Type Of Cation Research Articles

A Comparison of the Effect of Activator Cations (Sodium and Potassium) on the Fresh and Hardened Properties of Mine Tailing-Slag Binders

This study develops alkali-activated mine tailing (MT)-based binders containing MT as the major source material and slag (S) as a minor additive, using alkaline activators containing sodium or potassium as the cationic species. The influence of the cationic species (Na or K), slag content, alkalinity (expressed using the activator silica modulus, Ms), and alkali oxide-to-powder ratio, n, on the setting behavior, paste rheology, early-age reaction kinetics, and compressive strength development are discussed. The effects of using solid activators are also considered. Changes in Ms values have a stronger impact on setting times compared to n values, underscoring the significant role of silicate species from the activator in the initial reaction mechanisms. The type of cation and physical state of the activator (in the case of K–Si-activated systems) are found to determine the dissolution rate and mobility of ionic species in the system, resulting in significant differences in the early age reaction mechanisms (e.g., K-based activators show >2× enhancement in early heat release as compared to Na-based activators) of the alkali-activated binders prepared using the same activator parameters. The difference in the viscosities of the activator solutions strongly influences the rheological characteristics of the activated systems. MT-based binders with 28-day compressive strengths ranging from 10 to 35 MPa, which are suitable for several structural/non-structural applications, are attained. The strong dependence of the compressive strength development on the alkali activation parameters and slag content in the system presents an opportunity to develop sustainable binders, with MT as their major constituent, to provide twin benefits of recycling MT wastes and mitigating the environmental impacts associated with traditional ordinary Portland cement-based binder systems.

Effect of cation size of binary cation ionic liquid mixtures on capacitive energy storage

Ionic liquid mixtures show promise as electrolytes for supercapacitors with nanoporous electrodes. Herein, we investigate theoretically and with experiments how binary electrolytes comprising a common anion and two types of differently-sized cations affect capacitive energy storage. We find that such electrolytes can enhance the capacitance of single nanopores and nanoporous electrodes under potential differences negative relative to the potential of zero charge. For a two-electrode cell, however, they are beneficial only at low and intermediate cell voltages, while a neat ionic liquid performs better at higher voltages. We reveal subtle effects of how the distribution of pores accessible to different types of ions correlates with charge storage and suggest approaches to increase capacitance and stored energy density with ionic liquid mixtures.

Effect of particle size and environmental conditions on the release of di(2-ethylhexyl) phthalate from microplastics

The extensive use and improper handling of plastics have caused extensive microplastic (MP) pollution in terrestrial environments. Di(2-ethylhexyl) phthalate (DEHP), the main additive used in plastics, is toxic to organisms and may pose risks to human and animal reproductive functions. However, research on the release behavior of DEHP from MPs is scarce. In this study, the effects of particle size and environmental conditions (temperature, pH, ionic strength, and cation type) on DEHP release from polylactide (PLA), polystyrene (PS), and polyvinyl chloride (PVC) MPs were determined by performing leaching experiments. The results showed that when particle size decreased, the content of DEHP in the MPs and the amount of released DEHP increased though increasing specific surface area. An increase in temperature also promoted DEHP release; when the temperature increased from 15 °C to 45 °C, the amount of DEHP released from PLA, PS, and PVC increased by 38.4%, 71.0%, and 109%, respectively. The lower the crystallinity, the greater the increase in the amount of DEHP released. Ionic strength inhibited the release of DEHP from MPs. When Na+ concentration increased from 0 to 200 mM, the amount of DEHP released from PLA, PS, and PVC decreased by 27.4%, 41.6%, and 35.3%, respectively. The effect of Ca2+ on DEHP release from MPs was greater than that of Na+. In addition, the process of DEHP release from MPs fit well with a pseudo-first-order kinetic model. The results of this study provide a theoretical basis for managing and controlling the risks associated with plastic wastes.

