Hydrated Magnesium Carbonate Research Articles

Facile Synthesis of Low-Dimensional and Mild-Alkaline Magnesium Carbonate Hydrate for Safe Multiple Protection of Paper Relics

Paper-based cultural relics inevitably face a variety of diseases such as acidification, yellowing, and strength loss during long-term preservation, where weakly alkaline inorganic materials play an important role in their deacidification treatments. In this work, by simply adjusting the supersaturation of crystal growing solution without the use of any organic additives, one-dimensional (1D) and two-dimensional (2D) weakly alkaline materials—magnesium carbonate hydrates (MCHs)—were controllably synthesized. It is worth noting that the coatings of 1D/2D MCHs not only cause little change in chromatic aberration and water wettability, but also ensure their safety for alkali-sensitive pigments. Meanwhile, the deacidification, anti-aging, strength-enhancing, and flame-retardant effects of these materials have been tested on ancient book papers, all of which achieved good protective effects. In contrast, 1D MCH materials brought about significant enhancement in both mechanical strengths and flame-retardant effects, and the related effects were investigated. Based on this facile micromorphology control strategy, more low-dimensional nanomaterials are expected to be synthesized by design for the protection of paper-based relics, which will expand our knowledge on functional deacidification and protection mechanisms.

Production of Magnesium Dilactate through Lactic Acid Fermentation with Magnesium Carbonate.

Magnesium dilactate is increasingly sought after for its applications in the pharmaceutical, food, and dietary supplement industries due to its essential role in various physiological processes. This study explores a sustainable method for synthesizing magnesium dilactate through lactic acid fermentation using tomato juice, coupling the neutralization of lactic acid with hydrated magnesium carbonate hydroxide. Utilizing the lactic acid bacteria Lactobacillus paracasei and Lactobacillus plantarum, fermentation was optimized in a 50% diluted MRS medium supplemented with glucose and tomato juice supplemented with glucose, yielding a maximum lactate concentration of 107 g/L. Notably, fermentation in diluted media proved more effective than in undiluted tomato juice, highlighting the inhibitory effects of certain organic compounds and the physical nature of the original tomato juice. Post-fermentation, magnesium lactate was crystallized, achieving high recovery rates of up to 95.9%. Characterization of the product through X-ray diffraction and scanning electron microscopy confirmed its crystalline purity. This research underscores the viability of tomato juice as a fermentation substrate, promoting the valorization of agricultural by-products while providing an eco-friendly alternative to traditional chemical synthesis methods for magnesium dilactate production.

Dense Hydrated Magnesium Carbonate MgCO3·3H2O Phases.

The study of the structural stability of carbonates under different pressure and temperature conditions is important for modeling the carbon budget in the Earth's interior and the stability of carbonation products of carbon capture and storage (CCS) solutions. In this work, we confirm the existence of the two dense polymorphs of the hydrated magnesium carbonate MgCO3·3H2O nesquehonite mineral previously reported, and we characterize their structures using synchrotron single-crystal X-ray diffraction at 3.1 and 11.6 GPa. Phase transitions entail the distortion and atomic rearrangement of the Mg-centered polyhedra and the tilting of the [CO3] carbonate units. In particular, the Mg coordination number increases from 6 in nesquehonite to 7 in the second high-pressure phase, while maintaining a topology based on complex MgCO3(H2O)2 chains. We also studied their vibrational behavior upon compression using Raman spectroscopy and complemented the experimental results with density-functional theory (DFT) calculations. The role played by hydrogen bonds in the compressibility and the polymorphism of this hydrated carbonate is also discussed.

