Oil-water Interfacial Tension Research Articles

Surfactant–Polymer Flooding: Chemical Formula Design and Evaluation for High-Temperature and High-Salinity Qinghai Gasi Reservoir

The Gasi reservoir in the Qinghai oilfield is a typical high-temperature and high-salinity reservoir, with an average temperature and average salinity of 70.0 °C and 152,144 mg/L, respectively. For over 30 years since 1990, water flooding has been the primary method for enhancing oil recovery. Recently, the Gasi reservoir has turned into a mature oilfield. It possesses a high water cut of 76% and a high total recovery rate of 47%. However, the main developing enhanced oil recovery (EOR) technology for the development of the Gasi reservoir in the next stage is yet to be determined. Surfactant–polymer (SP) flooding, which can reduce the oil–water interfacial tension and increase the viscosity of the water phase, has been widely applied to low-temperature and low-salinity reservoirs across China in the past few decades, but it has rarely been applied to high-temperature and high-salinity reservoirs such as the Gasi reservoir. In this study, the feasibility of SP flooding for high-temperature and high-salinity reservoirs was established. Thanks to the novel surfactant and polymer products, an SP flooding formula with surfactants ZC-2/B2 and polymer BRH-325 was proposed for Gasi. The formula showed a low interfacial tension of 10−2 mN/m and a high viscosity of 18 mPa·s in simulated reservoir conditions. The oil displacement experiment demonstrated that this formula can enhance the oil recovery rate by 26.95% upon water flooding at 64.64%. This study provides a feasible EOR candidate technology for high-temperature and high-salinity reservoirs, as exemplified by the Qinghai Gasi reservoir.

Development of 1 Month Sustained-Release Microspheres Containing Liraglutide for Type 2 Diabetes Treatment.

Liraglutide has been extensively applied in the treatment of type 2 diabetes mellitus (T2DM), but its 11-15 h half-life resulted in daily administration, which led to poor patient compliance. This study aimed to solve this problem by developing liraglutide-loaded microspheres with a 1 month sustained release prepared by the W1/O/W2 method combined with the premix membrane emulsification technique to improve therapeutic efficacy. Remarkably, we found that the amphiphilic properties of liraglutide successfully reduced the oil-water interfacial tension, resulting in a stable primary emulsion and decreasing the level of drug leakage into the external water phase. As a result, exceptional drug loading (>8%) and encapsulation efficiency (>85%) of microspheres were achieved. Furthermore, the uniformity in microsphere size facilitated an in-depth exploration of the structural characteristics of liraglutide-loaded microspheres. The results indicated that the dimensions of the internal cavities of the microspheres were significantly influenced by the size of the inner water droplets in the primary emulsion. A denser and more uniform cavity structure decreased the initial burst release, improving the release process of liraglutide from the microspheres. To evaluate the release behavior of liraglutide from microspheres, a set of in vitro release assays and in vivo pharmacodynamics were performed. The liraglutide-loaded microspheres effectively decreased fasting blood glucose (FBG) levels and hemoglobin A1c (HbA1c) levels while enhancing the pancreatic and hepatic functions in db/db mice. In conclusion, liraglutide sustained-release microspheres showed the potential for future clinical applications in the management of T2DM and provided an effective therapeutic approach to overcoming patient compliance issues.

Performance and mechanism of organic solid-phase sediment composite plugging agent

