Search

Nanocomposites formed by mixing nanoparticles and polymers offer a limitless creative space for the design of functional advanced materials with a broad range of applications in materials and biological sciences. Here we focus on aqueous dispersions of hydrophobic colloidal soot particles, namely carbon black (CB) dispersed with a sodium salt of carboxymethylcellulose (CMC), a food additive known as cellulose gum that bears hydrophobic groups, which are liable to bind physically to CB particles. Varying the relative content of CB nanoparticles and cellulose gum allows us to explore a rich phase diagram that includes a gel phase. We investigate this hydrogel using rheometry and electrochemical impedance spectroscopy. CB-CMC hydrogels display two radically different types of mechanical behaviors that are separated by a critical CMC-to-CB mass ratio $r_c$. For $rr_c$ CB-CMC gels display a power-law viscoelastic spectrum that depends strongly on the CMC concentration. These relaxation spectra can be rescaled onto a master curve that exhibits a power-law scaling in the high-frequency limit, with an exponent that follows Zimm theory, showing that CMC plays a key role in the gel viscoelastic properties for $r>r_c$. Our results offer a characterization of CB-CMC dispersions that will be useful for designing nanocomposites based on hydrophobic interactions., Comment: 18 pages, 10 figures, and 6 supplemental figures

Oscillatory rheometric techniques such as small amplitude oscillatory shear (SAOS) and, more recently, medium amplitude oscillatory shear and large amplitude oscillatory shear (LAOS) are widely used for rheological characterization of the viscoelastic properties of complex fluids. However, in a time-evolving or mutating material, the build-up or breakdown of microstructure is commonly both time- and shear-rate (or shear-stress) dependent, and thixotropic phenomena are observed in many complex fluids including drilling fluids, biopolymer gels, and many food products. Conventional applications of Fourier transforms for analyzing oscillatory data assume the signals are time-translation invariant, which constrains the mutation number of the material to be extremely small. This constraint makes it difficult to accurately study shear-induced microstructural changes in thixotropic and gelling materials, and it is becoming increasingly important to develop more advanced signal processing techniques capable of robustly extracting time-resolved frequency information from oscillatory data. In this work, we explore applications of the Gabor transform (a short-time Fourier transform combined with a Gaussian window), for providing optimal joint time-frequency resolution of a mutating material’s viscoelastic properties. First, we show using simple analytic models and measurements on a bentonite clay that the Gabor transform enables us to accurately measure rapid changes in both the storage and/or loss modulus with time as well as extract a characteristic thixotropic/aging time scale for the material. Second, using the Gabor transform we demonstrate the extraction of useful viscoelastic data from the initial transient response following the inception of oscillatory flow. Finally, we consider extension of the Gabor transform to nonlinear oscillatory deformations using an amplitude-modulated input strain signal, in order to track the evolution of the Fourier–Tschebyshev coefficients of thixotropic fluids at a specified deformation frequency. We refer to the resulting test protocol as Gaborheometry (Gabor-transformed oscillatory shear rheometry). This unconventional, but easily implemented, rheometric approach facilitates both SAOS and LAOS studies of time-evolving materials, reducing the number of required experiments and the data postprocessing time significantly.

We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low functionality ( f) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high- f junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high- f junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high- f) and metal ion (low- f) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high- f networks.

Soft particulate gels include materials we can eat, squeeze, or 3D print. From foods to bio-inks to cement hydrates, these gels are composed of a small amount of particulate matter (proteins, polymers, colloidal particles, or agglomerates of various origins) embedded in a continuous fluid phase. The solid components assemble to form a porous matrix, providing rigidity and control of the mechanical response, despite being the minority constituent. The rheological response and gel elasticity are direct functions of the particle volume fraction $\phi$: however, the diverse range of different functional dependencies reported experimentally has, to date, challenged efforts to identify general scaling laws. Here we reveal a hidden hierarchical organization of fractal elements that controls the viscoelastic spectrum, and which is associated with the spatial heterogeneity of the solid matrix topology. The fractal elements form the foundations of a viscoelastic master curve, which we construct using large-scale 3D microscopic simulations of model gels, and can be described by a recursive rheological ladder model over a range of particle volume fractions and gelation rates. The hierarchy of the fractal elements provides the missing general framework required to predict the gel elasticity and the viscoelastic response of these ubiquitous complex materials.

