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.

Controlling water-mediated interactions by designing self-assembled monolayer coatings

Engineered nanoparticles have been broadly used in biological and geological systems. Hydrophilic molecules such as polyols have been used as coatings on nanoparticle surfaces due to their good biocompatibility and solubility in saline water. However, polyol coatings can cause huge retention of nanoparticles when encountering mineral surfaces. Here, molecular dynamics simulations enlightened that the strong adhesion of hydrophilic coatings to mineral surfaces stemming from the partitioning of the hydroxy groups on the hydrophilic molecules to the well-defined bound hydration layers on the mineral surfaces. To mitigate the nanoparticle adhesion, we investigated introducing small percentages of omniphobic fluoroalkanes to form a bicomponent system of hydrophilic and fluoroalkanes, which greatly perturbed the hydration layers on mineral surfaces and resulted in nonstick surface coatings. Our results provide important insight for the design of tunable “stickiness” nanoparticle coatings in different mineralogies, such as applications in subsurface environments or targeted delivery in mineralized tissues.

Atomically resolved interfacial water structures on crystalline hydrophilic and hydrophobic surfaces

Hydration layers are formed on hydrophilic crystalline surfaces immersed in water.

Structuring of High-Fine Mineral Particles to Prevent Wind and Water Erosion

The results of the study of the mechanism of structuring highly dispersed mineral particles by dust-pressing polymer solution StabOL are presented, using the example of overburden rocks of the Taseevsky, Baleisky and Kamensky quarries (Transbaikal Territory). Mineral and polymer-mineral samples were studied by differential scanning calorimetry, thermogravimetry, and infrared spectroscopy. The formation of intermolecular hydrogen bonds is confirmed by the shift of the absorption bands of the stretching vibrations of hydroxyl groups in the infrared spectra of polymer-mineral samples towards lower frequencies and a significant increase in the intensities of these absorption bands. It was found that structuring of mineral particles during their treatment with a polymer solution occurs through the formation of organomineral complexes as a result of intercalation, exfoliation (stratification) and adsorption of polymers. The important role of hydration layers and clay minerals in this process has been revealed.

Control of the hydration layer states on phosphorus-containing mesoporous silica films and their reactivity evaluation with biological fluids

Phosphorus-containing mesoporous silica films were synthesized by the introduction of phosphoric acid. The hydration layers on the films had the asymmetric stretching vibration of water molecules to provide the specific fibronectin adsorption.

Unraveling nucleation pathway in methane clathrate formation

Methane clathrates are widespread on the ocean floor of the Earth. A better understanding of methane clathrate formation has important implications for natural-gas exploitation, storage, and transportation. A key step toward understanding clathrate formation is hydrate nucleation, which has been suggested to involve multiple evolution pathways. Herein, a unique nucleation/growth pathway for methane clathrate formation has been identified by analyzing the trajectories of large-scale molecular dynamics (MD) simulations. In particular, ternary water-ring aggregations (TWRAs) have been identified as fundamental structures for characterizing the nucleation pathway. Based on this nucleation pathway, the critical nucleus size and nucleation timescale can be quantitatively determined. Specifically, a methane hydration layer compression/shedding process is observed to be the critical step in (and driving) the nucleation/growth pathway, which is manifested through overlapping/compression of the surrounding hydration layers of the methane molecules, followed by detachment (shedding) of the hydration layer. As such, an effective way to control methane hydrate nucleation is to alter the hydration layer compression/shedding process during the course of nucleation.

Towards an Understanding of Crystallization by Attachment

Crystallization via particle attachment was used in a unified model for both classical and non-classical crystallization pathways, which have been widely observed in biomimetic mineralization and geological fields. However, much remains unknown about the detailed processes and driving mechanisms for the attachment. Here, we take calcite crystal as a model mineral to investigate the detailed attachment process using in situ Atomic Force Microscopy (AFM) force measurements and molecular dynamics simulations. The results show that hydration layers hinder the attachment; however, in supersaturated solutions, ionic bridges are formed between crystal gaps as a result of capillary condensation, which might enhance the aggregation of calcite crystals. These findings provide a more detailed understanding of the crystal attachment, which is of vital importance for a better understanding of mineral formation under biological and geological environments with a wide range of chemical and physical conditions.

Gas molecules sandwiched in hydration layers at graphite/water interfaces

Frequency shift-distance curves reveal that each adsorbed gas layer is sandwiched between hydration layers with high water density.