Controlling molecular self-assembly of inverse-phosphocholine lipids at oxide interfaces with divalent cations

Sub-100 nm vesicles composed of inverse-phosphocholine (CP) lipids are versatile building blocks for interfacing with inorganic material surfaces and demonstrate unique chemical functionalities due to outward-facing phosphate groups. Compared to typical phospholipids, the surface presentation of CP lipids has enabled new covalent possibilities like click chemistry for drug delivery and imaging applications while utilizing this phosphate chemistry in noncovalent self-assembly contexts remains unexplored. Herein, we report that the presence of phosphate-binding divalent cations such as Ca2+ and Mg2+ can dramatically shift the self-assembly behavior of CP lipid vesicles on TiO2 and SiO2 surfaces, inhibiting spontaneous supported lipid bilayer (SLB) formation on TiO2 in cases where it typically occurs and promoting SLB formation on SiO2 in cases where lipid adsorption is otherwise negligible. Quartz crystal microbalance-dissipation (QCM-D) measurements were performed to track the corresponding adsorption kinetics and self-assembly outcomes. Importantly, an optimal combination of CP lipid fraction in vesicles and specific divalent cation type was also identified, which enabled SLB formation on both TiO2 and SiO2 surfaces under equivalent conditions. SLB fluidity on SiO2 surfaces was additionally confirmed by fluorescence recovery after photobleaching (FRAP) experiments. We rationalize these molecular-level phenomena in terms of vesicle stability and lipid-surface interactions, demonstrating a versatile approach to control CP lipid self-assembly with divalent cations.

Cation-Intercalated Lamellar MoS2 Adsorbent Enables Highly Selective Capture of Cesium.

Highly selective capture of cesium (Cs+) from complex aqueous solutions has become increasingly important owing to its (133Cs) indispensable role in some cutting-edge technologies and the environmental mobility of radioactive nuclide (137Cs) from nuclear wastewater. Herein, we report the development of cation-intercalated lamellar MoS2 as an effective Cs+ adsorbent with the advantages of facile synthesis and highly tunable layer spacing. Two types of cations, including Na+ and NH4+, were employed for the intercalations between adjacent layers of MoS2. The results demonstrated that the adsorption capacity of the NH4+-intercalated material (M-NH4+, 134 mg/g) for Cs+ clearly outperformed the others due to higher loading percentages of cations and larger layer spacing. The cesium partition coefficients for M-NH4+ in the presence of 100-fold competing ions all exceed 1 × 103 mL/g. A simulated complex aqueous solution containing 15.37 mg/L Cs+ and highly excess of competing ions Li+, Na+, K+, Mg2+, and Ca2+ (20-306 times higher) was introduced to prove the practical application potential using our best-performing M-NH4+, showing a good to excellent partition ability of Cs+ among other cations, especially for Cs/K and Cs/Na with separation factors of 58 and 212, respectively. The adsorption and selectivity mechanisms were clearly elucidated using various advanced techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. These results revealed that the good selectivity for Cs+ can be ascribed to the differences in Lewis acidities, hydration energy, cation sizes, and in particular, the divergence of coordination modes which was successfully achieved after tuning the layer distance via the cation intercalation strategy. In addition, the material has fast kinetics (<30 min), wide range of pH tolerance (4-10), and good reusability. Overall, our studies point out that the tunable lamellar MoS2-based materials are promising adsorbents for Cs+ capture and separation.

Designing V2O5/MXene van der Waals heterostructure for complementary electrochromic dual-ion capacitor

Developing highly efficient electrochromic energy storage device (EESD) is desirable for yielding ample color variation and large electrochemical capacity from the viewpoint of practical energy-saving. However, only a single type of cation or anion traveled back and forth between the cathode and anode in conventional electrochromic devices (ECDs) results in low coloration efficiency and long switching time. Herein, for the first time, we designed a multicolor complementary electrochromic dual-ion capacitor (EDIC) based on ion insertion/extraction and doping/de-doping of the anodic and cathodic electrochromic materials, respectively, to realize the fast faradic reaction and rich color variation. Significantly, the prepared V2O5/MXene van der Waals heterostructure with improved conductivity and more “active” sites favors the charge transfer, effectively improving the switching speed and coloration efficiency. Since the excellent ion matching and synergy effect of Li+ insertion/extraction in V2O5/MXene anode and ClO4- doping/de-doping at PANI/TiO2 cathode, the complementary EDIC exhibits significant color changes, large optical modulation (51%), short switching time (2.4/7.2 s) and high coloration efficiency (111 cm2 C−1), which is much superior to traditional V2O5-based ECDs. We believe that this work provides a general strategy for building a complementary EDIC with excellent electrochromic and energy storage performances.

