Design of robust superhydrophobic surfaces.

The ability of superhydrophobic surfaces to stay dry, self-clean and avoid biofouling is attractive for applications in biotechnology, medicine and heat transfer1-10. Water droplets that contact these surfaces must have large apparent contact angles (greater than 150 degrees) and small roll-off angles (less than 10 degrees). This can be realized for surfaces that have low-surface-energy chemistry and micro- or nanoscale surface roughness, minimizing contact between the liquid and the solid surface11-17. However, rough surfaces-for which only a small fraction of the overall area is in contact with the liquid-experience high local pressures under mechanical load, making them fragile and highly susceptible to abrasion18. Additionally, abrasion exposes underlying materials and may change the local nature of the surface from hydrophobic to hydrophilic19, resulting in the pinning of water droplets to the surface. It has therefore been assumed that mechanical robustness and water repellency are mutually exclusive surface properties. Here we show that robust superhydrophobicity can be realized by structuring surfaces at two different length scales, with a nanostructure design to provide water repellency and a microstructure design to provide durability. The microstructure is an interconnected surface frame containing 'pockets' that house highly water-repellent and mechanically fragile nanostructures. This surface frame acts as 'armour', preventing the removal of the nanostructures by abradants that are larger than the frame size. We apply this strategy to various substrates-including silicon, ceramic, metal and transparent glass-and show that the water repellency of the resulting superhydrophobic surfaces is preserved even after abrasion by sandpaper and by a sharp steel blade. We suggest that this transparent, mechanically robust, self-cleaning glass could help to negate the dust-contamination issue that leads to a loss of efficiency in solar cells. Our design strategy could also guide the development of other materials that need to retain effective self-cleaning, anti-fouling or heat-transfer abilities in harsh operating environments.

A standing Leidenfrost drop with Sufi whirling.

When a water drop is placed on a hot solid surface, it either undergoes explosive contact boiling or exhibits a stable state. In the latter case, the drop floats over an insulating layer of vapor generated by rapid vaporization of water at the surface/drop interface; this is known as the Leidenfrost state. Here, we discuss a previously unrecognized steady state in which a water drop "stands" on a hot smooth surface. In this state, the drop stabilizes itself with partial adhesion on the hot surface, leading to unique deformation and rotation behavior reminiscent of Sufi whirling-a form of spinning dance. Our analysis of this standing Leidenfrost state reveals the underlying mechanisms that drive the drop's stable partial adhesion and subsequent deformation with rotation. The heat-transfer efficiency of this standing state is up to 390% greater than that of the traditional floating Leidenfrost state.

Interfacial Nanoblisters Formed in Water Serving as Freestanding Platforms for Measuring Elastic Moduli of Polymeric Nanofilms.

Polymeric nanofilms have been widely utilized in diverse cutting-edge technologies, yet accurately determining their elastic moduli remains challenging. Here we demonstrate that interfacial nanoblisters, which are produced by simply immersing substrate-supported nanofilms in water, represent natural platforms for assessing the mechanical properties of polymeric nanofilms using the sophisticated nanoindentation method. Nevertheless, high-resolution, quantitative force spectroscopy studies reveal that the indentation test must be performed on an effective freestanding region around the nanoblister apex and meanwhile under an appropriate loading force, to obtain load-independent, linear elastic deformations. The nanoblister stiffness increases with either decreasing its size or increasing its covering film thickness, and such size effects can be adequately rationalized by an energy-based theoretical model. The proposed model also enables an exceptional determination of the film elastic modulus. Given that interfacial blistering is a frequently occurring phenomenon for polymeric nanofilms, we envision that the presented methodology would stimulate broad applications in relevant fields.

Spectacular Behavior of a Viscoelastic Droplet Impinging on a Superhydrophobic Mesh.

Spray formation using the droplet impact on superhydrophobic mesh surfaces is particularly important because of its application in different industries. The present study revealed that adding a trivial amount of the poly(ethylene oxide) (PEO) polymer to a water droplet can considerably change the impact phenomena on the superhydrophobic mesh surfaces and suppress the spray formation. Droplet rebound is observed only in a narrow range of impact velocities of PEO aqueous droplets when the tiny filaments still connect the surface and droplet. Rebound suppression and deposition of the PEO aqueous droplet is attributed to the higher interaction between the polymer chains and the superhydrophobic mesh surface. After a critical impact velocity and We number which is independent of the PEO concentration, the liquid penetrates the mesh pores. The penetrated liquid formed the ligaments that grow until they reach the maximum length and surprisingly retract back to the mesh surface and the mother droplet. The ligaments destabilized at low PEO concentrations (c = 0.5 and 1 g/L) and a mesh opening size of H = 357 µm to the crest swell droplets when the droplet size is reduced by increasing the impact velocity. The ligament fragmentation and droplet detachment are observed only at high impact velocities when c = 0.5 and 1 g/L and H = 357 µm. The result shows that the PEO additive does not significantly affect the maximum spreading diameter. An empirical model to calculate the maximum spreading factor is developed.

