex fluids lead to new flow phenomena because they can be comparable to, or even larger than, the shear stress. In addition, they are of paramount importance for formulating and testing constitutive equations for predicting nonviscometric flow behavior. Very little attention has thus far been paid to the normal stresses of yield stress fluids, which are difficult to measure. We report the first systematic study of the first and second normal stress differences in both continuous and slow oscillatory shear of three model nonthixotropic yield stress fluids, with N1 > 0 and N2

International audience; A novel method is presented for the rapid direct 3D visualization of the contact between two surfaces by means of fluorescence microscopy using a fluorescent liquid. Distances between the surfaces of up to several hundred nanometers can be determined with subnanometer accuracy in 3D and within seconds of measurement time. The method opens new possibilities for research in the areas of contact mechanics, friction, wear, and lubrication.

We observe a novel type of shear banding in the rheology of thixotropic yield-stress fluids that is due to the coupling of both non-locality and thixotropy. The latter is known to lead to shear banding even in homogeneous stress fields, but the bands observed in the presence of non-local effects appear different as the shear rate varies continuously over the shear band. Here, we introduce a simple non-local model for the shear banding (NL-SB), and we implement it for the analysis of micron-scale rheo-MRI velocimetry measurements of a milk microgel suspension in a cone-and-plate geometry. The proposed NL-SB model accurately quantifies the cooperativity length and yields values in the order of the aggregate size in the microgel.

When a droplet hits a surface fast enough, droplet splashing can occur: Smaller secondary droplets detach from the main droplet during impact. While droplet splashing on smooth surfaces is by now well understood, the surface roughness also affects at which impact velocity a droplet splashes. In this paper, the influence of the surface roughness on droplet splashing is investigated. By changing the root-mean-square roughness of the impacted surface, we show that the droplet splashing velocity is only affected when the droplet roughness is large enough to disrupt the spreading droplet lamella and change the droplet splashing mechanism from corona to prompt splashing. Finally, using Weber and Ohnesorge number scaling models, we also show that the measured splashing velocity for both water and ethanol on surfaces with different roughnesses and water-ethanol mixtures collapses onto a single curve, showing that the droplet splashing velocity on rough surfaces scales with the Ohnesorge number defined with the surface roughness length scale.

The macroscopic viscosity of polymer solutions in general differs strongly from the viscosity at the nanometer scale, and the relation between the two can be complicated. To investigate this relation, we use a fluorescent molecular rotor that probes the local viscosity of its molecular environment. For a range of chain lengths and concentrations, the dependence of the fluorescence on the macroscopic viscosity is well described by the classical Förster-Hoffmann (FH) equation, but the value of the FH exponent depends on the polymer chain length. We show that all data can be collapsed onto a master curve by plotting the fluorescence versus polymer concentration, which we explain in terms of the characteristic mesh size of the polymer solution. Using known scaling laws for polymers then allows us to quantitatively explain the relation between the FH exponent and the polymer chain length, allowing us to link the nano- to the macroviscosity.

Droplets impacting on a surface are key to a wide range of applications such as spray deposition and inkjet printing. Yet, a full understanding of how they spread and retract is still lacking. Surfactants are often added to improve spreading and coverage of aqueous solutions, resulting in variations of the surface tension at timescales beyond the reach of conventional dynamic surface tension measurement methods. Here we study the impact dynamics of aqueous surfactant solutions on hydrophobic surfaces at millisecond timescales. We find that the spreading and retraction of droplets cannot be adequately described by the equilibrium surface tension. We infer the dynamic surface tension in the first milliseconds after impact from the spreading dynamics of droplets. "Slow"surfactants that take a lot of time to reach newly created droplet surface, only slightly decrease or even increase the surface tension, while "fast"surfactants, on the other hand, allow efficient wetting of aqueous solutions on hydrophobic surfaces. Our findings allow us to tailor surfactants for efficient drop deposition or spray application.

