Synergistic effects between a non-ionic and an anionic surfactant on the micellization process and the adsorption at liquid/air surfaces.

Predicting the behaviour of solutions with surfactants of significantly different critical micelle concentration (CMC) values remains a challenge. The study of the molecular interactions within micelles and interfaces in surfactant combinations used in everyday products is essential to understand these complex systems. In this work, the equilibrium and dynamic surface tension in the presence of mixed non-ionic (tristyrylphenol ethoxylates) and anionic (sodium benzene sulfonate with alkyl chain lengths of C10-C13) surfactants, commonly encountered as delivery systems in agrochemicals, were studied and their CMC values were determined. For the surfactant mixtures, four molar ratios were examined: nEOT/nNaDDBS = 0.01, 0.1, 1, 4 and two different cases were analysed, the premixed and the add one by one surfactant. The surface tension for single surfactants stabilised quickly, while the mixtures needed a long time to reach equilibrium; up to 15 h for the premixed mixtures and 40 min when surfactants were added one by one. The CMC values for the nEOT/nNaDDBS = 0.01, 0.1 premixed surfactant mixtures were found to be in between the CMC values of the single surfactants, but those for the nEOT/nNaDDBS = 1 and 4 mixtures were lower than the CMCs of both single surfactants. Calculations based on the regular solution theory suggested that there are attractive forces in the mixed micelles and at the interface layers, while the supramolecular assemblies in the bulk (i.e., micelles) and at interfaces (surfactant films) are preferentially enriched in EOT.

Analyzing the Accuracy of Critical Micelle Concentration Predictions Using Deep Learning.

This paper presents a novel approach to predicting critical micelle concentrations (CMCs) by using graph neural networks (GNNs) augmented with Gaussian processes (GPs). The proposed model uses learned latent space representations of molecules to predict CMCs and estimate uncertainties. The performance of the model on a data set containing nonionic, cationic, anionic, and zwitterionic molecules is compared against a linear model that works with extended connectivity fingerprints (ECFPs). The GNN-based model performs slightly better than the linear ECFP model when there is enough well-balanced training data and achieves predictive accuracy that is comparable to published models that were evaluated on a smaller range of surfactant chemistries. We illustrate the applicability domain of our model using a molecular cartogram to visualize the latent space, which helps to identify molecules for which predictions are likely to be erroneous. In addition to accurately predicting CMCs for some surfactant classes, the proposed approach can provide valuable insights into the molecular properties that influence CMCs.

Pinching Dynamics and Multiple Droplet Generation in Partial Coalescence.

When a drop merges with its homophase, a liquid cylinder appears in certain conditions, which is pinched off leading to partial coalescence. We investigate the process experimentally and numerically, and find that the Rayleigth-Plateau instability is able to pinch off the cylinder when its height-to-neck ratio exceeds one. Surfactants are found to attenuate the cylinder and produce multiple droplets at moderate concentrations. For both the pinch-off of the mother drop and the subsequent breakup of the liquid threads in partial coalescence, the neck thinning is initially in the inertial (I) regime and then shifts to the inertial-viscous (IV) regime. An intermediate regime is seen at larger surfactant concentrations, which accelerates the thinning and favours the generation of multiple droplets.

A review of acoustofluidic separation of bioparticles.

Acoustofluidics is an emerging interdisciplinary research field that involves the integration of acoustics and microfluidics to address challenges in various scientific areas. This technology has proven to be a powerful tool for separating biological targets from complex fluids due to its label-free, biocompatible, and contact-free nature. Considering a careful designing process and tuning the acoustic field particles can be separated with high yield. Recently the advancement of acoustofluidics led to the development of point-of-care devices for separations of micro particles which address many of the limitations of conventional separation tools. This review article discusses the working principles and different approaches of acoustofluidic separation and provides a synopsis of its traditional and emerging applications, including the theory and mechanism of acoustofluidic separation, blood component separation, cell washing, fluorescence-activated cell sorting, circulating tumor cell isolation, and exosome isolation. The technology offers great potential for solving clinical problems and advancing scientific research.

