Three-phase Contact Research Articles

Effect of Anionic Surfactants on the Oil-Water-Rock Interactions by an Improved Washburn Method.

The complex and variable structure of subsurface oil reservoirs as well as the small pore throat size of reservoirs make it extremely important to investigate the effect of oil-water-rock interactions for enhancing oil recovery. In this paper, the powder wettability of oil sand with different polar solvents was investigated using the improved Washburn capillary rise method, and the surface free energy of oil sand was calculated in combination with the OWRK method. In addition, the wettability of anionic surfactants HABS and PS solutions on the surface of oil sand was determined, and it showed that their wetting rates showed different trends after CMC (critical micelle concentration). The C×cosθ value of HABS decreased significantly with increasing concentration, whereas PS showed little changes. This may be related to the aggregate structure formed by HABS on the oil sand surface. Meanwhile, the interfacial free energy between crude oil and oil sand was obtained by crude oil-to-oil sand wetting experiments, and found that the wetting rate of crude oil to oil sand was much lower than that of solvents and surfactants. In combination with the above results and the oil-water interfacial tension (IFT), the oil-water-rock three-phase contact angle and the work of adhesion between the crude oil and the solid were obtained by Young's equation. From the three-phase contact angle results, it can be found that the contact angle values of both HABS and PS are obviously higher than that of the simulated water, and both HABS and PS have the ability to significantly reduce the work of adhesion, which shows a strong ability to strip the oil film on the surface of the solid. The research results of this paper are helpful to understand the oil displacement mechanism of chemical flooding in reservoir pores, which is of great significance for improving oil recovery.

Proposing moderate unfolding of interfacial proteins to enhance the techno-functional features of complex microgel particles formed by whey protein-chitooligosaccharide conjugation

To elucidate the roles of interfacial protein microstructure in regulating techno-functional attributes of complex microgel, this work explored the effects of transglutaminase cross-linking alone or in combination with ultrasonication on conformation and functional properties of whey protein isolate-chitooligosaccharide microgel dispersion (WPI–COS). It was found that transglutaminase-crosslinked WPI-COS microgels presented improved interfacial properties when a moderate unfolding process was induced by sonication, validating the existence of optimum flexibility of complex Pickering particles during unfolding/refolding of interfacial proteins. Particularly, TG induced excessive crosslinking of WPI-COS to form aggregates, causing a lower surface hydrophobicity. In contrast, ultrasound was inclined to increase the surface hydrophobicity for TG-catalyzed and uncatalyzed samples, suggesting differential unfolding degrees of WPI induced by transglutaminase and ultrasonication. Correspondingly, interfacial properties of ultrasonicated WPI-COS complexes, as revealed by percentage of adsorbed protein, interfacial tension and three-phase contact angle and emulsifying properties, were improved significantly. Confocal laser scanning microscopy and transmission electron microscopy consistently observed WPI-COS tightly adsorbed at the oil-water interface, with smaller emulsion droplets, more uniform distribution and thicker interfacial films at the oil-water interface in WPI-COS microgel particles with sonication-induced unfolding. This investigation demonstrated the feasibility of conformational regulation of interfacial proteins in tuning techno-functional features of microgel particles.

Contact Angle Modulation: In Situ Polymer Deposition during Sessile Drop Evaporation.

The drying kinetics of a sessile drop on a solid surface are a widely studied phenomenon because of their relevance to various fields such as coating, printing, medical diagnostics, sensing, and microfluidic technology. Typically, the drop undergoes drying either at a constant contact radius (R) with a decrease in the three-phase contact angle or at a constant contact angle (θ) with a reduction in the radius with time. These two drying modes are referred to as CCR and CCA, respectively. It is not uncommon where both R and θ may decrease during drying, especially in the penultimate stage of drying. In this work, we report a scenario wherein the θ increases while R decreases during the drying process of an aqueous polymer solution on a high surface energy substrate. This behavior is observed across different polymer systems (such as poly(ethylene oxide) and polyvinyl pyrrolidine), varying molecular weights, and polymer concentrations. As the drop dries, the polymer gets deposited at the three-phase contact line, thus reducing the surface energy of the substrate and leading to an increase in the contact angle. The drop responds by attempting to reach a new equilibrium contact angle through slipping. The temporal increase in contact angle follows a power law scaling behavior. This study demonstrates an in situ modulation of contact angle facilitated by evaporation and polymer deposition, showcasing unconventional drying dynamics.

