Line tension of alkane lenses on aqueous surfactant solutions at phase transitions of coexisting interfaces

Alkane droplets on aqueous solutions of surfactants exhibit a first-order wetting transition as the concentration of surfactant is increased. The low-concentration or “partial wetting” state corresponds to an oil lens in equilibrium with a two-dimensional dilute gas of oil and surfactant molecules. The high-concentration or “pseudo-partial wetting” state consists of an oil lens in equilibrium with a mixed monolayer of surfactant and oil. Depending on the combination of surfactant and oil, these mixed monolayers undergo a thermal phase transition upon cooling, either to a frozen mixed monolayer or to an unusual bilayer structure in which the upper leaflet is a solid layer of pure alkane with hexagonal packing and upright chains while the lower leaflet remains a disordered liquid-like mixed monolayer. Additionally, certain long-chain alkanes exhibit a surface freezing transition at the air–oil interface where the top monolayer of oil freezes above its melting point. In this review, we summarize our previous studies and discuss how these wetting and surface freezing transitions influence the line tension of oil lenses from both an experimental and theoretical perspective.     

Wetting of surfactant solutions by alkanes.

Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided.     

Competitive adsorption of fibrinogen and dipalmitoylphosphatidylcholine at the air/aqueous interface

The competitive adsorption of fibrinogen (FB) and DPPC at the air/aqueous interface, in phosphate buffer saline at 25 degrees C, was studied with tensiometry, infrared reflection absorption spectroscopy (IRRAS), and ellipsometry. For FB/DPPC mixtures with 750 ppm (0.075 wt%) FB and 1000 ppm (0.10 wt%) DPPC, the tension behavior was found to be similar to that of FB when alone, even with DPPC and FB being at the interface. Thus, FB interferes with adsorption of DPPC and inhibits its surface tension lowering ability. When FB protein is introduced in the solution after a DPPC monolayer has formed, the adsorption of FB is inhibited by the DPPC monolayer. When a DPPC monolayer is spread onto a solution with a preadsorbed FB layer, the DPPC monolayer excludes FB from the surface and controls the tension behavior with little inhibition by FB. When a DPPC dispersion is introduced with the Trurnit method, or sprayed dropwise, onto an aqueous FB/DPPC surfaces, the DPPC layer formed on the surface prevents the adsorption of FB and dominates the surface tension behavior. These results have implications in controlling the inhibition of lung surfactant tension behavior by serum proteins, when they leak at the alveolar lining layer, and in developing surfactant replacement therapies for alveolar respiratory diseases.     

Wetting and freezing of hexadecane on an aqueous surfactant solution: triple point in a 2-D film

Wetting of water by hexadecane has been investigated by ellipsometry as a function of the concentration of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) in the aqueous phase and temperature. Three phases are identified: a 2-D gas of hexadecane molecules and DTAB molecules, a 2-D liquid comprising a mixed monolayer of hexadecane and DTAB, and a 2-D 'solid' phase. Evidence is presented to support the hypothesis that the liquid-solid phase transition is actually a wetting transition in which a surface-frozen layer of pure hexadecane wets the liquid-like mixed monolayer of hexadecane and DTAB. The triple point, at which the three phases coexist, is located at a temperature of 17.3 degrees C and DTAB concentration of 0.75 mmol kg (-1). The slopes of the three phase boundaries are analyzed thermodynamically.     

Co-adsorption of carboxymethyl-cellulose and cationic surfactants at the air-water interface

We investigated the interaction between an anionic polyelectrolyte (carboxymethylcellulose) and cationic surfactants (DTAB, TTAB, and CTAB) at the air/water interface, using surface tension, ellipsometry, and Brewster angle microscopy techniques. At low surfactant concentration, a synergistic phenomenon is observed due to the co-adsorption of polyelectrolyte/surfactant complexes at the interface, which decreases the surface tension. When the surfactant critical aggregation concentration (cac) is reached, the adsorption saturates and the thickness of the adsorbed monolayer remains constant until another characteristic surfactant concentration, C0, is reached, at which all the polymer charges are bound to surfactant in bulk. Above C0, the absorbed monolayer becomes much thicker, suggesting adsorption of bulk aggregates, which have become more hydrophobic due to charge neutralization.     

