Contact Angle Hysteresis on Polymer Surfaces: An Experimental Study

In order to characterize a solid surface, the commonly used approach is to measure the advancing and receding contact angles, i.e., the contact angle hysteresis. However, often an estimate of the average wettability of the solid–liquid system is required, which involves both the dry and wetted states of the surface. In this work, we measured advancing and receding contact angles on six polymer surfaces (polystyrene, poly(ethylene terephthalate), poly(methyl methacrylate), polycarbonate, unplasticized poly(vinyl chloride), and poly(tetrafluoroethylene)) with water, ethylene glycol and formamide using the sessile drop and captive bubble methods. We observed a general disagreement between these two methods in the advancing and receding contact angles values and the average contact angle determined separately by each method, although the contact angle hysteresis range mostly agreed. Surface mobility, swelling or liquid penetration might explain this behaviour. However, we found that the 'cross' averages of the advancing and receding angles coincided. This finding suggests that the cross-averaged angle might be a meaningful contact angle for polymer–liquid systems. Hence, we recommend using both the sessile drop and captive bubble methods.     

Water Contact Angles on Poly(ethylene terephthalate) Film Exposed to Atmospheric Pressure Plasma

The poly(ethylene terephthalate), PET, film was exposed to atmospheric pressure plasma under various plasma processing parameters. The wettability of the PET film immediately after the exposure and after storage in air, which was determined by the sessile drop method, was strongly dependent on the plasma processing parameters. The contact angle hysteresis on the plasma-exposed PET film was examined by the Wilhelmy method. It was found that the hydrophobic recovery of the PET surface on storage after the plasma exposure was observed only for the advancing contact angle and that the receding angle remained almost the same. These experimental findings were explained on the basis of the calculation by Johnson and Dettre for the advancing and receding contact angles on model heterogeneous surfaces.     

Microsphere tensiometry to measure advancing and receding contact angles on individual particles

In this paper, a method to measure the advancing and receding contact angles on individual colloidal spheres is described. For this purpose, the microspheres were attached to atomic force microscope cantilevers. Then the distance to which the microsphere jumps into its equilibrium position at the air-liquid interface of a drop or an air bubble was measured. From these distances the contact angles were calculated. To test the method, experiments were done with silanized silica spheres (4.1 μm in diameter). From the experiments with drops, an advancing contact angle of 101 ± 4° was determined. A receding contact angle of 101 ± 2° was calculated from the jump-in distance into a bubble. Both experimental techniques gave the same contact angle. In contrast, on similarly prepared planar silica surfaces, a clear hysteresis was measured with the sessile drop method; contact angles of 104.5 ± 1° and 93.8 ± 1° were determined for the advancing and receding contact angles, respectively.     

Analysis of evaporating thick liquid films on solids

The diffusion-controlled evaporation of small circular volatile liquid films from solid surfaces was monitored by employing video microscopy from a plan view and then applying digital image analysis techniques. The decrease of the liquid-solid contact area of these films during the last stages of the evaporation was found to be linear with time. This paper presents experimental results of four organic liquid films (n-nonane, n-octane, toluene, n-butanol) on three substrates poly(methyl methacrylate), poly(ethylene terephthalate) (Mylar), and glass. The linear decreases of the surface areas of hanging drops from a polypropylene fiber for the same liquids were also monitored using both plan and side view video cameras for comparison. Analyses of optically recorded liquid film and drop shapes were carried out and a diffusion model depending on the presence or absence of the substrate was developed. By combining the experimental area decrease of a spherical drop due to the diffusion-controlled evaporation with that of a small spherical cap shaped liquid film resting on a solid surface, it is possible to calculate the small contact angles (less than 10°) of the wetting thick liquid films on solids. The relationship between film evaporation rate and the solid-liquid interfacial interactions is also discussed.     

粗糙固体平面上液滴的接触角滞后的简单流体静力学模型

The phenomenon of hysteresis of contact angle is an important topic subject to a long time of argument.A simple hydrostatic model of sessile drops under the gravity in combination with an ideal surface roughness model is used to interpret the process of drop volume increase or decrease of a planar sessile drop and to shed light on the contact angle hysteresis and its relationship with the solid surface roughness. With this model, the advancing and receding contact angles are conceptually explained in terms of equilibrium contact angle and surface roughness only,without invoking the thermodynamic multiplicity. The model is found to be qualitatively consistent to experimental observations on contact angle hysteresis and it suggests a possible way to approach the hysteresis of three-dimensional sessile drops.     

