Microdroplet Formation Research Articles

Modeling for formation of microdroplets prepared by pulsated orifice ejection method

Abstract This study investigated the preparation of metallic microdroplets by pulsed orifice ejection method. Computational fluid dynamics simulations, combined with volume-of-fluid model, were employed to analyze the jet break-up and droplet formation behaviors of various metallic materials within a certain Weber number (We) range. An energy-based physical model under inlet boundary conditions was established to precisely control the generation of droplets. The results indicate that the break-up state of metal jets is significantly influenced by material properties within the range that We = 12 ∼ 24, which makes the materials exhibiting higher surface tension and density relatively favorable to the production of mono-sized microdroplets. Moreover, the break-up behavior of the jet is closely related to the ratio of volume force to surface tension (Bond number). And the proposed model effectively predicts the properties of droplets. This research provides theoretical guidance and technical support for the precise preparation of metallic microdroplets.

Corrosion-life prediction model for 316L stainless steel under electronic special gases containing trace moisture employed in semiconductor manufacturing industry

Special gases with trace moisture cause the formation of dynamic acidic microdroplets (DMD), which results in corrosion of semiconductor manufacturing devices. In this study, a predictive model for corrosion damage in 316L stainless steel (SS) was developed by combining the DMD process and the pitting initiation model. The DMD process was modeled using the BET model to describe the moisture-to-solution conversion. The pitting initiation model was reconstructed by incorporating the Sridhar model, temporal corrosion model, and Macdonald model. Finally, the predicted results were validated by various experimental data, indicating that the prediction model was accurate and highly reliable.

Thermo‐Assisted Deep Eutectic Solvent Based on Dispersive Liquid‐Liquid Microextraction for Preconcentration of Phthalate Esters in Water Samples and Determination by Gas Chromatography With Flame Ionization Detection

ABSTRACTA thermo‐assisted deep eutectic solvent (DES) based on dispersive liquid‐liquid microextraction followed by gas chromatography with flame ionization detection was developed for the analysis of five phthalate esters in different water samples. In the procedure involved, a DES composed of lidocaine, an amphiphilic amine, and oleic acid, was mixed with the sample assisted by ultrasound, and phase separation was achieved with increasing temperature. The heating of the extraction system induced the change of acid‐base properties of the DES components. Thus, the formation of microdroplets of DES in the sample was provided, and two phases were separated. The structure of the upper hydrophobic layer was characterized by Fourier‐transform infrared spectroscopy. Also, the amount of water in the DES phase was analyzed by mass spectrometer and Karl Fischer titration. Some critical variables on the extraction yield were assessed. The proposed method achieved 1.2–1.3 and 4.1–4.3 µg/L for limits of detection and limits of quantification, respectively. The intra‐day and inter‐day percentage relative standard deviations (n = 5) were determined to be in the range of 4.2–6.2% and 5.1–7.2%, respectively. Ultimately, this method analyzed the five phthalate esters in different water samples with high recoveries.

Prebiotic Synthesis of Microdroplets from Formate over a Bimetallic Cobalt-Nickel Nanomotif.

The hypothesis underlying the abiogenic origin of life suggests that the nonenzymatic synthesis of long-chain fatty acids led to the construction of vesicles for compartmentalization in an early stage during the transition from geochemistry to biochemistry. However, evidence for this theory remains elusive as C5+ carboxylic acids cannot be synthesized using current laboratory simulations. Here, we report the synthesis of long-chain carboxylic acids (C3-C7) with a 42 mmol/gCo+Ni yield and 87.7% selectivity from formate (an intermediate of the acetyl-CoA pathway) over a cobalt-nickel alloy under alkaline hydrothermal conditions and the subsequent formation of microdroplets from organics. Density functional theory (DFT) calculations confirmed that the synergistic effect of the bimetal catalyst is key for catalyzing C-C coupling. Investigations by infrared spectroscopy, electron paramagnetic resonance, and isotope-labeled experiments revealed that HCO* serves as a reaction intermediate and is involved in the subsequent elementary steps for synthesizing long-chain carboxylic acids from formate. Taken together, these findings may help explain how the first protocells emerged geochemically and provide support for the hypothesis of the abiogenic origin of life. The hydrothermal system developed may also be applicable for the sustainable synthesis of long-chain carboxylates from one-carbon substrates using nonnoble metal catalysts.