Adsorptive modification of hydrophobic solid surfaces by mixed surfactant solutions

We studied the reciprocal influence of a nonionic surfactant (triton X-305) and a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB) on their adsorption from aqueous solution on hydrophobic glass, interfacial tension at the solution/solid interface, composition of the mixed adsorption layer, and interaction parameters between surfactant molecules in mixed adsorption layers.     

不等链长的碳氟、碳氢正负离子表面活性剂混合体系的表面活性

研究了全氟辛酸钠与溴化十四烷基三甲铵混合水溶液的表面活性. 测定了不同比例混合物水溶液的表面张力-浓度曲线, 得出临界胶团浓度(cmc)及监 界胶团浓度时的溶液表面张力(γcmc)值. 应用Gibbs吸附公式及吸附层中两表面活性剂分子相互作用参数法求出表面总吸附量、吸附层组成及两表面活性剂分别吸附量等. 指示此吸附层具有多分子层性质. 这可能是碳氢、碳氟正负离子混合体系的特点.     

Surface freezing in normal alkanes: a statistical physics approach

The present paper aims to understand the surface freezing occurring on the interface between liquid normal alkane and air. After proposing a simple microscopic model, it reveals that the model can describe the surface freezing of normal alkanes. Subsequently, surface freezing is immediately proved to be a first order phase transition, which has been illustrated by numerous experiments. Moreover, our calculation predicts a new first order phase transition on the interface. These two transitions correspond to the liquid to monolayer and monolayer to perfect solid transitions, respectively. A phase diagram is obtained directly from the calculations as well. The model indicates that both van der Waals interaction and the entropy influenced by the surface are essential for explaining the surface phase transition.     

Wetting characteristics of aqueous rhamnolipids solutions

The wetting properties of surfactants on solid surfaces form the basis of many industrial and biological processes. The preferential adsorption of the surfactants from aqueous solutions onto solid surfaces alter the adhesion tension of the surface and this behavior may cause partial to complete wetting of the surfaces by the aqueous surfactant solutions. However, different types of surfactants show different wetting characteristics. To study the wetting properties of biologically produced rhamnolipids (RL), advancing contact angles of the aqueous solutions of the RL mixture of R1 and R2 in a ratio of R2/R1=1.1 were measured as a function of surfactant concentration. For a comparison of the wetting performance, sodium dodecyl sulfate (SDS) was chosen as the reference surfactant. A hydrophilic glass surface, a hydrophobic polymer, polyethylene terephthalate (PET), and gold surface were used as the solid surfaces to determine the wetting characteristics of rhamnolipids. At low surfactant concentrations (RL concentration <3x10(-5)M, SDS concentration<3x10(-4)M) contact angle (Theta) varied in a certain range depending on the character of the surfactant interactions with the surface. This was followed by a decrease in contact angle. Parallel to this behavior, at low surfactant concentrations the adhesion tension decreased, then remained constant and an increase at higher surfactant concentrations was obtained on hydrophobic surfaces. On hydrophilic surfaces a steady decrease in adhesion tension was observed with both surfactant solutions.     

Distribution features of Triton-X100, a nonionic surfactant,in the quartz-water-cyclohexane system during preferential wetting

The distribution of TX-100, a nonionic surfactant, over solid surfaces in cyclohexane (CH), with quartz being preferentially wetted by aqueous solutions of TX-100, is studied using radioactive labels and wetting. From low-concentration solutions, the surfactant is adsorbed from the aqueous phase on the quartz surface preferentially near the three-phase contact line. At higher TX-100 concentrations, adsorption on the solid surface occurs from both liquid phases. The TX-100 distribution on quartz influences the kinetics of acquisition of the contact angle of preferential wetting.     

