Liquid Interface Research Articles

Stagnation point slip flow of Al2O3/γ-Al2O3 nanofluids subject to Lorentz force and nonlinear thermal radiation over a stretching sheet

The flow analysis of Al 2 O 3 and γ ‐Al 2 O 3 nanofluids near a stagnating point over a stretching sheet having velocity slip at the solid–liquid interface is presented. There is a quadratic surface temperature and a linear deformation acting on the wall boundary. Due to the uniformly applied transverse magnetic flux, the Lorentz force has an impact on the flow. The effect of nonlinear TR is integrated into the heat equation. Further, water H2O and EG C2H6O2 are base fluids. The governing boundary equations are translated into dimensionless ODEs using relevant similarity variables and solved numerically using the Runge-Kutta algorithm scheme (fourth-order) and the shooting algorithm. The impacts of the parameters, that is, velocity ratio ε , velocity slip δ , nonlinear TR Rd, the temperature ratio parameter θ w , and magnetohydrodynamics M are observed for the velocity h 2 ≤ y ≤ 0 and temperature θ ( η ) fields graphically. The results of local skin friction and local Nusselt number are shown in the table. A comparative analysis of the present results and the results of previous studies has also been made in tabular form. The research indicates that water as a base fluid gives better thermal conductivity than ethylene glycol. The consequence of TR enhances the heat transfer rate of both Al 2 O 3 / γ ‐Al 2 O 3 with H2O and C2H6O2.

Liquid Interfacial Gating of Superhydrophobic Plasmonic Metal-Organic Frameworks for Three-in-One Separation, Enrichment, and Recognition in Bacterial Quorum Sensing.

Poor adsorption properties of nonadsorbing targets and competing adsorption of nontargets at a liquid interface always hamper the development of interface sensing techniques. There is a need to fabricate materials that are applicable to various interface assemblies and, meanwhile, could be employed as interfacial gating to improve the performance of interface sensing by separating, enriching, and recognizing targets at the liquid interface. Here, superhydrophobic zeolite imidazole frameworks-8@gold nanoparticles-1H,1H,2H,2H-perfluorodecanethiol (ZIF-8@GNPs-PFDT) with a static water contact angle (WCA) of 155° was constructed via electrostatic self-assembly and surface graft modification. The plasmonic metal-organic framework (PMOF) nanohybrid realized all-purpose self-assembly at air/liquid and liquid/liquid interfaces and also facilely assembled on the surface of liquid droplets, hydrogels, and foams. The self-assembled porous materials displayed the capability for separating, enriching, and recognizing analytes at various oil/water interfaces and thus could be used to adsorb nonadsorbing targets and block the competing adsorption of nontargets. The self-assembled ZIF-8@GNPs-PFDT structures were employed as a three-in-one interfacial gating to endow the excellent surface-enhanced Raman scattering (SERS) sensing capability and has become a promising tool for dye molecular analysis, oil/water separation, organic phase identification, and in situ cultivation and monitoring of bacterial quorum sensing (QS).

Interfacial-Assembly-Induced In Situ Transformation from Aligned 1D Nanowires to Quasi-2D Nanofilms.

As the dimensionality of materials generally affects their characteristics, thin films composed of low-dimensional nanomaterials, such as nanowires (NWs) or nanoplates, are of great importance in modern engineering. Among various bottom-up film fabrication strategies, interfacial assembly of nanoscale building blocks holds great promise in constructing large-scale aligned thin films, leading to emergent or enhanced collective properties compared to individual building blocks. As for 1D nanostructures, the interfacial self-assembly causes the morphology orientation, effectively achieving anisotropic electrical, thermal, and optical conduction. However, issues such as defects between each nanoscale building block, crystal orientation, and homogeneity constrain the application of ordered films. The precise control of transdimensional synthesis and the formation mechanism from 1D to 2D are rarely reported. To meet this gap, we introduce an interfacial-assembly-induced interfacial synthesis strategy and successfully synthesize quasi-2D nanofilms via the oriented attachment of 1D NWs on the liquid interface. Theoretical sampling and simulation show that NWs on the liquid interface maintain their lowest interaction energy for the ordered crystal plane (110) orientation and then rearrange and attach to the quasi-2D nanofilm. This quasi-2D nanofilm shows enhanced electric conductivity and unique optical properties compared with its corresponding 1D geometry materials. Uncovering these growth pathways of the 1D-to-2D transition provides opportunities for future material design and synthesis at the interface.

