Transition of Liquid Drops on Microstructured Hygrophobic Surfaces from the Impaled Wenzel State to the "Fakir" Cassie-Baxter State.

Low adhesion of liquids on solid surfaces can be achieved with protrusions that minimize the contact area between the liquid and the solid. The wetting state where an air cushion forms under the drop is known as the Cassie-Baxter state. Surfaces where liquids form macroscopic contact angles above 150° are called superhydrophobic and superhygrophobic, if we refer to water or any liquid, respectively. The Cassie state is desirable for applications, but it is usually unstable compared to the Wenzel state, where the drop is in direct contact with the rough surface. The Cassie-to-Wenzel transition can be triggered by an increase in pressure and vibrations, but the inverse Wenzel-to-Cassie is much more difficult to observe. Here, we examine under what conditions the Wenzel-to-Cassie transition is triggered when the microscopic contact angle changes abruptly. For this, we applied a lubricant of low surface tension around drops that were in the Wenzel state on microstructured surfaces. The increase of the microscopic contact angle lifted the drop from the rough surface, when the pillar height and spacing are large and small, respectively. Numerical calculations for the drop-lubricant interface showed that the surface geometry requirements for the Wenzel-to-Cassie transition are stricter than the ones for the stability of the Cassie state. A surface geometry where the Cassie state is more stable than the Wenzel for a given Laplace pressure of the drop may not always allow the Wenzel-to-Cassie transition to take place. Therefore, the stability of the Cassie state is a necessary but insufficient condition for the inverse transition.

Impact of substrate elasticity on contact angle saturation in electrowetting.

The electrostatically assisted wettability enhancement of dielectric solid surfaces, commonly termed as electrowetting-on-dielectric (EWOD), facilitates many microfluidic applications due to simplicity and energy efficiency. The application of a voltage difference between a conductive droplet and an insulated electrode substrate, where the droplet sits, is enough for realizing a considerable contact angle change. The contact angle modification is fast and almost reversible; however it is limited by the well-known saturation phenomenon which sets in at sufficiently high voltages. In this work, we experimentally show and computationally support the effect of elasticity and thickness of the dielectric on the onset of contact angle saturation. We found that the effect of elasticity is important especially for dielectric thickness smaller than 10 µm and becomes negligible for thickness above 20 µm. We attribute our findings on the effect of the dielectric thickness on the electric field, as well as on the induced electric stresses distribution, in the vicinity of the three phase contact line. Electric field and electric stresses distribution are numerically computed and support our findings which are of significant importance for the design of soft materials based microfluidic devices.

Detaching Microparticles from a Liquid Surface.

The work required to detach microparticles from fluid interfaces depends on the shape of the liquid meniscus. However, measuring the capillary force on a single microparticle and simultaneously imaging the shape of the liquid meniscus has not yet been accomplished. To correlate force and shape, we combined a laser scanning confocal microscope with a colloidal probe setup. While moving a hydrophobic microsphere (radius 5-10 µm) in and out of a 2-5 µm thick glycerol film, we simultaneously measured the force and imaged the shape of the liquid meniscus. In this way we verified the fundamental equations [D. F. James, J. Fluid Mech. 63, 657 (1974)JFLSA70022-112010.1017/S0022112074002126; A. D. Scheludko, A. D. Nikolov, Colloid Polymer Sci. 253, 396 (1975)] that describe the adhesion of particles in flotation, deinking of paper, the stability of Pickering emulsions and particle-stabilized foams. Comparing experimental results with theory showed, however, that the receding contact angle has to be applied, which can be much lower than the static contact angle obtained right after jump in of the particle.

Wetting of soft superhydrophobic micropillar arrays.