Characterization of the Liquid-Gas Interface of Aqueous Systems Containing a Derivative from Castor Oil

An anionic surfactant, synthesized with ricinoleic acid from castor oil, was obtained and its behavior in terms of microemulsion formation (via pseudo-ternary diagram analysis) and liquid-gas surface tension (both for microemulsions and pure surfactant-water systems) was determined as a function of temperature and NaCl concentration in the aqueous phase. Microemulsions were formed by using butanol as co-surfactant and kerosene as the oil phase. Concerning the pseudoternary diagrams, the increase in NaCl concentration resulted in a decrease in the Winsor IV region, which was correlated to a possible occurrence of nonmicellar aggregates, induced by the high concentration of NaCl in the aqueous phase. Surface tension measurements also indicated that at the very high NaCl concentrations used there could be the formation of surfactant aggregates. The oil phase in microemulsionated systems decreased surface tension (but increased CMC): Possible interactions between isolated surfactant molecules and molecules from the oil phase were used to explain these results.     

Effect of anionic surfactant and short-chain alcohol mixtures on adsorption at quartz/water and water/air interfaces and the wettability of quartz

Measurements of the advancing contact angles for aqueous solutions of sodium dodecyl sulfate (SDDS) or sodium hexadecyl sulfonate (SHS) in mixtures with methanol, ethanol, or propanol on a quartz surface were carried out. On the basis of the obtained results and Young and Gibbs equations the critical surface tension of quartz wetting, the composition of the surface layer at the quartz-water interface, and the activity coefficients of the anionic surfactants and alcohols in this layer as well as the work of adhesion of aqueous solutions of anionic surfactant and alcohol mixtures to the quartz surface were determined. The analysis of the contact angle data showed that the wettability of quartz changed visibly only in the range of alcohol and anionic surfactant concentration at which these surface-active agents were present in the solution in the monomeric form. The analysis also showed that there was a linear dependence between the adhesion and the surface tension of aqueous solutions of anionic surfactant and alcohol mixtures. This dependence can be described by linear equations for which the constants depend on the anionic surfactant and alcohol concentrations. The slope of all linear dependence between adhesion and surface tension was positive. The critical surface tension of quartz wetting determined from this dependence by extrapolating the adhesion tension to the value equal to the surface tension (for contact angle equal zero) depends on the assumption whether the concentration of anionic surfactant or alcohol was constant. Its average value is equal to 29.95mN/m and it is considerably lower than the quartz surface tension. The positive slope of the adhesion-surface tension curves was explained by the possibility of the presence of liquid vapor film beyond the solution drop which settled on the quartz surface and the adsorption of surface-active agents at the quartz/monolayer water film-water interface. This conclusion was confirmed by the work of adhesion of aqueous solutions of anionic surfactants and short-chain alcohol mixtures to the quartz surface determined on the basis of the contact angle data and molar fraction of anionic surfactants and alcohols and their activity coefficient in the surface layer.     

Adsorption and direct probing of fibrinogen and sodium myristate at the air/water interface

Fibrinogen (FB), a serum protein, is considered a major inhibitor of lung surfactant function at the lining layer of the alveoli. In this study, the adsorption of aqueous bovine FB at the air/water interface was investigated with tensiometry and directly probed for the first time with ellipsometry and infrared reflection adsorption spectroscopy (IRRAS). The tension results show that FB has moderate surface activity. The surface densities of FB were calculated by using two different ellipsometry models to range from 3±0.2 to 17±2 mg/m², for 7.5 to 750 ppm of FB in water at 25°C. Although FB at concentrations from 75 to 750 ppm reached about the same steady surface tension value, the surface densities at 750 ppm FB were substantially larger. The same techniques were used for studying aqueous mixtures of 7.5 to 750 ppm FB with 2 mM of sodium myristate (SM) to investigate a possible interaction of the SM with the protein. The behavior of the FB/SM mixtures was found to be close to that of SM alone. The surface tension of the FB/SM mixtures reached values less than 10 mN/m under surface area oscillation at 20 or 80 rpm. These results and the ellipsometry and the IRRAS results indicate that at a concentration of 2 mM SM, FB, up to 750 ppm, does not inhibit the surfactant surface-tension-lowering function. In certain cases the results demonstrate that FB and SM may act cooperatively in lowering the surface tension.     

