Showing papers on "Contact angle published in 2015"

Surface nanobubbles and nanodroplets

Abstract: Surface nanobubbles are nanoscopic gaseous domains on immersed substrates which can survive for days. They were first speculated to exist about 20 years ago, based on stepwise features in force curves between two hydrophobic surfaces, eventually leading to the first atomic force microscopy (AFM) image in 2000. While in the early years it was suspected that they may be an artifact caused by AFM, meanwhile their existence has been confirmed with various other methods, including through direct optical observation. Their existence seems to be paradoxical, as a simple classical estimate suggests that they should dissolve in microseconds, due to the large Laplace pressure inside these nanoscopic spherical-cap-shaped objects. Moreover, their contact angle (on the gas side) is much smaller than one would expect from macroscopic counterparts. This review will not only give an overview on surface nanobubbles, but also on surface nanodroplets, which are nanoscopic droplets (e.g., of oil) on (hydrophobic) substrates immersed in water, as they show similar properties and can easily be confused with surface nanobubbles and as they are produced in a similar way, namely, by a solvent exchange process, leading to local oversaturation of the water with gas or oil, respectively, and thus to nucleation. The review starts with how surface nanobubbles and nanodroplets can be made, how they can be observed (both individually and collectively), and what their properties are. Molecular dynamic simulations and theories to account for the long lifetime of the surface nanobubbles are then reported on. The crucial element contributing to the long lifetime of surface nanobubbles and nanodroplets is pinning of the three-phase contact line at chemical or geometric surface heterogeneities. The dynamical evolution of the surface nanobubbles then follows from the diffusion equation, Laplace’s equation, and Henry’s law. In particular, one obtains stable surface nanobubbles when the gas influx from the gas-oversaturated water and the outflux due to Laplace pressure balance. This is only possible for small enough surface bubbles. It is therefore the gas or oil oversaturation ζ that determines the contact angle of the surface nanobubble or nanodroplet and not the Young equation. The review also covers the potential technological relevance of surface nanobubbles and nanodroplets, namely, in flotation, in (photo)catalysis and electrolysis, in nanomaterial engineering, for transport in and out of nanofluidic devices, and for plasmonic bubbles, vapor nanobubbles, and energy conversion. Also given is a discussion on surface nanobubbles and nanodroplets in a nutshell, including theoretical predictions resulting from it and future directions. Studying the nucleation, growth, and dissolution dynamics of surface nanobubbles and nanodroplets will shed new light on the problems of contact line pinning and contact angle hysteresis on the submicron scale.

Robust superhydrophobic TiO2@fabrics for UV shielding, self-cleaning and oil–water separation

Abstract: Inspired by the surface geometry and composition of the lotus leaf with its self-cleaning behavior, in this work, a TiO2@fabric composite was prepared via a facile strategy for preparing marigold flower-like hierarchical TiO2 particles through a one-pot hydrothermal reaction on a cotton fabric surface. In addition, a robust superhydrophobic TiO2@fabric was further constructed by fluoroalkylsilane modification as a versatile platform for UV shielding, self-cleaning and oil–water separation. The results showed TiO2 particles were uniformly distributed on the fibre surface with a high coating density. In comparison with hydrophobic cotton fabric, the TiO2@fabric exhibited a high superhydrophobic activity with a contact angle of ∼160° and a sliding angle lower than 10°. The robust superhydrophobic fabric had high stability against repeated abrasion without an apparent reduction in contact angle. The as-prepared composite TiO2@fabric demonstrated good anti-UV ability. Moreover, the composite fabric demonstrated highly efficient oil–water separation due to its extreme wettability contrast (superhydrophobicity/superoleophilicity). We expect that this facile process can be readily and widely adopted for the design of multifunctional fabrics for excellent anti-UV, effective self-cleaning, efficient oil–water separation, and microfluidic management applications.

One-Step Electrodeposition Process To Fabricate Corrosion-Resistant Superhydrophobic Surface on Magnesium Alloy

Abstract: A simple, one-step method has been developed to construct a superhydrophobic surface by electrodepositing Mg–Mn–Ce magnesium plate in an ethanol solution containing cerium nitrate hexahydrate and myristic acid. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy were employed to characterize the surfaces. The shortest electrodeposition time to obtain a superhydrophobic surface was about 1 min, and the as-prepared superhydrophobic surfaces had a maximum contact angle of 159.8° and a sliding angle of less than 2°. Potentiodynamic polarization and electrochemical impedance spectroscopy measurements demonstrated that the superhydrophobic surface greatly improved the corrosion properties of magnesium alloy in 3.5 wt % aqueous solutions of NaCl, Na2SO4, NaClO3, and NaNO3. Besides, the chemical stability and mechanical durability of the as-prepared superhydrophobic surface were also examined. The presented method is rap...