Superhydrophobic surfaces are usually assumed to be rigid so that liquids do not deform them. Here we analyze how the relation between microstructure and wetting changes when the surface is flexible. Therefore we deposited liquid drops on arrays of flexible micropillars. We imaged the drop's surface and the bending of micropillars with confocal microscopy and analyzed the deflection of micropillars while the contact line advanced and receded. The deflection is directly proportional to the horizontal component of the capillary force acting on that particular micropillar. In the Cassie or "fakir" state, drops advance by touching down on the next top faces of micropillars, much like on rigid arrays. In contrast, on the receding side the micropillars deform. The main force hindering the slide of a drop is due to pinning at the receding side, while the force on the advancing side is negligible. In the Wenzel state, micropillars were deflected in both receding and advancing states.

Nonlinear control of high-frequency phonons in spider silk.

Spider dragline silk possesses superior mechanical properties compared with synthetic polymers with similar chemical structure due to its hierarchical structure comprised of partially crystalline oriented nanofibrils. To date, silk's dynamic mechanical properties have been largely unexplored. Here we report an indirect hypersonic phononic bandgap and an anomalous dispersion of the acoustic-like branch from inelastic (Brillouin) light scattering experiments under varying applied elastic strains. We show the mechanical nonlinearity of the silk structure generates a unique region of negative group velocity, that together with the global (mechanical) anisotropy provides novel symmetry conditions for gap formation. The phononic bandgap and dispersion show strong nonlinear strain-dependent behaviour. Exploiting material nonlinearity along with tailored structural anisotropy could be a new design paradigm to access new types of dynamic behaviour.

Energy Dissipation of Moving Drops on Superhydrophobic and Superoleophobic Surfaces.

A water drop moving on a superhydrophobic surface or an oil drop moving on a superoleophobic surface dissipates energy by pinning/depinning at nano- and microprotrusions. Here, we calculate the work required to form, extend, and rupture capillary bridges between the protrusions and the drop. The energy dissipated at one protrusion WS is derived from the observable apparent receding contact angle Θrapp and the density of protrusions n by Ws = γ(cos Θrapp + 1)/n, where γ is the surface tension of the liquid. To derive an expression for Ws that links the microscopic structure of the surface to apparent contact angles, two models are considered: A superhydrophobic array of cylindrical micropillars and a superoleophobic array of stacks of microspheres. For a radius of a protrusion R and a receding materials contact angle Θr, we calculate the energy dissipated per protrusion as Ws = πγR2[A - ln(R/κ)]f(Θr). Here, A = 0.60 for cylindrical micropillars and 2.9 for stacks of spheres. κ is the capillary length. f(Θr) is a function which depends on Θr and the specific geometry, f ranges from ≈0.25 to 0.96. Combining both equations above, we can correlate the macroscopically observed apparent receding contact angle with the microscopic structure of the surface and its material properties.

Shape of a sessile drop on a flat surface covered with a liquid film.

Motivated by the development of lubricant-infused slippery surfaces, we study a sessile drop of a nonvolatile (ionic) liquid which is embedded in a slowly evaporating lubricant film (n-decane) on a horizontal, planar solid substrate. Using laser scanning confocal microscopy we imaged the evolution of the shape of the liquid/liquid and liquid/air interfaces, including the angles between them. Results are compared to solutions of the generalized Laplace equations describing the drop profile and the annular wetting ridge. For all film thicknesses, experimental results agree quantitatively with the calculated drop and film shapes. With the verified theory we can predict height and volume of the wetting ridge. Two regimes can be distinguished: for macroscopically thick films (excess lubrication) the meniscus size is insensitive to changes in film thickness. Once the film is thin enough that surface forces between the lubricant/air and solid/lubricant interfaces become significant the meniscus changes significantly with varying film thickness (starved lubrication). The size of the meniscus is particularly relevant because it affects sliding angles of drops on lubricant-infused surfaces.

Long-Term Repellency of Liquids by Superoleophobic Surfaces.

