Apparent Water Contact Angle Research Articles

Design and Fabrication of Teflon-Coated Tungsten Nanorods for Tunable Hydrophobicity

The nature of water interaction with tungsten nanorods (WNRs) fabricated by the glancing-angle deposition technique (GLAD)-using RF magnetron sputtering under various Ar pressures and substrate tilting angles and then subsequent coating with Teflon-has been studied and reported. Such nanostructured surfaces have shown strong water repellency properties with apparent water contact angles (AWCA) of as high as 160°, which were found to depend strongly upon the fabrication conditions. Variations in Ar pressure and the substrate tilting angle resulted in the generation of WNRs with different surface roughness and porosity properties. A theoretical model has been proposed to predict the observed high AWCAs measured at the nanostructure interfaces. The unique pyramidal tip geometry of WNRs generated at low Ar pressure with a high oblique angle reduced the solid fraction at the water interface, explaining the high AWCA measured on such surfaces. It was also found that the top geometrical morphologies controlling the total solid fraction of the WNRs are dependent upon and controlled by both the Ar pressure and substrate tilting angle. The water repellency of the tungsten nanorods with contact angles as high as 160° suggests that these coatings have enormous potential for robust superhydrophobic and anti-icing applications in harsh environments.

Highly Transparent Superhydrophobic Surfaces from the Coassembly of Nanoparticles (≤100 nm)

We report a simple and versatile approach to creating a highly transparent superhydrophobic surface with dual-scale roughness on the nanoscale. 3-Aminopropyltrimethoxysilane (APTS)-functionalized silica nanoparticles of two different sizes (100 and 20 nm) were sequentially dip coated onto different substrates, followed by thermal annealing. After hydrophobilization of the nanoparticle film with (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane for 30 min or longer, the surface became superhydrophobic with an advancing water contact angle of greater than 160° and a water droplet (10 μL) roll-off angle of less than 5°. The order of nanoparticles dip coated onto the silicon wafer (i.e., 100 nm first and 20 nm second or vice versa) did not seem to have a significant effect on the resulting apparent water contact angle. In contrast, when the substrate was dip coated with monoscale nanoparticles (20, 50, and 100 nm), a highly hydrophobic surface (with an advancing water contact angle of up to 143°) was obtained, and the degree of hydrophobicity was found to be dependent on the particle size and concentration of the dip-coating solution. UV-vis spectra showed nearly 100% transmission in the visible region from the glass coated with dual-scale nanoparticles, similar to the bare one. The coating strategy was versatile, and superhydrophobicity was obtained on various substrates, including Si, glass, epoxy resin, and fabrics. Thermal annealing enhanced the stability of the nanoparticle coating, and superhydrophobicity was maintained against prolonged exposure to UV light under ambient conditions.

Facile synthesis of superhydrophobic TiO2/polystyrene core-shell microspheres

In this paper, core-shell TiO2/polystyrene (TiO2/PS) microspheres with superhydrophobic properties were pre- pared via a facile method. Our method needs neither special apparatus nor complicated chemical treatment. The whole process includes two steps: firstly, coupling agent was used to modify TiO2 by sol-gel method; secondly, fabrication of TiO2/PS dispersions was carried out via in-situ free-radical polymerization strategy. The component and structure of the TiO2/PS particles were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), field emission scanning electron microscope (FE-SEM) and transmission electron microscopy (TEM). The TiO2 gel particles with average diameter of 1 ∝m exhibited irregular spherical shape and obvious aggregation. Compared with the TiO2 particles, the resulting TiO2/PS particulates showed regular spherical shape, better dispersion and bigger size. By directly depositing the resulted TiO2/PS dispersion on a Cu foil, the coating showed superhydrophobic property which was reflected by the contact angle (CA) of water on the surface with high water adhesion. The apparent CA of water is 153.5±1.5°, suggesting that this composite possesses well superhydrophobicity.

