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.     

Comparison of the Lifshitz–van der Waals/acid–base and contact angle hysteresis approaches for determination of solid surface free energy

Total surface free energy, γ_S ^TOT, for several solids (glass, PMMA, duralumin, steel and cadmium) was calculated from the surface free energy components: apolar Lifshitz–van der Waals, γ_S ^LW, and acid–base electron–donor, γ_S ^-, and electron–acceptor, γ_S ⁺. Using van Oss and coworkers' approach (Lifshitz–van der Waals/acid–base (LWAB) approach), the components were determined from advancing contact angles of the following probe liquids: water, glycerol, formamide, diiodomethane, ethylene glycol, 1-bromonaphthalene and dimethyl sulfoxide. Moreover, receding contact angles were also measured for the probe liquids, and then applying the contact angle hysteresis (CAH) approach very recently proposed by Chibowski, the total surface free energy for these solids was calculated. Although the thus determined total surface free energy for a particular solid was expected to depend on the combination of three probe liquids used (LWAB approach), as well as on the kind of the liquid used (CAH approach), surprisingly the average values of the surface free energy from the two approaches agreed very well. The results obtained indicate that both approaches can deliver some useful information about the surface free energy of a solid.     

Critical Surface Tension of Wetting and Flotation Separation of Hydrophobic Solids

Abstract

Wetting characteristics of a number of minerals including layer-type hydrophobic minerals as well as common sulfides were investigated. For the majority of the minerals, the critical surface tension of wetting, γ_c determined using Zisman's technique was in the range of 40 to 45 mN/m. Surface pressures of water, II_e, on molybdenite and coal samples were determined from adsorption isotherms. The dispersion component of the surface-free energy, γ_s ^d, for molybdenite was estimated to be 113 ± 3 mJ/m² as compared to the γ_s ^d value for graphite, 109 mJ/m². The wettability data of aqueous methanol solutions, presented in the form of adhesion tension diagrams, yielded significantly lower γ_c values. Flotation behavior of common sulfides, which was similar to that of inherently hydrophobic polymers and minerals, was attributed to elemental sulfur formation. The relevance of critical surface tension of wetting to selective flotation and separation of hydrophobic solids is discussed.     

Direct Measurement of Energy Barriers on Rough and Heterogeneous Solid Surfaces

The “three-liquid” contact angle approach to the surface free energy components of solids was applied to poly (vinyl fluoride), rough and flattened, with and without flame treatment. Lifshitz-van der Waals (LW), γ ^LW _SL , and acid-base (AB), γ ^LW _SL , components were determined and used to calculate ?δG _SL (W ^adhesion _SL ) for the formation of interfaces of five liquids with polymer. The automated goniometer allowed the determination of the energy barriers, ?δ G? _SL as the advancing liquid moved from pinned configuration to a metastable one. The acid-base component of the barriers was much greater than the LW, and the magnitude of the barriers was only slightly reduced by flattening.     

Measurement of the Surface Free Energy of Amorphous Cellulose by Alkane Adsorption: A Critical Evaluation of Inverse Gas Chromatography (IGC)

Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ^d _s and γ^d _l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ^d _s was determined to be 71.5 mJ/m², and its temperature dependence was 0.36 mJ m^?2 K^?1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ^d _s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ^d _s and d(γ^d _s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.     

The Unified Lewis Acid - Base Approach to Adhesion and Solvation at the Liquid-Polymer Interface

We present our unified Lewis acid–base approach to adhesion and solvation at the liquid-polymer interface. This approach is to complement the original methodologies proposed by Fowkes and by van Oss, Chaudhury and Good (VCG). Intermolecular interactions are primarily dominated by dispersion, d, hydrogen bonding, h, and secondarily affected by orientation, o, and induction, i. Generally, the polarization component, p, represents both i and o interactions. Fowkes suggested that the acid–base component, γ^ab, of the surface tension should consist of both h and p interactions. However, VCG proposed that the acid–base components, γ^ab, result solely from hydrogen bonding, γ^h, that is equivalent to 2(γ⁺ γ^?)^1/2, where γ⁺ and γ^? are the two hydrogen bonding parameters. VCG defined γ^LW as the Lifshitz-van der Waals component consisting of d, o and i contributions, thus, surface tension, γ, equals γ^ab(VCG)+γ^LW. Both Fowkes and VCG assumed that the polar interactions for a liquid on a low energy surface are negligible.

