Phospholipid black foam films: dynamic film tension of DMPC bilayer films

The film tension of bilayer Newton black films (NBF) from aqueous dispersions of dimyristoylphosphatidylcholine (DMPC) has been studied in dynamic conditions. The dynamic film tension values γ have been measured using the capillary method for direct measurement of the film tension. Two different solutions have been used: DMPC vesicle suspension in water obtained through sonication, denoted as ‘DMPC(Son)’ (the DMPC adsorption layers are insoluble monolayers) and DMPC dissolved in ethanol plus water mixed solvent, denoted as ‘DMPC(EthW)’ (the DMPC adsorption layers are soluble). Both solutions contain 0.1 M NaCl. The behavior of the dynamic film tension is different for NBF from the two types of solutions. In the case DMPC(Son) γ strongly depends on the film area, while in the case DMPC(EthW) this dependence is less pronounced but still exists. The dependence of the film tension on the film area in case DMPC(Son) is well described by the Frumkin equation modified for bilayer films. Reasonable values of the parameters of Frumkin equation are determined from its fit to the experimental data.     

Thin wetting films from aqueous solutions of surfactants and phospholipid dispersions

The microscopic thin wetting film method was used to study the stability of wetting films from aqueous solution of surfactants and phospholipid dispersions on a solid surface. In the case of tetradecyltrimethylammonium bromide (C(14)TAB) films the experimental data for the receding contact angle, film lifetime, surface potential at the vapor/solution and solution/silica interface were used to analyze the stability of the studied films. It is shown that with increasing C(14)TAB concentration charge reversal occurs at both (vapor/solution and solution/silica) interfaces, which affects the thin-film stability. The spontaneous rupture of the thin aqueous film was interpreted in terms of the earlier proposed heterocoagulation mechanism. The presence of the mixed cationic/anionic surfactants was found to lower contact angles and suppresses the thin aqueous film rupture, thus inducing longer film lifetime, as compared to the pure amine system. In the case of mixed surfactants hetero-coagulation could arise through the formation of ionic surfactant complexes. The influence of the melting phase-transition temperature T(c) of the dimyristoylphosphatiddylcholine (DMPC) on the stability of thin films from dispersions of DMPC small unilamellar vesicles on a silica surface was studied by measuring the film lifetime and the TPC expansion rate. The stability of thin wetting films formed from dispersions of DMPC small unilamellar vesicles was investigated by the microinterferometric method. The formation of wetting films from diluted dispersions of DMPC multilamellar vesicles was studied in the temperature range 25-32 degrees C. The stability of thin film of lipid vesicles was explained on the basis of hydrophobic interactions. The results obtained show that the stability of wetting films from aqueous solutions of single cationic and mixed cationic-anionic surfactants has electrostatic origin, whereas the stability of the phospholipid film is due to hydrophobic interaction.     

Gas permeability in polymer- and surfactant-stabilized bubble films

The gas permeabilities of thin liquid films stabilized by poly(N-isopropylacrylamide) (PNIPAM) and PNIPAM-SDS (sodium dodecyl sulfate) mixtures are studied using the "diminishing bubble" method. The method consists of forming a microbubble on the surface of the polymer solution and measuring the shrinking rates of the bubble and the bubble film as the gas diffuses from the interior to the exterior of the bubble. PNIPAM-stabilized films exhibit variable thicknesses and homogeneities. Interestingly, despite these variable features, the gas permeability of the film is determined principally by the structure of the adsorbed polymer layer that provides an efficient gas barrier with a value of gas permeability coefficient that is comparable to that of an SDS Newton black film. In the presence of SDS, both the film homogeneity and the gas permeability coefficient increase. These changes are related to interactions of PNIPAM with SDS in the solution and at the interface, where coadsorption of the two species forms mixed layers that are stable but that are more porous to gas transfer. The mixed PNIPAM-SDS layers, studied previously for a single water-air interface by neutron reflectivity, are further characterized here in a vertical free-draining film using X-ray reflectivity.     

