Low Contact Angle Hysteresis Research Articles

Stretchable Superhydrophobicity from Monolithic, Three-Dimensional Hierarchical Wrinkles.

We report the design of three-dimensional (3D) hierarchical wrinkle substrates that can maintain their superhydrophobicity even after being repeatedly stretched. Monolithic poly(dimethysiloxane) with multiscale features showed wetting properties characteristic of static superhydrophobicity with water contact angles (>160°) and very low contact angle hysteresis (<5°). To examine how superhydrophobicity was maintained as the substrate was stretched, we investigated the dynamic wetting behavior of bouncing and splashing upon droplet impact with the surface. On hierarchical wrinkles consisting of three different length scales, superhydrophobic bouncing was observed. The substrate remained superhydrophobic up to 100% stretching with no structural defects after 1000 cycles of stretching and releasing. Stretchable superhydrophobicity was possible because of the monolithic nature of the hierarchical wrinkles as well as partial preservation of nanoscale structures under stretching.

Effect of treatment temperature on surface wettability of methylcyclosiloxane layer formed by chemical vapor deposition

The surface wettability of the native Si oxide surfaces were tuned by chemical adsorption of 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) molecules through thermal CVD method at different temperature. Water contact angle measurements revealed that the water contact angles of the TMCTS-modified Si oxide surfaces at the temperature of 333–373K were found to be in the range of 92±2–102±2°. The advancing and receding water contact angle of the surface prepared at 333K were found to be 97±2/92±2°, showing low contact angle hysteresis surface. The water contact angles of the surfaces prepared at the temperature of 373–413K increased with an increase in the treatment temperature. When the treatment temperature was more than 423K, the water contact angles of TMCTS-modified surfaces were found to become more than 150°, showing superhydrophobic surface. AFM study revealed that the surface roughness of the TMCTS-modified surface increased with an increase in the treatment temperature. This geometric morphology enhanced the surface hydrophobicity. The surface roughness could be fabricated due to the hydrolysis/condensation reactions in the gas phase during CVD process. The effect of the treatment temperature on the reactivity of the TMCTS molecules were also investigated using a thermogravimetric analyzer.

Durable Superhydrophobic Surfaces via Spontaneous Wrinkling of Teflon AF.

We report the fabrication of both single-scale and hierarchical superhydrophobic surfaces, created by exploiting the spontaneous wrinkling of a rigid Teflon AF film on two types of shrinkable plastic substrates. Sub-100 nm to micrometric wrinkles were reproducibly generated by this simple process, with remarkable control over the size and hierarchy. Hierarchical Teflon AF wrinkled surfaces showed extremely high water repellence (contact angle 172°) and very low contact angle hysteresis (2°), resulting in droplets rolling off the surface at tilt angles lower than 5°. The wrinkling process intimately binds the Teflon AF layer with its substrate, making these surfaces mechanically robust, as revealed by macroscale and nanoscale wear tests: hardness values were close to that of commercial optical lenses and aluminum films, resistance to scratch was comparable to commercial hydrophobic coatings, and damage by extensive sonication did not significantly affect water repellence. By this fabrication method the size of the wrinkles can be reproducibly tuned from the nanoscale to the microscale, across the whole surface in one step; the fabrication procedure is extremely rapid, requiring only 2 min of thermal annealing to produce the desired topography, and uses inexpensive materials. The very low roll-off angles achieved in the hierarchical surfaces offer a potentially up-scalable alternative as self-cleaning and drag-reducing coatings.

Rapid synthesis of inherently robust and stable superhydrophobic carbon soot coatings

The fabrication of superhydrophobic coatings using a candle flame or rapeseed oil has become very attractive as a novel approach for synthesis of water repellent surfaces. Here, we report an improved, simplified and time-efficient method for the preparation of robust superhydrophobic carbon soot that does not require any additional stabilizers or chemical treatment. The soot's inherent stabilization is achieved using a specially-designed cone-shaped aluminum chimney, mounted over an ignited paper-based wick immersed in a rapeseed oil. Such configuration decreases the level of oxygen during the process of combustion; altering the ratio of chemical bonds in the soot. As a result, the fractal-like network of the carbon nanoparticles is converted into dense and fused carbon chains, rigidly coupled to the substrate surface. The modified carbon coating shows thermal sustainability and retains superhydrophobicity up to ∼300°C. Furthermore, it demonstrates a low contact angle hysteresis of 0.7–1.2° accompanied by enhanced surface adhesion and mechanical durability under random water flows. In addition, the soot's deposition rate of ∼1.5μm/s reduces the exposure time of the substrate to heat and consequently minimizes the thermal effects, allowing the creation of superhydrophobic coatings on materials with low thermal stability (e.g. wood or polyethylene).