Reliable Determination of Contact Angle from the Liquid Fence.

Traditional methods of measuring contact angles often face difficulties in precisely defining the three-phase contact points. A novel method for accurately defining three-phase contact points based on liquid fences is proposed in this article. The tested liquid is placed in a cubic liquid fence composed of a pair of narrow strips of the tested solid and a pair of transparent wide strips. The transparent wide strip serves as the measurement window, and the surface tension of the liquid on it can be almost ignored. In experimental measurements, the horizontal coordinates of the end points of the liquid profile are fixed by the liquid fence, thus determining the horizontal coordinates of the three-phase contact points, which helps to accurately survey the contact angle. Additionally, since the parameters of the liquid fence are known, the size of the contact angle can also be calculated by measuring the height of the liquid level dome inside the liquid fence. Using the electric wetting effect as an example, we experimentally extracted a series of liquid contour maps with circular tops and square columns under varying voltages. The relationship curve between contact angle and voltage variation was obtained using the above methods, and a contact angle variation tendency seemed to agree well with the theoretical value.

Modulation of wetting state switching of droplets on superhydrophobic microstructured surfaces by external electric field

HypothesisElectrowetting on conventional dielectrics requires direct fluid-electrode contact to generate strong electric fields at the three-phase contact line to modulate the wetting. Since the electric field alters wetting, the modulation of wetting can be achieved by applying an external electric field through insulated electrodes, preventing the liquid from contacting the electrodes. ExperimentA simple and efficient method for non-contact between the fluid and the electrode external electric field modulation of fluid wetting was proposed. The switching ability of droplets on microgroove surfaces from Cassie-Baxter to Wenzel wetting state under an external electric field was used to drive and quantify the relationship between wetting, contact angle, and the applied voltage. FindingsApplying an external electric field modulates the wetting of deionized water, ionic liquids, and high-viscosity liquids on microgrooves. The wetting degree of liquid can be controlled by adjusting the external voltage parameters. The finite element simulations revealed that the Maxwell force drove this process. The effects of substrate size and liquid properties on wetting behavior were also examined. Post-application cross-sectional imaging showed the formation of a conformal interface, highlighting the relevance of the proposed method in advanced adaptive shape fabrication and microfluidic control, among other applications.

Fabrication, characterization and application of Pickering emulsion gels stabilized by defatted grape seed powder

The feasibility of defatted grape seed powder (DGSP) stabilizing Pickering emulsion gels as butter substitute was investigated. The Pickering emulsion gel was constructed using DGSP through high-speed homogenization, and the effects of particle concentration (c) and oil-phase (Medium chain triglyceride) volume fraction (φ) on its structure and properties were investigated. Its application as a butter substitute was also evaluated. The results showed that DGSP had various particle shapes, a wide particle size distribution (3–130 μm), and a three-phase contact angle of 128.9 ± 2.3°. The O/W Pickering emulsion gels with φ ≥ 60% could be obtained at c ≥ 2%. The droplet diameter was negatively correlated with c and positively correlated with φ, while the gel strength was positively related to c and φ. The resulting emulsion gel demonstrated solid-like viscoelastic behavior and pseudoplasticity, and had the potential to serve as a butter substitute. The results can promote the application of grape seeds in food.

Elastocapillary interaction for particles trapped at the isotropic-nematic liquid crystal interface.

