First Steps towards Understanding the Non-Linear Impact of Mg on Calcite Solubility: A Molecular Dynamics Study

Magnesium (Mg2+) is one of the most common impurities in calcite and is known to have a non-linear impact on the solubility of magnesian calcites. Using molecular dynamics (MD), we observed that Mg2+ impacts overall surface energies, local free energy profiles, interfacial water density, structure and dynamics and, at higher concentrations, it also causes crystal surface deformation. Low Mg concentrations did not alter the overall crystal structure, but stabilised Ca2+ locally and tended to increase the etch pit nucleation energy. As a result, Ca-extraction energies over a wide range of 39 kJ/mol were observed. Calcite surfaces with an island were less stable compared to flat surfaces, and the incorporation of Mg2+ destabilised the island surface further, increasing the surface energy and the calcium extraction energies. In general, Ca2+ is less stable in islands of high Mg2+ concentrations. The local variation in free energies depends on the amount and distance to nearest Mg in addition to local disruption of interfacial water and the flexibility of surface carbonate ions to rotate. The result is a complex interplay of these characteristics that cause variability in local dissolution energies. Taken together, these results illustrate molecular scale processes behind the non-linear impact of Mg2+ concentration on the solubility of magnesium-bearing calcites.

Improving the Anticorrosion Characteristics of Polymer Coatings in the Case of Their Modification with Compositions Based on Organosilanes

The effect of a series of organosilanes and their mixtures with corrosion inhibitors on the anticorrosion properties of polymer and paint coatings on steel, namely, on the adhesive characteristics of the coatings and corrosion behavior of the metal in the presence of coatings modified with organosilanes, corrosion inhibitors, and their mixtures, is studied. It is shown that mixtures of 1,2,3-benzotriazole (BTA) with vinyltrimethoxysilane (VTMS) or aminoethylaminopropyltrimethoxysilane—diaminosilane (DAS) inhibit the local dissolution and underfilm corrosion of carbon steel, and the potential of local depassivation shifts by 0.3–0.4 V. Here, compact polymer-like layers that are strongly bound to the metal surface are formed on the surface of steel. Corrosion and mechanical tests of the samples of pipe steels with different types of inhibiting compositions are conducted. The effect of the inhibitors on the crack growth under static loading in a model soil electrolyte (pH of 5.5) and on the crack resistance of steel under slow tension in an NS-4 model underfilm electrolyte (pH of 7.0) is evaluated. The tests are performed in media free from and containing hydrogen sulfide. It is shown that the best inhibiting properties are manifested by the mixtures of corrosion inhibitors with organosilanes. Comparative laboratory and bench tests for the adhesive strength, water resistance, and resistance to cathodic detachment of the adhesive junctions obtained upon applying the modified polymer and paint coatings onto the surface of steel are performed. It is found that introducing a mixture of organosilane and a corrosion inhibitor improves the adhesive properties of polymer and paint coatings.

Synthesis of Hierarchical Zeolites with Morphology Control: Plain and Hollow Spherical Beads of Silicalite-1 Nanosheets

Binderless pure silica zeolites (zeosils) spheres and hollow spheres with a diameter of 20 µm composed of silicalite-1 nanosheets particles were prepared by pseudomorphic transformation of spherical silica beads using different temperatures (110, 130, and 150 °C) and treatment times (1–5 days) in order to adapt the local dissolution rate of silica to the crystallization rate of silicalite-1 nanosheets allowing to preserve the initial morphology of the silica beads. Fully crystalline beads of 20 µm were obtained at 110 °C for 5 days, whereas hollow spheres similar in size were synthesized at higher temperatures. The crystallization process seems to begin at the outer surface of the amorphous silica beads and spreads with the time in the interior of the beads leading to a dissolution of the inner amorphous part of the beads to create zeosil hollow spheres for the highest treatment temperatures (130 and 150 °C). The dissolution rate of the inner amorphous part of the beads increases by increasing the hydrothermal treatment temperature from 130 to 150 °C. The silicalite-1 beads synthesized at 110 °C for 5 days showed to be promising for rapid molecular decontamination by adsorbing n-hexane in larger amount than the silicalite-1 conventional big crystals in powder forms.

Staged Local Dissolution of Stainless Steel in Chloride Solutions

The paper defines galvanostatic polarization parameters (current density and test duration), to simulate self-dissolution conditions; the results are confirmed by potentiostatic tests. It is shown that under the conditions of self-dissolution simulation, increasing the solution concentration reduces the nucleation rate, while prolonging the pitting development time. Spectral analysis of chronopotentiograms reveals low-frequency potential fluctuations that characterize the nucleation and passivation of pits at the onset of pitting corrosion. The paper describes the basic regularities, observed in the alteration of surface electrochemistry by impedance spectroscopy; such alteration corresponds to the transition from the passive area to the pitting area. The researchers propose optimal electric equivalent circuits to reflect the surface conditions in early nucleation of pits. The paper also proposes an additional pitting resistance criterion, that is, cumulative electric-charge density.

From granulite hydration to metamorphic differentiation: Evolution of a shear zone.

