Recent advances in studies of bubble-solid interactions and wetting film stability

Research in the area of bubble-solid interactions is reviewed and highlighted, with a focus on studies of wetting film drainage using theoretical approaches and experimental (interferometric) approaches, and also studies probing the stability of wetting films, where the stability has been affected by physical and chemical modification/factors. Significant advances have been made in recent years in the area of interferometry and force measurement of bubble-surface encounters, with multiple light wavelengths used to improve accuracy and certainty with regard to thickness of wetting films, as well as high speed interferometry. These advances have been accompanied with improvements to models to describe nonequilibrium aspects of opposing interfaces. Experimental studies of the influence of air bubbles and surface roughness have highlighted the importance of dissolved gas and surface condition in determining whether wetting films are stable. Finally, many new studies on the influence of polymer layers on wetting film stability and rupture have been published, and these are described in relation to the increase in our understanding of the role of adsorbed polymers in altering surface chemistry and physics of the underlying substrate.     

Wetting and surface forces

In this review we discuss the fundamental role of surface forces, with a particular emphasis on the effect of the disjoining pressure, in establishing the wetting regime in the three phase systems with both plane and curved geometry. The special attention is given to the conditions of the formation of wetting/adsorption liquid films on the surface of poorly wetted substrate and the possibility of their thermodynamic equilibrium with bulk liquid. The calculations of contact angles on the basis of the isotherms of disjoining pressure and the difference in wettability of flat and highly curved surfaces are discussed. Mechanisms of wetting hysteresis, related to the action of surface forces, are considered.     

Direct measurement of molecular interaction forces in foam films from lung surfactant fraction

Molecular interaction forces, operative in microscopic foam films obtained from the isolated hydrophobic fractions of porcine lung surfactant (AS-B) are investigated by monitoring film thickness h as a function of electrolyte concentration (C _el) and direct measurements of disjoining pressure/thickness (Π(h)) isotherms. The steep decrease of the common film thickness with the increase of C _el evidences the action of long-range electrostatic surface forces. The experimental h(C _el) curve indicates that non-Derjaguin-Landau-Verwey-Overbeek (DLVO) repulsive forces are operative at C _el where common black (CBF) and Newton black films (NBF) are obtained including the physiologically relevant C _el=0.14 mol dm⁻³ NaCl. The action of additional non-DLVO forces is corroborated by the comparison of the experimentally measured Π(h) isotherm with the DLVO theory. Considering the presence of proteins in AS-B and the formation of lipid-protein complexes it is inferred that steric type forces are operative in CBF and NBF.     

Surface forces and friction tuned by thermo-responsive polymer films

Thermo-responsive polymer films have enabled the development of various functional surfaces with switchable interfacial properties. Assessing the surface forces and friction on such films is of paramount importance. On the one hand, it allows us to extract a great deal of information on the interfacial properties of the films, e.g., adhesiveness and lubricity, and how they could be tuned using different stimuli. On the other hand, surface force measurements complement other thin-film analysis methods, e.g., ellipsometry, to better perceive the correlation between the molecular properties of the polymer chains and the interfacial properties of the film. On this basis, we will, herein, provide a concise review of some recent studies on surface forces and friction tuned by thermo-responsive polymer films. This outline comprises a summary of several research works addressing the effects of temperature, solvent composition, and salts on surface forces and friction. In the end, we briefly discuss a few select studies in which the regulation of surface forces by thermo-responsive polymers is examined with an emphasis on the potential applications.     

Surface forces in foam films from DPPC and lung surfactant phospholipid fraction

Surface properties of foam films formed from aqueous dispersions of dipalmitoyl-phosphatidylcholine (DPPC) and from solutions of a phospholipid fraction of lung surfactant (TPL) are studied employing the foam film method. Experiments are carried out within a wide range of NaCl concentrations (C_el) and the ranges of C_el determining formation of common films (CF), common black films (CBF) and bilayer Newton black films (NBF) are found. The thickness (h) of the CF and CBF decreases with the increase of C_el until the critical electrolyte concentrations (C_{el, cr}) is reached. The determined C_{el, cr} that characterize the transition to NBF show that C_{el, cr} of the TPL films is an order of magnitude higher than that of the DPPC films. The measured h of the TPL films is higher than that of the DPPC films in the whole C_el range. Besides, only the h(C_el) curve of the DPPC films outlines a metastable C_el range where both CF and NBF are obtained. Both the h(C_el) curves and the direct measurements of the disjoining pressure isotherms of the DPPC films (Π(h) isotherms) demonstrate the role of electrostatic repulsive forces for the stability of the phospholipid films The obtained results are compared with the DLVO theory equations and the evaluated potentials of the diffuse electric layer φ₀  20 mV for the DPPC films and φ₀  100 mV for TPL films show the strong effect of the charged phospholipids in the TPL mixture on the electric properties at the film interfaces.     