Permeability of Newtonian black foam films to gas

The gas permeability of Newtonian black foam films, formed on the top of a small bubble at the solution surface, was studied experimentally. The aqueous solutions contained sodium dodecylsulphate with concentrations in the range 1.5×10^–4 to 3×10^–3 mol/dm³ and sodium chloride (constant concentration of 0.5 mol/dm³). A dependence of the gas permeability coefficient on the surfactant concentration was obtained. The experimental results are discussed on the basis of a theory assuming the presence of clusters of molecule vacancies (holes) in the bilayer foam film, their number and size depending on the surfactant concentration. The experimental results are in agreement with this film structure and confirm the existence of flow through both the hole-free bilayer film and the holes. It was found that the holes of three molecule vacancies make the main contribution to gas permeability at low surfactant concentration. The diffusion coefficients through the hole-free film and through the three-vacancy holes are calculated.Dedicated to Professor Dr. Armin Weiss on the occassion of his 60th birthday.     

Surface modification of PET films by atmospheric pressure plasma exposure with three reactive gas sources

The surface modification of poly (ethylene terephthalate) (PET) film was carried out using an atmospheric pressure plasma (APP) jet device with three reactive gases: air, N₂, and Ar. The water contact angles on the PET film were found to decrease considerably after the APP exposure. The changes in the advancing and receding contact angles of water on the APP-exposed PET film with aging time were examined by the wetting force measurements employing the Wilhelmy method. The hydrophobic recovery due to the rinsing with water as well as the aging in air was observed only for the advancing angle, which was probably caused by the dissolution of low molecular weight oxidized materials into water, the loss of volatile oxidized species to the atmosphere and the reorientation and the migration of polymer chains. The wettability and the surface free energy of the APP-exposed PET film after diminishing hydrophobic recovery was sufficiently large compared with the untreated film. X-ray photoelectron spectroscopy confirmed that the PET film surface was oxidized due to the APP exposure. When N₂ gas was used for the APP exposure, the surface nitrogen concentration was found to increase with decreasing D. The surface oxygen concentration on the APP-exposed PET film was reduced by rinsing with water, in accordance with the hydrophobic recovery behavior. From atomic force microscopy, surface topographical change due to the APP exposure was observed. The changes in the PET surface properties due to the APP exposure as mentioned above were remarkable for using N₂ gas.     

Control of Ostwald ripening by using surfactants with high surface modulus

We describe results from systematic measurements of the rate of bubble Ostwald ripening in foams with air volume fraction of 90%. Several surfactant systems, with high and low surface modulus, were used to clarify the effect of the surfactant adsorption layer on the gas permeability across the foam films. In one series of experiments, glycerol was added to the foaming solutions to clarify how changes in the composition of the aqueous phase affect the rate of bubble coarsening. The experimental results are interpreted by a new theoretical model, which allowed us to determine the overall gas permeability of the foam films in the systems studied, and to decompose the film permeability into contributions coming from the surfactant adsorption layers and from the aqueous core of the films. For verification of the theoretical model, the gas permeability determined from the experiments with bulk foams are compared with values, determined in an independent set of measurements with the diminishing bubble method (single bubble attached at large air-water interface) and reasonably good agreement between the results obtained by the two methods is found. The analysis of the experimental data showed that the rate of bubble Ostwald ripening in the studied foams depends on (1) type of used surfactant-surfactants with high surface modulus lead to much slower rate of Ostwald ripening, which is explained by the reduced gas permeability of the adsorption layers in these systems; (2) presence of glycerol which reduces the gas solubility and diffusivity in the aqueous core of the foam film (without affecting the permeability of the adsorption layers), thus also leading to slower Ostwald ripening. Direct measurements showed that the foam films in the studied systems had very similar thicknesses, thus ruling out the possible explanation that the observed differences in the Ostwald ripening are due to different film thicknesses. Experiments with the Langmuir trough were used to demonstrate that the possible differences in the surface tensions of the shrinking and expanding bubbles in a given foam are too small to strongly affect the rate of Ostwald ripening in the specific systems studied here, despite the fact that some of the surfactant solutions have rather high surface modulus. The main reason for the latter observation is that the rate of surface deformation of the coarsening bubbles is extremely low, on the order of 10(-4) s(-1), so that the relaxation of the surface tension (though also slow for the high surface modulus systems) is still able to reduce the surface tension variations down to several mN/m. Thus, we conclude that the main reason for the reduced rate of bubble Ostwald ripening in the systems with high surface modulus is the low solubility and diffusivity of the gas molecules in the respective condensed adsorption layers (which have solid rather than fluid molecular packing).     

