On the Predominant Electron-Donicity of Polar Solid Surfaces

The reasons for the predominant electron-donicity of almost all solid polar surfaces and its implications are discussed in this paper. By contact angle or interfacial tension measurements, the electron-accepting as well as the electron-donating properties of polar liquids can be ascertained, through the interplay between their energies of adhesion and cohesion. For the solid-liquid interface, direct interfacial tension measurements are not possible, but indirectly, solid/liquid interfacial tensions of polar systems can be obtained by contact angle measurement. However, as the energy of cohesion of a solid does not influence the contact angle formed by a liquid drop placed upon its surface, one can only measure the solid surface'ks residual polar property, manifested by the energy of adhesion between solid and liquid. This residual polar property is of necessity the dominant component; in most cases this turns out to be its electron donicity. When, by means of contact angle measurements with polar liquids, both electron-accepting and electron-donating potentials are found on a polar solid, it is most likely still partly covered with a polar liquid: usually water. The amount of residual water of hydration of a polar solid follows from its polar (Lewis acid-base) surface tension component (γ^AB). The degree of orientation of the residual water of hydration on a polar solid can be expressed by the ratio of the electron-donating to electron-accepting potentials (γ^⊖/γ^⊕), measured on the hydrated surface.     

Contact angle,wetting, and adhesion: a critical review

The theory of the contact angle of pure liquids on solids, and of the determination of the surface free energy of solids, γ_s, is reviewed. The basis for the three components γ^LW _s, γ⊕_s, and γ?_s is developed, and an algebraic expression for these properties in terms of measured contact angles is presented. The inadequacy of the 'two-liquid' methodology (which yields a parameter, 'γ^p') is demonstrated. Attention is given to contact angle hysteresis and to the film pressure, π_e. Some recommendations are made with regard to contact angle measurements. A new treatment of hydrophilicity, and of the scale of hydrophobic/hydrophilic behavior, is proposed. It is shown that there are two kinds of hydrophilic behavior, one due to Lewis basicity (electron-donating or proton-accepting structures) and the other due to Lewis acidity (electron-accepting or proton-donating structures). The properties γ^? and γ^⊕ are the quantitative measures of these types of behavior and they are structurally independent of each other. A triangular diagram, with γ^LW at the hydrophobic corner, and γ^⊕ and γ^? at the two hydrophillic corners, is suggested.     

Spreading of liquid drops over solid substrates: 'like wets like'

The classic hydrodynamic wetting theory leads to a linear relationship between spreading speed and the capillary force, being determined only by the surface tension of the liquid and its viscosity. Both equilibrium and dynamic processes of wetting are important in adhesion phenomena. The theory appears to be in good agreement with the results generated from experiments conducted on the spreading of poly(dimethylsiloxane) (PDMS) on soda-lime glass substrate and fails to account for the behavior of other liquids. In this study, the spreading kinetics of four different liquids (hexadecane, undecane, glycerol and water) was determined on three different solids, namely, soda-lime glass, poly(methyl methacrylate) (PMMA) and polystyrene (PS). Droplets from the same liquid allowed to spread under identical conditions on three different substrates produce distinctly different behaviors. The results show that the equilibrium contact angles are qualitatively ranked in accordance with the critical surface tension of wetting (γ _c) of the respective solid, i.e., high-γ _c solids caused the low surface tension liquids to assume the least equilibrium spreading (largest contact angle). On the other end, low-γ _c solids with the lowest surface tension liquid produce the most wetting (smallest contact angle). The results suggest that equilibrium spreading could be explained on the basis of the axiom 'like wets like'; in other words, polar surfaces tend to be wetted by polar liquids and vice versa.     

Low-rate dynamic contact angles on polystyrene and the determination of solid surface tensions

Low-rate dynamic contact angles of 13 liquids on a polystyrene polymer are measured by an automated axisymmetric drop shape analysis – profile (ADSA-P). It is found that 7 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the other 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_lvcosθ 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 (7–13, 24–26). The solid-vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions (33) is found to be 29.8 mJ/m², with a 95% confidence limit of ±0.5 mJ/m² from the experimental contact angles of 6 liquids.     

