Complex Fluid Models of Mixed Quantum-Classical Dynamics.

Several methods in nonadiabatic molecular dynamics are based on Madelung's hydrodynamic description of nuclear motion, while the electronic component is treated as a finite-dimensional quantum system. In this context, the quantum potential leads to severe computational challenges and one often seeks to neglect its contribution, thereby approximating nuclear motion as classical. The resulting model couples classical hydrodynamics for the nuclei to the quantum motion of the electronic component, leading to the structure of a complex fluid system. This type of mixed quantum-classical fluid models has also appeared in solvation dynamics to describe the coupling between liquid solvents and the quantum solute molecule. While these approaches represent a promising direction, their mathematical structure requires a certain care. In some cases, challenging higher-order gradients make these equations hardly tractable. In other cases, these models are based on phase-space formulations that suffer from well-known consistency issues. Here, we present a new complex fluid system that resolves these difficulties. Unlike common approaches, the current system is obtained by applying the fluid closure at the level of the action principle of the original phase-space model. As a result, the system inherits a Hamiltonian structure and retains energy/momentum balance. After discussing some of its structural properties and dynamical invariants, we illustrate the model in the case of pure-dephasing dynamics. We conclude by presenting some invariant planar models.

Fluid fibers in true 3D ferroelectric liquids.

We demonstrate an exceptional ability of a high-polarization 3D ferroelectric liquid to form freely suspended fluid fibers at room temperature. Unlike fluid threads in modulated smectics and columnar phases, where translational order is a prerequisite for forming liquid fibers, recently discovered ferroelectric nematic forms fibers with solely orientational molecular order. Additional stabilization mechanisms based on the polar nature of the mesophase are required for this. We propose a model for such a mechanism and show that these fibers demonstrate an exceptional nonlinear optical response and exhibit electric field-driven instabilities.

Molecular Processes Leading to Shear Banding in Entangled Polymeric Solutions.

The temporal and spatial evolution of shear banding during startup and steady-state shear flow was studied for solutions of entangled, linear, monodisperse polyethylene C3000H6002 dissolved in hexadecane and benzene solvents. A high-fidelity coarse-grained dissipative particle dynamics method was developed and evaluated based on previous NEMD simulations of similar solutions. The polymeric contribution to shear stress exhibited a monotonically increasing flow curve with a broad stress plateau at intermediate shear rates. For startup shear flow, transient shear banding was observed at applied shear rates within the steady-state shear stress plateau. Shear bands were generated at strain values where the first normal stress difference exhibited a maximum, with lifetimes persisting for up to several hundred strain units. During the lifetime of the shear bands, an inhomogeneous concentration distribution was evident within the system, with higher polymer concentration in the slow bands at low effective shear rate; i.e., γ˙<τR-1, and vice versa at high shear rate. At low values of applied shear rate, a reverse flow phenomenon was observed in the hexadecane solution, which resulted from elastic recoil of the molecules within the slow band. In all cases, the shear bands dissipated at high strains and the system attained steady-state behavior, with a uniform, linear velocity profile across the simulation cell and a homogeneous concentration.

Drying Drops of Colloidal Dispersions.

Drying drops of colloidal dispersions have attracted attention from researchers since the nineteenth century. The multiscale nature of the problem involving physics at different scales, namely colloidal and interfacial phenomena as well as heat, mass, and momentum transport processes, combined with the seemingly simple yet nontrivial shape of the drops makes drying drop problems rich and interesting. The scope of such studies widens as the physical and chemical nature of dispersed entities in the drop vary and as evaporation occurs in more complex configurations. This review summarizes past and contemporary developments in the field, emphasizing the physicochemical and hydrodynamical principles that govern the processes occurring within a drying drop and the resulting variety of patterns generated on the substrate.

Numerical Simulation of Rheological Models for Complex Fluids Using Hierarchical Grids.