Comparative crystal chemistry of monovalent cation-exchanged birnessite

Birnessite (ideally, Na0.54Mn2O4∙1.5H2O) is a layered manganese oxide mineral formed by edge-sharing of MnO6 octahedral sheets stacked in ∼7 Å spacing where variable amounts of water molecules and Na+ cations are occupied in a loosely disordered fashion. As such, the interlayer cations can be mixed with or substituted by other cations to contain diverse rare metals and chemical species to endow unique sensitivity on natural environments. To understand comparative crystal chemistry of birnessite as a function of interlayer cation substitution, a series of monovalent cation-exchanged forms, i.e., H-, Li-, K-, NH4-, Rb-, and Cs-exchanged birnessite, were produced from the original Na-birnessite under ambient conditions and analyzed using synchrotron X-ray powder diffraction, thermo-gravimetry, and X-ray photoluminescence spectroscopy. The (001) interplanar spacing generally expands as a function of ionic radius while it contracts as a function of the water content. Compared to the original Na-birnessite, MnO6 octahedral sheets of cation-exchanged forms become generally reduced and show higher MnIII to MnIV ratio, which affects the interlayer cation and water population. Based on the Rietveld structural refinements, the interlayer structural models are categorized into two groups depending on the distribution fashion of cations and water molecules, i.e., water molecules and cations in the Li-, K-, Rb-, Cs-birnessite models occupy separate interlayer sites whereas those are statistically mixed in the H-, Na-, NH4-birnessite models. The interlayer bonding between water molecules and oxygen atoms of the MnO6 layer appears to be a controlling factor for the interlayer spacing. The complex interplay among cation type, water content, Mn oxidation state, and related structural and chemical parameters are discussed to understand the comparative crystal chemistry of birnessite, which would serve as a basis to understanding its potential role in the geochemical cycle of cationic species in aqueous terrestrial environments.

Probing Cation Effects on *CO Intermediates from Electroreduction of CO2 through Operando Raman Spectroscopy.

Cations in an electrolyte modulate microenvironments near the catalyst surface and affect product distribution from an electrochemical CO2 reduction reaction, and thus, their interaction with intermediate states has been tried to be probed. Herein, we directly observed the cation effect on *CO intermediates on the Cu(OH)2-derived catalyst in real time through operando surface-enhanced Raman spectroscopy at high overpotentials (-1.0 VRHE). Atop *CO peaks are composed of low-frequency binding *CO (*COLFB) and high-frequency binding *CO (*COHFB) because of their adsorption sites. These two *CO intermediates are found to have different sensitivities to the cation-induced field, and each *CO is proposed to be suitably stabilized for efficient C-C coupling. The proportions between *COHFB and *COLFB are dependent on the type of alkali cations, and the increases in the *COHFB ratio have a high correlation with selective C2H4 production under K+ and Cs+, indicating that *COHFB is the dominant and fast active species. In addition, as the hydrated cation size decreases, *COLFB is more sensitively red-shifted than *COHFB, which promotes C-C coupling and suppresses C1 products. Through time-resolved operando measurements, dynamic changes between the two *CO species are observed, showing the rapid initial adsorption of *COHFB and subsequently reaching a steady ratio between *COLFB and *COHFB.

Nalidixic Acid and Fe(II)/Cu(II) Coadsorption at Goethite and Akaganéite Surfaces.

Interactions between aqueous Fe(II) and solid Fe(III) oxy(hydr)oxide surfaces play determining roles in the fate of organic contaminants in nature. In this study, the adsorption of nalidixic acid (NA), a representative redox-inactive quinolone antibiotic, on synthetic goethite (α-FeOOH) and akaganéite (β-FeOOH) was examined under varying conditions of pH and cation type and concentration, by means of adsorption experiments, attenuated total reflectance-Fourier transform infrared spectroscopy, surface complexation modeling (SCM), and powder X-ray diffraction. Batch adsorption experiments showed that Fe(II) had marginal effects on NA adsorption onto akaganéite but enhanced NA adsorption on goethite. This enhancement is attributed to the formation of goethite-Fe(II)-NA ternary complexes, without the need for heterogeneous Fe(II)-Fe(III) electron transfer at low Fe(II) loadings (2 Fe/nm2), as confirmed by SCM. However, higher Fe(II) loadings required a goethite-magnetite composite in the SCM to explain Fe(II)-driven recrystallization and its impact on NA binding. The use of a surface ternary complex by SCM was supported further in experiments involving Cu(II), a prevalent environmental metal incapable of transforming Fe(III) oxy(hydr)oxides, which was observed to enhance NA loadings on goethite. However, Cu(II)-NA aqueous complexation and potential Cu(OH)2 precipitates counteracted the formation of ternary surface complexes, leading to decreased NA loadings on akaganéite. These results have direct implications for the fate of organic contaminants, especially those at oxic-anoxic boundaries.