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.

Summary Manganese dioxide is abundant, low-cost, and has the potential to be utilized as a semi-solid electrode for long-duration energy storage technologies such as flow batteries. However, the more stringent pumping requirements of semi-solid electrodes compared to the electrolytes of all-liquid flow battery might limit their techno-economic feasibility. Here, we developed a rechargeable MnO2 semi-solid electrode, performed electrochemical and rheological characterizations, and bottom-up techno-economic analysis of the Zn-MnO2 semi-solid flow battery (SSFB) system. The high power needed for pumping (ranging from 8% to 50% of the power output) leads to a system with high cost of power. Using our experimental results, we suggest strategies to minimize the pumping power requirement for Zn-MnO2 SSFB. As a result of the low cost of its chemical constituents, we show that a Zn-MnO2 SSFB can be cheaper than Li-ion and vanadium redox flow battery solutions for long discharge durations (e.g., >24 h per cycle).

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.

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.

Characterizing and understanding the viscoelastic mechanical properties of natural and synthetic fibers is of great importance in many biological and industrial applications. Microscopic techniques such as micro/nano indentation have been successfully employed in such efforts, yet these tests are often challenging to perform on fibers and come with certain limitations in the interpretation of the obtained results within the context of the macroscopic viscoelasticity in the fiber. Here we instead explore the properties of a series of natural and synthetic fibers, using a freely-oscillating torsional pendulum. The torsional oscillation of the damped mass-fiber system is precisely recorded with a simple HD video-camera and an image processing algorithm is used to analyze the resulting videos. Analysis of the processed images show a viscoelastic damped oscillatory response and a simple mechanical model describes the amplitude decay of the oscillation data very well. The natural frequency of the oscillation and the corresponding damping ratio can be extracted using a logarithmic decrement method and directly connected to the bulk viscoelastic properties of the fiber. We further study the sensitivity of these measurements to changes in the chemo-mechanical properties of the outer coating layers on one of the synthetic fibers. To quantify the accuracy of our measurements with the torsional pendulum, a complementary series of tests are also performed on a strain-controlled rheometer in both torsional and tensile deformation modes.

Patchy particle interactions are predicted to facilitate the controlled self-assembly and arrest of particles into phase-stable and morphologically tunable "equilibrium" gels, which avoids the arrested phase separation and subsequent aging that is typically observed in traditional particle gels with isotropic interactions. Despite these promising traits of patchy particle interactions, such tunable equilibrium gels have yet to be realized in the laboratory due to experimental limitations associated with synthesizing patchy particles in high yield. Here, we introduce a supramolecular metal-coordination platform consisting of metallic nanoparticles linked by telechelic polymer chains, which validates the predictions associated with patchy particle interactions and facilitates the design of equilibrium particle hydrogels through limited valency interactions. We demonstrate that the interaction valency and self-assembly of the particles can be effectively controlled by adjusting the relative concentration of polymeric linkers to nanoparticles, which enables the gelation of patchy particle hydrogels with programmable local anisotropy, morphology, and low mechanical percolation thresholds. Moreover, by crowding the local environment around the patchy particles with competing interactions, we introduce an independent method to control the self-assembly of the nanoparticles, thereby enabling the design of highly anisotropic particle hydrogels with substantially reduced percolation thresholds. We thus establish a canonical platform that facilitates multifaceted control of the self-assembly of the patchy nanoparticles en route to the design of patchy particle gels with tunable valencies, morphologies, and percolation thresholds. These advances lay important foundations for further fundamental studies of patchy particle systems and for designing tunable gel materials that address a wide range of engineering applications.