We present numerical simulations on pairwise interactions between particles trapped at an isotropic-nematic liquid crystal (Iso-N) interface. The particles are subject to elastocapillary interactions arising from interfacial deformations and elastic distortions of the nematic phase. We use a recent model based on a phase-field approach [see Qiu etal., Phys. Rev. E 103, 022706 (2021)2470-004510.1103/PhysRevE.103.022706] to take into account the coupling between elastic and capillary phenomena. The pair potential is computed in a two-dimensional geometry for a range of particle separations and two anchoring configurations. The first configuration leads to the presence of an anchoring conflict at the three-phase contact line, whereas such a conflict does not exist for the second one. In the first case, the results show that significant interfacial deformations and downward particle displacements occur, resulting in sizable attractive capillary interactions able to overcome repulsive elastic forces at intermediate separations. The pair potential exhibits an equilibrium distance since elastic repulsions prevail at short range and prevent the clustering of particles. However, in the absence of any anchoring conflict, the interfacial deformations are very small and the capillary forces have a negligible contribution to the pair potential, which is fully repulsive and overwhelmed by elastic forces. These results suggest that the self-assembly properties of particles floating at Iso-N interfaces might be controlled by tuning anchoring conflicts.

Effect of heat treatment on the structural and emulsifying properties of copra meal protein: Improving interfacial properties to enhance performance of its Pickering emulsion

This study investigated the impact of different temperatures and durations on the structural and emulsifying properties of copra meal protein. Additionally, the stability of copra meal protein Pickering emulsions was assessed through rheological and interfacial characteristics. Findings revealed a positive correlation between emulsification properties and heating temperature and duration. Thermal aggregates, facilitated by hydrogen bonds, hydrophobic interactions, and disulfide bonds, significantly enhanced surface hydrophobicity. Heat-treated copra meal protein-based Pickering emulsions demonstrate enhanced adsorption at the oil-water interface and resistance to diffusion. The three-phase contact angle increases from 57.7° to 79.8° following heating at 95 °C for 30 min. The addition of NaCl and heating treatment did not affect emulsion particle size or interface adsorption ability. But it improved the rheological properties to varying degrees. These results offer valuable insights for optimizing the physicochemical and functional attributes of copra meal protein in the food industry.

A Molecular Expression for "Line Tension".

"Line tension", a concept that features in an additional term to the Young's equation, was introduced to describe the size dependence of contact angles of nanodroplets on surfaces. Although this concept describes the observations in a succinct, elegant manner, theorists have long had misgivings about the physical interpretation of the phenomenon. Papers have been published that attempt to nail down its value, which is reportedly very small (∼10 pN) and evidently even the sign has been uncertain. Attempts to interpret it in a mechanical manner analogous to interfacial tension, i.e., due to the curvature of the three-phase contact line, have run into conceptual problems that require invocations of ever more complex models. In this work, we have used molecular simulations to systematically relate "line tension" to the additional free energy per unit length of the three-phase line and found no direct relation. However, when we rederived the Young's equation without ignoring the interfacial molecules, we found a physically satisfying explanation for the size dependence of the contact angle of nanodroplets without invoking the curvature of the three-phase contact line. The new model does not have the elegant form of the modified Young's equation, but each parameter in it has an unambiguous physical interpretation. An approximate form of this model, linearized in the inverse droplet radius, yields a quantity that is mathematically analogous to what is conventionally called "line tension", but unpacked at the molecular level, showing that it is unrelated to a restoring force associated with the curvature of the macroscopic three-phase contact line.

Morphological evolution of nano-droplets impinging on cylindrical wall: A molecular dynamics study

The impact of droplets on solid walls is the primary behavior in spray cooling, seawater desalination, self-cleaning, and other technological processes. Based on the molecular dynamics (MD) method, the morphological evolution characteristics of nanodroplets impinging on the copper cylinder wall are studied. The effects of droplet size, initial velocity, impact position, and wall wettability on nanodroplet dynamics are analyzed. The results indicate that a single nanodroplet impacting on a nanocylinder exhibits four distinct impact modes: spread-partially wrapped-deposition (SPD), spread-completely wrapped-deposition (SCD), spread-completely wrapped-splitting-deposition (SCSD), and spreading-partially wrapped-splitting-deposition (SPSD). The trend of the influence of initial velocity and droplet size on the impact mode is similar. As the initial velocity and droplet size increase, the droplet’s kinetic energy and inertia force increase, successively exhibiting the SPD, SCD, and SCSD modes. The trend of the influence of impact position and wall wettability on the droplet impact mode is similar. When the impact eccentricity distance is small, and the wall is highly hydrophilic, it exhibits the SCD mode. With increasing impact eccentricity and enhanced wall hydrophobicity, the adhesion force between the droplet and the cylinder wall decreases, making the droplet less likely to be captured and more prone to splitting, exhibiting the SPSD mode. The change in droplet centroid height and mean square displacement could predict whether the droplet undergoes a splitting mode, and its influence is most significant at the impact position. Constrained by the cylindrical wall, the droplet impacts radially and spreads primarily in that direction. With the enhancement of wall hydrophilicity, the migration region of the three-phase contact line expands, and the droplet spreading transforms into synchronous development along the radial and axial directions. The research results can enrich the dynamic mechanism of micro-nano scale droplet impact and provide potential guidance for optimizing relevant technologies.