Thermoelectricity at a gallium–mercury liquid metal interface

We present experimental evidence of a thermoelectric effect at the interface between two liquid metals. Using superimposed layers of mercury and gallium in a cylindrical vessel operating at room temperature, we provide a direct measurement of the electric current generated by the presence of a thermal gradient along a liquid–liquid interface. At the interface between two liquids, temperature gradients induced by thermal convection lead to a complex geometry of electric currents, ultimately generating current densities near boundaries that are significantly higher than those observed in conventional solid-state thermoelectricity. When a magnetic field is applied to the experiment, an azimuthal shear flow, exhibiting opposite circulation in each layer, is generated. Depending on the value of the magnetic field, two different flow regimes are identified, in good agreement with a model based on the spatial distribution of thermoelectric currents, which has no equivalent in solid systems. Finally, we discuss various applications of this effect, such as the efficiency of liquid metal batteries.

Unveiling the pathways of ethanol decomposition to carbon radicals by nanosecond pulse bubble discharge in liquid: a two-step hybrid model

In recent years, bubble discharge in liquid has become a novel approach for the synthesis of carbon nanomaterials; however, the fundamental discharge process and synthesis mechanism are still not well understood. In this work, we build a two-step simulation model (combining 2D fluid dynamics and zero-dimensional plasma kinetics) to investigate nanosecond pulse discharge in an Ar bubble immersed in liquid ethanol and chemical reaction processes inside. The 2D simulation results show that discharge develops along the gas‒liquid interface where ethanol decomposes, resulting in much higher densities of active species (CH3, C2H5 and OH). The electric field of the selected reference point near the interface obtained by the 2D model is transmitted into the 0D model. The numerical results show that the decomposition of ethanol mainly occurs at the discharge stage, in which electron impact dissociation (e.g. C2H5OH + e → CH2OH + CH3 + e) and Penning dissociation (e.g. C2H5OH + Ar* → CH2OH + CH3 + Ar) dominate. The density of all carbonaceous species rapidly increases during discharge, while that of some carbon radicals (CH and C) continues to increase due to neutral species reactions when discharge ceases. By quantitative analysis of the reaction contributions, the dominant pathways of C2, CH and C are revealed, i.e. C2H5OH → C2H5 → [C2H, C2H2, C2H3] → C2 and C2H5OH → CH3 → CH2 → CH → C. In addition, the formation pathways of H and OH radicals, which are indispensable for the transformation of carbonaceous intermediates, are also analysed.

Templated silver nanoparticle deposition on laser-induced periodic surface structures for SERS sensing

Organized assemblies of metal nanoparticles exhibit unique optical properties and can be used as platforms for surface-enhanced Raman scattering (SERS) to detect small amounts of analyte molecules. In this work, we demonstrate that using Yb:KGW femtosecond laser structuring of silicon wafer we can modify surface properties by creating laser-induced quasi periodic surface structures (LIPSS) of 850 ± 43 nm periodicity. We show that silicon with LIPSS is a suitable surface for direct nanoparticle deposition because of its superhydrophilic properties and the nanoparticle density affects the density of the hot spots contributing in the Raman enhancement. We have analyzed the influence of the silver nanoparticle deposition on the structured silicon surface conditions on their density and coverage. 101±8 nm size silver nanoparticles were deposited by two methods, namely drop casting colloidal solution at three different temperatures (4 °C, 21 °C, 35 °C) and their SERS enhancements were compared with the monolayers deposited by liquid-liquid interface. It was found that monolayer deposition on a structured surface was the best approach in the sense of even silver nanoparticles coverage which exhibited best SERS performance reaching a limit of detection of 10−7 M for 2-naphthalenethiol. The obtained LoD is comparable with that of commercial substrates available in the market.

Mastering the complex time-scale interaction during Stress Corrosion Cracking phenomena through an advanced coupling scheme

Stress corrosion cracking (SCC) failure is a multi-physics phenomena and is usually modelled at the microstructural level, which includes mechanical, chemical, and electrochemical contributions. In aggressive corrosive environments, materials prone to localized corrosion, can suffer heavy pitting corrosion. Subsequently, pit-to-crack transition events might be initiated. Respective mechanical assisted pitting corrosion propagation processes are determined by mechanical, chemical, and electrochemical properties as well as transport properties of ions at grain boundaries. Variations in the electrolyte exposure conditions (including the kinetics at the solid–liquid interface), different mechanical loading scenarios, grain-specific crystal anisotropies, and other local factors combine to produce a highly complex SCC-type interaction scenario at various time and length scales. Since corrosion is a slow process whereas brittle fracture is a rapid failure mechanism, the individual domain discretization-based solvers need to use distinct time steps and appropriate solver settings to become capable to accurately simulate such coupled events. In order to address the issues that arise while accounting for scaling effects in both time and space, and retaining coupled mechanistic interplay and including the aspects specified earlier, a sophisticated modelling method is necessary for the analysis of structural failure by SCC. In this work, a partitioned multi-physics computational approach is presented, using two separate single physics solvers coupled by the open-source coupling library preCICE. In the proposed computational setup, two separate software environments are used, with dedicated solver settings and different time steps, to simulate the mechanical fracture and dissolution-driven pitting corrosion for various loading and corrosion conditions, while also taking into account the effects of microstructural anisotropy. For a 2D polycrystalline model representing face-centered-cubic (fcc) material systems, selected numerical experiments are conducted that predict the evolution of fracture and crack path resulting from SCC. The framework has been further extended to simulate 3D problems as well. The corresponding results are evaluated to show the applicability of the proposed methodology.