A new mathematical representation for nonlinear viscoelasticity is presented based on application of the Volterra series expansion to the general nonlinear relationship between shear stress and shear strain history. This theoretical and experimental framework, which we call Medium Amplitude Parallel Superposition (MAPS) Rheology, reveals a new material property, the third order complex modulus, which describes completely the weakly nonlinear response of a viscoelastic material in an arbitrary simple shear flow. In this first part, we discuss several theoretical aspects of this mathematical formulation and new material property. For example, we show how MAPS measurements can be performed in strain- or stress-controlled contexts and provide relationships between the weakly nonlinear response functions measured in each case. We show that the MAPS response function is a super-set of the response functions that have been previously reported in medium amplitude oscillatory shear and parallel superposition rheology experiments. We also show how to exploit inherent symmetries of the MAPS response function to reduce it to a minimal domain for straightforward measurement and visualization. We compute this material property for a few constitutive models to illustrate the potential richness of the data sets generated by MAPS experiments. Finally, we discuss the MAPS framework in the context of some other nonlinear, time-dependent rheological probes and explain how the MAPS methodology has a distinct advantage over these others because it generates data embedded in a very high dimensional space without driving fluid mechanical instabilities, and is agnostic to the flow protocol., Comment: 29 pages, 10 figures

© 2020 The Society of Rheology. To enable robust rheological measurements of the properties of yield stress fluids, we introduce a class of modified vane fixtures with fractal-like cross-sectional structures. A greater number of outer contact edges leads to increased kinematic homogeneity at the point of yielding and beyond. The vanes are 3D printed (3DP) using a desktop stereolithography machine, making them inexpensive (disposable), chemically compatible with a wide range of solvents, and readily adaptable as a base for further design innovations. To complete the tooling set, we introduce a textured 3DP cup, which attaches to a standard rheometer base. We discuss general design criteria for 3DP rheometer vanes, including consideration of sample volume displaced by the vanes, stress homogeneity, and secondary flows that constrain the parameter space of potential designs. We also develop a conversion from machine torque to material shear stress for vanes with an arbitrary number of arms. We compare a family of vane designs by measuring the viscosity of Newtonian calibration oils with error

Asphaltenes, heavy aromatic components of crude oil, are known to adsorb on surfaces and can lead to pipe clogging or hinder oil recovery. Because of their multicomponent structure, the details of their interactions with surfaces are complex. We investigate the effect of the physicochemical properties of the substrate on the extent and mechanism of this adsorption. Using wetting measurements, we relate the initial kinetics of deposition to the interfacial energy of the surface. We then quantify the long-term adsorption dynamics using a quartz crystal microbalance and ellipsometry. Finally, we investigate the mechanism and morphology of adsorption with force spectroscopy measurements as a function of surface chemistry. We determine different adsorption regimes differing in orientation, packing density, and initial kinetics on different substrate functionalizations. Specifically, we find that alkane substrates delay the initial monolayer formation, fluorinated surfaces exhibit fast adsorption but low bonding strength, and hydroxyl substrates lead to a different adsorption orientation and a high packing density of the asphaltene layer.

Chlorosulfonic acid and oleum are ideal solvents for enabling the transformation of disordered carbon nanotubes (CNTs) into precise and highly functional morphologies. Currently, processing these solvents using extrusion techniques presents complications due to chemical compatibility, which constrain equipment and substrate material options. Here, we present a novel acid solvent system based on methanesulfonic or p -toluenesulfonic acids with low corrosivity, which form true solutions of CNTs at concentrations as high as 10 g/liter (≈0.7 volume %). The versatility of this solvent system is demonstrated by drop-in application to conventional manufacturing processes such as slot die coating, solution spinning continuous fibers, and 3D printing aerogels. Through continuous slot coating, we achieve state-of-the-art optoelectronic performance (83.6 %T and 14 ohm/sq) at industrially relevant production speeds. This work establishes practical and efficient means for scalable processing of CNT into advanced materials with properties suitable for a wide range of applications.

Carbonated droplets deposited on a superhydrophobic surface float on a self-generated cushion of gas.