Machine learning and physics-driven modelling and simulation of multiphase systems

We highlight the work of a multi-university collaborative programme, PREMIERE (PREdictive Modelling with QuantIfication of UncERtainty for MultiphasE Systems), which is at the intersection of multi-physics and machine learning, aiming to enhance predictive capabilities in complex multiphase flow systems across diverse length and time scales. Our contributions encompass a variety of approaches, including the Design of Experiments for nanoparticle synthesis optimisation, Generalised Latent Assimilation models for drop coalescence prediction, Bayesian regularised artificial neural networks, eXtreme Gradient Boosting for microdroplet formation prediction, and a sub-sampling based adversarial neural network for predicting slug flow behaviour in two-phase pipe flows. Additionally, we introduce a generalised latent assimilation technique, Long Short-Term Memory networks for sequence forecasting mixing performance in stirred and static mixers, active learning via Bayesian optimisation to recover coalescence model parameters for high current density electrolysers, Gaussian process regression for drop size distribution predictions for sprays, and acoustic emission signal inversion using gradient boosting machines to characterise particle size distribution in fluidised beds. We also offer perspectives on the development of a shape optimisation framework that leverages the use of a multi-fidelity multiphase emulator. The results presented have applications in chemical synthesis, microfluidics, product manufacturing, and green hydrogen generation.

Temperature-responsive deep eutectic solvent-based microextraction for the determination of bisphenols in beverages by HPLC-FLD

In this work, a homogeneous liquid-liquid microextraction approach based on temperature-responsive deep eutectic solvent for pretreatment of beverages was developed for the first time. The procedure assumed the heating of the homogeneous solution, consisting of sample, precursors of temperature-responsive deep eutectic solvent (amphiphilic amine and carboxylic acid) and salting-out agent in a disposable polyethylene pipette. The heating of extraction system induced the change of acid-base properties of the precursors, and thus it attributed to in situ formation of microdroplets of deep eutectic solvent in beverage sample. The significant difference in densities of aqueous sample phase and the extraction solvent allowed to obtain spontaneous phase separation, while the presence of a thin capillary on top of the pipette facilitated microvolume sampling of the resulting extract. The approach was utilized for the determination of bisphenols (bisphenol A, bisphenol C, bisphenol E and bisphenol F) in beverages by high-performance liquid chromatography with fluorometric detection. The temperature-responsive deep eutectic solvent based on lidocaine and heptanoic acid provided the highest preconcentration of analytes (enrichment factor – 22). Under optimal conditions, the RSD in terms of inter-day precision was < 11 %, limits of detection for bisphenols were 0.01–0.03 μg L−1.

Microdroplets initiate organic-inorganic interactions and mass transfer in thermal hydrous geosystems

Organic-inorganic interactions regulate the dynamics of hydrocarbons, water, minerals, CO2, and H2 in thermal rocks, yet their initiation remains debated. To address this, we conducted isotope-tagged and in-situ visual thermal experiments. Isotope-tagged studies revealed extensive H/O transfers in hydrous n-C20H42-H2O-feldspar systems. Visual experiments observed water microdroplets forming at 150–165 °C in oil phases near the water-oil interface without surfactants, persisting until complete miscibility above 350 °C. Electron paramagnetic resonance (EPR) detected hydroxyl free radicals concurrent with microdroplet formation. Here we propose a two-fold mechanism: water-derived and n-C20H42-derived free radicals drive interactions with organic species, while water-derived and mineral-derived ions trigger mineral interactions. These processes, facilitated by microdroplets and bulk water, blur boundaries between organic and inorganic species, enabling extensive interactions and mass transfer. Our findings redefine microscopic interplays between organic and inorganic components, offering insights into diagenetic and hydrous-metamorphic processes, and mass transfer cycles in deep basins and subduction zones.

Drop-On-Demand Microdroplet Generation under Charge Injection by Corona Discharge.

In printing, microreactors, and bioassays, the precise control of micrometer-scale droplet generation is essential but challenging, often restricted by the equipment and nozzles used in traditional methods. We introduce a needle-plate electrode corona discharge technique that injects charges into an oil layer, enabling the precise manipulation of droplet polarization and splitting. This method allows for meticulous adjustment of microdroplet formation regarding location, size, and quantity by modulating the discharge voltage, discharge time, and electrode positioning. It enables the immediate initiation and cessation of droplet production, thereby facilitating on-demand droplet generation. Our study on the voltage-dependent droplet stretch coefficient shows that as the voltage increases, the droplets transition from controlled splitting to regular Taylor cone-like ejections, eventually reaching the Rayleigh limit and fully breaking apart. These advancements significantly improve microfluidic droplet manipulation, offering considerable benefits for applications in targeted drug delivery, rapid disease diagnostics, and precise environmental monitoring.

