Interpretation of contact angle measurements on two different fluoropolymers for the determination of solid surface tension

Contact angle measurements with a large number of liquids on the semi-fluorinated acryl polymer EGC-1700 films are reported. The surface tension was determined to be gammasv=13.84 mJ/m2 from contact angles of octamethylcyclotetrasiloxane (OMCTS) and decamethylcyclopentasiloxane (DMCPS). Inertness of these two liquids makes them ideal for determination of surface tension of low-energy fluoropolymers. On the other hand, contact angles of many other liquids deviated somewhat from a smooth contact angle pattern that represents the EGC-1700 surface tension. It is argued that noninertness of the molecules of these liquids gives rise to specific interactions with the polymer film, causing the deviations. Furthermore, contact angles of a series of n-alkanes (n-hexane to n-hexadecane) showed systematic deviations from this curve, similar to the trend observed for n-alkanes/Teflon AF 1600 systems studied earlier. Adsorption of vapor of short-chain liquids onto the polymer film caused their contact angles to fall above the gammasv=13.84 mJ/m2 curve, and a parallel alignment of molecules of the long-chain n-alkanes in the vicinity of the solid was the explanation for the deviation of their contact angles below it. It is found that vapor adsorption effect is more significant in the case of Teflon AF 1600, while the alignment of liquid molecules close to the surface is more pronounced for EGC-1700.     

Recent progress in the determination of solid surface tensions from contact angles

Advancing contact angles of different liquids measured on the same solid surface fall very close to a smooth curve when plotted as a function of liquid surface tension, i.e., gamma(lv)costheta versus gamma(lv). Changing the solid surface, and hence gamma(sv), shifts the curve in a regular manner. These patterns suggest that gamma(lv)costheta depends only on gamma(lv) and gamma(sv). Thus, an "equation of state for the interfacial tensions" was developed to facilitate the determination of solid surface tensions from contact angles in conjunction with Young's equation. However, a close examination of the smooth curves showed that contact angles typically show a scatter of 1-3 degrees around the curves. The existence of the deviations introduces an element of uncertainty in the determination of solid surface tensions. Establishing that (i) contact angles are exclusively a material property of the coating polymer and do not depend on experimental procedures and that (ii) contact angle measurements with a sophisticated methodology, axisymmetric drop shape analysis (ADSA), are highly reproducible guarantees that the deviations are not experimental errors and must have physical causes. The contact angles of a large number of liquids on the films of four different fluoropolymers were studied to identify the causes of the deviations. Specific molecular interactions at solid-vapor and/or solid-liquid interfaces account for the minor contact angle deviations. Such interactions take place in different ways. Adsorption of vapor of the test liquid onto the solid surface is apparently the only process that influences the solid-vapor interfacial tension (gamma(sv)). The molecular interactions taking place at the solid-liquid interface are more diverse and complicated. Parallel alignment of liquid molecules at the solid surface, reorganization of liquid molecules at the solid-liquid interface, change in the configuration of polymer chains due to contact with certain probe liquids, and intermolecular interactions between solid and liquid molecules cause the solid-liquid interfacial (gamma(sl)) tension to be different from that predicted by the equation of state, i.e., gamma(sl) is not a precise function of gamma(lv) and gamma(sv). In other words, the experimental contact angles deviate from the "ideal" contact angle pattern. Specific criteria are proposed to identify probe liquids which eliminate specific molecular interactions. Octamethylcyclotetrasiloxane (OMCTS) and decamethylcyclopentasiloxane (DMCPS) are shown to meet those criteria, and therefore are the most suitable liquids to characterize surface tensions of low energy fluoropolymer films with an accuracy of +/-0.2 mJ/m2.     

Determination of accurate surface tensions of maleimide copolymers containing fluorinated side chain from contact angle measurements

Surface energetics of two fluorinated maleimide copolymers containing fluorinated side chain, i.e., poly(ethene-alt-N-(4-(perfluoroheptylcarbonyl)aminobutyl)maleimide) (ETMF) and poly(octadecene-alt-N-(4-(perfluoroheptylcarbonyl)aminobutyl)maleimide) (ODMF), are studied by contact angle measurements with 10 liquids consisting of fairly bulky molecules. Because of the inertness of octamethylcyclotetrasiloxane (OMCTS) and decamethylcyclopentasiloxane (DMCPS) molecules, their contact angles are used to determine the surface tension of the two polymers. It is found that other liquids show specific interactions with the ETMF films, and their contact angles deviate from a smooth curve that represents the surface tension of ETMF, i.e., 11.00 mJ/m². On ODMF surfaces, only OMCTS and DMCPS yield useful contact angles. Other liquids either dissolve the polymer film or show a slip-stick pattern. This finding is discussed in terms of interactions between segments of the polymer chains and the test liquids. OMCTS and DMCPS are suggested as the appropriate probe liquids, meeting specific criteria necessary for the determination of accurate surface tension of fluoropolymers.     

