Effect of Adsorbed Water on the Spreading of Organic Liquids on Soda-Lime Glass

The spreading behavior and equilibrium contact angle, θ, of organic liquids on soda-lime glass surfaces were observed at relative humidities (rh) varying from 1 to 95%. Increasing rh increased θ for many nonhydrophilic liquids on glass; no comparable effects occurred with nonadsorptive solid surfaces. The decrease in wettability of the glass with increasing rh resulted from the physical adsorption of a surface layer of water molecules sufficient to convert the normally high-energy glass surface into one that behaves as a low-energy surface, i.e. a surface with a low critical surface tension for spreading, γ_c, toward nonhydrophilic liquids. As the thickness of the adsorbed water layer increased, glass behaved like a surface with progressively decreasing γ_c, approaching that of bulk water. These results are discussed in relation to the effect of moisture on the spreading or adhesion of resins to glass and other hydrophilic solids.     

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.     

Dynamic wetting of glass fibre and polymer fibre

To achieve high strength and chemical resistance in glass-reinforced plastics, it has been found essential to have a good bond between matrix and reinforcement. To obtain this bond it is necessary that good wetting of reinforcement by matrix must occur at some stage in the production cycle. Modern process developments have reduced the time during which wetting can occur to a few seconds in continuous sheeting manufacture. The wetting stage of this process has been investigated by the observation of dynamic contact angles. The rate of wetting has been found to be controlled by liquid flow and not surface tension at high processing speeds. Breakdown of this flow and intermittent wetting have been observed directly. When low energy surfaces are wetted by water, a different limiting factor is found. It is observed that a maximum dynamic contact angle is reached at relatively low wetting rates. It is suggested that these maximum angles offer a new means of assessing Zisman's ‘critical surface tension’ (γ_c) and by an extension of the technique may enable values of spreading pressure (π) to be measured.     

Critical Surface Tension of Non-crosslinking Linear Low Density Polyethylene-graft-acrylic Acid by the Contact Angle Method

Abstract

The contact angles θ of polar liquid on surface of non-crosslinking linear low density polyethylene-graft-acrylic acid (LLDPE-g-AA) were measured. The critical surface tension (γ_c) of LLDPE-g-AA films were evaluated by three different plots, the Zisman plot, the Young-Dupre-Good-Girifalco plot, and the log(1 + cos θ) versus log θ _L , plot. The θ _c of LLDPE-g-AA obtained by the 1 + cosθ versus θ _L ^?1/2 plot were higher than those obtained by other plots.     

The gap between the measured and calculated liquid–liquid interfacial tensions derived from contact angles

We present our new findings about the causes of discrepancies between the measured and calculated liquid-liquid interfacial tensions derived from contact angles. The calculated ones are based on either the equation developed by Fowkes or that by van Oss, Chaudhury and Good (VCG), while the measured ones are based on the sessile drop, weight-volume by Jańzuk et al. and the axisymmetric drop shape analysis (ADSA) by Kwok and Neumann. Indeed, there are deviations between the calculated and measured results. For an immiscible liquid-liquid or liquid-solid interface, we prefer to employ Harkins spreading model, which requires the interfacial tension to be constant. However, for the initially immiscible liquid-liquid pairs, we propose an adsorption model, and our model requires the interfacial tension to be varying and the surface tensions of bulk liquids at a distance from the interface to remain unchanged. Thus, the difference between the initial and final interfacial spreading coefficients (S_i) equals the equilibrium interfacial film pressure (π_i)_e. According to our findings, the calculated interfacial tension represents the initial value (γ₁₂)_o, which differs from the equilibrium value (γ₁₂)_e obtained experimentally after some time delay. This expected gap at a reasonable time frame is chiefly caused by the equilibrium interfacial film pressure between the two liquids. The initial (or calculated) interfacial tension can be positive or negative, while the equilibrium (or measured) one can reach zero. In fact, the former is shown to have more predictive value than the latter. A negative initial interfacial tension is described to favor miscibility or spontaneous emulsification but it tends to revert to zero instantaneously. Thus, a miscible liquid mixture should have zero interfacial tension. In response to recent papers by Kwok et al., we show that the disagreements between the calculated and measured interfacial tensions are definitely not caused by the failure of the VCG approach. Correct interfacial tensions are calculated for liquid pairs containing formamide or dimethyl sulfoxide (DMSO) by using the dispersion components cited in Fowkes et al.'s later publication. With the corrected surface tension components, the equilibrium interfacial film pressures (π_i)_e's for at least 34 initially immiscible liquid pairs have been calculated. These values are generally lower than the corresponding spreading pressures π_e's obtained by others using the Harkins model. Recently, we established a relationship between these two film pressures with the Laplace equation and found a new criterion for miscibility to be (π_i)_e = π_e.     

