Dissolution-precipitation Reactions Research Articles

The role of sulfate in the hydrothermal replacement of aragonite single crystals by calcite

Aragonite (CaCO3) is a stable calcium carbonate phase under high pressure conditions. However, its formation in (sub)surface environments, where calcite is the stable polymorph, is widespread. Regardless of its origin, aragonite is expected to undergo transformation into calcite under moderate pressures and temperatures. However, this transformation does not always take place, which results in the presence of abundant aragonitic relics in the geological record. Traditionally, this preservation has been explained by the presence of chemical inhibitors that prevent the conversion of aragonite to calcite. While it is widely accepted that magnesium (Mg) plays a key role in the polymorphic selection of CaCO3, the influence of other ions has also been suggested. This work evaluates the effect that different concentrations of sulfate (SO42−) in the fluid has on the progress of the aragonite-to-calcite transformation at 220 °C. Our results show that, upon reaction with deionized water or sulfate-poor solutions ([SO42−]aq < 0.1 mM), aragonite single crystals are extensively replaced by calcite aggregates (crystal size > 15 µm) through an interface coupled dissolution-precipitation reaction. The replacement starts at the aragonite crystal surfaces and advances inwards thanks to the development of an extensive network of fractures. Contrarily, when the solution bears higher concentrations of sulfate ([SO42−]aq > 0.1 mM), only a thin layer of smaller crystals of calcite (< 10 µm) form on the aragonite substrates, without any further transformation taking place. We interpret that these smaller crystals exert too little crystallization pressure and fail to promote the development of a network of fractures. In the absence of this network, the aragonite-calcite transformation cannot take place. The transformation does not occur neither when the experiments are conducted with deionized water and fragments of gypsum or anhydrite together with the aragonite grains. The results of this study shed light on the influence of dissolved sulfate in the kinetics of the fluid-driven transformation of aragonite into calcite. These results are useful to understand the preservation of aragonite in a variety of current geological settings and provide valuable insights for better understanding the diagenesis of sedimentary carbonates.

Shannon entropy of transport self-organization due to dissolution–precipitation reaction at varying Peclet numbers in initially homogeneous porous media

Abstract. Dissolution and precipitation processes in reactive transport in porous media are ubiquitous in a multitude of contexts within the field of Earth sciences. In particular, the dynamic interaction between the reactive dissolution and precipitation processes and the solute transport is of interest as it is capable of giving rise to the emergence of preferential flow paths in the porous host matrix. It has been shown that the emergence of preferential flow paths can be considered to be a manifestation of transport self-organization in porous media as these create spatial gradients that distance the system from the state of perfect mixing and allow for a faster and more efficient fluid transport through the host matrix. To investigate the dynamic feedback between the transport and the reactive processes in the field and its influence on the emergence of transport self-organization, we consider a two-dimensional Darcy-scale formulation of a reactive-transport setup, where the precipitation and dissolution of the host matrix are driven by the injection of an acid compound, establishing local equilibrium with the resident fluid and an initially homogeneous porous matrix, composed of a calcite mineral. The coupled reactive process is simulated in a series of computational analyses employing the Lagrangian particle-tracking (LPT) approach, capable of capturing the subtleties of the multiple-scale heterogeneity phenomena. We employ the Shannon entropy to quantify the emergence of self-organization in the field, which we define as a relative reduction in entropy compared to its maximum value. Scalability of the parameters, which characterize the evolution of the reactive process, with the Peclet number in an initially homogeneous field is derived using a simple one-dimensional ADRE model with a linear adsorption reaction term and is then confirmed through numerical simulations, with the global reaction rate, the mean value, and the variance of the hydraulic-conductivity distribution in the field all exhibiting dependency on the reciprocal of the Peclet number. Our findings show that transport self-organization in an initially homogeneous field increases with time, along with the emergence of the field heterogeneity due to the interaction between the transport and reactive processes. By studying the influence of the Peclet number on the reactive process, we arrive at a conclusion that self-organization is more pronounced in diffusion-dominated flows, characterized by small Peclet values. The self-organization of the breakthrough curve exhibits the opposite tendencies, which are observed from the perspective of a thermodynamic analogy. The hydraulic power, required to maintain the driving head pressure difference between the inlet and outlet of the field, was shown to increase with the increasing variance, as well as with the increasing mean value of the hydraulic-conductivity distribution in the field, using a simple analytic model. This was confirmed by numerical experiments. This increase in power, supplied to the flow in the field, results in an increase in the level of transport self-organization. Employing a thermodynamic framework to investigate the dynamic reaction–transport interaction in porous media may prove to be beneficial whenever the need exists to establish relations between the intensification of the preferential flow path phenomenon, represented by a decline in the Shannon entropy of the transport, with the amount of reaction that occurred in the porous medium and the change in its heterogeneity.

