Free Ion Concentration Research Articles

Prediction model for equivalent exposure time in indoor dry-wet cycling tests for concrete in marine tidal zones

Chloride ion erosion poses a major threat to the durability of concrete structures in coastal environments, particularly in tidal zones with periodic seawater exposure. This study developed a predictive model based on Fick's second law, utilizing data from over 20 coastal structures across six countries. The model, grounded in the principle of equivalent free chloride ion concentration at a certain depth after a given exposure time, estimates the number of dry-wet cycles required in accelerated laboratory testing to simulate real-world conditions. It has been validated using data from actual marine structures. Key environmental factors such as temperature and humidity, along with regional climate differences, are incorporated to predict the relative deterioration rates of concrete in various marine environments. Additionally, an accelerated indoor dry-wet cycle test was designed based on the theory of environmental similarity, tracking the performance evolution of concrete. The model was verified through experiments, showing that 30 indoor dry-wet cycles correspond to 79 years of exposure in a coastal environment. The physical property changes observed in the accelerated tests further confirmed the model’s reliability and accuracy. This research provides critical insights into the impact of environmental factors on concrete degradation and offers a scientific basis for the application of accelerated laboratory testing.

Influence of water scouring on chloride ion diffusion in rice husk ash recycled aggregates concrete

This study investigates the chloride ion diffusion behavior in concrete incorporating rice husk ash (RHA) and recycled aggregates (RA) under water scouring conditions. The research results indicate that both free and total chloride ion concentrations in recycled aggregate concrete (RAC) exhibit an initial increase, followed by a subsequent decrease, as the distance from the concrete surface increases. The incorporation of RHA reduces both free and total chloride ion concentrations while increasing bound chloride ion content. However, an excessive amount of RHA can weaken the resistance of RAC to chloride ion penetration. Water erosion deteriorates the internal microstructure of RAC, accelerating the transport of free and total chloride ions. However, it does not compromise the chloride ion binding mechanism conferred by RHA. The fine particulate of RHA provides additional nucleation sites for cement hydration, while the reservoir effect ensures a steady supply of free water to these sites. This synergistic interaction enhances the pozzolanic reaction between cement hydration products and RHA, resulting in reduced Ca(OH)₂ content and increased formation of C-S-H gel.

Study on the role of alkali halides on the mutarotation and dehydration of d-xylose in aqueous solution

Although the xylose mutarotation and transformation have been investigated largely separately, their relationship has been rarely systematically elaborated. The effect of several factors such as xylose concentration, temperature, and salt concentration, affecting the mutarotation of xylose are discussed. Nine alkali halides (LiCl, NaCl, KCl, LiBr, NaBr, KBr, LiI, NaI, and KI) are used to test salt effects. The relationship between xylose rotation rate constant (kM), specific optical rotation at equilibrium ([α]eqm), α/β ratio, H chemical shift difference (ΔΔδ), Gibbs free energy difference (ΔG), hydrogen ion or hydroxide ion concentration ([H+] or [OH−]), and xylose conversion is discussed. Different salts dissolved in water result in different pH of the solutions, which affect the mutarotation of xylose, with the nature of both cation and anion. Shortly, the smaller the cation radius is and the larger the anion radius is, the greater the mutarotation rate is. In the dehydration of xylose to furfural in salty solutions, xylose conversion is positively correlated to mutarotation rate, H+ or OH− concentration, and the energy difference between α-xylopyranose and β-xylopyranose. Although the [α]eqm of xylose is positively correlated with α/β configuration ratio, there is no obvious correlation with xylose dehydration. The conversion to furfural in chlorides is superior to that in bromines and iodides, which is due to the fact that the pH of chloride salts is smaller than that of the corresponding bromide and iodized salts. Higher H+ concentration prefers to accelerate the formation of furfural. In basic salt solutions, the xylulose selectivity is higher than that of furfural at the initial stage of reaction. The furfural selectivity and carbon balance are better in acidic condition rather than in basic condition. In H2O-MTHF (2-Methyltetrahydrofuran) biphasic system, the optimal furfural selectivity of 81.0 % is achieved at 190 °C in 1 h with the assistance of LiI and a little HCl (0.2 mmol, 8 mmol/L in aqueous phase). A high mutarotation rate represents rapid xylose conversion, but a high furfural selectivity prefers in acidic solutions, which would be perfect if organic solvents were available to form biphasic systems.

