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.     

Investigation of the surface rearrangement of poly(imide-siloxane) using dynamic contact angle measurements

Dynamic contact angle measurements and X-ray photoelectron spectroscopy (XPS) were used to investigate the surface compositions and surface rearrangement of poly(imide-siloxane) with various molecular weights and contents of amine-terminated poly(dimethyl siloxane) (ATPDMS). Four different water contact angles were measured to study the poly(imide-siloxane) surface: the initial advancing angle, the equilibrium advancing angle, the initial receding angle, and the equilibrium receding angle. Poly(imide-siloxane) with 2350 and 4300 g/mol of ATPDMS showed higher initial and equilibrium advancing contact angles than those of poly(imide-siloxane) with 433 g/mol of ATPDMS. Since the mobility of ATPDMS segments depended on the chain length of ATPDMS, the molecular weight of ATPDMS determined the surface composition of poly(imide-siloxane), the rate of surface rearrangement, and the contact angle hysteresis. Poly(imide-siloxane)s with 2850 and 4300 g/mol of ATPDMS were mostly covered with ATPDMS even if just 1 wt% of ATPDMS was incorporated, while poly(imide-siloxane) with 433 g/mol of ATPDMS was mostly covered with polyimide segments and partially with ATPDMS. The rate of surface rearrangement and the contact angle hysteresis decreased with the increasing molecular weight as well as content of ATPDMS. The actual ATPDMS-enriched layer thickness was also investigated by XPS. The actual thickness of the ATPDMS-enriched layer was about 15 nm for 2850 g/mol and 4300 g/mol of ATPDMS-modified poly(imide-siloxane) and about 7.5 nm for 433 g/mol of ATPDMS-modified poly(imide-siloxane)     

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.     

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.     

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.     

Contact angle measurements and interpretation: wetting behavior and solid surface tensions for poly(alkyl methacrylate) polymers

Low-rate dynamic contact angles of a large number of liquids were measured on a poly(ethyl methacrylate) (PEMA) polymer using an automated axisymmetric drop shape analysis profile (ADSA-P). The results suggested that not all experimental contact angles can be used for the interpretation in terms of solid surface tensions: eight liquids yielded non-constant contact angles and/or dissolved the polymer on contact. From the experimental contact angles of the remaining four liquids, we found that the liquid-vapor surface tension times the cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γlv cos ζ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is again in harmony with those from other methacrylate polymer surfaces of different compositions and side-chains. The solid-vapor surface tension of PEMA calculated from the equation-of-state approach for solid-liquid interfacial tensions was found to be 33.6 ± 0.5 mJ/m2 from the experimental contact angles of the four liquids. The experimental results also suggested that surface tension component approaches do not reflect physical reality. In particular, experimental contact angles of polar and nonpolar liquids on polar methacrylate polymers were employed to determine solid surface tension and solid surface tension components. Contrary to the results obtained from the equation-of-state approach, we obtained inconsistent values from the Lifshitz-van der Waals/acid-base (van Oss and Good) approach using the same sets of experimental contact angles.     

Analysis and surface energy estimation of various model polymeric surfaces using contact angle hysteresis

Wetting of hydrophobic polymer surfaces commonly employed in electronic coatings and their interaction with surfactant-laden liquids and aqueous polymer solutions are analyzed using a contact angle hysteresis (CAH) approach developed by Chibowski and co-workers. In addition, a number of low surface tension acrylic monomer liquids, as well as common probe liquids are used to estimate solid surface energy of the coatings in order to facilitate a thorough analysis of surfactant effects in adhesion. Extensive literature data on contact angle hysteresis of surfactant-laden liquids on polymeric surfaces are available and are used here to estimate solid surface energy for further understanding and comparisons with the present experimental data. In certain cases, adhesion tension plots are utilized to interpret wetting of surfaces by surfactant and polymer solutions. Wetting of an ultra-hydrophobic surface with surfactant-laden liquids is also analyzed using the contact angle hysteresis method. Finally, a detailed analysis of the effect of probe liquid molecular structure on contact angle hysteresis is given using the detailed experiments of Timmons and Zisman on a hydrophobic self-assembled monolayer (SAM) surface. Hydrophobic surfaces used in the present experiments include an acetal resin [poly(oxymethylene), POM] surface, and silane, siloxane and fluoro-acrylic coatings. Model surfaces relevant to the literature data include paraffin wax, poly(methyl methacrylate) and a nano-textured surface. Based on the results, it is suggested that for practical coating applications in which surfactant-laden and acrylic formulations are considered, a preliminary evaluation and analysis of solid surface energy can be made using surfactant-laden probe liquids to tailor and ascertain the quality of the final coating.     