Tuning the solubility of polysulfides for constructing practical lithium-sulfur battery

Li-S batteries are regarded as one of the most promising candidates for next-generation battery systems with high energy density and low cost. However, the dissolution-precipitation reaction mechanism of the sulfur (S) cathode enhances the kinetics of the redox processes of the insulating sulfur, which also arouses the notorious shuttle effect, leading to serious loss of S species and corrosion of Li anode. To get a balance between the shuttle restraining and the kinetic property, a combined strategy of electrolyte regulation and cathode modification is proposed via introducing 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoroprpyl ether (HFE) instead of 1,2-dimethoxyethane (DME), and SeS7 instead of S8. The introduction of HFE tunes the solvation structure of the LiTFSI and the dissolution of intermediate polysulfides with Se doping (LiPSSes), and optimize the interface stability of the Li anode simultaneously. The minor Se substitution compensates the decrease in kinetic due to the decreased solubility of LiPSs. In this way, the Li-SeS7 batteries deliver a reversible capacity of 1062 and 1037 mAh g−1 with 2.0 and 5.5 mg SeS7 cm−2 loading condition, respectively. Besides, an electrolyte–electrode loading model is established to explain the relationship between the optimal electrolyte and cathode loading. It makes more sense to guide the electrolyte design for practical Li-S batteries.

Microstructural and isotopic analysis of shocked monazite from the Hiawatha impact structure: development of porosity and its utility in dating impact craters

U–Pb geochronology of shocked monazite can be used to date hypervelocity impact events. Impact-induced recrystallisation and formation of mechanical twins in monazite have been shown to result in radiogenic Pb loss and thus constrain impact ages. However, little is known about the effect of porosity on the U–Pb system in shocked monazite. Here we investigate monazite in two impact melt rocks from the Hiawatha impact structure, Greenland by means of nano- and micrometre-scale techniques. Microstructural characterisation by scanning electron and transmission electron microscopy imaging and electron backscatter diffraction reveals shock recrystallisation, microtwins and the development of widespread micrometre- to nanometre-scale porosity. For the first time in shocked monazite, nanophases identified as cubic Pb, Pb3O4, and cerussite (PbCO3) were observed. We also find evidence for interaction with impact melt and fluids, with the formation of micrometre-scale melt-bearing channels, and the precipitation of the Pb-rich nanophases by dissolution–precipitation reactions involving pre-existing Pb-rich high-density clusters. To shed light on the response of monazite to shock metamorphism, high-spatial-resolution U–Pb dating by secondary ion mass spectrometry was completed. Recrystallised grains show the most advanced Pb loss, and together with porous grains yield concordia intercept ages within uncertainty of the previously established zircon U–Pb impact age attributed to the Hiawatha impact structure. Although porous grains alone yielded a less precise age, they are demonstrably useful in constraining impact ages. Observed relatively old apparent ages can be explained by significant retention of radiogenic lead in the form of widespread Pb nanophases. Lastly, we demonstrate that porous monazite is a valuable microtexture to search for when attempting to date poorly constrained impact structures, especially when shocked zircon or recrystallised monazite grains are not present.

Pb Removal Efficiency by Calcium Carbonates: Biogenic versus Abiogenic Materials.

