Immiscible Phases Research Articles

Thermo-mechanical behavior of hypoeutectic Ni-Y-Zr alloys

Microstructure refinement and optimized alloying can improve metallic alloy performance: stable nanocrystalline (NC) alloys with immiscible second phases, e.g., Cu-Ta, are stronger than unstable NC alloys and their coarse-grained (CG) counterparts, but higher melting point matrices are needed. Hypoeutectic, CG Ni-Y-Zr alloys were produced via arc-melting to explore their potential as high-performance materials. Microstructures were studied to determine phases present, local composition and length scales, while heat treatments allowed investigating microstructural stability. Alloys had a stable, hierarchical microstructure with ∼250 nm ultrafine eutectic, ∼10 µm dendritic arm spacing and ∼1 mm grain size. Hardness and uniaxial compression tests revealed that mechanical properties of Ni-0.5Y-1.8Zr (in wt%) were comparable to Inconel 617 despite the small alloying additions, due to its hierarchical microstructure. Uniaxial compression at 600 °C showed that ternary alloys outperformed Ni-Zr and Ni-Y binary alloys in flow stress and hardening rates, which indicates that the Ni17Y2 phase was an effective reinforcement for the eutectic, which supplemented the matrix hardening due to increased solubility of Zr. Results suggest that ternary Ni-Y-Zr alloys hold significant promise for high temperature applications.

Bicontinuous microstructure formation of immiscible phases by the liquid metal replacement method and its application to Ti/Mg dissimilar joining

We designed a new microstructure control method (liquid metal replacement method) that creates entirely new composites using the original microstructure as a template. This method selectively replaces a specific phase from a composite with another phase based on differences in atomic interactions. We applied this method to the dissimilar material joining of immiscible titanium and magnesium. After diffusion bonding one side of an interlayer consisting of α-Ti / α-Sc phases to Ti, we butted the opposite side with Mg and reheated. At this interface, selective interdiffusion of Mg and Sc results in the replacement of only the α-Sc phase by the α-Mg phase, forming a new α-Ti / α-Mg bicontinuous microstructure using the α-Ti / α-Sc monotectoid microstructure as a template. The Sc that diffused to the Mg side formed a reaction layer where the MgSc (B2) and (Mg, Sc) solid solution coexisted. These novel composite structures and reaction layers strengthened the joint area. As a result, we suppressed fracture at the joint interface, causing fracture at Mg and achieving a maximum joint strength of 116 MPa.

Multifunctional gelatin nanoparticle stabilized-Pickering emulsion hydrogel based on dextran and amikacin with controlled drug release and enhanced antibacterial capability for promoting infected wound healing

Plant essential oils possess broad-spectral antimicrobial property, but the applications are impeded by their insolubility in water, extreme volatility, and strong irritation. Nanoparticle-stabilized emulsion (Pickering emulsion) gels are colloidal systems with ability to accommodate two immiscible phases in one system. The thick adsorption nanoparticle layers and the cross-linked networks in continuous phase could provide protective barriers for antibacterial oil and achieve on-demand controlled release. An emulsion hydrogel templated from gelatin nanoparticle-stabilized emulsion is one-pot constructed by conducting a tunable cross-linking process between oxidized dextran (Odex) and amikacin in the continuous phase and concomitantly trapping tea tree essential oil (TO) droplets in the three-dimensional network. The resulted emulsion hydrogel presents tunable gelation time, adequate mechanical strength, fascinating injectability, and self-healing capability. It is pH-responsiveness and presents controlled release of amikacin and TO, exhibiting a long-term bacteriostasis of 144 h. The emulsion hydrogel facilitates the outstanding wound healing efficiency in 14 days (95.2 ± 0.8 % of wound closure), accompanied with enhanced collagen deposition and angiogenic activities. The incorporation of TO into emulsion hydrogel system reduced its irritation and improved its biosafety, showing potential application in bacteria inhibition even as implants in vivo.