The effect of polymer surface on the wetting and adhesion of liquid systems

Young's equation describes the wetting phenomenon in terms of the contact angle between a liquid and a solid surface. However, the contact angle is not the only parameter that defines liquid–solid interactions, an additional parameter related to the adhesion between the liquid drop and the solid surface is also of importance in cases where liquid sliding is involved. It is postulated that wetting which is related to the contact angle, and interfacial adhesion, which is related to the sliding angle, are interdependent phenomena and have to be considered simultaneously. A variety of models that relate the sliding angle to the forces developed along the contact periphery between a liquid drop and a solid surface have been proposed in the literature. Here, a modified model is proposed that quantifies the drop-sliding phenomenon, based also on the interfacial adhesion that develops across the contact area of the liquid/solid interface. Consequently, an interfacial adhesion strength parameter can be defined depending on the mass of the drop, the contact angle and the sliding angle. To verify the proposed approach the adhesion strength parameter has been calculated, based on experimental results, for a number of polymer surfaces and has been correlated with their composition and structure. The interaction strength parameter can be calculated for any smooth surface from measurements of the contact and the sliding angles.     

Interpretation of contact angle hysteresis

Hysteresis of the contact angle, i.e. the difference between the advancing and receding contact angles, is discussed in terms of the liquid film presence behind the drop when it has receded. It is shown that values of receding contact angles in many systems result from a well-defined free energy balance in the solid/liquid drop system. If a duplex film is present behind the drop, experimental receding contact angles up to 15° may be considered as lying in the range of the experimental error. In the case of low-energy solids (e.g. Teflon), it is possible to determine graphically the minimum value of the surface tension below which a liquid will leave a duplex film behind the drop when receding.     

A new model to determine contact angles on swelling polymer particles by the column wicking method

The contact angle determination on swelling polymer particles by the Washburn equation using column wicking measurements may be problematic because swelling occurs during the wicking process. The objective of this research was to develop a new model to more accurately determine contact angles for polymer particles that undergo solvent swelling during the column wicking process. Two phenomena were observed related to the swelling effect during the wicking process: (1) a temperature rise was detected during the wicking process when the swelling polymer particles interacted with polar liquids, and (2) a smaller average capillary radius (r) was obtained when using methanol (polar liquid) compared to using hexane (non-polar liquid). The particle swelling will induce both particle geometry changes and energy loss which will influence the capillary rise rate. The model developed in this study considered the average pore radius change and the energy loss due to the polymer swelling effect. Contact angle comparisons were conducted on wood with formamide, ethylene glycol, and water as test liquids, determined by both the new model and the Washburn equation. It was shown that the contact angles determined by the new model were about 4-37° lower than those determined by the Washburn equation for water, formamide, and ethylene glycol. Todetermine whether the polymer particles are swelling, two low surface tension liquids, one polar (methanol) and the other non-polar (hexane), can be used to determine the average pore radius (r values) using the Washburn equation. If the same r values are obtained for the two liquids, no swelling occurs, and the Washburn equation can be used for the contact angle calculation. Otherwise, the model established in this study should be used for contact angle determination.     

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.     

Effect on wettability of the topography and oxidation state of biaxially oriented poly(propylene) film

Surface topography and surface chemistry heterogeneity are widely accepted as causes of contact angle hysteresis. Contact angle hysteresis occurs on essentially all industrial polymer films. Four unmodified and flame-treated biaxially oriented poly(propylene) (BOPP) films produced from the same poly(propylene) base resin, but differing in surface topography and orientation, were characterized by measurement of the advancing and receding contact angles of water and diiodomethane, by atomic force microscopy (AFM) and by x-ray photoelectron spectroscopy (XPS). Contact angle hysteresis was much larger on flame-treated samples than on untreated samples even though some of the untreated films have significantly different topography at the nanoscale.     