The sorption of heavy metals on mineral surfaces plays a key role in controlling the fate and bioavailability of harmful elements through dissolution-precipitation reactions. Here, we investigate the efficiency of Pb removal from highly contaminated waters by two calcium carbonate hard tissues, scallop shells (up to 99.9 mol %; -biocalcite) and cuttlefish bones (up to 90.0 mol %; bioaragonite), which template the precipitation of the highly insoluble mineral cerussite (PbCO3). The experiments show that both biomaterials are about five times more effective Pb scavengers (5 mmol of cerussite precipitated/g sample) than their inorganic counterparts (∼1 mmol/g). We relate this enhanced Pb scavenging capacity of biocarbonates to their composite organic-inorganic nature, which modulates their specific nano- and microstructural features and defines their larger surface areas, solubility, and reactivity compared to those of their inorganic counterparts. The oriented growth of cerussite progressively passivates the bioaragonite surface, reducing its long-term Pb scavenging capacity. In contrast, the randomly oriented growth of cerussite crystals on biocalcite prevents surface passivation and explains why biocalcite outperforms bioaragonite as a long-term Pb scavenger. The use of biocarbonates could be a key for designing more efficient decontamination strategies for heavy metal-polluted waters.

Ant-nest type porous scaffold with micro-struts consisting of carbonate apatite for promoting bone formation and scaffold resorption.

Scaffolds having appropriate mechanical strength and providing a proper microenvironment for osteogenesis are expected to be effective alternatives to autografts for bone regeneration. In this study, ant-nest type porous (ANP) scaffolds consisting of CO3 Ap were fabricated using calcium carbonate powder or slurry and two types of polyurethane foam through a dissolution-precipitation reaction. ANP-type, three-dimensional, interconnected porous CO3 Ap scaffolds were fabricated by burning out the struts of polyurethane foams embedded in CaCO3 , followed by compositional transformation from CaCO3 to CO3 Ap. The types of polyurethane foam and impregnation methods of CaCO3 into polyurethane form affected the geometry of the resulting ANP structures. Mechanical and in vivo biological performances of these scaffolds relied on the geometry of the ANP structures. The ANP structures displayed had a clear structural advantage in bone regeneration, owing to the promotion of cell and tissue migration throughout the scaffolds. In particular, ANP-structured scaffolds, which had highest porosity, interconnectivity, and smallest strut thickness, had a mechanical strength comparable to cancellous bone, formed more new bone, were highly resorbed, resulting in cancellous bone-like bone tissue regeneration at 12 weeks of healing. The results suggest that bone regeneration after the migration of cell and tissue into the entire scaffolds is affected by strut thickness preferentially over porosity and interconnectivity. ANP-structured CO3 Ap scaffolds are attractive for bone regeneration.

Modeling the Coulombic Efficiency of the Aqueous Iron Electrode

The aqueous iron electrode is attractive for large-scale energy storage because of its long life and low materials cost. The redox potential of the Fe ↔ Fe2+ reaction is approximately 50 mV negative of that of the hydrogen evolution reaction. Hydrogen evolution therefore causes self discharge of the iron electrode during rest and competes with the iron reaction during charge. Here we model the effect of electrode design and cell operation on the coulombic efficiency of charging the iron electrode at modest charging rates (<C/20). Kinetic parameters (exchange current density and transfer coefficients) for the iron dissolution-precipitation reaction and for the hydrogen evolution reaction are estimated from experimental measurements of electrode overpotential and hydrogen generation rate. The volume change from Fe(OH)2 to Fe metal results in a significant increase in porosity during charge and results in change in electrochemically active surface area. The porous-electrode model includes transport in the electrolyte, Butler-Volmer kinetics, and change in volume and surface area.The model provides a theoretical explanation for experimental observations that coulombic efficiency decreases with decreasing charge rate, and that coulombic efficiency is lower in thicker electrodes. We then use the model to explore the impact for large-format cells of electrode size and design on coulombic efficiency.