Contact angles of surface nanobubbles on mixed self-assembled monolayers with systematically varied macroscopic wettability by atomic force microscopy

The dependence of the properties of so-called "surface nanobubbles" at the interface of binary self-assembled monolayers (SAMs) of octadecanethiol (ODT) and 16-mercaptohexadecanoic acid (MHDA) on ultraflat template-stripped gold and water on the surface composition was studied systematically by in situ atomic force microscopy (AFM). The macroscopic water contact angle (θ(macro)) of the SAMs spanned the range between 107° ± 1° and 15° ± 3°. Surface nanobubbles were observed on all SAMs by intermittent contact-mode AFM; their size and contact angle were found to depend on the composition of the SAM. In particular, nanoscopic contact angles θ(nano) < 86° were observed for the first time for hydrophilic surfaces. From fits of the top of the bubble profile to a spherical cap in three dimensions, quantitative estimates of nanobubble height, width, and radius of curvature were obtained. Values of θ(nano) calculated from these data were found to change from 167° ± 3° to 33° ± 58°, when θ(macro) decreased from 107° ± 1° to 37° ± 3°. While the values for θ(nano) significantly exceeded those of θ(macro) for hydrophobic SAMs, which is fully in line with previous reports, this discrepancy became less pronounced and finally vanished for more hydrophilic surfaces.     

Effect of gas type on foam film permeability and its implications for foam flow in porous media

The aim of this paper is to provide a perspective on the effect of gas type on the permeability of foam films stabilized by different types of surfactant and to present a critical overview of the tracer gas experiments, which is the common approach to determine the trapped fraction of foam in porous media. In these experiments some part of the gas is replaced by a "tracer gas" during the steady-state stage of the experiments and trapped fraction of foam is determined by fitting the effluent data to a capacitance mass-transfer model. We present the experimental results on the measurement of the gas permeability of foam films stabilized with five surfactants (non-ionic, anionic and cationic) and different salt concentrations. The salt concentrations assure formation of either common black (CBF) or Newton black films (NBF). The experiments are performed with different single gasses. The permeability of the CBF is in general higher than that of the NBF. This behavior is explained by the higher density of the surfactant molecules in the NBF compared to that of CBF. It is also observed that the permeability coefficient, K(cm/s), of CBF and NBF for non-ionic and cationic surfactants are similar and K is insensitive to film thickness. Compared to anionic surfactants, the films made by the non-ionic surfactant have much lower permeability while the films made by the cationic surfactant have larger permeability. This conclusion is valid for all gasses. For all types of surfactant the gas permeability of foam film is largely dependent on the dissolution of gas in the surfactant solution and increases with increasing gas solubility in the bulk liquid. The measured values of K are consistent with rapid diffusion of tracer gasses through trapped gas adjacent to flowing gas in porous media, and difficulties in interpreting the results of tracer-foam experiments with conventional capacitance models. The implications of the results for foam flow in porous media and factors leading to difficulties in the modeling of trapped fraction of foam are discussed in detail. To avoid complications in the interpretation of the results, the best tracer would be one with a permeability close to the permeability of the gas in the foam. This puts a lower limit on the effective diffusion coefficient for tracer in an experiment.     

Air-facilitated three-phase contact formation at hydrophobic solid surfaces under dynamic conditions

The paper presents results documenting the mechanism of facilitation of the three-phase contact (TPC) formation due to gas entrapped during immersion of hydrophobic (Teflon) plates into distilled water and n-octanol solutions. Collisions, bouncing, the time scale of the TPC formation, and bubble attachment to Teflon plates of different surface roughness were studied using a high-speed camera. Processes occurring during the microscopic wetting film formation at the Teflon plates were monitored using the microinterferometric method (Scheludko-Exerowa cell). A strong relation between the time necessary to form a stable TPC and the roughness of the Teflon was observed. The higher the Teflon roughness was the shorter the time for the TPC formation. This effect can be attributed to two factors: (i) local differences in the thickness of the thinning intervening liquid layer (quicker attainment of rupture thickness at pillars of rough surface) and/or (ii) the presence of gas at the hydrophobic surface. Experimental findings, that (i) prolongation of the plate immersion time resulted in quicker TPC formation, (ii) white irregular and disappearing spots (air pockets) were recorded during the wetting film formation, and (iii) high n-octanol concentration caused prolongation of the time of the TPC formation, show that attachment (TPC formation) of the colliding bubble to hydrophobic surfaces was facilitated by air entrapped at the Teflon plates (and re-distributed) during their immersion into water phase. Thus, on collision instead of solid/gas wetting liquid film a thin gas/liquid/gas foam film was formed which facilitated the TPC formation.     