Scalable fabrication of superhydrophobic hierarchical colloidal arrays

Here we report a scalable bottom-up technology for assembling hierarchical colloidal arrays with superhydrophobic surface. Non-close-packed (NCP) colloidal multilayers, which facilitate the formation of more hydrophobic surface than close-packed arrays due to a higher fraction of entrapped air in between colloidal particles, are first fabricated by a simple spin-coating technology. Uniform silica nanoparticles are then assembled on the NCP microsphere arrays by a second spin-coating process. After surface functionalization of silica particles with fluorosilane, the resulting hierarchical colloidal arrays exhibit superhydrophobic surface with high apparent water contact angle (159°) and low contact angle hysteresis (4.7°). The experimental results on both the wettability and contact angle hysteresis can be qualitatively explained by adapting the Cassie's model. This spin-coating-based colloidal self-assembly technology is compatible with standard microfabrication and enables large-scale production of superhydrophobic coatings that could find important technological applications ranging from self-cleaning diffractive optics to microfluidic devices.

Substrate Effects on the Wettability of Electrospun Titania−Poly(vinylpyrrolidone) Fiber Mats

Titania-poly(vinylpyrrolidone) (PVP) core-shell nano/microfibers are electrospun on substrates of differing hydrophilicity and conductivity in order to investigate the connection between these substrate properties and the apparent water contact angles against the fiber mats. The focus of this study compares current data from silicon- and aluminum foil-supported mats to extant data from ITO and glass-supported fibers to detail the complexities of apparent contact angle dependence on mat structure related to substrate properties. Electrospinning time and collection distance were controlled parameters for producing thicker and denser mats. In all cases, contact angles increased with collection time for a given substrate series. A morphological wettability study of the fiber mat surface was conducted by applying Rhodamine B dye solution droplets. Using fluorescence microscopy, the stained fibers indicate the extent of true wetting contact and the lack of penetration into the fiber layers. Image comparisons with bright-field illumination confirms that even some fibers of the top layers are not wetted.

Self-Cleaning Diffractive Macroporous Films by Doctor Blade Coating

Here we report a scalable bottom-up technology for creating three-dimensionally highly ordered macroporous polymer films with excellent water-repelling and optical diffractive properties. A simple doctor blade coating process is first utilized to create silica colloidal crystal-polymer nanocomposites. The close-packed silica spheres are selectively removed to fabricate flexible macroporous polymer films with crystalline arrays of voids which are interconnected through small nanopores. The size of the voids can be easily controlled by tuning the duration of an oxygen reactive-ion etching process prior to the removal of the templating silica spheres. After surface functionalization with fluorosilane, superhydrophobic surface with large apparent water contact angle and small sliding angle can be obtained. The water-repelling property can be quantitatively explained by adapting the Cassie's dewetting model. We further demonstrate that self-cleaning functionality can be achieved on superhydrophobic macroporous coatings by preventing bacterial contamination. The high crystalline quality of the macroporous polymers also enables strong optical diffraction from the periodic lattice. The optical properties are evaluated by normal-incidence reflectance measurements and theoretical calculation using a scalar-wave approximation model. A good agreement between theory and experiment has been obtained. The simultaneous achievement of controlled dewetting and strong optical diffraction by templated porous films could open new applications in self-cleaning diffractive optics.

Wetting response of KrF laser ablated polyimide surfaces

The wettability of polyimide surfaces microstructured using KrF laser radiation at fluences above the material ablation threshold was studied by static contact angle measurements. The laser-treated surfaces present a morphology consisting of conical features whose dimensions and areal density depend on the fluence. The effect of these parameters on the surface apparent contact angle depends on the wetting regime. When wetting occurs in the homogeneous regime, the apparent contact angle of the treated surfaces increases with the radiation fluence because the cone dimensions increase. In contrast, when wetting occurs in the heterogeneous regime, the apparent contact angle increases with the radiation fluence because the average distance between cones increases. The apparent water contact angle of the laser-treated surfaces can reach values as high as 162°, as compared to 75° for virgin polyimide.