Influence of electronic properties of naphthalene compounds on contact angles

Contact angles of a homologous series of naphthalene compounds on films of a fluorinated acrylate polymer (EGC-1700) deviate from an ideal pattern of contact angles. The deviations increase with the electronegativity of the constituent atoms of the liquid molecules. The results suggest that an uneven distribution of electrostatic charges over the molecules creates strong dipole moments, giving rise to fairly strong dipole-dipole and dipole-induced dipole interactions between liquid molecules and the EGC-1700 chains, which have large dipole moments. In comparison, contact angles of the same probe liquids on the films of Teflon AF 1600, which have small dipole moments, fall on a smooth curve representing the surface tension of the polymer film.     

Study of the advancing and receding contact angles: liquid sorption as a cause of contact angle hysteresis

Two types of experiments were used to study the behavior of both advancing and receding contact angles, namely the dynamic one-cycle contact angle (DOCA) and the dynamic cycling contact angle (DCCA) experiments. For the preliminary study, DOCA measurements of different liquids on different solids were performed using an automated axisymmetric drop shape analysis-profile (ADSA-P). From these experimental results, four patterns of receding contact angle were observed: (1) time-dependent receding contact angle; (2) constant receding contact angle; (3) 'stick/slip'; (4) no receding contact angle. For the purpose of illustration, results from four different solid surfaces are shown. These solids are: FC-732-coated surface; poly(methyl methacrylate/n-butyl methacrylate) [P(MMA/nBMA)]; poly(lactic acid) (DL-PLA); and poly(lactic/glycolic acid) 50/50 (DL-PLGA 50/50). Since most of the surfaces in our studies exhibit time dependence in the receding contact angle, a more extended study was conducted using only FC-732-coated surfaces to better understand the possible causes of decreasing receding contact angle and contact angle hysteresis. Contact angle measurements of 21 liquids from two homologous series (i.e. n-alkanes and 1-alcohols) and octamethylcyclotetrasiloxane (OCMTS) on FC-732-coated surfaces were performed. It is apparent that the contact angle hysteresis decreases with the chain length of the liquid. It was found that the receding contact angle equals the advancing angle when the alkane molecules are infinitely large. These results strongly suggest that the chain length and size of the liquid molecule could contribute to contact angle hysteresis phenomena. Furthermore, DCCA measurements of six liquids from the two homologous series on FC-732-coated surfaces were performed. With these experimental results, one can construe that the time dependence of contact angle hysteresis on relatively smooth and homogeneous surfaces is mainly caused by liquid retention/sorption. The results also suggested that the contact angle hysteresis will eventually approach a steady state, where the rate of liquid retention-evaporation or sorption process would balance out each other. If the existence of contact angle hysteresis can be attributed to liquid sorption/retention, one should only use the advancing contact angles (measured on a dry surface) in conjunction with Young's equation for surface energetic calculations.     

Determination of line tension for systems near wetting

Contact angle measurements for three n-alkanes, heptane, octane, and nonane, on two different self-assembled surfaces (SAM) are reported as a function of drop size. These liquids all formed low contact angles (below 20 degrees ); the measurements were performed using an accurate method for systems with low contact angle, ADSA-D. The observed drop size dependence of the contact angles was interpreted using the modified Young equation. It was concluded that the observed drop size dependence of contact angles was due to line tension. The choice of systems also provided the opportunity to examine the behavior of the line tension for systems near wetting (i.e., low contact angles). It was determined that the line tension is positive and ranges from below 10(-7) to just below 10(-6) J/m for the systems studied; the observations suggested that the line tension decreases as the contact angle decreases and likely vanishes at complete wetting.     

