The wetting behaviour of silver on carbon, pure and carburized nickel, cobalt and molybdenum substrates

Properties such as thermal and electrical conductivity or the expansion behaviour of silver matrix composites with carbon based inclusions are strongly affected by the contact angle between carbon and silver. In order to promote wetting of carbon, insertion of metallic interlayers such as nickel, cobalt or molybdenum is a feasible approach. This paper presents contact angle measurements done with the sessile drop method on carbon substrates (glassy carbon, polycrystalline graphite) and on pure nickel, cobalt and molybdenum foils. The ability of these interlayer elements to lower the high contact angles of silver on glassy carbon (117°) and polycrystalline graphite (124°) under vacuum conditions was verified. Unlike nickel (30°) and cobalt (26°), molybdenum (107°) nevertheless was not wettable by liquid silver (at 1273 K) under vacuum conditions. ToF-SIMS was used to identify oxygen on the surface, causing higher contact angles than expected. After oxide reduction a contact angle of 18° on molybdenum was detected. Furthermore, the influence of carbon diffusion on the contact angle was investigated by gas phase carburization of the metal foils. ToF-SIMS and XRD identified dissolved carbon (Ni, Co) and carbide formation (Mo). However, only nickel and cobalt showed a slight decrease of the contact angle due to carbon uptake.     

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.     

Observation of a Sharp Transition in Contact Angle in the Wetting of Graphite by Solid Pb-Ni Alloys

The wetting of Pb-Ni crystals on graphite has been observed at 558 K in a Scanning Auger Microprobe. Samples were prepared so as to produce 10 m crystals of Pb with Ni contents increasing from 0 to 0.3 wt% along one axis of the graphite substrate. In the low Ni region, the contact angle was found to decrease slowly from 119° to 98° with increasing Ni content. In the region of high Ni content, a constant contact angle of 83° was measured. In between, crystals with contact angles of 98° and 83° were observed to coexist, near the limit of solubility of Ni in Pb, indicating the presence of a first order transition in contact angle. The continuous decrease in contact angle, in the low Ni region, is due to Ni adsorption at the Pb-graphite interface, which leads to a decrease in interfacial energy. The constant contact angle in the high Ni region is associated with the precipitation of a Ni-rich phase. Various hypotheses are advanced to account for the first order transition in contact angle as a function of Ni concentration.     

Formation of functional groups on graphite during oxygen plasma treatment

Improved sample wettability was obtained by oxygen plasma functionalization of pyrolytic graphite. The samples were exposed to highly dissociated oxygen plasma with the density of 1 × 10¹⁶ m⁻³, the electron temperature of about 5.5 eV and the density of neutral oxygen atoms of 8 × 10²¹ m⁻³ for 20 s. The surface wettability was measured by a contact angle of water drop. The contact angle dropped from original 112° down to about 1°. The functional groups were detected by XPS analyses. The survey spectrum showed a substantial increase of oxygen concentration on the surface, while high-resolution analyses showed additional oxygen was bonded onto the graphite surface in the form of C-O polar functional group responsible for the increase of the surface energy.     

Water adsorption on hydrogenated Si(1 1 1) surfaces

The adsorption of water on the hydrogen terminated Si(1 1 1) surface is studied by means of first-principles calculations as well as contact angle measurements. Possible initial adsorption configurations for single water molecules and the potential energy surface are calculated. Only small adsorption energies of the order of meV are predicted. Calculations for higher coverage show that the water-water interactions are stronger than the water-surface bonding. The contact angle formed between a water droplet on the surface approximated from the total-energy calculations amounts to 88°, while our measured value is 91°.     

Characterisation of wettability in gas diffusion layer in proton exchange membrane fuel cells

This paper presents a detailed study of the wetting properties of three fuel cell gas diffusion layers (GDLs) having different morphologies and different contents of hydrophobic agent. An internal contact angle to water at temperature representative of PEM fuel cell operating conditions was directly obtained using the Washburn method with 66 ° C water as test liquid. These results show that the surface of the carbon fibres is hydrophilic under fuel cell operating conditions. Surface energy values of the GDL fibres, determined by a combination of the Washburn method and the Owens-Wendt two parameters theory, were found to be low, indicating that GDLs are wet very poorly by most liquids. About 40% of the total surface free energy values was related to a polar component allowing dipole-dipole and hydrogen bonding interactions with water. The origin of this polar character is discussed.     