Biomimetic mineralization of hydrated magnesium carbonate for hydrogel reinforcement and heavy metal adsorption

With excessive Mn(Ⅱ) and Cu(Ⅱ) pollution in aquatic environments posing potential health risks to inhabitants, the emergence of carbon capture, utilization and storage (CCUS) technology has promoted the improvement of heavy metal remediation technologies. Using hydrothermal sediment as a crystal seed, rhamnolipid was used to mediate biomimetic mineralization to prepare hydrated magnesium carbonate (HMC) composites to enhance the Mn(Ⅱ)/Cu(Ⅱ) adsorption performance of alginate hydrogels. Hydrothermal sediment is beneficial for accelerating biomimetic mineralization, while rhamnolipid can induce a crystalline phase transformation from dypingite to nesquehonite. The addition of sediment significantly enhanced the compressive mechanical properties and thermal stability of the hydrogels. The adsorption performances of the nesquehonite and dypingite hydrogels were better for Mn(II) and Cu(II), respectively. An increase in the amount of sediment improved the adsorption of Cu(II) by the hydrogels appropriately, resulting in stronger selectivity for Cu(II). The adsorption of Mn(II) and Cu(II) on the hydrogel beads was thermodynamically spontaneous. The inhibitory effects of sodium dodecyl benzene sulfonate (SDBS), fulvic acid (FA) and alginate on Cu(II) adsorption were more obvious than those of bovine serum albumin (BSA). Both the complexation of functional groups on alginate and mineralization by HMC participated in the adsorption of Mn(II) and Cu(II).

Mechanisms of enhancing MgO for stabilization/solidification of Pb-contaminated red clay through CO2 sequestration

Pb-contaminated soil poses significant environmental and health risks as well as soil stability issues. Research on sandy soils highlights CO2-enhanced reactive MgO as a promising solution for improving the solidification of Pb-contaminated soils. However, carbonation effects can differ markedly between soil types owing to varying soil properties. In this study, we evaluated the effects of CO2-enhanced reactive MgO on the engineering and environmental characteristics of Pb-contaminated red clay and explored its mechanism of carbonation solidification. The results showed that CO2-enhanced reactive MgO increased the strength of Pb-contaminated red clay to over 3 MPa within 1 h, which was approximately 25 times the strength of untreated soil (0.2 MPa) and significantly higher than that of reactive MgO-treated, uncarbonated soil (0.8 MPa). The pH of the carbonated soil (9–10) facilitated Pb2+ immobilization, and the increase over the initial parameter elevated the electrical conductivity value. Moreover, CO2-enhanced reactive MgO reduced the Pb2+ leaching concentration to below 0.1 mg/L, even at high Pb concentrations (10,000 mg/kg). Pb2+ transformed into lead carbonates during the carbonation process, with the hydrated magnesium carbonates forming a dense internal structure. This solidification mechanism included chemical precipitation, physical adsorption, and encapsulation. Notably, the carbonation time should be controlled within 1 h to prevent soil expansion. Together, these findings support the potential of CO2-enhanced reactive MgO for efficient and low-carbon application in the solidification of Pb-contaminated red clay.

New insights into chitosan-induced biomimetic mineralization of hierarchical spherical nesquehonite: Characterization, DFT calculations and construction mechanism

Recently, CO2 mineralization with magnesium salts is a cost-effective method for CO2 utilization and sequestration. The obtained hydrated magnesium carbonate can serve as high-value added functional materials. Inspired by biomineralization, nesquehonite (NSQ) was prepared via chitosan-induced mineralization of MgCl2-(NH4)2CO3, achieving indirect mineralization of CO2. The effects of chitosan (CTS) addition, reaction temperature, and reaction time on the phase composition and micromorphology of the products were systematically investigated. When the chitosan addition was 2%, the reaction temperature was 60℃, and the reaction time was 300 min, the obtained product was hierarchical spherical NSQ with an average diameter of 10 μm. The construction mechanism of the hierarchical spherical NSQ was elucidated. Zeta potential and 1H NMR analyses indicated the interaction of CTS with Mg2+, binding Mg2+ through –OH and –NH2 groups, thereby prolonging the nucleation and growth process of NSQ. FT-IR, XPS, TEM, and AFM analyses revealed that CTS induced directional growth of nanosheets by chemisorption on the crystal surface. Ultimately, through CTS bridging, the nanosheets aggregated and assembled into NSQ sphere. DFT calculations further indicated that CTS forms Mg-O and Mg-N bonds with Mg2+ and that there are Mg-O, Mg-N bonds and hydrogen bonding interactions between CTS and NSQ. This work provides new insights into the preparation of hierarchical NSQ via a biomimetic mineralization mechanism. Additionally, NSQ with a multiscale hierarchical structure has a promising future in the fields of adsorbents, templating agents, and drug carriers.