PyChelator: a Python-based Colab and web application for metal chelator calculations

BackgroundMetal ions play vital roles in regulating various biological systems, making it essential to control the concentration of free metal ions in solutions during experimental procedures. Several software applications exist for estimating the concentration of free metals in the presence of chelators, with MaxChelator being the easily accessible choice in this domain. This work aimed at developing a Python version of the software with arbitrary precision calculations, extensive new features, and a user-friendly interface to calculate the free metal ions.ResultsWe introduce the open-source PyChelator web application and the Python-based Google Colaboratory notebook, PyChelator Colab. Key features aim to improve the user experience of metal chelator calculations including input in smaller units, selection among stability constants, input of user-defined constants, and convenient download of all results in Excel format. These features were implemented in Python language by employing Google Colab, facilitating the incorporation of the calculator into other Python-based pipelines and inviting the contributions from the community of Python-using scientists for further enhancements. Arbitrary-precision arithmetic was employed by using the built-in Decimal module to obtain the most accurate results and to avoid rounding errors. No notable differences were observed compared to the results obtained from the PyChelator web application. However, comparison of different sources of stability constants showed substantial differences among them.ConclusionsPyChelator is a user-friendly metal and chelator calculator that provides a platform for further development. It is provided as an interactive web application, freely available for use at https://amrutelab.github.io/PyChelator, and as a Python-based Google Colaboratory notebook at https://colab.research.google.com/github/AmruteLab/PyChelator/blob/main/PyChelator_Colab.ipynb.

Polyunsaturated Fatty Acids in Quinoa Induce Ferroptosis of Colon Cancer by Suppressing Stemness.

Polyunsaturated fatty acids (PUFAs) are essential nutrients for the human body, playing crucial roles in reducing blood lipids, anti-inflammatory responses, and anticancer effect. Quinoa is a nutritionally sound food source, rich in PUFAs. This study investigates the role of quinoa polyunsaturated fatty acids (QPAs) on quelling drug resistance in colorectal cancer. The results reveal that QPA downregulates the expression of drug-resistant proteins P-gp, MRP1, and BCRP, thereby enhancing the sensitivity of colorectal cancer drug-resistant cells to the chemotherapy drug. QPA also inhibits the stemness of drug-resistant colorectal cancer cells by reducing the expression of the stemness marker CD44. Consequently, it suppresses the downstream protein SLC7A11 and leads to ferroptosis. Additionally, QPA makes the expression of ferritin lower and increases the concentration of free iron ions within cells, leading to ferroptosis. Overall, QPA has the dual-function reversing drug resistance in colorectal cancer by simultaneously inhibiting stemness and inducing ferroptosis. This study provides a new option for chemotherapy sensitizers and establishes a theoretical foundation for the development and utilization of quinoa.

Quantitative Chemical Imaging of Organelles.

ConspectusDNA nanodevices are nanoscale assemblies, formed from a collection of synthetic DNA strands, that may perform artificial functions. The pioneering developments of a DNA cube by Nadrian Seeman in 1991 and a DNA nanomachine by Turberfield and Yurke in 2000 spawned an entire generation of DNA nanodevices ranging from minimalist to rococo architectures. Since our first demonstration in 2009 that a DNA nanodevice can function autonomously inside a living cell, it became clear that this molecular scaffold was well-placed to probe living systems. Its water solubility, biocompatibility, and engineerability to yield molecularly identical assemblies predisposed it to probe and program biology.Since DNA is a modular scaffold, one can integrate independent or interdependent functionalities onto a single assembly. Work from our group has established a new class of organelle-targeted, DNA-based fluorescent reporters. These reporters comprise three to four oligonucleotides that each display a specific motif or module with a specific function. Given the 1:1 stoichiometry of Watson-Crick-Franklin base pairing, all modules are present in a fixed ratio in every DNA nanodevice. These modules include an ion-sensitive dye or a detection module and a normalizing dye for ratiometry that along with detection module forms a "measuring module". The third module is an organelle-targeting module that engages a cognate protein so that the whole assembly is trafficked to the lumen of a target organelle. Together, these modules allow us to measure free ion concentrations with accuracies that were previously unattainable, in subcellular locations that were previously inaccessible, and at single organelle resolution. By revealing that organelles exist in different chemical states, DNA nanodevices are providing new insights into organelle biology. Further, the ability to deliver molecules with cell-type and organelle level precision in animal models is leading to biomedical applications.This Account outlines the development of DNA nanodevices as fluorescent reporters for chemically mapping or modulating organelle function in real time in living systems. We discuss the technical challenges of measuring ions within endomembrane organelles and show how the unique properties of DNA nanodevices enable organelle targeting and chemical mapping. Starting from the pioneering finding that an autonomous DNA nanodevice could map endolysosomal pH in cells, we chart the development of strategies to target organelles beyond the endolysosomal pathway and expanding chemical maps to include all the major ions in physiology, reactive species, enzyme activity, and voltage. We present a series of vignettes highlighting the new biology unlocked with each development, from the discovery of chemical heterogeneity in lysosomes to identifying the first protein importer of Ca2+ into lysosomes. Finally, we discuss the broader applicability of targeting DNA nanodevices organelle-specifically beyond just reporting ions, namely using DNA nanodevices to modulate organelle state, and thereby cell state, with potential therapeutic applications.

