Wetting and superhydrophobic properties of PECVD grown hydrocarbon and fluorinated-hydrocarbon coatings

Wetting characteristics of micro-nanorough substrates of aluminum and smooth silicon substrates have been studied and compared by depositing hydrocarbon and fluorinated-hydrocarbon coatings via plasma enhanced chemical vapor deposition (PECVD) technique using a mixture of Ar, CH₄ and C₂F₆ gases. The water contact angles on the hydrocarbon and fluorinated-hydrocarbon coatings deposited on silicon substrates were found to be 72° and 105°, respectively. However, the micro-nanorough aluminum substrates demonstrated superhydrophobic properties upon coatings with fluorinated-hydrocarbon providing a water contact angle of ∼165° and contact angle hysteresis below 2° with water drops rolling off from those surfaces while the same substrates showed contact angle of 135° with water drops sticking on those surfaces. The superhydrophobic properties is due to the high fluorine content in the fluorinated-hydrocarbon coatings of ∼36 at.%, as investigated by X-ray photoelectron spectroscopy (XPS), by lowering the surface energy of the micro-nanorough aluminum substrates.     

Superhydrophobic and icephobic surfaces prepared by RF-sputtered polytetrafluoroethylene coatings

A superhydrophobic and icephobic surface were investigated on aluminum alloy substrate. Anodizing was used first to create a micro-nanostructured aluminum oxide underlayer on the alloy substrate. In a second step, the rough surface was coated with RF-sputtered polytetrafluoroethylene (PTFE or Teflon^®). Scanning electron microscopy images showed a “bird's nest”-like structure on the anodized surface. The RF-sputtered PTFE coating exhibited a high static contact angle of ∼165° with a very low contact angle hysteresis of ∼3°. X-ray photoelectron spectroscopy (XPS) results showed high quantities of CF₃ and CF₂ groups, which are responsible for the hydrophobic behavior of the coatings. The performance of this superhydrophobic film was studied under atmospheric icing conditions. These results showed that on superhydrophobic surfaces ice-adhesion strength was 3.5 times lower than on the polished aluminum substrate.     

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.     

Transparent water repellent silica films by sol-gel process

Non-wettable surfaces with high contact angles and facile sliding angle of water droplets have received tremendous attention in recent years. The present paper describes the room temperature (∼27 °C) synthesis of dip coated water repellent silica coatings on glass substrates using iso-butyltrimethoxysilane (iso-BTMS) as a co-precursor. Emphasis is given to the influence of the hydrophobic reagent (iso-BTMS) on the water repellent properties of the silica films. Silica sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:16.53:8.26 respectively, with 0.01 M NH₄F throughout the experiment and the molar ratio of iso-BTMS/TEOS (M) was varied from 0 to 0.965. The effect of M on the surface structure and hydrophobicity has been researched. The static water contact angle values of the silica films increased from 65° to 140° and water sliding angle values decreased from 42° to 16° with an increase in the M value from 0 to 0.965. The water repellent silica films are thermally stable up to a temperature of 280 °C and above this temperature the film shows hydrophilic behavior. The water repellent silica films were characterized by the Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), % of optical transmission, thermal and chemical aging tests, humidity tests, static and dynamic water contact angle measurements.     

Preparation of porous super-hydrophobic and super-oleophilic polyvinyl chloride surface with corrosion resistance property

Porous super-hydrophobic polyvinyl chloride (PVC) surfaces were obtained via a facile solvent/non-solvent coating process without introducing compounds with low surface energy. The microstructure, wetting behavior, and corrosion resistance of resultant super-hydrophobic PVC coatings were investigated in relation to the effects of dosage of glacial acetic acid and the temperature of drying the mixed PVC solution spread over glass slide substrate. As-prepared PVC coatings had porous microstructure, and the one obtained at a glacial acetic acid to tetrahydrofuran volume ratio of 2.5:10.0 and under a drying temperature of 17 °C had a water contact angle of 150 ± 1.5°, showing super-hydrophobicity. In the meantime, it possessed very small contact angles for liquid paraffin and diiodomethane and good corrosion resistance against acid and alkali corrosive mediums, showing promising applications in self-cleaning, waterproof for outer wall of building, seawater resistant coating, and efficient separation of oil and water.     