Anti-smudge behavior of facilely fabricated liquid-infused surfaces with extremely low contact angle hysteresis property

Facile fabrication of hysteresis-free liquid-infused surfaces.

Ultraporous superhydrophobic gas-permeable nano-layers by scalable solvent-free one-step self-assembly.

Superhydrophobic materials with excellent humidity tolerance, high porosity and light transmittance are being investigated for numerous applications including moisture-sensitive catalysts and perovskite solar cells. Here, we report the one-step solvent-free synthesis of ultraporous superhydrophobic nano-layers by the on-the-fly functionalization of nanoparticle aerosols. Short exposure of surfaces to hot Mn3O4, ZnO and TiO2 aerosols results in ultraporous nanoparticle networks with repulsive dewetting state approaching ideal Cassie-Baxter superhydrophobicity. In addition to showcasing sliding angles of ca. 0° and very low contact angle hysteresis of 3° ± 2°, these optimal nano-layers have up to 98% porosity and pore size of several micrometres, a key feature to enable efficient penetration of gases to the substrate surface. The stability of this ultraporous superhydrophobic morphology is demonstrated by rapidly applying Moses effect-functionality to substrates that parts water up to 5 mm high. This scalable synthesis method offers a flexible and rapid approach for the production of numerous moisture-resistant devices including gas sensors, catalysts and perovskite solar cells.

Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency.

Recent strategies to prepare "omniphobic" surfaces have demonstrated that minimizing contact angle hysteresis (CAH) is the key criterion for effectiveness. CAH is affected by chemistry and topography defects at the molecular and higher levels, thus most surfaces exhibit significant CAH. Preparative methods for stable coatings on smooth substrates with negligible CAH (<2°) for a broad range of liquids have not been reported. In this work, we describe a simple and rapid procedure to prepare omniphobic surfaces that are stable under pressure and durable at elevated temperatures. Consistent with theory, they exhibit sliding angles that decrease with liquid surface tension. Slippery omniphobic covalently attached liquid (SOCAL) surfaces are obtained through acid-catalyzed graft polycondensation of dimethyldimethoxysilane. The smooth, stable, and temperature-resistant coatings show extremely low CAH (≤1°) and low sliding angles for liquids that span surface tensions from 78.2 to 18.4 mN m(-1).

Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency

AbstractRecent strategies to prepare “omniphobic” surfaces have demonstrated that minimizing contact angle hysteresis (CAH) is the key criterion for effectiveness. CAH is affected by chemistry and topography defects at the molecular and higher levels, thus most surfaces exhibit significant CAH. Preparative methods for stable coatings on smooth substrates with negligible CAH (&lt;2°) for a broad range of liquids have not been reported. In this work, we describe a simple and rapid procedure to prepare omniphobic surfaces that are stable under pressure and durable at elevated temperatures. Consistent with theory, they exhibit sliding angles that decrease with liquid surface tension. Slippery omniphobic covalently attached liquid (SOCAL) surfaces are obtained through acid‐catalyzed graft polycondensation of dimethyldimethoxysilane. The smooth, stable, and temperature‐resistant coatings show extremely low CAH (≤1°) and low sliding angles for liquids that span surface tensions from 78.2 to 18.4 mN m−1.

Humidity Tolerant Organic Vapor Detection Using a Superhydrophobic Quartz Crystal Microbalance

The organic vapor sensitivity of a quartz crystal microbalance (QCM) with an epoxy resin–carbon soot coating designed to be tolerant to humidity is reported. This is achieved using nonengulfed, but attached, hydrophobic carbon soot nanoparticles, coated in an irregular surface topography composed of islands and cavities. The root mean square roughness ( $R_{\mathrm {{rms}}}$ ) of 130 nm, together with the hydrophobic soot, convert the epoxy surface to a superhydrophobic (SH) one with high static contact angle ( $\sim 151^{\circ }$ ) and low contact angle hysteresis ( $\sim 1.1^{\circ }$ ). The frequency shift of the SH QCM at 100% relative humidity is $\sim 7$ times lower compared with an uncoated device, and thus indicating low water vapor adsorption due to superhydrophobicity. In addition, the SH QCM shows between three and six times higher gas sensitivity and lower detection limit compared with the conventional polymer coated QCMs. These results correlate well with the $R_{\mathrm {{rms}}}$ and surface topography of the coating, which ensure enhanced sensing area. Furthermore, the sensor demonstrates reproducibility, reversibility, and fast response-recovery time ( $\sim 10$ s) to ethanol, methanol, and isopropanol vapor. These experiments reveal that superhydrophobicity increases the organic vapor sorption at the expense of water vapor sorption, and thus allowing operation of the QCM gas sensors in an uncontrolled humidity environment.