In this work, we implement models that are able to describe complex rheological behaviour (such as shear-banding and elastoviscoplasticity) in the HiGTree/HiGFlow system, which is a recently developed Computational Fluid Dynamics (CFD) software that can simulate Newtonian, Generalised-Newtonian and viscoelastic flows using finite differences in hierarchical grids. The system uses a moving least squares (MLS) meshless interpolation technique, allowing for more complex mesh configurations while still keeping the overall order of accuracy. The selected models are the Vasquez-Cook-McKinley (VCM) model for shear-banding micellar solutions and the Saramito model for viscoelastic fluids with yield stress. Development of solvers and numerical simulations of inertial flows of these models in 2D channels and planar-contraction 4:1 are carried out in the HiGTree/HiGFlow system. Our results are compared with those predicted by two other methodologies: the OpenFOAM-based software RheoTool that uses the Finite-Volume-Method and an in-house code that uses the Vorticity-Velocity-Formulation (VVF). We found an excellent agreement between the numerical results obtained by these three different methods. A mesh convergence analysis using uniform and refined meshes is also carried out, where we show that great convergence results in tree-based grids are obtained thanks to the finite difference method and the meshless interpolation scheme used by the HiGFlow software. More importantly, we show that our methodology implemented in the HiGTreee/HiGFlow system can successfully reproduce rheological behaviour of high interest by the rheology community, such as non-monotonic flow curves of micellar solutions and plug-flow velocity profiles of yield-stress viscoelastic fluids.

Passive and Active Microrheology for Biomedical Systems.

Microrheology encompasses a range of methods to measure the mechanical properties of soft materials. By characterizing the motion of embedded microscopic particles, microrheology extends the probing length scale and frequency range of conventional bulk rheology. Microrheology can be characterized into either passive or active methods based on the driving force exerted on probe particles. Tracer particles are driven by thermal energy in passive methods, applying minimal deformation to the assessed medium. In active techniques, particles are manipulated by an external force, most commonly produced through optical and magnetic fields. Small-scale rheology holds significant advantages over conventional bulk rheology, such as eliminating the need for large sample sizes, the ability to probe fragile materials non-destructively, and a wider probing frequency range. More importantly, some microrheological techniques can obtain spatiotemporal information of local microenvironments and accurately describe the heterogeneity of structurally complex fluids. Recently, there has been significant growth in using these minimally invasive techniques to investigate a wide range of biomedical systems both in vitro and in vivo. Here, we review the latest applications and advancements of microrheology in mammalian cells, tissues, and biofluids and discuss the current challenges and potential future advances on the horizon.

Swimming faster despite obstacles: a universal mechanism behind bacterial speed enhancement in complex fluids.

Bacteria constitute about 15% of global biomass and their natural environments often contain polymers and colloids, which show complex flow behaviors. It is crucial to study their motion in such environments to understand their growth and spreading as well as to design synthetic microswimmers for biomedical applications. Bacterial motion in complex viscous environments, although extensively studied over the past six decades, still remains poorly understood. In our recent study combining experimental data and theoretical analysis, we found a surprising similarity between bacterial motion in dilute colloidal suspensions and polymer solutions, which challenged the established view on the role of polymer dynamics on bacterial speed enhancement. We subsequently developed a physical model that provides a universal mechanism explaining bacterial speed enhancement in complex fluids.

Continuous Percoll Gradient Centrifugation of Erythrocytes-Explanation of Cellular Bands and Compromised Age Separation.

(1) Background: When red blood cells are centrifuged in a continuous Percoll-based density gradient, they form discrete bands. While this is a popular approach for red blood cell age separation, the mechanisms involved in banding were unknown. (2) Methods: Percoll centrifugations of red blood cells were performed under various experimental conditions and the resulting distributions analyzed. The age of the red blood cells was measured by determining the protein band 4.1a to 4.1b ratio based on western blots. Red blood cell aggregates, so-called rouleaux, were monitored microscopically. A mathematical model for the centrifugation process was developed. (3) Results: The red blood cell band pattern is reproducible but re-centrifugation of sub-bands reveals a new set of bands. This is caused by red blood cell aggregation. Based on the aggregation, our mathematical model predicts the band formation. Suppression of red blood cell aggregation reduces the band formation. (4) Conclusions: The red blood cell band formation in continuous Percoll density gradients could be explained physically by red blood cell aggregate formation. This aggregate formation distorts the density-based red blood cell age separation. Suppressing aggregation by osmotic swelling has a more severe effect on compromising the RBC age separation to a higher degree.