The water/graphitic-carbon interaction energy

The water/graphitic-carbon interaction energy was obtained for a sample having a water surface site adsorption density of 13.3 μmol m⁻². The interaction energy was determined from the spreading pressure of water, its surface tension and the water contact angle and using a formula obtained by the combination of the Young equation with a general equation of pair interaction. The values obtained for contact angles 42° and 86° are 7.63 and 7.18 kJ mol⁻¹ of water are similar to the water binding energies obtained from molecular dynamic simulations of water droplets on a graphite surface: 6.7-8.33 kJ mol⁻¹.     

Wetting behavior of magnesite and dolomite surfaces

Magnesite and dolomite are salt-type minerals that show similar chemical composition and flotation behavior due to same crystal structure, and sparingly soluble nature. The surface properties of minerals play a major role in determining their separation from each other in processes such as flotation. During flotation process, selectivity problem arises between magnesite and associated gangue minerals such as dolomite. There is a close relationship between floatability of minerals and their contact angles. Therefore, surface hydrophobicity of magnesite and dolomite minerals was investigated by contact angle measurements in the absence and presence of flotation reagents.Magnesite and dolomite show hydrophilic properties and they have got a small contact angle (magnesite ∼10.4° and dolomite ∼6.6°) in distilled water in the absence of any surfactant. The contact angle values at the magnesite and dolomite surfaces remained at 9.7°-10.9° in the presence of petroleum sulphonates (R825 and R840) while sodium oleate affected hydrophobicity of magnesite, and the contact angle value increased up to 79°. The contact angle value of 39° at dolomite surface was obtained in the solution of sodium oleate, respectively.     

Preparation and properties of super-hydrophobic coating on magnesium alloy

The super-hydrophobic coating was successfully fabricated on the surface of magnesium alloy AZ31 by chemical etching and surface modification. The surface morphologies, compositions, wettability and corrosion resistance of the coating were investigated with SEM, XPS, contact angle measurement and electrochemical method, respectively. It shows that the rough and porous micro-nano-structure was presented on the surface of magnesium alloy, and the contact angle could reach up to 157.3 ± 0.5° with sliding angle smaller than 10°. The super-hydrophobic coating showed a long service life. The results of electrochemical measurements showed that anticorrosion property of magnesium alloy was improved. The super-hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it finds that only about 10% of the water surface is contacted with the metal substrate and the rest 90% is contacted with the air cushion.     

Modification of surface properties of electrospun polyamide nanofibers by means of a perfluorinated acridine

Polyamide 6 (PA6) nanofibers were prepared from formic acid solutions by using electrospinning technique. The fibers were smooth, defects free and with diameters smaller than 200 nm. Small amounts of a perfluorinated acridine were added as dopant to the feed solution to modify the wettability of the fibers. The effect of doping on the contact angle values is well apparent. The contact angle values go from 50° of pure PA6 to 120° when 6% of acridine is added. A comparison between fibers and films of pure and doped polyamide 6 was carried out in order to determine the effect of morphology on wettability. Thermal annealing near the T_g of the polymer promoted the segregation of the molecules to the surface, reaching contact angles of 131° with smaller amounts (4%) of acridine. The surface segregation was also promoted by time aging.     

Two-dimensional self-assembly of esters with different configurations at the liquid-solid interface

Self-assembled monolayers of hexadecyl palmitate (HP) and 3,3′-thiodipropionic acid di-n-octadecyl ester (TADE) physisorbed on highly oriented pyrolytic graphite (HOPG) are investigated using scanning tunneling microscope (STM) and computer simulation. Both molecules form alkane-like linear shapes to maximize the interactions with substrate when they adsorb on HOPG surface. The HP molecules self-assemble into lamellae with the chain-trough angle of 48°, which is the result of a shifting 3/2 units from the adjacent molecule in a lamella. Based on the simulation insights combined with STM images, we confirm that a perpendicular orientation appears in which the HP molecular backbone is rotated 90° with respect to the substrate such that the carbonyl points away from the HOPG surface. TADE molecules form three kinds of configurations with chain-trough angles of 90°, 72° and 60° by shifting 0, 1/2 and 1 units from their adjacent molecules, respectively. The bright stripes in STM images reveal the electron density distribution of the part between two ester groups. The energy differences of three TADE adsorption configurations by molecular mechanics (MM) simulation are used to explain the structural coexistence phenomenon. It is also shown that lattice match between alkyl chain of molecules and HOPG substrate could change molecular conformation upon self-assembly.     