Spatially and Temporally Resolved Analysis of Bleeding in a Centrifugal Partition Chromatography Rotor

Centrifugal Partition Chromatography (CPC) is a separation technique that utilizes immiscible liquid phases to purify compounds. The selection of solvents in Liquid–Liquid Chromatography offers flexibility and optimization possibilities for specific separation tasks. Understanding the hydrodynamics inside the apparatus is crucial for optimizing a CPC process. The phase retention ratio (Sf) determines the apparatus’s operating point and separation efficiency. However, stationary phase leakage, known as bleeding, complicates the immobilization of this phase. We used a partly transparent single-disc rotor to investigate the time and space dependency of bleeding inside a CPC apparatus, enabling real-time and localized determination of the phase retention ratio. By tracking the retention values over time, we observed the bleeding phenomenon and its progression from the inlet to the rotor outlet. Depending on the phase system used, the CPC was utilizable for a separation task for only 173–500 dimensionless residence times. Systems with a higher stability parameter (as described in the literature) showed a lower bleeding rate and increased stability over time. Accordingly, our results demonstrate the importance of maintaining an optimal ratio of mobile to stationary phase for efficient separation.

Liquid-liquid phase separation as triggering factor of fibril formation.

Liquid-liquid phase separation (LLPS) refers to the phenomenon, where a homogeneous solution spontaneously undergoes a transition into two or more immiscible phases. Through transient weak multivalent macromolecular interactions, a homogeneous solution can spontaneously separate into two phases: one rich in biomolecules and the other poor in biomolecules. Phase separation is believed to serve as the physicochemical foundation for the formation of membrane-less organelles (MLOs) and bio-molecular condensates within cells. Moreover, numerous biological processes depend on LLPS, such as transcription, immunological response, chromatin architecture, DNA damage response, stress granule formation, viral infection, etc. Abnormalities in phase separation can lead to diseases, such as cancer, neurodegeneration, and metabolic disorders. LLPS is regulated by various factors, such as concentration of molecules undergoing LLPS, salt concentration, pH, temperature, post-translational modifications, and molecular chaperones. Recent research on LLPS of biomolecules has progressed rapidly and led to the development of databases containing information pertaining to various aspects of the biomolecule separation analysis. However, more comprehensive research is still required to fully comprehend the specific molecular mechanisms and biological effects of LLPS.

Exploring the potential of all-aqueous immiscible systems for preparing complex biomaterials and cellular constructs.

All-aqueous immiscible systems derived from liquid-liquid phase separation of incompatible hydrophilic agents such as polymers and salts have found increasing interest in the biomedical and tissue engineering fields in the last few years. The unique characteristics of aqueous interfaces, namely their low interfacial tension and elevated permeability, as well as the non-toxic environment and high water content of the immiscible phases, confer to these systems optimal qualities for the development of biomaterials such as hydrogels and soft membranes, as well as for the preparation of in vitro tissues derived from cellular assembly. Here, we overview the main properties of these systems and present a critical review of recent strategies that have been used for the development of biomaterials with increased levels of complexity using all-aqueous immiscible phases and interfaces, and their potential as cell-confining environments for micropatterning approaches and the bioengineering of cell-rich structures. Importantly, due to the relatively recent emergence of these areas, several key design considerations are presented, in order to guide researchers in the field. Finally, the main present challenges, future directions, and adaptability to develop advanced materials with increased biomimicry and new potential applications are briefly evaluated.

Impact of a spherical interface on a concentrical spherical droplet

<p>In this paper, an analytical and numerical technique are examined in order to analyse the Stokes flow determination problem due to a viscous sphere droplet moving at a concentric instantaneous position inside a spherical interface separating finite and semi-infinite immiscible fluid phases. Here, when only one of the three phases of the fluid (micropolar fluid) has a microstructure, attention is focused on this case. The motion is considered when Reynolds- and capillary-numbers are low, and the droplet surface and the fluid-fluid interface have insignificant deformation. A general solution is obtained in a spherical coordinate system based on a concentric position to analyse the slow axisymmetric movement of the micropolar fluid, considering microrotation and velocity components. Boundary conditions are initially fulfilled at the fluid-fluid interface and subsequently at the droplet surface. The normalised hydrodynamic drag force applying to a moving viscous droplet appears to be a function of the droplet-to-interface radius ratio, which increases monotonically and becomes unbounded when the droplet surface touches the fluid-fluid interface. The numerical outcomes of the normalised drag force acting on the viscous droplet are derived for different values of the parameters, and are presented in a tabular and graphical framework. A comparison was made between our numerical outcomes for the drag force and the pertinent data for the special cases found in the literature.</p>