Superhydrophobic hierarchical surfaces fabricated by anodizing of oblique angle deposited Al-Nb alloy columnar films

A combined process of oblique angle magnetron sputtering and anodizing has been developed to tailor superhydrophobic surfaces with hierarchical morphology. Isolated submicron columns of single-phase Al-Nb alloys are deposited by magnetron sputtering at several oblique deposition angles on a scalloped substrate surface, with the gaps between columns increasing with an increase in the deposition angle from 70° to 110°. Then, the columnar films have been anodized in hot phosphate-glycerol electrolyte to form a nanoporous anodic oxide layer on each column. Such surfaces with submicron-/nano-porous structure have been coated with a fluoroalkyl phosphate layer to reduce the surface energy. The porous surface before coating is superhydrophilic with a contact angle for water is less than 10°, while after coating the contact angles are larger than 150°, being superhydrophobic. The beneficial effect of dual-scale porosity to enhance the water repellency is found from the comparison of the contact angles of the submicron columnar films with and without nanoporous oxide layers. The larger submicron gaps between columns are also preferable to increase the water repellency.     

Novel strategy in increasing stability and corrosion resistance for super-hydrophobic coating on aluminum alloy surfaces

A novel super-hydrophobic coating was prepared by chemical modification on the anodized aluminum alloy surface. The surface structure was characterized by water contact angle measurement, scanning electron microscopy (SEM), and the composition was measured by X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the super-hydrophobic coating was evaluated by the polarization curve and the electrochemical impedance spectroscopy (EIS). It was found that the static water contact angle on the surface of super-hydrophobic coating was as high as 167.7 ± 1.2°, and the sliding angle was 5°. The super-hydrophobic coating resulted in excellent corrosion resistance property and the super-hydrophobic coating showed a good stability.     

Fabrication of superhydrophobic nanostructured surface on aluminum alloy

A superhydrophobic surface was prepared by consecutive immersion in boiling water and sputtering of polytetrafluoroethylene (PTFE or Teflon®) on the surface of an aluminum alloy substrate. Immersion in boiling water was used to create a micro-nanostructure on the alloy substrate. Then, the rough surface was coated with RF-sputtered Teflon film. The immersion time in boiling water plays an important role in surface morphology and water repellency of the deposited Teflon coating. Scanning electron microscopy images showed a “flower-like” structure in first few minutes of immersion. And as the immersion time lengthened, a “cornflake” structure appeared. FTIR analyses of Teflon-like coating deposited on water treated aluminum alloy surfaces showed fluorinated groups, which effectively reduce surface energy. The Teflon-like coating deposited on a rough surface achieved with five-minute immersion in boiling water provided a high static contact angle (～164°) and low contact angle hysteresis (～4°).     

Effect of plasma pretreatment on adhesion and mechanical properties of UV-curable coatings on plastics

An attempt was made to study the effect of plasma surface activation on the adhesion of UV-curable sol-gel coatings on polycarbonate (PC) and polymethylmethacrylate (PMMA) substrates. The sol was synthesized by the hydrolysis and condensation of a UV-curable silane in combination with Zr-n-propoxide. Coatings deposited by dip coating were cured using UV-radiation followed by thermal curing between 80 °C and 130 °C. The effect of plasma surface treatment on the wettability of the polymer surface prior to coating deposition was followed up by measuring the water contact angle. The water contact angle on the surface of as-cleaned substrates was 80° ± 2° and that after plasma treatment was 43° ± 1° and 50° ± 2° for PC and PMMA respectively. Adhesion as well as mechanical properties like scratch resistance and taber abrasion resistance were evaluated for coatings deposited over plasma treated and untreated surfaces.     

Wettability of ZnO: A comparison of reactively sputtered; thermally oxidized and vacuum annealed coatings

We have studied the wettability of sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The X-ray diffraction patterns showed the formation of hexagonal-wurtzite structure of ZnO, which was further confirmed by micro-Raman spectroscopy data. The X-ray photoelectron spectroscopy data indicated that the sputter deposited ZnO coatings were more stoichiometric than thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The wettability measurements indicated that water contact angles of 158.5° and 155.2° with sliding angles of 2° and 4° were achieved for thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings, respectively. The superhydrophobicity observed in thermally oxidized Zn-ZnO and vacuum annealed coatings is attributed to the nanorod cluster like morphology along with the presence of high fraction of micron scale air pockets. The water droplet on such surfaces is mostly in contact with air pockets rather than solid surface, leading to high contact angle. Whereas, the sputter deposited ZnO coatings exhibited a maximum water contact angle of 110.3°. This is because the sputter deposited ZnO coatings exhibited a densely packed nanograin-like microstructure without any air pockets. The work of adhesion of water was very low for thermally oxidized Zn-ZnO (5.06 mJ/m²) and vacuum annealed ZnO coatings (6.71 mJ/m²) when compared to reactively sputtered ZnO coatings (90.41 mJ/m²). The apparent surface free energy (SFE) for these coatings was calculated using Neumann method and the SFE values for sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings were 32.95, 23.21 and 18.78 mJ/m², respectively.     

Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent

The superhydrophobic surfaces have drawn lot of interest, in both academic and industries because of optically transparent, adherent and self-cleaning behavior. Surface chemical composition and morphology plays an important role in determining the superhydrophobic nature of coating surface. Such concert of non-wettability can be achieved, using surface modifying reagents or co-precursor method in sol-gel process. Attempts have been made to increase the hydrophobicity and optical transparency of methyltrimethoxysilane (MTMS) based silica coatings using polymethylmethacrylate (PMMA) instead of formal routes like surface modification using silylating reagents. The optically transparent, superhydrophobic uniform coatings were obtained by simple dip coating method. The molar ratio of MTMS:MeOH:H₂O was kept constant at 1:5.63:1.58, respectively with 0.5 M NH₄F as a catalyst and the weight percent of PMMA varied from 1 to 8. The hydrophobicity of silica coatings was analyzed by FTIR and contact angle measurements. These substrates exhibited 91% optical transmittance as compared to glass and water drop contact angle as high as 171 ± 1°. The effect of humidity on hydrophobic nature of coating has been studied by exposing these films at relative humidity of 90% at constant temperature of 30 °C for a period of 45 days. The micro-structural studies carried out by transmission electron microscopy (TEM).     

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.     

Mechanically stable and corrosion resistant superhydrophobic sol-gel coatings on copper substrate

Development of the anticorrosion coatings on metals having both passive matrix functionality and active response to changes in the aggressive environment has raised tremendous interest in material science. Using a sol-gel deposition method, superhydrophobic copper substrate could be obtained. The best hydrophobic coating sol was prepared with methyltriethoxysilane (MTES), methanol (MeOH), and water (as 7 M NH₄OH) at a molar ratio of 1:19.1:4.31 respectively. The surface morphological study showed the ball like silica particles distributed on the copper substrate with particle sizes ranging from 8 to 12 μm. The coatings showed the static water contact angle as high as 155° and the water sliding angle as low as 7°. The superhydrophobic nature was maintained even though the deposited copper substrate was soaked for 100 h in 50% of HCl solution. The coatings are stable against humidity and showed superhydrophobic behavior even after 90 days of exposure. The coatings are mechanically stable and water drops maintained the spherical shape on the bent copper substrate, which was bent more than 90°.     

Fabrication and characterization of a cotton candy like surface with superhydrophobicity

Superhydrophobic thin films were prepared on glass by air-brushing the in situ polymerization compositions of D₅/SiO₂. The wettability and morphology were investigated by contact angle measurement and scanning electron microscopy. The most superhydrophobic samples prepared had a static water contact angle of 157° for a 5 μl droplet and a sliding angle of ∼1° for 10 μl droplet. Thermal stability analysis showed that the surface maintained superhydrophobic at temperature up to 450 °C. Air trapping and capillary force on superhydrophobic behavior were evaluated.     

Room temperature synthesis of water repellent silica coatings by the dip coat technique

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings onto stainless steel substrates using 1,1,1,3,3,3-hexamethyldisilazane as a surface modifying agent. The hydrophobic property of the silica coating was enhanced by increasing its surface roughness, which was achieved by a proper control over the MeOH/TMOS molar ratio (S) during the synthesis. The contact angle of a water droplet (10 μl) increased from 72° to 145° with an increase in the S value from 9.1 to 36.4. The silica coating showed a minimum sliding angle of 15° for a water droplet of 10 μl. The water repellent silica coatings are thermally stable up to a temperature of 340 °C. The results have been discussed by taking into consideration the contact angle measurements, surface morphology and sol-gel parameters.     