Contact-angle hysteresis on rough surfaces: mechanical energy balance framework

Using as a starting point conservation of momentum, a multiphase mechanical energy balance equation is derived that accounts for multiple material phases and interfaces present within a moving control volume. This balance is applied to a control volume that is anchored to a three-phase contact line as it advances continuously over the surface of a rough and chemically homogeneous and inert solid. Using semi-quantitative models for the material behaviour occurring within the control volume, an order of magnitude analysis is performed to neglect insignificant terms, producing an equation for predicting contact-angle hysteresis from a knowledge of the interface dynamics occurring around the three-phase contact line. It is shown that the viscous energy dissipation that occurs during the ‘stick–slip’ motion of the three-phase contact line, being the cause of contact-angle hysteresis on rough surfaces, can be calculated from changes in intermediate equilibrium interface states. The balance is applied to the Wenzel, Cassie–Baxter and Fakir (super-hydrophobic) wetting states, showing for the Fakir case that significant dissipation occurs during both interface advance and recede, and relating these dissipations to interfacial area changes that occur around the ‘stick–slip’ events.

Mechanism analysis of injection technique of water composition modification for enhanced oil recovery

ABSTRACT By adjusting the composition of injection water, including ionic type and strength, the goal of enhance oil recovery rate can be achieved. However, there is no clear understanding of which factor, ionic type or strength, has a greater impact. In this paper, based on the formation water of the offshore G oilfield, various brines with different ionic strengths and types were prepared. By measuring the zeta potential of rock powder and oil droplets, three-phase contact angle, interfacial tension between oil and water, emulsification properties of brines, and film strength of oil-water interface, the variation rules of the core wettability and emulsification performance of brine were systematically analyzed when the ionic strength and ionic type were changed. The experimental results showed that ionic strength has a greater impact than that of ionic type. For the oil-water-solid (rock) system of the G oilfield, an ionic strength of 82 mM/kg is the threshold for low salinity effect. Reducing ionic strength resulted in an increase in the hydrophilicity of rock and the ability of water flooding to emulsify oil droplets, which contribute to the improvement of oil displacement efficiency. Theoretically, water flooding to enhance oil recovery can be achieved by only reducing the ionic strength. This understanding was verified by dual polarization interferometry (DPI) experiments and low-field nuclear magnetic resonance experiments, which showed that reducing the salinity of the injection water from 42,000 mg/L (ionic strength of 820 mM/kg) to 4200 mg/L (ionic strength of 82 mM/kg) enhanced the oil recovery by 7.9%.

Features of the contact angle hysteresis at the nanoscale: A molecular dynamics insight

Understanding the physics of a three-phase contact line between gas, liquid, and solid is important for numerous applications. At the macroscale, the response of a three-phase contact line to an external force action is often characterized by a contact angle hysteresis, and several models are presented in the literature for its description. Yet, there is still a need for more information about such model applications at the nanoscale. In this study, a molecular dynamics approach was used to investigate the shape of a liquid droplet under an external force for different wetting regimes. In addition, an analytic model for describing the droplet shape was developed. It gives us the possibility to evaluate the receding and advancing wetting angle accurately. With our modeling, we found that the interplay between capillary forces and viscous forces is crucial to characterize the droplet shape at the nanoscale. In this frame, the importance of the rolling movement of the interface between liquid and vapor was pointed out. We also demonstrate that in the range of the external forces when capillary forces are most significant compared to others, hysteresis is well described by the macroscale Cox–Voinov model.

