Water Film Structure and Wettability of Different Quartz Surfaces: Hydrogen Bonding Across Various Cutting Planes.

Quartz is ubiquitous in subsurface formations. The crystal faces have different atomic arrangements. Knowledge of the molecular structures on the surface of quartz is key in many processes. Molecular dynamics simulations are conducted to investigate the atomic arrangement effect on the water film structure, ion adsorption, and wettability at three different α-quartz surfaces. The interfacial structures depend on the quartz surface. Intrasurface hydrogen bonding between surface silanols differs in the α-quartz surface. At the (0001) surface, the OH density is 9.58 nm-2, consisting of Q2 units with two hydroxyl groups per silicone atom. At the (101̅0)-ß surface, the OH density is 7.54 nm-2, consisting of Q3 units with one hydroxyl group per silicone atom; there is significant intrasurface hydrogen bonding. At the (101̅0)-α surface, the OH density is 7.54 nm-2, consisting of Q2 units; however, there is little intrasurface hydrogen bonding. The intrasurface hydrogen bonding results in the exposure of hydrogen-bond acceptors to the aqueous phase, causing water molecules to have an H-up (hydrogen toward surface) orientation. This orientation can be found at the (0001) and (101̅0)-ß surfaces; it is related to the degree of ordering at the surface. The ordering at the (0001) and (101̅0)-ß surfaces is higher than that at the (101̅0)-α surface. In aqueous systems with ions, cation adsorption is the most dominant at the (0001) surface due to the largest surface density of the intrasurface hydrogen bonding, providing interaction sites for cations to be adsorbed. We observe a pronounced decrease in water film thickness from the ions at the (0001) surface only, likely due to significant cation adsorption. In this work, we demonstrate that the hydrogen-bond network, which varies from the plane cut, affects the water film structure and ion adsorption. The contact is nearly zero despite the changes in the film thickness and molecular structure at the temperature of 318 K.

Effect of fluids on the critical energy release rate of typical components in shale and andesite by molecular simulations.

The critical energy release rate (Gc) is a key parameter in numerical simulations of hydraulic fracturing, which may be affected by a fluid. Molecular dynamics (MD) simulations of minerals' tensile failure can be performed to gain insights into the mechanisms relevant to the critical energy release rate at the microscale. The methodology of calculating the critical energy release rate for solid-fluid systems is challenging. In this study, we conduct extensive MD simulations for solid-vacuum and solid-fluid systems. Typical components in shale and andesite, including quartz, muscovite, and kerogen, are selected in our investigation. The effect of H2O and CO2 on the critical energy release rate is analyzed. Fracture propagation and fluid invasion in fractures are also monitored. The results show that quartz and muscovite are brittle in H2O and CO2 and kerogen has very pronounced ductile behavior. H2O can reduce the critical energy release rate of quartz and muscovite slightly, but may increase that of kerogen. The effect of CO2 on quartz and muscovite is mild, while it reduces Gc of kerogen significantly. The implication is the creation of a much higher surface area in kerogen by CO2 than by H2O, which is in line with large-scale observations.

Surfactant-Enhanced Spontaneous Emulsification Near the Crude Oil-Water Interface.

Spontaneous emulsification near the oil-water interface and destabilization of water-in-oil emulsions in the bulk oil phase may affect the efficiency of improved oil recovery. In this study, we investigate the effect of a demulsifier surfactant on spontaneous emulsification near the oil-aqueous phase interface and in the bulk oil phase through imaging. The results show that pronounced spontaneous emulsions may form near the oil-aqueous phase interfaces. The mechanism of diffusion and stranding is believed to dominate spontaneous emulsification. A demulsifier surfactant, which has been used for demulsification of water-in-oil emulsions in the bulk oil phase, is found to enhance spontaneous emulsification near the oil-water interface. The diffusive flux of water through the interface can be enhanced if the demulsifier is added into the aqueous phase, in which the demulsifier may act as a carrier. It can generate a region of local supersaturation combined with hydrated asphaltenes and result in faster and stronger spontaneous emulsification. We also investigate the effect of a viscosifier polymer on emulsion formation. The polymer is used to improve sweep efficiency in oil displacement. In this work, we show that it can inhibit emulsification in the bulk oil phase, but its effect on spontaneous emulsification near the interface is not pronounced.

