Solidification of a Charged Colloidal Dispersion Investigated Using Microfluidic Pervaporation

We investigate the dynamics of solidification of a charged colloidal dispersion using an original microfluidic technique referred to as micropervaporation. This technique exploits pervaporation within a microfluidic channel to extract the solvent of a dilute colloidal dispersion. Pervaporation concentrates the colloids in a controlled way up to the tip of the channel until a wet solid made of closely packed colloids grows and invades the microfluidic channel. For the charged dispersion under study, we however evidence a liquid to solid transition (LST) preceding the formation of the solid, owing to the presence of long-range electrostatic interactions. This LST is associated with the nucleation and growth of domains confined in the channel. These domains are then compacted anisotropically up to forming a wet solid of closely packed colloids. This solid then invades the whole channel as in directional drying with a growth rate which depends on the microfluidic geometry. In the final steps of the solidification, we observed the occurrence of cracks and shear bands, the delamination of the wet solid from the channel walls, and its invasion by a receding air front. Interestingly, this air front follows specific patterns within the solid which reveal different microscopic colloidal organizations

Solidification of a Charged Colloidal Dispersion Investigated Using Microfluidic Pervaporation

We investigate the dynamics of solidification of a charged colloidal dispersion using an original microfluidic technique referred to as micropervaporation. This technique exploits pervaporation within a microfluidic channel to extract the solvent of a dilute colloidal dispersion. Pervaporation concentrates the colloids in a controlled way up to the tip of the channel until a wet solid made of closely packed colloids grows and invades the microfluidic channel. For the charged dispersion under study, we however evidence a liquid to solid transition (LST) preceding the formation of the solid, owing to the presence of long-range electrostatic interactions. This LST is associated with the nucleation and growth of domains confined in the channel. These domains are then compacted anisotropically up to forming a wet solid of closely packed colloids. This solid then invades the whole channel as in directional drying with a growth rate which depends on the microfluidic geometry. In the final steps of the solidification, we observed the occurrence of cracks and shear bands, the delamination of the wet solid from the channel walls, and its invasion by a receding air front. Interestingly, this air front follows specific patterns within the solid which reveal different microscopic colloidal organizations

Solidification of a Charged Colloidal Dispersion Investigated Using Microfluidic Pervaporation

We investigate the dynamics of solidification of a charged colloidal dispersion using an original microfluidic technique referred to as micropervaporation. This technique exploits pervaporation within a microfluidic channel to extract the solvent of a dilute colloidal dispersion. Pervaporation concentrates the colloids in a controlled way up to the tip of the channel until a wet solid made of closely packed colloids grows and invades the microfluidic channel. For the charged dispersion under study, we however evidence a liquid to solid transition (LST) preceding the formation of the solid, owing to the presence of long-range electrostatic interactions. This LST is associated with the nucleation and growth of domains confined in the channel. These domains are then compacted anisotropically up to forming a wet solid of closely packed colloids. This solid then invades the whole channel as in directional drying with a growth rate which depends on the microfluidic geometry. In the final steps of the solidification, we observed the occurrence of cracks and shear bands, the delamination of the wet solid from the channel walls, and its invasion by a receding air front. Interestingly, this air front follows specific patterns within the solid which reveal different microscopic colloidal organizations

Solidification of a Charged Colloidal Dispersion Investigated Using Microfluidic Pervaporation

We investigate the dynamics of solidification of a charged colloidal dispersion using an original microfluidic technique referred to as micropervaporation. This technique exploits pervaporation within a microfluidic channel to extract the solvent of a dilute colloidal dispersion. Pervaporation concentrates the colloids in a controlled way up to the tip of the channel until a wet solid made of closely packed colloids grows and invades the microfluidic channel. For the charged dispersion under study, we however evidence a liquid to solid transition (LST) preceding the formation of the solid, owing to the presence of long-range electrostatic interactions. This LST is associated with the nucleation and growth of domains confined in the channel. These domains are then compacted anisotropically up to forming a wet solid of closely packed colloids. This solid then invades the whole channel as in directional drying with a growth rate which depends on the microfluidic geometry. In the final steps of the solidification, we observed the occurrence of cracks and shear bands, the delamination of the wet solid from the channel walls, and its invasion by a receding air front. Interestingly, this air front follows specific patterns within the solid which reveal different microscopic colloidal organizations

Solidification of a Charged Colloidal Dispersion Investigated Using Microfluidic Pervaporation