Emulsifying and interfacial properties of glutenin processed by pH-shifting treatment

Modifying and improving protein functionality is crucial for expanding the application of proteins in the food industry. The aim of this study was to investigate the effect of pH-shift treatments on the emulsifying and interfacial properties of glutenin (Glu). Glu was exposed to acidic (pH 1–3) and basic (pH 10–13) pH values for 4 h and subsequently neutralized for refolding. The pH-shifting treatments significantly improved Glu surface wettability with three-phase contact angle from 66.21 ± 2.31° to 91.4 ± 0.88°. The alkali shift treatment resulted in samples with larger Kdiff values. The treated samples also showed amplitude and frequency dependence in their E, Ev, and Ed values, with higher E and Ed values indicating an elastic membrane at the interface. Emulsions prepared from Glu treated with alkali shift treatment exhibited smaller particle size, larger ζ-potential, and more stable storage properties. The rheological results indicated higher viscosity, thixotropy and creep of emulsions prepared from alkali shift treated Glu. In conclusion, treatment of Glu with alkali shift resulted in significant improvements in emulsifying and interfacial properties, suggesting that Glu may be a more promising ingredient for use in food.

Effect of xanthan gum (XG) and carrageenan (CG) ratio on casein (CA)-XG-CG ternary complex: Used to improve the stability of liquid diabetes formula food for special medical purposes

Poor storage stability limits the application of liquid diabetes formula food for special medical purposes (L-D-FSMP) in maintaining blood sugar stability in diabetic patients. This work aims to improve the stability of L-D-FSMP by adjusting the ratio of xanthan gum (XG) and carrageenan (CG) in casein (CA)-XG-CG ternary complex. The centrifugal sedimentation rate results showed that the compound ratio of XG and CG had a greater impact on L-D-FSMP storage stability. Transmission electron microscopy (TEM) results showed that the combination of CA, XG and CG occurred. Fourier transform infrared spectroscopy (FTIR) results showed that CA, XG and CG were mainly combined through hydrogen bonds and ionic bonds to form a CA-XG-CG ternary complex. When the ratio of XG and CG was 1:1, the number of disulfide bonds was the largest. The results of three-phase contact angle and emulsifying ability confirmed that when the ratio of XG and CG was 1:1, CA-XG-CG had the strongest emulsifying ability. The particle size distribution and zeta-potential results showed that when the ratio of XG and CG was 1:1, L-D-FSMP had the narrowest particle size distribution range and the strongest stability. These results may provide valuable information for the production of stable L-D-FSMP.

Understanding the Role of Loss Modulus of Viscoelastic Substrates in the Evaporation Dynamics of Sessile Drops.

Viscoelastic properties of soft substrates play a crucial role in the evaporation dynamics of sessile drops. Recent studies have revealed that the modification of the viscoelastic properties of substrates changes the dynamics of the three-phase contact line, consequently affecting the evaporation behavior of sessile drops. Notably, these modifications occur without any noticeable changes to the substrate's wetting characteristics or surface topography. However, the individual role of storage (G') and loss (G″) moduli of substrates on drop evaporation dynamics remains unexplored. In this study, we investigate the evaporation dynamics of water drops on two groups of poly(dimethylsiloxane)-based viscoelastic substrates possessing either identical G' with varying G″ or identical G″ with varying G'. Our study reveals that on a substrate with constant shear modulus (G'), a reduction of an order of magnitude in loss modulus shifts the evaporation process from the constant contact radius mode to the constant contact angle mode. We hypothesize that this observed shift in behavior stems from the varying viscoelastic dissipation influenced by the plateau modulus and characteristic relaxation time of polymer gels. Our hypothesis is further supported from the observation that the evaporation process persists on the substrate with constant loss modulus (G″). Our study advances the current understanding of drop evaporation on soft substrates that may find potential applications involving soft composites, biological entities, tissue engineering, and wearable electronics.

High Internal Phase Emulsions Stabilized with Ultrasound-Modified Spirulina Protein for Curcumin Delivery.

