Search

What measurable physical properties allow one to distinguish surfactant-stabilised from Pickering emulsions? Whereas surfactants influence oil/water interfaces by lowering the oil/water interfacial tension, particles are assumed to have little effect on the interfacial tension. Here we perform interfacial tension (IFT) measurements on three different systems: (1) soybean oil and water with ethyl cellulose nanoparticles (ECNPs), (2) silicone oil and water with the globular protein bovine serum albumin (BSA), and (3) sodium dodecyl sulfate (SDS) solutions and air. The first two systems contain particles, while the third system contains surfactant molecules. We observe a significant decrease in interfacial tension with increasing particle/molecule concentration in all three systems. We analyse the surface tension data using the Gibbs adsorption isotherm and the Langmuir equation of state for the surface, resulting in surprisingly high adsorption densities for the particle-based systems. These seem to behave very much like the surfactant system: the decrease in tension is due to the presence of many particles at the interface, each with an adsorption energy of a few kBT. Dynamic interfacial tension measurements show that the systems are in equilibrium, and that the characteristic time scale for adsorption is much longer for particle-based systems than for surfactants, in line with their size difference. In addition, the particle-based emulsion is shown to be less stable against coalescence than the surfactant-stabilised emulsion. This leaves us with the conclusion that we are not able to make a clear distinction between the surfactant-stabilised and Pickering emulsions.

The desiccation of bio-fluid droplets leads to the formation of complex deposits which are morphologically affected by the environmental conditions, such as temperature. In this work, we examine the effect of substrate temperatures between 20oC and 40oC, on the desiccation deposits of foetal bovine serum (FBS) droplets. The final dried deposits consist of different zones: a peripheral protein ring, a zone of protein structures, a protein gel, and a central crystalline zone. We focus on the crystalline zone showing that its morphological and topographical characteristics vary with substrate temperature. The area of the crystalline zone is found to shrink with increasing substrate temperature. Additionally, the morphology of the crystalline structures changes from dendritic at 20oC, to cell-like for substrate temperatures between 25oC and 40oC. Calculation of the thermal and solutal Bénard-Marangoni numbers shows that, whilst thermal effects are negligible when drying takes place at 20oC, for higher substrate temperatures (25oC-40oC), both thermal and solutal convective effects manifest within the drying drops. Thermal effects dominate earlier in the evaporation process leading, we believe, to the development of instabilities, and in turn, to the formation of convective cells in the drying drops. Solutal effects, on the other hand, are dominant towards the end of drying, maintaining circulation within the cells and leading to crystallisation of salts in the formed cells. Thus, we believe that the cell-like structures result from the interplay between thermal and solutal convection during drying. Dendritic growth is associated with a thicker fluid layer in the crystalline zone, compared to cell-like growth with thinner layers. For cell-like structures, we show that the number of cells increases with temperature and the area occupied by each cell decreases. The average distance between cells decreases linearly with substrate temperature.

Hydrodynamic lubrication is studied for both shear thinning and viscoelastic polymer solutions. We find that elasticity, notably strong normal stresses, does not change the friction significantly for the range of parameters tested in this manuscript. Shear-thinning properties, on the other hand, do change the formation of the lubricating layer thickness and the dependence of friction on velocity relative to Newtonian fluids. A hydrodynamic model that includes shear thinning is developed and compared to experimental data. The model describes the dependence on lubrication parameters well, but underestimates the lubricating layer thickness by a constant factor of roughly 1.5. The theory allows us to define a Hersey-like number for shear-thinning fluids that describes the lubricating layer thickness as a result of the balance between normal load and viscous force. For each tested liquid it succeeds in collapsing friction measurements onto the same curve. The friction analysis for both lubrication theory and experiments then reveals that shear thinning mainly changes the layer thickness, which is the main determinant of the friction coefficient.