Influence of NaCl on the behavior of PEO-PPO-PEO triblock copolymers in solution, at interfaces, and in asymmetric liquid films

The solution behavior of the polymeric surfactant Pluronic F127 (PEO(99)PPO(65)PEO(99)) and its adsorption behavior on aqueous-silica and aqueous-air interfaces, as well as the disjoining pressure isotherms of asymmetric films (silica/aqueous film/air) containing F127, are studied. The interfacial properties of adsorbed F127 layers (the adsorbed amount Gamma and the thickness h) as well as the aqueous wetting film properties [film thickness (h) and refractive indexes] were studied via ellipsometry. The solution properties of F127 were investigated using surface tensiometry and light scattering. The interactions between the air-water and silica-water interfaces were measured with a thin film pressure balance technique (TFB) and interpreted in terms of disjoining pressure as a function of the film thickness. The relations between the behaviors of the asymmetric films, adsorption at aqueous air, and aqueous silica interfaces and the solution behavior of the polymeric surfactant are discussed. Special attention is paid to the influence of the concentrations of F127 and NaCl. Addition of electrolyte lowers the critical micelle concentration, diminishes adsorption on silica, and increases the thickness of the asymmetric film.     

Wetting in oil/water/surfactant systems

The behaviour of oils at aqueous interfaces is ubiquitous to many industrially and biologically relevant processes. In this review we consider modifications to the wetting properties of oils at the air/water, oil/water and solid/liquid interfaces in the presence of surfactants. First-order wetting transitions can be induced in a wide range of oils by varying the aqueous surfactant concentration, leading to the formation of mixed monolayers at the interface. In certain cases, these mixed monolayers display novel surface freezing behaviour, including the formation of unusual bilayer structures, which further modifies the properties of the interface. The effects of surfactant on line tension at the three-phase contact line and differences between the air/liquid and liquid/liquid interfaces are discussed.     

Fluorescence evidence that a phase transition causes the induction time in the reduction in dynamic tension during surfactant adsorption to a clean air/water interface and a kinetic-diffusive transport model for the phase-induced induction

An aqueous soluble surfactant adsorbing from solution onto an initially clean air/water interface often exhibits an induction period in the surface tension relaxation in which, as the adsorption begins, the tension remains near the clean interface value for an extended period of time before decreasing rapidly to the equilibrium value. In this study, using a model nonionic soluble surfactant, C14E6(CH3(CH2)13-(OCH2CH2)6-OH), we present direct fluorescence evidence that this induction is due to a first-order phase transition from a gaseous (G) to a liquid expanded (LE) phase that the assembling monolayer undergoes at constant surface pressure. An open channel flow cell is initially filled with water, and onto its air/water interface is spread an insoluble amphiphilic dye that fluoresces upon irradiation in the LE phase and whose fluorescence is quenched in the G phase. An aqueous solution of C14E(6) is then allowed to flow through the channel. We observe the immediate appearance of bright islands of the LE phase growing in a dark (G) background, confirming the presence of the G/LE phase transition. These islands eventually occupy the entire surface, after which the interface remains uniformly bright. We correlate this phase transition to the induction period by simultaneously measuring the tension of the interface of the open channel, and verifying that as the islands grow the tension remains at the clean value until the bright LE phase occupies the entire surface, whereupon the tension rapidly decreases. We further develop a phase transition surfactant transport model for the induction period in which surfactant diffuses toward and kinetically adsorbs onto the surface, and then rapidly equilibrates between the G and LE phases. For our model surfactant C14E6, we independently measure the surface concentration of the nucleating LE phase, the LE phase surfactant equation of state, the kinetic rate constants for adsorption into the LE phase, and the bulk diffusion coefficient. Using these measurements, we predict induction times for adsorption onto a clean surface without convection. We also measure these induction times in tension relaxation for adsorption onto a pendant bubble using axisymmetric shape analysis, and demonstrate agreement with the simulations with no adjustable constants.     