Extreme wettability due to dendritic copper nanostructure via electrodeposition

Dendritic copper film with convertible extreme wettability is prepared on metal surface via electrodeposition. With field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and electrochemical measurement, the morphology, composition and formation mechanism of dendritic copper film were studied. It is found that the film is mainly composed of metallic copper. Also some residual cuprous oxide and chloride exist in the deposit. The single micron-sized dendrite consists of a main stem with side branches, on which the higher-order branches with the dimension of tens of nanometers grow. A hydrophobic modification can induce the conversion of the apparent wettability of film from super-hydrophilicity (with apparent water contact angle of 5 ± 3°) to super-hydrophobicity (with apparent water contact angle of 154.1 ± 3°), which is due to the capillary effect. The method proposed in this paper is time-saving and facile to operate, and it offers a promising technique to prepare metallic surface with a high wettability contrast for water.     

Control on wetting properties of spin-deposited silica films by surface silylation method

Control on the wettability of solid materials by liquid is a classical and key issue in surface engineering. Optically transparent water-repellent silica films have been spin-deposited on glass substrates at room temperature (∼27 °C). The wetting behavior of silica films was controlled by surface silylation method using dimethylchlorosilane (DMCS) as a silylating reagent. A coating sol was prepared by keeping the molar ratio of methyltrimethoxysilane (MTMS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:8.8:2.64 respectively, with 4 M NH₄OH as a catalyst throughout the experiments and the amount of DMCS in hexane was varied from 0 to 12 vol.%. It was found that with an increase in vol.% of DMCS, the water contact angle values of the films increased from 78° to 136°. At 12 vol.% of DMCS, the film shows static water contact angle as high as 136° and water sliding angle as low as 18°. The hydrophobic silica films retained their water repellency up to a temperature 295 °C and above this temperature the films show superhydrophilic behavior. These results are compared with our earlier research work done on silylation of silica surface using hexamethyldisilazane (HMDZ) and trimethylchlorosilane (TMCS). The hydrophobic silica films were characterized by taking into consideration the Fourier transform infrared (FT-IR) spectroscopy, thermo gravimetric-differential thermal (TG-DT) analyses, 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.     

Estimating critical surface tension from droplet spreading area

Critical surface tension (CST) is a measure of solid surface tension and is mainly determined by measuring the contact angle of a droplet on a target solid surface. The concept of CST makes it possible to determine solid surface tension without any unprovable assumptions such as the Fowkes hypothesis. However, it requires somewhat special devices and skills for measuring the contact angle. In this work, we propose a simple method to determine the CST of a solid by measuring the droplet spreading area. This method is developed by combining the conventional CST with a simple analytical droplet model. The difference in estimated CSTs between our method and the conventional one is within 3.0%. Our method enables a quick and simple evaluation of the solid surface tension without special devices for measuring the contact angle.     

Tunable surface wettability of ZnO nanorods prepared by two-step method

Zinc oxide (ZnO) nanorods were deposited on silicon substrate by two-step method. The crystal structure, surface morphology and water contact angle (WCA) were measured by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), and water contact angle apparatus. It is demonstrated that the WCA of the as-grown ZnO nanorods varies between 136° and 43° and the contact angle reduction rate of ZnO nanorods changes rapidly with increasing growth time. The variation of contact angle in the as-grown samples and contact angle reduction rate has been attributed to the combined effects of the proportion of nonpolar planes in the outermost surface, the area fraction of vapor on the surface and the increase of surface energy of ZnO nanorods.     