We investigate the dynamics of solidification of a charged colloidal dispersion using an original microfluidic technique referred to as micropervaporation. This technique exploits pervaporation within a microfluidic channel to extract the solvent of a dilute colloidal dispersion. Pervaporation concentrates the colloids in a controlled way up to the tip of the channel until a wet solid made of closely packed colloids grows and invades the microfluidic channel. For the charged dispersion under study, we however evidence a liquid to solid transition (LST) preceding the formation of the solid, owing to the presence of long-range electrostatic interactions. This LST is associated with the nucleation and growth of domains confined in the channel. These domains are then compacted anisotropically up to forming a wet solid of closely packed colloids. This solid then invades the whole channel as in directional drying with a growth rate which depends on the microfluidic geometry. In the final steps of the solidification, we observed the occurrence of cracks and shear bands, the delamination of the wet solid from the channel walls, and its invasion by a receding air front. Interestingly, this air front follows specific patterns within the solid which reveal different microscopic colloidal organizations

Role of Vapor Mass Transfer in Flow Coating of Colloidal Dispersions in the Evaporative Regime

In flow-coating processes at low substrate velocity, solvent evaporation occurs during the film withdrawal and the coating process directly yields a dry deposit. In this regime, often referred to as the evaporative regime, several works performed on blade-coating-like configurations have reported a deposit thickness <i>h</i>_d proportional to the inverse of the substrate velocity <i>V</i>. Such a scaling can be easily derived from simple mass conservation laws, assuming that evaporation occurs on a constant distance, referred to as the evaporation length, noted <i>L</i>_ev in the present paper and of the order of the meniscus size. However, the case of colloidal dispersions deserves further attention. Indeed, the coating flow leads to a wet film of densely packed colloids before the formation of the dry deposit. This specific feature is related to the porous nature of the dry deposit, which can thus remain wet when capillary forces are strong enough to prevent the receding of the solvent through the pores of the film (the so-called pore-emptying). The length of this wet film may possibly be much larger than the meniscus size, therefore modifying the solvent evaporation rate, as well as the scaling <i>h</i>_d ∼ 1/<i>V</i>. This result was suggested recently by different groups using basic modeling and assuming for simplicity a uniform evaporation rate over the wet film. In this article, we go a step further and investigate the effect of multidimensional vapor mass transfer in the gas phase on <i>L</i>_ev and <i>h</i>_d in the specific case of colloidal dispersions. Using simplified models, we first provide analytical expressions in asymptotic cases corresponding to 1D or 2D diffusive vapor transport. These theoretical investigations then led us to show that <i>L</i>_ev is independent of the evaporation rate amplitude, and roughly independent of its spatial distribution. Conversely, <i>h</i>_d strongly depends on the characteristics of vapor mass transfer in the gas phase, and different scaling laws are obtained for the 1D or the 2D case. These theoretical findings are finally tested by comparison with experimental results supporting our theoretical simplified approach

Gold Nanooctahedra with Tunable Size and Microfluidic-Induced 3D Assembly for Highly Uniform SERS-Active Supercrystals

Shape-controlled synthesis of uniform noble metal nanoparticles (NPs) is crucial for the development of future plasmonic devices. The use of nanocrystals with well-defined morphologies and crystallinity as seed particles is expected to provide excellent shape control and monodispersity. We report the aqueous-based seed-mediated growth of monodisperse gold octahedra with wide range of sizes (50–150 nm in side length) by reducing different amounts of HAuCl₄ on preformed single crystalline gold nanorods using butenoic acid as reducing agent. Butenoic acid plays a key role as a mild reducing agent as well as favoring the thermodynamic control of the reaction. The uniformity of the as-prepared Au octahedra combined with the use of a microfluidic technique based on microevaporation will allow the self-assembly of octahedra into uniform 3D supercrystals. Additionally, these plasmonic substrates exhibit high and uniform SERS signals over extended areas with intensities increasing with the Au nanoparticle size

Microfluidic-Induced Growth and Shape-Up of Three-Dimensional Extended Arrays of Densely Packed Nanoparticles

We use evaporation within a microfluidic device to extract the solvent of a (possibly very dilute) dispersion of nanoparticles and concentrate the dispersion until a solid made of densely packed nanoparticles grows and totally invades the microfluidic geometry. The growth process can be rationalized as an interplay between evaporation-induced flow and kinetic and thermodynamic coefficients which are system-dependent; this yields limitations to the growth process illustrated here on two main cases: evaporation- and transport-limited growth. Importantly, we also quantify how colloidal stability may hinder the growth and show that care must be taken as to the composition of the initial dispersion, especially regarding traces of ionic species that can destabilize the suspension upon concentration. We define a stability chart, which, when fulfilled, permits us to grow and shape-up solids, including superlattices and extended and thick arrays of nanoparticles made of unary and binary dispersions, composites, and heterojunctions between distinct types of nanoparticles. In all cases, the geometry of the final solid is imparted by that of the microfluidic device