Inspired by ideas from NMR, we have developed Infrared Diffusion-Ordered Spectroscopy (IR-DOSY), which simultaneously characterizes molecular structure and size. We rely on the fact that the diffusion coefficient of a molecule is determined by its size through the Stokes-Einstein relation, and achieve sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration in an IR-frequency resolved manner. Analogous to NMR-DOSY, a two-dimensional IR-DOSY spectrum has IR frequency along one axis and diffusion coefficient (or equivalently, size) along the other, so the chemical structure and the size of a compound are characterized simultaneously. In an IR-DOSY spectrum of a mixture, molecules with different sizes are nicely separated into distinct sets of IR peaks. Extending this idea to higher dimensions, we also perform 3D-IR-DOSY, in which we combine the conformation sensitivity of femtosecond multi-dimensional IR spectroscopy with size sensitivity.

We investigate the effect of the addition of polymers on the flow properties of emulsions. Surfactant-stabilised 80 v% oil-in-water emulsions, exhibiting a yield stress, with either xanthan gum (a stiff, rodlike polymer) or polyethylene oxide (PEO, a flexible, elastic polymer) in the continuous phase (concentrations between 0.005 wt% and 0.5 wt%) are prepared and investigated using shear rheology and confocal microscopy. The flow properties of the emulsions are very robust, and only at high concentrations of polymer (≥ 0.2 wt%), significant changes in the flow properties are observed. In the case of xanthan gum, higher shear stresses are measured. For high concentrations the yield stress is masked by the high zero shear viscosity and shear thinning behaviour of the xanthan gum giving rise to an apparent second power law regime. In the case of PEO, an increase in the shear thinning exponent is observed, together with a decrease in the yield stress. The interaction of PEO with the surfactant SDS (sodium dodecyl sulfate) at higher PEO concentrations strongly affects the emulsion rheology, perhaps by reducing the friction coefficient between the oil droplets.

A circular jet breaks up into droplets via the Rayleigh-Plateau instability, retaining a circular cross section throughout. If, however, the nozzle from which the jet issues is elongated, the circular symmetry is broken, and the jet forms a chainlike structure with neighboring links separated by 90∘. The cause of this structure is two-dimensional capillary-inertial oscillation of jet cross sections in their own plane. We perform an experimental study of chain oscillations as a function of flow rate using careful prelaminarization and 12 elliptical nozzles with different areas and eccentricities. The oscillation frequencies inferred from the observed chain-link structure do not agree with those predicted by Rayleigh's infinitesimal theory [L. Rayleigh, Proc. R. Soc. London 29A, 71 (1879)]. However, they do agree with an extended nonlinear theory of Bohr [N. Bohr, Philos. Trans. R. Soc. A 209, 281 (1909)10.1098/rsta.1909.0012] that accounts for finite-amplitude effects. This agreement shows that our fluid chains are nonlinear oscillations whose frequency decreases with increasing amplitude. We perform direct numerical simulations of chain oscillations using a volume-of-fluid method and find good agreement with the predictions of Bohr's theory. Finally, we generalize Bohr's theory to the case of two interacting modes with quadrupolar and octapolar azimuthal dependencies. The resulting solution explains qualitatively the "dimpled"shape of the jet's surface observed in the experiments.

The remarkable elastic properties of polymers are ultimately due to their molecular structure, but the relation between the macroscopic and molecular properties is often difficult to establish, in particular for (bio)polymers that contain hydrogen bonds, which can easily rearrange upon mechanical deformation. Here we show that two-dimensional infrared spectroscopy on polymer films in a miniature stress tester sheds new light on how the hydrogen-bond structure of a polymer is related to its visco-elastic response. We study thermoplastic polyurethane, a block copolymer consisting of hard segments of hydrogen-bonded urethane groups embedded in a soft matrix of polyether chains. The conventional infrared spectrum shows that upon deformation, the number of hydrogen bonds increases, a process that is largely reversible. However, the 2DIR spectrum reveals that the distribution hydrogen-bond strengths becomes slightly narrower after a deformation cycle, due to the disruption of weak hydrogen bonds, an effect that could explain the strain-cycle induced softening (Mullins effect) of polyurethane. These results show how rheo-2DIR spectroscopy can bridge the gap between the molecular structure and the macroscopic elastic properties of (bio)polymers.

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

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.