Innovative MOS-based fiber cement boards: Effect of kraft pulp mills waste and curing by accelerated carbonation

The increasing global waste generated by industrial activities poses significant environmental challenges. Eco-waste management emerges as an economically viable solution for converting, valorizing, and repurposing these byproducts, aligning with circular economy principles, and aiming to reduce greenhouse gas emissions. Construction, known for its unsustainability due to high energy consumption, non-renewable resource utilization, waste generation, and greenhouse gas emissions, particularly from cement production, has led to the exploration of alternative materials. Magnesium oxide (MgO)-based cement, an alternative to Ordinary Portland Cement (OPC), has gained attention, leveraging Brazil's prominence as a major magnesite producer. This study explores the valorization of waste from kraft pulp mills of the paper industry, specifically lime sludge (LS) and lime slaker grits (grits), to produce magnesium oxysulfate (MOS)-based fiber cement boards. The effect of accelerated carbonation on cementitious composites produced with formulations containing grits and LS was investigated. Replacing 25% of the limestone with grits showed no noticeable differences in the properties of the boards, and MOR values close to 11.17 MPa were obtained. However, the physical-mechanical performance showed a decrease with the use of LS and higher concentrations of grits, associated with Na2SO4.XH2O formation in the system and ITZ structure formed around the aggregated particle, respectively. Carbonation in a saturated atmosphere led to the carbonation of the 5–1–7 phase, which was related to the decrease in mechanical strength of the boards after the curing process. The thermal decomposition of the Hydrated Magnesium Carbonates (HMCs) formed during accelerated carbonation corroborated with the changes in the physical properties of the composites, demonstrating that the carbonation products are formed within the voids and pores of the material and contribute to the reduction in water absorption of the boards.

Safety evaluation of synthesized magnesium carbonate hydrate particles following inhalation exposure

Numerous fine particles or mist from environmental substances significantly contribute to human beings, affecting health issues for both humans and the environment by irritating the respiratory system. To achieve scarcity of information regarding exposure routes and the relationship between substance and health effects needs to be investigated more. Here, we investigated flame retardants (FRs): magnesium carbonate was synthesized, and its inhalation toxicity was examined for the first time by applying it to Sprague-Dawley rats using a mist aerosol-supplying chamber condition. The synthesized magnesium carbonate was fully physiochemically characterized, exhibiting a mesoporous sheet-like morphology, size distribution of 4.971 ± 2.363 μm, the dypingite phase, a surface area of 10.718 m² g−1, and a pore volume of 0.051 cm³ g−1. As a result of the inhalation toxicity study, the 50% lethal concentration (LC50) of magnesium carbonate was determined to be equal to or greater than 1.91 mg m−3. Microscopic examination for assessing pulmonary residue levels of magnesium carbonate reveals the presence of residues in the lungs up to 3 days post-administration. However, over time, there is a gradual decrease of pulmonary residues, and by the 14th day of administration, it is regarded that no residual presence is observable within the pulmonary system.

Autogenous healing of the interface between hollow natural fiber (HNF) and reactive magnesia cement (RMC) matrix

The fiber-matrix interface healing determines the restoration of tensile strength of fiber reinforced cementitious composites (FRCCs). This work first-timely investigates the autogenous healing of debonded interface between hollow natural fiber (HNF) and reactive magnesia cement (RMC) matrix and subsequent tensile strength recovery. HNF-RMC single-fiber specimens are preloaded to induce interfacial debonding, and then conditioned under water-air cycles for healing. The healing-induced recovery of the interfacial properties in the HNF-RMC group are significantly higher than the control PVA-RMC and PVA-PC groups. Tensile test of notched FRCCs demonstrated that the tensile strength of HNF-RMC can be more than doubled after cracking-healing, and its healing efficiency is around 50% higher than that of PVA-PC and PVA-RMC. Based on microstructural characterization in situ and finite element modeling, the increased healing degree is attributed to two new mechanisms related to the special porous microstructure of HNF. First, the lumens and micropores within cell of HNF can be the pathway for CO2 and water penetration, which promotes the formation of healing products (e.g., hydrated magnesium carbonates) within fiber-matrix interface and hence the recovery of chemical and frictional bonds. Second, the healing products formed within lumens caused lateral fiber expansion, and thus prominently enhanced the frictional bond.