Influence of the pH of Water on its Electron-Accepticity and Donicity

By means of contact angle measurements on dry layers of electrostatically neutral dextran with pure water (pH 6.1), water acidified with HCl (to pH 1.94) and water made alkaline with NaOH (to pH 12.8), it could be shown that there was essentially no change as a function of pH in the ratio of γ⁺/γ^? of water as compared with the aqueous acid and alkaline solutions. (Here γ⁺ is the Lewis acid parameter of the polar surface tension component of water and γ^? is its Lewis base parameter). In contrast, with contact angles measured with the same liquids on negatively charged clean glass, a significant decrease in contact angle was observed with water at pH 12.8, which was caused by the fact that at this alkaline pH an increase in surface hydrophilicity took place. This is because surfaces that have a given surface electrical potential at neutral pH generally acquire an even higher surface potential under more alkaline conditions which, concomitantly, also gives rise to an increase in surface hydrophilicity, and thus to lower contact angles with water. Finally, contact angles with acid water, pure water, and alkaline water, deposited on hydrophobic Parafilm surfaces, were exactly the same.     

Polar Interfacial Interactions in RPLC

The three principal forces that govern the interaction between dissolved proteins and solid (flat or particulate) surfaces immersed in a polar liquid are: A. Lifshitz-van der Waals forces (LW interactions) B. Polar (hydrogen bond, or Lewis acid-base) forces (AB interactions, which include “hydrophobic” interactions) C. Electrostatic forces (EL interactions) EL interaction energies can be determined via electrokinetic measurements. LW and AB interaction energies are derived from the LW component and the electron-acceptor (γ⊕) and electron-donor (γ⊖) parameters of the AB component of the surface tension, all three of which can be determined by contact angle (Θ) measurements on (a) hydrated layers of protein and (b) flat layers of particulate surface, using at least 3 polar liquids in each case. By this approach, the optimal conditions for attachment as well as for detachment of a given protein to a well-characterized solid surface or particle can be determined quantitatively. Reversed phase liquid chromatography of immunoglobulin G (1) on phenyl Sepharose (2) shows that the elution of the protein, by an increasing concentration of ethylene glycol (EG) in the aqueous medium (3), occurs at the EG concentration where the value of ΔG₁₃₂^TOT changes from negative to positive.     

DETERMINATION OF SOLID SURFACE TENSION FROM CONTACT ANGLES: THE ROLE OF SHAPE AND SIZE OF LIQUID MOLECULES

Accurate surface tension of Teflon® AF 1600 was determined using contact angles of liquids with bulky molecules. For one group of liquids, the contact angle data fall quite perfectly on a smooth curve corresponding to γ_sv = 13.61 mJ/m², with a mean deviation of only ±0.24 degrees from this curve. Results suggest that these liquids do not interact with the solid in a specific fashion. However, contact angles of a second group of liquids with fairly bulky molecules containing oxygen atoms, nitrogen atoms, or both deviate somewhat from this curve, up to approximately 3 degrees. Specific interactions between solid and liquid molecules and reorientation of liquid molecules in the close vicinity of the solid surface are the most likely causes of the deviations. It is speculated that such processes induce a change in the solid–liquid interfacial tension, causing the contact angle deviations mentioned above. Criteria are established for determination of accurate solid surface tensions.     

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.     

Surface free energy and pretilt angle on rubbed polyimide surfaces

To investigate surface free energy of rubbed polyimide surfaces as a function of the rubbing strength, we measured the contact angle of distilled water and methylene iodide on the polyimide surfaces. For this purpose, a main‐chain‐type and two side‐chain‐type polyimides were used. The dispersion force (γ^d) and the polar force (γ ^p) of the rubbed polyimide surfaces was measured. The rubbing induced polarity on the polyimide surfaces. Also, polar forces contributed to form a pretilt angle of liquid crystals on the rubbed polyimide surfaces. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 267–271, 1999     

Low-rate Dynamic Contact Angles on Poly(methyl methacrylate/n-butyl methacrylate) and the Determination of Solid Surface Tensions

Low-rate dynamic contact angles of 12 liquids on a poly(methyl methacrylate/n-butyl methacrylate) P(MMA/nBMA) copolymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 6 liquids yield non-constant contact angles, and/or dissolve the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid- vapour surface tension times the cosine of the contact angle changes smoothly with the liquid-vapour surface tension, i.e., γ_iv cos θ depends only on γ_iv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and noninert (polar and non-polar) surfaces [34-42, 51 -53]. The solid-vapour surface tension calculated from the equation-of-state approach for solid -liquid interfacial tensions [14] is found to be 34.4 mJ/m², with a 95% confidence limit of \pm 0.8mJ/m², from the experimental contact angles of the 6 liquids.     