The surface pipeline sediments of the Yingmai and Hade oil fields mainly contain substances such as asphalt and paraffin. The formation of sediment can increase the backpressure during pipeline transportation, and in severe cases, it can also lead to pipeline blockage. In order to solve this on-site situation, indoor experiments were conducted in the early stage, and an efficient organic unblocking system LXW was optimized and formulated. Based on this system, this article selects the wire mesh filtration method to evaluate the unblocking performance of LXW and on-site unblocking agents in the study and comparison of three evaluation methods. At the same time, based on the analysis of the chemical composition, microstructure, and melting point of organic sediments, from the perspectives of safety, environmental protection, and economic factors, further compares the performance and universality of the three unblocking systems, optimizes the process parameters of the LXW unblocking system, explores its stability and impact on the demulsification and dehydration of crude oil emulsions, and evaluates its safety performance. The LXW unblocking system has a more efficient unblocking effect and better universality, which can solve the problem of multiple block blockages on site. In addition, compared with existing unblocking agents, it has better economic benefits and is in line with the characteristics of low cost on site. On this basis, the dissolution and dispersion mechanism of the blockage system on sediment was studied through laser scattering system and fluorescence microscope, and its microscopic mechanism was further verified. At the same time, the oil-water interfacial tension under the action of the unblocking system was studied, and it was found that adding the agent can significantly reduce the equilibrium interfacial tension, which is of great significance for increasing production and injection.

Impact mechanism of active nanofluid on oil–water two-phase seepage during and after fracturing fluid invasion in tight oil reservoirs

Due to damage caused by fracturing fluid invasion, tight oil reservoirs exhibit slow post-hydraulic fracturing production recovery and low productivity. This study investigates the impact of a nanoclay-based active agent system on oil–water two-phase flow during and after fracturing fluid invasion, emphasizing its potential for enhancing recovery in tight oil reservoirs. Laboratory experiments using crude oil and natural core samples analyze the mechanism of how nanofluids affect oil–water distribution and flow characteristics during fracturing fluid invasion and oil recovery stages. Results show that nanofluids rapidly disrupt the emulsified state of “water-in-oil” emulsions, reducing emulsion viscosity by 84.19% and oil–water interfacial tension by two orders of magnitude, facilitating oil droplet dispersion and deformation and altering the wettability of oil-wet rock surfaces to aid crude oil detachment. Nanofluids increase the accessible volume of the water phase in pores and throats, enlarging flow paths for fracturing fluid flowback and oil recovery. The oil recovery process post-fracturing fluid invasion is delineated into three stages: substantial fracturing fluid flowback in the first stage, with nanofluids reducing the fluid return rate by 11.08% upon crude oil breakthrough; emulsion droplets occupying pores and throats in the second stage, with nanofluids reducing additional resistance during emulsion flow; and continuous oil production in the third stage, with nanofluids consistently and stably altering rock surface wettability to reduce invaded rock matrix resistance to oil flow. The findings of this study hold potential value in mitigating damage from fracturing fluid invasion in tight oil reservoirs.

Simulation and experimental study on amphiphilic modified graphene oxide for EOR

The application of nanosheet in enhanced oil recovery (EOR) offers a practical approach to resolving some surface-related problems. In this study, theoretical calculation and experiment were combined to study the interfacial behavior and mechanism of amphiphilic modified graphene oxide. Octadecyl amine and aspartic acid were successfully grafted onto graphene oxide nanosheets by starch template method. The stability of the modified structure was verified by IR, XRD and SEM. The change of microstructure in molecular simulation can enhance the understanding of the structure of amphiphilic modified nanosheets under SEM. The contact angle experiment directly shows its amphiphilicity, which shows that the contact angle of hydrophilic surface is 34.6° and that of hydrophobic surface is 103.5°. The interfacial elasticity experiment shows that the interfacial film formed by synthetic GOTA has certain elasticity. When the concentration increases, the interfacial film formed in the adsorption process can effectively separate the oil and water phases. Based on the interfacial tension value, the ability of graphene oxide and modified graphene oxide with different concentrations to reduce the interfacial tension between distilled water and diesel oil was investigated successively. The mechanism of GOTA action was explained from the aspects of molecular structure and energy by molecular simulation. The results show that the interfacial tension fluctuates around 16 mN/m when the GOTA concentration is 0.005%, and the average interfacial tension is 17.48 mN/m when the GOTA concentration (molecular number percentage) is 0.004% in the simulation process, which is highly consistent. Further studies have shown that the interface formation energy of the system is significantly reduced after the addition of zwitterionic surfactants, and the interfacial tension can be reduced to 11.95 mN/m. With the help of molecular simulation, the adsorption mechanism of GOTA on the interface is explained from the aspects of microstructure change, interaction energy, cohesion energy, interface density and conformation. The adjustment of these interactions will directly affect the oil-water interface morphology and interfacial tension.

