Insights into capillary-driven motion of micro-particles interacting with advancing meniscus on a substrate.

Liquid-particle interactions at the micro-scale are quite different from the corresponding macro-scale interactions due to the substantial role of capillary forces. Herein, we explore the interaction of a single micro-particle with an air-liquid-substrate contact line. The interaction features ballistic-like motion of micro-particles toward the interacting three-phase contact line with velocities as high as 0.46 m s-1. Through high-speed optical imaging, we elucidate the interaction mechanism and associated intertwined dynamics, including evolution and backward dragging of the transient air-liquid-particle contact line, capillary-inertial launch of micro-particles and its subsequent trapping at the air-liquid-substrate contact line. Based on the force analysis, we build a model to predict the particle velocity profile during the interaction. Our experimental results show that both hydrophilic and hydrophobic micro-particles exhibit capillary-driven motion. The maximum velocity of the hydrophobic particle, as well as its total displacement, is smaller than that of the hydrophilic one with the same particle size. Micro-particle lifting, like dust removal from self-cleaning surfaces, is observed when the dynamic contact angle of the air-liquid-substrate contact line is sufficiently high (i.e. >100°). We also develop criteria for the capillary-driven motion of particles and predict the critical size for particle motion. These findings are valuable to various applications including capillary-driven self-cleaning, pickering emulsions, micro-scale fluid structure interactions and capillary dynamics in porous media.

Impact of PEGDA photopolymerization in micro-stereolithography on 3D printed hydrogel structure and swelling.

3D printing complex architectures of responsive-hydratable polymers are enabled by stereolithography via photopolymerization. Yet, insufficient crosslinking leads to compromised structural integrity of the photopolymerized samples, which affects the functionality and reliability of hydrogel devices significantly. Here we investigate how curing parameters and ink formulation affect 3D printed PEGDA samples by using a combination of microfabrication, structural characterization, and reactive coarse-grained molecular dynamics simulation. Our findings show that the degree of curing exhibits a graded profile from confocal Raman spectroscopy and submicron pores from atomic force microscopy, both of which are also observed in our molecular simulations. Moreover, with environmental scanning electron microscopy, we probe the microscopic swelling and bending dynamics of 3D printed hydratable PEGDA structures as well as their structural integrity. Our in-depth characterization results reveal how hydrogel elasticity and irreversible densification due to pore formation highly depends on the exposure time, light intensity and the associated degree of crosslinking. This work provides new molecular insights into processing-structure relation in stereolithography 3D printing.

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.

Hybrid graphene metasurface for near-infrared absorbers.

We experimentally demonstrated an amorphous graphene-based metasurface yielding near-infrared super absorber characteristic. The structure is obtained by alternatively combining magnetron-sputtering deposition and graphene transfer coating fabrication techniques. The thickness constraint of the physical vapor-deposited amorphous metallic layer is unlocked and as a result, the as-fabricated graphene-based metasurface absorber achieves near-perfect absorption in the near-infrared region with an ultra-broad spectral bandwidth of 3.0 µm. Our experimental characterization and theoretical analysis further point out that the strong light-matter interaction observed is caused by localized surface plasmon resonance of the metal film's particle-like surface morphology. In addition to the enhanced light absorption characteristics, such an amorphous metasurface can be used for surface-enhanced Raman scattering applications. Meanwhile, the proposed graphene-based metasurface relies solely on CMOS-compatible, low cost and large-area processing, which can be flexibly scaled up for mass production.

Sustainable biomimetic solar distillation with edge crystallization for passive salt collection and zero brine discharge.

The urgency of addressing water scarcity and exponential population rise has necessitated the use of sustainable desalination for clean water production, while conventional thermal desalination processes consume fossil fuel with brine rejection. As a promising solution to sustainable solar thermal distillation, we report a scalable mangrove-mimicked device for direct solar vapor generation and passive salt collection without brine discharge. Capillarity-driven salty water supply and continuous vapor generation are ensured by anti-corrosion porous wicking stem and multi-layer leaves, which are made of low-cost superhydrophilic nanostructured titanium meshes. Precipitated salt at the leaf edge forms porous patch during daytime evaporation and get peeled by gravity during night when saline water rewets the leaves, and these salt patches can enhance vaporization by 1.6 times as indicated by our findings. The proposed solar vapor generator achieves a stable photothermal efficiency around 94% under one sun when treating synthetic seawater with a salinity of 3.5 wt.%. Under outdoor conditions, it can produce 2.2 L m-2 of freshwater per day from real seawater, which is sufficient for individual drinking needs. This kind of biomimetic solar distillation devices have demonstrated great capability in clean water production and passive salt collection to tackle global water and environmental challenges.