Surface modification of bacterial cellulose aerogels' web-like skeleton for oil/water separation.

Abstract: The cellulose nanofibers of bacterial cellulose aerogel (BCA) are modified only on their surfaces using a trimethylsilylation reaction with trimethyichlorosilane in liquid phase followed by freeze-drying. The obtained hydrophobic bacterial cellulose aerogels (HBCAs) exhibit low density (≤6.77 mg/cm3), high surface area (≥169.1 m2/g), and high porosity (≈ 99.6%), which are nearly the same as those of BCA owing to the low degrees of substitution (≤0.132). Because the surface energy of cellulose nanofibers decreased and the three-dimensional web-like microstructure, which was comprised of ultrathin (20–80 nm) cellulose nanofibers, is maintained during the trimethylsilylation process, the HBCAs have hydrophobic and oleophilic properties (water/air contact angle as high as 146.5°) that endow them with excellent selectivity for oil adsorption from water. The HBCAs are able to collect a wide range of organic solvents and oils with absorption capacities up to 185 g/g, which depends on the density of the liquids. ...

Vapour-mediated sensing and motility in two-component droplets

Abstract: The ability to control the movement of fluid droplets is of practical use in many applications including microfluidic liquid handling. Existing techniques demand large energy gradients on the solid surfaces on which the droplets are placed or a carefully prepared surface to overcome contact line pinning (an effect which usually limits droplet motion). This paper reports a previously unrecognized phenomenon that could provide a convenient means of manipulating fluid droplets. Droplets consisting of two miscible components in which one component has both a higher vapour pressure and higher surface tension than the other such as water and propylene glycol exhibit a contact angle when deposited on a high-energy surface (clean glass), but rest on a fluid film so do not suffer from contact line pinning. The droplets are stabilized by evaporation-induced surface tension gradients and can move under the influence of tiny forces, including the vapour emitted by neighbouring droplets. A wide range of interesting interactions is recorded for example, one droplet bouncing off another, a droplet 'chasing' another in a circle and a rainbow of different droplets sorted according to their surface tensions.

Direct observation of drops on slippery lubricant-infused surfaces

Abstract: 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.

Exceptional Hydrophobicity of a Large-Pore Metal-Organic Zeolite.

Abstract: Porous materials combining high hydrophobicity, large surface area, as well as large and uniform pore size are very useful but rare. The nanoporous zeolitic metal azolate framework, RHO-[Zn(eim)2] (MAF-6, Heim = 2-ethylimidazole), is an attractive candidate but thought to be unobtainable/unstable. In this work, the supramolecular isomerism of [Zn(eim)2] is thoroughly studied using a rapid solution mixing reaction of [Zn(NH3)4](OH)2 and Heim, which enables MAF-6 with high crystallinity, purity, and thermal/chemical stabilities to be synthesized in large quantity. Gas and vapor adsorption isotherms, gas chromatography, and water contact angle measurements, as well as transient breakthrough and molecular dynamics simulations show that MAF-6 exhibits large surface area (langmuir surface area 1695 m2 g–1), pore volume (0.61 cm3 g–1), pore size (d = 18.4 A), and aperture size (d = 7.6 A) with high hydrophobicity on both the internal pore and external crystal surfaces. It can barely adsorb water or be wetted by ...

Robust Superhydrophobic Graphene-Based Composite Coatings with Self-Cleaning and Corrosion Barrier Properties

Abstract: Superhydrophobic surfaces for self-cleaning applications often suffer from mechanical instability and do not function well after abrasion/scratching. To address this problem, we present a method to prepare graphene-based superhydrophobic composite coatings with robust mechanical strength, self-cleaning, and barrier properties. A suspension has been formulated that contains a mixture of reduced graphene oxide (rGO) and diatomaceous earth (DE) modified with polydimethylsiloxane (PDMS) that can be applied on any surface using common coating methods such as spraying, brush painting, and dip coating. Inclusion of TiO2 nanoparticles to the formulation shows further increase in water contact angle (WCA) from 159 ± 2° to 170 ± 2° due to the structural improvement with hierarchical surface roughness. Mechanical stability and durability of the coatings has been achieved by using a commercial adhesive to bond the superhydrophobic “paint” to various substrates. Excellent retention of superhydrophobicity was observed ...