Now, we assume otherwise, and we treat the specific acid-base interaction to be hydrogen bonding. In addition, we also take into account the nonspecific polarization, p, interaction in terms of the equilibrium spreading pressure, π_e, resulting from the adsorption of a liquid vapor on the polymer surface. Thus, our unified approach uses the dispersion component, γ^d, of Fowkes, the hydrogen bonding, h, of VCG and the polarization, p, in terms of π_e. The difference between the initial (theoretical) and equilibrium (experimental) surface tensions is π_e, and others have observed that π_e on some polymers is substantial. The determination of several initial surface tensions of polymers by considering the effect of polarization is discussed.

In the Appendix, we shall illustrate that this polar component, π_e, is equivalent to the LESR polarity-dipolarity parameter, π^e, (represented by the same symbol but in different context) for the solvatochromic treatment. Furthermore, the surface tension components, π^d, γ⁺, γ^? and π_e, are now somewhat comparable with the four parameters in the original Taft-Kamlet relationship, δ, α, B, and π^e. Thus, our proposed unified approach may finally help elucidate the long-debated Lewis acid–base theories pertaining to adhesion and solvation of polymers.     

Acid-base effects in polymer adhesion at metal surfaces

The Lewis acid-Lewis base properties of various polymers have been determined by measuring the contributions γ_s ⁺ and γ_S ^- to the solid surface free energy using the contact angle approach of van Oss, Chaudhury, and Good. A new linear method to solve for γ_S ⁺ and γ_S ^- is employed in addition to the usual approach which uses three simultaneous equations. The set of liquid surface tension parameters developed by van Oss, Chaudhury, and Good, and the recent set of values developed by Della Volpe and Siboni are both useful in distinguishing between acidic and basic polymers. The adhesion (peel force) of an acidic pressure-sensitive adhesive is greatest on a basic oxide film. In addition, the adhesion (pull-off force) of the basic polymer poly(methyl methacrylate) is greatest for acidic oxide films. Thus, direct experimental evidence is provided as to the importance of Lewis acid-Lewis base effects in the adhesion of polymers on oxide-covered metals.     

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.     

Studies on the surface free energy and surface structure of PTFE film treated with low temperature plasma

The surface free energy and surface structure of poly(tetrafluoroethylene) (PTFE) film treated with low temperature plasma in O₂, Ar, He, H₂, NH₃, and CH₄ gases are studied. The contact angles of the samples were measured, and the critical surface tension γ_c (Zisman) and γ_c (max) were determined on the basis of the Zisman's plots. Furthermore, the values of nonpolar dispersion force γ^a_s, dipole force γ^b_s, and hydrogen bonding force γ^c_s to the surface tensions for the plasma-treated samples were evaluated by the extended Fowkes equation. Mainly because of the contribution of polar force, the surface free energy and surface wettability of PTFE film which was treated with H₂, He, NH₃, Ar, and CH₄ for a short time increased greatly. Electron spectroscopy for chemical analysis (ESCA) shows that the reason was the decrease of fluorine and the increase of oxygen or nitrogen polar functional group on the surface of PTFE. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1733–1739, 1997     

Allylamine plasma‐polymerization on PLLA surface evaluation of the biodegradation

Biodegradation of poy(L ‐lactide) (PLLA) films and filaments recovered with hydrophilic layer (contact angle = 14°, surface energy γ_s = 70.9 mJ m^?2) from allylamine plasma polymerization was investigated under aerobic conditions in sludge. XPS and FTIR‐ATR analysis of the plasma layer showed 14.4% N and 16.6% O mainly as amide group. Optical microscopy showed much bacteria colonies on treated PLLA surface than on untreated one. Weight loss and oxygen consumption after 65 days were 4–5% and 4 mg h^?1 per gram polymer respectively. The fact that biodegradation lag‐phase for treated PLLA was released quicker (7 days) than untreated one (14 days), could be related to the presence of hydrophilic plasma layer that improved swelling‐dissolution of hydrolyzed molecular fragments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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.     

Quantification of Bacillus subtilis and Bacillus sp. Adhesion on Fez Medina Cedar Wood

The adhesion of Bacillus subtilis and Bacillus sp. isolated from Fez cedar wood decay has been investigated. Furthermore, the physicochemical proprieties including hydrophobicity and electron donor/electron acceptor (Lewis acid–base) of both bacteria and substrata were evaluated using contact angle measurements. The results show that Bacillus subtilis has a hydrophobic character (ΔG _iwi = –20 mJ/m²). In contrast, Bacillus sp. exhibits a hydrophilic (ΔG _iwi = –20 mJ/m²), electron donating (γ^–) and weakly electron accepting (γ⁺) character. With respect to the substrata surface, we found that the cedar wood used in this work, was hydrophobic in character, having relatively more electron-donor that electron-acceptor properties (γ^– = 6 ± 4 mJ/m²; γ⁺ = 0 ± 3 mJ/m²). The phenomena of adhesion were observed by environmental scanning electron microscopy (ESEM) and cell adhesion was quantified using a Matlab program. The analysis of images obtained by ESEM show that the both cells was able to adhere to the wood substrata and the quantitative adhesion results showed that the surface coverage by Bacillus sp. (90%) was higher than that by the Bacillus subtilis strain (40%).     