On the coupling of intracellular to glycolytic oscillations in yeast.

We have investigated the interplay between glycolytic oscillations and intracellular concentration in the yeastSaccharomyces cerevisiae. Intracellular concentration was measured using the fluorophore potassium-binding benzofuranisophthalate(PBFI). We found that is an essential ion for the occurrence of glycolytic oscillations and that intracellular concentration oscillates synchronously with other variables such as nicotinamide adenine dinucleotide hydride (NADH), intracellular adenosine triphosphate (ATP), and mitochondrial membrane potential. We also investigated if glycolysis and intracellular concentration oscillate in a number of yeast strains with mutations in transporters in the plasma membrane, mitochondrial membrane and in the vacuolar membrane. Most of these strains are still capable of showing glycolytic oscillations, but two strains are not: (i) a strain with a deletion in the mitochondrial Mdm38p transporter and (ii) a strain with deletion of the late endosomal Nhx1p ( ) transporter. In these two mutant strains intracellular concentration seems to be low, indicating that the two transporters may be involved in transport of into the cytosol. In the strain, Mdm38p oscillations in glycolysis could be restored by addition of the exchange ionophore nigericin. Furthermore, in two nonoscillating mutant strains with a defective V-ATPase and deletion of the Arp1p protein the intracellular is relatively high, suggesting that the V-ATPase is essential for transport of out of the cytosol and that the cytoskeleton may be involved in binding to reduce the concentration of free ion in the cytosol. Analyses of the time series of oscillations of NADH, ATP, mitochondrial membrane potential, and potassium concentration using data-driven modeling corroborate the conjecture that ion is essential for the emergence of oscillations and support the experimental findings using mutant strains.

Study of corrosion resistance of superhydrophobic hydrotalcite cement mortar in chlorine salt environment

Reinforced concrete structures are susceptible to reduced service life owing to the erosion caused by the of chlorine-containing, external environment and internal chloride. In this paper, a superhydrophobic hydrotalcite cement mortar was studied with internal and external cooperation against chloride ion erosion. The effect of different hydrotalcite substitution amounts on the chlorine corrosion resistance of the mortar was investigated. The mortar exhibited good resistance to chlorine corrosion, and the corrosion resistance rate increased by 91.83 %. The free chloride ion concentration measurement and rapid chloride migration test exhibited that the prepared mortar effectively resisted chloride ion invasion and reduced the content of free chloride ions in the mortar. The proposed anticorrosion method is expected to have potential application prospects for concrete structures under chloride salt environments.

Understanding the Thermodynamics of Magnesium Binding to RNA Structural Motifs.

Divalent magnesium ions (Mg2+) serve a vital role in defining the structural and catalytic chemistry of a wide array of RNA molecules. The body of structural information on RNA motifs continues to expand and, in turn, the functional importance of Mg2+ is revealed. A combination of prior work on the structural characterization of magnesium binding ligands with inner- and outer-sphere coordination modes, with recorded experimental binding energies for inner- and outer-sphere contacts, demonstrates the relative affinity and thermodynamic hierarchy for these sites. In turn, these can be correlated with cellular concentrations of free available magnesium ions, allowing the prioritization of populating important functional sites and a correlation with physiological function. This paper summarizes some of the key results of that analysis and provides predictive rules for the affinity and role of newly identified Mg binding sites on complex RNA structures. The influence of crystal packing on magnesium binding to RNA motifs, relative to their solution form, is addressed and caveats made.

