Fabrication of superhydrophilic or superhydrophobic self-cleaning metal surfaces using picosecond laser pulses and chemical fluorination

Bioinspired superhydrophilic/phobic self-cleaning surfaces have recently drawn a lot of interest in both fundamental and applied research. A hybrid method to produce the self-cleaning property of micro/nanostructured surface using ultra-fast laser pulses followed by chemical fluorination is proposed. The typical micro/nanocomposite structures that form from microporous arrays and microgroove groups have been processed by picosecond laser on titanium alloy surface. The surface hydrophilic/phobic and self-cleaning properties of micro/nanostructures before and after fluorination with fluoroalkyl-silane were investigated using surface contact angle measurements. The results indicate that surface properties change from hydrophilic to hydrophobic after fluorination, and the micro/nanostructured surface with increased roughness contributes to the improvement of surface hydrophobicity. The micro/nanomodification can make the original hydrophilic titanium alloy surface more hydrophilic or superhydrophilic. It also can make an originally hydrophobic fluorinated titanium alloy surface more hydrophobic or superhydrophobic. The produced micro/nanostructured titanium alloy surfaces show excellent self-cleaning properties regardless of the fluorination treatment, although the fluorinated surfaces have slightly better self-cleaning properties. It is found that surface treatment using ultra-fast laser pulses and subsequent chemical fluorination is an effective way to manipulate surface wettability and obtain self-cleaning properties.     

Hydrophobization of epoxy nanocomposite surface with 1H,1H,2H,2H-perfluorooctyltrichlorosilane for superhydrophobic properties

Nature inspires the design of synthetic materials with superhydrophobic properties, which can be used for applications ranging from self-cleaning surfaces to microfluidic devices. Their water repellent properties are due to hierarchical (micrometer- and nanometre-scale) surface morphological structures, either made of hydrophobic substances or hydrophobized by appropriate surface treatment. In this work, the efficiency of two surface treatment procedures, with a hydrophobic fluoropolymer, synthesized and deposited from 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) is investigated. The procedures involved reactions from the gas and liquid phases of the PFOTS/hexane solutions. The hierarchical structure is created in an epoxy nanocomposite surface, by filling the resin with alumina nanoparticles and micron-sized glass beads and subsequent sandblasting with corundum microparticles. The chemical structure of the deposited fluoropolymer was examined using XPS spectroscopy. The topography of the modified surfaces was characterized using scanning electron microscopy (SEM), and atomic force microscopy (AFM). The hydrophobic properties of the modified surfaces were investigated by water contact and sliding angles measurements. The surfaces exhibited water contact angles of above 150° for both modification procedures, however only the gas phase modification provided the non-sticking behaviour of water droplets (sliding angle of 3°). The discrepancy is attributed to extra surface roughness provided by the latter procedure.     

Tailoring the wetting response of silicon surfaces via fs laser structuring

Control over the wettability of solids and manufacturing of functional surfaces with special hydrophobic and self-cleaning properties has aroused great interest because of its significance for a vast range of applications in daily life, industry and agriculture. We report here a simple method for preparing stable superhydrophobic surfaces by irradiating silicon (Si) wafers with femtosecond (fs) laser pulses and subsequently coating them with chloroalkylsilane monolayers. It is possible, by varying the laser pulse fluence on the surface, to achieve control of the wetting properties through a systematic and reproducible variation of roughness at micro- and nano-scale which mimics both the topology of the “model” superhydrophobic surface—the natural lotus leaf—, as well as its wetting response. Water droplets can move along these irradiated superhydrophobic surfaces, under the action of small gravitational forces, and experience subsequent immobilization, induced by surface tension gradients. These results demonstrate the potential of manipulating liquid motion through selective laser patterning.     