Zwitterionic Nanofibers of Super-Glue for Transparent and Biocompatible Multi-Purpose Coatings.

Here we show that macrozwitterions of poly(ethyl 2-cyanoacrylate), commonly called Super Glue, can easily assemble into long and well defined fibers by electrospinning. The resulting fibrous networks are thermally treated on glass in order to create transparent coatings whose superficial morphology recalls the organization of the initial electrospun mats. These textured coatings are characterized by low liquid adhesion and anti-staining performance. Furthermore, the low friction coefficient and excellent scratch resistance make them attractive as solid lubricants. The inherent texture of the coatings positively affects their biocompatibility. In fact, they are able to promote the proliferation and differentiation of myoblast stem cells. Optically-transparent and biocompatible coatings that simultaneously possess characteristics of low water contact angle hysteresis, low friction and mechanical robustness can find application in a wide range of technological sectors, from the construction and automotive industries to electronic and biomedical devices.

Antiwetting Fabric Produced by a Combination of Layer-by-Layer Assembly and Electrophoretic Deposition of Hydrophobic Nanoparticles.

This work describes a nanoparticle coating method to produce durable antiwetting polyester fabric. Electrophoretic deposition is used for fast modification of polyester fabric with silica nanoparticles embedded in polymeric networks for high durability coatings. Typically, electrophoretic deposition (EPD) is utilized on electrically conductive substrates due to its dependence on an applied electrical field. EPD on nonconductive materials has been attempted but are limited by weak adhesion, cracks, and other irregularities. To resolve these issues, we coat polyester fabric with thin polymer layers using electrostatic self-assembly (layer-by-layer self-assembly). Next, silica nanoparticles are uniformly dispersed on the polymer layers. Finally, polymerically stabilized silica nanoparticles are deposited by EPD on the fabric, followed by heat treatment. The modified fabric shows high static contact angle and low contact angle hysteresis, while keeping its original color, flexibility, and air permeability. During a skin fiction resistance test, the hydrophobicity of the coating layer was maintained over 500 h. Furthermore, we also show that this approach facilitates patterned regions of wettability by modifying the electric field in EPD.

Fabrication and Characterization of Superhydrophobic Poly(vinylidene fluoride-co- hexafluoropropylene)/TiO2 Nanocomposite Coating for Corrosion Protection Applications

Superhydrophobic surfaces have a strong potential for implementation in variety of fields, including self-cleaning surfaces, biomedical and coatings for corrosion protection. Preparation of superhydrophobic surfaces requires both an optimum roughness and low surface energy; therefore, these surfaces are conventionally prepared employing two steps: roughening a surface and lowering its surface energy. In this study, the superhydrophobic Poly(vinylidene fluoride-co-hexafluoropropylene)/TiO2 nanocomposite coatings were fabricated using a simple one-step coating method on a carbon steel substrate to study the corrosion behavior in harsh environments. The surface wettability and morphology of the prepared coatings were characterized using the sessile droplet method and scanning electron microscopy, respectively. X-ray photoelectron spectroscopy and X-ray diffractometer were used to identify the elemental composition and chemical oxidation states of the prepared surface. The surface roughness of the coatings was measured using atomic force microscope. The chemical stability of the prepared coatings was inspected by immersion the specimens in different pH solutions. The results showed that stable superhydrophobic surfaces with high water contact angle and low contact angle hysteresis can be fabricated on the carbon steel surface. As well as, the corrosion resistant performance of the produced superhydrophobic surface on carbon steel was carried out by electrochemical impedance spectroscopy (EIS) measurements and potentiodynamic polarization in 3.5 wt % NaCl solution. The electrochemical corrosion tests revealed that the as-prepared superhydrophobic surface significantly improved the corrosion resistant of the C-steel substrate.

Superhydrophobic laser ablated PTFE substrates

The effect of femtosecond laser irradiation process parameters (fluence, scanning speed and beam overlap) on the wettability of the resulted micro/nano-patterned morphologies on polytetrafluoroethylene is studied in detail. Several distinctly different micro/nano-patterns were fabricated including uniaxial and biaxial patterns. In particular, using biaxial scanning well defined pillared morphology was fabricated. The wettability analysis of the biaxially scanned samples revealed enhanced superhydrophobicity exhibiting high contact angles and low contact angle hysteresis.