Calculation of Solid-Fluid Interfacial Free Energy with Consideration of Solid Deformation by Molecular Dynamics Simulations.

Fluid-fluid interfacial free energy can be measured accurately and can also be calculated from molecular simulations. However, it is challenging to measure solid-fluid interfacial free energy directly. Accurate computation has not yet been advanced by molecular simulations. In this study, we derive working expressions for estimating solid-fluid interfacial free energy based on the free-energy perturbation method with consideration of solid deformation. A Lennard-Jones solid-fluid system is simulated. Our derivations indicate that the effect of solid deformation is pronounced on solid-fluid interfacial free energy, and the results may be significantly different from the conventional test area method. Our results reveal that the contribution of the solid deformation highly depends on the stress conditions in the solid, which can be either positive or negative. Adsorption of fluids onto the solid surface has a significant effect on interfacial free energy. In weak adsorption, the interfacial free energy is close to the solid-vacuum surface free energy. Strong adsorption results in a significant reduction in interfacial free energy.

Improved Oil Recovery in Carbonates by Ultralow Concentration of Functional Molecules in Injection Water through an Increase in Interfacial Viscoelasticity.

Injection of sea water is the most common practice to displace oil in porous media in subsurface formations. In numerous studies, conventional surfactants at concentrations in a range of one weight percent have been proposed to be added to the injected water to improve oil recovery. Surfactants accumulate at the oil-water interface and may reduce the interfacial tension by three orders of magnitude or more, resulting in higher oil recovery. Recently, we have proposed the addition of ultralow concentration of a non-ionic surfactant to the injected water to increase interface viscoelasticity as a new process. The increase in interface viscoelasticity increases oil recovery from porous media. This alternative approach requires only a concentration of 100 ppm (two orders less than the conventional improved oil recovery) and therefore is potentially a much more efficient process. In this work, we present a comprehensive report of the process in an intermediate-wet carbonate rock. There is very little adsorption of the functional molecules to the rock surface. Because the critical micelle concentration is low (around 30 ppm), most of the molecules move to the fluid-fluid interface to form molecular structures, which give rise to an increase in interface elasticity. We also demonstrate that interface elasticity has a non-monotonic behavior with the salt concentration of injected brine, and an optimum salinity exists for maximum oil recovery.

Effect of Low-Concentration of 1-Pentanol on the Wettability of Petroleum Fluid-Brine-Rock Systems.

High-concentration brines generally cause the wettability of petroleum fluid-brine-rock systems to become less water-wet (more oil-wet). The addition of alcohols to the brine, however, may produce an opposite effect. In this work, we investigate the synergic effects of a low concentration of 1-pentanol and brines on the wettability of petroleum fluid-brine-rock systems. The variables examined include the mineral type (mica, quartz, calcite), brine concentration (0-3 M), ion type (monovalent and divalent), crude oil (samples from sandstone and carbonate reservoirs), and 1-pentanol concentration (0.5 and 1 wt %). Adding 1 wt % 1-pentanol to the brine only slightly affects the wettability of a petroleum fluid on sandstone-like mineral surfaces (mica and quartz), whereas the effect is significant for carbonate-like mineral surfaces (calcite). A maximum reduction of 80° in contact angle (measured through the brine phase) is observed at 0.1 M NaCl and 0.5 wt % 1-pentanol. ζ-Potentials of both brine-petroleum fluid and brine-rock interfaces are found to be insensitive to the presence of 1-pentanol in the brine. Based on these observations, we propose that the accumulation of 1-pentanol in the thin brine film confined between the petroleum fluid and the rock surface results in a significant change of the wettability. Our finding may have various practical applications, one of which is the use of a low concentration of 1-pentanol for improving oil production.

Fickian and thermal diffusion coefficients of binary mixtures of isobutylbenzene and n-alkanes at different concentrations from the optical beam deflection technique.