Effect of Anionic, Cationic, and Non-Ionic Surfactants on the Structural Stability and Morphology of Perfluorinated Sulfonic Acid Membranes

Redox flow batteries (RFB) are a critical technology for stationary grid-scale energy storage, with potential usage with intermittent power sources, such as wind and solar. RFBs are attractive for long-duration energy storage because the anolyte and catholyte are stored separately external to the electrochemical reactor, which allows the RFBs to be modular and stationary. Separating the electrolytes and the electrochemical cell decouples energy and power densities, unlike batteries that store charge in the solid-state, such as Li-ion, Pb-acid, or Ni-Cd. A standard RFB chemistry is the all-vanadium redox flow battery (VRFB), which utilizes the four oxidation states of vanadium, with V2+, V3+, V4+, and V5+. Recently, new electrolytes are being studied in energy storage devices. Such as the first redox flow battery to utilize microemulsions as the electrolyte.Microemulsions are a breakthrough electrolyte for energy storage (BEES) that is emerging as an alternative to traditional RFB electrolytes because they produce thermodynamically stable, homogeneous solutions of polar and non-polar molecules. The stabilization of oil and water solutions allows microemulsion electrolytes to accommodate organic redox species with fast electron transfer rates that are not soluble in the aqueous phase while still offering the high conductivity of an aqueous salt electrolyte. Microemulsions consist of two immiscible phases stabilized by a surfactant, a non-polar "oil" phase, solubilizing the redox material, and the polar phase, which typically consists of an aqueous brine that provides charge balance and conductivity. Additionally, if the redox molecule was a non-polar liquid, it could serve as the entire oil phase, maximizing the energy density. An attractive property of a microemulsion electrolyte is that each component can be environmentally and biologically safe. For example, the aqueous phase only contains salt and water, and surfactants are found in many household, personal, and food products. Furthermore, some redox materials investigated in our lab are vitamins such as menadione (vitamin K3) and tocopherol (vitamin E).This talk describes the structural, mechanical, and morphological studies of surfactants' effects on perfluorinated sulfonic acid membranes. Small-angle X-ray scattering monitored the morphological changes as a function of surfactant concentration and soaking time, revealing how the surfactant penetrated and altered the polymer membrane. FTIR and NMR spectroscopy are also employed, providing insight into any polymer membrane degradation or dissolution. We demonstrate that surfactant choice is not only crucial to the stability of the microemulsion used as an electrolyte but can ultimately destroy the separator in a redox flow battery.This work was supported as part of the Breakthrough Electrolytes for Energy Storage and Systems (BEES2), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409.

Numerical Modeling of Water Jet Plunging in Molten Heavy Metal Pool

The hydrodynamic and thermal interaction of water with the high-temperature melt of a heavy metal was studied via the Volume-of-Fluid (VOF) method formulated for three immiscible phases (liquid melt, water, and water vapor), with account for phase changes. The VOF method relies on a first-principle description of phase interactions, including drag, heat transfer, and water evaporation, in contrast to multifluid models relying on empirical correlations. The verification of the VOF model implemented in OpenFOAM software was performed by solving one- and two-dimensional reference problems. Water jet penetration into a melt pool was first calculated in two-dimensional problem formulation, and the results were compared with analytical models and empirical correlations available, with emphasis on the effects of jet velocity and diameter. Three-dimensional simulations were performed in geometry, corresponding to known experiments performed in a narrow planar vessel with a semi-circular bottom. The VOF results obtained for water jet impact on molten heavy metal (lead–bismuth eutectic alloy at the temperature 820 K) are here presented for a water temperature of 298 K, jet diameter 6 mm, and jet velocity 6.2 m/s. Development of a cavity filled with a three-phase melt–water–vapor mixture is revealed, including its propagation down to the vessel bottom, with lateral displacement of melt, and subsequent detachment from the bottom due to gravitational settling of melt. The best agreement of predicted cavity depth, velocity, and aspect ratio with experiments (within 10%) was achieved at the stage of downward cavity propagation; at the later stages, the differences increased to about 30%. Adequacy of the numerical mesh containing about 5.6 million cells was demonstrated by comparing the penetration dynamics obtained on a sequence of meshes with the cell size ranging from 180 to 350 µm.