Low‐rate dynamic contact angles on poly(methyl methacrylate/ethyl methacrylate, 30/70) and the determination of solid surface tensions

Low‐rate dynamic contact angles of 12 liquids on a poly(methyl methacrylate/ethyl methacrylate, 30/70) P(MMA/EMA, 30/70) copolymer were measured by an automated axisymmetric drop shape analysis‐profile (ADSA‐P). It was found that five liquids yield nonconstant contact angles, and/or dissolve the polymer on contact. From the experimental contact angles of the remaining seven liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension (i.e., γ_l|Kv cos θ depends only on γ_l|Kv for a given solid surface or solid surface tension). This contact angle pattern is in harmony with those from other methacrylate polymer surfaces previously studied.^45,50 The solid–vapor surface tension calculated from the equation‐of‐state approach for solid–liquid interfacial tensions¹⁴ is found to be 35.1 mJ/m², with a 95% confidence limit of ± 0.3 mJ/m², from the experimental contact angles of the seven liquids. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2039–2051, 1999     

Equilibrium contact angles of liquid droplets on ideal rough solids

This work proposes a theoretical model for predicting the apparent equilibrium contact angle of a liquid on an ideal rough surface that is homogeneous and has a negligible body force, line tension, or contact angle hysteresis between solid and liquid. The model is derived from the conservation equations and the free-energy minimization theory for the changes of state of liquid droplets. The work of adhesion is expressed as the contact angles in the wetting process of the liquid droplets. Equilibrium contact angles of liquid droplets for rough surfaces are expressed as functions of the area ratios for the solid, liquid, and surrounding gas and the roughness ratio and wetting ratio of the liquid on the solid for the partially and fully wet states. It is found that the ideal critical angle for accentuating the contact angles by the surface roughness is 48°. The present model is compared with existing experimental data and the classical Wenzel and Cassie-Baxter models and agrees with most of the experimental data for various surfaces and liquids better than does the Wenzel model and accounts for trends that the Wenzel model cannot explain.     

Validity of the "sharp-kink approximation" for water and other fluids

The contact angle of a liquid droplet on a solid surface is a direct measure of fundamental atomic-scale forces acting between liquid molecules and the solid surface. In this work, the validity is assessed of a simple equation, which approximately relates the contact angle of a liquid on a surface to its density, its surface tension, and the effective molecule-surface potential. This equation is derived in the sharp-kink approximation, where the density profile of the liquid is assumed to drop precipitously within one molecular diameter of the substrate. It is found that this equation satisfactorily reproduces the temperature-dependence of the contact angle for helium on alkali metal surfaces. The equation also seems be applicable to liquids such as water on solid surfaces such as gold and graphite, on the basis of a comparison of predicted and measured contact angles near room-temperature. Nevertheless, we conclude that, to fully test the equation's applicability to fluids such as water, it remains necessary to measure the contact angle's temperature-dependence. We hypothesize that the effects of electrostatic forces can increase with temperature, potentially driving the wetting temperature much higher and closer to the critical point, or lower, closer to room temperature, than predicted using current theories.     

Effect of surfactants on wetting of super-hydrophobic surfaces

The effect of surfactants on wetting behavior of super-hydrophobic surfaces was investigated. Super-hydrophobic surfaces were prepared of alkylketene dimer (AKD) by casting the AKD melt in a specially designed mold. Time-dependent studies were carried out, using the axisymmetric drop shape analysis method for contact angle measurement of pure water on AKD surfaces. The results show that both advancing and receding contact angles of water on the AKD surfaces increase over time ( approximately 3 days) and reach the values of about 164 and 147 degrees , respectively. The increase of contact angles is due to the development of a prickly structure on the surface (verified by scanning electron microscopy), which is responsible for its super-hydrophobicity. Aqueous solutions of sodium acetate, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, and n-decanoyl-n-methylglucamine were used to investigate the wetting of AKD surfaces. Advancing and receding contact angles for various concentrations of different surfactant solutions were measured. The contact angle results were compared to those of a number of pure liquids with surface tensions similar to those of surfactant solutions. It was found that although the surface tensions of pure liquids and surfactant solutions at high concentrations are similar, the contact angles are very different. Furthermore, the usual behavior of super-hydrophobic surfaces that turn super-hydrophilic when the intrinsic contact angle of liquid on a smooth surface (of identical material) is below 90 degrees was not observed in the presence of surfactants. The difference in the results for pure liquids and surfactant solutions is explained using an adsorption hypothesis.     