Biomimetic on-chip filtration enabled by direct micro-3D printing on membrane.

Membrane-on-chip is of growing interest in a wide variety of high-throughput environmental and water research. Advances in membrane technology continuously provide novel materials and multi-functional structures. Yet, the incorporation of membrane into microfluidic devices remains challenging, thus limiting its versatile utilization. Herein, via micro-stereolithography 3D printing, we propose and fabricate a "fish gill" structure-integrated on-chip membrane device, which has the self-sealing attribute at structure-membrane interface without extra assembling. As a demonstration, metallic micromesh and polymeric membrane can also be easily embedded in 3D printed on-chip device to achieve anti-fouling and anti-clogging functionality for wastewater filtration. As evidenced from in-situ visualization of structure-fluid-foulant interactions during filtration process, the proposed approach successfully adopts the fish feeding mechanism, being able to "ricochet" foulant particles or droplets through hydrodynamic manipulation. When benchmarked with two common wastewater treatment scenarios, such as plastic micro-particles and emulsified oil droplets, our biomimetic filtration devices exhibit 2 ~ 3 times longer durability for high-flux filtration than devices with commercial membrane. This proposed 3D printing-on-membrane approach, elegantly bridging the fields of microfluidics and membrane science, is instrumental to many other applications in energy, sensing, analytical chemistry and biomedical engineering.

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.

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.

Sunlight-Sensitive Anti-Fouling Nanostructured TiO2 coated Cu Meshes for Ultrafast Oily Water Treatment.

Nanostructured materials with desired wettability and optical property can play an important role in reducing the energy consumption of oily water treatment technologies. For effective oily water treatment, membrane materials with high strength, sunlight-sensitive anti-fouling, relative low fabrication cost, and controllable wettability are being explored. In the proposed oily water treatment approach, nanostructured TiO2-coated copper (TNS-Cu) meshes are used. These TNS-Cu meshes exhibit robust superhydrophilicity and underwater oleophobicity (high oil intrusion pressure) as well as excellent chemical and thermal stability (≈250 °C). They have demonstrated high separation efficiency (oil residue in the filtrate ≤21.3 ppm), remarkable filtration flux (≥400 kL h(-1 )m(-2)), and sunlight-sensitive anti-fouling properties. Both our theoretical analysis and experimental characterization have confirmed the enhanced light absorption property of TNS-Cu meshes in the visible region (40% of the solar spectrum) and consequently strong anti-fouling capability upon direct solar light illumination. With these features, the proposed approach promises great potential in treating produced oily wastewater from industry and daily life.

Fabrication of superhydrophobic films with robust adhesion and dual pinning state via in situ polymerization.

Superhydrophobic films on glass substrate with robust adhesion and dual pinning to the water droplets were fabricated utilizing a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) having drooping aliphatic chains and incorporated SiO2 nanoparticles (SiO2 NPs). By employing the F-PBZ/SiO2 NPs modification, the as-prepared composite films possess the robust adhesion to the glass substrate and superhydrophobic pinned state with water contact angle (WCA) of 150° and the non-pinned state with WCA approaching to 165°. Surface morphological studies have indicated that the wettability of the resultant films could be controlled by tuning the surface composition as well as the hierarchical structures. The key role of micro and sub-micro-sized structures and the nanometer sized voids is discussed by the investigation into static contact angle, contact angle hysteresis, droplet evaporation, and propensity for air pocket formation. The as-prepared films exhibited high adhesion toward the glass substrate with considerable durability in corrosive water and proved their simultaneous use in the transportation of micro-droplets, which could be helpful to design large-area and highly scalable superhydrophobic films.

Tortuously structured polyvinyl chloride/polyurethane fibrous membranes for high-efficiency fine particulate filtration.

