Interfacial rheological properties of adsorbed protein layers and surfactants: a review

Proteins and low molecular weight (LMW) surfactants are widely used for the physical stabilisation of many emulsions and foam based food products. The formation and stabilisation of these emulsions and foams depend strongly on the interfacial properties of the proteins and the LMW surfactants. Therefore these properties have been studied extensively. In this review an overview is given of interfacial properties of proteins at a mesoscopic scale and the effect of LMW surfactants (emulsifiers) on them. Properties addressed are the adsorbed amount, surface tension (reduction), network formation at interfaces and possible conformational changes during and after adsorption. Special attention is given to interfacial rheological behaviour of proteins at expanding and compressing interfaces, which simulate the behaviour in real emulsions and foams. It will be illustrated that information on interfacial rheological properties, protein conformation and interactions between adsorbed molecules can be obtained by changing experimental conditions. The relation between interfacial rheology and emulsion and foam stabilisation is subsequently addressed. It is concluded that there is a need for new measuring devices that monitor several interfacial properties on a mesoscopic and microscopic scale at the same time, and for physical models describing the various processes of importance for proteins. Real progress will only be possible if both are combined in an innovative way.     

The interfacial tension and phase diagram of the Widom-Rowlinson mixture via Monte Carlo simulations

Results of Monte Carlo simulations are reported for the interfacial tension between two fluid phases in a binary mixture of penetrable spheres in which molecular pairs of like species do not interact, while those of unlike species interact as hard spheres. Semigrand canonical ensemble Monte Carlo simulations in a cubic cell with periodic boundary conditions are used to obtain histograms for various system sizes at various densities. At a given density, the interfacial tension and compositions of coexisting phases for an infinite system are evaluated via histogram analysis combined with finite-size scaling. The density dependence of the interfacial tension and phase diagram for an infinite system are thus obtained. The simulated behavior of the interfacial tension close to the critical density corroborates previous suggestions that the model belongs to the three-dimensional Ising universality class.     

Nematic-isotropic interfacial tension anisotropy of a calamitic lyotropic liquid crystal

In a planar oriented sample of a calamitic nematic lyotropic system (mixture of sodium lauryl sulphate/water/decanol), isotropic pretransitional domains appear at the nematic to isotropic transition. The domains are oblong in shape with the long axis along the orientational direction. We show experimental evidence that this oblong shape is determined by the nematic-isotropic interfacial tension anisotropy. Two uniparametric models of simple angular dependences for the interfacial tension are tested. Using the differential system obtained from the Young-Laplace condition at the nematic-isotropic interface, the domain shape can be numerically calculated for each value of the interfacial tension anisotropy. By processing the values of the transmitted light through both an isolated isotropic domain and its surrounding nematic zone, we obtain the anisotropy of the interfacial tension as the main fitting parameter. An estimation of the ratio of the extreme values for the interfacial tension is given.     

Probing in vitro digestion at oil–water interfaces

Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions.     

A simple operational relationship between drop-time and interfacial tension at a charged mercury/aqueous solution interface

This paper describes a simple operational relationship between the drop-time of a dropping mercury electrode and the interfacial tension at a charged mercury/aqueous solution interface. An apparatus and technique for measuring drop-times is reported, and examples are given of the fit of experimental drop-times to literature values of interfacial tensions. The operational relationship is independent of temperature in the range 293-313 K.     

Viscoelastic theory for nematic polymer interfaces

A macroscopic theory for the dynamics of compressible nematic polymer‐viscous fluid interfaces is developed from first principles. The theory is used to define and characterize the basic interfacial viscoelastic material properties of the ordered interfaces. The theory is based on a decomposition of the kinematic fields and nematic tensor order parameter that takes into account the symmetry breaking of the interface. The interfacial rate of entropy production used to identify the interfacial viscoelastic modes is given in terms of surface rate of deformation tensor and the surface Jaumann derivative of the tangential component nematic tensor order parameter. The derived surface viscous stress tensor is asymmetric and thus describes surface flow‐induced changes in the tensor order parameter. Consistency with the Boussinesq surface fluid appropriate for Newtonian interfaces is established. The interfacial material functions are identified as the dynamic surface tension, the interfacial dilational viscosities, and the interfacial shear viscosities. The interfacial material functions depend on the surface tensor order parameter and as a consequence anisotropy is their characteristic feature. Two characteristic interfacial tensions and two dilational viscosities are predicted depending on the director orientation. In addition six interfacial shear viscosities arise as the directors sample the velocity, velocity gradient, and vorticity directions. Finally the theory provides for the necessary theoretical tools needed to describe the interfacial dynamics of nematic polymer interfaces, such as capillary instabilities, Marangoni flows, and wetting phenomena.     