Probing the surface forces between air bubbles and bitumen via direct force Measurements: Effects of aqueous chemistry

The surface interactions of air bubbles and other components (e.g., particles, oil droplets) significantly influence the operation efficiency of a variety of engineering processes such as oily water treatment, bitumen extraction and flotation. Herein, the surface interactions of air bubbles with two types of Athabasca bitumen samples in aqueous solutions of varying pH, salinity, type of cations and in the presence of surfactants have been systematically characterized using a bubble probe atomic force microscope (AFM) technique. AFM imaging has revealed that exposure to high concentrations of NaCl and CaCl2 solutions or alkaline environments causes roughening of the bitumen surfaces. The results of surface force measurements demonstrate that the interaction and attachment behaviors between bubbles and bitumen are significantly affected by ionic strength, solution pH, and the presence of surfactants. The experimental force measurement results could be accurately described by a theoretical model that incorporates Reynolds lubrication theory and augmented Young-Laplace equation, with the inclusion of disjoining pressure. In low-salinity conditions, the bubble-bitumen interaction is dominated by electric double layer (EDL) repulsion, which prevents surface attachment. This effect is more pronounced at elevated pH conditions. In high-salinity solutions, however, the EDL interactions are significantly reduced, and the hydrophobic interaction becomes the dominant factor, overcoming the van der Waals repulsion and leading to the attachment of bubbles to bitumen surfaces. Raising aqueous pH weakens the bubble-bitumen hydrophobic interaction, whereas the introduction of calcium ions strengthens this interaction, resulting in enhanced surface attachment. Interestingly, even in high-salinity conditions, the presence of a small number of surfactants can inhibit bubble-bitumen contact, mainly caused by reduced hydrophobic attraction and increased steric repulsion. This work provides valuable nanoscale insights into how bubbles and bitumen interact in intricate aqueous environments, and the results show practical implications for controlling similar interfacial phenomena in various engineering processes.

From Coupling Second-Order Stresses to Understanding and Predicting the Structural Response of a Dioctahedral Smectite

AbstractThe employment of clay minerals in the transport of water, nutrients, and contaminants depends on a few factors, including permeability, hydration behavior, ion-exchange efficiency, and more. With the application of external stress, it is still difficult to understand how clay particles swell and collapse, how water is retained, how hydration heterogeneities are formed within crystallites, and how interlamellar space is organized. The present work studied the link between geochemical, thermal, kinetic constraints (established at the laboratory scale), and intrinsic clay features by exchanging Na-rich montmorillonite (SWy2) with Ni2+, Mg2+, or Zn2+ cations. By comparing the experimental 00l reflections with the calculated reflections obtained from the structural models, quantitative X-ray diffraction (XRD) analysis has enabled the building of a theoretical profile describing the layer stacking mode (LSM) and allowed the description of interlayer space (IS) configuration along the c* axis. Regardless of the type of the exchangeable cations (EC), XRD modeling revealed that all samples exhibited interstratified hydration behavior within the crystallite size, which probably indicates partial or incomplete saturation of the IS. This theoretical result was defined by the appearance of two hydration states (1W and 2W), which were unrelated to the strain strength creating a higher degree of structural heterogeneity. Using the theoretical decomposition of the observed XRD patterns, the identification of all distinct layer populations and their stacking mode was achieved. The segregated LSM are, therefore, obviously superior as a function of stress strength.

Strength Degradation of Foamed Lightweight Soil Due to Chemical Erosion and Wet-Dry Cycle and Its Empirical Model.