A simple fabrication method for mechanically robust superhydrophobic surface by hierarchical aluminum hydroxide structures

Superhydrophobic surfaces with uniformly superhydrophobic surface where nano-scale structures were fabricated by alkali surface modification method and self-assembled monolayer coating. To enhance mechanical durability of the superhydrophobicity, we propose the fabrication process for dual-scale hierarchical structures combining both microstructure via sandblasting techniques and the nanostructured aluminum hydroxide layer. The superhydrophobic surfaces fabricated by both methods exhibited a high water contact angle and very low contact angle hysteresis. By forming the hierarchical structure, the mechanical durability of superhydrophobic aluminum hydroxide surface was improved. The resulting hierarchical structures are suitable for diverse applications of aluminum in various industrial areas, including self-cleaning, anti-frosting, and microfluidic devices for rigorous environments.     

Facile approach in fabricating superhydrophobic coatings from silica-based nanocomposite

This study develops a one-step technique to synthesize various super water-repellent coatings with addition of modified silica nanoparticles. Surface topography observation showed that stacking of spherical silica nanoparticles formed primary surface roughness. The wettability of the products was investigated. It was found that the as-prepared surface possesses superhydrophobic properties not only for pure water but also for corrosive water under both acidic and basic conditions. The silica-based nanocomposite coatings can be fabricated on glass substrates and other functional engineering material surfaces, such as copper, iron, aluminum alloy, to form self-cleaning coatings.     

Superhydrophobic wind turbine blade surfaces obtained by a simple deposition of silica nanoparticles embedded in epoxy

Samples of wind turbine blade surface have been covered with a superhydrophobic coating made of silica nanoparticles embedded in commercial epoxy paint. The superhydrophobic surfaces have a water contact angle around 152°, a hysteresis less than 2° and a water drop sliding angle around 0.5°. These surfaces are water repellent so that water drops cannot remain motionless on the surface. Examination of coated and uncoated surfaces with scanning electron microscopy and atomic force microscopy, together with measurements of water contact angles, indicates that the air trapped in the cavity enhances the water repellency similarly to the lotus leaf effect. Moreover, this new coating is stable under UVC irradiation and water pouring. The production of this nanoscale coating film being simple and low cost, it can be considered as a suitable candidate for water protection of different outdoor structures.     

A comparative study of the self-propelled jumping capabilities of coalesced droplets on RTV surfaces and superhydrophobic surfaces

Understanding the mechanism of coalescence-induced self-propelled jumping behavior provides distinct insights in designing and optimizing functional coatings with self-cleaning and anti-icing properties.However,to date self-propelled jumping phenomenon has only been observed and studied on superhydrophobic surfaces,other than those hydrophobic surfaces with weaker but fairish water-repellency,for instance,vulcanized silicon rubber(RTV) coatings.In this work,from the perspective of thermodynamic-based energy balance aspect,the reason that self-propelled jumping phenomenon does not happen on RTV coatings is studied.The apparent contact angles of droplets on RTV coatings can be less than the theoretical critical values therefore cannot promise energy surplus for the coalesced droplets onside.Besides,on RTV and superhydrophobic surfaces,the droplet-size dependent variation characteristics of the energy leftover from the coalescence process are opposite.For the droplets coalescing on RTV coatings,the magnitudes of energy dissipations are more sensitive to the increase in droplet size,compared to that of released surface energy.While for superhydrophobic coatings,the energy generated during the coalescence process can be more sensitive than the dissipations to the change in droplet size.     

A new model for thermodynamic analysis on wetting behavior of superhydrophobic surfaces

Superhydrophobic surfaces have shown inspiring applications in microfluidics, and self-cleaning coatings owing to water-repellent and low-friction properties. However, thermodynamic mechanism responsible for contact angle hysteresis (CAH) and free energy barrier (FEB) have not been understood completely yet. In this work, we propose an intuitional 3-dimension (3D) droplet model along with a reasonable thermodynamic approach to gain a thorough insight into the physical nature of CAH. Based on this model, the relationships between radius of three-phase contact line, change in surface free energy (CFE), average or local FEB and contact angle (CA) are established. Moreover, a thorough theoretical consideration is given to explain the experimental phenomena related to the superhydrophobic behavior. The present study can therefore provide some guidances for the practical fabrications of the superhydrophobic surfaces.     