Interface Binding Mechanism of Nanoclay Hybridized Coacervate Microdroplets for the Controllable Construction of Protocells.

Coacervate microdroplets, a protocell model in exploring the origin of life, have gained significant attention. Clay minerals, catalysts during the origin of life, are crucial in the chemical evolution of small molecules into biopolymers. However, our understanding of the relationship between clay minerals and the formation and evolution of protocells on early Earth remains limited. In this work, the nanoclay montmorillonite nanosheet (MMT-Na) was employed to investigate its interaction with coacervate microdroplets formed by oligolysine (K10) and adenine nucleoside triphosphate (ATP). As an anionic component, MMT-Na was noted to promote the formation of coacervate microdroplets. Furthermore, the efficiency of ssDNA enrichment and the degree of ssDNA hybridization within these microdroplets were significantly improved. By combining inorganic nanoclay with organic biopolymers, our work provides an efficient way to enrich genetic biomolecules in the primitive Earth environment and builds a nanoclay-based coacervate microdroplets, shedding new light on life's origin and protocell evolution.

Microdroplet formation of water and alumina nanofluid in a T-junction microchannel

A scarcity of studies about nanofluids’ utilization in droplet formation inside microdevices currently hovers in the literature although potential applications of nanoparticles in a microfluidic environment are foreseen. For this purpose, experimentally assessing both nanofluid and microdroplet characteristics is fundamental. This work reports a series of experimental tests on the microdroplet formation of distilled water (DIW) and DIW-based aluminum oxide (Al2O3) nanofluid in a microfluidic T-junction. While water and nanofluid are used as the dispersed phase, mineral oil is used as the continuous phase. Microdroplet formation in the squeezing, transitional, and dripping regimes is characterized and scaling laws for the non-dimensional droplet volumes are presented. The effects of flow rate, capillary number, microchannel aspect ratio, and nanoparticle concentration are investigated. The addition of Al2O3 nanoparticles to the water is observed to have a major impact in the transitional regime (up to 40% increase), whereas in the dripping regime its influence is lower, with less than 10% difference. This was attributed to the nanofluid's enhanced interfacial tension and viscosity compared to the DIW, as well as possible adsorption at the surface.

Dynamics of microdroplet generation via drop impact on a superhydrophobic micropore

This study delves into the dynamics of generating microdroplets by impacting a droplet onto a micropore on superhydrophobic copper substrates. It identifies the necessary impact velocities for single microdroplet formation for each micropore and characterizes microdroplet size in relation to micropore diameter. The results underscore the significant role of viscosity, especially as the diameter of the micropore decreases. For micropores measuring 400 μm, an increase in viscosity up to 8 cP does not alter the critical impact velocities, while smaller diameters of 50 and 100 μm see a notable change in critical velocities with even minor increases in viscosity. Remarkably, the diameter of the microdroplet remains consistent regardless of changes in the liquid viscosity or impact velocity. This research showcases two practical uses of single microdroplets: printing on paper and fabricating microbeads. The insights gained from these findings pave the way for advancements in printing technology and microfabrication techniques.

On-chip fabrication and in-flow 3D-printing of microgel constructs: from chip to scaffold materials in one integral process

Bioprinting has evolved into a thriving technology for the fabrication of cell-laden scaffolds. Bioinks are the most critical component for bioprinting. Recently, microgels have been introduced as a very promising bioink, enabling cell protection and the control of the cellular microenvironment. However, the fabrication of the bioinks involves the microfluidic production of the microgels, with a subsequent multistep process to obtain the bioink, which so far has limited its application potential. Here we introduce a direct coupling of microfluidics and 3D-printing for the continuous microfluidic production of microgels with direct in-flow printing into stable scaffolds. The 3D-channel design of the microfluidic chip provides access to different hydrodynamic microdroplet formation regimes to cover a broad range of droplet and microgel diameters. After exiting a microtubing the produced microgels are hydrodynamically jammed into thin microgel filaments for direct 3D-printing into two- and three-dimensional scaffolds. The methodology enables the continuous on-chip encapsulation of cells into monodisperse microdroplets with subsequent in-flow cross-linking to produce cell-laden microgels. The method is demonstrated for different cross-linking methods and cell lines. This advancement will enable a direct coupling of microfluidics and 3D-bioprinting for scaffold fabrication.

