Liquid Interfacial Properties Research Articles

Molecular dynamic simulation study on effect of anionic–nonionic surfactants on decane desorption from SiO2 surface

During oil production, some amount of crude oil is adsorbed on the rock layer. Therefore, surfactants are needed to detach the residual crude oil from this layer, thereby improving the overall oil recovery rate. In this study, five kinds of anionic–nonionic surfactants were designed by changing the length of ethylene oxide (EO) chains based on the structure of saturated cardanol. 8PO8EOSO3 exhibited good oil-detachment effectiveness, and this was assessed by studying the energy of interface interaction between the solid phase (SiO2) and the liquid phase (oil phase molecules, surfactants, and water). The density distribution data further elucidated that the good interface properties of 8PO8EOSO3 affected the degree of aggregation of the oil phase molecules on the SiO2 surface. This was mainly because the appropriate length of EO chains could realize optimal diffusion coefficients at the oil–water interface. Thus, in the 8PO8EOSO3 system, the oil phase molecules exhibited greater intermolecular distance and weak interactions with SiO2 (radial distribution function). Further, the study of the solid–liquid interface properties and effect of different chain lengths of EO chains on desorption showed that the appropriate number of and EO chains was an important factor in designing the structure of the extended surfactant to ensure that the surfactant realizes a high degree of detachment of the oil phase from SiO2.

Modeling the thermal and hydrodynamic performance of grooved wick flat heat pipes

A compact model is developed to predict the thermal and hydrodynamic performance of a flat heat pipe with a rectangular grooved wick. The present model relies on the analytical solution to the energy equation in the wall and an equivalent heat transfer coefficient predicted using a computationally efficient iterative method. This efficient iterative method can also provide a framework for modeling other grooved or porous wick heat pipes for which analytical or semi-analytical solutions to the wall conduction, fluid flow, and film equations exist. Compared to prior numerical tools, the present modeling approach is computationally efficient, making it compelling for use in parametric and optimization studies. Instead of numerically solving a set of coupled differential equations, the present model considers only analytical and semi-analytical solutions for evaporation and condensation heat transfer rates. The non-discretized nature of the present model allows computations on a typical workstation to be completed within seconds as opposed to the hours required for prevalent numerical tools. The present model accounts for varying liquid fill volumes, geometry, and interfacial properties, such as surface tension and contact angle. The present model closely agrees with published numerical and experimental results for wall temperatures and maximum heat transfer rates. Parametric studies, which vary wall thermal conductivity, water contact angle, and groove dimensions are conducted on a previously experimentally investigated heat pipe to demonstrate the present model’s capabilities. The present model found that the maximum heat transfer rate of the heat pipe can be enhanced by about 15 and 20% by varying its wetting angle and groove dimensions, respectively.

Dynamic and interfacial properties for dichloromethane absorption in ionic liquids: Experimental and molecular dynamic insights

In this study, a strategy for dichloromethane (DCM) capture using ionic liquids (ILs) was systematically investigated from the perspective of dynamic analysis. The diffusion coefficient, Henry’s law constant (H), saturated absorption capacity, and overall volumetric liquid-side mass-transfer coefficient (KLao) of four types of ILs were obtained. Among all the ILs studied, tetrabutylphosphonium caproate ([P4444][C5COO]) demonstrated superior DCM absorption capabilities, and its corresponding H value (3.13 Pa m3/mol at 25 °C) was markedly lower than those of solvents documented in the literature. Furthermore, its KLao value was determined to be 2.77 × 10−3/s at 25 °C, which was measured in a customized cylindrical absorption bottle with a height of 150 mm and an inner diameter of 16 mm. The absorption bottle, fitted with a gas inlet tube having an inner diameter of 5 mm and positioned 5 mm above its base, utilized a simple bubbling technique to introduce gas into the liquid phase, eliminating the need for gas-dispersion equipment. Nevertheless, ILs with high affinities showed relatively high initial mass-transfer rates for DCM. Based on molecular dynamics (MD) simulations, the vapor–liquid interface properties, including mass and number density profiles, molecular orientation, and surface tension, were investigated. This revealed that in the pure [P4444][C5COO] system, the alkyl chain of the anion was oriented toward the gas phase, while the carboxyl group was oriented toward the bulk. The tilt angle of [C5COO]− with respect to the interface was within the range of 37° < θ′ < 70°. For the [P4444][C5COO]/DCM mixture, at the interface, the anion exhibits an enhanced ordered orientation, while the cation shows a more disordered orientation.