Foamed lightweight soils (FLS) have been extensively used as backfill material in the construction of transportation infrastructures. However, in the regions consisting of salt-rich soft soil, the earth structure made by FLS experiences both fluctuation of groundwater and chemical environment erosion, which would accelerate the deterioration of its long-term performance. This study conducted laboratory tests to explore the deterioration of FLS in strength after being eroded by sulfate attack and/or wet-dry cycling, where the influencing factors of FLS density, concentration of sulfate solution, and cation type (i.e., Na+ and Mg2+) were considered. An unconfined compressive test (UCT) was conducted, and the corrosion-resistant coefficient (CRC) was adopted to evaluate the erosion degree after the specimens experienced sulfate attack and/or dry-wet cycling for a certain period. The research results show that the erosion of the FLS specimen under the coupling effect of sulfate attack and dry-wet cycling was more remarkable than that only under chemical soaking, and Na2SO4 solution had a severe erosion effect as compared with MgSO4 solution when other conditions were kept constant. An empirical model is proposed based on the test results, and its reliability has been verified with other test results from the literature. The proposed model provides an alternative for engineers to estimate the strength deterioration of FLS on real structures in a preliminary design.

High-Efficiency Mono-Cyclopentadienyl Titanium and Rare-Earth Metal Catalysts for the Production of Syndiotactic Polystyrene.

Syndiotactic polystyrene (SPS) refers to a type of thermoplastic material with phenyl substituents that are alternately chirally attached on both sides of an aliphatic macromolecular main chain. Owing to its excellent physical and mechanical properties, as well as its chemical stability, high transparency, and electrical insulation characteristics, SPS is used in a wide variety of technical fields. SPS is commonly produced via the stereoselective transition metal-catalyzed coordination polymerization method mediated by stereospecific catalysts, which consists of anionic mono-cyclopentadienyl derivative η5-coordinated single active metal centers (referred to as "mono-Cp'-M"), with active center metals involving Group 4 transition metals (with an emphasis on titanium) and rare-earth (RE) metals of the periodic table. In this context, the use of mono-cyclopentadienyl titanocene (mono-Cp'Ti) catalysts and mono-cyclopentadienyl rare-earth metal (mono-Cp'RE) metallocene catalysts for the syndiospecific polymerization of styrene is discussed. The effects of the mono-cyclopentadienyl ligand structure, cationic active metal types, and cocatalysts on the activity and syndiospecificity of mono-Cp' metallocene catalysts are briefly surveyed.

Understanding the Behavior of Sodium Polyacrylate in Suspensions of Silica and Monovalent Salts.

This study investigated the interaction of monovalent cations with different sizes on quartz surfaces and the rheological impact that this causes in concentrated suspensions when subjected to the action of a rheological modifier, in this case, sodium polyacrylate (NaPA). Yield stress was determined using a rheometer with a vane-in-cup configuration to establish the relationship between shear stress and strain. Experiments were carried out in LiCl, NaCl, KCl, and CsCl solutions. The results show that the yield stress increases following the order Li < Na < K < Cs in the absence of PAA. However, the addition of NaPA significantly reduced the yield stress in all cases. This reduction was more noticeable in the LiCl and NaCl solutions than in the KCl and CsCl solutions, suggesting a more pronounced effect of PA in maker salts. We conducted molecular dynamics simulations to understand how PA interacts with dissolved salts on the quartz surface. Our results showed that Li had the highest adsorption, followed by Na, K, and Cs. As the salt concentration increased, so did the adsorption. We validated these simulation results with rheological experiments, which helped us understand the observed differences. The molecular interactions indicate that, in the lithium system, cationic bridges and the synergy between hydrogen bridges and hydrophobic bridges predominate mainly. This tendency decreases as the type of cation is changed due to the decrease in the electrical density of the cation in the following order: Li < Na < K < Cs. This reduces bridging with the quartz surface and, therefore, directly impacts the system's rheological properties.

Intrinsic Ferromagnetic Semiconductors with High Saturation Magnetization from Hybrid Perovskites.