Nanostructured fluids for polymeric coatings removal: Surfactants affect the polymer glass transition temperature.

HYPOTHESIS: Nanostructured fluids (NSFs) based on water, organic solvents and surfactants are a valid alternative to the use of neat unconfined organic solvents for polymer coatings removal in art conservation. The physico-chemical processes underpinning their cleaning effectiveness in terms of swelling/dewetting of polymer films were identified as key in this context. The role of surfactants on polymers' dewetting was considered to be mainly restricted to the lowering of interfacial tensions. However, recent experiments evidenced that surfactants have an important role in swelling polymer films. EXPERIMENTS: Five different amphiphiles were selected, namely: sodium dodecylsulfate, dimethyldodecyl amine oxide, hexaoxyethylene decyl ether (C9-11E6), pentadecaoxyethylene dodecyl ether (C12E15), and methyoxypentadecaoxyethylene dodecanoate (C11COE15CH3). They were combined with a carefully selected organic solvents' mixture (1-butanol/butanone/dimethyl carbonate) to formulate new NSFs, differing for the surfactant only, and used to perform cleaning tests on surfaces coated with Paraloid B72® and Primal AC33®. Here for the first time, polymer swelling induced by surfactants was quantified and correlated with the glass transition temperature of the two polymers by differential scanning calorimetry, before and after the exposure to the fluids. Confocal laser scanning microscopy and small-angle X-ray scattering provided additional insights on the interaction mechanism. FINDINGS: Nonionics were proven more efficient than zwitterionic/ionic amphiphiles in the polymer swelling, and, overall, methyoxy pentadecaoxyethylene dodecanoate resulted the most effective among the selected surfactants. A direct relation between the effect of surfactants on the polymers' glass transition temperature and cleaning capacity was established. This finding, fundamental to understand the interaction mechanism between NSFs and polymer coatings or paint layers, is key to achieve a selective, effective and complete removal of polymer coatings, as recently shown in the removal of vandalism and over-paintings from street art.

Viscosity Model for Nanoparticulate Suspensions Based on Surface Interactions.

In this paper, a widely mechanistic model was developed to depict the rheological behaviour of nanoparticulate suspensions with solids contents up to 20 wt.%, based on the increase in shear stress caused by surface interaction forces among particles. The rheological behaviour is connected to drag forces arising from an altered particle movement with respect to the surrounding fluid. In order to represent this relationship and to model the viscosity, a hybrid modelling approach was followed, in which mechanistic relationships were paired with heuristic expressions. A genetic algorithm was utilized during model development, by enabling the algorithm to choose among several hard-to-assess model options. By the combination of the newly developed model with existing models for the various physical phenomena affecting viscosity, it can be applied to model the viscosity over a broad range of solids contents, shear rates, temperatures and particle sizes. Due to its mechanistic nature, the model even allows an extrapolation beyond the limits of the data points used for calibration, allowing a prediction of the viscosity in this area. Only two parameters are required for this purpose. Experimental data of an epoxy resin filled with boehmite nanoparticles were used for calibration and comparison with modelled values.

Origins of Clustering of Metalate-Extractant Complexes in Liquid-Liquid Extraction.