We report the Fickian diffusion (D12), thermal diffusion (DT), and Soret (ST) coefficients of 4 binary mixtures of isobutylbenzene (IBB) and n-alkanes (n-hexane, n-octane, n-decane, and n-dodecane) at 298.15 K and atmospheric pressure. The concentration is varied in the whole range. The Optical Beam Deflection technique is used in the measurements. We first verify our measurements with published data. The concepts of molecular similarity and mobility are invoked to investigate D12 and DT dependency on molecular weight and concentration. Our analysis reveals a combined effect of molecular mobility and similarity dependency of DT on concentration and molecular weight of the n-alkanes. The mobility of individual molecules describes the D12 dependency on concentration and molecular weight of alkanes. The dependency of D12 on concentration weakens as the n-alkane molecular weight increases. DT increases with IBB concentration for nC6 and nC8 and decreases with IBB concentration for nC10 and nC12. In this work, we demonstrate that the temperature contrast factors can be accurately estimated without the use of an interferometer.

Molecular Thermodynamic Modeling of Reverse Micelles and Water-in-Oil Microemulsions.

Surfactant aggregation plays an important role in a variety of chemical and biological nanoscale processes. On a larger scale, using small amounts of amphiphiles compared to large volumes of bulk-phase modifiers can improve the efficiency and reduce the environmental impact of many chemical and industrial processes. To model ternary mixtures of polar, nonpolar, and amphiphilic molecules, we develop a molecular thermodynamic theory for polydisperse water-in-oil (W/O) droplet-type microemulsions and reverse micelles based on global minimization of the Gibbs free energy of the system. The incorporation of size polydispersity into the theoretical formulation has a significant effect on the Gibbs free energy landscape and allows us to accurately predict micelle size distributions and micelle size variation with composition. Results are presented for two sample ionic surfactant/water/oil systems and compared with experimental data. By predicting the structural and compositional characteristics of w/o microemulsions, the molecular thermodynamic approach provides an important bridge between the modeling of ternary systems at the molecular and the macroscopic level.

Temperature Effect on Micelle Formation: Molecular Thermodynamic Model Revisited.

Temperature affects the aggregation of macromolecules such as surfactants, polymers, and proteins in aqueous solutions. The effect on the critical micelle concentration (CMC) is often nonmonotonic. In this work, the effect of temperature on the micellization of ionic and nonionic surfactants in aqueous solutions is studied using a molecular thermodynamic model. Previous studies based on this technique have predicted monotonic behavior for ionic surfactants. Our investigation shows that the choice of tail transfer energy to describe the hydrophobic effect between the surfactant tails and the polar solvent molecules plays a key role in the predicted CMC. We modify the tail transfer energy by taking into account the effect of the surfactant head on the neighboring methylene group. The modification improves the description of the CMC and the predicted micellar size for aqueous solutions of sodium n-alkyl sulfate, dodecyl trimethylammonium bromide (DTAB), and n-alkyl polyoxyethylene. The new tail transfer energy describes the nonmonotonic behavior of CMC versus temperature. In the DTAB-water system, we redefine the head size by including the methylene group, next to the nitrogen, in the head. The change in the head size along with our modified tail transfer energy improves the CMC and aggregation size prediction significantly. Tail transfer is a dominant energy contribution in micellar and microemulsion systems. It also promotes the adsorption of surfactants at fluid-fluid interfaces and affects the formation of adsorbed layer at fluid-solid interfaces. Our proposed modifications have direct applications in the thermodynamic modeling of the effect of temperature on molecular aggregation, both in the bulk and at the interfaces.

Nonmonotonic Elasticity of the Crude Oil-Brine Interface in Relation to Improved Oil Recovery.