Stable superhydrophobic surface with hierarchical mesh-porous structure fabricated by a femtosecond laser

Inspired by the lotus leaf, a new superhydrophobic surface with hierarchical mesh-porous structure is fabricated by femtosecond laser irradiation on silicon. The fabricated surface shows a superhydrophobic character with water contact angle being found to reach up to 158^°±1^° and sliding angle of 4^°±0.5^°. The superhydrophobicity is stable even if the PH of solution changes from 1 to 14. And the surface also exhibits excellent self-cleaning effect and bouncing behavior, implying that the adhesion of the surface is extremely low. This work will enhance further understanding of the wettability of a solid surface with special surface morphology.     

Laser microstructuring for fabricating superhydrophobic polymeric surfaces

In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157°. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces.     

Preliminary study on different technological tools and polymeric materials towards superhydrophobic surfaces for automotive applications

Nature-inspired fabrication of micro-structured superhydrophobic plastic film was aimed in this work in order to achieve smart materials with self-cleaning properties. Replicas of silicon masters were fabricated from different mixtures of base elements and by different processes. Corresponding microstructures were investigated by contact angle measurements, scanning electron microscopy and spectrophotometric analysis. Independently of the technology employed, the obtained films exhibited high contact angle value (larger than 150°), but while the acrylic polymers presented strong demoulding drawbacks, the polydimethylsiloxane (PDMS) films had good properties in terms of both contact angle and optical transparency. The results showed that most of the patterns realized by replica moulding and hot-embossing (on PDMS and polypropylene (PP), respectively) produced superhydrophobic self-cleaning surfaces.     

Preparation of hybrid film with superhydrophobic surfaces based on irregularly structure by emulsion polymerization

A superhydrophobic surface originated from quincunx-shape composite particles was obtained by utilizing the encapsulation and graft of silica particles to control the surface chemistry and morphology of the hybrid film. The composite particles make the surface of film form a composite interface with irregular binary structure to trap air between the substrate surface and the liquid droplets which plays an essential role in obtaining high water contact angle and low water contact angle hysteresis. The water contact angle on the hybrid film is determined to be 154 ± 2° and the contact angle hysteresis is less than 5°. This is expected to be a simple and practical method for preparing self-cleaning hydrophobic surfaces on large area.     

Superhydrophobic surfaces fabricated by microstructuring of stainless steel using a femtosecond laser

Fabrication of superhydrophobic surfaces induced by femtosecond laser is a research hotspot of superhydrophobic surface studies nowadays. We present a simple and easily-controlled method for fabricating stainless steel-based superhydrophobic surfaces. The method consists of microstructuring stainless steel surfaces by irradiating samples with femtosecond laser pulses and silanizing the surfaces. By low laser fluence, we fabricated typical laser-induced periodic surface structures (LIPSS) on the submicron level. The apparent contact angle (CA) on the surface is 150.3°. With laser fluence increasing, we fabricated periodic ripples and periodic cone-shaped spikes on the micron scale, both covered with LIPSS. The stainless steel-based surfaces with micro- and submicron double-scale structure have higher apparent CAs. On the surface of double-scale structure, the maximal apparent CA is 166.3° and at the same time, the sliding angle (SA) is 4.2°.     

A simple way to fabricate an aluminum sheet with superhydrophobic and self-cleaning properties

<正>A superhydrophobic aluminum sheet is fabricated via a hot water immersing process and subsequently surface modification with heptadecafluorodecyltrimethoxy-silane(HTMS).As revealed by the scan electron microscopy(SEM), X-ray diffraction(XRD),and Fourier-transform infrared spectrophotometer(FTIR) results,a rough pseudoboehmite film is formed on the aluminum sheet,and HTMS molecules are grafted on the film surface successfully.These two factors make the treated aluminum sheet present superhydrophobicity with a water contact angle larger than 160°and sliding angle less than 5°,and possess a self-cleaning property.Furthermore,the flexible superhydrophobic aluminum sheet could be pasted to a cylinder surface without destroying its superhydrophobicity.At the end,the effect of hot water treatment time on superhydrophobicity is investigated.     