Surfactant-laden droplet size prediction in a flow-focusing microchannel: a data-driven approach.

The control of droplet formation and size using microfluidic devices is a critical operation for both laboratory and industrial applications, e.g. in micro-dosage. Surfactants can be added to improve the stability and control the size of the droplets by modifying their interfacial properties. In this study, a large-scale data set of droplet size was obtained from high-speed imaging experiments conducted on a flow-focusing microchannel where aqueous surfactant-laden droplets were generated in silicone oil. Three types of surfactants were used including anionic, cationic and non-ionic at concentrations below and above the critical micelle concentration (CMC). To predict the final droplet size as a function of flow rates, surfactant type and concentration of surfactant, two data-driven models were built. Using a Bayesian regularised artificial neural network and XGBoost, these models were initially based on four inputs (flow rates of the two phases, interfacial tension at equilibrium and the normalised surfactant concentration). The mean absolute percentage errors (MAPE) show that data-driven models are more accurate (MAPE = 3.9%) compared to semi-empirical models (MAPE = 11.4%). To overcome experimental difficulties in acquiring accurate interfacial tension values under some conditions, both models were also trained with reduced inputs by removing the interfacial tension. The results show again a very good prediction of the droplet diameter. Finally, over 10 000 synthetic data were generated, based on the initial data set, with a Variational Autoencoder (VAE). The high-fidelity of the extended synthetic data set highlights that this method can be a quick and low-cost alternative to study microdroplet formation in future lab on a chip applications, where experimental data may not be readily available.

Comparison of surfactant mass transfer with drop formation times from dynamic interfacial tension measurements in microchannels.

Dynamic interfacial tension was studied experimentally during drop formation in a flow-focusing microchannel. A low viscosity silicone oil (4.6 mPa s) was the continuous phase and a mixture of 48% w/w water and 52% w/w glycerol was the dispersed phase. An anionic (sodium dodecylsulfate, SDS), a cationic (dodecyltrimethylammonium bromide, DTAB) and a non-ionic (Triton™ X-100, TX100) surfactant were added in the dispersed phase, at concentrations below and above the critical micelle concentration (CMC). For SDS and DTAB the drop size against continuous phase flowrate curves initially decreased with surfactant concentration and then collapsed to a single curve at concentrations above CMC. For TX100 the curves only collapsed at surfactant concentrations 8.6 times the CMC. From the collapsed curves a correlation of drop size with capillary number was derived, which was used to calculate the dynamic interfacial tension at times as low as 3 ms. The comparison of the surfactant mass transport and adsorption times to the interface against the drop formation times indicated that surfactant adsorption also contributes to the time required to reach equilibrium interfacial tension. Criteria were proposed for drop formation times to ensure that equilibrium interfacial tension has been reached and does not affect the drop formation.

Effect of D-Mannitol on the Microstructure and Rheology of Non-Aqueous Carbopol Microgels.

D-mannitol is a common polyol that is used as additive in pharmaceutical and personal care product formulations. We investigated its effect on the microstructure and rheology of novel non-aqueous Carbopol dispersions employing traditional and time-resolved rheological analysis. We considered two types of sample, (i) fresh (i.e., mannitol completely dissolved in solution) and aged (i.e., visible in crystalline form). The analysis of the intracycle rheological transitions that were observed for different samples revealed that, when completely dissolved in solution, mannitol does not alter the rheological behaviour of the Carbopol dispersions. This highlights that the chemical similarity of the additive with the molecules of the surrounding solvent allows preserving the swollen dimension and interparticle interactions of the Carbopol molecules. Conversely, when crystals are present, a hierarchical structure forms, consisting of a small dispersed phase (Carbopol) agglomerated around a big dispersed phase (crystals). In keeping with this microstructural picture, as the concentration of Carbopol reduces, the local dynamics of the crystals gradually start to control the integrity of the microstructure. Rheologically, this results in a higher elasticity of the suspensions at infinitesimal deformations, but a fragile yielding process at intermediate strains.