Evaluation of the surface properties of PTFE foam coating filter media using XPS and contact angle measurements

A newly developed PTFE foam coating filter was developed which can be used for hot gas cleaning at temperatures up to 250 °C. The emulsion-type PTFE was coated onto a woven glass fiber using a foam coating method. The filter surface was closely examined using X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The XPS results were used to determine the binding force between the carbon and fluorine of PTFE, which imparts coating stability to the filter medium. More than 95% of the bonds of the PTFE foam coating filter were between carbon and fluorine, and this filter demonstrated excellent hydrophobic and good oleophobic properties at the same time. The contact angles of liquid droplets on the filter surface were used to predict the potential wetability of the filter against water or oil. In addition, the very low surface free energy of the filter medium, which was evaluated using the Owens-Wendt method, demonstrates a very stable surface and a high de-dusting quality.     

Morphological stability analysis of partial wetting

We develop a macroscopic static theory of the morphological stability of partial wetting. The system we studied consist of a smooth horizontal solid surface and some non-volatile liquid on it. A necessary condition for the stable equilibrium of such systems is known as the Young condition on the contact angle made at the contact line where the free surface of liquid meets the solid surface. But this condition is local and is not sufficient for the stability. We present a formulation for studying the stability of systems which satisfy the Young condition. Then we apply this to several morphologies of wetting. We find that there are at least two fundamental morphologies that we call a hole and a ridge, which are thermodynamically unstable against certain infinitesimal deformations of the contact lines. The hole type instability has also been found recently [D. J. Srolovitz and S. A. Safran, J. Appl. Phyys., 60 (1986), 1]. We also derived a reduced expression for the wetting energy as a functional of the contact line positions under the assumption of almost flat free surface of the liquid. This serves us to understand the characteristic length scale which appears in the ridge type instability. Besides these instabilities there is another category of morphological instability in which the system becomes unstable against an infinitesimal deformation of the free surface of liquid. We show this by an illustrating example in which the instability is described as the so-called tangent bifureation in nonlinear systems.     

Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent

A superhydrophobic complex coating for cotton fabrics based on silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent (PFSC) was reported in this article. The complex thin film was prepared through a sol-gel process using cotton fabrics as a substrate. Silica nanoparticles in the coating made the textile surface much rougher, and perfluorooctylated quaternary ammonium silane coupling agent on the top layer of the surface lowered the surface free energy. Textiles coated with this coating showed excellent water repellent property, and water contact angle (CA) increased from 133° on cotton fabrics treated with pure PFSC without silica sol pretreatment up to 145°. The oil repellency was also improved and the contact angle of CH₂I₂ droplet on the fabric surface reached to 131°. In contrast, the contact angle of CH₂I₂ on the fabric surface treated with pure PFSC was only 125°.     

Surface chemistry of atmospheric plasma modified polycarbonate substrates

Surface of polycarbonate substrates were activated by atmospheric plasma torch using different gas pressure, distance from the substrates, velocity of the torch and number of treatments. The modifications were analyzed by contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-vis spectrophotometry. Plasma treatment caused the surface characteristics to become more hydrophilic as measured by the water contact angle, which decreased from 88° to 18°. The decrease in contact angle was mainly due to oxidation of the surface groups, leading to formation of polar groups with hydrophilic property. XPS results showed an increase in the intensity of -(C-O)- groups and also introduction of new functional groups i.e. -(O-CO)- after the treatment process. AFM topographic images demonstrated an increase in the rms roughness of the surface from 2.0 nm to 4.0 nm caused by the treatment. Increase in rms roughness of the surface caused relevant decrease in transmission up to ∼2-5%.     

A Monte Carlo simulation study of Nitrogen on LiF(0 0 1)

The adsorption of N₂ gas on the LiF(0 0 1) surface is studied by canonical Monte Carlo (CMC) computer simulation. These results show that N₂ forms an ordered structure where the molecules are arranged in a unit cell of symmetry at temperatures below 23 K with 50% coverage. The nitrogen molecules are tilted by 53° from the surface normal and have the same azimuthal orientation along diagonals, with diagonals alternating their orientation. Beyond 23 K, the molecules become azimuthally disordered but with residual short-range order. No change in the position of the peak of the polar (tilt) angle distribution was observed above the transition temperature. This transition is purely of the order-disorder type.