Hydration forces near charged interfaces in terms of effective ion potentials

Experiments and simulations provide detailed information on the structure and interaction of charged interfaces in aqueous solutions. In order to understand this information in terms of general principles it is favourable to use effective potentials, which describe the interaction of ions and surfaces in the presence of solvent. Effective potentials are derived from molecular simulations and are capable of discerning ion-specific behaviour. We argue that short-range interactions in aqueous solutions involve two characteristic lengths, the range of the interaction and the spatial periodicity, both about 2.5 ± 0.5 Å.     

Alkane films on water: stability and wetting transitions

Types of surface forces determining the disjoining pressure isotherms of wetting films of low-molecular-weight alkanes on water surface are discussed. The van der Waals forces in alkane interlayers at different temperatures were calculated using a combination of exact equations of the Dzyaloshinsky—Lifshitz—Pitaevsky macroscopic theory and the multi-oscillator model for representation of the dielectric permittivity spectra of contacting bodies. Taking account of competitive action of the van der Waals and image forces allows one not only to reproduce specific features of wetting in the systems studied at different temperatures, but also to describe quantitatively the contact angles and the experimentally observed isotherms of polymolecular adsorption. The experimentally detected wetting transition in the water—pentane—vapor system was rationalized using the results of calculations mentioned above and the Derjaguin—Frumkin theory of wetting. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 256–266, February, 2008.     

Surface forces between bottlebrush polymer layers

In this review, I summarize recent experimental investigations of surface and friction forces between bottlebrush structure macromolecules including biolubricants and biomimetic ones by direct force measurements. I also discuss recent experimental investigations of synergy in lubrication in which a question, ‘How do lubricants act together?’, is aimed to be answered. Lastly, challenges and opportunities for developing efficient lubricating systems are outlined.     

Dilatational properties and morphology of surface films spread from clinically used lung surfactants

The dilatational properties, structure, and morphology of the surface films spread at the air–water interface from complex lipid/protein systems were studied by measuring the surface pressure–area and surface potential–area isotherms, the surface rheological properties, and AFM images. The commercially available lung surfactants Alveofact, Curosurf, Survanta, and Exosurf were used as examples.The isotherms of the studied lung surfactant surface films are compared with model lipid and protein monolayers spread from bulk solutions. On the basis of a simple rheological model, the values for the elasticity and the specific time of relaxation related to the reorganization processes occurring in the monolayers were calculated. The spread films of natural surfactants Curosurf and Alveofact show a high effectiveness of spreading and respreading under the conditions of this study. These observations were confirmed by AFM imaging.     

Hydration force due to the reduced screening of the electrostatic repulsion in few-nanometer-thick films

Experiments with foam films from solutions of 1 mM SDS + 100 mM electrolyte (LiCl, NaCl and CsCl) were carried out by a thin-film-pressure balance. The measured dependences of disjoining pressure versus film thickness exhibit a steep increase when the thickness of the film's water core becomes smaller than 3.7 nm. This behavior can be interpreted as a manifestation of the hydration force. We unsuccessfully tried to interpret the data with different available theoretical models. Eventually, we found that a relatively simple model of “reduced screening” can fit the data. Such reduced screening of the electric field could exist only in a narrow range of film thicknesses, which practically coincides with the region where the hydration repulsion is acting. This model and its experimental verification are described in the article.     

Boundary layers and surface forces in pure nonaqueous liquids

Further progress has taken place in the experimental studies and molecular simulations of the structure and properties of boundary layers and thin interlayers of pure nonaqueous liquids. Recent findings in the field, including a deviation of density and shear response, layering static and dynamic structuring upon interlayer thinning are discussed in the context of the surface forces and the disjoining pressure contribution to the liquid film stability.     

Redox Flow Batteries: Electrolyte Chemistries Unlock the Thermodynamic Limits

Redox flow batteries (RFBs) represent a promising approach to enabling the widespread integration of intermittent renewable energy. Rapid developments in RFB materials and electrolyte chemistries are needed to meet the cost and performance targets. In this review, special emphasis is given to the recent advances how electrolyte design could circumvent the main thermodynamic restrictions of aqueous electrolytes. The recent success of aqueous electrolyte chemistries has been demonstrated by extending the electrochemical stability window of water beyond the thermodynamic limit, the operating temperature window beyond the thermodynamic freezing temperature of water and crystallization of redox-active materials, and the aqueous solubility beyond the thermodynamic solubility limit. They would open new avenues towards enhanced energy storage and all-climate adaptability. Depending on the constituent, concentration and condition of electrolytes, the performance gain has been correlated to the specific solvation environment, interactions among species and ion association at a molecular level.     