We present sphere-on-ice friction experiments as a function of temperature, contact pressure, and speed. At temperatures well below the melting point, friction is strongly temperature dependent and follows an Arrhenius behavior, which we interpret as resulting from the thermally activated diffusive motion of surface ice molecules. We find that this motion is hindered when the contact pressure is increased; in this case, the friction increases exponentially, and the slipperiness of the ice disappears. Close to the melting point, the ice surface is plastically deformed due to the pressure exerted by the slider, a process depending on the slider geometry and penetration hardness of the ice. The ice penetration hardness is shown to increase approximately linearly with decreasing temperature and sublinearly with indentation speed. We show that the latter results in a nonmonotonic dependence of the ploughing force on sliding speed. Our results thus clarify the complex dependence of ice friction on temperature, contact pressure, and speed.

Friction reduction is a major issue in multiple domains, and lubrication is often used in order to achieve it. Gas lubrication is a very efficient way to increase slipperiness, reducing the friction coefficient to almost zero. The main challenge with gas lubrication is to keep the gas inside the contact area due to the fact that it is easily squeezed out because of its low viscosity. Here we use the Leidenfrost effect to form a lubricating gas layer in between a disk of dry ice and a substrate, thus leading to lubricated friction. The gas is continuously provided by sublimation due to the temperature difference between dry ice and substrate. We perform different experiments on dry ice, measuring friction and parameters inside the gas layer. We then chart the crossover from high to low friction as a function of pressure and temperature, and we reveal the role of gas layer thickness. The substrate temperature and macroscopic pressure are found to strongly affect the friction, and very low friction is reached only in particular conditions. These conditions are easily controlled through external parameters, which allows us to use the Leidenfrost effect to efficiently modify friction.

Fluorescent molecular rotors have been used for measurements of local mobility on molecular length scales, for example to determine viscosity, and for the visualization of contact between two surfaces. In the present work, we deepen our insight into the excited‐state deactivation kinetics and mechanics of dicyanodihydrofuran‐based molecular rotors. We extend the scope of the use of this class of rotors for contact sensing with a red‐shifted member of the family. This allows for contact detection with a range of excitation wavelengths up to ∼600 nm. Steady‐state fluorescence shows that the fluorescence quantum yield of these rotors depends not only on the rigidity of their environment, but – under certain conditions – also on its polarity. While excited state decay via rotation about the exocyclic double bond is rapid in nonpolar solvents and twisting of a single bond allows for fast decay in polar solvents, the barriers for both processes are significant in solvents of intermediate polarity. This effect may also occur in other molecular rotors, and it should be considered when applying such molecules as local mobility probes., Either way: Molecular fluorescent rotors based on the DCDHF motif can decay via twisting of two different bonds, with different sensitivities to solvent polarity. An implication of this mechanistic complexity is that their fluorescence intensity may depend on viscosity and polarity. Nonetheless, two probes that differ only in their conjugation length can both be used fruitfully to monitor viscosity and mechanical contact. The high local pressure in the mechanical contact leads to confinement

Utilisation of plant waste materials contributes to sustainable food production and allows preparation of functional ingredients from natural bio-materials. Microfibrillated cellulose (MFC) from plant waste materials such as citrus peels has been suggested to have potential as “clean label” thickener. This study compared rheological (shear and extensional rheology, hysteresis, yield stress), tribological and sensory properties of MFC dispersions (0.2–2.0 wt%) to xanthan gum (XG) solutions (0.04–4.3 wt%) and linked sensory characteristics to instrumental properties. Concentrations of MFC and XG were chosen so that shear viscosities of MFC dispersions and XG solutions were similar over a large range of shear rates. XG had higher extensional viscosity at high deformation rates than MFC. XG had higher yield stress than MFC at similar shear viscosity. Yield stress increased linearly with increasing concentrations for XG, while it increased exponentially for MFC. Seventy-three consumers evaluated the appearance, flavour, and mouthfeel of all samples using the Rate-All-That-Apply (RATA) method. Sensory differences between MFC and XG were generally larger at higher concentrations. MFC dispersions were less transparent and had more intense cardboard flavour than XG solutions of comparable shear viscosity. At high thickener concentrations, XG solutions were perceived as glossier, stickier, slimier and more mouthcoating than MFC dispersions of similar shear viscosity. Sticky, slimy and mouthcoating perception were correlated with extensional viscosity at higher deformation rates. We conclude that MFC can thicken foods similar to XG while avoiding undesired texture sensations such as mouthcoating, sliminess and stickiness. The flavour and dispersibility of MFC need to be improved further before it can be applied as thickener in foods.