Applications of superoleophobic surfaces depend on the stability of the air cushion formed under liquid drops. To analyze the longevity of air cushions we used reflection-interference contrast microscopy (RICM) for drops on a porous fractal-like structure of sintered nanoparticles. RICM permits us to monitor the height of the air cushion with nanometer resolution. Whereas the air cushion under all investigated liquids was stable on a time scale of a few seconds to minutes and liquids rolled off, liquids with low surface tension penetrated the coating on the time scale of hours and longer. The penetration speed showed a power law dependence on time, dz/dt∼t^{p}, the exponent p varying from -0.5 to -1.2. Thus, penetration is qualitatively different from the Lucas-Washburn law that governs spontaneous capillary filling of porous structures.

Understanding the Formation of Anisometric Supraparticles: A Mechanistic Look Inside Droplets Drying on a Superhydrophobic Surface.

Evaporating drops of nanoparticle suspensions on superhydrophobic surfaces can give anisotropic superaparticles. Previous studies implied the formation of a stiff shell that collapses, but the exact mechanism leading to anisotropy was unclear so far. Here we report on a new experiment using confocal laser scanning microscopy for a detailed characterization of particle formation from droplets of aqueous colloidal dispersions on superhydrophobic surfaces. In a customized setup, we investigated droplets of fumed silica suspensions using two different fluorescent dyes for independently marking silica and the water phase. Taking advantage of interfacial reflection, we locate the drop-air interface and extract normalized time-resolved intensity profiles for dyed silica throughout the drying process. Using comprehensive image analysis we observe and quantify shell-like interfacial particle accumulation arising from droplet evaporation. This leads to a buildup of a stiff fumed silica mantle of ∼20 µm thickness that causes deformation of the droplet throughout further shrinkage, consequently leading to the formation of solid anisometric fumed silica particles.

The Cassie-Wenzel transition of fluids on nanostructured substrates: Macroscopic force balance versus microscopic density-functional theory.

Classical density functional theory is applied to investigate the validity of a phenomenological force-balance description of the stability of the Cassie state of liquids on substrates with nanoscale corrugation. A bulk free-energy functional of third order in local density is combined with a square-gradient term, describing the liquid-vapor interface. The bulk free energy is parameterized to reproduce the liquid density and the compressibility of water. The square-gradient term is adjusted to model the width of the water-vapor interface. The substrate is modeled by an external potential, based upon the Lennard-Jones interactions. The three-dimensional calculation focuses on substrates patterned with nanostripes and square-shaped nanopillars. Using both the force-balance relation and density-functional theory, we locate the Cassie-to-Wenzel transition as a function of the corrugation parameters. We demonstrate that the force-balance relation gives a qualitatively reasonable description of the transition even on the nanoscale. The force balance utilizes an effective contact angle between the fluid and the vertical wall of the corrugation to parameterize the impalement pressure. This effective angle is found to have values smaller than the Young contact angle. This observation corresponds to an impalement pressure that is smaller than the value predicted by macroscopic theory. Therefore, this effective angle embodies effects specific to nanoscopically corrugated surfaces, including the finite range of the liquid-solid potential (which has both repulsive and attractive parts), line tension, and the finite interface thickness. Consistently with this picture, both patterns (stripes and pillars) yield the same effective contact angles for large periods of corrugation.

How superhydrophobicity breaks down.

A droplet deposited or impacting on a superhydrophobic surface rolls off easily, leaving the surface dry and clean. This remarkable property is due to a surface structure that favors the entrainment of air cushions beneath the drop, leading to the so-called Cassie state. The Cassie state competes with the Wenzel (impaled) state, in which the liquid fully wets the substrate. To use superhydrophobicity, impalement of the drop into the surface structure needs to be prevented. To understand the underlying processes, we image the impalement dynamics in three dimensions by confocal microscopy. While the drop evaporates from a pillar array, its rim recedes via stepwise depinning from the edge of the pillars. Before depinning, finger-like necks form due to adhesion of the drop at the pillar's circumference. Once the pressure becomes too high, or the drop too small, the drop slowly impales the texture. The thickness of the air cushion decreases gradually. As soon as the water-air interface touches the substrate, complete wetting proceeds within milliseconds. This visualization of the impalement dynamics will facilitate the development and characterization of superhydrophobic surfaces.

