Microfluidic extensional flow device to study mass transfer dynamics in the polymer microparticle formation process.

Polymer microparticles are often used to encapsulate drugs for sustained drug-release treatments. One of the ways they are manufactured is by using a solvent extraction process, in which the polymer solution is emulsified into an aqueous bulk phase using a surfactant as a stabilizing agent, followed by the removal of the solvent. The radius of a polymer drop decreases as a function of time until the polymer reaches the gelling point, after which it is separated and dried. Among the various operating parameters, the rate of solvent extraction is a critical step that affects the morphology and porosity, and consequently, the kinetics of drug release. But a fundamental mechanistic understanding of the solvent extraction dynamics as a function of shear is still unexplored. In this study, we have developed an experimental mass transfer model to predict the extraction by using the microfluidic extensional flow device (MEFD) to probe the shear and extraction dynamics at the level of a single drop in a linear extensional flow field. We used a computer-controlled feedback algorithm to manipulate the flow field and hydrodynamically trap a Hele-Shaw drop and observe the extraction process. For the polymer solution, we used a biocompatible polymer, poly-lactic-co-glycolic acid (PLGA) with ethyl acetate (EtOAc) as the solvent. Our experiments were conducted by varying the extensional rate (G) in the channel from ∼0.1 s-1 to ∼10 s-1, and using an analytical solution of the flow field, we captured the dissolution process and measured the change in drop radius (R) with time (t). Interestingly, we initially observed a short-time asymptote R ∼ t, and later the long-time asymptote of R = constant; both trends were physically explained. The transport model developed in this work can be used to predict extraction rates and polymer microparticle composition for any polymer-solvent system. This work is also an important contribution to the literature on convective mass transfer in partially miscible emulsions.

Formulating and Retaining the Structure of Polymerized Surfactant Phases Using a Microemulsion Curvature Framework.

Nanostructured polymers contain features smaller than 100 nm that are useful in a wide range of areas, including photonics, biomedical materials, and environmental applications. Out of the myriad of nanostructured polymers, surfactant-templated polymers are versatile because of their ability to have tunable domain sizes, structure, and composition. This work addresses the gap between the formulation with industrial-grade polymerizable surfactants and the final structure of the polymer, using the hydrophilic-lipophilic difference (HLD) and net-average curvature (NAC) frameworks. HLD indicates the proximity of the formulation (surfactant and oil monomer selection, temperature, electrolyte concentration) to the phase inversion point, where HLD = 0. NAC uses the HLD to determine the curvature of the surfactant-oil-water interface, leading not only to the size and shape of micelles and bicontinuous isotropic (L3) systems but also to defining the most likely regions for lyotropic liquid crystal (LLC) existence and phase separation in ternary phase diagrams. Polymerizing LLC fluids produced nanostructured polymers with similar LLC structures that were highly swellable, but with low compressive strength. Polymerizing L3 fluids produced strong, but less water-swellable nanostructured polymers with a similar characteristic length to the parent L3 microemulsion. The relatively small scale of the parent LLC (∼6-8 nm) or L3 (∼3-4 nm) systems is consistent with the translucent nature of the polymers produced and the HLD-NAC predicted sizes.

Mass transfer dynamics in the dissolution of Taylor bubbles.

The knowledge of thermodynamic and mass transfer parameters in gas-liquid systems is critical for the design of macroscale units for separation and reaction processes. The phenomenon of shrinkage of Taylor bubbles upon dissolution has the capability of supplying these design parameters, provided a reliable mathematical model is available for data deconvolution. Unfortunately, the existing models in the literature suffer from at least one of the following three major limitations. First, mass transfer between the bulk liquid segment and the surrounding liquid film has been incorrectly estimated. Second, the liquid segment is assumed to be well mixed, even though there is clear evidence of the contrary in the literature [Yang et al., Chem. Eng. Sci., 2017, 169, 106]. Third, an average mass transfer coefficient is assumed to be valid throughout the dissolution process, despite the fact that bubble velocities can change significantly during dissolution. In this work, we have rectified these limitations and developed a detailed model that takes into account the local concentration gradients and the flow profiles, without resorting to the computationally expensive, full numerical simulations of the fluid flow and concentration distribution equations. To validate the model, experiments were carried out in circular, silica capillaries of different radii by generating segmented flow of CO2 in physical solvents, and the diffusivity and the solubility were subsequently extracted with an error of less than 5%. This work can be extended to the study of gas-liquid-solid reactions in the Taylor flow configuration, and applied to the design of catalyst-coated monolithic reactors.

Intravital Imaging for Tracking of Angiogenesis and Cellular Events Around Surgical Bone Implants.

IMPACT STATEMENT: These new experimental methods allow us to image, and quantify, angiogenesis and perivascular cell dynamics in the endosseous healing compartment. As such, the method is capable of providing a new perspective on, and unique information regarding, healing that occurs around orthopedic and dental implants.

Dispersion of a passive tracer in the pressure-driven flow of a non-colloidal suspension.

This paper numerically quantifies the dispersion of a solute, and in particular, the Taylor dispersion, in the pressure-driven flow of a non-colloidal suspension at moderately high volume fractions (0.2 to 0.5) through conduits of different cross-sectional shapes. An obvious intuition is that the Taylor dispersivity should increase owing to a decrease in the molecular diffusivity of the solute in the presence of particles impermeable to the solute; however, this is true only at low volume fractions. At higher volume fractions, three other physical effects become important, all of which lead to a reduction in Taylor dispersivity relative to a Newtonian fluid. The first is the blunting of the velocity profile resulting from particle migration into the low shear-stress regions, an effect that has been alluded to in the past by Roht et al. [J. Contam. Hydrol., 2013, 14, 10] and is important only at low Péclet numbers (Pe). At higher Pe, the two stronger effects are shear-induced solute self-diffusion, which arises due to shear-induced particle-particle interactions, and secondary convection, which is observed in non-axisymmetric cross-sections as a result of the second normal stress differences exhibited by concentrated suspensions. For a given volume fraction and cross-sectional geometry, a regime map, developed using a scaling analysis, delineates five regimes of dispersion involving one or a combination of the mass transfer mechanisms mentioned above. Our analysis also suggests that the cross-sectional shape can be exploited to enhance or suppress solute dispersion by modifying the secondary current strength and profile.