Four different methods for measuring droplet size distributions are evaluated: the Image Analysis VisiSizer technique, a stroboscopic imaging method developed in-house, phase Doppler particle analysis (PDPA), and laser diffraction (Malvern Spraytec). We find that the larger the droplets, the bigger the differences between the results obtained by the different methods. The Image Analysis VisiSizer technique yields results that are comparable with those of the stroboscopic imaging method, provided that the raw Visisizer data are used, as the VisiSizer software makes corrections that can skew the results. Our measurements confirm how the limitations of PDPA can influence its outcomes; the presence of air bubbles inside droplets will cause PDPA to mistake them for smaller droplets. The fact that PDPA reports no droplets larger than 1200 μm might be caused by large drops often not being spherical. The results of the laser diffraction technique are influenced by its fitting method to obtain the droplet size distribution and by overestimation of the number of small droplets due to their low velocity and thus higher concentration in the sample volume. Our results emphasize the need for selecting the size measurement technique to fit the physical nature and expected range of droplet parameters.

We investigate the influence of surfactants on capillary rise and corner flow in angular pores. We therefore study capillary rise for simple fluids and surfactant solutions, comparing square to cylindrical capillaries. We show that fingers start to form in the corners of the square capillaries when the capillary rise slows down before reaching the equilibrium height. The corner flow scales as t1/3 and its quantitative understanding necessitates that the surface wettability is taken into account in terms of the liquid’s advancing contact angle on the capillary walls inside the corner. Adding surfactants to water greatly influences the corner flow in square capillaries: depending on the nature of the surfactant, the corner flow can be either suppressed completely due to autophobic effects or enhanced due to the presence of Marangoni stresses caused by a surface tension gradient inside the liquid fingers.

When pushed out of a syringe, polymer solutions form droplets attached by long and slender cylindrical filaments whose diameter decreases exponentially with time before eventually breaking. In the last stages of this process, a striking feature is the self-similarity of the solution shape near the end of the filament. This means that shapes at different times, if properly rescaled, collapse onto one universal shape. A theoretical description inspired by this similarity observation and based on the Oldroyd-B model was recently shown to disagree with existing experimental results. By revisiting these measurements and analysing the interface profiles of very diluted polyethylene oxide solutions at high temporal and spatial resolution, we show that they are very well described by the model., Comment: 9 pages, 5 figures

The processes in which droplets evaporate from solid surfaces, leaving behind distinct deposition patterns, have been studied extensively for variety of solutions. In this work, by combining different microscopy techniques (confocal fluorescence, video and Raman) we investigate pattern formation and evaporation-induced phase change in drying oil-in-water emulsion drops. This combination of techniques allows us to perform drop shape analysis while visualizing the internal emulsion structure simultaneously. We observe that drying of the continuous water phase of emulsion drops on hydrophilic surfaces favors the formation of ring-like zones depleted of oil droplets at the contact line, which originate from geometrical confinement of oil droplets by the meniscus. From such a depletion zone, a "coffee ring" composed of surfactant molecules forms as the water evaporates. On all surfaces drying induces emulsion destabilization by coalescence of oil droplets, commencing at the drop periphery. For hydrophobic surfaces, the coalescence of the oil droplets leads to a uniform oil film spreading out from the initial contact line. The evaporation dynamics of these composite drops indicate that the water in the continuous phase of the emulsion drops evaporates predominantly by diffusion through the vapor, showing no large differences to the evaporation of simple water drops.

The processes in which droplets evaporate from solid surfaces, leaving behind distinct deposition patterns, have been studied extensively for variety of solutions. In this work, by combining different microscopy techniques (confocal fluorescence, video and Raman) we investigate pattern formation and evaporation-induced phase change in drying oil-in-water emulsion drops. This combination of techniques allows us to perform drop shape analysis while visualizing the internal emulsion structure simultaneously. We observe that drying of the continuous water phase of emulsion drops on hydrophilic surfaces favors the formation of ring-like zones depleted of oil droplets at the contact line, which originate from geometrical confinement of oil droplets by the meniscus. From such a depletion zone, a “coffee ring” composed of surfactant molecules forms as the water evaporates. On all surfaces drying induces emulsion destabilization by coalescence of oil droplets, commencing at the drop periphery. For hydrophobic surfaces, the coalescence of the oil droplets leads to a uniform oil film spreading out from the initial contact line. The evaporation dynamics of these composite drops indicate that the water in the continuous phase of the emulsion drops evaporates predominantly by diffusion through the vapor, showing no large differences to the evaporation of simple water drops.

