38 research outputs found
Étude expérimentale de la ségrégation d'un liquide binaire par une bulle de cavitation acoustique
La cristallisation assistée par ultrasons a été étudiée pour une large variété de produits depuis quelques décennies. Ces études mettent en évidence une influence claire des ultrasons sur la nucléation, attribuée de façon incertaine au phénomène de cavitation acoustique. La présente étude propose une hypothèse de ségrégation des espèces autour d’une bulle de cavitation, provoquée par le gradient de pression engendré par ses oscillations radiales. La résolution analytique de l’équation de transport incluant cet effet de diffusion forcée met en évidence une ségrégation possible des molécules, aggrégats moléculaires ou nano-particules au voisinage de la bulle, dans des conditions d’insonification typiques. Une expérimentation utilisant soit la fluorescence induite par nappe laser, soit l’ombroscopie, a été mise au point et testée pour observer ce phénomène de ségrégation dans une cellule de lévitation de bulle unique, remplie d’un mélange d’eau et de nanocristaux, fluorescents ou non. ABSTRACT : Ultrasound-assisted crystallization has been studied for a large variety of products over the last decades. These studies demonstrate a clear influence of ultrasounds on nucleation, which is loosely attributed to acoustic cavitation. The present study proposes an hypothesis of species segregation around a cavitation bubble, driven by the pressure gradient arising from its radial motion. The analytical solution of the transport equation accounting for this forced diffusion process predicts a possible segregation of molecules, clusters of molecules, or nanoparticles in the vicinity of the bubble, in typical insonification conditions. An experiment using either plan-laser induced fluorescence, or shadowscopy , has been designed and tuned in order to evidence this segregation phenomenon in a single-bubble levitation cell, filled with fluorescent nano-crystals, either fluorescent or not, dispersed in water
Microdroplet Approach for Measuring Aqueous Solubility and Nucleation Kinetics of a Metastable Polymorph: The case of KDP Phase IV
Solubility and interfacial energy are two fundamental parameters underlying
the competitive nucleation of polymorphs. However, solubility measurement of
metastable phases comes with a risk of solventmediated transformations which
can render the results unreliable. In this work, we present a rapid
microfluidic technique for measuring aqueous solubility of the metastable form
using KDP Phase IV as a model system. This bracketing approach involves
analyzing the dissolution behavior of crystals in contact with supersaturated
microdroplets generated via evaporation. Then, with the help of our recently
developed nucleation time measurement technique, together with Mersmann
calculation of interfacial energies from solubilities, we were able to access
the interfacial energies of both metastable and stable phases. To gain further
insights into the observed nucleation behavior, we employed the Classical
Nucleation Theory (CNT) to model the competition of polymorphs using our
measured solubility and calculated interfacial energies. The results show that
the stable form is favored at lower supersaturation while the metastable form
is favored at higher supersaturation, in good agreement with our observations
and experimental reports in the literature. Overall, our microfluidic approach
allows access to unprecedentedly deep levels of supersaturation and reveals an
interesting interplay between thermodynamics and kinetics in polymorphic
nucleation. The experimental methods and insights presented herein can be of
great interest, notably in the mineral processing and pharmaceutical industry
CNT effective interfacial energy and pre-exponential kinetic factor from measured NaCl crystal nucleation time distributions in contracting microdroplets
Nucleation, the birth of a stable cluster from disorder, is inherently
stochastic. Yet up to date, there are no quantitative studies on NaCl
nucleation that accounts for its stochastic nature. Here, we report the first
stochastic treatment of NaCl-water nucleation kinetics. Using a recently
developed microfluidic system and evaporation model, our measured interfacial
energies extracted from a modified Poisson distribution of nucleation time show
an excellent agreement with theoretical predictions. Furthermore, analysis of
nucleation parameters in 0.5 pL, 1.5pL and 5.5 pL microdroplets reveals an
interesting interplay between kinetic confinement and shifting of nucleation
mechanisms. Overall, our findings highlight the need to treat nucleation
stochastically rather deterministically to bridge the gap between theory and
experiment
A microfluidic method generating monodispersed microparticles with controllable sizes and mechanical properties
International audienceSeeking to produce microparticles that mimic red blood cells (RBCs), we present a microfluidic method of generating monodispersed hydrogel microparticles of Na-/Ca-alginate with controllable sizes (micrometer range) and mechanical properties. No surfactant is used. Transformation from Na-alginate to Ca-alginate microparticles is realized via ex situ gelation, which proves essential to obtaining desired microparticle properties, such as insolubility in water and RBC-like mechanical properties. For both Na-alginate and Ca-alginate microparticles, a smooth surface and a porous inner structure are observed under a scanning electron microscope. A platform of microgrippers is successfully developed to manipulate the microparticles. The Young’s modulus measured using an atomic force microscope on the surface of Ca-alginate microparticles is of the same order as that of RBCs
Étude expérimentale de la ségrégation d'un liquide binaire par une bulle de cavitation acoustique