Synergistic collaborations between surfactant and polymer for in-situ emulsification and mobility control to enhance heavy oil recovery

Surfactant-polymer (SP) combined systems is an effective nonthermal method to enhance the heavy oil recovery, through in-situ emulsification and mobility control mechanisms. In this study, a novel SP system was developed using 0.2 wt% anionic surfactant (alkyl naphthol polyoxyethylene ether sulfonate, ANES) and 0.1 wt% polymer (partially hydrolyzed polyacrylamide, HPAM). The SP system had viscosity reduction rate of ∼ 98 %, viscosity ratio of oil to displaced water (μo/μd) of ∼ 3.95 and IFT of ∼ 0.29 mN/m, beneficial for decreasing the mobility ratio of water to heavy oil. Then, the applied performances including emulsion morphologies and stability, wettability alteration ability were systematically characterized. The results showed that the freshly O/W emulsions formed by SP system displayed uniform droplet size distribution, as well as high stability with tight interfacial film. In addition, the SP system exhibited excellent wettability alteration property with low contact angle of 18.3°. The synergistic collaboration mechanisms of surfactant and polymer include heavy oil–water interfacial tension reduction, in-situ emulsification, oil-viscosity reduction and water-viscosity increase. Finally, the static oil washing and dynamic sand-pack flooding experiments showed that the SP system exhibited high oil washing efficiency (62.89 %) and enhanced oil recovery efficiency (56.9 %) with improving the mobility controllability after the primary water-flooding process. This study indicated that the synergistic collaborations between surfactant and polymer had great potential to enhance the heavy oil recovery.

Numerical Investigation on Alkaline-Surfactant-Polymer Alternating CO2 Flooding

For over four decades, carbon dioxide (CO2) has been instrumental in enhancing oil extraction through advanced recovery techniques. One such method, water alternating gas (WAG) injection, while effective, grapples with limitations like gas channeling and gravity segregation. To tackle the aforementioned issues, this paper proposes an upgrade coupling method named alkaline-surfactant-polymer alternating gas (ASPAG). ASP flooding and CO2 are injected alternately into the reservoir to enhance the recovery of the WAG process. The uniqueness of this method lies in the fact that polymers could help profile modification, CO2 would miscible mix with oil, and alkaline surfactant would reduce oil–water interfacial tension (IFT). To analyze the feasibility of ASPAG, a couples model considering both gas flooding and ASP flooding processes is established by using the CMG-STARS (Version 2021) to study the performance of ASPAG and compare the recovery among ASPAG, WAG, and ASP flooding. Our research delved into the ASPAG’s adaptability across reservoirs varying in average permeability, interlayer heterogeneity, formation rhythmicity, and fluid properties. Key findings include that ASPAG surpasses the conventional WAG in sweep and displacement efficiency, elevating oil recovery by 12–17%, and in comparison to ASP, ASPAG bolsters displacement efficiency, leading to a 9–11% increase in oil recovery. The primary flooding mechanism of ASPAG stems from the ASP slug’s ability to diminish the interfacial tension, enhancing the oil and water mobility ratio, which is particularly efficient in medium-high permeability layers. Through sensitivity analysis, ASPAG is best suited for mid-high-permeability reservoirs characterized by low crude oil viscosity and a composite reverse sedimentary rhythm. This study offers invaluable insights into the underlying mechanisms and critical parameters that influence the alkaline-surfactant-polymer alternating gas method’s success for enhanced oil recovery. Furthermore, it unveils an innovative strategy to boost oil recovery in medium-to-high-permeability reservoirs.