Printing of liquid metal by electrically modulating of interface tension in liquid environment

In recent years, gallium-based liquid metal has emerged as a prominent research material in the realm of flexible electronics, owing to its exceptional electrical conductivity and deformability. The crux of developing flexible electronic devices using liquid metal as a conductive material lies in the patterning of the liquid metal. Inkjet printing technology possesses the capability to efficiently craft functional patterns by printing any inkable material. However, due to the facile oxidation of the gallium-based liquid metal surface in ambient air, leading to the formation of oxide films and the presence of high surface tension, conventional inkjet printing techniques are incapable of directly rendering liquid metal prints. This manuscript introduces a refined and remarkably efficient approach to inkjet printing utilizing the liquid metal. By deftly adjusting the interfacial tension of the liquid metal at the nozzle with ultra-low potentials, falling within the 2-V range, the achievement of on-demand, micron-scale liquid metal microdroplet ejection printing surpassing 3 kHz is brought to fruition. This article delves into unraveling the mechanisms of potential modulation on the interfacial tension of the liquid metal at the nozzle, as well as the fundamental theories pertaining to the formation and migration of liquid metal microdroplets. These insights establish a theoretical and technical foundation for the application of liquid metals in the field of electronic printing.

The impact of viscosity asymmetry on phase separating binary mixtures with suspended colloids.

The introduction of neutrally wetting colloidal particles into coarsening binary fluids is known to arrest the dynamics of the phase separation, as the colloids tend to be captured by the growing interfaces to reduce the free energy of the system. This phenomenon has often been studied in systems with symmetric fluid viscosities. In this study, we investigate the behavior of colloidal particles introduced into asymmetric binary fluids with a viscosity contrast. Our results show that due to the broken symmetry the colloidal particles more easily escape from the interface towards the more viscous fluid, which reduces the lifetime of the jammed phase. Moreover, the presence of colloidal particles near the interfaces promotes the formation of micro-droplets with typical sizes comparable to the colloids.

Formation of a planar biomimetic membrane with a novel zwitterionic polymer for nanopore sequencing.

Biological membranes containing transmembrane channels play a crucial role in numerous cellular processes, and mimicking of cell membranes has garnered significant interest in various biomedical applications, particularly nanopore sequencing technology, where remarkable progress has been made with nanopore membranes. Considering the fragility of biomimetic membranes formed by artificial lipids and the limited mimicry of those formed by common block copolymers, this study developed a novel amphiphilic polymer by covalently linking hydrophilic heads of phospholipids to the ends of hydrophobic poly(dimethyl siloxane) (PDMS) chains. The absence of hydrophilic blocks allowed for good control over the polydispersity of this polymer within a narrow range. The high flexibility of PDMS chains, combined with relatively uniform molecular weights, would confer enhanced stability and robustness to polymeric membranes. Dynamic light scattering measurements and microdroplet formation tests demonstrated good amphipathic properties of these novel polymers when maintaining an appropriate hydrophilic-hydrophobic ratio. Moreover, the high similarity between the hydrophilic heads and natural phospholipids makes this polymer more compatible with biomolecules. A successful protein insertion experiment confirmed both the stability of this polymeric membrane and its compatibility with membrane proteins. As a result, this novel amphiphilic polymer exhibits great potential for biomembrane mimicking and paves a new path for material design in biomedical applications.

Hydrodynamic characteristics of core/shell microdroplets formation: Map of the flow patterns in double-T microchannel

Liquid-liquid–liquid (L/L/L) flows in microchannels involving three-phase interactions are important in various chemical applications that entail liquid–liquid–liquid reactions. This work comprehensively investigates core (silicone oil)/shell (Polycaprolactone) microdroplet formation using a continuous third phase (distilled water) in a double T-junction microchannel with a diameter of 600 µm, employing Volume-of-Fluid (VOF) simulations and high-speed imaging experimental observation. Due to the satisfactory agreement between computational and experimental techniques, the theoretical flow patterns were identified and categorized into three distinct categories at various flow rates of three phases: core/shell dripping, core/shell slug, and core/shell jetting. The shell thickness increases as the ratio of shell to core phase velocity (ushell:ucore) increases. Based on the continuous phase Capillary number (Cac) and core and shell phases Weber number (Wecore,shell), a flow pattern map was generated that segregates the distinct flow patterns into different regions. When the flow of the core and shell phases fails to form a droplet due to the inertia of the continuous phase, a core/shell dripping/slug pattern is observed. The channel walls encompass the droplets that form in the slug pattern (2×10-5≤Cac≤5×10-4, 0<Weshell≤1.5×10-3, and 0<Wecore≤5×10-5) because the continuous phase has less inertia, whereas, in the dripping pattern (5.5×10-5≤Cac≤9×10-4, 7×10-5≤Weshell≤2.5×10-4, and 1×10-5≤Wecore≤7×10-5), the shell phase fluid is enclosed by the continuous phase. The transition from dripping to jetting (Cac≥0.5, 0<Weshell≤0.15, and 1×10-2≤Wecore≤8×10-2) occurs as the flow rate of a continuous fluid or shell fluid increases. A dimensionless correlation for shell thickness estimation with a 12 % tolerance was proposed with a core/shell/continuous phase's physical properties, surface tensions, and microdroplet size, using Buckingham's theory based on 200 CFD simulations. Additionally, the flow rate and viscosity substantially impact the internal fluid velocity and vorticity of core/shell microdroplets, whereas the influence of interfacial tension can be disregarded. This research lays the groundwork for future studies on mass transfer and reaction behaviors in liquid–liquid–liquid three-phase flow in double T-junction microchannels by exploring various hydrodynamic characteristics under different operating conditions for core/shell microdroplet formation.