Ice repellency behaviour of superhydrophobic surfaces: Effects of atmospheric icing conditions and surface roughness

This paper presents a novel view on ice repellency of superhydrophobic surfaces in terms of contact angle hysteresis, surface roughness and icing condition. Ice repellency performance of two superhydrophobic silicone rubber nanocomposite surfaces prepared via spin coating and spray coating methods were investigated. High contact angle (>150°), low contact angle hysteresis (<6°) and roll-off property were found for both spin and spray coated samples. The results showed a significant reduction of ice adhesion strength on the spin-coated sample while ice adhesion strength on the spray-coated sample was found to be unexpectedly similar to that of the uncoated sample. Indeed, this research study showed that the icephobic properties of a surface are not directly correlated to its superhydrphobicity and that further investigations, like taking icing condition effect into account, are required. It was found that icephobic behaviour of the spray coated sample improved at lower levels of liquid water content (LWC) and under icing conditions characterized by smaller water droplet size.

Influence of the coating method on the formation of superhydrophobic silicone–urea surfaces modified with fumed silica nanoparticles

Abstract Effect of the coating method on the formation of superhydrophobic polydimethylsiloxane–urea copolymer (TPSC) surfaces, modified by the incorporation of hydrophobic fumed silica nanoparticles was investigated. Four different coating methods employed were: (i) layer-by-layer spin-coating of hydrophobic fumed silica dispersed in an organic solvent onto TPSC films, (ii) spin-coating of silica–polymer mixture onto a glass substrate, (iii) spray coating of silica/polymer mixture by an air-brush onto a glass substrate, and (iv) direct coating of silica–polymer mixture by a doctor blade onto a glass substrate. Influence of the coating method, composition of the polymer/silica mixture and the number of silica layers applied on the topography and wetting behavior of the surfaces were determined. Surfaces obtained were characterized by scanning electron microscopy (SEM), white light interferometry (WLI) and advancing and receding water contact angle measurements. It was demonstrated that superhydrophobic surfaces could be obtained by all methods. Surfaces obtained displayed hierarchical micro-nano structures and superhydrophobic behavior with static and advancing water contact angles well above 150° and fairly low contact angle hysteresis values.

Wettability properties of PTFE/ZnO nanorods thin film exhibiting UV-resilient superhydrophobicity

In this research, initially anodization process was used to fabricate ZnO nanorods on Zn substrate and then RF sputtering technique was applied to grow a thin layer of polytetrafluoroethylene (PTFE, Teflon) on the coated ZnO nanorods for producing a superhydrophobic surface. According to scanning electron microscopy (SEM) observations, ZnO nanorods were formed with average diameter and length of about ∼180nm and 14μm, respectively. Superhydrophilic property of ZnO nanorods and superhydrophobic property of PTFE/ZnO nanorods was investigated by water contact angle (WCA) measurements. It was found that the contact angle varied with the PTFE deposition time. The highest contact angle measurement was obtained at 160° for the PTFE (60min coating)/ZnO as optimum sample which indicates its superhydrophobic property. X-ray photoelectron spectroscopy (XPS) determined surface chemical composition and F/C ratio of about 1.27 for this sample. A change of water contact angle from 3° to 160° indicates transition from superhydrophilic to superhydrophobic state. Very low contact angle hysteresis (CAH) of ∼2° and sliding angle (SA) of ∼1° as well as unchanged contact angle under UV illumination was observed for the synthesized optimum PTFE/ZnO sample exhibits an excellent superhydrophobic property. Based on our data analysis, the ZnO nanorods and the PTFE/ZnO nanorods obey Wenzel and Cassie–Baxter model, respectively.

Thermodynamic analysis of stable wetting states and wetting transition of micro/nanoscale structured surface