The FENE-P (Finitely-Extensible Nonlinear Elastic) dumbbell constitutive equation is widely used in simulations and stability analyses of free and wall-bounded viscoelastic shear flows due to its relative simplicity and accuracy in predicting macroscopic properties of dilute polymer solutions. The model contains three independent material parameters, which expressed in dimensionless form correspond to a Weissenberg number ($\textrm{Wi}$), i.e., the ratio of the dumbbell relaxation time scale to a characteristic flow time scale, a finite extensibility parameter ($L$), corresponding to the ratio of the fully extended dumbbell length to the root mean square end-to-end separation of the polymer chain under equilibrium conditions, and a solvent viscosity ratio, commonly denoted $\beta$. An exact solution for the rheological predictions of the FENE-P model in steady simple shear flow is available [Sureshkumar et al., Phys Fluids (1997)], but the resulting nonlinear and nested set of equations do not readily reveal the key shear-thinning physics that dominates at high $\textrm{Wi}$ as a result of the finite extensibility of the polymer chain. In this note we review a simple way of evaluating the steady material functions characterizing the nonlinear evolution of the polymeric contributions to the shear stress and first normal stress difference as the shear rate increases, provide asymptotic expansions as a function of $\textrm{Wi}$ , and show that it is in fact possible to construct universal master curves for these two material functions as well as the corresponding stress ratio. Steady shear flow experiments on three highly elastic dilute polymer solutions of different finite extensibilities also follow the identified master curves. The governing dimensionless parameter for these master curves is $\textrm{Wi}/L$ and it is only in strong shear flows exceeding $\textrm{Wi}/L \gtrsim 1$ that the effects of finite extensibility of the polymer chains dominate the evolution of polymeric stresses in the flow field. We suggest that reporting the magnitude of $\textrm{Wi}/L$ when performing stability analyses or simulating shear-dominated flows with the FENE-P model will help clarify finite extensibility effects.

This study examines the movement of a small freely rotating spherical particle in a two-dimensional trajectory through a viscoelastic fluid described by the Giesekus model. The fluid equations of motion in the inertialess limit and the Giesekus constitutive equation are expanded as a power series in the Weissenberg number, for which analytical solutions for velocity and pressure profiles at low order can be determined for the case of a steady-state flow. These steady solutions are then related to Fourier-transformed variables in frequency space through the use of correspondence relationships, allowing the analysis of time-dependent particle trajectories. The relative unsteadiness and nonlinearity of these time-dependent flows are quantified through a Deborah and Weissenberg number, respectively. The impact of changing these dimensionless parameters on the characteristics of the flow is discussed at length. We calculate the predicted rate of rotation of a small particle undergoing an arbitrary two-dimensional translation through a viscoelastic fluid, as well as the predicted correction to the force exerted on the particle arising from the interaction of particle rotation and translation. Finally, we calculate the angular velocity and total force including second-order corrections for particles executing a few specific trajectories that have been studied experimentally, as well as the predicted trajectory for a particle being directed by a known time-dependent forcing protocol.

Aqueous foams are useful in several applications, especially to reduce liquid loading in the oil and gas industry. The rheology of these foams evolves rapidly, and suitable constitutive models are required to describe the resulting multiphase flow. We describe a new experimental setup for advanced rheometry involving 4-arm and 12-arm vane-in-textured-cup toolsets. The cup was designed to provide in situ foaming to minimize injection times and flow-history artifacts before measurement, while the 12-arm vane was selected to eliminate slip and generate a homogeneous stress field in a weak foam. Using these tools, we measure the decay of linear viscoelasticity and yield stress and link the rheological evolution to optical measurements of the bubble size distribution. Time-resolved rheological measurements of the full flow curve of an aging foam are performed and used to construct a rheological master curve. Measurements of the transient linear viscoelastic response and observations of the bubble size distribution show that foams, after an initial induction period, experience an increase in the Sauter mean bubble radius that scales as t1/2. Using the well-known Princen and Kiss model as a framework, we define a single unique time-dependent shift factor that varies with the Sauter mean bubble radius and enables us to use the rheological master curve to predict the temporal evolution of the foam's elastic and steady-state viscoplastic properties.

