Hypothesis: Thin films are central structural elements of foams and valuable model systems for probing liquids under confinement. Classical methods relate film thickness to disjoining pressure but rarely resolve molecular origins such as film composition, adsorbed amounts, ion-specific effects, and interfacial structure. Combining complementary spectroscopic techniques with thin film pressure control should provide direct molecular-level insights into confined film structure and the forces governing film stability. Experiments: A Thin Film Pressure Balance capable of measuring surface forces was coupled with UV/Vis, infrared (IR), and Raman spectroscopies to characterise foam films under controlled confinement. IR spectroscopy enabled direct, quantitative, model-free determination of water core thickness. Raman spectroscopy probed both the surfactant and aqueous adlayers, revealing adsorbed amounts and structural changes upon confinement. Anion-specific effects and the influence of the alkyl chain length of films stabilised by alkyltrimethylammonium surfactants were systematically investigated by varying the halide counterions (Br−, Cl−, F−) and chain length (C12, C14, C16). Findings: Surfactant surface excess and molecular orientation were independent of disjoining pressure across the studied range, whereas water structural features varied with confinement. Counterion identity strongly influenced monolayer dissociation, following the order Br− < Cl− < F−, consistent with headgroup binding affinities. The combined spectroscopic approach resolved both core water and surfactant layer thicknesses without reliance on model assumptions. This methodology provides a powerful new route to interrogate molecular structure in confined films, extending the scope of foam film studies beyond macroscopic stability to the fundamental chemistry of interfaces. 

Hydrophilic anti-icing coatings can be energy-effective passive solutions for combating ice accretion and reducing ice adhesion. However, their underlying mechanisms of action remain inferential and are ill-defined from a molecular perspective. Here, we systematically investigate the influence of the counterion identity on the shear ice adhesion strength to cationic polymer coatings having quaternary alkyl ammonium moieties as chargeable groups. Temperature-dependent molecular information on the hydrated polymer films is obtained using total internal reflection (TIR) Raman spectroscopy, complemented with differential scanning calorimetry (DSC) and ellipsometry. Ice adhesion measurements show a pronounced counterion-specific behavior with a sharp increase in adhesion at temperatures that depend on the anion identity, following the order Cl– < F– < SCN– < Br– < I–. Linked to the freezing of hydration water, the specific ordering results from differences in ion pairing and the amount of water present within the polymer film. Moreover, similar effects can be promoted by varying the cross-linking density in the coating while keeping the anion identity fixed. These findings shed new light on low ice adhesion mechanisms and may inspire novel approaches for improved anti-icing coatings. 

A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.

We discuss the origin of the breakloose (or static) friction force when an ice block is slid on a hard randomly rough substrate surface. If the substrate has roughness with small enough amplitude (of order a 1 nm or less), the breakloose force may be due to interfacial slip and is determined by the elastic energy per unit area, Uel/A0, stored at the interface after the block has been displaced a short distance from its original position. The theory assumes complete contact between the solids at the interface and that there is no elastic deformation energy at the interface in the original state before the application of the tangential force. The breakloose force depends on the surface roughness power spectrum of the substrate and is found to be in good agreement with experimental observations. We show that as the temperature decreases, there is a transition from interfacial sliding (mode II crack propagation, where the crack propagation energy GII = Uel/A0) to opening crack propagation (mode I crack propagation with GI the energy per unit area to break the ice-substrate bonds in the normal direction).

Calcium carbonate, particularly in the form of calcite, is an abundant mineral widely used in both human-made products and biological systems. The calcite surface possesses a high surface energy, making it susceptible to the adsorption of organic contaminants. Moreover, the surface is also reactive towards a range of chemicals, including water. Consequently, studying and maintaining a clean and stable calcite surface is only possible under ultrahigh vacuum conditions and for limited amounts of time. When exposed to air or solution, the calcite surface undergoes rapid transformations, demanding a comprehensive understanding of the properties of calcite surfaces in different environments. Similarly, attention must also be directed towards the kinetics of changes, whether induced by fluctuating environments or at constant condition. All these aspects are encompassed in the expression “dynamic nature”, and are of crucial importance in the context of the diverse applications of calcite. In many instances, the calcite surface is modified by adsorption of fatty acids to impart a desired nonpolar character. Although the binding between carboxylic acid groups and calcite surfaces is strong, the fatty acid layer used for surface modification undergoes significant alterations when exposed to water vapour and liquid water droplets. Therefore, it is also crucial to understand the dynamic nature of the adsorbed layer. This review article provides a comprehensive overview of the current understanding of both the dynamics of the calcite surface as well as when modified by fatty acid surface treatments.

