Advances in Colloid and Interface Science (v.220, #C)

Wetting properties of phospholipid dispersion on tunable hydrophobic SiO2–glass plates by Lidia Alexandrova; Stoyan I. Karakashev; L. Grigorov; Chi M. Phan; Stoyan K. Smoukov (1-7).
We study the wetting properties of very small droplets of salty aqueous suspensions of unilamellar liposomes of DMPC (dimyristoylphosphatidylcholine), situated on SiO2 glass surfaces with different levels of hydrophobicity. We evaluated two different measures of hydrophobicity of solid surfaces - receding contact angles and the thickness of wetting films trapped between an air bubble and the solid surface at different levels of hydrophobicity. We established a good correlation between methods which differ significantly in measurement difficulty and experimental setup. We also reveal details of the mechanism of wetting of different surfaces by the DMPC liposome suspension. Hydrophilic surfaces with water contact angles in the range of 0° to 35° are readily hydrophobized by the liposomes and only showed corresponding contact angles in the range 27°−43°. For same range of surface hydrophobicities, there was a clear reduction of the thickness of the wetting films between the surface and a bubble, reaching a minimum in the 35°−40° range. At higher levels of hydrophobicity both pure water and the liposome suspension show similar contact angles, and the thickness of wetting films between a bubble and those surfaces increases in parallel. Our analysis showed that the only force able to stabilize the film under these experimental conditions is steric repulsion. The latter suggests that nanobubbles adsorbed on hydrophobic parts of the surface, and coated with a DMPC layer, may be the cause of the 40−70 nm thickness of wetting films we observe.Display Omitted
Keywords: Phospholipid vesicles; DMPC; Wetting contact angle; Thin wetting film;

Liquid spreading on solid surfaces and penetration into porous matrices (powders and coated papers) are investigated. The influence of chemical and structural heterogeneity on equilibrium and dynamic surface wetting is evaluated both experimentally and theoretically. Single capillary systems are used to identify the predominating mechanisms for acceleration, momentum, inertial and viscous liquid penetration. Different stages of vertical and horizontal penetration of liquids from non-limited, restricted (sessile drop) and cut-off sources into powders and papers are evaluated with reference to a range of frequently used models. For all types of liquid transport power-law exponents are used to relate all observations. The applicability of models from which the exponents are derived is discussed. Results are compared to theoretical predictions for liquid penetration. Models are of general validity, but the focus is placed on probe liquid spreading on and penetrating into coated and uncoated papers. This sets a particular challenge, since papers are heterogeneous layered composites of powder compacts on fibrous network. For the evaluation of models published results are supported by extended original results.Time dependent liquid (sessile drop) spreading on chemically and structurally heterogeneous surfaces and penetration into porous matrices are investigated. Penetration occurs via: Stage 1: Vertical and horizontal penetration under the drop, Stage 2: Radial penetration outside the sessile drop and Stage 3: Competitive penetration within the porous matrix. The most frequent models for surface spreading and bulk penetration are evaluated.Display Omitted
Keywords: Liquid; Wetting; Spreading; Penetration; Power-law; Models;

Changing the wetting state of materials is a growing field of research in many areas of engineering and science. In the oil industry, the term wettability alteration usually refers to the process of making the reservoir rock more water-wet. This is of particular importance in naturally hydrophobic carbonates, fractured formations, and heavy-oil systems. This shift in wettability enhances oil recovery in oil-wet and weakly water-wet reservoirs and eventually increases the ultimate oil recovery.For wettability alteration, two methods have been traditionally used: Thermal and chemical. Although many attempts have been made on reviewing the advancement of research in certain aspects of wettability, a comprehensive review of these techniques, especially in terms of the classification of the chemicals used, has been ignored. In this paper, we begin with this review and provide the past experience of wettability alteration in sandstone and carbonate reservoirs. More than 100 papers were reviewed extensively with an in-depth analysis of different methods suggested in literature. The areas of controversy and contradicted observations are discussed. The limitations and the applicability of each method were analyzed. Concerns on up-scaling laboratory findings to field scale are also addressed. The most promising potential methods are identified and their critical conditions highlighted.At the end, a selection of reviewed methods is validated experimentally for one of the most challenging cases: Extra heavy-oil and bitumen recovery from fractured-strongly-oil-wet carbonates. Berea sandstone (aged to be oil-wet) and Indiana limestone samples were saturated with heavy oil (3600 cp). Next, the process was initiated by soaking the cores into solvent (heptane or diluent oil) and the oil recovery was estimated using refractive index measurements. Note that solvent was selected to dilute the oil and recover a considerable amount of oil as any chemical or thermal methods yielded inefficiently low recoveries. After the solvent phase, the samples were exposed to wettability alteration through selected chemicals at different temperature conditions through spontaneous imbibition tests to recover more oil and retrieve the solvent diffuse into the sample back. The most promising wettability alteration agents for each type of rock were marked and optimal application conditions (temperatures, injection sequence) were identified. Selected wettability alteration chemicals were finally tested on the bitumen (5–9° API-1,600,000 cp) containing Grosmont carbonate sample from Alberta, Canada.It is hoped that this review fills in the gap in the area of wettability alteration processes by summarizing, critically analyzing, and testing the methods suggested in the literature.Display Omitted
Keywords: Wettability alteration; Heavy-oil; Solvent injection;