Photon control of liquid motion on reversibly photoresponsive surfaces

The movement of a liquid droplet on a flat surface functionalized with a photochromic azobenzene may be driven by the irradiation of spatially distinct areas of the drop with different UV and visible light fluxes to create a gradient in the surface tension. In order to better understand and control this phenomenon, we have measured the wetting characteristics of these surfaces for a variety of liquids after UV and visible light irradiation. The results are used to approximate the components of the azobenzene surface energy under UV and visible light using the van Oss-Chaudhury-Good equation. These components, in combination with liquid parameters, allow one to estimate the strength of the surface interaction as given by the advancing contact angle for various liquids. The azobenzene monolayers were formed on smooth air-oxidized Si surfaces through 3-aminopropylmethyldiethoxysilane linkages. The experimental advancing and receding contact angles were determined following azobenzene photoisomerization under visible and ultraviolet (UV) light. Reversible light-induced advancing contact-angle changes ranging from 8 to 16 degrees were observed. A large reversible change in contact angle by photoswitching of 12.4 degrees was achieved for water. The millimeter-scale transport of 5 microL droplets of certain liquids was achieved by creating a spatial gradient in visible/UV light across the droplets. A criterion for light-induced motion of droplets is shown to be consistent with the response of a variety of liquids. The type of light-driven fluid movement observed could have applications in microfluidic devices.     

Experimental Study on Contact Angle Patterns: Liquid Surface Tensions Less Than Solid Surface Tensions

The interpretation of contact angles in terms of solid surface tensions is not trivial. In the past, we and others have postulated that contact angles should be measured with liquid of surface tension larger than the anticipated solid surface tension, i.e., gamma(lv)>gamma(sv). This has recently been disputed. It is also not entirely obvious how to proceed experimentally since gamma(sv) is not known initially. Typically, one starts with a liquid of high gamma(lv) (such as water) and goes lower. We have stopped in the past when the contact angles became small. A question arises as to what would happen if we would go on. Contact angles of liquids with gamma(lv) less than or near gamma(sv) were measured on eight polymer-coated solid surfaces. The experimental contact angle patterns for gamma(lv)gamma(sv) were compared. Results suggest that contact angle interpretation in terms of solid surface tensions requires contact angles to be measured for gamma(lv)>gamma(sv) because the Young equation is not applicable for gamma(lv)相似文献   

Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency

Recent strategies to prepare “omniphobic” surfaces have demonstrated that minimizing contact angle hysteresis (CAH) is the key criterion for effectiveness. CAH is affected by chemistry and topography defects at the molecular and higher levels, thus most surfaces exhibit significant CAH. Preparative methods for stable coatings on smooth substrates with negligible CAH (<2°) for a broad range of liquids have not been reported. In this work, we describe a simple and rapid procedure to prepare omniphobic surfaces that are stable under pressure and durable at elevated temperatures. Consistent with theory, they exhibit sliding angles that decrease with liquid surface tension. Slippery omniphobic covalently attached liquid (SOCAL) surfaces are obtained through acid‐catalyzed graft polycondensation of dimethyldimethoxysilane. The smooth, stable, and temperature‐resistant coatings show extremely low CAH (≤1°) and low sliding angles for liquids that span surface tensions from 78.2 to 18.4 mN m^?1.     

Quantitative testing of robustness on superomniphobic surfaces by drop impact

The quality of a liquid-repellent surface is quantified by both the apparent contact angle θ(0) that a sessile drop adopts on it and the value of the liquid pressure threshold the surface can withstand without being impaled by the liquid, hence maintaining a low-friction condition. We designed surfaces covered with nanowires obtained by the vapor-liquid-solid (VLS) growth technique that are able to repel most of the existing nonpolar liquids including those with very low surface tension as well as many polar liquids with moderate to high surface tension. These superomniphobic surfaces exhibit apparent contact angles ranging from 125 to 160° depending on the liquid. We tested the robustness of the surfaces against impalement by carrying out drop impact experiments. Our results show how this robustness depends on Young's contact angle θ(0) related to the surface tension of the liquid and that the orientational growth of nanowires is a favorable factor for robustness.     

Drop size dependence of contact angles on two fluoropolymers

Young’s equation predicts that the contact angle of a liquid drop is independent of its size. Nevertheless, large drop size dependences of contact angles have been observed, especially for millimetre-sized drops, on a variety of solid surfaces. We report new measurements of drop size dependence of contact angles for several liquids on two fluoropolymer surfaces, Teflon AF 1600 and EGC-1700. We demonstrate a new strategy for contact angle measurement that allows detection of approximately 0.1° changes in the contact angle during the growth of a drop. We find that on the surfaces examined, drop size dependence of contact angles is ten times smaller than on all previously studied fluoropolymers at the millimetre scale. The data are insensitive to various attempted surface modifications. We discuss the interpretation of the data and possible physical sources.     