Aggregation behavior of polyoxyethylene (20) sorbitan monolaurate (tween 20) in imidazolium based ionic liquids

Surface tension measurements were carried out for the solutions of polyoxyethylene (20) sorbitan monolaurate (Tween 20) in 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF 4) and hexafluorophosphate (bmimPF 6) at various temperatures. Two transition points were found in the surface tension-concentration curves at each temperature. The freeze-fracture transmission electron microscopy revealed that two kinds of particles with different sizes are formed at the concentrations of each transition point. Thus, the surfactant concentrations of the two transition points are regarded as critical aggregation concentrations, CAC 1 and CAC 2. From the CAC values and their temperature dependence, we estimated the thermodynamic parameters of the aggregate formation, Delta G agg (0), Delta H agg (0), and Delta S agg (0). The thermodynamic parameters related to CAC 1 are almost independent of temperature. On the other hand, as for the aggregate formation at CAC 2, a positiveDelta S agg (0) contributes to a negative Delta G agg (0) at low temperature, while a negative Delta H agg (0) contributes to a negative Delta G agg (0) at high temperature. The behavior of the thermodynamic parameters as a function of temperature, combined with the variation of (1)H NMR chemical shifts of the bmim (+) protons as a function of the surfactant concentration, demonstrated that the aggregates formed at CAC 1 are nanodroplets of Tween 20 segregated from the solution phase, while those formed at CAC 2 are similar to the usual surfactant micelles formed in aqueous solution.     

Mechanism and Influencing Factors of Wettability Alteration of Water-Wet Sandstone Surface by CTAB

Different experimental methods including ellipsometry, zeta potential measurements, imbibition studies, and contact angle measurements were used to study the mechanism and influencing factors of wettability alteration of water-wet sandstone surface caused by CTAB (hexadecyl trimethyl ammonium bromide). Results show that when the concentration of CTAB reaches a certain level (below CMC), due to the electrostatic attraction between the positively charged head groups of CTAB and the negatively charged sandstone surface, the monolayer of CTAB is formed and hydrophobic chains of CTAB molecules are toward the aqueous phase, making the solid surface oil-wet. When the concentration of CTAB continues to increase (above CMC), due to the hydrophobic interaction, the compact bilayer of CTAB is formed and hydrophilic head groups of CTAB molecules are toward the aqueous phase, rendering the solid surface water-wet. The contact angles between the oil–water interface and the surface treated with CTAB increase with the increase of the concentration of NaCl and CaCl_2. Compared to NaCl, the inorganic salt CaCl₂ has a greater impact on the contact angle. In addition, the contact angles increase with the increase of temperature and decrease with the increase of pH value of the aqueous solution.     

Wetting effect of aqueous binary mixed solutions of cationic and nonionic surfactants

Wetting of low-energy solid surfaces (polymers, hydrophobized glass) with aqueous solutions of binary mixtures of cationic and nonionic surfactants was investigated at molar fractions of the cationic surfactant of 0.2, 0.5, and 0.8. In a narrow concentration range, the non-additive effect of wetting was observed: wetting of the solid surfaces with solutions of the mixtures is better than that would be expected from the additive behavior of the components. The magnitude of the effect depends on the surface energy of the solid substrate, total surfactant concentration in a mixture, and molar fraction of the cationic component. The wetting effect of surfactant mixtures with respect to low-energy solid surfaces can be predicted using the surface tension isotherms.     

阳离子和两性表面活性剂对石英表面润湿性的影响

利用座滴法研究了阳离子表面活性剂十六烷基醚羟丙基季铵盐(C16PC)和两性离子表面活性剂十六烷基醚羟丙基羧酸甜菜碱(C16PB)溶液在石英表面上的润湿性质, 考察了表面活性剂类型及浓度对接触角的影响趋势, 讨论了黏附张力和黏附功的变化规律. 研究发现, 两种表面活性剂在高能的石英表面的吸附造成石英-水的界面自由能(γsl)增大. C16PB通过弱相互作用随机吸附到石英表面, 其增大γsl的能力与降低表面张力(γ1g)的能力相当, 接触角(θ)随浓度变化不大. C16PC 随体相浓度增大能够在石英表面通过静电作用形成定向排列的单分子层, 而后在临界胶束浓度(cmc)附近形成双层结构, 接触角随浓度变化的趋势可分为4个区域, 并通过一个极大值.