用“表面离子”法制备组分可控的LB膜超分子体系

综述了LB膜超分子体系中“表面离子”法的概念及其与传统的“亚相离子”法的区别. 分别以钌螯合物(Ru(ph2phen)32＋)和金属β-二酮螯合物为例,详细描述这两类不同的“表面离子”在水面上的成膜作用机理,并举例说明“表面离子”法在铺展膜和LB膜中,功能分子二维密度和凝聚态结构精确可调,并对“表面离子”法在多功能分子体系中的应用作了详细描述.     

Surface forces in foam films from ABA block copolymer: a dynamic method study

The thinning of foam films from aqueous solutions of an ABA triblock copolymer of polyethylene oxide and polypropylene oxide (average molecular weight 14,000 g/mol) is studied experimentally. The dependence of the surface forces on film thickness is obtained by the dynamic method of Scheludko and Exerowa.The total surface force measured in foam films (radius 60–70 m) from 10^–5 M (0.014 wt%) polymer solution with 0.1 M NaCl is positive at thicknesses from about 800 down to 460 . The electrostatic repulsion is negligible while the contribution of van der Waals attraction is small (within 15%). Therefore a positive surface force component predominates. Most probably it arises from steric interactions between the hydrophilic polyethylene oxide tails of the polymer. The dynamic method appears to be a suitable technique for exploring the stabilization of foam films from ABA copolymers.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Wetting films of lipids in the development of sensitive interfaces. An electrochemical approach

Solid-supported thin liquid films of lipids, contacting an electrolyte phase, turned out to be a dependable system in the field of bosensors. The investigations of these objects during the past decade reveal some of their intriguing features enabling the application in constructions of receptor part with 'two-dimensional' arrangement. As a model system, complementary to the other artificial analogs of biomembranes, the wetting films of lipids offer certain advantages concerning the compromise between the stability and flexibility of the molecular structures involved in sensing. The basic principles underlaying the techniques of formation, as well as the conditions of the films stability are emphasized in the present consized review. While no limitations are imposed by the way of preparation, the films seem especially profitable in conjunction with methods for electrochemical signal transduction. In this regard some prominent examples are discussed.     

在电解质溶液中测定非电解质溶解度的新方法

提出了一种可以同时测定电解质溶液中非电解质的溶解度和饱和溶液水活度的新方法。该法把等压平衡与传统化学分析统一起来,其优点是：（1）将多元饱和溶液中非电解质溶解度的测定转变为共存离子的溶度测定,避开了对非电解质难于进行精确化学分析的难题;（2）可以同时确定所测饱和体系的水活度。用该法测定了NaCl和KCl溶液中甘露醇的溶解度并与文献值进行了比较,结果表明二者符合得很好。     

乙醇/水混合溶剂中Gemini表面活性剂的表面性质

通过对Gemini表面活性剂12-s-12 (Et)(s=4, 6, 8, 10, 12)体系在乙醇/水混合溶剂中的表面张力曲线的测定, 对该体系的表面性质进行了研究. 发现随乙醇/水比例变化, Gemini各种表面化学性质, 如临界胶束浓度(cmc)、表面张力(γcmc)、饱和吸附量(Γmax)和最小分子占有面积(Amin)等的变化规律. 拓展了Gemini表面活性剂在混合溶剂中表面吸附的研究.     

Some results from 50 years' research on surface forces

A review is presented about research on surface forces and surface interactions conducted over the past half-century, with some emphasis on the pioneering contributions of the Department of Surface Phenomena at the Institute of Physical Chemistry of the USSR Academy of Sciences.     

Surface Lattice Modulation Enables Stable Cycling of High-Loading All-solid-state Batteries at High Voltages

Halide solid electrolytes, known for their high ionic conductivity at room temperature and good oxidative stability, face notable challenges in all–solid–state Li–ion batteries (ASSBs), especially with unstable cathode/solid electrolyte (SE) interface and increasing interfacial resistance during cycling. In this work, we have developed an Al³⁺–doped, cation–disordered epitaxial nanolayer on the LiCoO₂ surface by reacting it with an artificially constructed AlPO₄ nanoshell; this lithium–deficient layer featuring a rock–salt–like phase effectively suppresses oxidative decomposition of Li₃InCl₆ electrolyte and stabilizes the cathode/SE interface at 4.5 V. The ASSBs with the halide electrolyte Li₃InCl₆ and a high–loading LiCoO₂ cathode demonstrated high discharge capacity and long cycling life from 3 to 4.5 V. Our findings emphasize the importance of specialized cathode surface modification in preventing SE degradation and achieving stable cycling of halide–based ASSBs at high voltages.