Metal oxide-based nanoparticles: revealing their potential to enhance oil recovery in different wettability systems

Abstract: This paper presents systematic studies of hydrophilic metal oxide nanoparticles (NPs) dispersed in brine intended to reveal their potential to enhance oil recovery (EOR) in various rock wettability systems. The stability in suspension (nanofluid) of the NPs has been identified as a key factor related to their use as an EOR agent. Experimental techniques have been developed for nanofluid stability using three coupled methods: direct visual observation, surface conductivity and particle size measurements. The use of a dispersant has been investigated and has been shown to successfully improve metal oxide nanofluid stability as a function of its concentration. The dispersant alters the nanofluid properties, i.e. surface conductivity, pH and particle size distribution. A two-phase coreflood experiment was conducted by injecting the stable nanofluids as a tertiary process (nano-EOR) through core plugs with various wettabilities ranging from water-wet to oil-wet. The combination of metal oxide nanofluid and dispersant improved the oil recovery to a greater extent than either silica-based nanofluid or dispersant alone in all wettability systems. The contact angle, interfacial tension (IFT) and effluent were also measured. It was observed that metal oxide-based nanofluids altered the quartz plates to become more water-wet, and the results are consistent with those of the coreflood experiment. The particle adsorption during the transport process was identified from effluent analysis. The presence of NPs and dispersant reduced the IFT, but its reduction is sufficient to yield significant additional oil recovery. Hence, wettability alteration plays a dominant role in the oil displacement mechanism using nano-EOR.

Effect of Experimental Parameters on Morphological, Mechanical and Hydrophobic Properties of Electrospun Polystyrene Fibers

Abstract: Polystyrene (PS) dissolved in a mixture of N, N-dimethylformamide (DMF) and/or tetrahydrofuran (THF) was electrospun to prepare fibers with sub-micron diameters. The effects of electrospinning parameters, including solvent combinations, polymer concentrations, applied voltage on fiber morphology, as well as tensile and hydrophobic properties of the fiber mats were investigated. Scanning electron microscope (SEM) images of electrospun fibers (23% w/v PS solution with applied voltage of 15 kV) showed that a new type of fiber with double-strand morphology was formed when the mass ratio of DMF and THF was 50/50 and 25/75. The tensile strength of the PS fiber film was 1.5 MPa, indicating strong reinforcement from double-strand fibers. Bead-free fibers were obtained by electrospinning 40% (w/v) PS/DMF solution at an applied voltage of 15 kV. Notably, when the ratio of DMF and THF was 100/0, the maximum contact angle (CA) value of the electrospun PS films produced at 15 kV was 148°.

A mechanically bendable superhydrophobic steel surface with self-cleaning and corrosion-resistant properties

Abstract: We present an effective way to develop superhydrophobic steel surface which shows stable superhydrophobicity under harsh mechanical bending. The roughness on the steel surface was created by etching in acid solution and its surface energy was lowered by subsequent hydrophobic silane treatment. The steel etching time in sulfuric acid solution was optimized to 8 h which provides high surface roughness required for superhydrophobicity. A water contact angle of 164 ± 3° and a sliding angle of 9 ± 2° were obtained for the steel surface after surface chemical modification by methyltrichlorosilane. We bent this superhydrophobic steel to 90° and 180° and studied the wetting properties on the bent area, which showed absolutely no change in superhydrophobicity. This superhydrophobic steel surface showed excellent self-cleaning behaviour as well as maintained its superhydrophobic wetting properties under a stream of water jet. Further, the stability of the wetting state was evaluated using a sandpaper abrasion test, adhesive tape peeling test, and under prolonged UV irradiation. Energy-dispersive X-ray spectroscopy was used to confirm the surface chemical composition of the superhydrophobic steel surface. This approach can be applied to steel surfaces of any size and shape to advance their industrial applications.