Functional superhydrophobic surfaces made of Janus micropillars.

We demonstrate the fabrication of superhydrophobic surfaces consisting of micropillars with hydrophobic sidewalls and hydrophilic tops, referred to as Janus micropillars. Therefore we first coat a micropillar array with a mono- or bilayer of polymeric particles, and merge the particles together to shield the top faces while hydrophobizing the walls. After removing the polymer film, the top faces of the micropillar arrays can be selectively chemically functionalised with hydrophilic groups. The Janus arrays remain superhydrophobic even after functionalisation as verified by laser scanning confocal microscopy. The robustness of the superhydrophobic behaviour proves that the stability of the entrapped air cushion is determined by the forces acting at the rim of the micropillars. This insight should stimulate a new way of designing super liquid-repellent surfaces with tunable liquid adhesion. In particular, combining superhydrophobicity with the functionalisation of the top faces of the protrusions with hydrophilic groups may have exciting new applications, including high-density microarrays for high-throughput screening of bioactive molecules, cells, or enzymes or efficient water condensation. However, so far chemical attachment of hydrophilic molecules has been accompanied with complete wetting of the surface underneath. The fabrication of superhydrophobic surfaces where the top faces of the protrusions can be selectively chemically post-functionalised with hydrophilic molecules, while retaining their superhydrophobic properties, is both promising and challenging.

Direct observation of drops on slippery lubricant-infused surfaces.

For a liquid droplet to slide down a solid planar surface, the surface usually has to be tilted above a critical angle of approximately 10°. By contrast, droplets of nearly any liquid "slip" on lubricant-infused textured surfaces - so termed slippery surfaces - when tilted by only a few degrees. The mechanism of how the lubricant alters the static and dynamic properties of the drop remains elusive because the drop-lubricant interface is hidden. Here, we image the shape of drops on lubricant-infused surfaces by laser scanning confocal microscopy. The contact angle of the drop-lubricant interface with the substrate exceeds 140°, although macroscopic contour images suggest angles as low as 60°. Confocal microscopy of moving drops reveals fundamentally different processes at the front and rear. Drops recede via discrete depinning events from surface protrusions at a defined receding contact angle, whereas the advancing contact angle is 180°. Drops slide easily, as the apparent contact angles with the substrate are high and the drop-lubricant interfacial tension is typically lower than the drop-air interfacial tension. Slippery surfaces resemble superhydrophobic surfaces with two main differences: drops on a slippery surface are surrounded by a wetting ridge of adjustable height and the air underneath the drop in the case of a superhydrophobic surface is replaced by lubricant in the case of a slippery surface.

Superamphiphobic particles: how small can we go?

Water and oil repellent coatings--so-called superamphiphobic coatings--greatly reduce the interaction between a liquid and a solid. So far, only flat or weakly curved superhydrophobic and superamphiphobic surfaces have been designed. This raises the question of whether highly curved structures or microspheres are feasible. Therefore, we coated microspheres with a superamphiphobic layer and measured the force between the spheres and a liquid. A qualitatively different dependence of the adhesion force on the applied load for superamphiphobic and smooth spheres is detected. Furthermore, we demonstrate both experimentally and theoretically that superamphiphobicity fails below a critical particle radius, depending on topological details and type of liquid. Therefore, this study sets a fundamental physical limit to the application of superamphiphobic layers for small objects with high curvature.

Comparison of Cross-Pin Versus Cortical Button Femoral Fixation in Anterior Cruciate Ligament Reconstruction With Hamstrings Autograft: A Long-Term Clinical Study and Review of the Literature.