A drop of an aqueous suspension of nanoparticles placed on a substrate forms a solid deposit as it dries. For dilute suspensions, particles accumulate within a narrow ring at the drop edge, whereas a uniform coating covering the entire wetted area forms for concentrated suspensions. In between these extremes, we report two additional regimes characterized by non-uniform deposit thicknesses and by distinct crack morphologies. We show that both the deposit shape and the number of cracks are controlled exclusively by the initial particle volume fraction. The different regimes share a common avalanche-like crack propagation dynamics, as a result of the delamination of the deposit from the substrate.

Flow battery technology offers a promising low-cost option for stationary energy storage applications. Aqueous zinc–nickel battery chemistry is intrinsically safer than non-aqueous battery chemistry (e.g. lithium-based batteries) and offers comparable energy density. In this work, we show how combining high power density and low-yield stress electrodes can minimize energy loss due to pumping, and have demonstrate methods to achieve high energy and power density for ZnO/Ni(OH)2 electrodes by changing composition and optimizing testing protocols. Firstly, mechanically stable and homogeneous Ni(OH)2/carbon and ZnO/Zn flowable electrodes in 7 M KOH electrolyte were designed using a microgel dispersion as the suspending matrix. By determining the critical volume fractions for conductivity percolation, colloidal suspensions with 6.2 vol% of carbon and 23.1 vol% of Zn were selected for preparing catholytes and anolytes to ensure that these semi-solid electrodes possess high voltage and high coulombic efficiencies. The resulting flowable electrodes exhibited non-Newtonian rheology with a yield stress of approximately ∼200 Pa, which assists in maintaining mechanical stability of the suspensions. An energy density of up to 134 W h Lcatholyte−1 and power density up to ∼159 mW cmgeo.−2 was demonstrated for semi-solid ZnO/Ni(OH)2 electrodes, and coulombic efficiency of 94% was achieved during cycling by optimizing the charging protocol to 60% SOC of Ni(OH)2. Lastly, semi-solid ZnO and Ni(OH)2 flow cells were built and tested using an intermittent mode of operation. The high energy and power densities, high coulombic efficiency, and negligible pumping loss of the Zn–Ni semi-solid electrodes developed in the present work present a promising system for further development.

In this work we propose a novel generalised form of the Phan–Thien and Tanner (PTT) model by considering a new functional form of the nonlinear expression characterizing the destruction of physical network junctions and entanglements. This new function of the trace of the stress tensor is given by the generalized Mittag–Leffler function, and contains the familiar exponential form of the original Phan–Thien and Tanner model as a limiting case, but affords additional fitting flexibility through the inclusion of one or two additional fitting constants. We perform fits to experimental data in shear and extension and show that this generalized expression allows a better description of the rheological responses for a range of complex materials such as polymer melts and semidilute polymer solutions. By using an appropriate information criterion, we also demonstrate that the resulting generelized model remains parsimonious but provides improved fits of real world data.

The pinch-off of a bubble is an example of the formation of a singularity, exhibiting a characteristic separation of length and time scales. Because of this scale separation, one expects universal dynamics that collapse into self-similar behavior determined by the relative importance of viscous, inertial, and capillary forces. Surprisingly, however, the pinch-off of a bubble in a large tank of viscous liquid is known to be nonuniversal. Here, we show that the pinch-off dynamics of a bubble confined in a capillary tube undergo a sequence of two distinct self-similar regimes, even though the entire evolution is controlled by a balance between viscous and capillary forces. We demonstrate that the early-time self-similar regime restores universality to bubble pinch-off by erasing the system’s memory of the initial conditions. Our findings have important implications for bubble/drop generation in microfluidic devices, with applications in inkjet printing, medical imaging, and synthesis of particulate materials.