Injection of optimized chemistry water in enhanced oil recovery (EOR) has gained much interest in the past few years. Crude oil-water interfaces can have a viscoelastic character affected by the adsorption of amphiphilic molecules. The brine concentration as well as surfactants may strongly affect the fluid-fluid interfacial viscoelasticity. In this work we investigate interfacial viscoelasticity of two different oils in terms of brine concentration and a nonionic surfactant. We correlate these measurements with oil recovery in a glass-etched flow microchannel. Interfacial viscoelasticity develops relatively fast in both oils, stabilizing at about 48 h. The interfaces are found to be more elastic than viscous. The interfacial elastic (G') and viscous (G″) moduli increase as the salt concentration decreases until a maximum in viscoelasticity is observed around 0.01 wt % of salt. Monovalent (Na(+)) and divalent (Mg(2+)) cations are used to investigate the effect of ion type; no difference is observed at low salinity. The introduction of a small amount of a surfactant (100 ppm) increases the elasticity of the crude oil-water interface at high salt concentration. Aqueous solutions that give the maximum interface viscoelasticity and high salinity brines are used to displace oil in a glass-etched "porous media" micromodel. Pressure fluctuations after breakthrough are observed in systems with high salt concentration while at low salt concentration there are no appreciable pressure fluctuations. Oil recovery increases by 5-10% in low salinity brines. By using a small amount of a nonionic surfactant with high salinity brine, oil recovery is enhanced 10% with no pressure fluctuations. Interface elasticity reduces the snap-off of the oil phase, leading to reduced pressure fluctuations. This study sheds light on significance of interface viscoelasticity in oil recovery by change in salt concentration and by addition of a small amount of a nonionic surfactant.

Thermodiffusion of polycyclic aromatic hydrocarbons in binary mixtures.

Thermodiffusion in liquid mixtures may explain some counter-intuitive but naturally occurring phenomena such as hydrocarbon reservoirs with heavier component(s) stratified on top of lighter ones. However, beyond benchmark systems, systematic measurements of thermodiffusion in binary organic mixtures are lacking. We use an optical beam deflection apparatus to simultaneously probe Fickian and thermal diffusion in binary solution mixtures of polycyclic aromatic hydrocarbons dissolved in alkanes, and measure both Fickian diffusion D and the Soret coefficient ST, and then obtain the thermodiffusion coefficient DT. In a series of nine binary mixtures, we vary both the size of the aromatic compound from two to four rings, as well as the length of the alkane chain from 6 to 16 carbons. To probe the effect of increasing ring size, we include a 6-ringed aromatic compound, coronene, and toluene as a solvent, due to the insolubility of coronene in alkanes. Our results suggest that Fickian diffusion increases with the inverse of solvent viscosity and also with decreasing molecular weight of the solute. While both of these trends match our intuition, the behavior of ST and DT is more complicated. We find that ST and DT increase with the solute molecular weight when the solvent is held fixed and that the impact of solute ring size is higher in shorter chain alkane solvents.

Polar Solvents Trigger Formation of Reverse Micelles.

We use molecular dynamics simulations and molecular thermodynamics to investigate the formation of reverse micelles in a system of surfactants and nonpolar solvents. Since the early observation of reverse micelles, the question has been whether the existence of polar solvent molecules such as water is the driving force for the formation of reverse micelles in nonpolar solvents. In this work, we use a simple coarse-grained model of surfactants and solvents to show that a small number of polar solvent molecules triggers the formation of large permanent aggregates. In the absence of polar molecules, both the thermodynamic model and molecular simulations show that small aggregates are more populated in the solution and larger ones are less frequent as the system evolves over time. The size and shape of reverse micelles depend on the size of the polar core: the shape is spherical for a large core and ellipsoidal for a smaller one. Using the coarse-grained model, we also investigate the effect of temperature and surfactant tail length. Our results reveal that the number of surfactant molecules in the micelle decreases as the temperature increases, but the average diameter does not change because the size of the polar core remains invariant. A reverse micelle with small polar core attracts fewer surfactants when the tail is long. The uptake of solvent particles by a micelle of longer surfactant tail is less than shorter ones when the polar solvent particles are initially distributed randomly.

Flow of methane in shale nanopores at low and high pressure by molecular dynamics simulations.