The bile salt/phospholipid ratio determines the extent of in vitro intestinal lipolysis of triglycerides: Interfacial and emulsion studies

This study focused on the protein-stabilised triglyceride (TG)/water interfaces and oil-in-water emulsions, and explored the influence of varying molar ratios of bile salts (BSs) and phospholipids (PLs) on the intestinal lipolysis of TGs. The presence of these two major groups of biosurfactants delivered with human bile to the physiological environment of intestinal digestion was replicated in our experiments by using mixtures of individual BSs and PLs under in vitro small intestinal lipolysis conditions. Conducted initially, retrospective analysis of available scientific literature revealed that an average molar ratio of 9:4 for BSs to PLs (BS/PL) can be considered physiological in the postprandial adult human small intestine. Our experimental data showed that combining BSs and PLs synergistically enhanced interfacial activity, substantially reducing oil–water interfacial tension (IFT) during interfacial lipolysis experiments with pancreatic lipase, especially at the BS/PL–9:4 ratio. Other BS/PL molar proportions (BS/PL–6.5:6.5 and BS/PL–4:9) and an equimolar amount of BSs (BS–13) followed in IFT reduction efficiency, while using PLs alone as biosurfactants was the least efficient. In the following emulsion lipolysis experiments, BS/PL–9:4 outperformed other BS/PL mixtures in terms of enhancing the TG digestion extent. The degree of TG conversion and the desorption efficiency of interfacial material post-lipolysis correlated directly with the BS/PL ratio, decreasing as the PL proportion increased. In conclusion, this study highlights the crucial role of biliary PLs, alongside BSs, in replicating the physiological function of bile in intestinal lipolysis of emulsified TGs. Our results showed different contributions of PLs and BSs to lipolysis, strongly suggesting that any future in vitro studies aiming to simulate the human digestion conditions should take into account the impact of biliary PLs – not just BSs – to accurately mimic the physiological role of bile in intestinal lipolysis. This is particularly crucial given the fact that existing in vitro digestion protocols typically focus solely on applying specific concentrations and/or compositions of BSs to simulate the action of human bile during intestinal digestion, while overlooking the presence and concentration of biliary PLs under physiological gut conditions.

Flooding Performance and Optimization of Injection Parameters of Nanosized Oil Displacement Agents in Extra-Low-Permeability Reservoirs.

There have been few studies on the role of nanofluids in oil displacement and injection parameters, despite their significant impact on the oil displacement effect. To enhance oil recovery in an ultralow-permeability reservoir, the nanosized oil-displacement agent with nano-SiO2 modified by a silane coupling agent as a main component was selected for the first time in the Changqing oilfield. To assess the performance of the nanofluid, various factors such as particle size, contact angle, interfacial tension, and emulsion stability were taken into consideration. The oil displacement effect of nanofluids was evaluated by a microscopic model and ultralow-permeability core displacement experiment, and its optimal injection parameters were determined. The average particle size of the nano-oil displacement agent is 22-30 nm. It can change the wetting condition of the rock from oil-wet to water-wet and reduce the oil-water interfacial tension. Even at 80 °C, the emulsion formed by the agent remained stable. The oil displacement experiment shows that the nano-oil displacement agent whose injection pressure increases can displace the residual oil trapped in small pores that cannot be affected by conventional water flooding. The injection mode of "nanoflooding agent drive + water drive + nanoflooding agent drive", injection rate of 0.1 mL/min, injection concentration of 0.5%, and injection volume of 0.5 PV (0.25 PV per segment), which can effectively guide the injection of the oil displacement agent, achieve the best oil displacement effect.