Ribozyme activity modulates the physical properties of RNA-peptide coacervates.

Condensed coacervate phases are now understood to be important features of modern cell biology, as well as valuable protocellular models in origin-of-life studies and synthetic biology. In each of these fields, the development of model systems with varied and tuneable material properties is of great importance for replicating properties of life. Here, we develop a ligase ribozyme system capable of concatenating short RNA fragments into long chains. Our results show that the formation of coacervate microdroplets with the ligase ribozyme and poly(L-lysine) enhances ribozyme rate and yield, which in turn increases the length of the anionic polymer component of the system and imparts specific physical properties to the droplets. Droplets containing active ribozyme sequences resist growth, do not wet or spread on unpassivated surfaces, and exhibit reduced transfer of RNA between droplets when compared to controls containing inactive sequences. These altered behaviours, which stem from RNA sequence and catalytic activity, constitute a specific phenotype and potential fitness advantage, opening the door to selection and evolution experiments based on a genotype-phenotype linkage.

Coacervate Microdroplets as Synthetic Protocells for Cell Mimicking and Signaling Communications.

Synthetic protocells are minimal systems that mimic certain properties of natural cells and are used to research the emergence of life from a nonliving chemical network. Currently, coacervate microdroplets, which are formed via liquid-liquid phase separation, are receiving wide attention in the context of cell biology and protocell research; these microdroplets are notable because they can provide liquid-like compartment structures for biochemical reactions by creating highly macromolecular crowded local environments. In this review, an overview of recent research on the formation of coacervate microdroplets through phase separation; the design of coacervate-based stimuli-responsive protocells, multichamber protocells, and membranized protocells; and their cell mimic behaviors, is provided. The simplified protocell models with precisely defined and tunable compositions advance the understanding of the requirements for cellular structure and function. Efforts are then discussed to establish signal communication systems in protocell and protocell consortia, as communication is a fundamental feature of life that coordinates matter exchanges and energy fluxes dynamically in space and time. Finally, some perspectives on the challenges and future developments of synthetic protocell research in biomimetic science and biomedical applications are provided.

Fast on–off controlling of electrohydrodynamic printing based on AC oscillation induced voltage

Stability control of electrohydrodynamic (EHD) printing technology is urgent needed for efficient fabrication of flexible electronics. In this study, a new fast on–off controlling technology for micro droplets of EHD is proposed by applying an AC induced voltage. The suspending droplet interface is broken through quickly, and the impulse current can be significantly reduced from 527.2 to 50.14 nA, which greatly reduces its negative impact on jet stability. What’s more, time interval of jet generation can be shortened by a factor of three, while not only significantly improving the uniformity of the droplets, but effectively reducing the droplet size from 195 to 104 μm. Moreover, the controllable and mass formation of micro droplets are realized, but also the structure of each droplet is able to be controlled independently, which promoted the development of EHD printing technology in more fields.

Numerical simulation of vortex flow evolution during droplet formation in T-inlet microchannel

The formation of microdroplets in T-inlet microchannel device was numerically simulated based on the conservation level set method. The strength of the swirling flow is evaluated by defining the average rotational angular velocity of the fluid inside the microdroplet under the condition of no shear. The differences in the evolution of swirling flow caused by the alteration of viscosity ratio at low capillary number (Ca≤0.01) were analyzed, and the influence of two-phase interfacial tension on the vortex evolution is also discussed. Numerical simulation results show that the evolution process of swirling flow in the squeezing droplets can be divided into five phases. The increase of capillary number will lead to an improvement of internal swirling intensity during the development of microdroplet. However, raising the viscosity ratio will inhibit the swirling strength. The variation of the interfacial tension between the two-phase fluids has a significant effect on the swirling intensity, the swirling intensity inside the droplet increases with increasing interfacial tension.