Dislodgement of Hydrogen Bubbles in Microchannels with Embedded Pillars: An Analytical, Experimental, and Numerical Study.

Microchannels with integrated pillars have enhanced the production capabilities and performance of various applications due to their high surface-to-volume ratio. However, emerging gas bubbles can become trapped, potentially limiting the functionality or efficiency of the device when scaled down to the low-micrometer scale. Understanding the conditions required to dislodge these bubbles is thus critical for optimizing microfluidic devices with complex physical behaviors. Here an analytical model is presented that outlines the dislodgment conditions and driving forces for such gas-liquid flows. These terms are derived from the gas-liquid interface properties, geometry, and processing parameters. As the density of the pillar arrangement is scaled down, the resistance to bubble dislodgment typically increases. Nevertheless, the bubble is compelled to dislodge at lower pressure loads when critical volumes are reached. This newly discovered effect is particularly noticeable in densely packed arrays and can be explained by the interplay of increased surface tension, geometrical restrictions, and volume-preserving forces. The analytical terms and effects are validated through novel experimental and numerical methods tailored for microchannels in the low-micrometer scale, showing strong agreement.

Plasma‐induced formation of coatings on vegetable ivory microparticles immersed in silicone oil: Enhancing surface coverage using natural products

AbstractAiming to enhance the potential applications of bioproducts, we developed an innovative approach for their hydrophobization using plasma activation of liquids. In this study, microparticles of vegetable ivory, a porous hygroscopic material, were treated by an air plasma jet while immersed in silicone oil. The in‐liquid plasma treatment formed coatings that reduced particle water vapor sorption. Pore surface coverage and sorption reduction were enhanced by mixing silicone oil with copaiba oil‐resin (Copaifera spp.). Mulateiro extract (Calycophyllum spruceanum) was not as effective, owing to a lower affinity with silicone oil. For the first time, we demonstrate the plasma‐induced coating formation on particles immersed in liquid mixtures, a process in which liquid–liquid interfacial properties play a fundamental role.

Water/organic liquid interface properties with amine, carboxyl, thiol, and methyl terminal groups as seen from MD simulations.

Molecular dynamics simulations were performed to study structural and dynamic properties of polar butanamine/water/butanamine, pentanoic acid/water/pentanoic acid, butanethiol/water/butanethiol, and nonpolar pentane/water/pentane systems. The mass density profiles along the interface normal to the organic liquid/water system, the difference in the local structure of H O molecules in bulk and in the vicinity of interface, as well as the diffusion behavior of water molecules at the interface with above-mentioned organic liquids have been investigated. Our MD simulation has shown that the diffusion of water molecules across the water/organic liquid interface is influenced by the hydrogen bonds between water molecules and the terminal groups of organic liquids. It was found that the loss of the hydrogen bonds in the nonpolar organic liquid leads to a decrease in the value of the normal component of the diffusion coefficient , while the tangential diffusion coefficients, both and , increase.