Flow in shale nanopores may be vastly different from that in the conventional permeable media. In large pores and fractures, flow is governed by viscosity and pressure-driven. Convection describes the process. Pores in some shale media are in nanometer range. At this scale, continuum flow mechanism may not apply. Knudsen diffusion and hydrodynamic expressions such as the Hagen-Poiseuille equation and their modifications have been used to compute flow in nanopores. Both approaches may have drawbacks and can significantly underestimate molecular flux in nanopores. In this work, we use the dual control volume-grand canonical molecular dynamics simulations to investigate methane flow in carbon nanopores at low and high pressure conditions. Our simulations reveal that methane flow in a slit pore width of 1-4 nm can be more than one order of magnitude greater than that from Knudsen diffusion at low pressure and the Hagen-Poiseuille equation at high pressure. Knudsen diffusion and Hagen-Poiseuille equations do not account for surface adsorption and mobility of the adsorbed molecules, and inhomogeneous fluid density distributions. Mobility of molecules in the adsorbed layers significantly increases molecular flux. Molecular velocity profiles in nanopores deviate significantly from the Navier-Stokes hydrodynamic predictions. Our molecular simulation results are in agreement with the enhanced flow measurements in carbon nanotubes.

Specific ion effects on the self-assembly of ionic surfactants: a molecular thermodynamic theory of micellization with dispersion forces.

The self-assembly of amphiphilic molecules is a key process in numerous biological and chemical systems. When salts are present, the formation and properties of molecular aggregates can be altered dramatically by the specific types of ions in the electrolyte solution. We present a molecular thermodynamic model for the micellization of ionic surfactants that incorporates quantum dispersion forces to account for specific ion effects explicitly through ionic polarizabilities and sizes. We assume that counterions are distributed in the diffuse region according to a modified Poisson-Boltzmann equation and can reach all the way to the micelle surface of charge. Stern layers of steric exclusion or distances of closest approach are not imposed externally; these are accounted for through the counterion radial distribution profiles due to the incorporation of dispersion potentials, resulting in a simple and straightforward treatment. There are no adjustable or fitted parameters in the model, which allows for a priori quantitative prediction of surfactant aggregation behavior based only on the initial composition of the system and the surfactant molecular structure. The theory is validated by accurately predicting the critical micelle concentration (CMC) for the well-studied sodium dodecyl sulfate (SDS) surfactant and its alkaline-counterion derivatives in mono- and divalent salts, as well as the molecular structure parameters of SDS micelles such as aggregation numbers and micelle surface potential.

Effect of water on deposition, aggregate size, and viscosity of asphaltenes.

The aggregation and structure of polar molecules in nonpolar media may have a profound effect on bulk phase properties and transport. In this study, we investigate the aggregation and deposition of water and asphaltenes, the most polar fraction in petroleum fluids. In flow-line experiments, we vary the concentration of water from 500 up to 175,000 ppm and provide the evidence for clear changes in asphaltene deposition. Differential interference contrast (DIC) microscopy and dynamic light scattering (DLS) are used to measure the size of the aggregates. Rheological measurements are performed to get fixed ideas on the structural changes that water induces at different concentrations. This study demonstrates the significant effect of water on asphaltene aggregation and deposition and explores the molecular basis of water-asphaltene interaction. Our aggregate size measurements show that while asphaltene molecules increase the solubilization of water, there is no increase in the aggregate size. Our aggregation size measurements are different from the reports in the literature.

Work addiction risk, stress and well-being at work: testing the mediating role of sleep quality.

Introduction: Attention to work addiction risk is growing; however, more studies are needed to explore the possible impact of work addiction risk on various aspects of employees' work and life domains. Although several studies have considered the antecedents or consequences of work addiction risk, this study particularly focuses on sleep quality as a potential explanatory underlying mechanism in the relation between work addition risk and three outcome variables including stress at home, stress at work and well-being. Method: The data was collected using an online platform and participants consisted of 188 French employees who were selected using simple random sampling method. Participants responded to the survey including the Work Addiction Risk Test (WART), stress at work, well-being, and sleep quality. The data was analyzed using JASP and SPSS-26 programs. Results: The results revealed that there are significant positive relationships between work addiction risk and both stress at home and at work and negative relationships between work addiction risk and both sleep quality and well-being. In addition, the analyses of the mediation paths suggest the significant mediation role of sleep quality for the link between work addition risk and stress at work as well as the link between work addiction risk and well-being. Discussion: Given the verified mediating role of sleep quality in the relationship between work addiction, stress and wellbeing, it is recommended that organizations and companies pay particular attention to their employees' sleep quality.