Studies on synthetic-polymer plates with high surface energy. IV. Determination of critical surface tension with aqueous solutions of salts

The critical surface tension (γ_c) of synthetic-polymer plates with a functional group (amide, sulfonic, or carboxyl group) on their surface was determined by the Zisman plot using series of pure liquids (thiodiglycol, formamide, and water) and the aqueous solutions of the salts (NaCl, NaNO₃, etc.) as a hydrogen-bonding liquid. The Zisman plots gave a straight line, and the trends in the γ_c values coincide with those in the hydrophilicity anticipated from the θ values. The use of the aqueous salt solution coupled with the pure liquids as a hydrogen-bonding liquid offers a practical determination procedure of the γ_c value for the materials with high surface energy.     

Correlation of Flocculation and Agglomeration of Dolomite with its Wettability

Wettability is an important parameter which affects the shear flocculation and oil agglomeration behaviors of minerals. The critical surface tension of wetting (γ_c) as a wettability parameter describes wetting characteristics of any mineral. In this study, the correlation of shear flocculation and oil agglomeration processes of dolomite with its wettability parameter is investigated. The experimental studies have indicated that these processes improved with decreasing wettability depending on the increase of oleate adsorption despite a simultaneous increase in the zeta potential of dolomite. On the other hand, the flocculation and agglomeration of dolomite decreased with decreasing surface tension and did not occur below a particular value of surface tension, corresponding to the critical surface tension of wetting (γ_c) and the critical solution surface tension (γ_c-a) values, respectively. Also, the γ_c-a values are slightly higher than the γ_c values, indicating that the agglomeration of the particles requires a lower wettability.     

HOW LIQUIDS SPREAD ON SOLIDS

A theory of the wetting of solids by liquids is put forward. The theory accounts for capillary pressure gradient, gravitational potential gradient, surface tension gradient, disjoining pressure gradient driving forces of flow in thick thin-films and of surface diffusion in thin thin-films. Disjoining pressure stems from the way intermolecular forces aggregate in submicroscopically thin films. For thick thin-films of slowly varying thickness the lubrication approximation to velocity distributions is appropriate. With this approximation the spontaneous, unsteady, two-dimensional spreading of liquid is shown to be governed by a nonlinear convective-diffusion equation for the evolution of the film thickness profile. The predictions of the theory agree with Marmur and Lelah's (1980, 1981) observations of water drops spreading on glass and with Bascom, Cottington and Singleterry's (1964) and Ludviksson and Lightfoot's (1971) observations of oils spreading on high energy surfaces. The theory is used to analyze Derjaguin and co-workers' (1944, 1957, 1970) blowing-off experiments designed to measure thin-film rheology. The theory is also used to buttress the proposition that much contact angle hysteresis is due simply to slow attainment of equilibrium.     

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.     

Estimation of the Surface Energy of Polymer Solids

The methods to estimate the surface tension of polymer solids using contact angles have been reviewed in the first part. They are classified into the following three groups depending on the theories or the equations applied: (1) the methods using the Young's equation alone, (2) the methods using the combined equation of Young and Good-Girifalco, and (3) the methods using the equations of work of adhesion. Some notes and comments are given for each method and results are compared with each other. The two-liquids method for rather high energy surface is also introduced.

Next, some new possibilities to evaluate the surface tension of polymer solids are presented by our new contact angle theory in consideration of the friction between a liquid drop and a solid surface. The advancing and receding angles of contact (θ _a and θ _r ) are explained by the frictional tension γ_F and accordingly two kinds of the critical surface tension γ_C (γ_Ca and γ_Cr ) are given.

This work has shown that one of the recommendable ways to evaluate γ_S is either the maximum γ_LV cos θ_a or the maximum γ_C using the advancing contact angle θ_a alone, and another way is the arithmetic or the harmonic mean of the γ_Ca and γ_Cr . A depiction to determine the γ_C such as ln(1 + cos θ₀ ) vs. γ_LV with cos θ₀ = (cos θ₀ + cos θ_r )/2 has also been proposed.     

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.     

Surface Modification of Fluorinated Polymers by Microwave Plasmas

We developed a new plasma treating method, incorporating the use of microwaves generated by an electronic cooking range. Using this method, polytetrafluorethylene (PTFE) and a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) were treated. Dialkylphthalates (DAP) were used as the standard liquids of contact angle measurements for evaluation of the wetting properties of plasma treated polymers. The components of surface tension (γ_L) due to the dispersion force (γ^d _L) and the polar force (γ^P _L) of DAP were calculated by Fowkes' equation from the contact angles (θ) on polypropylene. After plasma treatment cos θ of several standard liquids on PTFE and FEP increased. The linear relationship between γ_L(1 + cos θ)/(γ^d _L)^½ and (γ^P _L/γ^P _L)^½ was verified. γ_s and γ^d _s and γ^d _s of the plasma treated PTFE and FEP also increased. From the results of ESCA analysis, it was found that a significant amount of oxygen was introduced to the polymer surface by the plasma treatment. Peel strengths of a pressure sensitive adhesive bonded to PTFE and FEP increased approximately two-to threefold if the plasma treatment was used prior to bonding.     

