Separation of manganese from calcium and magnesium in sulfate solutions via carbonate precipitation

The separation of manganese from sulfate solutions containing 14.59 g/L Mn2+, 1.89 g/L Mg2+ and 1.54 g/L Ca2+ was preformed successfully by carbonate precipitation. The results of thermodynamic analysis and tests indicate that carbonate precipitation holds better selectivity for manganese over magnesium than hydroxide precipitation and the feeding method is the most critical factor for minimizing the co-precipitation of calcium and magnesium. Furthermore, with adding MnSO4 solution to NH4HCO3 solution, the effects of the initial NH4HCO3 concentration, NH4HCO3 amount, solution pH value, reaction temperature and time on carbonate precipitation were evaluated and the optimum precipitation conditions were obtained. Under the optimum conditions, the precipitation rates of Mn2+, Ca2+ and Mg2+ are 99.75%, 5.62% and 1.43%, respectively. Moreover, the prepared manganese carbonate was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDX). The results demonstrate that the product can be indexed to the rhombohedral structure of MnCO3.

Synthesis of cyclic carbonates from epoxides and CO_2 in acetonitrile via the synergistic action of BMIMBr and electrogenerated magnesium

Using 1-butyl-3-methyl-imidazolium bromide （BM1MBr） as the supporting electrolyte and magne- sium as the sacrificial anode, a new and highly efficient electrochemically catalytic route was devel- oped for the synthesis of cyclic carbonates from epoxides and CO2. Based on the cooperative action of BMIMBr and an electrogenerated magnesium salt obtained under a N2 atmosphere, CO2 reacted with a wide range of epoxides to readily generate cyclic carbonates in moderate to excellent yields under mild conditions.

Effects of Temperature on the Preparation of Magnesium Carbonate Hydrates by Reaction of MgCI2 with Na2CO3

Homogeneous(unseeded)precipitation of magnesium carbonate hydrates by the reaction of MgCl2 with Na2CO3 in supersaturated solutions between 273 and 363K was investigated.The compositions,morphologies and filtration characteristics of the precipitates were studied in detail.The magnesium carbonate hydrates obtained at 313K and in the range of 343-363K showed good morphologies and filtration characteristics.Magnesium oxides(MgO)with high purity(97.6%-99.4%)were obtained by calcining magnesium carbonate hydrates at 1073K.

Efficient Solvent-free Synthesis of Chloropropene Carbonate from the Coupling Reaction of CO_2 and Epichlorohydrin Catalyzed by Magnesium Porphyrins as Chlorophyll-like Catalysts

Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.

Preparation and growth mechanism of plate-like basic magnesium carbonate by template-mediated/homogeneous precipitation method

In order to expand the application of the basic magnesium carbonate in the field of flame retardant,the plate-like basic magnesium carbonate(Mg5(CO3)4(OH)2.4H2O)was prepared successfully by template-mediated/homogeneous precipitation method,using magnesium chloride hexahydrate(MgCl2.6H2O)and urea(CO(NH2)2)as reaction materials.Phase and morphology of the product were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM)and atomic force microscope(AFM),respectively.The results showed that well-crystallized plate-like Mg5(CO3)4(OH)2.4H2O can be prepared at the water bath temperature of 100°C,water bath time of 24 h,the aging time of 5 h after adding organic template agent.The investigation on organic template mediated mechanism shows that the template affects the crystal morphology by changing surface energy of different crystal plane.Through a preliminary study on the growth mechanism of the product,it is found that the generation of the plate-like Mg5(CO3)4(OH)2.4H2O could be explained by two-dimensional nucleation/step growth mechanism.

Balanced Fracturing and Cold-welding of Magnesium during Ball Milling Assisted by Carbon Coating:Experimental and Molecular Dynamic Simulation

The lignite-derived carbon from self-protection pyrolysis was employed to balance the fracturing and cold-welding of magnesium during ball milling.Particle size analysis indicates that the introduction of lignite-derived carbon can effectively reduce the particle size of Mg while the introduction of graphite does no help.Besides,the effect of lignite-derived carbon on crystallite size reduction of Mg is also better than graphite.A moderate cold-welding phenomenon was observed after ball-milling Mg with the lignite-derived carbon,suggesting less Mg is wasted on the milling vials and balls.Molecular dynamic simulations reveal that the balanced fracturing and cold-welding of magnesium during ball milling is mainly attributed to the special structure of the lignite-derived carbon:graphitized short-range ordered stacking function as dry lubricant and irregular shape/sharp edge function as milling aid.The preliminary findings in current study are expected to offer implications for designing efficient Mg-based hydrogen storage materials.

Preparation of basic magnesium carbonate and its thermal decomposition kinetics in air

The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.