Superhydrophobicity of biological surfaces with micro/nanoscale hierarchical roughness has recently been given great attention and widely reported in many experimental studies due to the unique wettability. For example, the dual-scale structure of the lotus leaf not only shows high contact angle and low contact angle hysteresis but also presents good stability and mechanical properties. Though lots of experimental studies on the wettability of artificial hierarchical rough surface have been carried out, a thorough analysis on the contribution of micro- and nano-scaled roughness to the metastable wetting states and their transition is still lack. In this paper, a thermodynamic approach is applied to analyze all the wetting states (including four stable wetting states and five transition states) of a water droplet on a surface with micro/nanoscale hierarchical roughness, and the corresponding free energy expressions and apparent contact angle equations are deduced. The stable wetting states are confirmed by the principle of minimum free energy. And the calculated results by these state equations can fit well with the experimental results reported in the literature when compared with the previous models. Meanwhile, the influence of micro/nanoscale roughness on the stable wetting states and metastable-stable transition has been analyzed thermodynamically. It is found that there is a synergistic effect of micro and nanoscale roughness on wettability, which nlay result in many different wetting states. There are four wetting states during increasing relative pitch of a microscaled structure at a given nanoscaled structure, but two wetting states can be obtained as increasing relative pitch of nanoscaled structure at a given microscaled structure. The change of nondimensional energy and nondimensional energy barrier in the metastable-stable transition process of water droplet wetting micro and nanoscaled structure is quantitatively analyzed. Results indicate that the micro-scaled structure is never wetted in a special size range of the nanoscaled structure, and the special size range is of great significance to enhance superhydrophobic stability of the microscaled structure. Furthermore, the existence of microscaled structure decreases the transition energy barrier of water droplet wetting nanoscaled structure, which is helpful for understanding the experimental results reported in the literature. Finally, all possible stable wetting states of water droplet no a surface with micro/nanoscale hierarchical roughness are discribed in a wetting map. A design principle of superhydrophobic surface with micro/nanoscale hierarchical roughness is put forward, which is helpful to ensure the size of micro/nanoscale structure in the “stable superhydrophobic region” and to provide a theoretical guidance in the preparation of superhydrophobic surface.

Image Analysis Determination of the Influence of Surface Structure of Silicone Rubbers on Biofouling

This study focuses on how the texture of the silicone rubber material affects the distribution of microbial growth on the surface of materials used for high voltage insulation. The analysis of surface wetting properties showed that the textured surfaces provide higher receding contact angles and therefore lower contact angle hysteresis. The textured surfaces decrease the risk for dry band formation and thus preserve the electrical properties of the material due to a more homogeneous distribution of water on the surface, which, however, promotes the formation of more extensive biofilms. The samples were inoculated with fungal suspension and incubated in a microenvironment chamber simulating authentic conditions in the field. The extent and distribution of microbial growth on the textured and plane surface samples representing the different parts of the insulator housing that is shank and shed were determined by visual inspection and image analysis methods. The results showed that the microbial growth was evenly distributed on the surface of the textured samples but restricted to limited areas on the plane samples. More intensive microbial growth was determined on the textured samples representing sheds. It would therefore be preferable to use the textured surface silicone rubber for the shank of the insulator.

Wear-resistant and antismudge superoleophobic coating on polyethylene terephthalate substrate using SiO2 nanoparticles.

It is of interest to create superoleophobic surfaces that exhibit high oil contact angle, low contact angle hysteresis, high wear resistance, antismudge properties, and optical transparency for industrial applications. In the superoleophobic surfaces developed to date, the mechanical durability data is lacking. By dip-coating polyethylene terephthalate substrate with hydrophobic SiO2 nanoparticles and methylphenyl silicone resin, followed by O2 plasma treatment and vapor deposition of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, a durable superoleophobic surface was fabricated. The degree of superoleophobicity was found to be dependent on the particle-to-binder ratio. The coatings were found to exhibit wear resistance on microscale and macroscale, antismudge properties, and transparency.

Superwetting Surfaces under Different Media: Effects of Surface Topography on Wettability.

Superwetting surfaces in air, such as superhydrophobic and superoleophobic surfaces that are governed by surface chemical compositions and surface topographies, are one of the most extensively studied topics in this field. However, it is not well-understood how surface topographies affect the behaviors of immiscible liquids and gases under other kinds of media, although it is significant in diverse fields. The main aim of this work is to systematically investigate the wetting behaviors of liquids (water and oil) and gas (air) on silicon surfaces with different topographies (i.e., smooth, micro, nano, and micro-/nanostructures) under various media (i.e., air, water, and oil). The contact angles, as well as contact-angle hysteresis, sliding angles, and adhesive forces, were utilized to evaluate the wettability of these surfaces. As a result, the microstructured surfaces typically exhibit high contact-angle hysteresis, high sliding angles, and high adhesive forces, whereas the micro-/nanostructured surfaces display low contact-angle hysteresis, low sliding angles, and low adhesive forces, even if they have high (>150°) and similar contact angles. Furthermore, when transferring the same surface from one kind of medium to another, different superwetting states can be reversibly switched.