Kinetics of Low-Salinity-Flooding Effect

Abstract: Low-salinity waterflooding (LSF) is one of the least-understood enhanced-oil-recovery (EOR)/improved-oil-recovery (IOR) methods, and proper understanding of the mechanism(s) leading to oil recovery in this process is needed. However, the intrinsic complexity of the process makes fundamental understanding of the underlying mechanism(s) and the interpretation of laboratory experiments difficult. Therefore, we use a model system for sandstone rock of reduced complexity that consists of clay minerals (Na-montmorillonite) deposited on a glass substrate and covered with crude-oil droplets and in which different effects can be separated to increase our fundamental understanding. We focus particularly on the kinetics of oil detachment when exposed to lowsalinity (LS) brine. The system is equilibrated first under high-salinity (HS) brine and then exposed to brines of varying (lower) salinity while the shape of the oil droplets is continuously monitored at high resolution, allowing for a detailed analysis of the contact angle and the contact area as a function of time. It is observed that the contact angle and contact area of oil with the substrate reach a stable equilibrium at HS brine and show a clear response to the LS brine toward less-oil-wetting conditions and ultimately detachment from the clay substrate. This behavior is characterized by the motion of the three-phase (oil/water/solid) contact line that is initially pinned by clay particles at HS conditions, and pinning decreases upon exposure to LS brine. This leads to a decrease in contact area and contact angle that indicates wettability alteration toward a more-waterwet state. When the contact angle reaches a critical value at approximately 40 to 50 , oil starts to detach from the clay. During detachment, most of the oil is released, but in some cases a small amount of oil residue is left behind on the clay substrate. Our results for different salinity levels indicate that the kinetics of this wettability change correlates with a simple buoyancyover adhesion-force balance and has a time constant of hours to days (i.e., it takes longer than commonly assumed). The unexpectedly long time constant, longer than expected by diffusion alone, is compatible with an electrokinetic ion-transport model (Nernst-Planck equation) in the thin water film between oil and clay. Alternatively, one could explain the observations only by more-specific [nonDerjaguin–Landau–Verwey–Overbeek (DLVO) type] interactions between oil and clay such as cation-bridging, direct chemical bonds, or acid/base effects that tend to pin the contact line. The findings provide new insights into the (sub) pore-scale mechanism of LSF, and one can use them as the basis for upscaling to, for example, pore-network scale and higher scales (e.g., core scale) to assess the impact of the slow kinetics on the time scale of an LSF response on macroscopic scales.

Wetting of mono and few-layered WS2 and MoS2 films supported on Si/SiO2 substrates.

Abstract: The recent interest and excitement in graphene has also opened up a pandora's box of other two-dimensional (2D) materials and material combinations which are now beginning to come to the fore. One family of these emerging 2D materials is transition metal dichalcogenides (TMDs). So far there is very limited understanding on the wetting behavior of "monolayer" TMD materials. In this study, we synthesized large-area, continuous monolayer tungsten disulfide (WS2) and molybdenum disulfide (MoS2) films on SiO2/Si substrates by the thermal reduction and sulfurization of WO3 and MO3 thin films. The monolayer TMD films displayed an advancing water contact angle of ∼83° as compared to ∼90° for the bulk material. We also prepared bilayer and trilayer WS2 films and studied the transition of the water contact angle with increasing number of layers. The advancing water contact angle increased to ∼85° for the bilayer and then to ∼90° for the trilayer film. Beyond three layers, there was no significant change in the measured water contact angle. This type of wetting transition indicates that water interacts to some extent with the underlying silica substrate through the monolayer TMD sheet. The experimentally observed wetting transition with numbers of TMD layers lies in-between the predictions of one continuum model that considers only van der Waals attractions and another model that considers only dipole-dipole interactions. We also explored wetting as a function of aging. A clean single-layer WS2 film (without airborne contaminants) was shown to be strongly hydrophilic with an advancing water contact angle of ∼70°. However, over time, the sample ages as hydrocarbons and water present in air adsorb onto the clean WS2 sheet. After ∼7 days, the aging process is completed and the advancing water contact angle of the aged single-layer WS2 film stabilizes at ∼83°. These results suggest that clean (i.e., nonaged) monolayer TMDs are hydrophilic materials. We further show that substitution of sulfur atoms by oxygen in the lattice of aged monolayer WS2 and MoS2 films can be used to generate well-defined 'hydrophobic-hydrophilic' patterns that preferentially accumulate and create microdrop arrays on the surface during water condensation and evaporation experiments.

Superhydrophobic CuO nanoneedle-covered copper surfaces for anticorrosion

Abstract: With unique water-repellency and self-cleaning properties, superhydrophobic surfaces promise a great potential of anticorrosion for engineered metals. The current study reports a facile and controllable anodization approach to fabricate superhydrophobic CuO nanoneedle array (NNA) films for the enhancement of corrosion resistance of copper substrates. The anodic CuO NNA films were grown on copper foils by electrochemical anodization in an aqueous KOH solution for different anodization times. The morphological features and crystalline structures of the anodic CuO NNA were characterized by SEM-EDS and XRD. The superhydrophobicity on the hierarchical CuO NNA films was achieved by chemical modification with fluoroalkyl-silane (FAS-17). The presence of low surface energy fluorosilanized carbon (–CFx) groups on the FAS-modified surfaces was ascertained by EDS, XPS and water contact angle analyses. The wetting behaviour of the FAS-modified surfaces was investigated to elucidate the correlation between the static water contact angles, surface roughness, dynamic water contact angle hysteresis, and anodization time. The FAS-modified copper surfaces demonstrated not only the desirable superhydrophobicity with a water contact angle as high as approximately 169° and contact angle hysteresis as low as about 5°, but also substantially improved corrosion resistance in an aqueous NaCl solution (3.5%) with an inhibition efficiency higher than 90%, as revealed by means of Tafel plots and EIS measurements. The stability and durability of the superhydrophobic FAS-modified surfaces were evaluated by observing the change in surface wettability and geometric microstructures as a function of exposure time in an aqueous NaCl solution.