We present sliding experiments of a sledge on wetted sand and describe that the frictional response is controlled by the penetration hardness of the granular medium. Adding a small amount of water to sand increases the hardness which results in a decrease of the sliding friction. Pouring even more water to sand results in a decrease of the hardness and a subsequent increase of the friction. This inverse correlation between hardness of a wetted granular material and its frictional response to sliding is found to be due to ploughing of the sledge. When the load of the sledge exceeds the penetration hardness of the water-sand mixture the granular material is irreversibly deformed, which is evident by a trace of the slider left after its passage. The penetration hardness sets how deep the trace of the slider is which, in turn, controls the ploughing force. Consequently, increasing the hardness of the water-sand mixtures makes pulling a sledge over it easier. In addition, we quantify the critical shear strain which sets the transition of an elastic to plastic response of (wet) granular materials which enables us to directly relate the shear modulus, in the elastic regime, to the hardness, in the plastic regime. Graphic abstract

We investigate the aggregation and phase separation of thin, living T. tubifex worms that behave as active polymers. Randomly dispersed active worms spontaneously aggregate to form compact, highly entangled blobs, a process similar to polymer phase separation, and for which we observe power-law growth kinetics. We find that the phase separation of active polymerlike worms does not occur through Ostwald ripening, but through active motion and coalescence of the phase domains. Interestingly, the growth mechanism differs from conventional growth by droplet coalescence: the diffusion constant characterizing the random motion of a worm blob is independent of its size, a phenomenon that can be explained from the fact that the active random motion arises from the worms at the surface of the blob. This leads to a fundamentally different phase-separation mechanism that may be unique to active polymers., Comment: 4 pages, 4 figures

The formation and destabilisation of viscoelastic filaments are of importance in many industrial and biological processes. Filament instabilities have been observed for viscoelastic fluids but recently also for soft elastic solids. In this work, we address the central question how to connect the dynamical behavior of viscoelastic liquids to that of soft elastic solids. We take advantage of a biopolymer material whose viscoelastic properties can be tuned over a very large range by its pH, and study the destabilization and ensuing instabilities in uniaxial extensional deformation. In agreement with very recent theory, we find that the interface shapes dictated by the instabilities converge to an identical similarity solution for low-viscosity viscoelastic fluids and highly elastic gels. We thereby bridge the gap between very fluid and strongly elastic materials. In addition, we provide direct evidence that at late times an additional filament instability occurs due to a dynamical phase separation., 11 pages, 13 figures

We use fluorescence microscopy to investigate how surface roughness affects the transition between different lubrication regimes., We investigate the transition between different regimes of lubrication and directly observe the thickness of nanometric lubrication films with a sensitivity of a single molecular layer at a multi-asperity interface through fluorescence microscopy. We redefine specific film thickness as the ratio of the lubricant film thickness and the surface roughness measured only at those regions of the interface where the gap is “minimal.” This novel definition of specific film thickness successfully captures the transition from full elastohydrodynamic lubrication to mixed and boundary lubrication. The transition can be triggered by increasing the surface roughness and is accurately predicted by using the new film thickness definition. We find that when the liquid carries part of the load, its apparent viscosity is greatly increased by confinement, and show how the transition between different lubrication regimes is well described by the viscosity increase and subsequent glass transition in the film.

Measurements of the friction coefficient of steel-on-ice over a large temperature range reveal very high friction at low temperatures (-100 °C) and a steep decrease in the friction coefficient with increasing temperature. Very low friction is only found over the limited temperature range typical for ice skating. The strong decrease in the friction coefficient with increasing temperature exhibits Arrhenius behavior with an activation energy of Ea ≈ 11.5 kJ mol-1. Remarkably, molecular dynamics simulations of the ice-air interface reveal a very similar activation energy for the mobility of surface molecules. Weakly hydrogen-bonded surface molecules diffuse over the surface in a rolling motion, their number and mobility increasing with increasing temperature. This correlation between macroscopic friction and microscopic molecular mobility indicates that slippery ice arises from the high mobility of its surface molecules, making the ice surface smooth and the shearing of the weakly bonded surface molecules easy.