Successive Rebounds of Impinging Water Droplets on Superhydrophobic Surfaces.

When a water droplet strikes a superhydrophobic surface, there may be several to a few tens of rebounds before it comes to rest. Although this intriguing multiphase flow phenomenon has received a great deal of attention from interfacial scientists and engineers, the underlying dynamics have not yet been completely resolved. In this paper, we report on an experimental investigation into the bouncing behavior of water droplets impinging on macroscopically flat superhydrophobic surfaces. We show that the restitution coefficient, which quantifies the energy consumed during impact and rebound, exhibits a nonmonotonic dependence on the Weber number. It is the droplet-surface friction that restricts the rebound height of the impinging droplet, so its restitution coefficient increases with the Weber number when the impact velocity is below a critical value. Above this value, the viscous friction within a thin liquid layer close to the superhydrophobic surface becomes dominant, and thus, the restitution coefficient decreases sharply. On the basis of energy analyses, semiempirical formulas are proposed to describe the restitution coefficient, and these can be employed to predict the number of successive rebounds of impinging droplets on superhydrophobic surfaces.

Elasticity-to-Capillarity Transition in Soft Substrate Deformation.

Whereas capillarity controls fluid dynamics at submillimeter scale and elasticity determines the mechanics of rigid solids, their coupling governs elastocapillary deformations on soft solids. Here, we directly probed the deformations on soft substrates induced by sessile nanodroplets. The wetting ridge created around the contact line and the dimple formed underneath the nanodroplet were imaged with a high spatial resolution using atomic force microscopy. The ridge height nonmonotonically depends on the substrate stiffness, and the dimple depth nonlinearly depends on the droplet size. The capillarity of the substrate overcomes the elasticity of the substrate in dominating the deformations when the elastocapillary length is approximately larger than the droplet contact radius, showing an experimental observation of the elasticity-to-capillarity transition. This study provides an experimental approach to investigate nanoscale elastocapillarity, and the insights have the potential to kick-off future work on the fundamentals of solid mechanics.

Droplet impact on pillar-arrayed non-wetting surfaces.

Droplet impact on pillar-arrayed polydimethylsiloxane (PDMS) surfaces with different solid fractions was studied. The lower and upper limits of Weber number, We, for complete rebound of impacting droplets decreased with decreasing solid fractions. Gaps were visible during the spreading and retraction processes of bouncing droplets on the surface with a solid fraction of 0.06 while no gaps were observed during the retraction process when We was greater than its upper limit, indicating that there existed a transition from the Cassie-Baxter wetting state to the Wenzel wetting state. Therefore, a novel model accounting for the penetration of a liquid into the cavities between the pillars was developed to predict the upper limit of the impact velocity of bouncing droplets. At high We, partial rebound was observed for surfaces with solid fractions of 0.50 and 0.20 while a sticky state was observed for the surface with a solid fraction of 0.06. Moreover, surface roughness has a great influence on the contact time of bouncing droplets. Besides, the maximum spreading parameter was found to follow a scaling law of We1/4.

Surface charge printing for programmed droplet transport.

The directed, long-range and self-propelled transport of droplets on solid surfaces is crucial for many applications from water harvesting to bio-analysis1-9. Typically, preferential transport is achieved by topographic or chemical modulation of surface wetting gradients that break the asymmetric contact line and overcome the resistance force to move droplets along a particular direction10-16. Nonetheless, despite extensive progress, directional droplet transport is limited to low transport velocity or short transport distance. Here we report the high-velocity and ultralong transport of droplets elicited by surface charge density gradients printed on diverse substrates. We leverage the facile water droplet printing on superamphiphobic surfaces to create rewritable surface charge density gradients that stimulate droplet propulsion under ambient conditions17 and without the need for additional energy input. Our strategy provides a platform for programming the transport of droplets on flat, flexible and vertical surfaces that may be valuable for applications requiring a controlled movement of droplets17-19.