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.     

Counterion‐Switched Reversibly Hydrophilic and Hydrophobic TiO2‐Incorporated Layer‐By‐Layer Self‐Assembled Membrane for Nanofiltration

The manipulation of surface wettability has been regarded as an efficient strategy to improve the membrane performances. Herein, the counterion‐switched reversibly hydrophilic and hydrophobic surface of TiO₂‐loaded polyelectrolyte membrane are prepared by layer‐by‐layer assembly of poly(sodium 4‐styrene sulfonate) (PSS) and poly(diallydimethyl‐ammoniumchloride (PDDA) containing TiO₂@PDDA nanoparticles (NPs) on the hydrolyzed polyacrylonitrile (PAN) substrate membrane. The obtained polyelectrolyte multilayer (PEM) membranes [PEM‐TiO₂]_4.5⁺X^? (X^? = Cl^?, PFO^? [perfluorooctanoate] etc.) show different hydrophilicity and hydrophobicity with various counterions. The integration of TiO₂ NPs obviously improves the wettability and nanofiltration (NF) performance of PEM membrane for (non)aqueous system of dyes (crystal violet, eriochrome black T) with a high recyclability. The highly hydrophilic [PEM‐TiO₂]_4.5⁺Cl^? (water contact angle [WCA]: 13.2 ± 1.8°) and hydrophobic [PEM‐TiO₂]_4.5⁺PFO^? (WCA: 115.4 ± 2.3°) can be reversibly switched via counterion exchange between Cl^? and PFO^?, verifying the surface with a reversible hydrophilic–hydrophobic transformation. For such membranes, the morphology, wettability, and NF performance rely on the loading of TiO₂@PDDA NPs and surface counterion. Meanwhile, the motion and interaction of water or ethanol in the hydrophilic or hydrophobic membrane are revealed by low‐field nuclear magnetic resonance. This work provides a facile and rapid approach to fabricate smart and tunable wetting surface for potential utilization in (non)aqueous NF separation.     

Wetting Behavior of Ibuprofen Racemate Surfaces

The wetting behavior and detailed surface energetics of a racemate crystalline system were measured via contact angle measurements and inverse gas chromatography at finite concentrations. The advancing contact angles for water, diiodomethane, formamide, and ethylene glycol were measured on specific facets for racemic ibuprofen and S-(+)-ibuprofen single macroscopic crystals, and were found to be facet dependent for both systems. This observation demonstrates that variation in molecular orientation within the crystal lattice results in variations in exposed surface chemistry for differing facets, which results in anisotropic wetting behavior as previously reported. Surface free energy profiles of the ibuprofen racemates determined using a novel inverse gas chromatography method showed that powder samples (75–150 µm particle diameter) exhibited relatively homogeneous surface energies, with similar values of γ_SV ^d to those obtained by the contact angle analysis. These results lead us to conclude that ibuprofen exhibited a low level of surface heterogeneity, with the dominant facet of these powders exhibiting a low γ_SV ^d, with high energetic sites estimated to be < 3% of exposed available surface.     

Characterization and comparative evaluation of polysulfone and polypropylene hollow fiber membranes for blood oxygenators

Blood oxygenators are used to saturate oxygen levels and remove carbon dioxide from the body during cardiopulmonary bypass. Although the natural lung is hydrophilic, commercially used oxygenator materials are hydrophobic. Surface hydrophobicity weakens blood compatibility, as long-term contact with the blood environment may lead to different degrees of blood activity. Polysulfone may be considered an alternative hydrophilic material in the design of oxygenators. Therefore, it may be directed toward developing hydrophilic membranes. This study aims to investigate the feasibility of achieving blood gas transfer with a polysulfone-based microporous hollow fiber membrane and compare it with the commercially available polypropylene membranes. Structural differences in the membrane morphology, surface hydrophilicity, tortuosity, mass transfer rate, and material properties under different operation conditions of temperature and flow rates are reported. The polysulfone membrane has a water contact angle of 81.3°, whereas a commercial polypropylene membrane is 94.5°. The mass transfer resistances (s/m) for the polysulfone and polypropylene membranes are calculated to be 4.8 × 10⁴ and 1.5 × 10⁴ at 25°C, respectively. The module made of polysulfone was placed in the cardiopulmonary bypass circuit in parallel with the commercial oxygenator, and pH, pO₂, pCO₂ levels, and metabolic activity were measured in blood samples.     