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.     

Surface energy parameters of polymers from directly measured interfacial tension with probe polymers

The surface energy parameters of polycaprolactone (PCL) were determined at 160 and 180^°C from its interfacial tensions with probe polymers. The probe polymers were polystyrene (PS) and poly(methyl methacrylate) (PMMA). This method is based on the well-known relationship between blend interfacial tension and polymer surface energy parameters, and requires the use of at least two probe polymers, whose surface energy parameters at the temperature of interest have been independently determined. It also requires direct measurement of blend interfacial tension at the high temperatures of interest. The interfacial tensions were obtained from direct measurements by the imbedded fiber retraction method. The following results were obtained: (a) γ ^P (polar component) values for PCL was within the range reported using other methods, (b) γ ^D (dispersion component) values for PCL decreased with increasing temperature, consistent with expectations and (c) γ ^D values for PCL were on the high end, but still within the rather broad range of reported values.     

Determination of the acid-base characteristics of clay mineral surfaces by contact angle measurements-implications for the adsorption of organic solutes from aqueous media

The apolar and the polar (electron-acceptor and electron-donor, or Lewis acid-base) surface tension components and parameters of solid surfaces can be determined by contact angle measurements using at least three different liquids, of which two must be polar. With swelling clay minerals (e.g. smectite clay minerals), smooth contiguous membranes can be fabricated, upon which contact angles can be measured directly. With non-swelling clay minerals (e.g. talc), contact angles can be determined by wicking, i.e. by the measurement of the rate of capillary rise of the liquids in question through thin layers of clay powder adhering to glass plates. The apolar and polar (acid-base) surface tension components and parameters thus found for various untreated and quaternary ammonium base-treated clays allowed the determination of the net interfacial free energy of adhesion of human serum albumin onto the various clay particle surfaces immersed in water. The free energies of adhesion, thus found, correlate well with the experimentally observed degree of adsorption of human serum albumin.     

Acid/Base Components in the Molecular Theory of Adhesion

A method has been devised to determine the acid/base parameters of reference liquids as absolute numbers, and not as values relative to a conventional set of parameters for water. Contact angle measurements are employed, using three liquids on three solids. The theory calls for the solution of nine simultaneous, nonlinear equations in nine variables–and unreasonably formidable task.

A preliminary set of solutions has been computed, for one set of polar liquids on five solids. These results must be rejected on grounds of physical reasonableness. They also fail the test of predicting liquid-liquid interfacial tension, which for miscible liquids must be negative or zero.     

Surface energetics of carbon fibers and its effects on the mechanical performance of CF/EP composites

To exploit the reinforcement potential of the fibers in advanced composites, it is necessary to reach a deeper understanding on the interrelations between fiber surface chemical and energetic characteristics, wetting properties, and mechanical performance. In this study CF/EP was chosen as a model thermoset composite material, whereby a hot-curing epoxy (EP) system served as the matrix. The fibers selected were PAN-based high-tenacity carbon fibers (CF) of varying surface treatment level and/or coating. Surface free energies for the carbon fibers were determined by dynamic contact angle measurements in a variety of test liquids of known polar and dispersive surface tension utilizing a micro-Wilhelmy wetting balance and following the methods proposed by Zisman and Owens and Wendt, respectively. Surface treatment resulted in an increase of the polar fraction of the fiber surface free energy, whereas its dispersive part remained unaffected. The interfacial shear strength (IFSS) as determined in the microdroplet pull-off test was enhanced both by intensification of the surface treatment and sizing the CF with an EP component. A linear relationship between IFSS and the polar fraction of the fiber surface free energy γ^p_s was found. Further attempts were made to find correlations between surface free energy of the CF and laminate strengths measured in shear and transverse tension. © 1996 John Wiley & Sons, Inc.     