Wettability of fibrous quartz with Langmuir-Blodgett films of arachidic acid and/or cellulose didecanoate

The wettability of quartz with Langmuir-Blodgett (LB) films of arachidic acid (AA) and/or cellulose didecanoate (CDD) was investigated by contact angle measurements, employing the Wilhelmy method. The advancing angles increased considerably with the film deposition, especially for the AA films, whereas the receding angles increased only slightly. A further increase in the advancing angles with time was found after the film deposition. The experimental results are discussed considering the quartz with the LB films to have a heterogeneous surface, i.e. predominantly high-energy surface with fractional low-energy regions. The increment in the advancing contact angle due to film deposition is explained by the increase in the percentage of the low-energy region. The time dependence of the advancing angle after the film deposition is considered to be caused by the increase in the difference in the intrinsic wettability between the low-energy and high-energy regions due to rearrangement of the molecules in the LB films and the migration of the AA molecules towards the air.     

Anisotropic Wetting of Liquids on Finely Grooved Surfaces

A photolithographically-prepared, parallel-grooved surface on silica has been employed as a model to study the influence of roughness on the spreading equilibrium of liquid drops. The equations generated by Oliver, Huh and Mason for cylindrically shaped drops were extended to account for wetting by liquid crystals. The observed drop shapes were dependent upon surface roughness. The equilibrium contact angles on a smooth surface can be calculated from the roughness, contact angles both parallel and perpendicular to the grooves, and the drop shape. Reasonably good agreement with experimental contact angles was obtained.     

Liquid/Fiber and Solidified-Liquid/Fiber Contact Angles Compared

Data are presented showing that the contact angle formed by a liquid resin droplet placed on a single fiber is comparable with a receding contact angle. This was ascertained by comparing Wilhelmy wetting force measurements with liquid droplet profile analysis. Subsequently, the latter analysis was carried out on cured (solidified) epoxy droplets placed on Kevlar fibers. Dimensional changes observed after curing showed that the contact angles of the solid droplets were smaller than that for liquid resin: however, the presence of residual stresses because of adhesion to the fiber may make droplet profile analysis inaccurate for obtaining an equilibrium receding contact angle for the solid droplets.     

Contact angle measurements on oxidized polymer surfaces containing water-soluble species

Advancing and receding contact angle measurements on polymer surfaces can be performed using a number of different methods. Ballistic deposition is a new method for both rapidly and accurately measuring the receding contact angle of water. In the ballistic deposition method, a pulsed stream of 0.15-μL water droplets is impinged upon a surface. The water spreads across the surface and then coalesces into a single 1.8-μL drop. High-speed video imaging shows that, on most surfaces, the water retracts from previously wetted material, thereby forming receding contact angles that agree with the receding angles measured by the Wilhelmy plate technique. The ballistic deposition method measures the receding angle within one second after the water first contacts the surface. This rapid measurement enables the investigation of polymer surface properties that are not easily probed by other wettability measurement methods. For example, meaningful contact angles of water can be obtained on the water-soluble low-molecular-weight oxidized materials (LMWOM) formed by the corona and flame treatment of polypropylene (PP) films. Use of the ballistic deposition method allows for a characterization of the wetting properties and an estimation of the surface energy components of LMWOM itself. Both corona- and flame-generated LMWOM have significant contact angle hysteresis, almost all of which is accounted for by the non-dispersive (polar) component of the surface rather than by the dispersive component. Surface heterogeneity is thus associated primarily with the oxidized functionalities added to the PP by the corona and flame treatments.     

STABILITY OF THE LENSLIKE LIQUID THICKENING (THE DROP) ON A SOLID SUBSTRATE

The quasi equilibrium of a liquid lens or a liquid drop on a solid substrate is considered on the basis of the thermodynamics of microscopic thin liquid films. Both contact angles, corresponding to the membrane model and to the finite thickness layer convention of the film, have been derived as a function of the disjoining pressure isotherm. The analytical expressions for the line tension terms have been obtained, and the criterion for the stability of a liquid drop on a solid substrate has been proposed.     

STABILITY OF THE LENSLIKE LIQUID THICKENING (THE DROP) ON A SOLID SUBSTRATE

The quasi equilibrium of a liquid lens or a liquid drop on a solid substrate is considered on the basis of the thermodynamics of microscopic thin liquid films. Both contact angles, corresponding to the membrane model and to the finite thickness layer convention of the film, have been derived as a function of the disjoining pressure isotherm. The analytical expressions for the line tension terms have been obtained, and the criterion for the stability of a liquid drop on a solid substrate has been proposed.     