Acetaminophen Adsorption on Carbon Materials from Citrus Waste

Biochar and carbon adsorbents from citrus waste have been prepared by thermal and chemical treatments; they have been used in the aqueous phase adsorption of acetaminophen (ACE) as a model emerging pollutant. These materials were fully characterized by elemental analysis, X-ray fluorescence (TXRF), adsorption/desorption of nitrogen, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), point of zero charge (pHpzc), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA/DTG/DTA). A magnetic carbon adsorbent was obtained by FeCl3 activation under an inert atmosphere, giving rise to the best results in ACE adsorption. Adsorption equilibrium data were obtained at 298, 318, and 338 K and fitted to different models, corresponding to the best fitting to the Redlich–Peterson model. The maximum adsorption capacity at equilibrium resulted in 45 mg ACE·g−1 carbon at 338 K. The free energy values were calculated, and values between −21.03 and −23.00 kJ·mol−1 were obtained; the negative values confirmed the spontaneity of the process. The enthalpy and entropy of the adsorption process were obtained, giving rise to −6.4 kJ·mol−1 and 49 J·mol−1·K−1, respectively, indicating a slightly exothermic process and an increase in the randomness at the solid–liquid interface upon adsorption, respectively. The adsorption kinetics were also studied, with the Elovich model being the one that gave rise to the best-fitting results.

Coarse-Grained Molecular Dynamics Simulations of Nanoscale Roughness Effects on Oil Film Delamination

In boundary lubrication, the detachment of lubricant molecules from a solid surface is likely to occur due to the presence of high compressive normal stress combined with shear stress exerted on the solid–liquid interface. This phenomenon often results in a delamination behavior at the interface. We aim to investigate the nanoscale roughness effect on the oil film delamination from sliding iron surfaces with grain boundaries by coarse-grained molecular dynamics simulations. As a result, the oil film delamination was effectively suppressed in higher roughness. Two distinct mechanisms of delamination were found depending on surface roughness when the critical normal stress is exceeded. High roughness enhanced the ability to prevent complete slip but had negligible influence on partial slip.Graphical

Real-time and operando observation of intermediates on TiO2 photoelectrocatalysis by soft X-ray absorption spectroscopy

The oxygen evolution reaction (OER) on the TiO2 surface at the solid–liquid interface was observed in real-time and operando using fluorescence-yield X-ray absorption spectroscopy (XAS) in the soft X-ray region. The OER was observed during a potential sweep with UV light on or off, focusing on the oxygen K-edge XAS. Although conventional XAS measurements require long measurement times, the spectra during the reaction were obtained every 3 s in the present experiment via wavelength-dispersive XAS technique. An increase in the X-ray absorption intensity at approximately 533.8 eV was observed during the potential sweep only with UV light on. The observed spectral change is discussed in relation to the reaction mechanism of the OER. The present technique can be applied to a wide range of analyses of (photo-) electrocatalysis and electrochemical reactions at solid–liquid interfaces to observe their products and intermediates during the reaction.

Kinetics and morphology of gas hydrate formation from MEG solution in under-inhibited systems

Natural gas hydrate blockages pose a major risk to deepwater oil and gas development. Thermodynamic under-inhibition is a cost-effective hydrate management strategy, but the impact of mono ethylene glycol (MEG) on hydrate formation kinetics and mass transfer at the gas–water interface requires further understanding for hydrate-related flow assurance. This study investigates the kinetics and morphology of hydrate growth from MEG solutions using in situ micro X-ray CT and a macro transparent reactor. MEG concentration emerged as the primary factor influencing hydrate growth morphology. Findings revealed that MEG alters the growth morphology of gas hydrates by inhibiting the formation of a hydrate film at the gas–liquid interface and inducing flocculent hydrate growth within the solution. MEG can also induce the formation of low-saturation hydrates, with no significant self-inhibition observed at concentrations below 20 %. Over time, a dense hydrate shell tended to form on the surface of the hydrate lump, increasing the risk of blockage. Additionally, it was observed that subcooling also affects the hydrate growth morphology; higher subcooling accelerates the hydrate growth rate and increases the density of the formed hydrate. This research explored the mechanisms underlying hydrate formation in under-inhibited systems, aiming to extend the safe operational boundary for oil and gas transportation and provide theoretical support for deepwater hydrate management.

