We use pervaporation-based microfluidic devices to concentrate species in aqueous solutions with spatial and temporal control of the process. Using experiments and modelling, we quantitatively describe the advection-diffusion behavior of the concentration field of various solutions (electrolytes, colloids, etc) and demonstrate the potential of these devices as universal tools for the kinetic exploration of the phases and textures that form upon concentration.PACS numbers: 07.90.+c, 64.75.+g Determination of the phase diagram of multicomponent systems is of importance in many realms: industrial formulation, protein cristallization, bottom up material assembly from spontaneous ordering of surfactant, polymeric or colloidal systems [1,2,3]. Depending on the application, one may want to access only the equilibrium phase diagram or gain additional information as to the metastable phases that can appear for kinetic reasons. Methods to reach these goals often imply tedious and systematic measurements, requiring for screening purposes the use of robotic platforms. Two generic strategies consist in varying (in space or time) the temperature of samples of given concentrations on the one hand, and on the other hand isothermal concentration by either removal of the solvent (osmosis, drying), external action on the solutes (sedimentation or dielectrophoresis for colloids), or studies of spontaneous interdiffusion in contact experiments.In this Letter we introduce microfluidic tools for controlled isothermal concentration of a wide range of systems, covering solutions of ions, polymers, proteins, surfactants and colloidal suspensions. Our work is inspired by recent observations [4,5] that in standard microsystems built of PolyDiMethylSiloxane (PDMS), spontaneous water permeation through the PDMS matrix induces flows that can be used to concentrate colloids. Taking a step further, we have engineered specialized microgeometries that allow us to control spatially and temporally the evaporation process as well as the resulting concentration of solutes. Their parallel implementation in microfluidic format could open the way to fast screening methods.After a brief description of the micro-devices, we demonstrate first our control of the concentration process on dilute aqueous solutions of fluorescein and nanoparticles in a simple geometry. We then discuss how microfabrication permits to widen the range of possibili- ties and applications of such devices. As a study case, we report controlled nucleation and growth of crystals of potassium chloride (KCl), and show how such experiments provide quantitative information on various thermodynamic quantities (solubility, crystal density) as well as kinetic features (sensitive to the rate of concentration).The devices -The devices used in this paper are twolayer PDMS on glass microsystems (Fig. 1) (fabrication procedure detailed in [6]). The microchannels of the bottom layer are filled with the solution of interest, while air (at controlled humidity) is circulated through the microchan...
The ability to self-assemble was evaluated for a large variety of amphiphilic block copolymers, including poly(ethyleneoxide-b-ε-caprolactone), poly(ethyleneoxide-b-d,l-lactide), poly(ethyleneoxide-b-styrene), poly(ethyleneoxide-b-butadiene) and poly(ethyleneoxide-b-methylmethacrylate). Different methods of formation are discussed, such as cosolvent addition, film hydration or electroformation. The influence of experimental parameters and macromolecular structures on the size and morphology of the final self-assembled structures is investigated and critically compared with the literature. The same process is carried out regarding the characterization of these structures. This analysis demonstrates the great care that should be taken when dealing with such polymeric assemblies. If the morphology of such assemblies can be predicted to some extent by macromolecular parameters like the hydrophilic/hydrophobic balance, those parameters cannot be considered as universal. In addition, external experimental parameters (methods of preparation, use of co-solvent, …) appeared as critical key parameters to obtain a good control over the final structure of such objects, which are very often not at thermodynamic equilibrium but kinetically frozen. A principal component analysis is also proposed, in order to examine the important parameters for forming the self-assemblies. Here again, the hydrophilic/hydrophobic fraction is identified as an important parameter.
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