DETERMINATION OF SOLID SURFACE TENSION FROM CONTACT ANGLES: THE ROLE OF SHAPE AND SIZE OF LIQUID MOLECULES

Accurate surface tension of Teflon® AF 1600 was determined using contact angles of liquids with bulky molecules. For one group of liquids, the contact angle data fall quite perfectly on a smooth curve corresponding to γ_sv = 13.61 mJ/m², with a mean deviation of only ±0.24 degrees from this curve. Results suggest that these liquids do not interact with the solid in a specific fashion. However, contact angles of a second group of liquids with fairly bulky molecules containing oxygen atoms, nitrogen atoms, or both deviate somewhat from this curve, up to approximately 3 degrees. Specific interactions between solid and liquid molecules and reorientation of liquid molecules in the close vicinity of the solid surface are the most likely causes of the deviations. It is speculated that such processes induce a change in the solid-liquid interfacial tension, causing the contact angle deviations mentioned above. Criteria are established for determination of accurate solid surface tensions.     

Wetting of fat crystals by triglyceride oil and water. 2. adhesion to the oil/water interface

Fat crystals influence the stability of food emulsions, such as margarine, butter, or cream, if adsorbed to the oil/water interface. During the adsorption process, a new fat crystal/water interface is created, while the oil/water interface is lost. The driving force for adsorption is therefore the difference between the interactions between fat crystal/water and oil/water. In this work, we have estimated this interaction difference and compared it to the displacement energy for fat crystals from the oil/water interface to the oil. Our calculations have shown that fat crystal adsorption to the oil/water interface (expressed by contact angle ϑ) is determined by polar energy, excess of fat crystal/water over oil/water (I _sw -I _ow ). The interfacial tension constitutes the resistance force for crystal adsorption to the interface. Polar interaction energy for fat crystal/water is stronger than the polar interaction energy for oil/water in all cases examined (I _sw -I _ow >0). The difference corresponds to about 10⁴–10⁶ hydrogen bonds for a hypothetical fat crystal with a diameter of 1 μm. The displacement energy for fat crystals to oil is lower than the polar energy excess in most cases examined. Thus, an additional interaction between fat crystals and oil makes it easy to displace the crystals to the oil. There is also a relationship between the adhesion tension (-γ _ow • cos ϑ) for the crystals at the oil/water interface and the interfacial tension γ _ow . A straight line of slope -1 is achieved for systems with low interfacial tensions (γ _ow ) and low polar energy excess (I _sw -I _ow ).     

Surface tension parameters of ice obtained from contact angle data and from positive and negative particle adhesion to advancing freezing fronts

From contact angle data obtained on flat ice surfaces with a number of liquids, combined with data on particle and macromolecule adhesion or non-adhesion to advancing freezing fronts, the apolar (Lifshitz-van der Waals or LW) and polar (Lewis acid-base or AB) surface tension (γ) components and parameters have been determined. At 0°C these are γ^LW _iee = 26.9 and γ^AB _ice = 39.6 mJ/m². The latter consists of an electron-acceptor (γ^⊕) and an electron-donor (γ^?) parameter: γ^⊕ = 14 and γ^? = 28 mJ/m².     

Surface tensions and contact angles due to lignin sulphonates in the system: Liquid sulphur,aqueous zinc sulphate and zinc sulphide

Surface tension and contact angle measurements were made in the liquid sulphur-aqueous zinc sulphate-zinc sulphide system at superatmospheric pressures, and showed that, in the absence of surfactants, the liquid sulphur-aqueous solution interfacial tension was 54.0 ± 1.0 mN/m, falling to 27.0-30.0 mN/m when 0.3 g/L or more of lignin sulphonate was added to the solution. At the same time, the contact angle between liquid sulphur and the same solution increased from 80 ± 5° to 148 ± 5°. As a result, the work of adhesion between liquid sulphur and zinc sulphide falls from 63.7 mJ/m² to about 5.3 mJ/m². The results indicate that adsorption of lignin sulphonate occurs on both the mineral-aqueous and the sulphur-aqueous interfaces.