Surface-Charge-Assisted Microdroplet Generation on a Superhydrophobic Surface.

The ability to generate and manipulate droplets down to microscales has attracted great attention in a variety of applications, such as in printing, microreactors, and biological assays. However, the production of microdroplets is often limited by special equipment or the size of needles. Here, an unexplored and facile approach is demonstrated; microdroplets can be generated and trapped yet not pinned on a micro-nano-structured superhydrophobic surface by controllable surface charge during drop impact. Tiny droplets with a size at a scale of tens of microns to millimeters are generated by simply changing the impacting velocity, the size of the impact drop, or impact frequency. Theoretical analysis suggests the generation of the microdroplet as a result of the surface-charge-regulated adhesion, competing with liquid dynamic and interfacial energy. The distribution of surface charge which determines the size and the location of the microdroplet is at the top of the micro-nano-structured surface and dependent on the pressure field applied on the surface during the drop impact. The mobility of the resulting microdroplet that can be easily manipulated without liquid retention is also shown, by taking advantage of the shielding property of the surface charge. This facile yet effective method provides a promising candidate for the realization of tiny droplet-generating and -manipulating applications.

Resolving the Apparent Line Tension of Sessile Droplets and Understanding its Sign Change at a Critical Wetting Angle.

Despite strenuous research efforts for more than one century, identifying the magnitude and sign of the apparent line tension for a liquid-solid-gas system remains an elusive goal. Herein we accurately determine the apparent line tension from the size-dependent contact angle of sessile nanodrops on surfaces with different wetting properties via atomic force microscopy measurements and molecular dynamics simulations. We show that the apparent line tension has a magnitude of 10^{-11}-10^{-10} J/m, in good agreement with theoretical predictions. Furthermore, while it is positive and favors shorter contact lines for droplets on very lyophilic surfaces, the apparent line tension changes its sign and favors longer contact lines on surfaces with an apparent contact angle higher than a critical value. By analyzing the density and the potential energy of liquid molecules within the sessile droplet, we demonstrate that the sign of the apparent line tension is a thermodynamic property of the liquid-solid-gas system rather than the local effect of intermolecular interactions in the three-phase confluence region.

Sessile Microdrop Coalescence on Partial Wetting Surfaces: Effects of Surface Wettability and Stiffness.

We experimentally investigated the coalescence of two sessile microdrops on rigid surfaces with diverse wettability (macroscopic apparent water contact angles of θapp ≈ 13-110°) and on hydrophobic surfaces (θapp ≈ 110-124°) with very different stiffness properties (Young's moduli of E ≈ 1.1 MPa to 130 GPa). We show that the coalescence contains two fast regimes, in which a liquid meniscus bridging the parent droplets rapidly grows, forming a hemi-ellipsoidal droplet, and a slow regime, in which the merged hemi-ellipsoidal droplet relaxes to the equilibrium hemispherical cap. Whereas the fast bridging regimes last less than 2 ms and are almost independent of surface wettability and stiffness, the relaxation regime, which was only observed on sufficiently hydrophobic and rigid surfaces with low wetting hysteresis, continues for a few tens to several hundreds of milliseconds depending on surface properties. We further demonstrate that the slow droplet relaxation can be described neither by the bulk hydrodynamics nor by a microscopic model concerning liquid evaporation near the droplet edge, but by the molecular kinetic theory for the motion of the three-phase contact line.

Helical Fibers via Evaporation-Driven Self-Assembly of Surface-Acylated Cellulose Nanowhiskers.

Many natural materials have helical or twisting shapes. Herein, we show the formation of helical fibers with the lengths of micrometers by the evaporation-driven self-assembly on silicon wafers of functionalized cellulose nanowhiskers (CNWs) with surface-attached acyl chains. The self-assembly process and the final helical structures were affected by parameters including the wettability of substrates, dispersing solvents, the amount of 10-undecenoyl groups, the crystallinity, the dimension of CNWs, and the length of acyl chains. In particular, surface-acylated CNWs with a certain amount of 10-undecenoyl groups (ca. 3.52 mmol g-1 ), an appropriate crystallinity (ca. 40 %), a length of about 135 nm, and a diameter of around 4 nm, preferentially self-assembled into explicit left-handed helical fibers from their THF suspensions on wafers. Thus, we showed novel particular self-assembly behaviors of surface-acylated CNWs, and we expanded the materials spectrum for the construction of helical structures.

Submillimeter-Sized Bubble Entrapment and a High-Speed Jet Emission during Droplet Impact on Solid Surfaces.

