Microfluidic devices have recently emerged as promising tools for the synthesis of polymer particles. Over conventional processes, microfluidic-assisted processes allow the production of polymer particles with an improved control over their sizes, size distributions, morphologies, and compositions. In this paper, the most common microfluidic devices are reviewed. Both projection photolithography and emulsification processes are reported for the continuous flow synthesis of polymer particles from a stream of polymerizable liquids. For the latter process, two distinct categories of microfluidic devices have been identified: microchannel-based and capillary-based microsystems. For each category, the existing geometries are described and the different emulsification methods including the coflowing, cross-flowing, or flow-focusing of the continuous and dispersed phases are commented upon. Finally, for each microsystem the various polymer particles achieved in such devices including, but not restricted to, janus, core-shell, or porous particles and capsules are reported.
We demonstrate the use of a microfluidic setup to prepare monodisperse and spherical beads from a liquid crystalline elastomer. These particles show a strong and reversible shape change into a cigar‐like conformation during the transition into the isotropic phase. These properies are a result of the monodomainic alignment of the mesogens in the flow field of the microfluidic setup.
An easy assembling-disassembling co-axial capillaries microfluidic device was built up for the production of double droplets. Uniform polymer core-polymer shell particles were synthesized by polymerizing the two immiscible monomer phases composing the double droplet. Thus poly(acrylamide) core-poly(tri(propylene glycol) diacrylate) shell particles with controlled core diameter and shell thickness were simply obtained by adjusting operating parameters. An empirical law was extracted from experiments to predict core and shell sizes. Additionally uniform and predictable non-spherical polymer objects were also prepared without adding shape-formation procedures in the experimental device. An empirical equation for describing the lengths of rod-like polymer particles is also presented.
This review is mostly intended for a broad readership and provides key tools regarding the choice of microfluidic setups, tailored to given specifications. We discuss the specificities and geometries of the microfluidic devices intended to nanoprecipitation, advantages, drawbacks and limitations.
In this article, we present the synthesis of highly shape-anisotropic, micrometer-sized particles from liquid crystalline elastomers, which have the ability to reversibly change their shape in response to a certain external stimulus. For their preparation, we utilized a microfluidic setup. We succeeded in preparing sets of particles with differing degrees of shape anisotropy in their ground state including highly anisotropic fiber-like objects. All samples produced movement during the phase transition from the nematic to the isotropic phase of the liquid crystal. Depending on the direction of this shape change, we classified the samples in two groups. One type showed a contraction, while the other showed an expansion during the actuation, generating displacements of 60% and 80%, respectively. Using X-ray diffraction experiments, we could show that the different actuation properties arise from different director patterns of the liquid crystalline moieties in the microparticles. While the weakly shape-anisotropic microparticles possess a concentric director field (director perpendicular to the symmetry axis), the highly anisotropic fiber-like particles show an alignment of the director along the fiber axis. We present an explanation, claiming that this is the result of two different orientation mechanisms involving elongational flow on the one side and "log-rolling" on the other.
Monodisperse and size-controlled spherical polymer particles were synthesized by in situ photopolymerization of O/W monomer emulsions. Monomer droplets were produced without surfactant or pretreatment at a needle tip in a simplified axisymmetric microfluidic device. The effect of the viscosity of the continuous phase on the particle size was studied. The system operated in the dripping mode, at a low Reynolds number. A dimensionless master curve describes the particle diameter as a function of the needle inner diameter as well as velocity and viscosity ratios of continuous and dispersed phases. An empirical law predicts the particle size. The normalized particle diameter depends upon the ratio of the capillary numbers of continuous and dispersed phases with an exponent equal to -0.22.
In this article new results on the preparation of monodisperse particles from a liquid crystalline elastomer in a microfluidic setup are presnted. For this, droplets from a liquid crystalline monomer are prepared in a microfluidic device and polymerized while they are flowing inside a microtube. The particles obtained by this method possess an internal orientation, which gives them actuating properties. When they are heated into the isotropic phase of the liquid crystalline material they show a reversible change in shape whereby they change their length in one direction by almost 100%. It is shown how the variation of experimental parameters during their synthesis impacts the properties of these micro‐actuators. Influence over their primal shape, the strength of their shape changing properties, their size, and their mechanical properties is demontrated. From the systematic variation of experimental parameters a deep understanding of the complex processes taking place in a flowing droplet of a liquid crystalline material is obtainted. Additionally NMR analysis and swelling experiments on these actuating materials are provided.
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