Robust Flower-Like TiO2@Cotton Fabrics with Special Wettability for Effective Self-Cleaning and Versatile Oil/Water Separation

Abstract: Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one-step hydrothermal strategy is developed to coat flower-like hierarchical TiO2 micro/nanoparticles onto cotton fabric substrates (TiO2@Cotton). Furthermore, robust superhydrophobic TiO2@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self-cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO2@Cotton exhibits a superior antiwetting and self-cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO2@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self-cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.

Measuring Forces and Spatiotemporal Evolution of Thin Water Films between an Air Bubble and Solid Surfaces of Different Hydrophobicity

Abstract: A combination of atomic force microscopy (AFM) and reflection interference contrast microscopy (RICM) was used to measure simultaneously the interaction force and the spatiotemporal evolution of the thin water film between a bubble in water and mica surfaces with varying degrees of hydrophobicity. Stable films, supported by the repulsive van der Waals-Casimir-Lifshitz force were always observed between air bubble and hydrophilic mica surfaces (water contact angle, θ(w) < 5°) whereas bubble attachment occurred on hydrophobized mica surfaces. A theoretical model, based on the Reynolds lubrication theory and the augmented Young-Laplace equation including the effects of disjoining pressure, provided excellent agreement with experiment results, indicating the essential physics involved in the interaction between air bubble and solid surfaces can be elucidated. A hydrophobic interaction free energy per unit area of the form: WH(h) = -γ(1 - cos θ(w))exp(-h/D(H)) can be used to quantify the attraction between bubble and hydrophobized solid substrate at separation, h, with γ being the surface tension of water. For surfaces with water contact angle in the range 45° < θ(w) < 90°, the decay length DH varied between 0.8 and 1.0 nm. This study quantified the hydrophobic interaction in asymmetric system between air bubble and hydrophobic surfaces, and provided a feasible method for synchronous measurements of the interaction forces with sub-nN resolution and the drainage dynamics of thin films down to nm thickness.

Superhydrophobic and anti-icing properties at overcooled temperature of a fluorinated hybrid surface prepared via a sol–gel process

Abstract: A superhydrophobic surface with anti-icing performance has been the focus of research, but few studies have reported the effective and low cost strategy that met the requirements under overcooled conditions. In this article, the fluorinated sol-gel colloid coatings were simply prepared via hydrolytic condensation of nanosilica sol, methyltriethoxysilane (MTES) and 3-[(perfluorohexylsulfonyl)amino]propyltriethoxysilane (HFTES). The multi scale morphology and chemical composition of the artificial surfaces were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The influence of the surface roughness structure and fluorinated groups on the wettability and freezing delay time of the colloid surface under overcooled conditions were explored. As the HFTES content was higher than 6 wt%, the prepared colloid surface showed excellent superhydropobicity with a contact angle (CA) of about 166° at room temperature. The CA gradually reduced with the decrease of the temperature. Only the samples with high HFTES contents (above 30 wt%) exhibited special superhydrophobic and anti-icing properties under freeze temperature. Besides the surface roughness structure, the high fluoride enrichment on the surface plays a major role in the superhydrophobic and anti-icing properties under overcooled conditions.

Understanding the Intrinsic Water Wettability of Molybdenum Disulfide (MoS2)

Abstract: 2D semiconductors allow for unique and ultrasensitive devices to be fabricated for applications ranging from clinical diagnosis instruments to low-energy light-emitting diodes (LEDs). Graphene has championed research in this field since it was first fabricated; however, its zero bandgap creates many challenges. Transition metal dichalcogenides (TMDCs), e.g., MoS2, have a direct bandgap which alleviates the challenge of creating a bandgap in graphene-based devices. Water wettability of MoS2 is critical to device fabrication/performance and MoS2 has been believed to be hydrophobic. Herein, we report that water contact angle (WCA) of freshly exfoliated MoS2 shows temporal evolution with an intrinsic WCA of 69.0 ± 3.8° that increases to 89.0 ± 3.1° after 1 day exposure to ambient air. ATR-FTIR and ellipsometry show that the fresh, intrinsically mildly hydrophilic MoS2 surface adsorbs hydrocarbons from ambient air and thus becomes hydrophobic.