Shear thickening is a phenomenon in which the viscosity of a suspension increases with increasing stress or shear rate, sometimes in a discontinuous fashion. While the phenomenon, when observed in suspensions of corn starch in water, or Oobleck, is popular as a science experiment for children, shear thickening is actually of considerable importance for technological applications and exhibited by far simpler systems. Concentrated suspensions of smooth hard spheres will exhibit shear thickening, and understanding this behavior has required a fundamental change in the paradigm of describing low-Reynolds-number solid-fluid flows, in which contact forces have traditionally been absent. Here, we provide an overview of our understanding of shear thickening and the methods that have been developed to describe it, as well as outstanding questions.

Polymer nanocomposites-materials in which a polymer matrix is blended with nanoparticles (or fillers)-strengthen under sufficiently large strains. Such strain hardening is critical to their function, especially for materials that bear large cyclic loads such as car tires or bearing sealants. Although the reinforcement (i.e., the increase in the linear elasticity) by the addition of filler particles is phenomenologically understood, considerably less is known about strain hardening (the nonlinear elasticity). Here, we elucidate the molecular origin of strain hardening using uniaxial tensile loading, microspectroscopy of polymer chain alignment, and theory. The strain-hardening behavior and chain alignment are found to depend on the volume fraction, but not on the size of nanofillers. This contrasts with reinforcement, which depends on both volume fraction and size of nanofillers, potentially allowing linear and nonlinear elasticity of nanocomposites to be tuned independently.

Steady shear measurements on three yield-stress fluids, a foam and two types of emulsions, were carried out using a smooth torsional parallel-plate geometry, with different gap spacings to assess the effect of wall slip on the normal stress differences. The classical Mooney analysis gave slip-corrected flow curves that agreed with data from a roughened cone-and-plate for all three materials, despite the fact that the compatibility requirement between the flow curve and slip velocity functionalities was not satisfied, indicating that the method is robust for this geometry. All three materials exhibited finite normal stresses following yielding, with power-law exponents of approximately 0.4, as well as shear stresses that can be represented by the Herschel–Bulkley model. The systems showed complete slip for shear stresses below the yield stress, with the stress transmitted to the unyielded material through a thin liquid layer causing an elastic deformation that was measurable for the unyielded foam, which can be represented by the Mooney–Rivlin elastic constitutive equation. The unyielded foam exhibited large sample-to-sample variations in the apparent modulus for identical loading conditions.

From everyday experience, we all know that a solid edge can deflect a liquid flowing over it significantly, up to the point where the liquid completely sticks to the solid. Although important in pouring, printing, and extrusion processes, there is no predictive model of this so-called "teapot effect." By grazing vertical cylinders with inclined capillary liquid jets, here we use the teapot effect to attach the jet to the solid and form a new structure: the liquid helix. Using mass and momentum conservation along the liquid stream, we first quantitatively predict the shape of the helix and then provide a parameter-free inertial-capillary adhesion model for the jet deflection and critical velocity for helix formation.

The spreading of liquid droplets impacting a surface at high speed is well understood by now. However, when a droplet impacts a surface at relatively low impact velocities (

In many applications where small, similar-sized droplets are needed, ultrasonic nebulizers are employed. Little is known about the mechanism of nebulization, for example about what determines the median droplet size. Even less understood, is the droplet size distribution, which is often simply fitted with a log-normal distribution or assumed to be very narrow. We perform the first systematic study of droplet size distributions for different nebulizer technologies, showing that these distributions can be very well fitted with distributions found for sprays, where the size distribution is completely determined by the corrugation of ligaments and the distribution of ligament sizes. In our case, breakup is believed to be due to pinch-off of Faraday instabilities. The droplet size distribution is then set by the distribution of wavelengths of the standing capillary waves and the roughness of the pinch-off ligaments. We show that different nebulizer technologies produce different size distributions, which we relate to (variation in) wavelengths of the waves that contribute to the droplet formation. We further show that the median droplet size scales with the capillary wavelength, with a proportionality constant that depends only slightly on the type of nebulizer, despite order-of-magnitude differences in other parameters.