Effect of composition on nucleation and growth of equiaxed dendrites in the transparent alloy Neopentylglycol-(d)Camphor during solidification in microgravity conditions

We investigate the effect of composition of hypoeutectic Neopentylglycol-(D)Camphor (NPG-DC) alloy on nucleation and microstructure kinetics during alloy solidification in low gravity conditions without convection and buoyancy effects. Two alloys with compositions of 0.2 and 0.3 wt-frac. DC have been solidified in a small thermal gradient to obtain equiaxed dendritic microstructures with different crystallographic growth orientation. In-situ optical and thermal characterization in the transparent material provided evolution of equiaxed dendrite density, nucleation undercooling, dendrite tip velocity and kinetic law. Significant differences in the results for the two compositions were found, which are discussed in relation to temperature and concentration dependent solid–liquid interfacial properties. For NPG-0.2 wt-frac. DC equiaxed dendrites with 〈100〉 crystallographic growth orientation exist which tend to grow faster and fill the liquid volume quicker compared to the NPG-0.3 wt-frac. DC alloy. This behavior hinders nucleation of further dendrites and decreases their final number. In contrast, for NPG-0.3 wt-frac. DC equiaxed dendrites with 〈111〉 crystallographic growth orientation nucleate at higher undercooling and the kinetic law indicates smaller dendrite tip velocities correlated to a larger number of dendrites.

Solid–Liquid Interfacial Properties Related to Ionic Conductivity of Mixtures of Metal Oxide Particles and Lithium Bis(fluorosulfonyl)amide-Sulfone Electrolytes

Solid–Liquid Interfacial Properties Related to Ionic Conductivity of Mixtures of Metal Oxide Particles and Lithium Bis(fluorosulfonyl)amide-Sulfone Electrolytes

Double layer in ionic liquids: Temperature effect and bilayer model

This work describes the effect of potential and temperature on the graphene–ionic liquid (EMImBF4) interfacial structure and properties with the focus on a novel phenomenon of ionic saturation. We apply classical molecular dynamics simulations to reproduce well-known phenomena of overscreening, monolayer formation, and temperature-induced smearing of the interfacial structure. Using quantum density functional theory calculations, we show how quantum capacitance dampens the influence of temperature and improves the agreement with the experimental data. Using a bilayer model, we study characteristic features of capacitance–potential dependence and relate them to the changes in interfacial structure. These insights are of fundamental and practical importance for the application of similar interfaces in electrochemical energy storage and transformation devices such as capacitors and actuators.

Target high‐efficiency ionic liquids to promote H2SO4‐catalyzed C4 alkylation by machine learning

AbstractTo predict and rationally design high‐efficiency ionic liquids (ILs) additives for H2SO4‐catalyzed alkylation, the quantitative structure–activity relationship between 11,000 ILs and interfacial properties of H2SO4 alkylation was established by combination of molecular dynamics simulation, semi‐empirical density function theory, and machine learning. The results indicate that ILs additives with longer alkyl chain can significantly broaden interfacial thickness and decrease interfacial tension, in which the cation‐ and anion‐based descriptors play a synergistic prominent role. Based on the intensified interfacial properties, series of novel ILs additives with different alkyl chain length in both cations and anions are prepared, which present the ability to efficiently promote catalytic performance of H2SO4 at trace addition amount and increase research octane number (RON) of alkylate up to 98.08 from 95.87 in pure H2SO4 system. This work provides a strategy for prediction and rational design of high‐efficiency additives to enhance the liquid–liquid interfacial properties.

An atomistic simulation study of rapid solidification kinetics and crystal defects in dilute Al–Cu alloys

Rapid solidification kinetics of dilute Al–Cu alloys is simulated using a quantum mechanics based bond-order potential (BOP), in free solidification conditions, to determine kinetic and thermodynamic properties of solidification, as well as point defects and chemical ordering of the solidified structures. We measure the anisotropic kinetic coefficient, anisotropic solid–liquid interface energy, as well as solute trapping kinetics in terms of partition coefficient versus velocity and solute drag coefficient. Furthermore, solid–liquid interface free energy and its anisotropy are measured in equilibrium simulations, showing reasonably good agreement with previous studies. We also verified the self-consistency of the MD simulations, by comparing the interfacial temperature vs. velocity to that predicted by the continuous growth model. These solid–liquid interface properties are important for quantitative parametrization of larger scale solidification modeling techniques such as phase field models. We also investigated the point defect content, local chemical ordering, and local crystalline structures in the rapidly solidified samples. We found clustering of solute with vacancies, whereas copper atoms repelled each other in these dilute alloy simulations. In addition to vacancies, a large number of interstitials were found. In solidification velocities approaching the complete solute trapping regime, we found that the vacancies and interstitials formed in conjunction, i.e. as Frenkel pairs. Finally, in addition to FCC, we detected BCC and HCP phases, where the latter two were accompanied by an increase in local copper content. Understanding the formation of point defects and their relationship to chemical ordering is an important step towards controlling the formation of pre-precipitates and precipitates, which are an important strengthening mechanism for aluminum–copper alloys.