Correlation between emulsification and butyryl group distribution in various butyrylated starches

Butyrylated starch, a modified starch with significant applications in the food and pharmaceutical industries, lacks sufficient research on its emulsification. In this study, butyrylation was performed using waxy corn starch, tapioca starch and corn starch as raw materials, and their group distribution were determined. X-ray photoelectron spectroscopy (XPS), Raman microscopy and water contact angle measurements showed that the distribution of butyryl group in B-WCS was highly uniform. The results of the emulsification assay illustrated that B-WCS exhibited significant emulsifying potential at similar degrees of substitution. Analysis of the interface behavior demonstrated that B-WCS reduced the oil-water interfacial tension and formed a rigid interface film that resisted external deformation, thereby maintaining emulsion stability. This indicates that B-WCS exhibiting a highly uniform group distribution has significant emulsification potential. This study revealed the emulsification mechanism of butyrylated starch from an interface perspective and analyzed the relationship between the butyryl group distribution and emulsifiability.

Enhancing Oil Recovery in Low-Permeability Reservoirs Using a Low-Molecular Weight Amphiphilic Polymer.

Polymer flooding has achieved considerable success in medium-high permeability reservoirs. However, when it comes to low-permeability reservoirs, polymer flooding suffers from poor injectivity due to the large molecular size of the commonly used high-molecular-weight (high-MW) partially hydrolyzed polyacrylamides (HPAM). Herein, an amphiphilic polymer (LMWAP) with a low MW (3.9 × 106 g/mol) was synthesized by introducing an amphiphilic monomer (Allyl-OP-10) and a chain transfer agent into the polymerization reaction. Despite the low MW, LMWAP exhibited better thickening capability in brine than its counterparts HPAM-1800 (MW = 1.8 × 107 g/mol) and HPAM-800 (MW = 8 × 106 g/mol) due to the intermolecular hydrophobic association. LMWAP also exhibited more significant shear-thinning behavior and stronger elasticity than the two counterparts. Furthermore, LMWAP possesses favorable oil-water interfacial activity due to its amphiphilicity. The oil-water interfacial tension (IFT) could be reduced to 0.88 mN/m and oil-in-water (O/W) emulsions could be formed under the effect of LMWAP. In addition, the reversible hydrophobic association endows the molecular chains of LMWAP with dynamic association-disassociation transition ability. Therefore, despite the similar hydrodynamic sizes in brine, LMWAP exhibited favorable injectivity under low-permeability conditions, while the counterpart HPAM-1800 led to fatal plugging. Furthermore, LMWAP could enhance oil recovery up to 21.5%, while the counterpart HPAM-800 could only enhance oil recovery by up to 11.5%, which could be attributed to the favorable interfacial activity of LMWAP.

Synthesis and emulsion stability of salt resistant viscosity reducer for heavy oil reservoirs with varying salinities

To address the inadequate salt resistance of viscosity reducers and their limited applicability to reservoirs with single salinity, we synthesized salt-resistant viscosity reducers PANxAn in this study. These compounds were derived from fatty alcohol polyoxyethylene ether acrylate, N-alkyl acrylamide, acrylamide, and 2-acrylamido-2-methylpropanesulfonic acid. The structures were identified using nuclear magnetic hydrogen spectroscopy. We investigated the effects of the hydrophilic group ethoxy-chain length (n = 14, 16, 18, 20 and 22) and hydrophobic group alkyl-chain length (x = 12, 14, 16, and 18) on the salt resistance, interfacial activity, wettability, interfacial viscoelasticity and emulsification viscosity reduction performance of the viscosity reducers. Futher, the structures of the viscosity reducers which can adapt to different salinities were determined. Based on the emulsification viscosity reduction effect, PAN14A16, PAN12A16, PAN12A18, PAN12A20/PAN16A16 and PAN12A22/PAN18A16 adapted to salinities range of 2 × 104-6 × 104, 4 × 104-8 × 104, 6 × 104-10 × 104, 8 × 104-12 × 104 and 10 × 104-14 × 104 mg/L, respectively. At the optimal salinity, PANxAn reduced the oil–water interfacial tension from 28.3 to 5.0 mN/m, dynamic contact angle from 130.0° to 61.0°, and heavy oil viscosity from 454.6 to 60.0 mPa·s with a viscosity reduction rate of 86.80 %. The synthesis of salt-resistant PANxAn provides theoretical guidance and application value for enhancing the recovery efficiency of viscosity-reducer flooding in high-salinity heavy oil reservoirs.