Estimation of interfacial tension components for liquid–solid systems from contact angle measurements

A technique has been developed for estimating the hydrogen bonding and London dispersion force components of liquid surface tension and solid surface free energy levels. The technique relies on (a) measuring contact angles generated by sessile drops of liquids on solids and (b) performing calculations based on theories of thermodynamic wetting of solids by liquids. The technique is used to estimate interfacial force components of certain liquids and papers typical of those used in xerographic processing.     

Correlation between surface tension and physical paint properties

Surface tension is a parameter of decisive importance for characterizing painted and unpainted surfaces related to wetting and adhesion phenomena. Measurements of the surface tension of solids by means of an automatic contact angle measurement device are presented. The theoretical evaluations provide for a separation of the surface tension into polar and disperse components. In addition, this paper briefly touches on other more far-reaching approaches (acid/base) and discusses a method for the determination of the dynamic surface tension of liquids.     

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.     

The Strength of Liquid Bridges Between Dissimilar Materials

The strength of the liquid bridge between a sphere and a plate of dissimilar materials was studied. An equation was derived using the surface energy approach. For small amounts of liquid, the force of adhesion f was f=2πRy(cosθ₁ + cosθ₂ where R is the sphere radius, y is the surface tension, and θ₂ , θ₂ the contact angles. In the derivationn, major simplications about the meniscus shape were possible.

The equation was experimentally tested with water, ethyl alcohol, aniline and iodobenzene using factorial combinations with different solids. Force of adhesion measurements were carried out using a tensile testing machine at controlled loading rates. Excellent agreement was obtained in the experimental and predicted adhesion values. The McFarlane-Tabor equation was identified as correct only for small amounts of liquids and similarly wet solids.     

Critical Surface Tension of Acrylamide-Grafted Polypropylene Copolymer by the Contact Angle Method

The contact angles θ of polar liquids on PP-g-AM copolymer (AM content 0.19, 0.26, and 0.37 wt%) were measured. The critical surface tension γ_C of PP-g-AM films were evaluated by the Zisman plot (cos θ versus-γl), the Young-Dupre-Good-Girifalco plot (1 + cos θ) versus 1/γ^0.5 l, and the log(1 + cos θ) versus log-γl plot. The-γl values estimated by the plot log(1 + cos θ) versus log-γl were smaller than those obtained by the other plots.     

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.     

On the surface properties of waterborne fluorinated coating polymers

In the present work the results of a study concerning the surface properties of coating materials obtained from fluorinated latices are reported. Better understanding is required regarding the influence of polymer structure, latex composition, and morphology on the surface properties of the resulting films. For this purpose, two commercial fluorinated waterborne polymer dispersions were compared with a model fluorinated acrylic latex purposely synthesized. The surface properties of mold samples, prepared from either the whole solid matter contained in the latices (dried latex) or the purified polymer, were determined by simple contact angle measurements. Two series of homologous liquids, namely H‐bonding alcohols and apolar hydrocarbons, were employed for determining the critical surface tension γ_c according to the method of Zisman. The results of the surface characterization indicate that the degree of fluorination plays a minor role in these materials, suggesting that the threshold above which the polymer surface is virtually saturated by CF₂ or CF₃ groups might have been largely exceeded. On the other hand, the effectiveness of the hydrophobic fluorinated coating resulted substantially unaffected by the presence of amphiphilic low molecular weight additives, such as surfactants and wetting agents, which can actually contribute to the reduction of the surface energy of these materials upon suitable thermal treatment.     

Peel Adhesion: Influence of Surface Energies and Adhesive Rheology

The adhesion properties of polymers are known to be influenced by both intermolecular forces operative at the interface and the rheological history of both bonding and unbonding. Recent adsorption and viscoelastic theories of adhesion and cohesion are implemented in a comprehensive examination of these phenomena. Eight peel force “master curves” extending over 14 decades of reduced rate and representing glassy state to flow region rheology are superimposed to provide a composite response envelope. Each master curve represents rate-temperature reduced adhesion of an alkyl acrylate adhesive (γ_c = 26 dyne/cm) to substrates ranging from low adhesion fluorinated polymers (γ_c = 15 to 17 dyne/cm) to polar poly-amide surfaces (γ_c = 45 dyne/cm) and glass. The rate dependent transition from interfacial to cohesive failure, a subject not treated by adsorption theory, is shown to be coincident with the onset of entanglement slippage within the polymeric adhesive. Thermodynamic criteria of polymer adhesion are shown to be applicable only to the flow region of polymeric response. This study indicates that measured surface tensions or calculated surface energies of polymeric solids do not properly account for the contributions of three dimensional network structure of the polymeric bulk phase to its total work of cohesion. Evidence of true interfacial failure of a polymer-polymer bond is supported by critical surface tension measurements.