Modulation of bubble flow resistance and surface fluidity :the effect of nanoparticle packing density at gas–liquid interface

Nanoparticles (NPs) adsorbed at bubble surface have a substantial impact on gas–liquid interface properties, but how to regulate the properties and further control foam flow remaining to be elucidated. Here, the effects of nanoparticle surfactancy on surface rheology, fluidity and shear force field around bubbles were quantitatively analyzed. It was found that the adsorption of nanoparticles on the bubble surface gives rise to surface solidification, the flow velocity close to surface decreased by 76%, meanwhile the shear stress loaded on bubble surface increases sharply. Furthermore, the surface solidification degree or fluidity can be controlled by regulating the packing density of nanoparticles on bubble surface, whereby the bubble flow could be control accordingly, which greatly contribute to the application of foam.

Molecular dynamics of liquid-liquid equilibrium and interfacial properties of aqueous solutions of methyl esters.

In this work, the liquid-liquid phase equilibria and interfacial properties of methyl ester + water binary mixtures are determined at atmospheric pressure and from 278 to 358 K combining the direct coexistence technique and molecular dynamics simulations. Methyl esters are modelled using new parametrizations based on the united atom TraPPE model force field proposed recently by us [E. Feria, J. Algaba, J. M. Míguez, A. Mejía, P. Gómez-Álvarez and F. J. Blas, Phys. Chem. Chem. Phys., 2019, 22, 4974-4983] that are able to predict the vapour-liquid interfacial properties of pure methyl esters with high accuracy. In the case of water, we consider the well-known TIP4P/2005 model, the most popular rigid and non-polarizable model to describe the interfacial properties of pure water. The simulations are performed using the direct coexistence technique in the isothermal-isobaric or NPzT ensemble in combination with molecular dynamics. We obtain density profiles, temperature-densities and temperature-composition projections of the phase diagrams, and interfacial tensions. The liquid-liquid interfacial tension is calculated from the normal and tangential components of the pressure tensor according to the mechanical virial route. We pay attention particularly to the ability of the molecular models in predicting the experimental behavior of the systems. Simulation results are able to account for the liquid-liquid phase equilibria of these binary mixtures, in good agreement with the experimental data taken from the literature. Unfortunately, experimental values for interfacial tensions are substantially overestimated by predictions from computer simulations in all cases. To our knowledge, this is the first time that the liquid-liquid phase equilibrium and interfacial properties of methyl ester + water mixtures have been predicted from computer simulations.

A temperature-dependent atomistic-informed phase-field model to study dendritic growth

The effects of solid–liquid interface anisotropy and kinetics on crystallization of highly undercooled titanium melts are studied by coupling molecular dynamics and phase-field simulations. Unlike previous models and to consider the actual physics of crystal growth, the phase-field parameters, representing interface mobility, solid–liquid transformation barrier, and interfacial energy gradient, are temperature dependent. The parameters are determined by a combination of molecular dynamics simulations and classical thermodynamic calculations based on the temperature-dependent solid–liquid interface properties and kinetic coefficient. We investigated Ti dendritic growth as a benchmark example to demonstrate that the phase-field model presented in this work is more compatible with the experimental data and theoretical models in comparison to the earlier models with constant model parameters. The capillary fluctuation method is used to determine the solid–liquid interface energy and its anisotropy for undercoolings up to 400 K. Similar to theoretical models, the average solid–liquid interface energy decreases with temperature, and the preferred dendrite growth direction shifts from 〈100〉 to 〈110〉 direction as the undercooling increases. Phase-field simulations also show other favorite growth directions, implying that there is a competition between the interface anisotropy and kinetics of the solid–liquid interface.