Marangoni Convection Velocity in Nonlinear Hanging-Droplet Vibration Phenomena

The Marangoni effect involves a mass transfer along an interface between two phases owing to the gradient of the interfacial tension. The flow caused by this phenomenon is called Marangoni convection, a complex phenomenon that involves mass transfer processes, such as surfactant adsorption/desorption processes, solvent dissolution phenomena, and viscous dissipation processes. Therefore, the strength of the convection depends on the various thermodynamic and physical properties of the fluids. In this study, we experimentally investigated the relationship between the Marangoni convection generated inside a hanging oil droplet and the interfacial tension of the oil droplet in an aqueous phase by the particle image velocimetry method. This convection velocity depended on the initial value of the interfacial tension in the oil–water interfacial tension oscillation phenomenon accompanied by the expansion and contraction of the hanging drop. Additionally, the droplet oscillation frequency decreased as the Marangoni convection velocity increased. Furthermore, continuous convection, which is unlike Marangoni convection, was observed within this spontaneously expanding and contracting hanging-droplet system. This buoyant convection was caused by the mutual dissolution of the hanging-droplet oil phase and the surrounding aqueous phase.

Mechanism of action of Geobacillus stearothermophilus on different shapes of residual oil

Feeding on crude oil and activator in porous medium, microbes remain active on the Oil-water interface under simulated reservoir conditions. At the same time, microbes degrade the residual oil and change the wettability of pore wall. Consequently, the displacement exhibits a decrease of 51.86% in membrane residual oil and an increase of 17.44% in recovery compared with water flooding. The Geobacillus stearothermophilus producing bio-emulsifier and its metabolic products can effectively emulsify reservoir crude oil and reduce the oil-water interfacial tension. In the end and the formed emulsion featured high viscosity can improve the oil flow rate and expanded wave volume of injected fluid. Correspondingly, the cluster-like, columnar residual oil were reduced by 64%, 68% respectively. In the micro porous test cell, the in-situ cultured microbes rely on specific life activities (interfacial tropism and in situ metabolism, etc.) to strip the residual oil off the wall of orifice deep inside the blind-ends, which cannot be achieved by the exogenous injection method. After the in-situ microbial culture process, the residual oil in deep blind-ends was reduced by about 47%, and the recovered oil was increased about 15% compared with exogenous injection method.

Preparation and performance evaluation of a novel temperature-resistant anionic/nonionic surfactant

Aiming at oil extraction from a tight reservoir, the Jilin oil field was selected as the research object of this study. Based on the molecular structures of conventional long-chain alkyl anionic surfactants, a new temperature-resistant anionic/nonionic surfactant (C8P10E5C) was prepared by introducing polyoxyethylene and polyoxypropylene units into double-chain alcohols. The resulting structures were characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR), and electrospray ionization mass spectrometry (ESI–MS). Then, based on surface tension, interfacial tension, adsorption resistance, wettability, and emulsification performance tests, the performance of C8P10E5C was evaluated. The FT-IR, ESI–MS, and NMR spectra confirmed that C8P10E5C was successfully prepared. The critical micelle concentration (CMC) of C8P10E5C in water was 2.9510 × 10−4 mol/L (the corresponding mass concentration is 0.26%), and the surface tension of the aqueous C8P10E5C solution at this concentration was 30.5728 mN/m. At 0.3% concentration, the contact angle of the C8P10E5C solution was 31.4°, which is 60.75% lower than the initial contact angle. Under high-temperature conditions, C8P10E5C can still reduce the oil–water interfacial tension to 10−2 mN/m, exhibiting good temperature resistance. At 110 °C, upon adsorption to oil sand, the C8P10E5C solution could reduce the oil–water interfacial tension to 0.0276 mN/m, and the interfacial tension can still reach the order of 10−2 mN/m, indicating that C8P10E5C has strong anti-adsorption capability. Additionally, it has good emulsifying performance; upon forming an emulsion with crude oil, the highest drainage rate was only 50%. The forced imbibition oil recovery of C8P10E5C is 65.8%, which is 38.54, 24.22, and 27.25% higher than those of sodium dodecyl benzene sulfonate, alkyl polyoxyethylene ether carboxylate, and alkyl ether carboxylate, respectively.