Production of low-carbon amorphous SiO2 for use as a supplementary cementitious material and nesquehonite from olivine

Amorphous silica and hydrated magnesium carbonate (nesquehonite, MgCO3·3H2O) have been produced by acid dissolution of olivine ((Mg,Fe)2·SiO4). The amorphous silica is a viable supplementary cementitious material, and the formation of nesquehonite by carbonation, results in a carbon negative process. Using the amorphous silica as a supplementary cementitious material produces low-carbon cement. The global reserve of olivine makes this a viable route to producing low-carbon concrete.

Polymorphism and Phase Stability of Hydrated Magnesium Carbonate Nesquehonite MgCO3·3H2O: Negative Axial Compressibility and Thermal Expansion in a Cementitious Material.

The P-T phase diagram of the hydrated magnesium carbonate nesquehonite (MgCO3·3H2O) has not been reported in the literature. In this paper, we present a joint experimental and computational study of the phase stability and structural behavior of this cementitious material at high-pressure and high-temperature conditions using in situ single-crystal and synchrotron powder X-ray diffraction measurements in resistive-heated diamond anvil cells plus density functional theory calculations. Our results show that nesquehonite undergoes two pressure-induced phase transitions at 2.4 (HP1) and 4.0 GPa (HP2) at ambient temperature. We have found negative axial compressibility and thermal expansivity values, likely related to the directionality of the hydrogen bonds. The equations of state of the different phases have been determined. All the room-temperature compression effects were reversible. Heating experiments at 0.7 GPa show a first temperature-induced decomposition at 115 °C, probably into magnesite and a MgCO3·4H2O phase.

Characterization of hydrated magnesium carbonate materials with synchrotron radiation-based scanning transmission X-ray spectromicroscopy

Soft X-ray spectromicroscopy reveals the evolution of different phases in the formation of green alternative cements.

Removing copper ion from wastewater by surface precipitation using novel hierarchical hydrated magnesium carbonate crystal

It is significant to develop a low-cost, easy-to-separate and efficient adsorbent to remove heavy metals from wastewater. Therefore, the hierarchical hydrated magnesium carbonate (HMC) crystal is prepared. The performances of HMC crystal at different adsorption conditions are studied. The surfaces of HMC crystal before and after Cu2+ adsorption are characterized by XRD, FTIR, XPS, SEM and EDS mapping. The removal efficiency of Cu2+ reaches 99 % under the conditions of an initial concentration of 300 mg/L, HMC dosage of 0.5 g/L, pH value of 4.5 and adsorption time of 180 min. The adsorption kinetic and isotherm can be described by the pseudo-second-order model and Langmuir adsorption model, respectively. The maximum adsorption capacity of Cu2+ is 1406 mg/g. The hierarchical structure provides HMC crystal with sufficient hydroxide ions for Cu2+ surface precipitation and large particle size (40–100 μm) for subsequent solid–liquid separation, presenting a promising application prospect in the future.