Bayesian Data Assimilation of Temperature Dependence of Solid-Liquid Interfacial Properties of Nickel.

Temperature dependence of solid–liquid interfacial properties during crystal growth in nickel was investigated by ensemble Kalman filter (EnKF)-based data assimilation, in which the phase-field simulation was combined with atomic configurations of molecular dynamics (MD) simulation. Negative temperature dependence was found in the solid–liquid interfacial energy, the kinetic coefficient, and their anisotropy parameters from simultaneous estimation of four parameters. On the other hand, it is difficult to obtain a concrete value for the anisotropy parameter of solid–liquid interfacial energy since this factor is less influential for the MD simulation of crystal growth at high undercooling temperatures. The present study is significant in shedding light on the high potential of Bayesian data assimilation as a novel methodology of parameter estimation of practical materials an out of equilibrium condition.

Vapour-liquid phase equilibria and interfacial properties of fatty acid methyl esters from molecular dynamics simulations.

We have determined the phase equilibria and interfacial properties of a methyl ester homologous series (from methyl acetate to methyl heptanoate) using direct simulations of the vapour-liquid interfaces. The methyl esters are modelled using the united atom approach in combination with transferable parameters for phase equilibria (TraPPE) force fields for alkanes, alkenes, carbon dioxide, ethers, and carboxylic acids in a transferable way. This allows us to take into account explicitly both dispersive and coulombic interactions, as well as the repulsive Pauli-exclusion interactions. Simulations are performed in the NVT or canonical ensemble using molecular dynamics. Vapour-liquid surface tension is determined using the virial route, i.e., evaluating the normal and tangential components of the pressure tensor along the simulation box. We have also calculated density profiles, coexistence densities, vapour pressures, surface entropies and enthalpies, and interfacial thickness as functions of temperature, as well as the normal boiling temperatures and the critical temperatures, densities, and pressures for each member of the series. Special attention is paid to the comparison between experimental data taken from the literature and our results obtained using molecular dynamics simulations. We also analyze the effect of increasing the molecular weight of the methyl esters (at fixed temperature) on all the properties considered, with special emphasis on phase equilibria envelopes and surface tension. The TraPPE force fields transferred from other molecules and chemical families are able to predict very accurately the experimental vapour-liquid phase envelopes of methyl esters. We also compare the results obtained from simulations of the surface tension, with experimental data taken from the literature. To our knowledge, this is the first time that vapour-liquid phase equilibria and interfacial properties, and particularly surface tension, of this methyl ester homologous series are obtained using computer simulation.

Molecular modelling techniques for predicting liquid-liquid interfacial properties of methanol plus alkane (n-hexane, n-heptane, n-octane) mixtures.

In this work, the liquid-liquid interfacial properties of methanol plus n-alkane (n-hexane, n-heptane, n-octane) mixtures are investigated at atmospheric pressure by two complementary molecular modelling techniques; namely, molecular dynamic simulations (MD) and density gradient theory (DGT) coupled with the PC-SAFT (perturbed-chain statistical associating fluid theory) equation of state. Furthermore, two molecular models of methanol are used, which are based on a non-polarisable three site approach. On the one hand, is the original (flexible) TraPPE-UA model force field. On the other hand, is the rigid approximation denoted as OPLS/2016. In both cases, n-alkanes are modelled using the TraPPE-UA model. Simulations are performed using the direct coexistence technique in the ensemble. Special attention is paid to the comparison between the estimations obtained from different methanol models, the available experimental data and theoretical calculations. In all cases, the rigid model is capable of predicting the experimental phase equilibrium and interfacial properties accurately. Unsurprisingly, the methanol-rich density and interfacial tension are overestimated using the TraPPE model combined with Lorentz-Berthelot mixing rules for predicting the mixture behaviour. Accurate comparison between MD and DGT plus PC-SAFT requires consideration of the cross-interactions between individual influence parameters and fitting the βij values. This latter aspect is particularly important because it allows the exploitation of the link between the EOS model and the direct molecular simulation of the corresponding fluid. At the same time, it was demonstrated that the key property defining the interfacial tension value is the absolute concentration of methanol in the methanol-rich phase. This behaviour indicates that there are more hydrogens bonded with each other, and they interact favourably with an increasing number of carbon atoms in the alkane.