Effective and energy-efficient separation of precious and rare metals is very important for a variety of advanced technologies. Liquid-liquid extraction (LLE) is a relatively less energy intensive separation technique, widely used in separation of lanthanides, actinides, and platinum group metals (PGMs). In LLE, the distribution of an ion between an aqueous phase and an organic phase is determined by enthalpic (coordination interactions) and entropic (fluid reorganization) contributions. The molecular scale details of these contributions are not well understood. Preferential extraction of an ion from the aqueous phase is usually correlated with the resulting fluid organization in the organic phase, as the longer-range organization increases with metal loading. However, it is difficult to determine the extent to which organic phase fluid organization causes, or is caused by, metal loading. In this study, we demonstrate that two systems with the same metal loading may impart very different organic phase organizations and investigate the underlying molecular scale mechanism. Small-angle X-ray scattering shows that the structure of a quaternary ammonium extractant solution in toluene is affected differently by the extraction of two metalates (octahedral PtCl62- and square-planar PdCl42-), although both are completely transferred into the organic phase. The aggregates formed by the metalate-extractant complexes (approximated as reverse micelles) exhibit a more long-range order (clustering) with PtCl62- compared to that with PdCl42-. Vibrational sum frequency generation spectroscopy and complementary atomistic molecular dynamics simulations on model Langmuir monolayers indicate that the two metalates affect the interfacial hydration structures differently. Furthermore, the interfacial hydration is correlated with water extraction into the organic phase. These results support a strong relationship between the organic phase organizational structure and the different local hydration present within the aggregates of metalate-extractant complexes, which is independent of metalate concentration.

The effect of viscoelasticity in an airway closure model.

The closure of a human lung airway is modeled as a pipe coated internally with a liquid that takes into account the viscoelastic properties of mucus. For a thick enough coating, the Plateau-Rayleigh instability blocks the airway by the creation of a liquid plug, and the pre-closure phase is dominated by the Newtonian behavior of the liquid. Our previous study with a Newtonian-liquid model demonstrated that the bifrontal plug growth consequent to airway closure induces a high level of stress and stress gradients on the airway wall, which is large enough to damage the epithelial cells, causing sub-lethal or lethal responses. In this study, we explore the effect of the viscoelastic properties of mucus by means of the Oldroyd-B and FENE-CR model. Viscoelasticity is shown to be very relevant in the post-coalescence process, introducing a second peak of the wall shear stresses. This second peak is related to an elastic instability due to the presence of the polymeric extra stresses. For high-enough Weissenberg and Laplace numbers, this second shear stress peak is as severe as the first one. Consequently, a second lethal or sub-lethal response of the epithelial cells is induced.

Chitin nanocrystals based complex fluids: A green nanotechnology.

Chitin biopolymer has received significant attention recently by many industries as a green technology. Nanotechnology has been used to make chitin nanocrystals (ChiNCs) that are rod-shaped natural nanomaterials with nanoscale size. Owing to the unique features such as biodegradability, biocompatibility, renewability, rod-shape, and excellent surface and interfacial, physiochemical, and thermo-mechanical properties; ChiNCs have been green and attractive products with wide applications specifically in medical and pharmaceutical, food and packaging, cosmetic, electrical, and electronic, and also in the oil and gas industry. This review aims to give a comprehensive and applied insight into ChiNCs technology. It starts with reviewing different sources of chitin and their extraction methods followed by the characterization of ChiNCs. Furthermore, a detailed investigation into various complex fluids (dispersions, emulsions, foams, and gels) stabilized by ChiNCs and their characterisation have been thoroughly deliberated. Finally, the current status including ground-breaking applications, untapped investigations, and future prospective have been presented.

Gradient stretching to produce variable aspect ratio colloidal ellipsoids.

Developing reliable synthetic methods for producing shape-anisotropic polymer colloids is essential for their use in novel functional materials. In designing such materials from ellipsoidal particles, it is often necessary to screen a wide range of particle sizes and aspect ratios to appropriately understand how microscopic particle characteristics dictate macroscopic material response. Here, we describe a technique to simultaneously produce a broad range of aspect ratio polymer ellipsoid samples from a single synthetic step. The technique extends the traditional film-stretching approach to create ellipsoids by introducing a gradient in strain and film cooling, which results in varying degrees of particle stretching. We empirically calibrate the device such that the final particle elongation may be predicted from the film characteristics, enabling the selective harvesting of ellipsoids with desired dimensions and which can be isolated by aspect ratio. The method is applied successfully to a wide range of seed particle diameters (500 nm - 10 µm) and enables the rapid synthesis of variable aspect ratio particles for systematic studies of anisotropic particles.