Synthesis of Ternary and Quaternary Group III-Arsenide Colloidal Quantum Dots via High-Temperature Cation Exchange in Molten Salts: The Importance of Molten Salt Speciation.

Colloidal semiconductor nanocrystals are an important class of materials which have many desirable optoelectronic properties. In their bulk phases, gallium- and aluminum-containing III-V materials such as GaAs, GaP, and Al1-xGaxAs represent some of the most technologically important semiconductors. However, their colloidal synthesis by traditional methods is difficult due to the high temperatures needed to crystallize these highly covalent materials and the extreme reactivity of Ga- and Al- precursors toward organic solvents at such high temperatures. A recently developed paradigm shift in the synthesis of these materials is to use molten inorganic salts as solvents to prepare Ga- containing III-V colloidal nanocrystals by cation exchange of the corresponding indium pnictide (InPn) colloidal nanocrystals. There have been several successful applications of molten salt solvents to prepare III-phosphide colloidal nanocrystals. However, little is known about the nature of these reaction environments at the relevant reaction conditions and synthesis of III-arsenide colloidal nanocrystals remains challenging. Herein we report a detailed study on cation exchange of InPn nanocrystals using nominally Lewis basic molten salt solvents with added gallium halides. Surprisingly, these salt systems phase separate into two immiscible phases, and the nanocrystals preferentially segregate to one of the phases. Using a suite of in situ spectroscopy tools, we identify the phase the nanocrystals segregate to as Lewis neutral alkali tetrahalogallate molten salts. We apply in situ high-temperature Raman spectroscopy to identify the chemical species present in several molten salt compositions at experimentally relevant reaction conditions to elucidate a molecular basis for the reactivity observed. We then employ Lewis neutral KGaI4 molten salts to prepare high-quality In1-xGaxAs and In1-xGaxP nanocrystals and demonstrate that deviation from Lewis neutral conditions accelerate nanocrystal decomposition in the case of III-arsenide materials. Further, we expand to KAlI4-based molten salts to prepare In1-x-yGaxAlyAs nanocrystals which represent an example of solution-synthesized quaternary III-V nanocrystals. These insights provide a molecular basis for the rational development of molten salt solvents, thus allowing the preparation of a diverse array of multicomponent III-V colloidal nanocrystals.

Carbon Paste Electrodes Surface-Modified with Surfactants: Principles of Surface Interactions at the Interface between Two Immiscible Liquid Phases.

Carbon paste electrodes ex-situ modified with different surfactants were studied using cyclic voltammetry with two model redox couples, namely hexaammineruthenium (II)/(III) and hexacyanoferrate (II)/(III), in 0.1 mol L-1 acetate buffer (pH 4), 0.1 mol L-1 phosphate buffer (pH 7), and 0.1 mol L-1 ammonia buffer (pH 9) at a scan rate ranging from 50 to 500 mV s-1. Distinct effects of pH, ionic strength, and the composition of supporting media, as well as of the amount of surfactant and its accumulation at the electrode surface, could be observed and found reflected in changes of double-layer capacitance and electrode kinetics. It has been proved that, at the two-phase interface, the presence of surfactants results in elctrostatic interactions that dominate in the transfer of model substances, possibly accompanied also by the effect of erosion at the carbon paste surface. The individual findings depend on the configurations investigated, which are also illustrated on numerous schemes of the actual microstructure at the respective electrode surface. Finally, principal observations and results are highlighted and discussed with respect to the future development and possible applications of sensors based on surfactant-modified composited electrodes.