Physicochemical characterization of actinomycetes isolated from decayed cedar wood: contact angle measurement

Physicochemical characterization of microorganism is very important in a wide range of scientific and technological fields. In this study, we reported the isolation and the molecular identification of actinomycetes recovered from cedar wood decay. The isolates named H5 and H8 were identified by 16S rDNA sequencing and were shown to belong to the genus Nocardia and Streptomyces, respectively. Furthermore, physicochemical proprieties including hydrophobicity, electron donor/acceptor, and the Lifshitz–van der Waals (γ^LW) of these strains were evaluated using contact angle measurements. The results showed that Nocardia sp. (H5) had a hydrophobic (ΔGiwi?=??78.56?mJ/m²) and a weak electron donor/acceptor character. In contrast, results from contact angle measurements showed that the surface free energy of Streptomyces strains (H2, H3, and H8) were ΔGiwi?=?20.71?mJ/m², ΔGiwi?=?30.63?mJ/m², and ΔGiwi?=?15.35?mJ/m², respectively, classifying these microorganisms as hydrophilic bacterium. Moreover, the three strains were predominantly electron donating (γ^–?) and exhibit a weak electron-accepting (γ⁺) character.     

On the determination of the surface energetics of porous polymer materials

The solid surface tension γsv of hydrophobic polymer powders has been determined using the capillary penetration technique. By plotting Kγlv cos ζ, where K is a geometric factor, versus the liquid surface tension γlv, the following values of γsv were directly derived from the curves: poly(tetrafluoroethylene) γsv = 20.4 mJ/m², polypropylene γsv = 30.2 mJ/m², polyethylene γsv = 34.4 mJ/m², and polystyrene γsv = 27.5 mJ/m². These values are in good agreement with the γsv values obtained from contact angle measurements on flat and smooth solid surfaces of the same materials. If the contact angles were first calculated from the capillary penetration experiments, which is the usual procedure applied in the literature, distinctly higher contact angles were obtained. Obviously these angles are affected by the powder morphology and are therefore meaningless contact angles in terms of a surface energetic interpretation.     

Solid surface free energy components determination by the thin-layer wicking technique

A thin-layer wicking technique [1] and van Oss et al.'s [2] approach to interfacial free energy interactions were tested to determine the solid surface free energy components: apolar Lifshitz-van der Waals, y^l,w _y; and polar, electron donor, γ^- _y, and electron acceptor, γ⁺ _y. For this purpose, the penetration rates of n-alkanes, diiodomethane, water, formamide, toluene and chloroform were measured. For these studies, silica, used for thin-layer chromatography, and α-Al₂O₃ were used as the model solids. It was found that both are strongly polar, electron donor solids with weak electron acceptor interactions. It is concluded that van Oss, Good et al.'S [2] approach to the interfacial free energy interactions and the thin-layer wicking technique are very useful for cxplaining many interfacial phenomena taking place in the dispersed systems. However, more experimental work using different systems is needed.     

Evolution of surface chemistry and physical properties during thin film polymerization of thermotropic liquid crystalline polymers

By applying a novel thin film polymerization technique, X-ray photoelectron spectroscopy (XPS), and the Lifshitz-van der Waals acid-base (LWAB) theory, we have determined the time evolution of surface chemistry and surface free energy during the polymerization of liquid crystalline poly(p-oxybenzoate/2,6-oxynaphthoate) at a molar ratio of 50/50. The surface free energy components of these main-chain liquid crystalline copolyesters were calculated from contact angle measurements using a Ramé-Hart goniometer and a three-liquid procedure (water, glycerol, and diiodomethane). The experimental data suggest that the Lewis base parameter (y-) during thin film polymerization decreases rapidly with the progress of polymerization, while the Lewis acid parameter (γ⁺) and the Lifshitz-van der Waals parameter (γ^LW) are almost invariant. The surface roughness data measured by atomic force microscopy (AFM) suggested that the increase in water contact angle (or the decrease in y-) was not caused by the change in surface roughness, but by the change in surface chemistry, i.e. due to the reaction of acetoxy and carboxy groups to release acetic acid during the polymerization reaction. In addition, the XPS results coincide with our previous Fourier transform infrared spectroscopy results showing that the condensation polymerization is much faster in the beginning than in the later stages. Consequently, the decrease in y- in the early stages of the polymerization is well explained.