Nanoparticle flotation collectors II: the role of nanoparticle hydrophobicity

The ability of polystyrene nanoparticles to facilitate the froth flotation of glass beads was correlated to the hydrophobicity of the nanoparticles. Contact angle measurements were used to probe the hydrophobicity of hydrophilic glass surfaces decorated with hydrophobic nanoparticles. Both sessile water drop advancing angles, θ(a), and attached air bubble receding angle measurements, θ(r), were performed. For glass surfaces saturated with adsorbed nanoparticles, flotation recovery, a measure of flotation efficiency, increased with increasing values of each type of contact angle. As expected, the advancing water contact angle on nanoparticle-decorated, dry glass surfaces increased with surface coverage, the area fraction of glass covered with nanoparticles. However, the nanoparticles were far more effective at raising the contact angle than the Cassie-Baxter prediction, suggesting that with higher nanoparticle coverages the water did not completely wet the glass surfaces between the nanoparticles. A series of polystyrene nanoparticles was prepared to cover a range of surface energies. Water contact angle measurements, θ(np), on smooth polymer films formed from organic solutions of dissolved nanoparticles were used to rank the nanoparticles in terms of hydrophobicity. Glass spheres were saturated with adsorbed nanoparticles and were isolated by flotation. The minimum nanoparticle water contact angle to give high flotation recovery was in the range of 51° < θ(np(min)) ≤ 85°.     

High oil-repellent poly(alkylpyrrole) films coated with fluorinated alkylsilane by a facile way

Coating of fluorinated alkylsilane on “needle”-like shaped surface of poly(alkylpyrrole) films was carried out by a facile way. The coated film showed contact angles of larger than 150° and 130° to water and salad oil, respectively. The SEM images showed that the geometrical factor of the film surface did not change during the coating. The film also showed excellent stability to heating and organic solvent treatments, in terms of the contact angles to both water and salad oil. The X-ray photospectroscopic (XPS) and infrared spectroscopic (IR) data revealed that thin layer of condensed heptadecafluorodecyltri-iso-propoxylsilane (HDFDTPS) homogeneously covered on the “needle”-like surface of the poly(alkylpyrrole) film even though without any thermal treatment.     

Surface Properties of Fluorinated Acrylate Polymer Latex Films

The surface chemical compositions of fluorinated latex films and the dynamic contact angles of water were determined using X-ray photoelectron spectroscopy (XPS) and a Kruss interface tension measurement, respectively. The surface tensions of the films were calculated by the equation of state approach using the dynamic contact angles, and the effect of temperature on the wetting behavior of these films was investigated. It was shown that the F 1s signal intensity from the outermost surface of these fluorinated latex films was stronger than that from the interior surface of the film and that the surface tension showed a linear decrease with the increase of density of fluorine atoms on the latex film surface to a certain extent. The surface tension rapidly decreased with the increase of fluorinated lateral chains (Rf) content in the copolymer with longer Rf (carbon atom number n>6). The water receding contact angles (θr) on the latex films sharply decreased with the increase of n value, then leveled off nearly at n=10, and remained almost unchanged when n>10. In addition, θr increased more remarkably with the increase of F content in the poly (protonated acrylate- co-fluorinated acrylate) with short hydrocarbon side chains. The water wetting ability of the fluorinate latex films became slightly better only when temperature was more than 40°C.     

