Selective Fabrication of Robust and Multifunctional Super Nonwetting Surfaces by Diverse Modifications of Zirconia-Ceria Nanocomposites.

The creation of surfaces with various super nonwetting properties is an ongoing challenge. We report diverse modifications of novel synthesized zirconia-ceria nanocomposites by different low surface energy agents to fabricate nanofluids capable of regulating surface wettability of mineral substrates to achieve selective superhydrophobic, superoleophobic-superhydrophilic, and superamphiphobic conditions. Surfaces treated with these nanofluids offer self-cleaning properties and effortless rolling-off behavior with sliding angles ≤7° for several liquids with surface tensions between 26 and 72.1 mN/m. The superamphiphobic nanofluid coating imparts nonstick properties to a solid surface whereby liquid drops can be effortlessly displaced on the coating with a near-zero tilt and conveniently lifted off using a needle tip, leaving no trace. Further, the superamphiphobic surface demonstrates good oil repellency toward ultralow surface tension liquids such as n-hexane and n-heptane. The superoleophobic-superhydrophilic surface repels oil droplets well regardless of whether it is in the air or underwater conditions. In addition, reaping the benefits of the ZrO2-CeO2 nanocomposites' photocatalysis feature, the superoleophobic-superhydrophilic coating exhibits self-cleaning ability by the degradation of color dyes. Modification of the wettability of substrates is carried out by a cost-effective and facile solution-immersion approach, which creates surfaces with hierarchical nano-submicron-scaled structures. The multipurpose coated surfaces have outstanding durability and mechanical stability. They also resist well high-temperature-high-pressure conditions, which will provide various practical applications in different fields, including the condensate banking removal in gas reservoirs or the separation of oil/water mixtures.

A Deep Look into the Dynamics of Saltwater Imbibition in a Calcite Nanochannel: Temperature Impacts Capillarity Regimes.

This research concerns fundamentals of spontaneous transport of saltwater (1 mol·dm-3 NaCl solution) in nanopores of calcium carbonates. A fully atomistic model was adopted to scrutinize the temperature dependence of flow regimes during solution transport under CaCO3 nanoconfinement. The early time of capillary filling is inertia-dominated, and the solution penetrates with a near-planar meniscus at constant velocity. Following a transition period, the meniscus angle falls to a stabilized value, characterizing the capillary-viscous advancement in the calcite channel. At this stage, brine displacement follows a parabolic relationship consistent with the classical Lucas-Washburn (LW) theory. Approaching the slit outlet, the meniscus contact lines spread widely on the solid substrate and brine leaves the channel at a constant rate, in oppose to the LW law. The brine imbibition rate considerably increases at higher temperatures as a result of lower viscosity and greater tendency to form wetting layers on slit walls. We also pointed out a longer primary inertial regime and delayed onset of the viscous-capillary regime at higher temperatures. Throughout the whole span of capillary displacement, transport of sodium and chloride ions is tied to dynamics and diffusion of the water phase, even at the mineral interface. The results presented in this study are of broad implications in diverse science and technological applications.

Ion-specific interactions at calcite-brine interfaces: a nano-scale study of the surface charge development and preferential binding of polar hydrocarbons.

This research provides an atomic-level insight into the synergic contribution of mono- and divalent ions to interfacial characteristics of calcite surfaces exposed to electrolyte solution containing organic compounds. The emphasis was placed on the ionic interactions responsible for charge developing mechanisms of calcite surfaces and also the capacity for adsorption of polar hydrocarbons, represented by benzoic acid (BA), at different brine compositions. For this purpose, molecular dynamics (MD) simulations were employed to explore the interplay of the main constituent ions of natural brines (Na+, Cl-, Mg2+, and SO42-) and BA at the interface of CaCO3. It was observed that surface accumulation of Na+ cations produces a positively charged layer immediate to the basal plane of calcite, validating the typical positive surface charge of carbonates reported by laboratory experiences. Meanwhile, a negatively charged layer appears beyond the sodium layer as a result of direct and solvent-mediated pairing of anions with Na+ cations lodged on the calcite substrate. In this process, sulfate adsorption severely diminishes surface charge to even a negative value in the case of a SO42--rich solution, providing an interpretation for the measurements reported in the literature. Our results revealed the inhibition of direct binding of BA molecules onto the calcite surface through complexation with protruding oxygen atoms of basal carbonates by the residing Na+ cations. Further, we noticed the sulfate-mediated pairing of BA molecules to the Na+ layer, which in effect intensifies surface adsorption of BA. However, BA-SO42- interaction is considerably reduced by magnesium cations shielding sulfate sites in the Mg2+-augmented brine. The findings presented in this study are of fundamental importance to advance our microscopic understanding of interfacial interactions in brine/oil/carbonate systems; with broad scientific and applied implications in the context of mobilizing organic contaminants trapped in aquifer sediments and enhancement of hydrophilicity of subsurface oil-bearing carbonate reservoirs by injecting ion-modified brine solutions.

The Impact of the Double Cross-Phase Diffusion Mechanism on Oil Recovery during CO2 Injection into Fractured Rocks: A Simulation Study.