Background Anterior cruciate ligament reconstruction (ACLR) is a common operative procedure and many options regarding the type of the selected graft and fixation technique have been described to date. Although many studies have addressed the issue of the optimal femoral fixation device during ACLR with a hamstring tendon (HT) autograft, no clear evidence to indicate one technique over another has been found. Objective The purpose of this study was to compare the long-term postoperative outcomes and complication rates between transfemoral Cross-pin (CP) and Endobutton-Cortical Button (CB) fixation techniques in patients undergoing ACLR with an HT autograft. Methods One hundred and seven consecutive patients underwent ACLR by using a quadruple HT autograft that was stabilized with either a CP (CP Group: 52 patients) or a CB (CB Group: 55 patients) fixation technique. The Lachman test (LT), the Pivot-shift test (PST), the side-to-side difference in anterior translation of the tibia, the International Knee Documentation Committee (IKDC), and the Lysholm knee scoring systems were evaluated before surgery and during long-term follow up. The femoral and tibial tunnel diameter was measured in the anteroposterior (AP) and lateral radiographs after surgery and at the final follow-up. A review of the literature was also carried out to identify any differences between both techniques. Results Study groups were comparable in terms of patient demographics. The mean follow-up was 10.4 ± 1.3 and 10.6 ± 1.3 years in the CP and CB Groups, respectively (p = 0.47). In the CP Group, improvements after surgery in LT and PST from grade 2 (n=34) or 3 (n=18) to grade 0 (n = 41) or 1 (n = 11) and from grade 2 (n=36) or 3 (n = 16) to grade 0 (n = 44) or 1 (n = 8), respectively, were observed. In the CB Group, similar improvements in LT and PST scores from grade 2 (n = 40) or 3 (n = 15) to grade 0 (n = 46) or 1 (n = 9) and from grade 2 (n = 41) or 3 (n = 14) to grade 0 (n = 47) or 1 (n = 8), respectively, were observed. However, no differences between the groups (p = 0.53 for LT and p = 0.90 for PST) were noted. The mean Lysholm scores were 89.7 ± 6.8 and 90.2 ± 7.2 in the CP and CB groups, respectively (p = 0.59). Side-to-side difference improved from 9.1 ± 2.8 to 1.7 ± 1.5 mm and from 8.6 ± 2.5 to 1.6 ± 1.4 mm in the CP and CB groups, respectively (p = 0.89 between groups). According to IKDC grades, 92.1% and 91.4% of knees in the CP and CB groups, respectively were reported to be Grade A (Normal) or B (Nearly Normal) with a p = 0.7. Femoral and tibial tunnel widening was found in the last follow-up in both groups. However, there was no difference in the degree of tunnel widening among the two techniques. With respect to LT, PST, anterior drawer test, and IKDC score, none of the 15 published comparative studies demonstrated any significant differences between the two techniques and only one study detected a difference regarding the Lysholm score in favor of CP fixation. Conclusion In the long term, both CB and CP femoral stabilization techniques were shown to be associated with similar functional outcomes and low complication rates. Further large multicenter random clinical trials are still required to identify the most effective method of femoral fixation for HT autograft during ACLR surgery.

Satisfactory Short-Term Outcomes of Reverse Shoulder Arthroplasty for Complex Three- and Four-Part Fractures of the Humeral Head in Octogenarians.

BACKGROUND: Proximal humeral fractures with severe comminution and poor bone quality are among the most common injuries in the elderly population. Reverse shoulder arthroplasty (RSA) has been widely used to manage complex three- and four-part humeral head fractures. The purpose of the present study was to report the result of this technique in the demanding population of octogenarians. MATERIALS AND METHODS:  Twenty-six patients above the age of 80 years were included in the study and followed for a minimum of one-year follow-up. To assess the functional outcomes the postoperative range of motion (ROM), the Constant score, the visual analog scale for pain, and the disability of the arm and shoulder score (DASH) were measured at 6 and 12 months. Radiological assessment and potential complications were also recorded. RESULTS: The mean age of the study population was 81.9 years (81-86) at the time of surgery. There was a statistically significant improvement in all outcomes over the follow-up intervals. Shoulder ROM was 125.7o for flexion, 98.2o for abduction, 42.2o for internal rotation, and 43.2o for external rotation at 12 months. The mean Constant, DASH, and VAS scores at the last follow-up were 61.3, 31.9, and 0.5, respectively. Reported complications include one superficial surgical site infection. CONCLUSION: RSA is a safe and reliable surgical option with satisfactory outcomes to manage complex three- and four-part fractures of the humeral head as it can provide prompt pain relief and function in octogenarians.