Moving contact lines and Langmuir-Blodgett film deposition

The objective of this paper is to point out the close relationship between contact line dynamics and LB film depositions, and it is designed to serve as a blueprint for future analysis of the LB technique. Moving contact lines and contact angles play a major role in Langmuir-Blodgett ultrathin film depositions. Although the effect of contact angles has been recognized for many years, a fundamental and comprehensive explanation of the phenomena taking place at the contact line has not been formulated before. Our understanding of contact line dynamics has improved thanks to careful experiments and new theoretical developments. Flow patterns depend on dynamic contact angle and the ratio of viscosities of the gas and liquid phases. More recently dynamic contact angles-and flow patterns-have been linked to forces of molecular and double-layer origin. The dynamic relationship of flow patterns to interfacial and transport properties can be used to explain seemingly contradictory experimental results reported by researchers during more than 60 years of experience with the L-B technique. Windows of operability can be defined for X-type and Z-type depositions that are useful in the design of experimental and industrial L-B deposition equipment.     

Black foam films from aqueous solutions of a mixture of phospholipids and a permeation enhancer

The influence of a permeation enhancer on the properties of phospholipid black foam films has been studied through the combination of three complementary techniques: surface tension measurements, X-ray reflectivity, and the "diminishing bubble" method. This permeation enhancer is said to optimize the delivery of active ingredients into or through the stratum corneum: the 4-decyl oxazolidin-2-one. We made films of a complex phospholipid mixture that mimic the behavior of the enhancer in a membrane cell. Mixed phospholipids/4-decyl oxazolidin-2-one/NaCl solutions were studied with various 4-decyl oxazolidin-2-one concentrations. Stable black films were obtained and their thicknesses examined. The evolution of the coefficient of gas permeability with 4-decyl oxazolidin-2-one concentration is also addressed.     

Diffusion-controlled adsorption kinetics at the interface between air and aqueous micellar solution of heptaethylene glycol monododecyl ether

The diffusion-controlled adsorption kinetics of micellar surfactant C₁₂E₇ (heptaethylene glycol monododecyl ether) solutions was studied theoretically and experimentally. The corrected diffusion equation, which was used to describe the diffusion of the monomers in the micellar solutions, was solved under the initial and boundary conditions by means of Laplace transformation. The dynamic surface adsorption γ(t) as a function of surface lifetime t, monomer diffusion coefficient D and the demicellization constant was derived. The dynamic surface tensions γ(t) of aqueous submicellar and micellar solutions were measured via maximal bubble pressure method. By analyzing the experimental data, the determined demicellization constant of C₁₂E₇ at 25°C was between 100–116 s^?1.     

Investigation of thin films formed from liposome suspensions on quartz substrate

The stability of thin wetting films formed from 0.15 M NaCl solutions containing small unilamellar dimyristoylphosphatidylcholine (DMPC) vesicles of different concentrations on quartz surface has been investigated by the microinterferometric method. The intensity of monochromatic light reflected from both film surfaces has been recorded as a function of the time of film thinning. Two temperatures were used in the experiments (20 and 35 degrees C). Films containing 10(-3), 5x10(-3) and 10(-2) mg/ml DMPC were unstable and ruptured, while films with 10(-1) and 1 mg/ml DMPC were stable. Film stability was explained on the basis of hydrophobic interactions. Film thickness dependence on time was calculated. The kinetics of film thinning did not obey Reynolds equation and a linearization was observed in co-ordinates ln(h) as a function of time. This phenomenon was explained by a non-homogeneous thinning process, which might be due to the existence of some areas of different structure of the DMPC adsorption layers.     

Effects of poly (ethylene glycol) chains conformational transition on the properties of mixed DMPC/DMPE-PEG thin liquid films and monolayers

Foam thin liquid films (TLF) and monolayers at the air–water interface formed by DMPC mixed with DMPE-bonded poly (ethylene glycol)s (DMPE-PEG₅₅₀, DMPE-PEG₂₀₀₀ and DMPE-PEG₅₀₀₀) were obtained. The influence of both (i) PEG chain size (evaluated in terms of Mw) and mushroom-to-brush conformational transition and (ii) of the liposome/micelle ratio in the film-forming dispersions, on the interfacial properties of mixed DMPC/DMPE-PEG films was compared.