Reversible Magnesium Metal Anode Enabled by Cooperative Solvation/Surface Engineering in Carbonate Electrolytes

Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping,while they fail to match most cathode materials toward highvoltage magnesium batteries. Herein,reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl_(2) additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg^(2+) desolvation barrier for accelerated redox kinetics,while the Mg^(2+)-conducting polymer coating on the Mg surface ensures the facile Mg^(2+) migration and the e ective isolation of electrolytes. As a result,reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover,benefitting from the wide electrochemical window of carbonate electrolytes,high-voltage(> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.

Prepartion of Flake-Like Basic Magnesium Carbonate from the Ammonium Sulfte Leaching Liquid of Asbestos Tailing

The flake-like basic magnesium carbonate was prepared from the ammonium sulfate leaching liquid of asbestos tailings. The method of X-ray diffraction, Fourier transform infrared spectra, TA-DTG and SEM analysis had been used to research the influence of the reaction temperature on the phase, structure and morphology of the product during the preparation of the basic magnesium carbonate. The results indicates that the product was needle-like magnesium carbonate hydrate at the lower reaction temperature (from 35 ℃ to 65℃), with the increase of the reaction temperature (75 ℃ to 95 ℃ ), the needle-like magnesium carbonate hydrate (MgCO3·xH2O) transformed to flake-like basic magnesium carbonate [Mg5(CO3)4(OH)2·4H2O], the reaction temperature plays an important role in the preparation of flake-like basic magnesium carbonate, the preparation of flake-like basic magnesium carbonate was a nucleation-dissolution-recrystallization growth mechanism process.

Cytotoxicity,in Vivo Skin Irritation and Acute Systemic Toxicity of the Mesoporous Magnesium Carbonate Upsalite^(█)

Upsalite®is a mesoporous magnesium carbonate synthesized without using surfactants and therefore highly attractive from environmental and production economy points of view. The material has recently been suggested as drug delivery vehicle and as topical bacteriostatic agent. In order to continue exploring these and other bio-related applications of the material, primary biocompatibility studies are needed. Herein we present the first in vivo acute systemic toxicity and skin irritation analyses as well as in vitro cytotoxicity evaluations of Upsalite®. The material was found to be non-toxic for human dermal fibroblasts cells up to a concentration of 1000 μg/ml and 48 h exposure in contrast to the mesoporous silica material SBA-15, used as reference, which significantly affected cell viability at particle concentration of 500 and 1000 μg/ml after the same exposure time. Topical application of Upsalite®resulted in negligible cutaneous reactions in a rabbit skin irritation model and no evidence of significant systemic toxicity was found when saline extracts of Upsalite®were injected in mice. Injection of sesame oil extract, however, resulted in transient weight loss, most likely due to injection of particles, and not toxic leachables. The presented results form the basis for future development of Upsalite®and similar mesoporous materials in biomedical applications and further toxicity as well as biocompatibility studies should be directed towards specific areas of use.

Hybrid solid electrolyte interphases formed in conventional carbonate electrolyte enable high-voltage and ultra-stable magnesium metal batteries

Magnesium metal batteries are considered as viable alternatives of lithium-ion batteries for their low cost and high capacity of magnesium.Nevertheless,the practical application of magnesium metal batteries is extremely challenging due to a lack of suitable electrolyte that can stabilize magnesium metal anode and high-voltage cathode simultaneously.Herein,we found that in-situ formed lithium/magnesium hybrid electrolyte interphases in conventional LiPF6-containing carbonate-based electrolyte can not only prevent the production of passivation layer on the magnesium metal anode,but also inhibit the oxidation of the electrolyte under high voltage.The symmetric magnesium‖magnesium battery can achieve reversible stripping/plating for 1600 and 600 h at 0.02 and 0.1 mA cm^(-2),respectively.In addition,when coupled with a carbon fiber cathode,the magnesium metal battery exhibited a capacity retention rate of 96.3% for 1000 cycles at a current density of 500 mA g^(-1)and presented a working voltage of ~3.1 V.This research paves a new and promising path to the commercialization process of rechargeable magnesium metal batteries.

Influence of Composts on Agrochemical Properties of Soils of Zarafshan Valley, Salted with Magnesium Carbonates and Yield Capacity of Corn

Peculiar characteristics of soils of Zarafshan valley are salinity with carbonates. It is recommended to introduce large amount of manure or other organic fertilizers in these soils to improve soil reclamation. But currently there is no possibility to collect so many organic fertilizers in Uzbekistan. That is why other ways of production of organic fertilizers for improving soil fertility were searched. In the experiment, the influence of composts was studied, which prepared from tobacco wastes and manure on agrochemical properties of soils of Zarafshan valley, and production of composts from these industrial wastes, two salted with magnesium carbonates and yield-capacity of com. With the problems that exist in Uzbekistan can be solved at once. These include problems of environmental contamination through wastes and ensuring with organic fertilizers in the irrigated soils. Introduction of composts in the doze of 30 t.ha1 separately and on the background of mineral-NPK （nitrogen, phosphorus and potassium） fertilizers increased the humus content, total NPK and mobile nutritious substances in soil. It is proved that composts, prepared from tobacco wastes with their effect on the yield capacity and quality ofcoru production, can successfully substitute manure. Composts positively influence on the balance of nutritious substances in the system of soil-corn.