Specific interactions of yttrium and lanthanum ions with a fatty acid Langmuir monolayer were investigated using vibrational sum frequency spectroscopy. The trivalent ions were shown to interact with the charged form of the carboxylic acid group from nanomolar concentrations (<300 nM). Analysis of the spectral features from both the symmetric and the asymmetric carboxylate modes reveals the presence of at least three distinct coordination structures linked to specific binding configurations. Although the same species were identified for both La3+ and Y3+, they display a different concentration dependence, highlighting the ion-specificity of the interaction. From the analysis of the response of interfacial water molecules, the reversal of the surface charge, as well as the formation of yttrium hydroxide complexes, were detected upon increasing the amount of salt in solution. The binding interaction and kinetics of absorption are sensitive to the solution pH, showing a distinct ion speciation in the interfacial region when compared to the bulk. Changing the subphase pH or adding a monovalent background electrolyte that promotes deprotonation of the carboxylic acid headgroup could further improve the detection limit of La3+ and Y-3(+) to concentrations < 100 nM. These findings demonstrate that nM concentrations of trace metals contaminants, typically found on monovalent salts, can significantly influence the binding structure and kinetics in Langmuir monolayers.

Unlike counterion interactions with charged interfaces, the influence of co-ions is only scarcely reported in the literature. In this work, the effect of SCN- and the halide co-ions in the interactions of Na+ with carboxylic acid Langmuir monolayers is investigated by using vibrational sum frequency spectroscopy. At 1 M concentrations in the subphase, the identity of the anion is shown to have a remarkable influence on the charging behavior and degree of deprotonation of the monolayer, with ions ordering in the sequence I- > SCN- > Cl- approximate to Br-. The same trend is observed at both pH 6 and pH 9 when the monolayer is intrinsically more charged. Spectroscopic evidence is found for both the presence of I- and SCN- in the interfacial region at levels close to their detection limits. The results contradict electrostatic theories on charged interfaces where co-ions are not expected to play any significant role. The higher propensity for the large polarizable anions to deprotonate the monolayer is explained in terms of their ability to modify the cations affinity toward the carboxylic acid groups present at the surface.

Despite the importance of the hydrogen ion in a wide range of biological, chemical, and physical processes, its molecular structure in solution remains lively debated. Progress has been primarily hampered by the extreme diffuse nature of the vibrational signatures of hydrated protons in bulk solution. Using the inherently surface-specific vibrational sum frequency spectroscopy technique, we show that at selected negatively charged interfaces, a resolved spectral feature directly linked to the H3O+ core in an Eigen-like species can be readily identified in a biologically compatible pH range. Centered at ~2540 cm−1, the band is seen to shift to ~1875 cm−1 when forming D3O+ upon isotopic substitution. The results offer the possibility of tracking and understanding from a molecular perspective the behavior of hydrated protons at charged interfaces.

The structure of water adjacent to silica is sensitive to the degree of deprotonation of surface silanol groups. As a result, close inspection of signals originating from these water molecules can be used to reveal the surface charge density. We have used nonlinear vibrational spectroscopy of the water O-H stretching band over a temperature range of 10-75 °C to account for the increase in surface potential from deprotonation. We demonstrate that the behavior at the silica surface is a balance between increasing surface charge and a decreasing contribution of water molecules aligned by the surface charge. Together with a model that accounts for two different types of silanol sites, we use our data to report the changes in enthalpy and entropy for deprotonation at each site. This is the first experimental determination of these thermodynamic parameters for hydrated silanol groups at the silica surface, critical to a wide range of geochemical and technological applications.

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing "chemical" versus "physical" interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming current measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In a 100 mM CaCl2 electrolyte, we observe evidence of charge neutralization at pH similar to 10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at similar to 3610 cm(-1). However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca2+ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.