Surface free energy of a solid from contact angle hysteresis

Nature of contact angle hysteresis is discussed basing on the literature data (Colloids Surf. A 189 (2001) 265) of dynamic advancing and receding contact angles of n-alkanes and n-alcohols on a very smooth surface of 1,1,2,-trichloro-1,2,2,-trifluoroethane (FC-732) film deposited on a silicon plate. The authors considered the liquid absorption and/or retention (swelling) processes responsible for the observed hysteresis. In this paper hysteresis is considered to be due to the liquid film left behind the drop during retreating of its contact line. Using the contact angle hysteresis an approach is suggested for evaluation of the solid surface free energy. Molecular spacing and the film structure are discussed to explain the difference in n-alkanes and n-alcohols behaviour as well as to explain the difference between dispersion free energy gamma(s)(d) and total surface free energy gamma(s)(tot) of FC-732, as determined from the advancing contact angles and the hysteresis, respectively.     

Contact angle kinetics of human albumin solutions at solid surfaces

Contact angle kinetics of sessile drops of albumin solution on hydrophilic acetal and hydrophobic FC 721 surfaces were measured using axisymmetric drop shape analysis. Young's equation is used to calculate the solid/liquid interfacial tension from measured contact angles and surface tensions as a function of time. The change in solid/liquid interfacial tension is a result of protein adsorption. It indicates that at the hydrophilic acetal surface the albumin molecules, interact only weakly, whereas the interaction with the hydrophobic FC 721 surface is quite strong.     

Thermoresponsive poly(N-isopropylacrylamide) copolymers: contact angles and surface energies of polymer films

Surface properties of poly(N-isopropylacrylamide) (PNIPAM) copolymer films were studied by contact angle measurements and optical and atomic force microscopy. We prepared a series of copolymers of N-isopropylacrylamide with N-tert-butylacrylamide (NtBA) in order of increasing hydrophobicity. The measurements of the advancing contact angle of water at 37 degrees C were hampered by the observation of a distinct stick/slip pattern on all polymers in the series with the exception of poly(NtBA) (PNtBA). We attributed this behavior to the film deformation by the vertical component of liquid surface tension leading to the pinning of the moving contact line. This was confirmed by the observation of a ridge formed at the pinned contact line by optical microscopy. However, meaningful contact (without the stick/slip pattern and with a time-independent advancing contact angle) angles for this thermoresponsive polymer series could be obtained with carefully selected organic liquids. We used the Li and Neumann equation of state to calculate the surface energy and contact angles of water for all polymers in the series of copolymers and van Oss, Chaudhury, and Good (vOCG) acid-base theory for PNtBA. The surface energies of the thermoresponsive polymers were in the range of 38.9 mJ/m2 (PNIPAM) to 31 mJ/m2 (PNtBA) from the equation of state approach. The surface energy of PNtBA calculated using vOCG theory was 29.0 mJ/m2. The calculated contact angle for PNIPAM (74.5 +/- 0.2 degrees ) is compared with previously reported contact angles obtained for PNIPAM-modified surfaces.     

Mean-field theory of liquid droplets on roughened solid surfaces: application to superhydrophobicity

We present calculations of the density distributions and contact angles of liquid droplets on roughened solid surfaces for a lattice gas model solved in a mean-field approximation. For the case of a smooth surface, this approach yields contact angles that are well described by Young's equation. We consider rough surfaces created by placing an ordered array of pillars on a surface, modeling so-called superhydrophobic surfaces, and we have made calculations for a range of pillar heights. The apparent contact angle follows two regimes as the pillar height increases. In the first regime, the liquid penetrates the interpillar volume, and the contact angle increases with pillar height before reaching a constant value. This behavior is similar to that described by the Wenzel equation for contact angles on rough surfaces, although the contact angles are underestimated. In the second regime, the liquid does not penetrate the interpillar volume substantially, and the contact angle is independent of the pillar height. This situation is similar to that envisaged in the Cassie-Baxter equation for contact angles on heterogeneous surfaces, but the contact angles are overestimated by this equation. For larger pillar heights, two states of the droplet can be observed, one Wenzel-like and the other Cassie-like.     

Low-rate dynamic contact angles on poly(n-butyl methacrylate) and the determination of solid surface tensions

 Low-rate dynamic contact angles of 22 liquids on a poly(n-butyl methacrylate) (PnBMA) polymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 16 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension, i.e. γ_lv cos θ depends only on γ_lv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and non-inert (polar and non-polar) surfaces [34–37, 45–47]. The solid–vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions [14] is found to be 28.8 mJ/m², with a 95% confidence limit of ±0.5 mJ/m², from the experimental contact angles of the 6 liquids. Received: 12 September 1997 Accepted: 22 January 1998