When a droplet impacts a solid surface, the entrapment of a submillimeter-sized bubble and the emission of a high speed jet can be observed at low impact velocities. In this work, we show that bubble entrapment occurs only on sufficiently hydrophobic surfaces within a narrow range of impact velocities. The bubble is entrapped on hydrophobic surfaces, whereas it is trapped into the top of the droplet on superhydrophobic surfaces. The collapse of the air cavity formed during droplet impact, which is dominated by inertia and influenced by surface wettability, is the cause of the bubble entrapment. The velocity of liquid jets emitted after cavity collapse for drop impact with and without bubble entrapment scales with their sizes according to different power laws, which is explained by simple scaling analyses.

Impact of Viscous Droplets on Superamphiphobic Surfaces.

The impact of a liquid droplet on a solid surface is one of the most common phenomena in nature and frequently encountered in numerous technological processes. Despite the significant progress on understanding the droplet impact phenomenon over the past century, the impact dynamics, especially the coupling effects between the properties of a liquid and surface wettability on the impact process, is still poorly understood. In this work, we experimentally investigated the impact of viscous droplets on superamphiphobic surfaces, with the viscosity of liquids ranging from 0.89 to 150 mPa s. We showed that an increase in liquid viscosity will slow down the impact process and cause bouncing droplets to rebound lower and fewer times. The critical impact velocity, above which droplets can rebound from the superamphiphobic surface, was found to linearly increase with the liquid viscosity. We also showed that the maximum spreading factor increases with Weber number or Reynolds number but decreases with the liquid viscosity. Scaling analyses based on energy conservation were carried out to explain these findings, and they were found to be in good agreement with our experimental results.

Anatomical Study and Locating Nasolacrimal Duct on Computed Topographic Image.

PURPOSE: We performed a novel anatomical and radiological investigation to understand the structure of nasolacrimal duct (NLD) and to provide data to help surgeons locate the openings of NLD efficiently based on landmarks. MATERIALS AND METHODS: We examined the NLD region using computed tomography images of 133 individuals and 6 dry skull specimens. Multiplanar reconstruction of the computed tomography images was performed, and the anatomical features of the NLD were studied in the coronal, sagittal, and axial planes. The long and short diameters of NLD were measured along its cross-section. The position of NLD was localized using the nostril, concha nasalis media, and medial orbital corner as landmarks. The free and open source software, 3D Slicer, was used for the segmentation of the NLD and 3D visualization of the superior and inferior openings of the NLD. RESULTS: The length, angle, and diameter of NLD were significantly influenced by the age in females compared to those in males. The inferior opening of the NLD could be located efficiently using the nostril and the midsagittal line while the superior opening of NLD could be located using the medial orbital corner. Third, 3D Slicer enabled us to measure the distance between the skin and the bony structure in the image. CONCLUSION: Our study indicates that the sex and age of the patient should be considered while selecting the optimal NLD stent for a patient, and that the precise location of NLD in reference to landmarks can simplify the surgical difficulties and reduce the risk of injury during the transnasal operation.

Pre-treatment estimation of future remnant liver function using gadoxetic acid MRI in patients with HCC.

BACKGROUND & AIMS: This study aimed to determine whether the predicted remnant liver function on dynamic hepatocyte-specific contrast media-enhanced magnetic resonance (DHCE-MR) imaging correlates with the results of the indocyanin green retention test (ICG R15) after hepatic resection or radiofrequency ablation (RFA). METHODS: This prospective multicenter study was approved by the Institutional Review Boards of each hospital. Informed consents were obtained from all. DHCE-MRI and ICG R15 were performed in 57 patients scheduled to undergo hepatectomy or RFA for hepatocellular carcinoma, once before treatment and repeated on post-treatment day 3. In nine donors and three recipients, DHCE-MRI and ICG R15 were performed only preoperatively. The predicted remnant liver function (HEFml) was estimated using the hepatic extraction fraction (HEF) multiplied by the remnant liver volume, and compared with post-treatment ICG R15. Intra-individual heterogeneity of HEF was assessed using pooled coefficients of variation (CV) among hepatic segments. Finally, development of post-treatment hepatic failure was assessed according to the 50-50 criteria on post-treatment day 5. RESULTS: Predicted remnant HEFml showed a negative correlation with post-treatment ICG R15 (r=-0.45, p=0.001), whereas liver volume did not (p>0.05). There were significant correlations between pre-treatment HEFml and pre-treatment ICG R15 (r=-0.33, p=0.006) and between post-treatment HEFml and post-treatment ICG R15 (r=-0.54, p<0.001). Pooled CV among segmental HEFs was 12.6%. No patients showed post-treatment liver failure on post-treatment day 5. CONCLUSIONS: DHCE-MRI using Gd-EOB-DTPA was able to provide both global and segmental liver function information, and post-treatment remnant liver function predicted on pre-treatment DHCE-MRI showed a significant negative correlation with post-treatment ICG R15. LAY SUMMARY: Post-treatment liver function could be predicted at pre-treatment DHCE-MRI. Liver function was heterogeneous among the liver segments. Liver anatomy, disease extent, and underlying liver function can be assessed in one DHCE-MRI examination. CLINICAL TRIAL NUMBER: ClinicalTrials.gov number, NCT01490203.