Aqueous surfactant solutions which exhibit ultra-low tensions at the oil-water interface

Ultra-low values of the tension at an oil-aqueous electrolyte solution interface can be developed by the addition of water-soluble surfactants of the petroleum sulfonate type. Interfacial tensions in the range of 10⁻³ dyne/cm or lower are readily achieved with surfactant concentrations of the order of 0.1 wt%. For a given oil and aqueous solution, the minimum interfacial tension resulting from the addition of a petroleum sulfonate depends markedly on the average equivalent weight of the sulfonate. Sulfonates having average equivalent weights higher and lower than a previously determined optimum weight, when mixed so as to yield this particular average weight, will also produce ultra-low interfacial tensions. For a given oil, additional control of this unusual type of interfacial activity is accomplished by adjustment of the electrolyte concentration of the aqueous phase.     

Water-in-crude oil emulsions from the Norwegian continental shelf

A destabilization study of water-in-crude oil emulsions based on crude oils from the Norwegian Continental Shelf is reported. It is found that medium-chain alcohols (1-butanol and benzyl alcohol) and amines are speeding up the separation of water. The destabilization mechanisms in these two cases seem to be fundamentally different. The alcohols seem to modify the rigidity of the interfacial film by a diffusion/partitioning process while the amines show a strong and specific interaction with interfacial groups, hence hydrophilizing the whole film. Observed trends in the time-dependence of the interfacial tension upon addition of alcohols and amines support these suggestions to destabilization mechanisms. Data for a commercial demulsifier Dissolvan 4455 are also given.     

Interfacial dynamics and structure of surfactant layers

The present article provides current opinion on studies of the interfacial dynamics, adsorption, and structure of surfactant layers. The physical principles and applications of physicochemical methods such as tensiometry, ellipsometry, photon correlation spectroscopy, and neutron reflectivity techniques, as well as relevant theoretical aspects related to the adsorption and desorption kinetics, interfacial structure development, wetting enhancement, and the effect of adsorbed surfactant films of the interfacial dynamics, are covered in detail. In order to make the text as self-contained as possible, essential mathematical derivations are given demonstrating how raw data, such as ellipsometric angles or neutron reflectivity, are transformed into sought layer characteristics, such as thickness or density.     

Interfacial dilational behaviour of adsorbed β-lactoglobulin layers at the different fluid interfaces

β-Lactoglobulin adsorption layers at the interfaces solution/air, /tetradecan and /sunflower oil were characterised by dynamic interfacial tension measurements and harmonic drop oscillation experiments in a time scale of some seconds. Axialsymmetric drop shape analysis (ADSA) was used to calculate drop volume, area and interfacial tension. Within a definite range of drop volume amplitude, the oscillation of the surface tension is harmonic and interfacial dilation parameters can be determined. Dependence of the dilational parameters on the amplitude and frequency of drop volume oscillation were determined and methodical demands are given for this special kind of ADSA application. The concentration of interfacial saturation is minimal at the interface with sunflower oil. Interfacial dilational elasticities, and viscosities are maximal at the saturation concentration of all systems investigated. The dilational viscosities are maximal in the frequency range 0.007–0.011 Hz and characterise molecular rearrangement processes in the adsorption layer. Interfacial dilational elasticity and viscosity are the largest at the interface with air. They are the smallest at the interface with sunflower oil. Similarities and differences of the systems investigated are discussed by taking into account the adsorption behaviour and the solvatation of different apolar and polar parts of the protein molecules in the neighbouring phase.     

Study of the dynamic interfacial tension at the oil/water interface

A review is given on three recently developed methods to measure the dynamic interfacial tension at the oil/water interface. These are respectively the dynamic drop volume method, the dynamic capillary method, and the (reversed) funnel method. For each method presented the basic principles are described and a few experimental results are given.Paper presented at the 7th International Conference on Surface Active Substances (Bad-Stuer, DDR, 25–30. April 1988).     

界面控制与复合膜的性能

以反渗透复合膜和气体分离用复合膜为例,介绍了复合膜中存在的界面现象,提出了界面控制影响复合膜性能的五个可能因素：界面粗糙度及其分布,界面极性与非极性,界面官能团与化学元素组成,界面荷电性和界面结合能,并对界面控制影响复合膜性能的机理和规律作出一一定的理论分析和预测。     

高温高压下水与非极性流体间的界面张力

The pendent drop or standing bubble method is applied to measure the interfacial tensions between water and nonpolar fluids (n-hexane, n-heptane, nitrogen, oxygen and methane) up to 473K and 220MPa. The high pressure autoclave with t wo visual windows and the auxiliary equipment are described. The sizes(ca 2mm) and shapes of drops or bubbles are recorded with microscope and video camera. The use of digital image permits fast, precise determination of the contour parameters. The densit y values of the liquids or gases have been chosen from literature. A special program is proposed to calculate the interfacial tensions automatically from drop shape at given temperature and pressure. The interfacial tensions σ12 increase with pr essure for the two liquid-liquid systems, but decrease with pressure for the three gas-liquid systems.     