Scale-Up Studies for Co/Ni Separations in Intensified Reactors.

In this paper, the effect of the scalability of small-scale devices on the separation of Co(II) from a binary Co(II)/Ni(II) mixture in a nitric acid solution by an organic Cyanex 272/TBP/kerosene (Exxsol D80) phase is studied. In particular, circular channels with diameters of 1, 2, and 3.2 mm are considered. The results were compared against those from a confined impinging-jets (CIJ) cell with a main channel diameter of 3.2 mm. The effects of total flowrate, residence time, Cyanex 272 concentration, and flowrate ratio on the mass transfer performance were investigated. It was found that at increased channel size, the throughputs were also increased but the extraction percentages remained the same. Higher extraction percentages were obtained by using the CIJ configuration at short residence times. However, for longer residence times, the mass transfer coefficients were similar and capillary channels should be preferred over the CIJ because of the ease of separation of the two phases at the end of the unit. The overall mass transfer coefficients ranged between 0.02 and 0.14 s-1 for the capillary channels during plug flow and between 0.05 and 0.45 s-1 for the CIJ cells during dispersed flow.

Investigation of the swollen state of Carbopol molecules in non-aqueous solvents through rheological characterization.

We explore how different types of solvent influence the rheological properties of non-aqueous Carbopol dispersions from the dilute to the jammed state. In novel non-aqueous formulations, polar solvents are used more and more frequently, because they can form Carbopol microgels without the need of any neutralizing agents. However, the swelling behaviour of Carbopol molecules in the absence of water, when ionic forces are weak, is still poorly understood. To this end, we study the swelling behaviour of Carbopol 974P NF in different polar solvents, i.e. glycerol, PEG400 and mixtures of the two solvents, by mapping the rheological behaviour of Carbopol suspensions from very dilute to highly concentrated conditions. The rheological study reveals that the onset of the jamming transition occurs at different critical polymer concentrations depending on the solvents used. Nevertheless, once the jammed state is reached, both elastic and yielding behaviours are scalable with the particle volume fraction. These results suggest that the type of solvent influences the final volume of the single Carbopol particles but does not alter the interactions between the particles. The final radius of the swollen particles is estimated from shear rheology measurements in dilute conditions, showing a decrease of the final swelling ratio of Carbopol molecules of almost 50% for PEG400 solutions, a result that confirms the shift to higher values of the critical jamming concentration obtained from linear viscoelasticity for the same solutions.

Mathematical Modeling for the Design and Scale-Up of a Large Industrial Aerosol-Assisted Chemical Vapor Deposition Process under Uncertainty.

Aerosol-assisted chemical vapor deposition (AACVD) can be used to produce coatings and thin films such as transparent conducting oxide (TCO) films, which are used in self-cleaning surfaces, solar cells, and other electronic and optoelectronic applications. A process based on AACVD consists of a number of steps: aerosol generation, aerosol transport, aerosol delivery, and chemical deposition. Predicting the behavior of such a process at an industrial scale is challenging due to a number of factors: the aerosol generation creates droplets of different sizes, losses are incurred in the transport, the delivery must evaporate the solvent to release the precursors, and the reactions on the surface of the deposition target may be complex. This paper describes a full process model, including the prediction of the size distribution of the generated aerosol, the number and size of droplets delivered, the carrier gas temperature profile at the reaction site, the solvent evaporation time, and the rate of film formation. The key modeling challenges addressed include incorporating the impact of uncertainties in parameters such as heat and mass transfer coefficients and reaction rate constants. Preliminary simulations demonstrate a proof of concept for the use of simulation for gaining insights into the feasibility of a process scale-up for an industrial-scale AACVD.

Surfactant effects on the coalescence of a drop in a Hele-Shaw cell.