MgO‐based binders

AbstractTo limit global temperature rise to below 2°C, we need to radically and rapidly change the way we build and use materials, since construction is responsible for 20‐40% of industrial CO2 emissions. Magnesium carbonate‐based cements have the potential to become a major carbon sink in construction industry, as CO2 will not be emitted during their production, but CO2 will rather be bound during hardening. Two different reaction mechanisms lead to setting and hardening of such HMC cements: i) hydration of MgO‐Mg‐carbonate, also in blends with silica and other mineral additions, in the presence of water or salt solutions (such as sodium bicarbonate solution) at ambient conditions or ii) carbonation hardening of MgO‐based systems at increased CO2 partial pressure and/or at increased temperatures.However, the utilization of hydrated magnesium carbonate and magnesium silicate cements is currently hampered by the lack of systematic experiments and of fundamental understanding of the factors affecting the hardening process, mechanical properties, long‐term behavior and durability. In particular, the role of temperature, relative humidity and addition of supplementary cementitious materials and/or industrial by‐products has not been systematically investigated. We need knowledge both on the practical side through systematic experiments with pastes, mortars and concretes as well as on a fundamental level through solubility and sorption experiments and thermodynamic modelling. In addition, reaction kinetics need to be optimized as well as the early formation of the preferred phases (stability enhancement) to develop efficient HMC cements for construction. Due to the socio‐economic relevance of cement and concrete, the impact of such “carbon”‐negative cements may go beyond a purely scientific one and lead to technological breakthroughs to the benefit of environment and society.

Stacking faults of the hydrous carbonate-containing brucite (HCB) phase in hydrated magnesium carbonate cements

Recently, a hydrous carbonate-containing brucite (HCB) with an approximate composition of MgCO3·35 Mg(OH)2·H2O was postulated as hydration product of binders based on mixtures of reactive magnesia and hydromagnesite (Mg5(CO3)4(OH)2·4H2O). X-ray diffraction showed that the 001 reflection of this phase was split into two reflections at 20 °C, whereas at 60 °C only one reflection occurred. Rietveld refinement revealed that the X-ray pattern of the HCB-phase could be fitted well when a random displacement (stacking faults) and a movement of the layers in x, y and z direction were allowed. The presence of water and/or carbonate leads to different distances between the layers, thus causing the splitting of the 001 reflection. At 60 °C, only carbonate is included in the brucite structure, leading to a similar distance between all brucite layers. The assignment of the additional reflection appearing at 20 °C to a separate, unknown hydrated magnesium carbonate, as suggested in earlier studies, can be excluded.

Influence of nesquehonite seeds on hydration and carbonation of reactive magnesia cement

Among all carbonation products of reactive magnesia cement (RMC), nesquehonite exhibited the highest CO2 amount of sequestration per molar. Inducing the nesquehonite formation may improve the CO2 sequestration capacity of RMC. In this paper, nesquehonite seeds were introduced to promote the formation of nesquehonite in RMC. The performances of RMCs with 0%, 0.5%, 1%, 1.5% and 2% nesquehonite seeds were studied and compared with that of RMC mixed with hydromagnesite seeds. It was found that the hydration of RMC could be facilitated by nesquehonite seeds, resulting in reduced setting times. The nucleation effect of nesquehonite seeds was demonstrated, resulting in increased nesquehonite formation and carbonation degree. Nesquehonite seeds combined with hydration agent can further promote the compressive strength of RMC through forming more amounts of nesqeuhonite crystals and amorphous hydrated magnesium carbonates. Compared with the hydromagnesite seeds, the nesquehonite seeds showed a more significant increase in the CO2 sequestration capacity of RMC.

Role of magnesium acetate in hydration and carbonation of magnesium oxide-based cements

MgO-based cements have the potential for low carbon binders especially when MgO is sourced from non‑carbonate minerals. Understanding the reaction kinetics and products formed are the keys to pave the way for these binders as construction materials. In this study, the influence of acetate on hydration and subsequent carbonation of reactive MgO is investigated. MgO hydrated in Mg-acetate solution of various concentrations (0 to 0.5 M) and CO2 cured afterward was characterized at different reaction times. Magnesium acetate in addition to enhancing the hydration kinetics modifies the morphology and crystallinity of the precipitated brucite. Acetate also influences the carbonate phases formed when samples are cured with CO2. Giorgiosite, a lesser-known hydrated magnesium carbonate, was formed in the presence of acetate, while the control specimens prepared with neat water produced nesquehonite. The findings reported here give insights into the use of organic additives in improving the reaction kinetics of MgO and the possibility to tune the formation pathways of different magnesium carbonates.