A rigorously-defined method that maps and quantifies the time-resolved dynamical yielding process of elastoviscoplastic materials is proposed and investigated. Building on the foundations of linear viscoelastic theory for oscillatory deformations, the method utilizes the motion of an instantaneous phase angle between the stress and strain of the rheological response within deformation space to quantify the yielding transition. Principal component analysis demonstrates that this phase angle velocity is based on the natural description for a material response in deformation space. The response of the Carreau model with constitutive parameters selected to correspond to a regularized viscoplastic fluid that undergoes an apparent yielding transition at a critical shear rate, and of a Carbopol microgel are investigated as canonical examples of theoretical and experimental model yield stress fluids. Calculation of the phase angle velocity clearly identifies the yield transition as being gradual. This approach provides a physically-motivated understanding of the dynamical processes occurring during yielding of elastoviscoplastic materials.

We introduce a new method for fabricating fiber-like field emitters using pointwise deposition of aqueous suspensions of carbon nanotubes (CNTs). Liquid ink is held between a flat base and an upper locating pin as the ink solvent dries and CNTs densify via capillary forces. The resulting field emitters have high aspect ratios, dense packing of CNTs and, importantly, a large base providing mechanical stability and enhanced thermal/electrical contact compared to emitters fabricated from wet-spun CNT fibers and CNT forests. These attributes enable excellent field emission properties—namely, a high field enhancement factor and low turn-on voltage—for a range of tested emitter sizes. The noteworthy improvements in emission from these CNT structures alongside the versatile fabrication process motivates future work on emitter array manufacturing and device integration.

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

Dissolving small amounts of polymer into a Newtonian fluid can dramatically change the dynamics of transitional and turbulent flows. We investigate the spatiotemporal dynamics of a submerged jet of dilute polymer solution entering a quiescent bath of Newtonian fluid. High-speed digital Schlieren imaging is used to quantify the evolution of Lagrangian features in the jet revealing a rich sequence of transitional and turbulent states. At high levels of viscoelasticity, we identify a new distinct transitional pathway to elastoinertial turbulence (EIT) that does not feature the conventional turbulent bursts and instead proceeds via a shear-layer instability that produces elongated filaments of polymer due to the nonlinear effects of viscoelasticity. Even though the pathways to the EIT state can be different, and within EIT the spatial details of the turbulent structures vary systematically with polymer microstructure and concentration, there is a universality in the power-law spectral decay of EIT with frequency, f^{-3}, independent of fluid rheology and flow parameters.

Periodic surface microtextures inspired by textures of shark denticles can alter the frictional response of a solid wall in flow. Using 3D-printed texture-covered rotors in a bespoke Taylor-Couette cell, the effect of the geometry of the textures and flow dynamics on the frictional torque measurements in Couette flow and Taylor vortex flow regimes are investigated. The changes in the torque measurements show direct dependence on the geometric features of the textures in both flow regimes, while the effect of the Reynolds number is only seen in the Taylor vortex flow.

The injection of long-chain polymer additives and the water-repellent (or superhydrophobic) texturing of submerged solid walls, have both evolved independently over the years into effective, stand-alone methods for frictional drag reduction in wall-bounded turbulent flows. Experiments performed in turbulent Taylor-Couette flow demonstrate that the two techniques, when combined carefully, result in an additive effect, producing significant enhancements in the overall level of drag reduction achieved.

Fizzy water drops levitate and slide freely when placed on a superhydrophobic solid at ambient temperature., As first described by Leidenfrost, liquid droplets levitate over their own vapor when placed on a sufficiently hot substrate. The Leidenfrost effect not only confers remarkable properties such as mechanical and thermal insulation, zero adhesion, and extreme mobility but also requires a high energetic thermal cost. We describe here a previously unexplored approach using active liquids able to sustain levitation in the absence of any external forcing at ambient temperature. We focus on the particular case of carbonated water placed on a superhydrophobic solid and demonstrate how millimetric fizzy drops self-generate a gas cushion that provides levitation on time scales on the order of a minute. Last, we generalize this new regime to different kinds of chemically reactive droplets able to jump from the Cassie-Baxter state to a levitating regime, paving the way to the levitation of nonvolatile liquids.