Mass Transfer Analysis of CO2-Water-Rock Geochemical Reactions in Reservoirs

It is difficult to exploit low-permeability reservoirs, and CO2 flooding is an effective method to improve oil recovery from low permeability reservoirs. However, in the process of CO2 flooding, acidic fluids dissolved in formation water will react with rock to cause dissolution and precipitation, resulting in pores and precipitates, changing the evolution law of seepage channels, destroying formation integrity, and affecting the effect of CO2 oil displacement. The change in rock’s physical properties and the mass transfer law between CO2-water-rock are unclear. This paper considers the coupling effects of seepage, mechanics, and chemistry when CO2 is injected into the formation. The mass transfer model of CO2-water-rock in the geochemical reaction process is established on this basis. The physical properties of the reservoir after CO2 injection are quantitatively studied based on the microscopic mechanism of chemical reaction, and the migration law of solute in the reservoir rock during CO2 flooding under the coupling effects of multiple fields is clarified. The experimental results show that with the increase in reaction time, the initial dissolution reaction of formation rocks will be transformed into a precipitation reaction of calcite, magnesite, and clay minerals. The porosity and permeability of the rocks near the well first increase and then decrease. The far well end is still dominated by dissolution reactions, and the average values of formation porosity and permeability show an upward trend. Although the dissolution reaction of CO2-water-rock can improve the physical properties of reservoir rocks to a certain extent, the mutual transformation of the dissolution reaction and precipitation reaction further exacerbates the heterogeneity of formation pore structure, leading to the instability of CO2 migration, uneven displacement, and destruction of formation stability. The research results of this paper solve the problem of quantitative calculation of physical parameters under the coupling effect of multiple fields after CO2 injection into reservoirs and can predict the changes in formation physical properties, which can provide a certain theoretical basis for evaluating formation integrity and adjusting CO2 injection under the condition of CO2 flooding.

Fabrication of low-crystalline Mg-substituted β-tricalcium phosphate foam via dissolution–precipitation reaction

Fabrication of low-crystalline Mg-substituted β-tricalcium phosphate foam via dissolution–precipitation reaction

A track record of Au–Ag nanomelt generation during fluid-mineral interactions

Recent studies have reported the significant role of Au-bearing nanoparticles in the formation of hydrothermal gold deposits. Despite the ever-increasing understanding of the genesis and stability of Au-bearing nanoparticles, it is still unknown how they behave when exposed to hydrothermal fluids. Here, we study the nanostructural evolution of Au–Ag nanoparticles hosted within Co-rich diarsenides and sulfarsenides of a natural hydrothermal deposit. We use high-resolution transmission electron microscopy to provide a singular glimpse of the complete melting sequence of Au–Ag nanoparticles exposed to the hydrothermal fluid during coupled dissolution–precipitation reactions of their host minerals. The interaction of Au–Ag nanoparticles with hydrothermal fluids at temperatures (400–500 ºC) common to most hydrothermal gold deposits may promote melting and generation of Au–Ag nanomelts. This process has important implications in noble metal remobilization and accumulation during the formation of these deposits.

Chemical characteristics and reactive transport of soil salt ions in frozen soil during the freeze and thaw period

Current researches on estimating soil salt movement during the freeze and thaw period are mainly based on total salt concentration, while ignoring the phase change of multi-component salts. In this study, the potential transport capability of soil water and salt ions in the frozen layer was investigated based on chemical characteristics and solute convection–diffusion theory. Field experiments were implemented to measure the change of total soil water, soil salt and its ion components. The soil water and salt content in liquid and solid phases were calculated by the FREZCHEM model, and then the movement of liquid soil water and soluble salt were simulated by the HYDRUS-1D model. The potential migration capability of soil water and salt components were then estimated by comparing the distribution profiles obtained by HYDRUS-1D and FREZCHEM. The results show that more than 74.5% of Cl, Na and SO4 were in liquid phase, which were less affected by precipitation-dissolution reaction and owned strong mitigation. The liquid soil water, soluble salt and salt ions in the frozen layer tended to decrease at the beginning of the freeze period and increase significantly at the end. The migration direction and quantity of various salt ions were different due to their concentration gradient and diffusion coefficient, causing the larger potential convection and dispersion quantity of Na+, Cl− and SO42- than those of Ca2+, Mg2+ and HCO3–. This study provides a new perspective for soil salt movement in frozen soil in agricultural areas with shallow groundwater table depth.

A frozen oceanic crystal mush

AbstractThe processes driving the evolution of crystal mushes are often documented in complex systems where crystallization, assimilation, magma replenishment and mixing occur concurrently and are generally overprinted by compaction and deformation. Documenting the characteristics of an undisturbed crystal mush is thus of upmost importance; it highlights the initial conditions with which complex crystal mush processes proceed. We here present the structure and composition of an oceanic crystal mush through detailed petro‐structural and chemical study of metre‐scale intrusions from the Mid‐Atlantic Ridge. Textures, bulk‐rock and mineral compositions indicate closed‐system crystallization of primitive melts, undisturbed by dissolution–precipitation reactions and subsequent deformation. These frozen crystal mushes record the simplest possible evolution of small‐scale intrusions and can be used as a baseline to pinpoint the impact of crystal mush processes on the evolution of complex systems. Any divergence from this reference results from processes occurring concomitantly to the progressive closure of the magmatic system.