Lignins interfacial behavior tailored by formulation parameters

Present work focuses on the understanding of lignins’ capacity to adsorb at the oil–water interface depending on both their concentration and particles size. To this purpose, the premise was that it should be possible to control lignins emulsifying capacities by modulation of both oil content and lignins content as well as particles size. In a first step, interfacial behavior of lignins dispersions was characterized through both interfacial tension and interfacial rheology. This allowed evidencing a strong ability to reduce oil–water interfacial tension, with an interfacial value going up to 1 mN/m. In addition, the occurrence of interfacial viscoelastic properties was established, with interfacial moduli values 1000 times higher than when no lignins were present in the dispersion, and with very different structuring kinetics depending on the characteristics of lignins. Then, corresponding emulsifying properties in the presence of sweet almond oil were investigated. High energy input for emulsification process allowed getting better lignins adsorption at the interface, explained by the decrease of lignins particles size, leading to a more homogeneous, and stable emulsion. Results showed that lignins have a strong emulsifying capacity as they could emulsify up to 60 % w/w of sweet almond oil and form stable concentrated O/W emulsions.

Oleic acid-modified layered double hydroxide for Pickering emulsion: (II) Emulsification behavior

Layered double hydroxides (LDHs) are plate-like particles, being potential Pickering emulsifiers. Surfactant modification can regulate their surface properties, and thus can influence their emulsifying behavior. However, there is a lack of full understanding on the correlation between the surface modification of LDHs and their emulsification behavior. In the current work, one LDH and five oleic acid (OA)-modified LDH (LDH@OA) samples were chosen as emulsifiers, and emulsifying tests for pentadecane (oil)-water mixtures were performed at different oil/water volume ratios (1/9−9/1) and solid dosages (Cs, 1.00−10.0 g/L). The type, droplet size, and stability of emulsions were determined. The interfacial adsorption energy (ΔGad) and the coverage of solid particles for droplet surfaces (Rcov) were estimated, and the oil-water interfacial tension and viscoelastic moduli were determined. Results showed that LDH and LDH@OA particles can emulsify the oil-water mixture, forming coalescence-stable Pickering emulsions. The emulsion type is only determined by the solid wettability, independent of the oil/water ratio and Cs. The OA modification can change the wettability of LDH from hydrophilic to hydrophobic, thereby can regulate the type of emulsions from oil-in-water (O/W) to water-in-oil (W/O). Enhancing solid hydrophobicity decreases droplet sizes and increases interfacial viscoelasticity, thus improving the stability of emulsions. The droplet size decreases with an increase in Cs, while it increases with an increase in the volume fraction of dispersed liquid, both independent of the type of emulsions. The solid particles can irreversibly adsorb at the oil-water interface (with |ΔGad|/kT > 107), forming interfacial particle-layers with Rcov ∼0.4 and strong viscoelasticity, which endow the Pickering emulsions with extremely strong stability against coalescence.

One-step in-situ fabrication of novel food-grade Janus droplets with zein and alginate: Dual effect of phase separation and interfacial equilibrium