The role of the local structure on the thermal transport within dissociated and complexed Molten salt mixtures

Contrary to the solid state, the understanding of thermal transport within molten salts remains limited. This study aims at establishing a robust theoretical framework for describing and predicting thermal transport in complex and dissociated multicomponent molten salt mixtures, considering both the composition and temperature variables. The proposed approach, based on kinetic theory, considers the local perturbation of kinetic energy through mass fluctuation, weighted by a function dependent on the thermal conductivity of the uncorrelated system and the local structure. The local structure is described in terms of the concentration of free and complex ions, determined either experimentally (using NMR) or through equilibrium atomistic simulations. The thermal transport within several molten salt systems, including KCl, Al2O3, LiF-KF, LiF-NaF-KF (FLiNaK), KCl-MgCl2, NaCl-KCl-MgCl2, and the NaF-AlF3 system, are presented as case studies using the proposed approach. Furthermore, a molecular-level perspective of thermal conduction within molten salts is discussed.

Modulating Ionic Conduction and Accelerating Sulfur Conversion Kinetics through Oxygen Vacancy Engineering for High‐Performance Solid‐State Lithium‐Sulfur Batteries

AbstractPoly(ethylene oxide) (PEO)‐based solid‐state lithium‐sulfur batteries (SSLSBs) have garnered considerable attention as potential energy storage solutions owing to their exceptional specific energy, ease of processing, and economic viability. Nevertheless, the inherently low Li+ conductivity of the PEO electrolyte and the inevitable dissolution of lithium polysulfides (LiPSs) within the sulfur cathode hinder the solid‐state sulfur conversion kinetics and lead to significant loss of active materials, thus posing challenges for practical applications. Herein, these concerns are addressed by incorporating oxygen vacancy enriched‐Nb22W20O102‐x (NWOx) nanorods as cathode additives in high‐performance PEO‐based SSLSBs. The uniformly dispersed NWOx nanorods effectively modify the coordination environment of Li ions by increasing the concentration of free Li ions in the PEO catholyte and alleviating the shuttle effect of dissolved LiPSs. Consequently, the developed SSLSB demonstrates excellent cyclic stability and rate capability. Specifically, it achieves a high discharge capacity of 1208.6 mAh g−1 during the initial cycle and maintains 927.8 mAh g−1 after 200 cycles at 0.1 C. Moreover, such a configuration can accommodate a high loading of active materials with stable capacity retention. Overall, this study presents an effective approach for developing solid‐state sulfur cathodes in PEO‐based SSLSBs.

Diversifying Ion-Transport Pathways of Composite Solid Electrolytes for High-Performance Solid-State Lithium-Metal Batteries.

The application of composite solid electrolytes (CSEs) in solid-state lithium-metal batteries is limited by the unsatisfactory ionic conductivity underpinned by the low concentration of free lithium ions. Herein, we propose an interface design strategy where an amine silane linker is employed as a coupling agent to graft the Li7La3Zr2O12 (LLZO) ceramic nanofibers to the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer matrix to enhance their interaction. The hydrogen bonding between amino-functionalized LLZO (NH2@LLZO) and PVDF-HFP not only effectively induces a uniform incorporation of high-content nanofibers (50 wt %) into the polymer matrix but also furnishes sufficient continuous surfaces to weaken the complexation between PVDF-HFP and Li-ion carriers. Additionally, introduction of the hydrogen bond and Lewis acid-base interplay strengthens the interfacial interactions between NH2@LLZO and lithium salts that release more free lithium ions for efficient interfacial transport. The impact of the linker's structure on the dissociation capacity of lithium salts is systematically studied from the steric effect perspective, which affords insights into interface design. Conclusively, the composite solid electrolyte achieves a high ionic conductivity (5.8 × 10-4 S cm-1) by synergy of multiple transport channels at ceramic, polymer, and their interface, which effectively regulates the lithium deposition behavior in symmetric cells. The excellent compatibility of the electrolyte with both LiFePO4 and LiNi0.8Co0.1Mn0.1O2 cathodes also results in a long lifetime and a high rate capability for full cells.