Daughter oil droplet entrainment by oil-coated bubble bursting

Compound bubbles with a liquid coating in another continuous immiscible bulk phase are ubiquitous in a wide range of natural and industrial processes. Their formation, rise and ultimate bursting at the air–liquid interface play crucial roles in the transport and fate of natural organic matter and contaminants. However, the dynamics of compound bubbles has not received considerable attention until recently. Here, inspired by our previous work (Yang et al., Nat. Phys., vol. 19, 2023, pp. 884–890), we investigate the entrainment of daughter oil droplets in bulk water produced by a bursting oil-coated bubble. We document that the size of the entrained daughter oil droplet is affected by the oil coating fraction and the bulk liquid properties. We rationalize this observation by balancing the viscous force exerted by the extensional flow produced by bubble bursting with the capillary force resisting the deformation of the oil coating, and considering the subsequent end-pinching process which finally entrains the daughter oil droplets. We propose a scaling analysis for the daughter oil droplet size that well captures the experimental results for a wide range of oil coating fractions and Ohnesorge numbers of the bulk liquid. In addition, we discuss the non-monotonic variation of daughter droplet size with the Ohnesorge number, and show the eventual absence of daughter droplets because of the strong viscous effect in the high-Ohnesorge-number regime. Our findings may advance the fundamental understanding of compound bubble bursting and provide guidance and modelling constraints for bubble-mediated contaminant transport in liquids.

Tailored Fluorosurfactants through Controlled/Living Radical Polymerization for Highly Stable Microfluidic Droplet Generation.

Droplet-based microfluidics represents a disruptive technology in the field of chemistry and biology through the generation and manipulation of sub-microlitre droplets. To avoid droplet coalescence, fluoropolymer-based surfactants are commonly used to reduce the interfacial tension between two immiscible phases to stabilize droplet interfaces. However, the conventional preparation of fluorosurfactants involves multiple steps of conjugation reactions between fluorinated and hydrophilic segments to form multiple-block copolymers. In addition, synthesis of customized surfactants with tailored properties is challenging due to the complex synthesis process. Here, we report a highly efficient synthetic method that utilizes living radical polymerization (LRP) to produce fluorosurfactants with tailored functionalities. Compared to the commercialized surfactant, our surfactants outperform in thermal cycling for polymerase chain reaction (PCR) testing, and exhibit exceptional biocompatibility for cell and yeast culturing in a double-emulsion system. This breakthrough synthetic approach has the potential to revolutionize the field of droplet-based microfluidics by enabling the development of novel designs that generate droplets with superior stability and functionality for a wide range of applications.

Tailored Fluorosurfactants through Controlled/Living Radical Polymerization for Highly Stable Microfluidic Droplet Generation

AbstractDroplet‐based microfluidics represents a disruptive technology in the field of chemistry and biology through the generation and manipulation of sub‐microlitre droplets. To avoid droplet coalescence, fluoropolymer‐based surfactants are commonly used to reduce the interfacial tension between two immiscible phases to stabilize droplet interfaces. However, the conventional preparation of fluorosurfactants involves multiple steps of conjugation reactions between fluorinated and hydrophilic segments to form multiple‐block copolymers. In addition, synthesis of customized surfactants with tailored properties is challenging due to the complex synthesis process. Here, we report a highly efficient synthetic method that utilizes living radical polymerization (LRP) to produce fluorosurfactants with tailored functionalities. Compared to the commercialized surfactant, our surfactants outperform in thermal cycling for polymerase chain reaction (PCR) testing, and exhibit exceptional biocompatibility for cell and yeast culturing in a double‐emulsion system. This breakthrough synthetic approach has the potential to revolutionize the field of droplet‐based microfluidics by enabling the development of novel designs that generate droplets with superior stability and functionality for a wide range of applications.

Precise particle size control during spherical agglomeration of benzoic acid by modification of the bridging liquid phase using TWEEN 20