The wettability of industrial surfaces: Contact angle measurements and thermodynamic analysis

The water wettability of surfaces, whose surface conditions are comparable to those used in heat and mass transfer equipment, has been investigated experimentally and theoretically.In the first part, results of contact angle measurements for water on metal and non-metal surfaces are reported. With hydrophobic non-metal surfaces (e.g. Teflon) water forms large advancing and receding contact angles, and the contact angle hysteresis is small. Surface contamination is of minor influence. Hydrophilic metal surfaces (copper, nickel) are completely wetted by water only if the surfaces are extremely clean. Surface contamination reduces the wettability drastically. Under most industrial conditions advancing contact angles between 40° and 80°, and receding contact angles smaller than 20° can be expected, and the contact angle hysteresis is large. Corrosion can enhance the water wettability.In the second part, a thermodynamic analysis of the wetting of heterogeneous surfaces is presented. Equilibrium considerations for a model surface consisting of two components of different wettability provide the advancing and receding contact angles for a heterogeneous surface as a function of the equilibrium contact angles, surface fractions, and the distribution function of the two components. The advancing and receding contact angles as well as all the intermediate contact angles indicate metastable states of equilibrium of the system. The results of the model calculations give a physically based explanation for the characteristic wetting behaviour of industrial surfaces found experimentally.     

The combined effect of roughness and heterogeneity on contact angles: the case of polymer coating for stone protection

The individual effects of heterogeneity and roughness on contact angles have been repeatedly analysed in the literature, but the application of the accepted models to practical situations is often not correctly performed. In the present paper the combined effects of roughness and heterogeneity on the contact angles of water on stone surfaces protected by a hydrophobic polymer coating are considered. Two different kinds of calcareous stone with different surface roughnesses and porosities were protected against the effect of water absorption by two different polymer coatings. The contact angles of water on the protected stone surfaces were measured by the Wilhelmy and the sessile drop techniques. A comparison of the results obtained shows not only the limits of the static sessile drop technique, but also the combined effect of roughness and heterogeneity. Some considerations are developed on the application of commonly accepted models to surfaces with a combination of roughness and heterogeneity. Some other results obtained with techniques such as roughness measurements, mercury porosimetry, energy dispersive X-ray spectroscopy (EDXS), thermogravimetric analysis (TGA), water absorption by capillarity experiments (WAC), all able to show the structure and properties of the obtained films, are also compared with those obtained from contact angle measurements. It is concluded that the static contact angle is not well correlated with the degree of protection; on the contrary, the receding contact angles are well correlated with the degree of protection actually obtained. An ideal protecting agent should have a receding contact angle greater than 90°.     

On the interpretation of contact angle hysteresis

The determination of solid surface free energy is still an open problem. The method proposed by van Oss and coworkers gives scattered values for apolar Lifshitz-van der Waals and polar (Lewis acid-base) electron-donor and electron-acceptor components for the investigated solid. The values of the components depend on the kind of three probe liquids used for their determination. In this paper a new alternative approach employing contact angle hysteresis is offered. It is based on three measurable parameters: advancing and receding contact angles (hysteresis of the contact angle) and the liquid surface tension. The equation obtained allows calculation of total surface free energy for the investigated solid. The equation is tested using some literature values, as well as advancing and receding contact angles measured for six probe liquids on microscope glass slides and poly(methyl methacrylate) PMMA, plates. It was found that for the tested solids thus calculated total surface free energy depended, to some extent, on the liquid used. Also, the surface free energy components of these solids determined by van Oss and coworkers' method and then the total surface free energy calculated from them varied depending on for which liquid-set the advancing contact angles were used for the calculations. However, the average values of the surface free energy, both for glass and PMMA, determined from these two approaches were in an excellent agreement. Therefore, it was concluded that using other condensed phase (liquid), thus determined value of solid surface free energy is an apparent one, because it seemingly depends not only on the kind but also on the strength of interactions operating across the solid/liquid interface, which are different for different liquids.     