Facile method to prepare stable superhydrophobic Co3O4 surface

A facile and novel method was developed to fabricate rough Co₃O₄ surface with hierarchical micro- and nanostructures by the combination of simple solid state reactions and coating process. After modification with stearic acid, a superhydrophobic surface with water contact angle of 155 ± 1.8° and sliding angle of 2° was obtained. The superhydrophobic Co₃O₄ surface remained superhydrophobic property in a wide pH range from 3 to 14. The superhydrophobic Co₃O₄ surface also showed excellent self-cleaning property and high stability in ambient environments.     

Controlling the micro/nanostructure of self-cleaning polymer coating

Polypropylene bio-mimic self-cleaning surfaces with porous micro-nano-binary morphology structures were prepared by a simple casting method. The influence of the cooling process and solvent composition on water contact angle, sliding angles and self-cleaning properties has been investigated. Detailed SEM morphology studies revealed that the polymer used in this work is commercial-grade granular low-density polyethylene (LDPE) forms petal-like crystalline, which are of micrometer scale in length and nanometer scale in thickness. The nano-crystallines on the surface represent a porous three-dimensional micro-nano-binary structure. It was found that a compromise to the film porosity and crystal nano structure is essential for achieving a satisfied self-cleaning surface. Under optimum condition, a water contact angle of 152.2°, and a sliding angle of 1.7° can be obtained using this simple method.     

Silicon nanowire and polyethylene superhydrophobic surfaces for discrete magnetic microfluidics

A microfluidic method to manipulate small drops of water is studied on two different superhydrophobic surfaces. Using this digital magnetofluidic method, water drops containing paramagnetic carbonyl-iron microparticles were displaced on silicon nanowire (Si NW) and low-density polyethylene (LDPE) superhydrophobic surfaces using magnetic fields. Horizontal, vertical, or upside-down drop movement is made possible by the action of capillary forces induced by paramagnetic particles aligning and following a magnetic field, indicating that three-dimensional digital microfluidics is possible. Also, both Si NW and LDPE superhydrophobic surfaces combine surface chemistry with nano and microscale surface roughness to make drop movement possible. Si NW superhydrophobic surfaces were prepared using vapor-liquid-solid growth systems followed by coating with a perfluorinated hydrocarbon. LDPE superhydrophobic surfaces were prepared by growing polyethylene crystals on a polyethylene substrate through careful rate control.     

Simple treatment of cotton textile to impart high water repellent properties

We describe two methods to impart the water repellency for the surface of cotton fabric, using a commercially available and a laboratory synthesized fluoroalkylsiloxanes. To characterize the wettability and the durability of water repellent properties of hydrophobic coating produced, we have studied the advancing water contact angles, rolling angles and the evolution of water contact angle in time during a continuous contact of the surface with the water drop. The quality of the coatings was also assessed after the washing procedure. The analysis of the wettability of hydrophobized fabrics indicated that a better effect, leading to the superhydrophobic state of the surface, was observed when the surface relief of the fabric with the coating is determined by not only the structure and braiding of the fabric, but also the additional elements of texture created by the aggregates of molecules of hydrophobic agent.     

天然超疏水生物表面研究的新进展

文章简要地论述了表面浸润性的基本理论，介绍了几种天然超疏水生物表面最新的研究进展，包括荷叶、蝉翼、水稻叶以及水黾腿，特别介绍了作者的研究小组利用从壁虎脚高黏附力获得的灵感仿生制备出一种对水滴具有高黏附的超疏水阵列聚苯乙烯纳米管材料，最后对超疏水材料的研究趋势作了展望。     

Tunable wettability of carbon nanotube/poly (?-caprolactone) hybrid films

We have realized a stable superhydrophobic surface, a thermally tunable superhydrophobic surface, and a thermally tunable hydrophobic surface by combining the crystalline/amorphous phase transition of the poly(?-caprolactone) (PCL) with the optimized surface roughness of the carbon nanotube/PCL hybrid films. The water droplet mobilities and wettabilities were reversibly thermally switched on the tunable superhydrophobic and the hydrophobic surfaces, respectively. These responsive surfaces have potential applications in microfluidic devices and microreactors and for liquid transportation.