The mechanism involved in stick-slip phenomena, such as earthquakes, is controlled by the interfacial shear stress., When two objects are in contact, the force necessary to overcome friction is larger than the force necessary to keep sliding motion going. This difference between static and dynamic friction is usually attributed to the growth of the area of real contact between rough surfaces in time when the system is at rest. We directly measure the area of real contact and show that it actually increases during macroscopic slip, despite the fact that dynamic friction is smaller than static friction. This signals a decrease in the interfacial shear strength, the friction per unit contact area, which is due to a mechanical weakening of the asperities. This provides a novel explanation for stick-slip phenomena in, e.g., earthquakes.

We investigate which property of non-Newtonian fluids determines the deceleration of a high-speed impacting object. Using high-speed camera footage, we measure the velocity decrease of a high-speed spherical object impacting a typical Newtonian fluid (water) as a reference and compare it with a shear thickening fluid (cornstarch) and a shear thinning viscoelastic fluid (a weakly cross-linked polymer gel). Three models describing the kinetic energy loss of the object are considered: fluid inertia, shear thickening and viscoelasticity. By fitting the three models to the experimental data, we conclude that the viscoelastic model works best for both the cornstarch and the polymer gel. Since the cornstarch is also viscoelastic, we conclude that the ability to stop objects of these complex fluids is given by their viscoelasticity rather than shear thickening or shear thinning.

We study the spreading of a droplet of surfactant solution on a thin suspended soap film as a function of dynamic surface tension and volume of the droplet. Radial growth of the leading edge (R) shows power-law dependence on time with exponents ranging roughly from 0.1 to 1 for different surface tension differences (Δσ) between the film and the droplet. When the surface tension of the droplet is lower than the surface tension of the film (Δσ > 0), we observe rapid spreading of the droplet with R ≈ tα, where α (0.4 < α < 1) is highly dependent on Δσ. Balance arguments assuming the spreading process is driven by Marangoni stresses versus inertial stresses yield α = 2/3. When the surface tension difference does not favor spreading (Δσ < 0), spreading still occurs but is slow with 0.1 < α < 0.2. This phenomenon could be used for stretching droplets in 2D and modifying thin suspended films.

Recent theories of drag reduction in wall turbulence assumed that the presence of the polymer leads to an effective viscosity, which increases linearly with the distance from the wall. Such a linear viscosity profile reduces the Reynolds stress (i.e., the momentum flux to the wall), which leads to drag reduction. For the usual flexible polymers employed in drag reduction, the effective viscosity is however a strongly non-linear effect that is difficult to quantify. We therefore investigate the turbulent drag reduction characteristics of a stiff rod-like polymer for which any effective viscosity changes are only due to the orientation of the polymers. The results show that close to the walls the polymers orient and the viscosity is low, whereas in the bulk the polymers are randomly oriented and the effective viscosity is high. This indeed leads to a reduction of the Reynolds stress and hence to a drag reduction.

Nanocomposites consisting of polymers reinforced with filler particles are important for a wide variety of industries and processes, but although they exhibit unique viscoelastic properties and as such are widely applied in e.g. tires, the precise mechanism of their reinforcement is at best incompletely understood at present. In order to understand it at a fundamental level, and ultimately control it in practice, it is essential to determine the impact of interactions between filler particles and polymer matrix on the nanocomposite microstructure and its macroscopic dynamic mechanical properties. To this end, we performed experiments on two model systems as well as molecular dynamics simulations, aiming to determine to what extent widely used shear-distortion models of the reinforcement are applicable as well as the role played by molecular interactions on the enhancement of the mechanical properties. In both experiments and simulations a linear dependence of the reinforcement on the inverse radius of the nanoparticles was obtained. Deformation simulations of a linearly increasing strain showed an overall increase of 50% in the linear modulus when fillers were added to the polymer matrix, regardless of the use of direct interactions among the nanoparticles. Furthermore, the use of attractive nanoparticle interactions resulted in a higher matrix densification at the interfaces and to a sharp increase in the reinforcement.