BACKGROUND: There is a persistent concern over the risk of respiratory pathogen transmission, including SARS-CoV-2, via the formation of aerosols (ie, a suspension of microdroplets and residual microparticles after evaporation) generated during high-flow nasal cannula (HFNC) oxygen therapy in critically ill patients. This concern is fueled by limited available studies on this subject. In this study, we tested our hypothesis that HFNC treatment is not associated with increased aerosol formation as compared to conventional oxygen therapy. METHODS: We used laser light scattering and a handheld particle counter to detect and quantify aerosols in healthy subjects and in adults with acute respiratory disease, including COVID-19, during HFNC or conventional oxygen therapy.RESULTS: The use of HFNC was not associated with increased formation of aerosols as compared to conventional oxygen therapy in both healthy subjects (n = 3) and subjects with acute respiratory disease, including COVID-19 (n = 17).CONCLUSIONS: In line with scarce previous clinical and experimental findings, our results indicate that HFNC itself does not result in overall increased aerosol formation as compared to conventional oxygen therapy. This suggests there is no increased risk of respiratory pathogen transmission to health care workers during HFNC.

Cardiac exercise stress testing (CEST) is an important diagnostic tool in daily cardiology practice. However, during intense physical activity microdroplet aerosols, potentially containing SARS-CoV-2 particles, can persist in a room for a long time. This poses a potential infection risk for the medical staff involved in CEST, as well as for the patients entering the same room afterwards. We measured aerosol generation and persistence, to perform a risk assessment for SARS-CoV-2 transmission through aerosols during CEST. We find that during CEST, the aerosol levels remain low enough that SARS-CoV-2 transmission through aerosols is unlikely, with the room ventilation system producing 14 air changes per hour. A simple measurement of CO2 concentration gives a good indication of the ventilation quality.

The effect of viscoelasticity on sprays produced from agricultural flat fan nozzles is investigated experimentally using dilute aqueous solutions of polyethylene oxide (PEO). Measurements of the droplet size distribution using laser diffraction reveal that polymer addition to water results in the formation of overall bigger droplets with a broader size distribution. The median droplet size $D_{50}$ is found to increase linearly with the extensional relaxation time of the liquid. The non-dimensional median droplet sizes of different polymer solutions, sprayed at different operating pressures from nozzles of different sizes, rescale on a single master curve when plotted against an empirical function of the Weber and Deborah numbers. Using high-speed photography of the spraying process, we show that the increase in droplet size with viscoelasticity can be partly attributed to an increase of the wavelength of the flapping motion responsible for the sheet breakup. We also show that droplet size distributions, rescaled by the average drop size, are well described by a compound gamma distribution with parameters $n$ and $m$ encoding for the ligament corrugation and the width of the ligament size distribution, respectively. These parameters are found to saturate to values $n=4$ and $m=4$ at high polymer concentrations., Comment: 21 pages, 11 figures

The convective transport rate of polymers through confined geometries depends on their size, allowing for size-based separation of polymer mixtures (chromatography). Here, we investigate whether mixtures of active polymers can be separated in a similar manner based on their activity. We use thin, living Tubifex tubifex worms as a model system for active polymers and study the transport of these worms by an imposed flow through a channel filled with a hexagonal pillar array. The transport rate through the channel depends strongly on the degree of activity, an effect that we assign to the different distribution of conformations sampled by the worms depending on their activity. Our results demonstrate a unique way to sort mixtures of active polymers based on their activity and provide a versatile and convenient experimental system to investigate the hydrodynamics of active polymers.

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.

Capillary adhesion due to water adsorption from the air can contribute to friction, especially for smooth interfaces in humid environments. We show that for multiasperity (naturally oxidized) Si-on-Si interfaces, the friction coefficient goes through a maximum as a function of relative humidity. An adhesion model based on the boundary element method that takes the roughness of the interfaces into account reproduces this nonmonotonic behavior very well. Remarkably, we find the dry friction to be significantly lower than the lubricated friction with macroscopic amounts of water present. The difference is attributed to the hydrogen-bonding network across the interface. Accordingly, the lubricated friction increases significantly if the water is replaced by heavy water (D2O) with stronger hydrogen bonding.

Viscosity is a key property of liquids, but it is difficult to measure in short-lived, metastable samples due to the long measuring times required by conventional rheology. Here, we show how this problem can be solved by using fluorescent molecular rotors. The excited-state fluorescence decay rate of these molecules is sensitive to the viscosity of their local environment, and by combining pulsed laser excitation with time-resolved fluorescence detection, we can measure viscosities with a time resolution of a few ns. We demonstrate this by measuring in real time the viscosity change in glycerol induced by a nanosecond temperature jump. This new approach makes it possible to measure the viscosity of extremely short-lived states of matter.