Protective effect of Trillium tschonoskii saponin on CCl4-induced acute liver injury of rats through apoptosis inhibition.

To explore hepatoprotective role and underlying mechanisms of Trillium tschonoskii Maxim (TTM), 36 rats were randomly divided into control, CCl4-induced liver injury model, and biphenyl dimethyl dicarboxylate (DDB) and low-, moderate-, and high-dose TTM treatment groups. After CCl4-induced model establishment, the rats from DDB and TTM groups were administrated with DDB at 0.2 g/kg per day and TTM at 0.1, 0.5, and 1.0 g/kg per day, while the rats from control and model groups were administrated with saline. After 5 days of treatments, all rats were sacrificed for determining serum ALT and AST levels and liver index, examining histopathological changes in liver through HE and TUNEL staining, and evaluating TNF-α and IL-6 mRNA expression by real-time PCR, and caspase-3, Bcl-2, and Bax expression by Western blot. Results indicated that CCl4 could induce acute liver injury and abnormal liver function in rats with obvious hepatomegaly, increased liver index, high ALT and AST levels, up-regulated TNF-α and IL-6, and overexpressed Bax and caspase-3. However, DDB and TTM could execute protective role in CCl4-induced liver injury in rats through reducing ALT and AST levels, rescuing hepatomegaly, down-regulating inflammatory factors and inhibiting hepatocyte apoptosis in a dose-dependent manner. Therefore, TTM has obvious protective role in CCl4-induced liver injury of rats through inhibiting hepatocyte apoptosis.

Collapse of surface nanobubbles.

Surface attached nanobubbles populate surfaces submerged in water. These nanobubbles have a much larger contact angle and longer lifetime than predicted by classical theory. Moreover, it is difficult to distinguish them from hydrophobic droplets, e.g., polymeric contamination, using standard atomic force microscopy. Here, we report fast dynamics of a three phase contact line moving over surface nanobubbles, polymeric droplets, and hydrophobic particles. The dynamics is distinct: across polymeric droplets the contact line quickly jumps and hydrophobic particles pin the contact line, while surface nanobubbles rapidly shrink once merging with the contact line, suggesting a method to differentiate nanoscopic gaseous, liquid, and solid structures. Although the collapse process of surface nanobubbles occurs within a few milliseconds, we show that it is dominated by microscopic dynamics rather than bulk hydrodynamics.

Initial electrospreading of aqueous electrolyte drops.

The early spreading of a liquid drop on a solid surface driven by inertial, capillary, and electrostatic forces is of fundamental interest, since most commonly used surfaces are (naturally) charged. We studied the effect of applying an electric potential between a drop and a surface on the early spreading of aqueous electrolyte drops. We found that spreading dynamics not only depended on the potential, but also on the electrolyte concentration. Based on molecular dynamics simulations of the ion distribution in spreading nanodrops under an applied potential, we propose a simple model to explain the relation between applied potential, electrolyte concentration, and early spreading dynamics.

Inertial to viscoelastic transition in early drop spreading on soft surfaces.

It has been known for many years that a spreading liquid droplet can be appreciably slowed on a soft, viscoelastic substrate by the appearance of a "wetting ridge" or protuberance of the solid near the triple phase contact line because of capillary forces. Viscoelastic dissipation in the solid surface can outweigh that of liquid viscosity and, therefore, dominate wetting dynamics. In this paper, we show that a short, rapid spreading stage exists after initial contact. The requisite balance determining the speed of motion is between capillary forces and inertial effects. As spreading proceeds, however, inertia lessens and the lower spreading speed allow for viscoelastic effects in the solid to increase. The transition between early inertial and viscoelastic regimes is studied with high-speed photography and explained by a simple theory.