Fertility Management in Salt Affected Soils under Rice-wheat Cropping System: A Review

Specific soil conditions such as salinity/ alkalinity are considered to be the major global concern causing a serious threat to sustainability of a particular production system. Salt affected soils are mainly characterized by low organic matter content, poor soil fertility with respect to available macro and micronutrients. Therefore, judicious management of nutrients in addition to reclamation of these soils is considered to be the need of an hour for enhancing agricultural productivity while sustaining our resources. The crop response to added nutrients also varies considerably due to their diverse chemical composition and behavior in such soils which in turn affect the precipitation-dissolution reactions and adsorption-desorption kinetics and thereby affecting their availability to crops during growing season. This review paper attempts to review the efficient fertility management techniques in problematic soils particularly the salt affected soils under rice -wheat cropping system.

Warm acidified seawater: a dolomite solution

ABSTRACTThe “dolomite problem” is the product of two distinct observations. First, there are massive amounts of ancient marine limestone (CaCO3) deposits that have been replaced by the mineral dolomite (MgCa(CO3)2). However, recent (Holocene and Pleistocene) marine deposits contain relatively minuscule amounts of dolomite, although the occurrence of small quantities of dolomite is observed in many modern settings, from deep marine to supratidal. Second, low-temperature synthesis of dolomite in laboratory settings has been elusive, particularly in comparison to the ease with which common marine calcium carbonate minerals (aragonite and calcite) can be synthesized. Since low-temperature solid-state diffusion can be discounted as a method for Mg incorporation into calcium carbonate (as it operates on time scales too long to matter), the replacement of CaCO3 by dolomite is one of dissolution followed by precipitation. Therefore, an often overlooked but required factor in the replacement of limestone by dolomite is that of undersaturation regarding the original calcium carbonate mineral during replacement. Such conditions could conceivably be caused by rapid dolomite growth relative to aragonite and calcite dissolution–precipitation reactions, but laboratory studies, modern systems analyses, and observations of ancient deposits all point to this possibility being uncommon because dolomite growth is kinetically inhibited at low temperature. Pressure solution by force of dolomite crystallization is a second possible driver for CaCO3 undersaturation, but requires a confining stress most likely attained through burial. However, based on petrographic observations, significant amounts of ancient dolomite replaced limestone before burial (synsedimentary dolomite), and many such platforms have not suffered any significant burial. Because these possibilities of undersaturation caused by dolomite precipitation and crystal growth can be largely discounted, the undersaturation required for “dolomitization” to proceed is most likely to be externally forced. In modern natural systems, undersaturation and selective CaCO3 dissolution in marine porewaters is very common, even in warm-water environments, being forced by the breakdown of organic matter. Such dissolution is frequently attended, to varying degrees, by precipitation of a kinetically-less-favored but thermodynamically more stable phase of CaCO3. Laboratory studies as well as observations of modern systems show that when undersaturation is reached with respect to all common marine CaCO3 phases, dolomite assumes the role of this kinetically-less-favored precipitate. This degree of undersaturation is uncommon in modern shallow marine pore systems in warm-water settings, but it was more common during times of elevated atmospheric CO2, and ocean acidification. Furthermore, because oxidation of organic matter drives dolomite formation, near-surface organic-rich deposits such as the remains of microbial mat communities, were more predisposed to dolomite replacement in the acidified oceans of the ancient past relative to contemporaneous deposits that contained less organic matter. These observations lend to a more harmonious explanation for the abundance and occurrence of dolomite through time.

Environmental and Mineralogical Controls on Biosignature Preservation in Magnesium Carbonate Systems Analogous to Jezero Crater, Mars.