Oscillatory wetting instability induced by liquid-liquid decomposition in a Ga--Pb alloy

We present the first experimental investigation and pertinent theoretical modeling of an interfacial oscillatory instability in a binary fluid alloy, the Ga-Pb system. It is characterized by spinodal decomposition at elevated temperatures and by a complete wetting transition at liquid-liquid coexistence. For the alloy Ga(0.95)Pb(0.05) the fluid interface has been probed by second harmonic generation (SHG) under UHV conditions at temperatures between 740 and 550 K. At conditions inside the miscibility gap clear oscillations of the SHG-intensity with a period of approximately 30 min are found for different cooling cycles and also at constant temperatures. These interfacial oscillatory instabilities simultaneously induce temperature oscillations in the bulk fluid with the same period. This phenomenon can be explained by a periodic variation of the fluid interfacial emissivity. A model has been developed which describes the wetting-dewetting dynamics by hydrodynamic equations within the Reynolds approximation. It is found that the interfacial oscillatory instability is determined by capillary-gravitation instability. The model quantitatively describes the time evolution of the interfacial and temperature oscillations and gives the correct value of the oscillation period. A detailed comparison of the experimental and model results is given.     

Thin liquid films: Where hydrodynamics,capillarity, surface stresses and intermolecular forces meet

Thin liquid films arise in many technological applications and biological phenomena. They also present a fascinating object of study, because of a rich interplay between capillarity, hydrodynamics, interfacial transport phenomena and interfacial rheology, as well as the effects of interaction forces when films thin down to molecular thicknesses. Recent advances in experimental techniques have given further insights in the variety of physical phenomena, which can occur. These techniques are briefly reviewed. How these techniques can be utilised is illustrated by recent studies addressing the effect of interfacial rheological stresses on drainage, the interplay between capillarity and hydrodynamics during film retraction, and the solutocapillary stabilisation of films. Finally, we briefly discuss the challenges of conducting drainage measurements at high and varied capillary numbers and how these could be overcome by the combined use of experiments and simulations.     

Electrophoresis and stability of nano-colloids: History,theory and experimental examples

The paper contains an extended historical overview of research activities focused on determining interfacial potential and charge of dispersed particles from electrophoretic and coagulation dynamic measurements. Particular attention is paid to nano-suspensions for which application of Standard Electrokinetic Model (SEM) to analysis of experimental data encounters difficulties, especially, when the solutions contain more than two ions, the particle charge depends on the solution composition and zeta-potentials are high. Detailed statements of Standard Electrokinetic and DLVO Models are given in the forms that are capable of addressing electrophoresis and interaction of particles for arbitrary ratios of the particle to Debye radius, interfacial potentials and electrolyte compositions. The experimental part of the study consists of two groups of measurements conducted for Pt/C nano-suspensions, namely, the electrophoretic and coagulation dynamic studies, with various electrolyte compositions. The obtained experimental data are processed by using numerical algorithms based on the formulated models for obtaining interfacial potential and charge. While analyzing the dependencies of interfacial potential and charge on the electrolyte compositions, conclusions are made regarding the mechanisms of charge formation. It is established that the behavior of system stability is in a qualitative agreement with the results computed from the electrophoretic data. The verification of quantitative applicability of the employed models is conducted by calculating the Hamaker constant from experimental data. It is proposed how to explain the observed variations of predicted Hamaker constant and its unusually high value.     

Two-layer model description of polymer thin film dynamics

Experiments in the past two decades have shown that the glass transition temperature of polymer films can become noticeably different from that of the bulk when the film thickness is decreased below ca. 100 nm. It is broadly believed that these observations are caused by a nanometer interfacial layer with dynamics faster or slower than that of the bulk. In this paper, we examine how this idea may be realized by using a two-layer model assuming a hydrodynamic coupling between the interfacial layer and the remaining, bulk-like layer in the film. Illustrative examples will be given showing how the two-layer model is applied to the viscosity measurements of polystyrene and polymethylmethacrylate films supported by silicon oxide, where divergent thickness dependences are observed.