<p><span>The studied outcrop, located within the Bergen arcs of southwestern Norway, preserves the hydration of an anorthositic granulite at amphibolite-facies conditions. The amphibolite-facies hydration is expressed as both a statically hydrated amphibolite and a shear zone rock, defined by the interlayering of amphibolite with leucocratic domains. Within the outcrop, quartz-filled fractures and their associated amphibolite alteration haloes crosscut the granulite. These fractures are relicts of the initial fluid infiltration event. The fracture assemblage (quartz + plagioclase + zoisite + kyanite ± muscovite ± biotite) is equivalent to that occurring locally within leucocratic domains of the shear zone. Due to the textural and compositional similarities between quartz-filled fractures and leucocratic domains, the compositional layering of the shear zone rock may be directly linked to fracturing during initial fluid infiltration. Mass-balance calculations indicate quartz-filled fractures and compositional differentiation of the shear zone form by internal fractionation rather than partial melting or precipitation of minerals from an eternally derived fluid. This inferred fluid connectivity combined with the enhanced local dissolution indicates the presence of a continuously replenished fluid along fracture pathways. The overall conclusion is that the mass transfer processes that result in metamorphic differentiation of the shear zone lithologies are dependent on both continuous fluid flux and heterogeneous strain distribution. </span></p>

Metamorphic differentiation via enhanced dissolution along high strain pathways

<p><span>Metamorphic differentiation, resulting in the segregation of minerals into compositional bands, is a common feature of metamorphic rocks. Considering the ubiquitous nature of compositionally layered metamorphic rocks, the processes that are responsible for metamorphic differentiation have received very little attention. The studied outcrop, located within the Bergen arcs of southwestern Norway, preserves the hydration of an anorthositic granulite at amphibolite-facies conditions. The amphibolite-facies hydration is expressed as both a statically hydrated amphibolite and a shear zone rock, defined by the interlayering of amphibolite with leucocratic domains. Detailed petrography, quantitative mineral chemistry and bulk rock analyses are applied to investigate compositional variation with assemblage microstructure. Within the outcrop, quartz-filled fractures and their associated amphibolite alteration haloes, are observed crosscutting the granulite. These fractures are demonstrated to be relict of the initial fluid infiltration event. The fracture assemblage (quartz + plagioclase + zoisite + kyanite ± muscovite ± biotite) is equivalent to that occurring locally within leucocratic domains of the shear zone. Due to the textural and compositional similarities between quartz-filled fractures and leucocratic domains, the compositional layering of the shear zone rock may be directly linked to fracturing during initial fluid infiltration. </span></p><p><span>            Mass-balance and thermodynamic calculations indicate quartz-filled fractures and compositional differentiation of the shear zone form by internal fractionation rather than partial melting or precipitation of minerals from an eternally derived fluid. The process of internal fractionation within the shear zone is attributed to enhanced dissolution along fracture pathways, resulting in the loss of MgO, Fe<sub>2</sub>O<sub>3</sub> and K<sub>2</sub>O within leucocratic domains. These elements, being more mobile in the fluid, are then transported and ultimately either precipitated in amphibolite lithologies or escape with the fluid, resulting in an overall volume loss in the shear zone. This inferred fluid connectivity combined with the enhanced local dissolution indicates the presence of a continuously replenished fluid along fracture pathways, leading to the overall conclusion that the mass transfer processes that result in metamorphic differentiation of the shear zone lithologies are dependent on both continuous fluid flux and heterogeneous strain distribution. </span></p>

Staged Local Dissolution of Stainless Steel in Chloride Solutions

The paper defines galvanostatic polarization parameters (current density and test duration) to simulate self-dissolution conditions; the results are confirmed by potentiostatic tests. It is shown that under the conditions of self-dissolution simulation, increasing the solution concentration reduces the nucleation rate, while prolonging the pitting development time. Spectral analysis of chronopotentiograpms reveals low-frequency potential fluctuations that characterize the nucleation and passivation of pits at the onset of pitting corrosion. The paper describes the basic regularities observed in the alteration of surface electrochemistry by impedance spectroscopy; such alteration corresponds to the transition from the passive area to the pitting area. The researchers propose optimal electric equivalent circuits to reflect the surface conditions in early nucleation of pits. The paper also proposes an additional pitting resistance criterion, that is, cumulative electric-charge density.

Lithium metal stripping beneath the solid electrolyte interphase

Lithium stripping is a crucial process coupled with lithium deposition during the cycling of Li metal batteries. Lithium deposition has been widely studied, whereas stripping as a subsurface process has rarely been investigated. Here we reveal the fundamental mechanism of stripping on lithium by visualizing the interface between stripped lithium and the solid electrolyte interphase (SEI). We observed nanovoids formed between lithium and the SEI layer after stripping, which are attributed to the accumulation of lithium metal vacancies. High-rate dissolution of lithium causes vigorous growth and subsequent aggregation of voids, followed by the collapse of the SEI layer, i.e., pitting. We systematically measured the lithium polarization behavior during stripping and find that the lithium cation diffusion through the SEI layer is the rate-determining step. Nonuniform sites on typical lithium surfaces, such as grain boundaries and slip lines, greatly accelerated the local dissolution of lithium. The deeper understanding of this buried interface stripping process provides beneficial clues for future lithium anode and electrolyte design.