The electrical bending instability in charged liquid jets is the phenomenon determining the process of electrospinning. A model of this phenomenon is lacking however, mostly due to the complicated interplay between the viscosity and elasticity of the solution. To investigate the bending instability, we performed electrospinning experiments with a solution of polyethylene oxide in water/ethanol. Using a fast camera and sensitive multimeter, we deduced an experimental dispersion relation describing the helix pitch length as a function of surface charge. To understand this relation, we developed a theoretical model for the instability for a wide range of visco-elastic materials, from conducting to nonconducting. The theoretical dispersion relation shows good agreement with the experimental results. Using the new model, we find that the elastic tension in the visco-elastic threads plays an important role in triggering the instability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1036–1042

Colloidal particles are often used to make Pickering emulsions that are reported to be very stable. Commonly the stabilization is a combined effect of particle adsorbing at the fluid interface and a particle network in the continuous phase; the contribution of each to the overall stability is difficult to assess. We investigate the role of LAPONITE® particles on high internal phase emulsion stability by considering three different situations: emulsion stabilization by surfactant only, by surfactant plus clay particles, and finally clay particles only. To clarify the structure of the emulsion and the role of the clay particles, we have succeeded in fluorescently labelling the clay particles by adsorbing the dye onto the particle surfaces. This allows us to show directly using confocal microscopy, that the clay particles are not only located at the interface but also aggregate and form a gel in the continuous aqueous phase. We show that the emulsions in the presence of surfactant (with or without clay) are stable to coalescence and shear. Without surfactant (with only LAPONITE® as stabilizer) the emulsions are stable to coalescence for several weeks, however they destabilize rapidly under shear. Our results suggest that the formation of the emulsions is mostly due to gel formation of the clay particles in the continuous phase, rather than that the clay is an emulsifier. This gel formation also accounts for the instability of the emulsions to shear that we observe caused by shear thinning of the continuous gel and inability of the adsorbed particles to rearrange effectively around the droplets due to their attractive nature.

The use of microchannels for catalytic reactions represents a considerable experimental opportunity, because of the high surface area to volume ratio these devices typically have. However, incorporating catalysts into microfluidic devices has proven technically challenging. We report the development of a new type of microfluidic device that has a catalytically active metal surface with a large active area built into one of the walls that constitute the microchannel. We test the catalytical activity on an important chemical reaction for drinking water purification: the catalytic ozonation of a typical organic pollutant that is otherwise difficult to remove from the water. pCBA was chosen as model pollutant since it is known to have slow reaction rates with molecular ozone and hence to pose problems in water purification. We find that the catalytic microreactor increases the overall reaction rate by a factor 350 compared to the bulk reaction, owing to both the catalytic activity and the confinement, and is thus highly efficient even for very short residence times.

The non-Newtonian flow behavior of thermal and athermal disordered systems of dispersed uniform particles at high densities have strikingly similar features. By investigating the flow curves of yield-stress fluids and colloidal glasses having different volume fractions, particle sizes, and interactions, we show that both thermal and athermal systems exhibit power-law scaling with respect to the glass and jamming point, respectively, with the same exponents. All yield-stress flow curves can be scaled onto a single universal curve using the Laplace pressure as the stress scale for athermal systems and the osmotic pressure for the thermal systems. Strikingly, the details of interparticle interactions do not matter for the rescaling, showing that they are akin to usual phase transitions of the same universality class. The rescaling allows us to predict the flow properties of these systems from the volume fraction and known material properties.

The friction for sliding objects over partially water-saturated granular materials is investigated as a function of the water volume fraction. We find that ploughing friction is the main sliding mechanism: The slider leaves a deep trace in the sand after its passage. In line with previous research and everyday experience, we find that the friction force varies nonmonotonically with the water volume fraction. The addition of a small amount of water makes the friction force sharply drop, whereas too much added water causes the friction force to increase again. We present a ploughing model that quantitatively reproduces the nonmonotonic variation of the friction force as a function of water volume fraction without adjustable parameters. In this model, the yield stress of the water-sand mixture controls the depth to which the hemisphere sinks into the sand and the force that is required to plough through the water-sand mixture. We show that the model can also be used for other ploughing friction experiments, such as an ice skate that leaves a ploughing track on ice.