Functional metal-organic framework membranes with uniform unsaturated pyridine-nitrogen sites as separators for high-performance lithium metal batteries

Lithium metal batteries are a promising successor to lithium-ion batteries due to high specific capacity, low density, and low electrochemical reduction potential. However, inhomogeneous lithium deposition on the Li surface will result in the formation of lithium dendrites and eventually puncture the separator and cause a short circuit. Herein, a functional metal-organic framework membrane with uniform unsaturated pyridine-nitrogen sites is synthesized via coating UiO-67-BPY (2,2 -bipyridine- 5,5 -dicarboxylic acid, named as BPY) on a commercial polypropylene (PP) separator. By replacing the benzene ring with a pyridine ring, the functionalization and porosity of MOF is fully utilized while maintaining the excellent porosity and pore size of MOF. The Li-ion transference number (tLi+) with the functional separator is 0.69 and the ionic conductivity is improved by order of magnitude compared to a plain PP separator. The N atom of the pyridine ring on the UiO-67-BPY has a strong electrostatic interaction force, and a weak coordination bond (N–Li bonding lattice) is formed between N and Li, which leads to an increase in the concentration of free lithium ions and makes their distribution more uniform. This allows lithium ions to migrate more smoothly, which is conducive to ionic conductivity and hinders dendrite formation.

Study on seawater corrosion resistance of calcium sulfoaluminate cement-based novel grouting materials

Grouting materials play a critical role in anchoring structures of cross-sea tunnels by safeguarding the anchors against seawater corrosion and enhancing durability. In this paper, a novel grouting material comprising ferrite-rich sulfoaluminate cement (FCSA), ordinary Portland cement (OPC), anhydrite and limestone were prepared. Accelerated corrosion immersion tests were conducted to assess the corrosion resistance of the grouting material using artificial seawater solutions with varying salt concentrations. Pull-out tests were performed to verify the material's performance, while potentiometric titration and X-ray diffraction (XRD) analysis were employed to analyze free chloride ion concentration (Cf) and corrosion products at the anchorage interface. Results indicate that after 1.5 years of corrosion in seawater with different salt concentrations, the bond strength stabilized at 1.05 MPa. No rust was observed on the anchor surfaces and the Cf exhibited a linear increase with salt concentration. The content of Friedel's salt increases with salt concentration, demonstrating adequate chloride ion binding capacity. The test results validate the exceptional seawater corrosion resistance and long-term stability of the novel grouting material.

Effect of chloride binding and sulfate ion attack on the chloride diffusion in calcium sulfoaluminate-based material under seawater environment

The diffusion of chloride ions in reinforced concrete under the seawater environment will affect the physical or mechanical properties and durability. Sulfate ions also influence the diffusion of chloride ions by generating expansion products through physical and chemical reactions. Further research on the effects of chloride binding and sulfate ion attack on chloride ion diffusion will deepen the understanding of concrete failure mechanism. In this paper, a quaternary blend based on calcium sulfoaluminate (CSA) cement was prepared and laboratory immersion tests were conducted in artificial seawater with varying salt concentrations. Initially, chloride ion concentration measurements and XRD tests were conducted at different corrosion ages and salt concentrations. Subsequently, the chloride binding properties of CSA-based materials was quantified through the analysis of chloride ion concentration and the phases of hydration products. Meanwhile, the corrosive effect of sulfate ions on chloride ion diffusion was determined corresponds to the content of expansive hydration products. Furthermore, numerical simulations were employed to evaluate the impact of sulfate ion corrosion, chloride binding, and their combined effects on chloride ion diffusion, and the results were compared with free chloride ion concentration (Cf). The results indicate that the total chloride ion concentration (Ct) exhibits a linear relationship with increasing salt concentrations of seawater in CSA-based materials. Meanwhile, the bound chloride ion concentration (Cb) follows a logarithmic growth pattern. The chloride binding rate experiences a linear decline with the increase of chloride ion concentration in the artificial seawater. Additionally, the relationship between Cf and Cb or Ct can be described using different isothermal adsorption models for the CSA-based materials. Among these models, the Langmuir model is suitable for characterizing the relationship between Cf and Cb, while the Freundlich model is suitable for describing the relationship between Cf and Ct. Furthermore, it is noteworthy that sulfate ion attack and chloride binding exert nearly equivalent effects on the diffusion of chloride ions in CSA-based materials at short corrosion age and low chloride ion concentration. However, the corrosive impact of sulfate ions gradually evolves into the dominant factor in the progression of corrosion over time and the increase in seawater salt concentration.