Ferromagnetic semiconductors (FMS) enable simultaneous control of both charge and spin transport of charge carriers, which have emerged as a class of highly desirable but rare material for applications in spin field-effect transistors and quantum computing. Organic-inorganic hybrid perovskite with high compositional adjustability and structural versatility can offer unique benefits in the design of FMS but has not been fully explored. Here we demonstrate a series of molecular FMSs based on two-dimensional organic-inorganic hybrid perovskite structure, namely (2ampy)CuCl4 , (3ampy)CuCl4 and (4ampy)CuCl4 , which exhibits high saturation magnetization, dramatic temperature-dependent conductivity change and tunable ferromagnetic resonance. Magnetic measurements revealed high saturation magnetization up to 18.56 emu/g for (4ampy)CuCl4 , which is one of the highest value among reported hybrid FMSs to date. Conductivity studies of the three FMSs demonstrate that the smaller adjacent octahedron distance in the two-dimensional layer results in higher conductivity. Systematic ferromagnetic resonance investigation shows that the gyromagnetic ratio and Landau factor values are strongly dependent on the types of organic cations used. This work demonstrates that two-dimensional hybrid perovskite materials can simultaneously possess both tunable long-range ferromagnetic ordering and semiconductivity, providing a straightforward strategy for designing and synthesizing high-performance intrinsic FMSs. This article is protected by copyright. All rights reserved.

Halide Ion Mixing across Colloidal 2D Ruddlesden-Popper Perovskites: Implication of Spacer Ligand on Mixing Kinetics.

Halide ion exchange seen in metal halide perovskites provide a substantial opportunity to control their halide composition and corresponding optoelectronic properties. Halide ion mixing across colloidal 3D perovskite nanocrystals have been extensively studied while the mixing within colloidal 2D counterparts remain underexplored. In this study, the halide ion exchange kinetics across colloidally stable 2D Ruddlesden-Popper layered bromide (Br) and iodide (I) perovskites using two different spacer ligands such as aromatic phenethylammonium (PEA) versus linear butyammonium (BA) is demonstrated. The halide exchange kinetic rate constant (k), as determined by tracking time-dependent absorbance changes, indicates that Br/I halide mixing in 2D PEA-based perovskites (2.7 × 10-3 min-1 ) occurs at an order of magnitude slower than in 2D BA-based perovskites (3.3 × 10-2 min-1 ). Concentration (≈1mM to 100mM) and temperature-dependent (50 to 80 °C) kinetic studies further allow for the determination of activation barrier for halide ion mixing across the 2D layered perovskites with 75.2 ± 4.4kJ mol-1 (2D PEA) and 57.8 ± 7.8kJ mol-1 (2D BA), respectively. The activation energy reveals that the type of spacer cations plays a crucial role in controlling the halide ion mobility and halide stability due mainly to the internal ligand chemical interaction within 2D structures.

Assessing stability and performance of fluorine-doped tin oxide electrodes for peroxide formation in carbonate-based electrolytes

Hydrogen peroxide (H2O2) is a valuable chemical currently produced industrially on a large scale by the anthraquinone process. Recently, carbonate and/or bicarbonate-induced selective water oxidation to hydrogen peroxide has been suggested as an environmentally friendly alternative. In this manuscript, we discuss the effect of electrolyte concentration and type of cation in selective water oxidation using carbonate-based electrolytes (i.e., Na2CO3, K2CO3 and Cs2CO3) on fluorine-doped tin oxide (FTO) electrodes. Based on the experimental observations and a techno-economic evaluation we reveal that K2CO3 is preferred over Na2CO3 and Cs2CO3 electrolytes. Using 5 M K2CO3 a Faradaic efficiency of > 60 % was achieved at industrially relevant current densities of 100 mA cm−2. Although for 5 M Cs2CO3 electrolytes lower potentials are required at otherwise similar process conditions, a lower efficiency for hydrogen peroxide formation has been observed which is assigned to higher degradation in Cs-containing electrolyte, rendering the use of potassium-based electrolytes more efficient. Independent of the electrolyte used, the electrodes suffered from stability issues as revealed by increasing concentrations of tin in the electrolyte and electrode failure after polarization for several hours. Overall, this work provides detailed knowledge about the impact of electrolyte concentration and type of cation and reveals the importance of appropriate cell design and process operation for meaningful hydrogen peroxide synthesis by mediated-anodic water oxidation.