Heat and mass transfer performance analysis of a vertical tubular ammonia/water bubble absorber based on CFD modeling

Bubble absorbers are highly efficient in mass transfer processes, but their popularization is limited by the risks associated with too much ammonia charging. In order to reduce the ammonia charge, it is essential to optimize the heat and mass transfer performance in the absorber. Existing models provide in-depth analysis of bubble motion and morphology, but insufficient attention has been paid to the concentration distribution and interfacial heat and mass transfer resistance. In this study, a two-dimensional axisymmetric vertical tubular ammonia/water bubble absorber was modeled based on Fluent and phase equilibrium, absorption heat data based on Aspen was imported. The relative deviations were 9%, 0.45%, and 4.1% in terms of the completely absorbed height, the liquid phase ammonia mass fraction, and the outlet temperature, respectively. The results showed that the mass transfer deterioration point was at the gas column closure and the heat transfer deterioration point was at the gas column contraction. Variable parameter studies have shown that turbulence effects at the gas–liquid interface can lead to enhancement and deterioration of local heat and mass transfer, which in turn cause local oscillations in the concentration and temperature profiles. While increasing the interphase mass transfer driving force promotes the interphase mass transfer process, it hinders the diffusion mass transfer process within the liquid phase. This effect is particularly pronounced in the absence of intense cooling, leading to an increase in the complete absorbed height.

Interplay between Membrane Wetting Resistance and the Carbon Dioxide Absorption Rate in a Membrane Contactor: The Critical Role of the Gas–Liquid Interface

Interplay between Membrane Wetting Resistance and the Carbon Dioxide Absorption Rate in a Membrane Contactor: The Critical Role of the Gas–Liquid Interface

Revealing the Existence of Long-Range Liquid-Liquid Interfacial Potential in Phase-Transfer Processes.

By employing fluorescence wide-field microscopy and a nanoparticle-based phase transfer catalyst (PTC), consisting of a fluorescent silica nanoparticle functionalized with trioctylpropylammonium bromide, we demonstrate that in the presence of NaOH, single nanoparticles display subdiffusive motion along the axis normal to an aqueous liquid-organic liquid interface. This is because of an extended interfacial potential with a shallow well (∼1 kBT) that stretches a few μm into the organic phase, in contrast to previous molecular dynamics studies that reported narrow interfaces on the order of ∼1 nm. Spontaneous interfacial emulsification induced by NaOH results in the propagation of water-in-oil nanoemulsions into the organic solvent that creates an equilibrium hybrid-solvent composition that solvates the PTC. A greater mobility and longer residence time of the PTC at the potential well enhance the interfacial phase transfer process and catalytic efficiency.

Facile interfacial synthesis of thin AuPd alloy nanowires for plasmon-enhanced selective photocatalytic oxidation of benzyl alcohol

Bimetallic AuPd plasmonic photocatalyst is a promising candidate for catalyzing selective oxidation of aromatic alcohol. However, developing a simple one-step method for the preparation of free-standing AuPd nanostructures with excellent photocatalytic performance remains a huge challenge. Here, a facile liquid–liquid interface route was exploited to one-pot prepare free-standing AuPd alloy nanowires (NWs) under mild conditions. Specifically, Au1Pd1 NWs are grown via oriented attachment at chloroform-water interface and 40 °C with Na2PdCl4 and HAuCl4 as precursors and 1-naphthol as reductant. Au1Pd1 NWs possess many advantages, such as thin diameter (4.0 nm), large aspect ratio, abundant defects and strong Au-Pd electronic interaction. During benzyl alcohol oxidation to benzaldehyde, Au1Pd1 NWs exhibit excellent photocatalytic activity and durability. At 40 min of visible light illumination, 98 % conversion of benzyl alcohol and 100 % selectivity to benzaldehyde are finished. After five cycles, Au1Pd1 NWs still maintain high photocatalytic activity. Compared to pure Au NWs, alloying Pd with Au in Au1Pd1 NWs dramatically enhances photocatalytic activity. The results indicate that the generated abundant •O2– under illumination play an important role in significantly improving benzyl alcohol oxidation to benzaldehyde.