In this research, a new diffusion mechanism called "double cross-phase diffusion" is introduced and applied to simulate the non-equilibrium gas injection process into fractured rocks. This new mechanism represents additional multicomponent gas diffusion into the crude oil through the water phase, existing in porous media as initial water saturation. Therefore, a lab-scale simulator, by implementing the generalized Fick's law of multicomponent diffusion, is developed and used for predicting the experimental data of oil recovery during CO2 injection in chalk fractured rocks in the presence of initial water saturation. The results revealed a significant difference in the oil recovery predicted by the model when the double cross-phase diffusion mechanism is considered. The transient behavior of produced oil composition, predicted by the simulation model, is matched well with the experimental data. The portion of active oil recovery mechanisms in the system has been evaluated for the first time and it was observed that the molecular diffusion mechanism induced 75.4% of the total oil transfer rate in the initial time oil recovery, in which 23.1% of this value was supplied by the double cross-phase diffusion mechanism, which is an interesting finding. Results of sensitivity analysis showed that by increasing the initial water saturation, the impact of the double cross-phase diffusion mechanism on oil recovery increases. In contrast, the transferred rate by the diffusion mechanism decreases from 85.4% to 60.8% when matrix permeability increases from 0.1 to 10 mD. The results of this work illustrate that the double cross-phase diffusion mechanism introduced in this study plays a significant role in the simulation results since the water is responsible for accelerating the diffusivity of CO2 into the crude oil and, in consequence, increasing the oil recovery.

Dissolution and remobilization of NAPL in surfactant-enhanced aquifer remediation from microscopic scale simulations.

In this paper, the dissolution and mobilization of non-aqueous phase liquid (NAPL) blobs in the Surfactant-Enhanced Aquifer Remediation (SEAR) process were upscaled using dynamic pore network modeling (PNM) of three-dimensional and unstructured networks. We considered corner flow and micro-flow mechanisms including snap-off and piston-like movement for two-phase flow. Moreover, NAPL entrapment and remobilization were evaluated using force analysis to develop the capillary desaturation curve (CDC) and predict the onset of remobilization. The corner diffusion mechanism was also applied in the modeling of interphase mass transfer to represent NAPL dissolution as the dominant mass transfer process. In addition, the effect of pore-scale heterogeneity on mass transfer rate coefficient and recovered residual NAPL was considered in the simulations. Sodium dodecyl sulfate (SDS) and Triton X-100 were used as the surfactant for the SEAR process. The results indicate that although surfactants enhance NAPL recovery during two-phase flow, surfactant-enhanced remediation of residual NAPL through dissolution is highly dependent on surfactant type. When SDS ─as a surfactant with high critical micelle concentration (CMC) and low micelle partition coefficient (Km)─ was injected into a NAPL contaminated site, the mass transfer rate coefficient decreased (due to considerable changes in interface chemical potentials) which leads to a significant reduction in NAPL recovery after the end of two-phase flow. In contrast, Triton X-100 (with low CMC and high Km) improved NAPL recovery, by enhancing solubility at surfactant concentrations greater than CMC which overcompensates the interphase mass transfer reduction.

Development of a Computational Fluid Dynamics Compositional Wellbore Simulator for Modeling of Asphaltene Deposition.

The asphaltene problem is a two-step process: (1) asphaltene precipitation, as predicted by the thermodynamic model, and (2) asphaltene deposition, the amount of which is estimated by the kinetic model. Asphaltene precipitation is a prerequisite but not a sufficient condition for deposition. Deposition is dependent on other factors such as surface properties, phase behavior, rheology, and flow patterns. As a result, in addition to understanding thermodynamic and kinetic models, it is critical to also understand flow models. In fact, multiphase flow modeling is at the core of simulation, and it must be coupled with thermodynamic and kinetic models. Numerous studies on modeling asphaltene deposition on pipe walls have been performed theoretically and experimentally, but a comprehensive theory to properly understand this phenomenon has not yet been presented. In thermodynamic modeling, the perturbed chain statistical associating fluid theory (PC-SAFT) equation of state is used to predict the asphaltene phase behavior. In this study, we show that the proposed PC-SAFT model is more accurate than the solid model used in commercial software. Unlike prior research that neglected flow patterns or used empirical relations to model multiphase flow, this study simulates multiphase flow using separate momentum equations for each phase. Among the existing kinetic models, the Kurup model has been used to predict the asphaltene deposition profile in the wellbore due to its greater compatibility for computational fluid dynamics application. The results of the proposed model show good agreement with field case data of asphaltene deposition thicknesses along the wellbore tubing.

Atomistic insight into salinity dependent preferential binding of polar aromatics to calcite/brine interface: implications to low salinity waterflooding.