A Facile Approach for the Fabrication of Highly Stable Superhydrophobic Cotton Fabric with Multi-Walled Carbon Nanotubes−Azide Polymer Composites

Homogeneous dispersion and functionalization of pristine multiwalled carbon nanotubes (MWNTs) in various organic solvents was achieved by a simple ultrasonic process in the presence of an azide copolymer, poly(4-azidophenyl methacrylate-co-methyl acrylate)(P(APM-co-MA)). The copolymes were noncovalently attached to the surface of the MWNTs via pi-pi interactions to form MWNT-P(APM-co-MA) composites. The composites were characterized by transmission electron microscopy, thermogravimetric analysis, Raman spectra and UV-vis spectra. The solution dispersion of the MWNT-P(APM-co-MA) composites were used to prepare superhydrophobic cotton fabric by a facile dip-coating approach. MWNTs were covalently attached to the surface of the cotton fabric through the chemical reactions between the azide groups of P(APM-co-MA) with both MWNTs and cotton fibers. The reactions are based on UV-activated nitrene chemistry. Owing to the nanoscale roughness introduced by the attachment of MWNTs, the cotton fabric surface was transformed from hydrophilic to superhydrophobic with an apparent water contact angle of 154 degrees . Since MWNTs were covalently attached on the surface of the cotton fabric, the superhydrophobicity possesses high stability and chemical durability.

Fabrication and tribological properties of super-hydrophobic surfaces based on porous silicon

In the present work, super-hydrophobic surfaces based on porous silicon (PS) were constructed by the self-assembled molecular films and their tribological properties were investigated. A simple chemical etching approach was developed to fabricate PS with the certain rough microstructure surface, which can be observed by the environmental scanning electron microscopy (ESEM). The hydrocarbon and fluorocarbon alkylsilane molecular films were self-assembled on PS, which was confirmed by the X-ray photoelectron spectroscopy (XPS) measurement. In contrast to PS, the alkylsilane molecular films modified PS (mPS) were super-hydrophobic since the apparent water contact angle (CA) exceeded 160°. The tribological properties of PS and the mPS were investigated by a ball-on-disk tribometer during the processes of different sliding velocities and normal loads. The experimental results showed that the alkylsilane molecular films could decrease the friction coefficient. Due to the difference of chain structure and functional groups, the fluorinated alkylsilane films are better candidates for improving the hydrophobicity and lubricating characteristics of PS comparing to the non-fluorinated ones. The carbon chain length of alkylsilane molecules self-assembling on the Si or PS substrates could have little effects on the hydrophobic properties and the tribology performances.

Adhesion Modeling on Rough Low Linear Density Polyethylene

Food adhesion is an important attribute that could have both positive and negative ramifications depending on the application. Yet, its quantification remains cumbersome and as a consequence adhesion models are scarce. The effect of surface roughness, free energy, and ozone treatment on adhesion of rough low linear density polyethylene films was investigated. Adhesion was measured by a 180 degrees peel strength test. The plastic films were roughened (surface roughness ratio, r, ranged from 1.00 to 1.15). Exposing the film to ozone treatment (0 to 300 s) modified its surface free energy, gamma(s) (32.4 to 37.9 mJ/m(2), respectively), and its polar component of the surface free energy, gamma(p)(s) (3.0 to 8.3 mJ/m(2), respectively). The films were coated with polyurethane capable of forming hydrogen bonds. Adhesion was found to be a function of the apparent contact angle of water, theta(ap[water]), surface roughness ratio, and surface free energy. The linear relationship between the apparent contact angle of water, theta(ap[water]), and gamma(p)(s) was incorporated in building an empirical model that quantifies peel strength as function of r and gamma(p)(s). The model showed good agreement with experimental data, especially for longer ozone exposures and rougher surfaces. The empirical model provides insight into the relationships between surface roughness, surface energy, and adhesion. Quantifying these effects could facilitate reducing biofilm forming on food equipment, antisticking treatments, or easy peel packages, or reducing food residues adhering to the food packages and consequently minimize oxidation, off flavors, and waste.