Jezero Crater on Mars is a paleolacustrine environment where Mg-carbonates may host evidence of ancient life. To elucidate the environmental and mineralogical controls on biosignature preservation, we examined samples from five terrestrial analogs: Lake Salda (Turkey), Lake Alchichica (Mexico), Qinghai-Tibetan Plateau (China), Mg-carbonate playas (British Columbia, Canada), and a mine with fine-grained ultramafic tailings (Yukon, Canada). The mineralogical compositions of the samples varied, yet were often dominated by either aragonite (CaCO3) or hydromagnesite [Mg5(CO3)4(OH)2·4H2O]. Aragonite-rich samples from Alchichica, Mg-carbonate playas, and the ultramafic mine contained an abundance of entombed microbial biomass, including organic structures that resembled cells, whereas hydromagnesite-rich samples were devoid of microfossils. Aragonite often precipitates subaqueously where microbes thrive, thereby increasing the likelihood of biomass entombment, while hydrated Mg-carbonates typically form by evaporation in subaerial settings where biofilms are less prolific. Magnesite (MgCO3), the most stable Mg-carbonate, forms extremely slowly, which may limit the capture of biosignatures. Hydrated Mg-carbonates are prone to transformation via coupled dissolution-precipitation reactions that may expose biosignatures to degradation. Although less abundant, aragonite is commonly found in Mg-carbonate environments and is a better medium for biosignature preservation due to its fast precipitation rates and relative stability, as well as its tendency to form subaqueously and lithify. Consequently, we propose that aragonite be considered a valuable exploration target on Mars.

Geneses of multi-stage carbonate minerals and their control on reservoir physical properties of dolomitic shales

The formation and distribution of carbonate minerals have important influences on reservoir development. The dissolution-precipitation effect plays an important role in controlling the reformation of reservoir physical properties. High-quality source rocks with abundant reserves exist in the Lower Permian Fengcheng Formation, Junggar Basin, China, and the basin reservoir contains a large amount of carbonate minerals. Multi-stage cementation and dissolution of these carbonate minerals have important influences on diagenesis-porosity evolution of the reservoirs. Because of the coupled influences of deep fluid transformation and volcanic activity in the diagenetic evolution of the Fengcheng Formation, it has experienced a complex evolution of carbonate minerals. In this study, through core observation, thin section, X-ray diffraction mineral composition, carbon and oxygen isotope, fluid inclusion homogenization temperature, and laser Raman and cathodoluminescence analysis, the material sources, development period, dissolution-precipitation reactions, and transformation mechanisms of carbonate minerals in the diagenetic evolution of the Fengcheng Formation reservoir were evaluated in detail. Finally, the controlling effect of multi-stage cementation of carbonate minerals on the reservoir physical properties was determined. The results showed that there are three stages of carbonate minerals in the Fengcheng Formation. The material source of the early carbonate was mainly terrigenous debris, and the formation temperature range was 30–70 °C. The material source of middle-late carbonate minerals was mainly decarboxylation of organic acid, and the formation temperature was 60–110 °C. In addition, some were generated through hydrothermal metasomatism at high ambient temperatures, up to 120 °C. In areas where early carbonate minerals are well developed, a large number of microcracks was more likely to form under the influence of tectonic movements, resulting in high-quality reservoirs. The formation of late carbonate minerals, which is the main reason for reservoir densification in the later stage of diagenesis, resulted in poor reservoir physical properties. This study provides information useful for predicting the distribution areas of favorable reservoirs in the Fengcheng Formation, and a theoretical basis and guidance for improving the accuracy of shale oil exploration and development.

Controlling Electrolyte Properties and Redox Reactions Using Solvation and Implications in Battery Functions: A Mini‐Review

AbstractElectrolytes will play a central role in the development of next‐generation batteries with increased energy density and cycle life and reduced cost. While molecular designs can enable electrolytes with favorable properties like increased (electro)chemical stability, such properties can be manipulated additionally through the intermolecular interactions among species within the electrolyte. In this mini‐review, a number of intermolecular interactions in the electrolyte that can give rise to significant enhancement in battery functions are highlighted. The critical role of reactant and product solubility is shown in battery reactions, where increasing solubility can enable a dissolution–precipitation reaction pathway, decrease overpotential, and increase capacity. Through the intermolecular interactions among solvent, additives, and ions, the reactivity of electrolyte species can be altered significantly by either enhancing solvent (electro)chemical stability or facilitating water deprotonation in Li–O2 reactions. It is shown that incorporating redox active species in the electrolyte can reduce the reaction overpotential and enhance cycle life. Moreover, intermolecular interactions that can increase the ionic conductivity and transference number of electrolytes are identified. Finally, future opportunities are highlighted to exploit these intermolecular interactions to gain unprecedented molecular control over the electrolyte and enable next‐generation batteries.