Exploring ion mobility mechanisms in poly indolequinone polymers: a case study on black soldier fly melanin

Black soldier fly (BSF) melanin is a new supply of the brown-black pigment eumelanin. Given that eumelanin is a model bioelectronic material for applications such as medical devices and sensors, understanding BSF melanin’s electrical properties is important to confirm its viability as an advanced material. Presented here is a systematic, hydration dependent alternating current study of BSF melanin utilising both H2O and D2O vapours. There is a clear difference between the vapours, enabling a thorough analysis including Nyquist plots with model circuit analysis, broad band dielectric spectroscopic modelling as well as applying the Trukhan model to understand free ion concentration and mobility changes as a function of hydration. We find that BSF melanin behaves similarly to previous reports on synthetic systems, and the analysis here sheds additional light on potential charge transport changes. Significantly, a key finding is that there are two different mobility mechanisms for ion transport depending on hydration.

Ocean acidification significantly alters the trace element content of the kelp, Saccharina latissima

Seaweeds are ecosystem engineers that can serve as habitat, sequester carbon, buffer ecosystems against acidification, and, in an aquaculture setting, represent an important food source. One health issue regarding the consumption of seaweeds and specifically, kelp, is the accumulation of some trace elements of concern within tissues. As atmospheric CO2 concentrations rise, and global oceans acidify, the concentrations of elements in seawater and kelp may change. Here, we cultivated the sugar kelp, Saccharina latissima under ambient (~400 μatm) and elevated pCO2 (600–2400 μatm) conditions and examined the accumulation of trace elements using x-ray powder diffraction, sub-micron resolution x-ray imaging, and inductively coupled plasma mass spectrometry. Exposure of S. latissima to higher concentrations of pCO2 and lower pH caused a significant increase (p < 0.05) in the iodine and arsenic content of kelp along with increased subcellular heterogeneity of these two elements as well as bromine. The iodine-to‑calcium and bromine-to‑calcium ratios of kelp also increased significantly under high CO2/low pH (p < 0.05). In contrast, high CO2/low pH significantly reduced levels of copper and cadmium in kelp tissue (p < 0.05) and there were significant inverse correlations between concentrations of pCO2 and concentrations of cadmium and copper in kelp (p < 0.05). Changes in copper and cadmium levels in kelp were counter to expected changes in their free ionic concentrations in seawater, suggesting that the influence of low pH on algal physiology was an important control on the elemental content of kelp. Collectively, these findings reveal the complex effects of ocean acidification on the elemental composition of seaweeds and indicate that the elemental content of seaweeds used as food must be carefully monitored as climate change accelerates this century.

Release of indium from In2O3 nanoparticles in model solutions and synthetic seawater

Indium oxide (In2O3) nanoparticles (NPs) are used in electronic devices, from which indium (as its nanoparticulate form or as other generated chemical species) can be released to natural waters. To assess for the impacts of such releases (e.g. toxic effects), information on the kinetics and thermodynamics of the In2O3 dissolution processes is key. In this work, the evolution with time of the dissolution process was followed with the technique AGNES (Absence of Gradients and Nernstian Equilibrium Stripping) by measuring the free indium concentration ([In3+]). AGNES can determine the free ion concentration in the presence of nanoparticles without a prior separation step, as shown in the case of ZnO nanoparticles, a procedure that is more accurate than the typical sequence of centrifugation+filtration+elemental analysis. Excess of indium oxide NPs were dispersed in 0.1 mol L−1 KNO3 at various pH values ranging from 2 to 8. Additional dispersions with bulk In2O3 at pH 3 or NPs in synthetic seawater at pH 8 were also prepared. The temperature was carefully fixed at 25 °C. The dispersions were continuously stirred and samples were taken from time to time to measure free indium concentration with AGNES. 180-day contact of In2O3 to solutions at pH 2 and 3 was not enough to reach equilibrium. The dissolution of the NPs at pH 3 was faster than that of the bulk (i.e. non nanoparticulate) material. Equilibrium of the NPs with the solution was reached at pH 4 and 5 in KNO3 and at pH 8 in seawater, in shorter times for higher pH values, with free indium concentrations decreasing by a factor of 1000 for each increase in one pH unit. The solubility products of In(OH)3 and In2O3 were compared. Equilibration of NPs with synthetic seawater took <18 days, with an average free [In3+] (up to 196 days) of 1.03 amol L−1.