Fluctuating viscoelasticity based on a finite number of dumbbells.

Two alternative routes are taken to derive, on the basis of the dynamics of a finite number of dumbbells, viscoelasticity in terms of a conformation tensor with fluctuations. The first route is a direct approach using stochastic calculus only, and it serves as a benchmark for the second route, which is guided by thermodynamic principles. In the latter, the Helmholtz free energy and a generalized relaxation tensor play a key role. It is shown that the results of the two routes agree only if a finite-size contribution to the Helmholtz free energy of the conformation tensor is taken into account. Using statistical mechanics, this finite-size contribution is derived explicitly in this paper for a large class of models; this contribution is non-zero whenever the number of dumbbells in the volume of observation is finite. It is noted that the generalized relaxation tensor for the conformation tensor does not need any finite-size correction.

Jet instability of a shear-thickening concentrated suspension.

We investigate the flow of a concentrated suspension of colloidal particles at deformation rates higher than the discontinuous shear-thickening transition shear rate. We show that, under its own weight, a jet of a concentrated enough colloidal suspension, simultaneously flows while it sustains tensile stress and transmits transverse waves. This results in a new flow instability of jets of shear-thickening suspensions: the jet is submitted to rapid transverse oscillations, that we characterize.

Pseudo-turbulence in two-dimensional buoyancy-driven bubbly flows: A DNS study.

We present a direct numerical simulation (DNS) study of buoyancy-driven bubbly flows in two dimensions. We employ the volume of fluid (VOF) method to track the bubble interface. To investigate the spectral properties of the flow, we derive the scale-by-scale energy budget equation. We show that the Galilei number (Ga) controls different scaling regimes in the energy spectrum. For high Galilei numbers, we find the presence of an inverse energy cascade. Our study indicates that the density ratio of the bubble with the ambient fluid or the presence of coalescence between the bubbles does not alter the scaling behaviour.

Relating the physical properties of aqueous solutions of ionic liquids with their chemical structures.

The physical properties of an aqueous solution of a macromolecule primarily depend on its chemical structure and the mesoscopic aggregates formed by many of such molecules. Ionic liquids (ILs) are the macromolecules that have caught significant research interests for their enormous industrial and biomedical applications. In the present paper, the physical properties, such as density, viscosity, ionic conductivity of aqueous solutions of various ILs, have been investigated. These properties are found to systematically depend on the shape and size of the anion and the cation along with the solution concentration. The ionic conductivity and viscosity behavior of the solutions do not strictly follow the Walden rule that relates the conductivity to the viscosity of the solution. However, the modified Walden rule could explain the behavior. A simple calculation based on the geometry of a given molecule could shed the light on the observed results.

Porosity effect on the linear stability of flow overlying a porous medium.

We study how the stability of a homogeneous incompressible fluid flow over a saturated Brinkman porous medium is affected by a change in porosity. We produce neutral curves using the shooting method in the area of bimodality. When the porosity decreases, the topology of these curves changes because of the interplay between two instability modes. The long-wave instability is dominant if the medium is highly porous. In contrast, the short-wave instability is the most significant at low porosity because of high tangential stress at the fluid-medium interface. We identify a stability gap between the neutral curve branches within a narrow range of porosity values. The calculated results show the development and disappearance of this gap when the porosity changes.

Ensembles, turbulence and fluctuation theorem.

The fluctuation theorem is considered intrinsically linked to reversibility and therefore its phenomenological consequence, the fluctuation relation, is sometimes considered not applicable. Nevertheless here is considered the paradigmatic example of irreversible evolution, the 2D Navier-Stokes incompressible flow, to show how universal properties of fluctuations in systems evolving irreversibily could be predicted in a general context. Together with a formulation of the theoretical framework several open questions are formulated and a few more simulations are provided to illustrate the results and to stimulate further checks.