Foam film studies demonstrated that DMPE-PEG addition to foam TLFs caused (i) delayed kinetics of film thinning and black spot expansion and (ii) film stabilization. At the mushroom-to-brush transition, due to steric repulsion increased DMPE-PEG films thickness reached 25 nm while pure DMPC films were only 8 nm thick Newton black films. It was possible to differentiate DMPE-PEG_2000/5000 from DMPE-PEG₅₅₀ by the ability to change foam TLF formation mechanism, which could be of great importance for “stealth” liposome design.

Monolayer studies showed improved formation kinetics and equilibrium surface tension decrease for DMPE-PEG monolayers compared with DMPC pure films.

SEM observations revealed “smoothing” and “sealing” of the defects in the solid-supported layer surface by DMPE-PEGs adsorption, which could explain DMPE-PEGs ability to stabilize TLFs and to decrease monolayer surface tension.

All effects in monolayers, foam TLFs and solid-supported layers increased with the increase of PEG Mw and DMPE-PEG concentration. However, at the critical DMPE-PEG concentration (where mushroom-to-brush conformational transition occurred) maximal magnitude of the effects was reached, which only slightly changed at further DMPE-PEG content and micelle/liposome ratio increase.     

Effect of geometry on steady wetting kinetics and critical velocity of film entrainment

The velocity dependence of receding dynamic contact, angles θ_r/ U for siliconized cylinders of different, radii withdrawn from a glycerol-water mixture [19] show an independence on geometry and substantial influence of the material properties of the solid surface. These data are compared with the results of Ngan and Dussan [16a,b] for advancing angles θ_α / U (silicon oil displacing air), which suggest a considerable effect of geometry. A similar asymmetry of the effects of geometry and material properties on the critical velocities of liquid and air film entrainment follows from the Juxtaposition of our previous results for u_cr^R[19,20] with literature data on U_cr^A onto different solid substrates.The experimental data are interpreted on the basis of the equations of Cox-Voinov [21,22], describing the data of Ngan and Dussan quantitatively. The data for the receding meniscus can be represented quantitatively only by a combined Blake-Haynes-Voinov equation taking into account the dissipation in the three-phase contact zone and in the bulk liquid.     

Influence of geometry on steady dewetting kinetics

The experimental velocity dependences of the receding contact angles θ_r and the critical velocities of liquid film entrainment U^R_cr are independent of the geometry of the solid surface but significantly influenced by its material properties. These results are interpreted on the basis of published equations and the analysis shows that these theoretical relationships do not describe the experimental results adequately over the entire steady velocity range (0 ⩽U ⩽U^R_cr).The negligible effect of geometry on the steady dewetting kinetics can be qualitatively explained in the framework of the Cox—Voinov hydrodynamic model. This effect is weaker for liophobic systems (large θ_o), where the solid surface properties are more important.     

Structures and properties of Newton black films characterized using molecular dynamics simulations

We used molecular dynamics (MD) simulations to investigate the structures and properties of Newton black films (NBF) for several surfactants: sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (C16TAB), and surfactin using film thicknesses up to 10 nm. By calculating the interface formation energy for various packing conditions on the surface pressure-area isotherm, we found that the most probable surface concentration is approximately 42 A(2)/molecule for SDS and C16TAB and approximately 170 A(2)/molecule for surfactin. We then used this most probable concentration of each surfactant to simulate NBF with various film thicknesses. From analyzing the disjoining pressure-film thickness isotherms with the density profiles and the solvation coordination number, we found that the increase of the disjoining pressure during the film thinning was coupled with the change in inner structure of the NBF (i.e., density profile and the solvation of ionic entities). In the range of film thicknesses less than approximately 30 A, the disjoining pressures for the SDS and C16TAB were found to be larger than that of the surfactin. We predicted the Gibbs elasticity (175 dyn/cm for surfactin; 109 dyn/cm for C16TAB; 38 dyn/cm for SDS) required to assess the stability of NBF against surface concentration fluctuations, and the shear modulus (6.5 GPa for the surfactin; 6.1 GPa for the C16TAB; 3.5 GPa for the SDS) and the yield stress (approximately 0.8 GPa for surfactin; approximately 0.8 GPa for C16TAB; approximately 0.4 GPa for the SDS) to assess the mechanical stability against the externally imposed mechanical perturbation.