Physical chemistry of highly concentrated emulsions by Reza Foudazi; Sahar Qavi; Irina Masalova; Alexander Ya. Malkin (78-91).
This review explores the physics underlying the rheology of highly concentrated emulsions (HCEs) to determine the relationship between elasticity and HCE stability, and to consider whether it is possible to describe all physicochemical properties of HCEs on the basis of a unique physical approach. We define HCEs as emulsions with a volume fraction above the maximum closest packing fraction of monodisperse spheres, φm  = 0.74, even if droplets are not of polyhedron shape. The solid-like rheological behavior of HCEs is characterized by yield stress and elasticity, properties which depend on droplet polydispersity and which are affected by caging at volume fractions about the jamming concentration, φj . A bimodal size distribution in HCEs diminishes caging and facilitates droplet movement, resulting in HCEs with negligible yield stress and no plateau in storage modulus. Thermodynamic forces automatically move HCEs toward the lowest free energy state, but since interdroplet forces create local minimums – points beyond which free energy temporarily increases before it reaches the global minimum of the system – the free energy of HCEs will settle at a local minimum unless additional energy is added. Several attempts have been undertaken to predict the elasticity of HCEs. In many cases, the elastic modulus of HCEs is higher than the one predicted from classical models, which only take into account spatial repulsion (or simply interfacial energy). Improved models based on free energy calculation should be developed to consider the disjoining pressure and interfacial rheology in addition to spatial repulsion. The disjoining pressure and interfacial viscoelasticity, which result in the deviation of elasticity from the classical model, can be regarded as parameters for quantifying the stability of HCEs.Display Omitted
Keywords: Highly concentrated emulsions; Elasticity; Yield stress; Stability; Disjoining pressure;

In this review, different aspects characterizing chitosan–surfactant mixtures are summarized and compared. Chitosan is a bioderived cationic polysaccharide that finds wide-ranged applications in various field, e.g., medical or food industry, in which synergistic effects with surfactant can play a fundamental role. In particular, the behavior of chitosan interacting with strong and weak anionic, nonionic as well as cationic surfactants is reviewed. We put a focus on oppositely charged systems, as they exhibit the most interesting features. In that context, we discuss the thermodynamic description of the interaction and in particular the structural changes as they occur as a function of the mixed systems and external parameters. Moreover, peculiar properties of chitosan coated phospholipid vesicles are summarized. Finally, their co-assembly at interfaces is briefly reviewed. Despite the behavior of the mentioned systems might strongly differ, resulting in a high variety of properties, few general rules can be pointed out which improve the understanding of such complex systems.Display Omitted
Keywords: Chitosan–surfactant complexes; Phospholipids; Fatty acids; Interfacial properties; Applications;

The role of acid–base effects on particle charging in apolar media by Matthew Michael Gacek; John C. Berg (108-123).
The creation and stabilization of electric charge in apolar environments (dielectric constant ≈ 2) have been an area of interest dating back to when an explanation was sought for the occurrence of what are now known as electrokinetic explosions during the pumping of fuels. More recently attention has focused on the charging of suspended particles in such media, underlying such applications as electrophoretic displays (e.g., the Amazon Kindle® reader) and new printing devices (e.g., the HP Indigo® Digital Press). The endeavor has been challenging owing to the complexity of the systems involved and the large number of factors that appear to be important. A number of different, and sometimes conflicting, theories for particle surface charging have been advanced, but most observations obtained in the authors' laboratory, as well as others, appear to be explainable in terms of an acid–base mechanism. Adducts formed between chemical functional groups on the particle surface and monomers of reverse micelle-forming surfactants dissociate, leaving charged groups on the surface, while the counter-charges formed are sequestered in the reverse micelles. For a series of mineral oxides in a given medium with a given surfactant, surface charging (as quantified by the maximum electrophoretic mobility or zeta potential obtained as surfactant concentration is varied) was found to scale linearly with the aqueous PZC (or IEP) values of the oxides. Different surfactants, with the same oxide series, yielded similar behavior, but with different PZC crossover points between negative and positive particle charging, and different slopes of charge vs. PZC. Thus the oxide series could be used as a yardstick to characterize the acid–base properties of the surfactants. This has led directly to the study of other materials, including surface-modified oxides, carbon blacks, pigments (charge transfer complexes), and polymer latices. This review focuses on the acid–base mechanism of particle charging in the context of the many other factors that are important to the phenomenon, including the presence of water, of other components (e.g., synergists and contaminants), and of electric field effects. The goal is the construction of a road map describing the anticipated particle charging behavior in a wide variety of systems, assisting in the choice or development of materials for specific applications.Display Omitted
Keywords: Particle charge; Apolar media; Acid–base interaction; Trace water; Interfacial phenomena;