Comparative investigation of liquid film thickness and interfacial wave properties of swirling gas-liquid flows

The liquid film in swirling flows plays an important role in mass, momentum and heat transfer, whose properties differ from those in non-swirling regimes. In this paper, we employ the image processing and statistical analysis to compare the liquid film thickness and wave properties of swirling gas column, swirling intermittent and swirling annular flow. The results indicate that the film thickness is intimately linked to the flow regimes, i.e., uniform in swirling gas column flow, gradual thickening in swirling intermittent flow, and increasing up to a maximum point and decreasing thereafter in swirling annular flow. Additionally, the wave frequency is proportional to jg but inversely proportional to jl in swirling gas column flow, which is to the contrary in swirling intermittent flow. In swirling annular flow, the waves show less correlation at a finite time and the frequency decreases with jg, but the influence of jl depends on flow distance.

Molecular insights on the microstructures of nanoconfined glycerol and its aqueous solutions: The effects of interfacial properties, temperature, and glycerol concentration

In this work, we conducted molecular dynamics simulations to investigate the effects of rutile–liquid and graphene–liquid interfacial properties, glycerol concentrations (i.e., 10%, 40%, 70%, and 100% molar contents), and temperature (i.e., 180, 273, and 320 K) on the microstructures of nanoconfined glycerol and its aqueous solutions. Results indicated that the effect of interfacial properties on the spatial and orientation distributions of nanoconfined glycerol and water molecules was more prominent than that of temperature. In glycerol aqueous solutions, water and glycerol molecules localized into two distinct layers on the hydrophilic rutile surface but partially mixed with each other near the hydrophobic graphene surface, because water molecules near the hydrophobic surface exhibited more random orientations and formed more hydrogen bonds with glycerol molecules than those near the hydrophilic surface. Moreover, interface introduction and increased temperature drastically reduced the hydrogen bonding ability of water molecules in glycerol aqueous solutions. The addition of glycerol molecules can break hydrogen bonds between water molecules and inhibit water crystallization in glycerol aqueous solutions. Temperature and glycerol concentration exerted limited effects on the hydrogen bonding ability of water molecules on hydrophilic surfaces in glycerol aqueous solutions. Meanwhile, the presence of a hydrophilic surface can effectively decelerate hydrogen bond breakage induced by increasing temperature or by decreasing glycerol contents.

Modeling of electrochemical properties of potential-induced defects in butane-thiol SAMs by using artificial neural network and impedance spectroscopy data

Electrochemical impedance spectroscopy (EIS) is commonly used in studying solid–liquid interfacial properties. In this work, the electrochemical behavior of potential-induced defects in self-assembled CH3(CH2)3SH monolayer (SAM) electrodeposited on the surface of a mono-crystalline gold rod has been experimentally investigated and theoretically modeled. An equivalent electrical circuit with mixed kinetic and charge transfer is applied to analyze the impedance of the experimental data of the interface. The results are compared to those obtained with a second model calculation based on an artificial neural network (ANN) for predicting the electrochemical properties of the same interface. The proposed approach defines the equivalent circuit elements for the interface under study. The latter is based on adjusting the electrical parameters by using a detailed methodology proposed to build up the equivalent circuit. We illustrated the experimental and predicted numerical simulation of the corresponding model. Numerical simulation of the neural network model shows the impact of using equivalent circuits to describe the features of the materials under study. The results demonstrate a high performance in predicting and optimizing the equivalent circuit. The advantage of our adopted model appears by comparing our model results and experimental data analysis.