Spirulina protein (SP) is recognized as a nutritious edible microbial protein and holds potential as a natural emulsifier. Due to the inherent challenges SP faces in stabilizing high internal phase emulsions (HIPEs), ultrasonic techniques were utilized for modification. Noticeable alterations in the structural and functional properties of SP were observed following ultrasonic treatment at various power levels (0, 100, 300, and 500 W). Ultrasound treatment disrupted non-covalent interactions within the protein polymer structure, leading to the unfolding of molecular structures and the exposure of hydrophobic groups. Importantly, the particle size of SP was reduced the most at an ultrasonic power of 300 W, and the three-phase contact angle reached its peak at 84.3°. The HIPEs stabilized by SP modified with 300 W ultrasonication have high apparent viscosity and modulus values and strong storage stability under different environmental conditions. Additionally, the encapsulation of curcumin in HIPEs led to improved retention of curcumin across various settings. The bioavailability increased to 35.36, which is 2.8 times higher than the pure oil. These findings suggest that ultrasound-modified SP is a promising emulsifier for HIPEs, and is expected to encapsulate hydrophobic nutrients such as curcumin more effectively.

Turning Non-Sticking Surface into Sticky Surface: Correlation between Surface Topography and Contact Angle Hysteresis.

We present a surface modification technique that turns CuNi foam films with a high contact angle and non-sticking property into a sticky surface. By decorating with mesh-like biaxially oriented polypropylene (BOPP) and adjusting the surface parameters, the surface exhibits water-retaining capability even when being held upside down. The wetting transition process of droplets falling on its surface were systematically studied using the finite element simulation method. It is found that the liquid filled the surface microstructure and curvy three-phase contact line. Moreover, we experimentally demonstrated that this surface can be further applied to capture underwater air bubbles.

Pickering emulsions with high ionic strength resistance stabilized by pea protein isolate-polyglycerol conjugate particles with good biocompatibility

Among various biopolymers, protein particles are widely used for stabilizing Pickering emulsions, yet their emulsifying ability are easily influenced by the ion concentration, pH, and high temperatures. To address these challenges, this study utilized chemical modification to prepare pea protein isolate-polyglycerol (PPI-PG) conjugates by Schiff-base reaction. Compared with other chemical modifications, this method produces conjugate particles with excellent biocompatibility, capable of promoting cell proliferation by up to 177 %. These conjugates showed improved dispersibility, with diffusion coefficients 3.5 times greater than pure PPI, and the isoelectric points shift from pH 4.6 to pH 1.5, which contribute to the pH stability of emulsions (pH 3–9). Additionally, the anisotropic nature of the conjugate particles, with a three-phase contact angle close to 90°, make particles need more energy for detachment from the oil-water interface, leading to good thermal stability of emulsion (80 °C, 48 h). Notably, after conjugation, these particles rely more on PG chains for dispersibility, which are less affected by ions, resulting in emulsions with high ionic strength resistance (3000 mM). Furthermore, the prepared Pickering emulsion demonstrates remarkable antioxidative properties (only a 10 % decrease), indicating widely potential applications in food, cosmetics, and pharmaceutical sectors.

Enhancement of the Rate of Surface Reactions by the Elastocapillary Effect.

We examined the effect of deformability of a solid substrate on the kinetics of a surface reaction that occurs between chemical species present in it and a liquid dispensed on it. In particular, we have dispensed aqueous solutions of gold and silver salt as sessile drops or as a liquid pool on a cross-linked film of poly(dimethylsiloxane) (PDMS). The PDMS surface contains organosilane (SiH), which reduces the salt, producing metallic nanoparticles at the solid-liquid interface. These experiments reveal that, for a sufficiently soft solid, the reaction proceeds about three times faster in the drop mode than in the pool mode. The reaction conditions in both cases remain exactly identical except that, for the drop, the vertical component of the liquid surface tension deforms the solid substrate at the three-phase contact line. We have estimated the solid-liquid and solid-air interfacial energy, which along with the surface energy of the liquid gives an estimate of excess free energy. This energy is found to be different for the drop and pool modes. By considering that this excess free energy decreases the activation energy barrier for the reaction, we have shown that the reaction rate constant in the drop mode should indeed exceed that in the pool mode by about three times.