The transition from static to dynamic friction is often described as a fracture instability. However, studies on slow sliding processes aimed at understanding frictional instabilities and earthquakes report slow friction transients that are usually explained by empirical rate-and-state formulations. We perform very slow ($$\sim$$ ∼ nm/s) macroscopic-scale sliding experiments and show that the onset of frictional slip is governed by continuous non-monotonic dynamics originating from a competition between contact aging and shear-induced rejuvenation. This allows to describe both our non-monotonic dynamics and the simpler rate-and-state transients with a single evolution equation.

Objectives Needle-free jet injectors are frequently used in dermatological practice. Injection-generated small-droplet aerosols could be harmful upon inhalation when chemotherapeutics, like bleomycin, are used. Here, we aim to explore jet injector-induced small-droplet aerosol formation of bleomycin in relation to air ventilation and to provide safety measures for clinical practice. Materials and Methods With a professional particle sensor, we measured airborne aerosol particles (0.2-10.0 mu m) after electronic pneumatic injection (EPI), spring-loaded jet injection (SLI), and needle injection (NI) of bleomycin and saline (100 mu l) on ex vivo human skin. Three levels of air ventilation were explored: no ventilation, room ventilation, and room ventilation with an additional smoke evacuator. Results EPI and SLI induced significant small-droplet aerosol formation compared with none after NI (0.2-1.0 mu m; no ventilation). The largest bleomycin aerosol generation was observed for the smallest particles (0.2-1.0 mu m) with 673.170 (528.802-789.453) aerosol particles/liter air (EPI; no ventilation). Room ventilation and smoke evacuation led to a reduction of >= 99% and 100% of measured aerosols, respectively. Conclusion Jet injectors generate a high number of small-droplet aerosols, potentially introducing harmful effects to patients and healthcare personnel. Room ventilation and smoke evacuation are effective safety measures when chemotherapeutics are used in clinical practice.

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.

We study the influence of high NaCl concentrations on the equilibrium and dynamic surface tensions of ionic (CTAB) and nonionic (Tween 80) surfactant solutions. Equilibrium surface tension measurements show that NaCl significantly reduces the critical micellar concentration (CMC) of CTAB but has no effect on the CMC of Tween 80. Dynamic surface tension measurements allow comparing the surface tension as a function of time for pure surfactant solutions and in the presence of NaCl. For the ionic surfactant, the dynamics agree with the usual diffusion-limited interfacial adsorption kinetics; however, the kinetics become orders of magnitude slower when NaCl is present. Sum-frequency generation spectroscopy experiments and the equilibrium adsorption measurements show that the presence of NaCl in CTAB solution leads to the formation of ion pairs at the surface, thereby neutralizing the charge of the head group of CTAB. This change, however, is not able to account for the slowing down of adsorption dynamics; we find that it is rather the decreases in the monomer concentration (CMC) in the presence of salt which has the major influence. For the nonionic surfactant, the kinetics of interfacial tension is seen to be already very slow, and the addition of salt does not influence it further. This also correlates very well to the very low CMC of Tween 80.

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.

Droplet impacts are common in many applications such as coating, spraying, or printing; understanding how droplets spread after impact is thus of utmost importance. Such impacts may occur with different velocities on a variety of substrates. The fluids may also be non-Newtonian and thus possess different rheological properties. How the different properties such as surface roughness and wettability, droplet viscosity, and rheology as well as interfacial properties affect the spreading dynamics of the droplets and the eventual drop size after impact are unresolved questions. Most recent work focuses on the maximum spreading diameter after impact and uses scaling laws to predict this. In this paper, we show that a proper rescaling of the spreading dynamics with the maximum radius attained by the drop and the impact velocity leads to a unique single and thus universal curve for the variation of diameter versus time. The validity of this universal functional shape is validated for different liquids with different rheological properties as well as substrates with different wettabilities. This universal function agrees with a recent model that proposes a closed set of differential equations for the spreading dynamics of droplets.