Purifying High-Purity Copper via Semi-Continuous Directional Solidification: Insights from Numerical Simulations

High-purity copper is essential for fabricating advanced microelectronic devices, particularly integrated circuit interconnects. As the industry increasingly emphasizes scalable and efficient purification methods, this study investigates the multi-physics interactions during the semi-continuous directional solidification process, utilizing a Cu-1 wt.%Ag model alloy. Coupled simulation calculations examine the spatial distribution patterns of the impurity element silver (Ag) within semi-continuously solidified ingots under varying pulling rates and melt temperatures. The objective is to provide technical insights into the utilization of the semi-continuous directional solidification method for high-purity copper purification. The findings reveal that increasing the pulling rate and melt temperature leads to a downward shift in the solid–liquid interface relative to the mold top during processing. Alongside the primary clockwise vortex flow, a secondary weak vortex emerges near the solid–liquid interface, facilitating the migration of the impurity element Ag toward the central axis and amplifying radial impurity fluctuations. Furthermore, diverse pulling rates and melt temperature conditions unveil a consistent trend along the ingot’s height, which is characterized by an initial increase in average Ag content, followed by stabilization and then a rapid ascent during the late stage of solidification, with higher pulling rates and melt temperatures expediting this rapid ascent. Leveraging these insights, a validation experiment using 4N-grade recycled copper in a small-scale setup demonstrates the effectiveness of the semi-continuous directional solidification process for high-purity copper production, with copper samples extracted at 1/4 and 3/4 ingot heights achieving a 5N purity level of 99.9994 wt.% and 99.9993 wt.%, respectively.

Toward Advanced QM/MM MD Simulations of Solid–Liquid Interfaces–Adsorption and Proton Transfer of Multilayer Water on R-TiO2(001)

Toward Advanced QM/MM MD Simulations of Solid–Liquid Interfaces–Adsorption and Proton Transfer of Multilayer Water on R-TiO₂(001)

Structure and properties of electrochemical interfaces with grafting polyelectrolyte: A fluid density functional theory study

The structure of the electrode/electrolyte interface directly determines electrochemical performance. One effective method for controlling this interface structure is by grafting polyelectrolyte onto the electrode surface, which can significantly alter the double layer structure and enhance electrochemical performance. This study focuses on the graft modification of polyelectrolytes at the electrochemical interface and investigates the impact of the length and density of the grafted polyelectrolyte chain on the structure and capacitance of the electrode/ionic liquid interface using fluid density functional theory (FDFT). The findings indicate that the grafted polymerbrush disrupts the alternating layer of anions and cations at the conventional interface and exerts an additional adsorption effect on counter ions, thereby reducing the density of freely movable co-ions. Consequently, this process increases the effective charge and capacitance of the interface. The results of this investigation contribute to a deeper comprehension of polyelectrolyte solutions at solid–liquid interfaces and guide the regulation of electrochemical interface properties.

Development and characterisation of a novel complex triple cell culture model of the human alveolar epithelial barrier

Owing to increased pressure from ethical groups and the public to avoid unnecessary animal testing, the need for new, responsive and biologically relevant in vitro models has surged. Models of the human alveolar epithelium are of particular interest since thorough investigations into air pollution and the effects of inhaled nanoparticles and e-cigarettes are needed. The lung is a crucial organ of interest due to potential exposures to endogenous material during occupational and ambient settings. Here, an in vitro model of the alveolar barrier has been created in preparation for use in the quasi-air liquid interface (qALI) and (aerosol) air–liquid interface (ALI) exposures. The model consists of an alveolar type 1-like cell line (TT1), an alveolar type 2-like cell line (NCI-H441) and a model of (alveolar) macrophages (dTHP-1). The model formulates a complex, multi-cellular system, cultured at the air–liquid interface, that mimics the apical layer of the alveolar epithelial region in the human lung. Characterisation data has shown that both TT1 and NCI-H441 epithelial cells are able to be cultured together in addition to dTHP-1 cells through imaging (morphology), pro-inflammatory response and viability measurements. This dataset also demonstrates evidence of a reasonable barrier created by the cell culture in comparison to negative controls. Furthermore, it shows that while maintaining a low baseline of (pro)-inflammatory mediator expression during normal conditions, the model is highly responsive to inflammatory stimuli. This model is proposed to be suitable for use in toxicology testing of inhaled exogenous agents.

Ionic Liquid Interface as a Cell Scaffold (Adv. Mater. 26/2024)

Ionic Liquid Interface as a Cell Scaffold (Adv. Mater. 26/2024)