Janus droplets exhibit an asymmetric structure, where one droplet has two compartments with different properties. However, food-grade Janus droplets are rarely reported. In this work, food-grade Janus droplets composed of alcohol-soluble protein and alginate were fabricated for the first time by the one-step in-situ method. Segregative phase separation and interfacial equilibrium of zein and alginate solutions were the prerequisites for the formation of food-grade Janus droplets. Segregative phase separation occurred when the concentration of zein and alginate solutions was increased. The zein in the aqueous phase synergistically reduced the oil-water interfacial tension with polyglycerol polyricinoleate (PGPR), but the alginate weakened the interfacial ability of PGPR, resulting in an increase of oil-water interfacial tension. Therefore, the interfacial tension difference between zein/oil and alginate/oil could be regulated by changing the concentration of zein and alginate solutions, which was beneficial to the interfacial equilibrium. The droplet size of food-grade Janus droplets could be adjusted by the concentrations of zein and alginate solutions. In addition, the Janus droplet structure could be further controlled by the volume ratio of zein and alginate solutions. The destabilization of food-grade Janus droplets was dominated by coalescence and sedimentation. The construction of food-grade Janus droplets is expected to provide a structural basis for the construction of food-grade Janus particles and promote the development of food technology.

Tunable Approach to Induce the Formation of Flexible Nanofilms from Small (3 nm) Gold Nanoparticles at Oil-Water Interfaces.

The self-assembly of gold nanoparticles (AuNPs) into thin films at the liquid-liquid interface has promising applications in industries such as catalysis, optics, and sensors. However, precise control over their formation is complex, influenced by several factors which scale differently with core size. Due to their small free energy of adsorption, there are few examples of AuNPs with core diameters <10 nm. The present research evaluates the adsorption of ∼3 nm AuNPs from either side of the oil-aqueous interface with variations in ligand shell composition, the oil phase composition, and the structure of alcohol additives to best drive thin-film formation. Film formation and quality are evaluated, and a recent thermodynamic model is used to gain insight into the primary forces promoting this adsorption. Results demonstrate that longer-chain alcohol additives (namely, n-butanol and n-hexanol) induced adsorption more efficiently than shorter-chain alcohols (ethanol). The volume of alcohol additive needed to induce adsorption was dependent upon the ligand composition, suggesting that the mechanism for induced interfacial adsorption is via interaction with the AuNP ligand shell. Comparison with the thermodynamic model indicates that the driving force for this induced adsorption is the alteration of the three-phase contact angle. Additionally, the use of various oils demonstrates that as oil-water interfacial tension increases, more AuNPs adsorb to the interface. This relationship is also supported by the model. Insight gained for favorable conditions of adsorption for AuNPs < 10 nm as well as the underlying thermodynamic mechanism is important in working toward the ability to fine-tune such films for industrial applications.

Dual-responsive emulsion system: Unraveling pH and host-guest interactions for emulsion stability and enhanced oil recovery

Surfactants facilitate the formation of crude oil emulsions in the petroleum reservoir and reduce oil-water interfacial tension, playing a crucial role in tertiary oil recovery. The host-guest interactions between β-cyclodextrin (β-CD) and surfactant molecules can regulate the solubility and hydrophobic interactions of surfactants, further regulating the interfacial and solution aggregation behaviors of the system. A ternary system composed of β-CD, nonionic surfactant Span 80, and anionic amino acid surfactant was designed to act as emulsion stabilizers and promote emulsion formation. Due to the pH responsiveness of the amino acid surfactant and host-guest interactions between the hydrophobic tail of the surfactant and β-CD, the emulsions exhibit dual responsiveness. The pH and β-CD host-guest interaction dual responsiveness determines the emulsion properties. By adjusting the proportion of β-CD in the ternary system and solution pH, the stability, droplet morphology, and rheological properties of the emulsions are all significantly affected. Interactions among emulsion stabilizers as well as their interfacial behaviors were analyzed using 1H NMR spectroscopy and interfacial tension analysis. This type of emulsion was also tested in core flooding experiments, clearly showing that the response of the emulsions to host-guest interactions can enhance crude oil recovery. Incorporating a higher concentration of β-CD into the system can boost additional secondary oil recovery by approximately 32%, while its pH responsiveness facilitates the demulsification of the system after the flooding. These research findings not only highlight the unique properties of the multi-responsive emulsion but also deepen our understanding of the interactions between surfactants. The ternary stabilizer system developed in this study demonstrates broad potential applications in flooding and oil-water separation.