Rare Hydrated Magnesium Carbonate Minerals Nesquehonite and Dypingite of the Obnazhennaya Kimberlite Pipe, in the Yakutian Kimberlite Province

The result of a complex mineralogical study of the first discovery of the rare hydrated magnesium carbonate minerals of Nesquehonite and Dypingite in the Obnazhennaya kimberlite pipe (of the Yakutian kimberlite province) is presented. The methods of X-ray phase analysis, electronic microscopy, and Raman spectroscopy have established that the main minerals of the samples found in the form of white crust on a small area of rock outcrop of kimberlite breccia are hydrated carbonates: Nesquehonite is MgCO3•3H2O, Dypingite is Mg5(CO3)4(OH)2•5H2O. The formation of Dypingite over Nesquehonite was shown using Raman imaging for the first time. Nesquehonite is represented as aggregates consisting of chaotically oriented prismatic crystals or kidney-shaped formations. Dypingite in the examined samples appears less frequently as rose-shaped aggregates formed from lamellar crystals. It is assumed that the formation of rare carbonates of the Obnazhennaya kimberlite pipe is mainly the result of the weathering of silicates, formation of mineralized solutions, and their subsequent crystallization, including the capture of CO2 from the air.

Influence of particle size distribution on biocarbonation method produced microbial restoration mortar for conservation of sandstone cultural relics

Biocarbonation of reactive magnesia based on microbially induced carbonate precipitation (MICP) process is a sustainable geotechnical reinforcement technology for strength development and permeability reduction. This method can be used to produce microbial restoration mortar (MRM) for the application of stone cultural relics restoration. In this paper, the influence of particle size distribution on the strength and porosity of MRM was examined. By mixing fine and coarse sandstone powder in various proportions, nine different particle size distributions were obtained to investigate the restoration performance, including the unconfined compressive strength (UCS), porosity, and color difference. The results indicate that the well-graded particle size distribution can lead to the UCS improvement and porosity reduction of MRM. The findings also imply that adding fine sandstone powder to the coarse sandstone powder can provide extra bridging contacts within the soil matrix. These bridging contacts can be easily connected by the precipitated hydrated magnesium carbonates (HMCs) minerals, consequently resulting in more effective bonding and filling within the pore matrix. The microstructural images of MRM confirm the formation of HMCs, which exhibited a dense network structure, filling out the gap and bonding the sandstone powders. Furthermore, the microbial restoration mortar showed a high weather resistance to dry-wet cycles, acid rain, and salt attack, which is attributed to better stability and strength of HMCs than the original calcic cemented minerals in sandstone.

Influence of Carbonation on the Properties of Steel Slag-Magnesium Silicate Hydrate (MSH) Cement.

Magnesium silicate hydrate (MSH) cement has the advantages of low energy consumption, minimal environmental pollution, carbon negativity, and reduced alkalinity, but excessive drying shrinkage inhibits its application. This paper analyzed the influence of steel slag (SS) dosage, carbon dioxide partial pressure, and carbonation curing time on the compressive strength, shrinkage rate, and phase composition of MSH cement. Various analysis methods, including X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and mercury intrusion porosimetry (MIP), were used to study the hydration products and microstructure. The results showed that under normal curing conditions, MSH cement mixed with different steel slag contents experienced a decline in strength at all ages. However, the greater the amount of SS incorporated, the lesser the degree of drying shrinkage. The compressive strength of all groups was improved, and the drying shrinkage was reduced by carbonation treatment. The samples with 5%, 10%, and 15% SS content exhibited shrinkage rates of 2.19%, 1.74%, and 1.60%, respectively, after 28 days of curing. The reason was that after carbonation treatment, hydrated magnesium carbonates (HMCs) were generated in the SS-MSH cement, and a Ca-Mg-C amorphous substance formed by hydration and carbonation of C2S in steel slag filled in the pores, which enhanced the density of the matrix, improved the compressive strength of the specimen, and reduced the shrinkage rate.