Evaluation of combined addition of nitrite and chloride on the corrosion behavior of steel bars in modified magnesium oxysulfate cement paste

Magnesium oxysulfate (MOS) cement, a new breed of eco-friendly and carbon-efficient material, boasts exceptional corrosion resistance, especially in harsh environments such as high salt and high humidity. Understanding how it affects the corrosion of steel bars is crucial for its widespread application in coastal concrete engineering. Nitrite-based inhibitors are known for their rust-preventing qualities in cementitious materials. However, more research is needed to determine if nitrite remains effective in MOS cement mixed with chloride salts. This study focuses on the combined effect of chloride and nitrite salts on the corrosion of steel bars in MOS cement. Methods like corrosion area rate, weight loss rate, natural potential, and electrochemical station are employed to study the corrosion behavior of steel in MOS cement. Microscopic techniques help unravel the influence mechanism of phase composition and microstructure on these materials. Furthermore, the study examines how chloride and nitrite contents affect the concentration of free nitrite and chloride ions in MOS cement paste. The analysis model is also established to compare simple linear adsorption, Langmuir adsorption, and Freundlich adsorption. The results indicate that chloride accelerates steel corrosion, while nitrite slows it down in the environment of mixed chloride and nitrite. In low-chloride environments, nitrite content has minimal impact on steel corrosion, but its effect becomes more pronounced in high-chloride settings. The MOS cement mixed with chloride and nitrite primarily consists of Mg(OH)2, MgCl2, MgCO3, MgO, and the 5Mg(OH)2·MgSO4·7 H2O (517 phase). The phase content of passive film on the surface of steel bar is composed primarily of Fe2O3, FeO, Fe, and FeOOH in descending order. As nitrite content increases, the absorption and concentration of free nitrite ions in the MOS cement paste gradually rise, exhibiting a linear trend. Based on the fitting calculations for three distinct adsorption relationships, notably, due to the limited adsorption capacity of MOS cement for nitrite, there's a considerable difference between the simple linear adsorption relationship and the two nonlinear adsorption models in high nitrite environments. However, in low nitrite concentrations, the difference among these three fitting adsorption relationships is little. This research can provide theoretical basis for enhancing the corrosion resistance and durability of coastal concrete engineering with high chloride exposure.

Microstructure and chloride transport of aeolian sand concrete under long-term natural immersion

Abstract River sand was consumed in large quantities, and alternatives to river sand were urgently needed. There are a large number of natural resources of aeolian sand in western China. Aeolian sand was prepared into aeolian sand concrete (ASC). It can greatly reduce the consumption of river sand and inhibit the process of desertification to protect the environment. ASC is a new type of concrete material prepared by using aeolian sand as fine aggregate. To clarify the chloride ion transport behaviour in the ASC under long-term natural immersion, the aeolian sand was 100% substituted for the river sand to prepare the full ASC with three water–binder ratios. The ASC was naturally immersed in 3 and 6% NaCl solutions for a long time, and nuclear magnetic resonance and microscopic scanning electron microscopy techniques were used. The change rule of chloride ion content at different depths of the ASC was studied, and its microstructure characteristics under different erosion times were analysed. The results showed that the free chloride ion concentration at different depths of the ASC increased with increasing water–binder ratio, immersion time, and chloride concentration. After soaking in the salt solution, the hydration products in the ASC reacted with chloride ions to form Friedel salt, which filled the internal pores and microcracks of the ASC, improved its interface transition zone structure, and increased the compactness of the test piece. The porosity of the three groups of ASC with different water–binder ratios decreased by 0.95, 1.03, and 1.15% after soaking in 6% salt solution for 12 m. To study the diffusion law of chloride ions in ASC, combined with influencing factors such as temperature, humidity, D value, deterioration effect and chloride ion combination, Fick’s second law was modified, and a chloride ion diffusion model of ASC with high accuracy was established, with a fitting correlation number above 0.93, which provided a reference for the research and application of ASC in saline areas.