A green route for the preparation of layered double hydroxides from basic magnesium carbonate

Layered double hydroxides(LDHs)have received extensive attention in many fields such as catalysis,environmental management and medical applications.Typically,expensive soluble metal salts are commonly used as the starting materials for the synthesis of LDHs.Here,we report a novel synthesis route for Mg/Al-LDH by using inexpensive basic magnesium carbonate as the starting material.X-ray diffraction(XRD)and solid-state nuclear magnetic resonance(ssNMR)data show that LDHs with rich defects are formed rapidly at room temperature and good crystallinity can be obtained after further hydrothermal treatment.These results provide a simple,rapid and green preparation method for LDHs.

Novel mechanism for the modification of Al_2O_3-based inclusions in ultra-low carbon Al-killed steel considering the effects of magnesium and calcium

Many researchers have explored the inclusion modification mechanism to improve non-metallic inclusion modifications in steelmaking. In this study, two types of industrial trials on inclusion modifications in liquid steel were conducted using ultra-low-carbon Al-killed steel with different Mg and Ca contents to verify the effects of Ca and Mg contents on the modification mechanism of Al_2O_3-based inclusions during secondary refining. The results showed that Al_2O_3-based inclusions can be modified into liquid calcium aluminate or a multi-component inclusion with the addition of a suitable amount of Ca. In addition, [Mg] in liquid steel can further reduce CaO in liquid calcium aluminate to drive its evolution into CaO–MgO–Al_2O_3 multi-component inclusions. Thermodynamic analysis confirmed that the reaction between [Mg] and CaO in liquid calcium aluminate occurs when the MgO content of liquid calcium aluminate is less than 3 wt% and the temperature is higher than 1843 K.

Corrosion protection investigations of carbon dots and polydopamine composite coating on magnesium alloy

A composite coating of nitrogen-doped carbon dots(N–CDs)and polydopamine(PDA)was prepared on magnesium alloy by combining electrodeposition with dip coating methods.The microstructure of the N–CDs/PDA composite coating,including composition,surface morphology,and crystalline structure,is characterized by Raman spectroscopy,scanning electron microscopy,transmission electron microscopy,and X-ray photoelectron spectroscopy,respectively.The corrosion protection performances of the composite coating are evaluated by potentiodynamic polarization tests,electrochemical impedance spectroscopy,and salt spray tests.The effect of the particle size of the N–CDs on the corrosion performance is also investigated.The results show that the corrosion performance of the N–CDs coatings are enhanced with the increase of the particle sizes.Furthermore,an obvious self-healing performance is observed on the surface of the N–CDs/PDA composite coating.These results indicate that N–CDs/PDA composite coating can improve the corrosion performance of the Mg alloy,and open a new design direction for the protective coating of metallic materials.

Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor. The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined, The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determi-nation of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process. The apparent activation energy was calculated to be 32.8kJ·mol-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

Carbon nanotube and graphene reinforced magnesium matrix composites:A state-of-the-art review

Magnesium(Mg)composites reinforced with carbon-based nanomaterial(CBN)often exhibit low density,enhanced strength,good conductivity,improved wear resistance,and excellent biocompatibility when compared to current industry Mg alloys.This review aims to critically evaluate recent developments in Mg-CBN composites and is divided into five sections:First,a brief introduction to Mg-CBN composites is provided,followed by a discussion of different fabrication techniques for these composites,including powder metallurgy,casting,friction stir processing,and selective laser melting.A particular focus is on the current processing challenges,including dispersion strategies to create homogeneous Mg-CBN composites.The effect of processing on the quantifying disorder in CBNs and distinguishing different sp2carbon materials is also highlighted.Then,the effect of CBN on various properties of Mg-CBN composites is thoroughly analyzed,and the strengthening efficiency of CNTs and graphene in the Mg matrix is examined.Finally,the potential applications of Mg-CBN composites in various industries are proposed,followed by a summary and suggestions for future research directions in the field of Mg-CBN composites.