The interest in spherical agglomeration processes in the pharmaceutical industry is rising due to the possibility of direct tableting of Active Pharmaceutical Ingredients and enhancements in bulk powder properties translating into improved powder processability. While agglomerating needle-shaped particles into spheres offers numerous advantages, such as improved flowability, filterability, and particle density, achieving precise control over the particle size and shape of the agglomerates remains a significant challenge. More specifically, the obtained agglomerate size rarely reaches values below 500 μm, which is the desired size range for pharmaceutical applications. To address this challenge, the current research investigates the effectiveness of incorporating surfactants at varying concentrations as a means to control the particle size and shape of the resulting agglomerates. Reversed addition antisolvent crystallization experiments were performed in ethanol/water using benzoic acid as a model compound, followed by the addition of a bridging liquid (toluene), which wets and bridges the single crystals into agglomerates. To modify the interfacial tension between the two immiscible liquid phases, different concentrations of the tween 20 surfactant were used, leading to a range of interfacial tensions spanning from 0.50 to 16.38 × 10−3 N/m. Both crystallization and agglomeration processes were monitored in situ using in-process microscopy tools. The experimental results demonstrated that by adjusting the surfactant concentration and thus the corresponding interfacial tension of the bridging liquid, highly tunable agglomerate sizes were achieved, ranging from 160 μm to 4412 μm. A higher surfactant concentration is correlated with smaller agglomerates and is key to control the final agglomerate size. However, it should be noted that the introduction of surfactants in the spherical agglomeration process negatively impacted the agglomerate's strength. Nonetheless, this method remains a promising and innovative technique for controlling the final particle size during spherical agglomeration.

Mixed Nanosphere Assemblies at a Liquid-Liquid Interface.

The in-plane packing of gold (Au), polystyrene (PS), and silica (SiO2) spherical nanoparticle (NP) mixtures at a water-oil interface is investigated in situ by UV-vis reflection spectroscopy. All NPs are functionalized with carboxylic acid such that they strongly interact with amine-functionalized ligands dissolved in an immiscible oil phase at the fluid interface. This interaction markedly increases the binding energy of these nanoparticle surfactants (NPSs). The separation distance between the Au NPSs and Au surface coverage are measured by the maximum plasmonic wavelength (λmax) and integrated intensities as the assemblies saturate for different concentrations of non-plasmonic (PS/SiO2) NPs. As the PS/SiO2 content increases, the time to reach intimate Au NP contact also increases, resulting from their hindered mobility. λmax changes within the first few minutes of adsorption due to weak attractive inter-NP forces. Additionally, a sharper peak in the reflection spectrum at NP saturation reveals tighter Au NP packing for assemblies with intermediate non-plasmonic NP content. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) measurements confirm a decrease in Au NP domain size for mixtures with larger non-plasmonic NP content. The results demonstrate a simple means to probe interfacial phase separation behavior using in situ spectroscopy as interfacial structures densify into jammed, phase-separated NP films.

Chaotropic Salt‐Aided “Water‐In‐Organic” Electrolyte for Highly Reversible Zinc‐Ion Batteries Across a Wide Temperature Range

AbstractAqueous zinc‐ion batteries are promising alternatives to lithium‐ion batteries due to their cost‐effectiveness and improved safety. However, several challenges, including corrosion, dendrites, and water decomposition at the Zn anode, hinder their performance. Herein, an approach is proposed, that deviates from the conventional design by adding water into a propylene carbonate‐based organic electrolyte to prepare a non‐flammable “water‐in‐organic” electrolyte. The chaotropic salt Zn(ClO4)2 exploits the Hofmeister effect to promote the miscibility of immiscible liquid phases. Interactions between propylene carbonate and water restrict water activity and mitigate unfavorable reactions. This electrolyte facilitates preferential Zn (002) deposition and the formation of solid electrolyte interphase. Consequently, the “water‐in‐organic” electrolyte achieves a 99.5% Coulombic efficiency at 1 mA cm−2 over 1000 cycles in Zn/Cu cells, and constant cycling over 1000 h in Zn/Zn symmetric cells. A Na0.33V2O5/Zn battery exhibits impressive cycling stability with a capacity of 175 mAh g−1 for 800 cycles at 2 A g−1. Additionally, this electrolyte enables sustainable cycling across a wide temperature range from −20 to 50 °C. The design of a “water‐in‐organic” electrolyte employing a chaotropic salt presents a potential strategy for high‐performance electrolytes in zinc‐ion batteries with a large stability window and a wide temperature range.

Electrokinetic Effect of a Two-Liquid Interface within a Slit Microchannel.