Liquid drops impacting superamphiphobic coatings.

The dynamics of liquid drops impacting superamphiphobic coatings is studied by high-speed video microscopy. Superamphiphobic coatings repel water and oils. The coating consists of a fractal-like hydrophobized silica network. Mixtures of ethanol-water and glycerin-water are chosen to investigate the influence of interfacial tension and viscosity on spreading and retraction dynamics. Drop spreading is dominated by inertia. At low impact velocity, the drops completely rebound. However, the contact time increases with impact velocity, whereas the restitution coefficient decreases. We suggest that the drop temporarily impales the superamphiphobic coating, although the drop completely rebounds. From an estimate of the pressure, it can be concluded that impalement is dominated by depinning rather than sagging. With increasing velocity, the drops partially pin, and an increasing amount of liquid remains on the coating. A time-resolved study of the retraction dynamics reveals two well-separated phases: a fast inertia-dominated phase followed by a slow decrease of the contact diameter of the drop. The crossover occurs when the diameter of the retracting drop matches the diameter of the drop before impact. We suggest that the depth of impalement increases with impact velocity, where impalement is confined to the initial impact zone of the drop. If the drop partially pins on the coating, the depth of impalement exceeds a depth, preventing the whole drop from being removed during the retraction phase.

Solvent-free synthesis of microparticles on superamphiphobic surfaces.

Polymeric and composite microspheres can be synthesized without solvents or process liquids by using superamphiphobic surfaces. In this method, the repellency of superamphiphobic layers to monomers and polymer melts and the extremely low adhesion to particles are taken advantage of.

Effect of nanoroughness on highly hydrophobic and superhydrophobic coatings.

The effect of nanoroughness on contact angles and pinning is investigated experimentally and numerically for low-energy surfaces. Nanoroughness is introduced by chemical vapor deposition of tetraethoxysilane and was quantified by scanning force microscopy. Addition of a root-mean-square roughness of 2 nm on a flat surface can increase the contact angle after fluorination by a semifluorinated silane by up to 30°. On the other hand, nanoroughness can improve or impair the liquid repellency of superhydrophobic surfaces that were made from assembled raspberry particles. Molecular dynamics simulations are performed in order to gain a microscopic understanding on how the length and the surface coating density of semifluorinated silanes influence the hydrophobicity. Solid-liquid surface free energy computations reveal that the wetting behavior strongly depends on the density and alignment of the semifluorinated silane. At coating densities in the range of experimental values, some water molecules can penetrate between the semifluorinated chains, thus increasing the surface energy. Combining the experimental and numerical data exhibits that a roughness-induced increase of the contact angle competes with increased pinning caused by penetration of liquid into nanopores or between neighboring semifluorinated molecules.

Wetting on the microscale: shape of a liquid drop on a microstructured surface at different length scales.

Describing wetting of a liquid on a rough or structured surface is a challenge because of the wide range of involved length scales. Nano- and micrometer-sized textures cause pinning of the contact line, reflected in a hysteresis of the contact angle. To investigate contact angles at different length scales, we imaged water drops on arrays of 5 µm high poly(dimethylsiloxane) micropillars. The drops were imaged by laser scanning confocal microscopy (LSCM), which allowed us to quantitatively analyze the local and large-scale drop profile simultaneously. Deviations of the shape of drops from a sphere decay at two different length scales. Close to the pillars, the amplitude of deviations decays exponentially within 1-2 µm. The drop profile approached a sphere at a length scale 1 order of magnitude larger than the pillars' height. The height and position dependence of the contact angles can be understood from the interplay of pinning of the contact line, the principal curvatures set by the topography of the substrate, and the minimization of the air-water interfaces.