Surface active agents (surfactants) are commonly used to improve the wetting of aqueous solutions on hydrophobic surfaces. The improved wettability is usually quantified as a decrease of the contact angle θ of a droplet on the surface, where the contact angle θ is given by the three surface tensions involved. Surfactants are known to lower the liquid-vapor surface tension, but what they do to the two other surface tensions is less clear. We propose an improved Zisman method for quantifying the wetting behavior of surfactants at the solid surface. This allows us to show that a number of very common surfactants do not change the wettability of the solid: they give the same contact angle as a simple liquid with the same liquid-vapor surface tension. Surface-specific sum-frequency generation spectroscopy shows that nonetheless surfactants are present at the solid surface. The surfactants therefore change the solid-liquid and solid-vapor surface tensions by the same amount, leading to an unchanged contact angle.

The growth of hopper crystals is observed for many substances, but the mechanism of their formation remains ill understood. Here we investigate their growth by performing evaporation experiments on small volumes of salt solutions. We show that sodium chloride crystals that grow very fast from a highly supersaturated solution form a peculiar form of hopper crystal consisting of a series of connected miniature versions of the original cubic crystal. The transition between cubic and such hopper growth happens at a well-defined supersaturation where the growth rate of the cubic crystal reaches a maximum (∼6.5 ± 1.8 μm/s). Above this threshold, the growth rate varies as the third power of supersaturation, showing that a new mechanism, controlled by the maximum speed of surface integration of new molecules, induces the hopper growth of cubic crystals in cascade., The Journal of Physical Chemistry Letters, 9 (11), ISSN:1948-7185

The free energy of hard-sphere systems provides a direct link between the particle-scale structure and macroscopic thermodynamic properties. Here, we employ this framework to investigate the shear-induced structure of a colloidal glass, and link it to its macroscopic mechanical and thermodynamic state. We measure the nonequilibrium free energy under shear from the free volumes of the particles, and monitor its evolution with the applied strain. Unlike crystals, for which the elastic energy increases quadratically with strain due to affine particle displacements, for glasses the free energy decreases due to non-affine displacements and dissipation, reflecting the ability of the glass to reach deeper free-energy minima. We model this decrease using the nonaffine shear modulus and a standard viscous dissipative term. Our model and measurements allow us to disentangle the complex contributions of affine and nonaffine particle displacements in the transient shear deformation of glasses.

In many instances, sprays are formed from the breakup of liquid jets or sheets. We investigate the different parameters that determine the characteristic drop size in the breakup of sheets. We vary both the spraying parameters, such as the pressure and geometry of the nozzle, and the fluid parameters, such as viscosity and surface tension. The combined results show that the drop size is determined by a competition between fluid inertia and surface tension, which allows for the prediction of the drop size from the Weber number and geometry of the nozzle. Once rescaled with the average drop size, the size distribution is found to be described by a compound gamma distribution with two parameters, n and m, with the former setting the ligament corrugation and the latter the width of the ligament size distribution. Fit values for m indicate that nozzles of a conical type produce ligaments of almost equal size, while the flat fan nozzles produce broader distributed ligament sizes. Values for n show that, for all nozzles, ligaments are very corrugated, which is not unexpected for such spray formation processes. By using high-speed photography of the sprays, the parameters m and n can be directly measured and, indeed, govern the drop-size distribution.

The spreading of evaporating drops without a pinned contact line is studied experimentally and theoretically, measuring the radius $R(t)$ of completely wetting alkane drops of different volatility on glass. Initially the drop spreads ($R$ increases), then owing to evaporation reverses direction and recedes with an almost constant non-zero contact angle $\unicode[STIX]{x1D703}\propto \unicode[STIX]{x1D6FD}^{1/3}$, where $\unicode[STIX]{x1D6FD}$ measures the rate of evaporation; eventually the drop vanishes at a finite-time singularity. Our theory, based on a first-principles hydrodynamic description, well reproduces the dynamics of $R$ and the value of $\unicode[STIX]{x1D703}$ during retraction.

Pearling instabilities of slender viscoelastic threads have received much attention, but remain incompletely understood. We study the instabilities in polymer solutions subject to uniaxial elongational flow. Two distinctly different instabilites are observed: beads on a string and blistering. The beads-on-a-string structure arises from a capillary instability whereas the blistering instability has a different origin: it is due to a coupling between stress and polymer concentration. By varying the temperature to change the solution properties we elucidate the interplay between flow and phase separation.