Low-Temperature Synthesis Approach for Calcium Hydroxyapatite Coatings on Titanium Substrate

In this study, a low-temperature synthetic approach was developed for the fabrication of calcium hydroxyapatite (CHAp) coatings on a titanium substrate. The titanium substrates were first coated with CaCO3 by a spin-coating technique using a sol–gel chemistry approach, and the obtained product was transformed into CHAp during a dissolution–precipitation reaction. The phase purity and structural and morphological features of the obtained CHAp coatings were evaluated by X-ray diffraction (XRD) analysis, FTIR spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM) and using a 3D optical profilometer. It was demonstrated that almost-single-phase CHAp formed on the titanium substrate with a negligible number of side phases, such as Na2HPO4 (starting material) and TiO2. In the Raman spectrum of the CHAp coating, the peaks of phosphate group vibrations were clearly seen. Thus, the obtained results of Raman spectroscopy correlated well with the results of X-ray diffraction analysis. The corrosive behaviour of CHAp coatings on a titanium substrate was also evaluated using electrochemical methods. It was found that the corrosion resistance of titanium coated with CHAp increased significantly. These CHAp thin films may be potential candidates for use in not only in regenerative medicine but also in the development of different sensors.

Substitution of dicarboxylate ions as succinate ion in lsquo;Apatite Worldrsquo;

In crystal chemistry, the apatite crystals is prepared by the dissolution precipitation reaction reaction, which led to HAP (hydroxyapatite; Ca10(PO4)6.(OH)2) nanocrystals formation under hydrothermal condition from OCP (octacalcium phosphate; Ca8(HPO4)2.(PO4)4.5H2O) at 180℃ for 3 hours with adjusted 5.5 pH range. The prepared solution is incorporating to dicarboxylate as succinate (OOC.(CH2)2.COO)2- ions. During incorporating of succinate ions in OCP crystals, the hydrogen phosphate (HPO42-) ions in the hydrated layers of OCP are being substituted by succinate ions. These organically modified OCP which generated to HAP have unique hexagonal nanostructure with micrometer thickness are characterized by reporting of scanning electron microscopy (SEM), X-ray diffraction analysis, Fourier transform infrared (FTIR) spectra and Scherrer’s equation as well.

Calcium Carbonate/Hydroxyapatite Microparticles and Osteoblast Responses

Calcium carbonate (CC)-hydroxyapatite (HAP) porous microparticles have gained a lot of popularity as a promising material for clinical applications. The objective of this study is to evaluate the effects of CC-HAP microparticles on osteoblast-like cells to be used as a bone-regeneration biomaterial. In this study, the different concentrations of conditioned media were used to compare the effects of released ions from CC-HAP microparticles. The material’s characteristics demonstrated that the immersion in cell culture medium did not change the crystal phases of CC-HAP. The decrease of calcium ions in cell culture medium is due to the dissolution-precipitation reactions on the material surfaces, which made more crystalline surfaces. The atomic absorption spectroscopy measurement demonstrated that the dissolution-precipitation reactions on the material surfaces in cell culture medium happened in 3 days and were stable between 3 to 5 days. The conditioned media immersed in cell culture medium for 4 days were used for further experiments. Cell evaluations demonstrated that excessive adding of CC -HAP could inhibit cell behaviors such as cell adhesion, proliferation, and differentiation. The cell adhesion indicated by the number of vinculin-positive focal adhesions per cell decreased with the increase of the CC-HAP concentrations. The cells cultured with CC-HAP proliferated at a lower rate than the control without CC-HAP. One of the reasons for the inhibition of cell proliferation was thought to be less formation of focal adhesions with higher concentrations of CC-HAP. The excessive adding of CC-HAP had an inhibitory effect on osteoblast differentiation. The results of this study revealed that the conditioned media prepared by immersion of CC-HAP porous microparticles in cell culture media had effects on the behaviors of osteoblast-like cells such as cell adhesion, proliferation, and differentiation.