In this work the coalescence of an aqueous drop with a flat aqueous-organic interface was investigated in a thin gap Hele-Shaw cell. Different concentrations of a nonionic surfactant (Span 80) dissolved in the organic phase were studied. We present experimental results on the velocity field inside a coalescing droplet in the presence of surfactants. The evolution of the neck between the drop and the interface was studied with high-speed imaging. It was found that the time evolution of the neck at the initial stages of coalescence follows a linear trend, which suggests that the local surfactant concentration at the neck region for this stage of coalescence can be considered quasiconstant in time. This neck expansion can be described by the linear law developed for pure systems when the surfactant concentration at the neck is assumed higher than in the bulk solution. In addition, velocity and vorticity fields were computed inside the coalescing droplet and the bulk homophase using a high-speed shadowgraphy technique. The significant wall effects in the Hele-Shaw cell in the transverse axis cause the two vertical velocity components towards the singularity rupture point, from the drop and from the bulk homophase, to be of the same order of magnitude. This movement together with the neck expansion creates two pairs of counteracting vortices in the drop and in the bulk phase. The neck velocity is the average of the advection velocities of the two counteracting vortex pairs on each side of the neck. The presence of the surfactant slows down the dynamics of the coalescence, affects the propagation direction of the pair of vortices in the bulk phase, and reduces their size faster compared to the system without surfactant.

Review and perspectives of AFM application on the study of deformable drop/bubble interactions.

The applications of Atomic Force Microscopy (AFM) on the study of dynamic interactions and film drainage between deformable bodies dispersed in aqueous solutions are reviewed in this article. Novel experimental designs and recent advances in experimental methodologies are presented, which show the advantage of using AFM as a tool for probing colloidal interactions. The effects of both DLVO and non-DLVO forces on the colloid stabilization mechanism are discussed. Good agreement is found between the force - drop/bubble deformation behaviour revealed by AFM measurements and the theoretical modeling of film drainage process, giving a convincing explanation of the occurrence of certain phenomenon. However, the behaviour and shape of deformable drops as they approach or retract is still not well resolved. In addition, when surfactants are present further research is needed on the absorption of surfactant molecules into the interfaces, their mobility and the effects on interfacial film properties.

Silica nanoparticles for micro-particle imaging velocimetry: fluorosurfactant improves nanoparticle stability and brightness of immobilized iridium(III) complexes.

To establish highly luminescent nanoparticles for monitoring fluid flows, we examined the preparation of silica nanoparticles based on immobilization of a cyclometalated iridium(III) complex and an examination of the photophysical studies provided a good insight into the Ir(III) microenvironment in order to reveal the most suitable silica nanoparticles for micro particle imaging velocimetry (µ-PIV) studies. Iridium complexes covalently incorporated at the surface of preformed silica nanoparticles, [Ir-4]@Si500-Z, using a fluorinated polymer during their preparation, demonstrated better stability than those without the polymer, [Ir-4]@Si500, as well as an increase in steady state photoluminescence intensity (and therefore particle brightness) and lifetimes which are increased by 7-fold compared with nanoparticles with the same metal complex attached covalently throughout their core, [Ir-4]⊂Si500. Screening of the nanoparticles in fluid flows using epi-luminescence microscopy also confirm that the brightest, and therefore most suitable particles for microparticle imaging velocimetry (µ-PIV) measurements are those with the Ir(III) complex immobilized at the surface with fluorosurfactant, that is [Ir-4]@Si500-Z. µ-PIV studies demonstrate the suitability of these nanoparticles as nanotracers in microchannels.

The design of a continuous reactor for fluorous biphasic reactions under pressure and its use in alkene hydroformylation.

A reactor, into which all reagents can be fed continuously and from which the reaction mixture can be continuously removed to a gravity separator, where product can be continuously removed and the catalyst phase recycled to the reactor, has been constructed and used for the hydroformylation of alkenes in fluorocarbon solvents.