Two-tier composite filtration medium exhibiting excellent filtration performance to airborne particulate was prepared by a facile deposition of electrospun polyvinyl chloride (PVC)/polyurethane (PU) fibers on a conventional filter paper support. The tortuous structure and composition of resultant fibrous membranes can be finely controlled by regulating the precursor solution composition. By employing the PU incorporation, the pristine PVC fibrous membranes were endowed with robust tensile strength approaching to 9.9 MPa. The plausible correlation between resultant blended fibrous structure and mechanical property of relevant membranes was discussed, and a three-step break mechanism upon the external stress was proposed. Additionally, quantitative pore size and porosity distribution analysis using the capillary flow porometry method has confirmed the tortuous structure of PVC/PU fibrous membranes. Furthermore, the as-prepared membranes with high abrasion resistance (134 cycles) and comparable air permeability (154.1mm/s) showed fascinating filtration efficiency (99.5%) and low pressure drop (144 Pa) performance for 300-500 nm sodium chloride aerosol particles, suggesting their use as a promising medium for variety of potential applications in air filtration.

An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil-water separation.

Superhydrophobic and superoleophilic nanofibrous membranes exhibiting robust oil-water separation performance were prepared by a facile combination of electrospun cellulose acetate (CA) nanofibers and a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) functional layer that incorporated silica nanoparticles (SiO(2) NPs). By employing the F-PBZ/SiO(2) NPs modification, the pristine hydrophilic CA nanofibrous membranes were endowed with a superhydrophobicity with the water contact angle of 161° and a superoleophilicity with the oil contact angle of 3°. Surface morphological studies have indicated that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. The quantitative hierarchical roughness analysis using the N(2) adsorption method has confirmed the major contribution of SiO(2) NPs on enhancing the porous structure, and a detailed correlation between roughness and solid-liquid interface pinning is proposed. Furthermore, the as-prepared membranes exhibited fast and efficient separation for oil-water mixtures and excellent stability over a wide range of pH conditions, which would make them a good candidate in industrial oil-polluted water treatments and oil spill cleanup, and also provided a new insight into the design and development of functional nanofibrous membranes through F-PBZ modification.

Synthesis of superamphiphobic breathable membranes utilizing SiO2 nanoparticles decorated fluorinated polyurethane nanofibers.

Superamphiphobic nanofibrous membranes exhibiting robust water/oil proof and breathable performances were prepared by the combination of a novel synthesized fluorinated polyurethane (FPU) containing a terminal perfluoroalkane segment and incorporated SiO(2) nanoparticles (SiO(2) NPs). By employing the FPU/SiO(2) NPs incorporation, the hybrid membranes possess superhydrophobicity with a water contact angle of 165° and superoleophobicity with an oil contact angle of 151°. Surface morphological studies have indicated that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. The quantitative hierarchical roughness analysis using N(2) adsorption method has confirmed a major contribution of SiO(2) NPs on enhancing the porous structure, and a detailed correlation between the fractal dimension and amphiphobicity is proposed. Furthermore, a designed concept test shows that the as-prepared membranes could load 1.5 kg water or oil at the same time maintained an extremely high air permeability of 2 L min(-1), suggesting their use as promising materials for a variety of potential applications in protective clothing, bioseparation, water purification, tissue engineering, microfluidic systems, etc., and also provided new insight into the design and development of functional hybrid membranes based on FPU.

Synthesis of superhydrophobic silica nanofibrous membranes with robust thermal stability and flexibility via in situ polymerization.

Superhydrophobic silica nanofibrous membranes exhibiting robust thermal stability and flexibility were prepared by a facile combination of electrospun silica nanofibers and a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) functional layer that incorporated SiO(2) nanoparticles (SiO(2) NPs). By using F-PBZ/SiO(2) NP modification, the pristine hydrophilic silica nanofibrous membranes were endowed with superhydrophobicity with a water contact angle (WCA) of up to 161°. Surface morphological studies have revealed that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. Quantitative fractal dimension analysis using the N(2) adsorption method has confirmed the correlation between hierarchical roughness and WCA for the modified membranes. Furthermore, the as-prepared membranes exhibited high thermal stability (450 °C), good flexibility (0.0127 gf cm), and comparable tensile strength (2.58 MPa), suggesting their use as promising materials for a variety of potential applications in high-temperature filtration, self-cleaning coatings, catalyst carriers, etc., and also provided new insight into the design and development of functional nanofibrous membranes through F-PBZ modification.