Branching in molecular structure enhancement of solubility in CO2.

Most compounds of some 1,000 amu molecular weight (MW) and higher are poorly soluble in carbon dioxide (CO2). Only at very high pressure, there may be mild solubility. This limits the use of CO2 as a solvent and modifications of CO2 properties through additives. We have developed a coarse-grained molecular model to investigate the dependency of the solubility of hydrocarbon oligomers (MW of ∼1,000 amu) in CO2 and on the molecular structure. The coarse-grained model is optimized by the particle swarm optimization algorithm to reproduce density, surface tension, and enthalpy of vaporization of a highly branched hydrocarbon oligomer (poly-1-decene with six repeating units). We demonstrate that branching in molecular structure of oligomers significantly increases solubility in CO2. The branching in molecular structure results in up to 270-time enhancement of solubility in CO2 than an n-alkane with the same MW. The number of structural edges (methyl group) is a key in improved CO2-philicity. The solubility of poly-1-decene with nine repeating units (MW of 1,264.4 amu) is higher in CO2 than poly-1-dodecene with six repeating units (MW of 1,011.93 amu) because it has more structural edges (10 vs. 7). These results shed light on the enhancement of CO2-philicity by altering molecular structure rather than modifying chemical composition in compounds.

Computation of Shear Viscosity by a Consistent Method in Equilibrium Molecular Dynamics Simulations: Applications to 1-Decene Oligomers.

Accurate computation of shear viscosity is fundamental for describing fluid flow and designing and developing new processes. Poly-α-olefins (PAO's), particularly from 1-decene, have been applied to a variety of industrial processes. Recently, these molecules have been applied as carbon dioxide thickeners, enhancing carbon dioxide viscosity, which is important in carbon dioxide injection, either for enhanced oil recovery or sequestration in geological formations. For these applications, knowledge of the pure oligomer viscosity is crucial to design and operate the oligomer upstream pipelines before mixing them with carbon dioxide. Using Green-Kubo formalism with equilibrium molecular dynamics simulations, two methods are presented in the literature to generate the traceless, symmetric pressure tensor. In this work, we show that these two methods provide different values of shear viscosity, from the analysis of how the diagonal components of the traceless, symmetric pressure tensor are computed in each method. Then, we examine the consistency and correctness of each method: one is found to be consistent. The other is corrected by scaling the fluctuations of the diagonal components. Shear viscosities of supercritical carbon dioxide, vapor and liquid n-pentane, and liquid n-decane are computed to illustrate the analysis. We also apply the consistent method to compute the viscosity of 1-decene oligomers, including for the first time larger-than-dimer oligomers (trimer, tetramer, hexamer, and decamer).

Thermodiffusion of CO2 in Water by Nonequilibrium Molecular Dynamics Simulations.

The components of a fluid mixture may segregate due to the Soret effect, a coupling phenomenon in which mass flux can be induced by a thermal gradient. In this work, we evaluate systematically the thermodiffusion of the CO2-H2O mixture, and the influence of the geothermal gradient on CO2 segregation in deep saline aquifers in CO2 storage. The eHeX method, a nonequilibrium molecular dynamics simulation approach, is judiciously selected to simulate the phenomenon. At 350 K, 400 bar, and CO2 mole fraction of 0.02 (aquifer conditions), CO2 accumulates on the cold side, and the thermal diffusion factor is close to 1 in a number of force fields. The lower the temperature, the higher is the separation and the thermal diffusion factor. In colder regions, water self-association is stronger, whereas the CO2-H2O cross-association and the CO2-CO2 interactions enhance at higher temperatures. Thermodiffusion and gravitational segregation have opposite effects on CO2 segregation. At typical subsurface conditions, the Soret effect is more pronounced than gravity segregation, and CO2 concentrates in the top (colder region). Our work sets the stage to model the effect of electrolytes on CO2 segregation in subsurface aquifers and other areas of interest.