La cristallisation assistée par ultrasons a été étudiée pour une large variété de produits depuis quelques décennies. Ces études mettent en évidence une influence claire des ultrasons sur la nucléation, attribuée de façon incertaine au phénomène de cavitation acoustique. La présente étude propose une hypothèse de ségrégation des espèces autour d une bulle de cavitation, provoquée par le gradient de pression engendré par ses oscillations radiales. La résolution analytique de l équation de transport incluant cet effet de diffusion forcée met en évidence une ségrégation possible des molécules, aggrégats moléculaires ou nano-particules au voisinage de la bulle, dans des conditions d insonification typiques. Une expérimentation utilisant soit la fluorescence induite par nappe laser, soit l ombroscopie, a été mise au point et testée pour observer ce phénomène de ségrégation dans une cellule de lévitation de bulle unique, remplie d un mélange d eau et de nanocristaux, fluorescents ou non.Ultrasound-assisted crystallization has been studied for a large variety of products over the last decades. These studies demonstrate a clear influence of ultrasounds on nucleation, which is loosely attributed to acoustic cavitation. The present study proposes an hypothesis of species segregation around a cavitation bubble, driven by the pressure gradient arising from its radial motion. The analytical solution of the transport equation accounting for this forced diffusion process predicts a possible segregation of molecules, clusters of molecules, or nanoparticles in the vicinity of the bubble, in typical insonification conditions. An experiment using either plan-laser induced fluorescence, or shadowscopy , has been designed and tuned in order to evidence this segregation phenomenon in a single-bubble levitation cell, filled with fluorescent nano-crystals, either fluorescent or not, dispersed in water.TOULOUSE-ENSEEIHT (315552331) / SudocALBI-ENSTIMAC (810042301) / SudocSudocFranceF
Advances in the Use of Microfluidics to Study Crystallization Fundamentals
International audienceThis review compares droplet-based microfluidic systems used to study crystallization fundamentals in chemistry and biology. An original high-throughput droplet-based microfluidic platform is presented. It uses nL droplets, generates a "chemical library" and directly solubilizes powder, thus economizing both material and time. It is compatible with all solvents without the need for surfactant. Its flexibility permits phase diagram determination and crystallization studies (screening and optimizing experiments), and makes it easy to use for non-specialists in microfluidics. Moreover, it allows concentration measurement via UV spectroscopy and solid characterization via XRD analysis
Segregation of a liquid mixture by a radially oscillating bubble
International audienceA theoretical formulation is proposed for forced mass transport by pressure gradients in a liquid binary mixture around a spherical bubble undergoing volume oscillations in a sound field. Assuming the impermeability of the bubble wall to both species, diffusion driven by pressure gradients and classical Fick-diffusion must cancel at the bubble wall, so that an oscillatory concentration gradient arises in the vicinity of the bubble. The Peclet number Pe is generally high in typical situations and Fick diffusion cannot restore equilibrium immediately, so that an asymptotic average concentration profile may progressively build up in the liquid over large times. Such a behaviour is reminiscent of the so-called rectified diffusion problem, leading to slow growth of a gas bubble oscillating in a sound field. A rigorous method formerly proposed by Fyrillas & Szeri (J. Fluid Mech. vol. 277, 1994, p. 381) to solve the latter problem is used to solve the present one. It is based on splitting the problem into a smooth part and an oscillatory part. The smooth part is solved by a multiple scales method and yields the slowly varying average concentration field everywhere in the liquid. The oscillatory part is obtained by matched asymptotic expansions in terms of the small parameter Pe(-1/2) : the inner solution is required to satisfy the oscillatory balance between pressure diffusion and Fick diffusion at the bubble wall, while the outer solution is required to be zero. Matching both solutions yields a unique splitting of the problem. The final analytical solution, truncated to leading order, compares successfully to direct numerical simulation of the full convection-diffusion equation. The analytical expressions for both smooth and oscillatory parts are calculated for various sets of bubble parameters: driving pressure, frequency and ambient radius. The smooth problem always yields an average depletion of the heaviest species at the bubble wall, only noticeable for large molecules or nano-particles. For driving pressures sufficiently high to yield inertial oscillations of the bubble, the oscillatory problem predicts a periodic peak excess concentration of the heaviest species at the bubble wall at each collapse, lingering on several tens of the time of the characteristic duration of the bubble rebound. The two effects may compete for large molecules and practical implications of this segregation phenomenon are proposed for various processes involving acoustic cavitation
Microdroplet Approach for Measuring Aqueous Solubility and Nucleation Kinetics of a Metastable Polymorph: The case of KDP Phase IV
Solubility and interfacial energy are two fundamental parameters underlying the competitive nucleation of polymorphs. However, solubility measurement of metastable phases comes with a risk of solventmediated transformations which can render the results unreliable. In this work, we present a rapid microfluidic technique for measuring aqueous solubility of the metastable form using KDP Phase IV as a model system. This bracketing approach involves analyzing the dissolution behavior of crystals in contact with supersaturated microdroplets generated via evaporation. Then, with the help of our recently developed nucleation time measurement technique, together with Mersmann calculation of interfacial energies from solubilities, we were able to access the interfacial energies of both metastable and stable phases. To gain further insights into the observed nucleation behavior, we employed the Classical Nucleation Theory (CNT) to model the competition of polymorphs using our measured solubility and calculated interfacial energies. The results show that the stable form is favored at lower supersaturation while the metastable form is favored at higher supersaturation, in good agreement with our observations and experimental reports in the literature. Overall, our microfluidic approach allows access to unprecedentedly deep levels of supersaturation and reveals an interesting interplay between thermodynamics and kinetics in polymorphic nucleation. The experimental methods and insights presented herein can be of great interest, notably in the mineral processing and pharmaceutical industry