Preparation and characterization of poly(vinyl chloride)‐graft‐acrylic acid membrane by electron beam

AbstractPoly(vinyl chloride) (PVC) was irradiated by electron beam in vacuum at 20 KGy to produce living free radicals, and then reacted with acrylic acid (AA) in solution to obtain the PVC‐g‐AA copolymers. The copolymers were characterized by Fourier transform infrared spectroscopy. Porous membranes were prepared from copolymers by the phase inversion technique. The morphology of PVC‐g‐AA membranes was studied by field emission scanning electron microscopy. The mean pore size and pore size distribution were determined by a mercury porosimeter. The mean pore size was 0.19 μm, and the bulk porosity was 56.02%. The apparent static water contact angle was 89.0°. The water drop penetration rate was 2.35 times to the original membrane. The maximum stress was 4.10 MPa. Filtration experiments were carried out to evaluate the fouling resistance of the PVC‐g‐AA membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Micrometrically scaled textured metallic hydrophobic interfaces validate the Cassie–Baxter wetting hypothesis

The possibility of forming a hydrophobic metallic interface is shown when it is micrometrically textured. On such surface obtained by gold coating the polymer honeycomb template, the apparent contact angle of water was observed to be close to or greater than 90°. The metal hydrophobicity is explained by trapping air inside pores of pattern according to the Cassie–Baxter wetting model. The agreement between calculated and observed values of the apparent contact angle justifies the applicability of this model in the present case. Formation of the acute local (Young) angle on the pore surface is provided by its concave form.

Stable Superhydrophobic Organic−Inorganic Hybrid Films by Electrostatic Self-Assembly

Organic-inorganic hybrid films were prepared through layer-by-layer (LBL) deposition of poly(allylamine hydrochloride) (PAH) and ZrO(2) nanoparticles coated with poly(acrylic acid) (PAA), allowing facile control of surface roughness and hydrophobicity. Superhydrophobic behavior was observed after deposition of silica nanoparticles and a simple fluorination of the surface. The structure of films was controlled by the number of deposition cycles using PAA-coated 100 nm ZrO(2) nanoparticles, the particle size, and the prelayer with PAH and PAA. The change in the apparent water contact angle of (PAH/PAA-coated ZrO(2)n surfaces without fluorination of the surface agrees with Cassie and Baxter's model for nonwetted surfaces even though the outermost surface itself is hydrophilic. Superhydrophobic surfaces were then successfully developed by the deposition of hydrophilic silica nanoparticles on a 10 bilayer surface of PAH/PAA-coated ZrO(2), and a simple fluorination. Moreover, the chemical stability of the film was greatly increased by heat-induced cross-linking of the film. The incorporation of ZrO(2) nanoparticles in superhydrophobic films promises better mechanical properties than the organic film.

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (3D) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106° to 153° through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie–Baxter model and Wenzel's equation.

Tailoring of the morphology and chemical composition of thin organosilane microwave plasma polymer layers on metal substrates

The growth of thin microwave organosilicon plasma polymers on model zinc surfaces was investigated as a function of the film thickness and the oxygen partial pressure during film deposition. The evolution of the topology of the film was studied by atomic force microscopy (AFM). The nano- and micro-roughness was investigated at the inner and the outer surfaces of the plasma polymers. A special etching procedure was developed to reveal the underside of the plasma polymer and thereby its inner surface. Rough films contained voids at the interface, which reduced the polymer/metal contact area. The increase in oxygen partial pressure led to a smoother film growth with a perfect imitation of the substrate topography at the interface. The chemical structure of the films was determined by infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). ToF-SIMS at the outer and the inner surface of the plasma polymers showed that the density of methylsilyl groups increases in the outer surface layer of the plasma polymer and depends on the oxygen partial pressure. The chemical composition of the films could be altered to pure SiO 2 without changing the morphology by using oxygen-plasma post-treatment. This was proved by means of IRRAS and AFM. Chemistry and topology of the films were correlated with the apparent water contact angle. It was found that a linear relationship exists between the nanoscopic roughness of the plasma polymer and the static contact angle of water. Superposition of a nanoscopic roughness of the metal surface and the nanoscopic roughness of methylsilyl-rich films led to ultra-hydrophobic films with water contact angles up to 160°.