About the possibility to liberate naturally present fixed cations from dioctahedral smectites by hydrothermal treatment

The chemical analysis of pure dioctahedral smectites exchanged by one of the typical CEC-index cations (e.g. Cu-trien) often shows significant Na-, Ca-, and K-contents which, in contrast to Mg, are not expected to occur in the octahedral sheet. They are supposed to occur in the interlayer but are not exchangeable - hence termed “fixed cations”. The aim of the study was to gain new evidence for the presence of naturally present fixed cations and find out if at least a part of these can be liberated by hydration after hydrothermal treatment.The methodological approach for cation liberation tests included different treatments with water at 60 °C and 150 °C, partly using an ultrasonic bath, and different reaction times prior to addition of the Cu-trien index cation for CEC analysis.The study proved that at least part of the naturally present fixed cations could be rendered exchangeable (liberated) by the hydrothermal treatment before an index cation is added. The differences were small but significant.Liberation of fixed cations was thought to increase the CEC but the increased amount of exchangeable cations was accompanied by a decrease of the CEC, which can probably be explained by partial smectite dissolution. This hypothesis was supported by measurements conducted at higher solid to liquid ratio in order to suppress smectite dissolution. The CEC decrease was less pronounced but at the same time less cations were liberated. In conclusion, the naturally present fixed cations are strongly bound and, supposedly, can only be liberated if the smectite structure is affected.Future work will be devoted to finding alternative methods which are suitable for quantification of naturally present fixed cations in bentonites/smectites.

Effects of Surfactants on the Chemical Mechanical Polishing Performance of a-Plane Sapphire Substrates

The effects of four different types of surfactants, cetyltrimethylammonium bromide (CTAB, cationic type), sodium dodecyl benzene sulfonate (SDBS, anion type), N-Laurylaminoacetic acid (NL, amphoteric type) and primary alcohol ethoxylate (AEO, non-ionic type), on the chemical mechanical polishing (CMP) performance of a-plane sapphire substrates in the range of pH 6–12 were investigated using colloidal silica as abrasive particles. The results demonstrated that cationic surfactants promoted the material removal of the sapphire substrate in the range of pH 9–12, while anionic, amphoteric, and non-ionic surfactants inhibited the material removal of the sapphire substrate in the range of pH 6–10. The mechanism of material removal in sapphire CMP was discussed through AFM observations, zeta potential measurements, particle size distribution tests, and friction behavior analysis.

Interfacial Tension-Temperature-Pressure-Salinity Relationship for the Hydrogen-Brine System under Reservoir Conditions: Integration of Molecular Dynamics and Machine Learning.

Hydrogen (H2) underground storage has attracted considerable attention as a potentially efficient strategy for the large-scale storage of H2. Nevertheless, successful execution and long-term storage and withdrawal of H2 necessitate a thorough understanding of the physical and chemical properties of H2 in contact with the resident fluids. As capillary forces control H2 migration and trapping in a subsurface environment, quantifying the interfacial tension (IFT) between H2 and the resident fluids in the subsurface is important. In this study, molecular dynamics (MD) simulation was employed to develop a data set for the IFT of H2-brine systems under a wide range of thermodynamic conditions (298-373 K temperatures and 1-30 MPa pressures) and NaCl salinities (0-5.02 mol·kg-1). For the first time to our knowledge, a comprehensive assessment was carried out to introduce the most accurate force field combination for H2-brine systems in predicting interfacial properties with an absolute relative deviation (ARD) of less than 3% compared with the experimental data. In addition, the effect of the cation type was investigated for brines containing NaCl, KCl, CaCl2, and MgCl2. Our results show that H2-brine IFT decreases with increasing temperature under any pressure condition, while higher NaCl salinity increases the IFT. A slight decrease in IFT occurs when the pressure increases. Under the impact of cation type, Ca2+ can increase IFT values more than others, i.e., up to 12% with respect to KCl. In the last step, the predicted IFT data set was used to provide a reliable correlation using machine learning (ML). Three white-box ML approaches of the group method of data handling (GMDH), gene expression programming (GEP), and genetic programming (GP) were applied. GP demonstrates the most accurate correlation with a coefficient of determination (R2) and absolute average relative deviation (AARD) of 0.9783 and 0.9767%, respectively.