Instability of the three-phase contact region and its effect on contact angle relaxation

Contact angle relaxation was measured for captive air bubbles placed on solid surfaces of varying degrees of heterogeneity, roughness, and stability, in water. The experimental results indicate that both advancing and receding contact angles undergo slow relaxation in these water-air-solid systems, due to instabilities of the three-phase contact line region. It is shown that the advancing contact angle decreases and the receding contact angle increases for many systems over a period of a few hours. Also, examples of reverse progressions are reported. Additionally, in extreme cases, the contact angle oscillates down and up, over and over again, preventing the system from stabilization/equilibration. Four different mechanisms are proposed to explain the contact angle relaxation. These include (i) pinning of the three-phase contact line and its slow evolution; (ii) the formation of microdroplets on the solid surface and their coalescence with the base of the gas bubble, which causes dynamic behavior of the three-phase contact line; (iii) deformation of the solid surface and its effect on the apparent contact angle; and (iv) chemical instability of the solid.     

Effects of hydroxypropyl cellulose and hydroxyethyl cellulose adsorption on the wetting of low energy solid surfaces

Advancing and receding contact angles on paraffin (PF) and poly(methyl methacrylate) (PMMA) have been measured for solutions of hydroxypropyl cellulose (HPC) and hydroxycthyl cellulose (HEC), two hydrophohic polymers differing considerably in their surface activity at the air-water interface. Consistent with observations made previously with hydrocarbon-chain surfactant solutions, advancing contact angles with PF are the same as those observed with pure liquids having the same surface tension, while those with PMMA are considerably greater. Receding contact angles for these polymer solutions appear to he the same as those observed with pure liquids. Consequently, this leads to less wettability in an advancing mode and greater apparent contact angle hysteresis than might be expected. Concurrent studies of HPC and HEC adsorption with the same PMMA samples used in the wetting studies and estimates of adsorption of HPC and HEC at the air-water interface indicate that these effects on wetting are due primarily to greater nonspecific polymer adsorption to the air-water interface than to the more polar PMMA-water interface.     

Surface nanostructures and dynamic contact angles of functionalized poly(ethylene terephthalate) fibers

An approach (a combination of techniques) to studying poly(ethylene terephthalate) (PET) fibers metal-coated by the sputtering of copper is reported. The effects of copper coatings on the surface morphology, surface chemistry, and surface energy were investigated with atomic force microscopy (AFM), energy-dispersive X-ray (EDX) analysis, and dynamic contact angle measurements. Functional nanostructures formed by sputter coating on the fiber surface were revealed with AFM. The introduction of copper onto the fiber surface was also detected by EDX analysis. The fibers functionalized by the sputter coating resulted in changes in the surface energy measured with the advancing and receding contact angles. Both the advancing and receding contact angles were reduced after sputter coating by copper, but the contact angle hysteresis was significantly increased as the coating was applied. The surface resistivity measurements revealed that sputter coating by copper considerably improved the surface conductivity of the PET fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The static contact angle hysteresis obtained by different experiments for the system PTFE/water

Different experimental methods have been used to determine the static contact angle hysteresis of the system polytetrafluoroethylene/water and the results compared. While the Wilhelmy plate method is not influenced by methodical variations, contact angles determined by the sessile drop and the pendant bubble methods vary with the drop or bubble diameter up to a minimal diameter d_K of the contact area with the solid. This condition seems to be a universal one and should always be checked to ensure that the measured values are comparable. Contact angles calculated from the geometrical parameters of a drop or bubble should be used with care. The surface energetic characters for the PTFE/water are δθ = 19.5°, θ_{a, e} = 108.5° and θ_{r, e} = 89°.     

Adhesion of solid particles to gas bubbles. Part 2: Experimental

In slurry bubble columns, the adhesion of solid catalyst particles to bubbles may significantly affect the G-L mass transfer and bubble size distribution. This feature may be exploited in design by modifying the hydrophilic or hydrophobic nature of the particles used. Previously we have proposed a generalised model, describing the adhesion of particles to G-L interface under stagnant conditions. In this work, we studied the adhesion of particles characterised by different degree of hydrophobicity and porosity: non-porous polystyrene and glass beads, unmodified and hydrophobised mesoporous silica, and activated carbon particles. Images recorded at high optical magnification show the particles adhering to gas bubbles individually or as aggregates. In aqueous media, higher liquid surface tension and particle surface hydrophobicity increase the adhesion strength and the tendency of particles to agglomerate, in agreement with the model. The adhesion of non-porous rough-surface particles to gas bubbles can be characterised by the receding contact angle. The advancing contact angle represents better the adhesion of the same particles to liquid droplets. We found that the “effective” contact angle of porous particles is much lower than an “intrinsic” contact angle calculated from the heat of immersion in water, or measured by sessile drop method. An equivalent contact angle derived from the Cassie rule explains the wetting behaviour of particles having the pores filled with liquid.