Empowering microfluidics by micro-3D printing and solution-based mineral coating.

Fluid-solid interaction in porous materials is of tremendous importance to earth, space, energy, environment, biological, and medical applications. High-resolution 3D printing enables efficient fabrication of porous microfluidic devices with complicated pore-throat morphology, but lacking desired surface functionality. In this work, we propose a novel approach to additively fabricate functional porous devices by integrating micro-3D printing and solution-based internal coating. This approach is successfully applied to create energy/environment-orientated porous micromodels that replicate the µCT-captured porous geometry and natural mineralogy of carbonate rock. The functional mineral coating in a 3D-printed porous scaffold is achieved by seeding calcite nanoparticles along the inner surface and enabling in situ growth of calcite crystals. For conformal and stable coating in confined pore spaces, we manage to control the wetting and capillarity effects during fabrication: (i) capillarity-enhanced nanoparticle immobilization for forming an adhered seeding layer; (ii) capillary pore-throat blockage mitigation for uniform crystal growth. These transparent micromodels are then used to directly image and characterize microscopic fluid dynamics including wettability-dependent fluid propagation and capillarity-held phase transition processes. The proposed approach can be readily tailored with on-demand-designed scaffold geometry and appropriate coating recipe to fit in many other emerging applications.

Condensation of Satellite Droplets on Lubricant-Cloaked Droplets.

Condensation on lubricant-infused micro- or nanotextured superhydrophobic surfaces exhibits remarkable heat transfer performance owing to the high condensation nucleation density and efficient condensate droplet removal. When a low surface tension lubricant is used, it can spread on the condensed droplet and "cloak" it. Here, we describe a previously unobserved condensation phenomenon of satellite droplet formation on lubricant-cloaked water droplets using environmental scanning electron microscopy. The presence of satellite droplets confirms the cloaking behavior of common lubricants on water such as Krytox oils. More interestingly, we have observed satellite droplets on BMIm ionic liquid-infused surfaces, which is unexpected because BMIm was used in previous reports as a lubricant to eliminate cloaking during water condensation. Our studies reveal that the cloaking of BMIm on water droplets is theoretically favorable due to the fast timescale spreading during initial condensation when compared to the long timescale required for dissolution of the lubricant in water. We utilize a novel characterization approach based on Raman spectroscopy to confirm the existence of cloaking lubricant films on water droplets residing on lubricant-infused surfaces. The selected lubricants include Krytox oil, ionic liquid, and dodecane, which have drastically different surface tensions and polarities. In addition, spreading dynamics of cloaking and noncloaking lubricants on water droplets show that ionic liquid has the capability to mobilize water droplets spontaneously owing to cloaking and its relatively high surface tension. Our studies not only elucidate the physics governing cloaking and satellite droplet condensation phenomena at micro- and macroscales but also reveal a subset of previously unobserved lubricant-water interfacial interactions for a large variety of applications.

Directional Passive Transport of Microdroplets in Oil-Infused Diverging Channels for Effective Condensate Removal.

Condensation widely exists in nature and industry, and its performance heavily relies on the efficiency of condensate removal. Recent advances in micro-/nanoscale surface engineering enable condensing droplet removal from solid surfaces without extra energy cost, but it is still challenging to achieve passive transport of microdroplets over long distances along horizontal surfaces. The mobility of these condensate droplets can be enhanced by lubricant oil infusion on flat surfaces and frequent coalescence, which lead to fast growth but random motion of droplets. In this work, we propose a novel design of diverging microchannels with oil-infused surfaces to achieve controllable, long-distance, and directional transport of condensing droplets on horizontal surfaces. This idea is experimentally demonstrated with diverging copper and silicon microchannels with nanoengineered surfaces. Along these hierarchical surface structures, microdroplets condense on the top channel wall and submerge into microchannels owing to the capillary pressure gradient in infusing oil. Confined by the microchannel walls, the submerged droplets deform and maintain the back-front curvature difference, which enables the motion of droplets along the channel diverging direction. Subsequent droplet coalescences inside the channel further enhance this directional transport. Moreover, fast-moving deformed droplets transfer their momentum to downstream spherical droplets through the infusing oil. As a result, simultaneous passive transport of multiple droplets (20-400 µm) is achieved over long distances (beyond 7 mm). On these oil-infused surfaces, satellite microdroplets can further nucleate and grow on an oil-cloaked droplet, demonstrating an enlarged surface area for condensation. Our findings on passive condensate removal offer great opportunities in condensation enhancement, self-cleaning, and other applications requiring directional droplet transport along horizontal surfaces.

Direct Prediction of Calcite Surface Wettability with First-Principles Quantum Simulation.

Prediction of intrinsic surface wettability from first-principles offers great opportunities in probing new physics of natural phenomena and enhancing energy production or transport efficiency. We propose a general quantum mechanical approach to predict the macroscopic wettability of any solid crystal surfaces for different liquids directly through atomic-level density functional simulation. As a benchmark, the wetting characteristics of calcite crystal (10.4) under different types of fluids (water, hexane, and mercury), including either contact angle or spreading coefficient, are predicted and further validated with experimental measurements. A unique feature of our approach lies in its capability of capturing the interactions among various polar fluid molecules and solid surface ions, particularly their charge density difference distributions. Moreover, this approach provides insightful and quantitative predictions of complicated surface wettability alteration problems and wetting behaviors of liquid/liquid/solid triphase systems.