The effects of nanostructure and composition on the hydrophobic properties of solid surfaces

The effects of nanoroughness and chemical composition on the contact and sliding angles on hydrophobic surfaces were studied theoretically and experimentally. A theoretical model based on forces developed at the contact area between a liquid drop and hydrophobic smooth or nanoroughened surface was developed and compared with the existing models, which are based on forces developed at the periphery between the drop and the solid surface. The contact area based model gives rise to an interfacial adhesion strength parameter that better describes the drop-sliding phenomenon. Consequently, relationships were derived describing the dependence between the interfacial adhesion strength of the liquid drop to the surface of a given composition, the mass of the drop, the measured contact angles and the sliding angle. For a given surface chemistry, the sliding angle on a nanometric roughened surface can be predicted based on measurements of contact angles and the sliding angle on the respective smooth surface. Various hydrophobic coatings having different surface nanoroughnesses were prepared and, subsequently, contact angles and sliding angles on them as a function of drop volume were measured. The validity of the proposed model was investigated and compared with the existing models and the proposed model demonstrated good agreement with experimental results.     

Evaluation of surface energy of solid polymers using different models

In the present work, contact angles formed by drops of diethylene glycol, ethylene glycol, formamide, diiodomethane, water, and mercury on a film of polypropylene (PP), on plates of polystyrene (PS), and on plates of a liquid crystalline polymer (LCP) were measured at 20°C. Then the surface energies of those polymers were evaluated using the following three different methods: harmonic mean equation and geometric mean equation, using the values of the different pairs of contact angles obtained here; and Neumann's equation, using the different values of contact angles obtained here. It was shown that the values of surface energy generated by these three methods depend on the choice of liquids used for contact angle measurements, except when a pair of any liquid with diiodomethane was used. Most likely, this is due to the difference of polarity between diiodomethane and the other liquids at the temperature of 20°C. The critical surface tensions of those polymers were also evaluated at room temperature according to the methods of Zisman and Saito using the values of contact angles obtained here. The values of critical surface tension for each polymer obtained according to the method of Zisman and Saito corroborated the results of surface energy found using the geometric mean and Neumann's equations. The values of surface energy of polystyrene obtained at 20°C were also used to evaluate the surface tension of the same material at higher temperatures and compared to the experimental values obtained with a pendant drop apparatus. The calculated values of surface tension corroborated the experimental ones only if the pair of liquids used to evaluate the surface energy of the polymers at room temperature contained diiodomethane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1831–1845, 2000     

New method of determining contact angle between monofilament and liquid

This paper describes a method to obtain contact angle by observing the shape of a liquid drop attached to a monofilament. The relations between contact angle and the dimensions of drops are theoretically obtained. Thus, it is possible to calculate the contact angle if drop shape is measured. Through use of this method, the contact angles of epoxy resin on various kinds of monofilaments were measured. It was found that this method has practical utility for measurement of the contact angle between liquid and monofilament.     

ON THERMODYNAMICS OF THIN FILMS: THE MECHANICAL EQUILIBRIUM CONDITION AND CONTACT ANGLES

A thermodynamic model for plane parallel thin liquid films applicable to solid-liquid-vapor systems was presented using the detailed method. The film was modeled as a bulk phase bound by two dividing surfaces. The thermodynamic thickness of the film was established as well as excess properties such as film tension. The analysis using this model yielded disjoining pressure definition identical to the literature reports. The effect of definition for contact angle on the resulting mechanical equilibrium condition was also demonstrated. It was concluded that from a theoretical perspective it is important to clearly define contact angles as the angle a sessile drop makes with either the solid phase or the thin film. However, on a practical level for most cases, the difference between using either of the two mechanical equilibrium conditions to determine film tension or contact angle will be minimal (ascertained by an order of magnitude analysis). The attempt was also made to bring about clarity concerning some of the questions in the literature regarding the thermodynamic model for thin films presented by Li and Neumann.     

ON THERMODYNAMICS OF THIN FILMS: THE MECHANICAL EQUILIBRIUM CONDITION AND CONTACT ANGLES

A thermodynamic model for plane parallel thin liquid films applicable to solid-liquid-vapor systems was presented using the detailed method. The film was modeled as a bulk phase bound by two dividing surfaces. The thermodynamic thickness of the film was established as well as excess properties such as film tension. The analysis using this model yielded disjoining pressure definition identical to the literature reports. The effect of definition for contact angle on the resulting mechanical equilibrium condition was also demonstrated. It was concluded that from a theoretical perspective it is important to clearly define contact angles as the angle a sessile drop makes with either the solid phase or the thin film. However, on a practical level for most cases, the difference between using either of the two mechanical equilibrium conditions to determine film tension or contact angle will be minimal (ascertained by an order of magnitude analysis). The attempt was also made to bring about clarity concerning some of the questions in the literature regarding the thermodynamic model for thin films presented by Li and Neumann.