Fabrication of superhydrophobic surfaces on aluminum

A superhydrophobic surface was prepared on aluminum substrate. Anodization and low-temperature plasma treatment were used to create micro-nano-structure and subsequently trichlorooctadecyl-silane modified the rough surface. The result shows that the water static contact of the aluminum surface after anodization and modification by trichlorooctadecyl-silane reaches to 152.1°. A rougher surface with some micro-nano-pores and small mastoids along the edges of pores was generated when low-temperature plasma treatment was applied to anodized aluminum film, resulting in water static contact angle up to 157.8°.     

Transparent Superhydrophobic silica coatings on glass by sol-gel method

Wetting behavior of solid surfaces is a key concern in our daily life as well as in engineering and science. In the present study, we demonstrate a simple dip coating method for the preparation of Thermally stable, transparent superhydrophobic silica films on glass substrates at room temperature by sol-gel process. The coating alcosol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), trimethylmethoxysilane (TMMS), methanol (MeOH), water (H₂O) constant at 1:0.09:12.71:3.58, respectively with 13 M NH₄OH throughout the experiments and the films were prepared with different deposition time varied from 5 to 25 h. In order to improve the hydrophobicity of as deposited silica films, the films were derivatized with 10% trimethylchlorosilane (TMCS) as a silylating agent in hexane solvent for 24 h. Enhancement in wetting behavior was observed for surface derivatized silica films which showed a maximum static water contact angle (172°) and minimum sliding angle (2°) for 25 h of deposition time. The superhydrophobic silica films retained their superhydrophobicity up to a temperature of 550 °C. The silica films were characterized by field emission scanning electron microscopy (FE-SEM), surface profilometer, Fourier transform infrared (FT-IR) spectroscopy, thermo-gravimetric and differential thermal analysis (TG-DTA), percentage of optical transmission, water contact angle measurements. The imperviousness behavior of the films was tested with various acids.     

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.     

Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate

Nano-sized calcium carbonate (CaCO₃) particles were modified by heptadecafluorodecyl trimethoxysilane under acidic water condition. An ordinary polyacrylate prepared via radical copolymerization of methyl methacrylate, butyl acrylate, acrylic acid and β-hydroxyethyl methacrylate was used as the binder to form hydrophobic coatings with the modified CaCO₃. Super hydrophobic coating with water contact angle of 155° was obtained from modified CaCO₃ and the polyacrylate at their weight ratio of 8/2 by a simple procedure. Based on surface analysis by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), the super hydrophobicity can be attributed to both the surface microstructure and surface enrichment of fluoroalkyl chains. Due to a low water sliding angle, carbon black powder on super hydrophobic surface was easily removed by rolling water droplet. Furthermore, the anti-frosting performance of different surfaces was investigated, which indicated that the frost formed on superhydrophobic surface was greatly retarded compared with that on bare copper surface. The surface kept super hydrophobicity even after freezing-thawing treatment for 10 times.     

Research on the icephobic properties of fluoropolymer-based materials

Fluoropolymer, because of the extremely low surface energy, could be non-stick to water and thus could be a good candidate as anti-icing materials. In this paper, the icephobic properties of a series of fluoropolymer materials including pristine PTFE plates (P-PTFE), sandblasted PTFE plates (SB-PTFE), two PTFE coatings (SNF-1 and SNF-CO1), a fluorinated room-temperature vulcanized silicone rubber coating (F-RTV) and a fluorinated polyurethane coating (F-PU) have been investigated by using SEM, XPS, ice adhesion strength (tensile and shear) tests, and static and dynamic water contact angle analysis. Results show that the fluoropolymer material with a smooth surface can significantly reduce ice adhesion strength but do not show obvious effect in reducing ice accretion at −8 °C. Fluoropolymers with sub-micron surface structures can improve the hydrophobicity at normal temperature. It leads to an efficient reduction in the ice accretion on the surface at −8 °C, due to the superhydrophobicity of the materials. But the hydrophobicity of this surface descends at a low temperature with high humidity. Consequently, once ice layer formed on the surface, the ice adhesion strength enhanced rapidly due to the existence of the sub-micron structures. Ice adhesion strength of fluoropolymers is highly correlated to CA reduction observed when the temperature was changed from 20 °C to −8 °C. This property is associated with the submicron structure on the surface, which allows water condensed in the interspace between the sub-micron protrudes at a low temperature, and leads to a reduced contact angle, as well as a significantly increased ice adhesion strength.