Use of HMDS/hexane double layers for obtaining low cost selective membrane

Sheets of paper commonly used for filtration were coated with double layers of HMDS (hexamethyl disilazane) and n-hexane using a low pressure plasma reactor. The organic compounds formed a thin film with very good adhesion to the substrate; the process produced water-repellent surfaces, with apparent water-contact angles higher than 100° and water adsorption around 15 g/m 2 . The paper porosity was not altered, indicating that the depositions were conformal. Preliminary tests to investigate the possibility of using the modified paper as a selective membrane for separation of water and organic-polar and non-polar compounds of different chain length were conducted. The non-polar compounds tested were: n-hexane, cyclohexane, heptane, dodecane, benzene and poly(dimethylsiloxane). The polar organic liquids were ethanol, 2-propanol, carbon tetrachloride, acetophenone and phenol. Three types of behaviour were observed: (a) in the case of water/non-polar mixture, the non-polar compound passed through the modified paper whereas water did not; (b) in the case of acetophenone, phenol and carbon tetrachloride, neither the water nor the polar compound percolated through the modified paper; (c) in the case of water/2-propanol or ethanol solution, it was observed that a minimum concentration of alcohol was necessary in order for both the alcohol and water to percolate through the paper; in this case the alcohol percolates first, followed by water.

Paper surface modification by plasma deposition of double layers of organic silicon compounds

In this work, filter paper was coated with plasma depositions of hexamethyldisilazane (HMDS), and double layers of HMDS and n-hexane, and HMDS and tetraethyl orthosilicate (TEOS). In the case of double layers of HMDS and TEOS, TEOS deposition times of 2, 4 and 6 minutes were studied. The double layers were interfaced by an intermixing layer, in which both reagents were present. All coating films formed adhered well to the substrate, and resulted in water repellent paper surfaces with apparent water contact angles above 100 degrees and water adsorption around 15 g m−2. Apparent water contact angles were not affected by immersion in strong basic and acid solutions, or by exposure to ultraviolet light for 106 hours. Water adsorption of HMDS, HMDS–n-hexane and HMDS–TEOS (6 min) coated samples was not significantly altered by these resistance tests, but HMDS–TEOS (2, 4 min) coated samples were hydrolysed by immersion in strong basic solution and by ultraviolet light. These results seemed to indicate that the HMDS–TEOS intermixing layer was fragile and malformed. This hypothesis was confirmed by Raman and atomic force microscopies, which showed heterogeneous structures with very high peaks, and by XPS analysis, which indicated oxidation of carbonic species and crosslinkings together with elimination of ethylene gas probably triggered in the intermixing layer. The porosity of paper was not altered showing that all depositions were conformal. FTIR analysis of HMDS coatings indicated that the films formed were crosslinked by ultraviolet light showing its potential for outdoor applications.

Adhesion of Epoxy Filleting Adhesive and Parylene Conformal Coating to Plasma Treated, Solder Mask Coated Substrates

Peel adhesion of an epoxy filleting compound and Parylene C conformal coating to plasma treated, solder mask coated substrates and the apparent contact angle of water on the treated surfaces were evaluated. No significant improvement was achieved in the case of the epoxy filleting adhesive for most solder mask coatings studied. On the other hand, Parylene C peel adhesion significantly increased after substrates were treated with air plasma and reached the level of Silane coupling agent primed substrates. This was in contrast to the decrease in Parylene adhesion to argon plasma treated substrates in comparison with the non‐treated substrates. This was related to the oxygen functionalities created on the surfaces by the air plasma versus the ablative nature of the argon plasma. No clear correlation was found between peel strength and the water contact angle in the case of the epoxy adhesive, while for the Parylene conformal coating peel strength achieved its maximum value at the middle of the contact angle range which resulted from the pretreatments applied in this study. It is concluded that air plasma is a very efficient solder mask pretreatment for Parylene conformal coating that can replace Silane primer. Also, if a calibration curve is established for each solder mask‐adhesive and solder mask‐coating system, the apparent water contact angle can serve as a convenient quality control tool for printed circuit finishing processes.