This paper presents an investigation of the electrokinetic effect at a two-liquid (immiscible liquid-aqueous solution) interface within a slit microchannel using a three-dimensional (3D) numerical model, with a particular focus on the impact of the surface ζ-potential and liquid phase height on the interface electrokinetic velocity. The findings indicate that the direction of the interface movement depends on the ζ-potentials at the two-liquid interface and the microchannel wall. When the absolute value of the negative ζ-potential at the interface is smaller than that at the wall, the interface moves toward the negative pole of the applied direct current (DC) electric field; conversely, it moves in the opposite direction. The velocity of interface motion decreases as the height of the aqueous phase and the dynamic viscosity ratio between the immiscible liquid and the aqueous solution increase. Conversely, the velocity increases with an elevation in the height of the immiscible liquid phase and the DC electric field intensity. This study holds significant importance in elucidating the patterns of change in fluid interface electrokinetic effects and their potential applications in manipulating and separating particulate pollutants within water systems.

New insights into reservoir on chip: Numerical investigation and experimental validation

The present study reports a numerical investigation of oil extraction from a pore-scale perspective using water as the injection fluid. The pore network is constructed from the statistical realization of the pore space of the reservoir rock. Conceptually, the pore network model used in the study miniaturizes the porous reservoir containing oil/gas onto a microfluidic platform, capturing the actual pore-level length scale and it complex features. The validity of the numerical model is established through an experimental investigation of single-phase flow. The experimentally calculated absolute permeability based on the Darcy law shows an excellent agreement with the numerically attained value. The two-phase numerical model uses the phase field technique to track the development of the interface between the two immiscible phases, i.e., oil and water. The numerical model shows a piston-like displacement and captures interesting pore-level phenomena like snap-off and trapping. Implementing the complete network for simulation reveals the unstable nature of the flooding, which is persistent with invasion percolation. The complete network simulation reveals the discontinuous flood front with a segregated flow configuration. Two-phase experiments conducted on a polydimethylsiloxane test chip with an equivalent pore level network also showed similar flow features, thereby establishing the credibility of our two-phase simulations. The recovery factor obtained from the simulation was found to be 0.78, which is in close agreement with experimental data reported in the literature. The modified Darcy law applied to the numerical model generates relative permeability plots similar to the experimental core flooding plots reported in the literature. The numerical model presented here provides valuable insight into the oil recovery process and its implications at field scale. To the best of our knowledge, this is the first instance involving numerical analysis of the full-scale system of Reservoir on a Chip system detailing the pore-level flow dynamics.

Magmatic–hydrothermal evolution of the Koktokay No. 3 pegmatite, Altai, northwestern China: Constraints from in situ boron isotope and chemical compositions of tourmaline

Lithium–Cs–Ta-enriched (LCT-type) pegmatites are characterized by zoning texture and extreme enrichment of rare-metals. The role of fluids in zonation development and rare-metal mineralization remains a topic of debate. The Koktokay No. 3 pegmatite in northwestern China represents a typical LCT-type pegmatite characterized by economically significant Li–Be–Nb–Ta–Cs mineralization. This pegmatite exhibits a complete evolutionary sequence from outer to inner zones, with diverse rare-metal mineralization. Tourmaline is ubiquitously present in all textural zones of LCT-type pegmatites. In the Koktokay No. 3 pegmatite, the tourmalines exhibit a range of compositions from dravite and schorl to elbaite and rossmanite. The tourmalines in this pegmatite are characterized by significantly enriched light B isotope compositions (δ11B = −14.8‰ to −8.1‰), similar to those typically observed in most pegmatites derived from continental crust sources. The tourmalines in the outer zones have less variable δ11B values (−13.8‰ to −11.5‰) and are interpreted to have crystallized in a viscous magma. The tourmalines in the inner zones exhibit larger variations in δ11B values (−14.8‰ to −8.1‰) than those from the outer zones. The decreasing δ11B values of tourmalines from the outer to inner zones are attributed to the separation of an immiscible fluid phase that preferentially incorporated heavy B isotopes. The occurrence of hydrothermal tourmaline as veinlets indicates the exsolution of fluids in inner zones, with high δ11B values ranging from −10.2‰ to −9.3‰. Therefore, the hydrothermal fluid can be saturated when the magma has been strongly evolved. In addition to fractional crystallization, exsolved fluids play a significant role in the formation of internal zones and rare-metal mineralization in LCT-type pegmatites. The rare-metals are gradually enriched through fractional crystallization of magma, and the fluid contains mobile elements such as Cs that facilitate precipitation of rare-metal minerals.