This paper resolve the salinity-dependent interactions of polar components of crude oil at calcite-brine interface in atomic resolution. Molecular dynamics simulations carried out on the present study showed that ordered water monolayers develop immediate to a calcite substrate in contact with a saline solution. Carboxylic compounds, herein represented by benzoic acid (BA), penetrate into those hydration layers and directly linking to the calcite surface. Through a mechanism termed screening effect, development of hydrogen bonding between -COOH functional groups of BA and carbonate groups is inhibited by formation of a positively-charged Na+ layer over CaCO3 surface. Contrary to the common perception, a sodium-depleted solution potentially intensifies surface adsorption of polar hydrocarbons onto carbonate substrates; thus, shifting wetting characteristic to hydrophobic condition. In the context of enhanced oil recovery, an ion-engineered waterflooding would be more effective than injecting a solely diluted saltwater.

Remediation of trapped DNAPL enhanced by SDS surfactant and silica nanoparticles in heterogeneous porous media: experimental data and empirical models.

The remediation of nonaqueous phase liquids (NAPLs) enhanced by surfactant and nanoparticles (NP) has been investigated in numerous studies. However, the role of NP-assisted surfactants in the dissolution process is still not well discussed. Besides, there is a lack of empirical dissolution models considering the effects of initial residual saturation Strap, NAPL distribution, and surfactant concentration in NAPL-aqueous phase systems. In this work, micromodel experiments are conducted to quantify mass transfer coefficients for different injected aqueous phases including deionized water, SDS surfactant solutions, and NP-assisted solutions with different levels of concentrations and flow rates. Observations reveal that silica nanoparticles (SNP) can significantly enhance interphase mass transfer, while SDS surfactant reduces the mass transfer coefficient. In addition, Strap and intrinsic interfacial area ai, as an indicator of dense nonaqueous phase liquids (DNAPL) distribution, influence the interphase mass transfer. The ai is also independent of DNAPL saturation SNAPL except for SNAPL < 7% when ganglia breakup occurs. Based on these observations, new empirical dissolution models are proposed in the presence and the absence of SDS surfactant and SNP in which ai, Strap, and surfactant concentrations are introduced as new parameters. The evaluated mass transfer rate coefficients using the proposed models show a significant improvement compared to available empirical models. The finding of this study might be attractive for application in field-scale simulations of surfactant-enhanced aquifer remediation (SEAR) and NP-assisted methods.

The Impact of Salinity on the Interfacial Structuring of an Aromatic Acid at the Calcite/Brine Interface: An Atomistic View on Low Salinity Effect.

This study aims to elucidate the impact of salinity on the interactions governing the adsorption of polar aromatic oil compounds onto calcite. To this end, molecular dynamics simulations were employed to assess adsorption of a model polar organic molecule (deprotonated benzoic acid, benzoate) on the calcite surface in NaCl brines of different concentration levels, namely, deionized water (DW), low-salinity water (LS, 5000 ppm), and sea water (SW; 45,000 ppm). Calcite was found to be completely covered by several well-ordered water layers. The top hydration layer is very compact and prevents direct adsorption of benzoates onto the substrate. Instead, Na+ ions form a distinct positively charged layer by adhering on the calcite substrate through inner-sphere complexion mode. Cl- ions mostly lodge on top of the adsorbed sodium cations, forming a negatively charged layer. The distribution of ions at the calcite/brine interface thus exhibits the features of an electrical double layer, composed of a Stern-like positive layer followed by a negative one. The positive charged layer attracts benzoates toward the surface. As such, the sodium ions attached onto the calcite can act as adsorption sites to connect benzoates to the surface. By increasing the salinity, more Na+ ions adsorb onto the calcite surface, and the density of benzoate molecules at the interface is enhanced as a result of more Na+ bridging ions. The monotonic salinity-dependent adsorption of benzoate molecules on calcite offers a mechanism driving additional oil recovery upon injection of diluted brine into subsurface carbonate reservoirs.

How do ions contribute to brine-hydrophobic hydrocarbon Interfaces? An in silico study.

HYPOTHESIS: The saltwater-oil interface is of broad implication in geochemistry and petroleum disciplines. To date, the main focus has been on the surface contribution of polar, heavy compounds of crude oil, widely neglecting the role of non-polar hydrocarbons. However, non-polar compounds are expected to contribute to characteristics of oil-brine interfaces. METHODOLOGY: Utilizing molecular dynamics simulation, we aim to characterize ion behavior adjacent to hydrophobic organic phases. Concerning natural environments, NaCl, CaCl2 and Na2SO4 electrolytes at low (5 wt%) and high (15 wt%) concentrations were brought in contact with heptane and/or toluene which account for aliphatic and aromatic constituents of typical crude oils, respectively. The reproduced experimental data for interfacial tension, brines density and ions' diffusivities adequately verify our molecular calculations. FINDINGS: Ions accumulate nearby the intrinsically charge-neutral oil surfaces. A disparate surface-favoring propensity of ions causes the interfacial region to resemble an electrical layer and impose an effective surface charge onto the oil surface. Despite absence of any polar site, the effective surface charge density is hydrocarbon-dependent, with the highest and lowest values observed for toluene and heptane interfaces, respectively. Due to accumulation of toluene molecules nearby the brines, the interfacial characteristics of heptol (toluene-heptane mixture) is comparable to that of the toluene phase.