Microstructure and tensile properties of magnesium nanocomposites fabricated using magnesium chips and carbon black

In this study,carbon black(0,0.01,0.03 and 0.08 wt%)and AZ31(Mg-3Al-lZn)magnesium chips were used to fabricate carbon black-reinforced magnesium matrix composites with extrusion or a combination of extrusion and high-ratio differential speed rolling.After hot pressing at 693 K and extrusion at 623 K with an extrusion ratio of 22,the magnesium chips coated with carbon black were soundly bonded into a bulk composite material.The grain sizes of the extruded materials were similar with a size of 48.2-51.5|im despite the difference in the amount of carbon black.The yield strength and ultimate tensile strength increased from 177 to 191 MPa and from 240 to 265 MPa,respectively,as a result of the addition of 0.01%carbon black;however,a further increase in the strength was marginal with additional carbon black.The same trend was observed in the strain hardening behavior.The tensile elongation increased by to the addition of 0.01%carbon black(from 15.8%to 17.4%)due to the increased work hardening effect,but decreased with additional carbon black due to its agglomeration and poor dispersion at higher concentration.After high-ratio differential speed rolling(HRDSR)on the extruded materials and subsequent annealing,the AZ31 and AZ31 composites had a similar fine grain size of 16.3-17.9 p.m.The annealed HRDSR composites showed the best mechanical properties at a higher content of carbon black(0.03%)compared to that(0.01%)for the extruded composites.This resulted from the enhanced dispersion effect of the carbon black due to the high shear flow induced during the HRDSR process.The extruded composites exhibited the three distinct hardening stages(stage II,stage III and stage IV),while the annealed HRDSR composites mainly displayed the stage III hardening.The addition of carbon black increased the strain hardening rate at all the strain hardening stages in both of the extruded and annealed HRDSR materials.At the initial hardening stage,the strain hardening rates of the extruded composites were higher than those of the annealed HRDSR composites,but this became reversed at the later stage of hardening.Possible explanations for this observation were discussed.The strength analysis suggests that dislocation-carbon black interaction by Orowan strengthening and dislocation generation due to a difference in thermal expansion between matrix and carbon black are the major strengthening mechanisms.

Bonding effect of liquid magnesium with open-celled carbon foam in interpenetrating phase composite

The issue of bonding formation in liquid metal/open-celled carbon foam(C_(of))systems was examined,taking into account the practical aspects of the synthesis of a new type of Mg-C metal material composite.The problem is complex due to the strong oxidation and intense evaporation of liquid magnesium,as well as the 3D geometry of the carbon component,where metal transport occurred through the foam cells’windows.Laboratory experiments performed at 700℃ in ceramic crucibles showed that spontaneous carbon foam infiltration by liquid metal is impossible under the applied conditions,either in an air atmosphere coupled with flux protection or under argon protection.Comparative tests performed in a UHV chamber filled with static pure Ar by a sessile drop method,coupled with non-contact heating and capillary purification at a test temperature of 700℃ directly in the UHV chamber,showed non-wetting behavior of the Mg/C_(of)couple with a correspondingly high contact angle of about 135°.The graphite capillary was then moved down,the liquid drop being slightly pressed into the foam,but these changes did not induce effective foam penetration.Despite the short contact time for the sessile drop test under an argon atmosphere,SEM+WDS analysis of the solidified Mg/C_(of)couple revealed the formation of an MgO interlayer at the interface,with a thickness of approx.1μm.The experimentally demonstrated presence of oxygen in the carbon foam sample,both before and after its contact with magnesium,points to oxide-type bonding being established between Mg and C_(of).This observation is in a good agreement with previous reports on the interface characterization of magnesium matrix composites reinforced with glassy carbon materials and carbon fibers by stir casting and pressure infiltration.Based on the findings of this study,a general structural scheme of the bonding process between carbon foam and liquid magnesium,as an important stage in the syntheses of Mg-C composites,was proposed.

High temperature tensile,compression and creep behavior of recycled short carbon fibre reinforced AZ91 magnesium alloy fabricated by a high shearing dispersion technique

The present study seeks the feasibility of using short carbon fibres recycled from polymer matrix composites as alternative to virgin carbon fibres in the reinforcement of magnesium alloys.The microstructures,high temperature mechanical and creep properties of AZ91 alloy and its composites with various recycled carbon fibre contents(2.5 and 5 wt.%)and lengths(100 and 500μm)were investigated in the temperature range of 25-200℃.The microstructural characterization showed that the high shear dispersion technique provided the cast composites with finer grains and relatively homogenous distribution of fibres.The materials tested displayed different behaviour depending on the type of loading.In general,while enhancements in the mechanical properties of composites is attributed to the load bearing and grain refinement effects of fibres,the fluctuations in the properties were discussed on the basis of porosity formation,relatively high reinforcement content leading to fibre clustering and interlayer found between the matrix and reinforcement compared to those of AZ91 alloy.The compressive creep tests revealed similar or higher minimum creep rates in the recycled carbon fibre reinforced AZ91 in comparison to the unreinforced AZ91.