Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

Geotechnical investigation of low-plasticity organic soil treated with nano-calcium carbonate

Soil stabilization using nanomaterials is an emerging research area although,to date,its investigation has mostly been laboratory-based and therefore requires extensive study for transfer to practical field ap-plications.The present study advocates nano-calcium carbonate(NCC)material,a relatively unexplored nanomaterial additive,for stabilization of low-plasticity fine-grained soil having moderate organic content.The plasticity index,compaction,unconfined compressive strength(UCS),compressibility and permeability characteristics of the 0.2%,0.4%,0.6%and 0.8%NCC-treated soil,and untreated soil(as control),were determined,including investigations of the effect of up to 90-d curing on the UCS and permeability properties.In terms of UCS improvement,0.4%NCC addition was identified as the optimum dosage,mobilizing a UCS at 90-d curing of almost twice that for the untreated soil.For treated soil,particle aggregation arising from NCC addition initially produced an increase in the permeability coef-ficient,but its magnitude decreased for increased curing owing to calcium silicate hydrate(CSH)gel formation,although still remaining higher compared to the untreated soil for all dosages and curing periods investigated.Compression index decreased for all NCC-treated soil investigated.SEM micro-graphs indicated the presence of gel patches along with particle aggregation.X-ray diffraction(XRD)results showed the presence of hydration products,such as CSH.Significant increases in UCS are initially attributed to void filling and then because of CSH gel formation with increased curing.

Optimization of growth medium for microbially induced calcium carbonate precipitation(MICP) treatment of desert sand

Wind-induced sand erosion is a natural process, and can have several negative impacts on human health, environment, and economy. To mitigate the wind-induced sand erosion, an environmental friendly technique that helps to bind soil particles is desirable. The microbially induced calcium carbonate precipitation(MICP) treatment has lately become renowned and a viable alternative to enhance the binding of sand particles(especially against wind erosion). The efficiency of Sporosarcina pasteurii bacteria in inducing calcite formation can be influenced by various factors, including the type of growth media used for bacterial culture. Most of the studies have mainly validated the efficiency of S. pasteurii bacteria usually under single growth media for the MICP treatment. However, the efficiency of S. pasteurii under different growth media on calcite formation is rarely explored. The current study explores the effect of S.pasteurii bacteria on calcite formation under the presence of three different growth media, namely,molasses(MS), tryptic soy broth(TB), and nutrient broth(NB). The three growth media have been applied in the laboratory with and without bacterial solution(control samples). Altered cementation media concentrations(0.5 and 1.0 M) with different pore volumes(PVs), namely, 0.25, 0.50, and 1.00 PV were used in sand-filled tubes for 7 and 14 treatment cycles(1 cycle=24 h). The pH and EC were measured for 12-h period in every 2 h interval, to monitor values at the time of treatment at room temperature. The calcite precipitation was confirmed using SEM(scanning electron microscope), PXRD(powder X-ray diffraction), and calcimeter tests. It was observed that MS generates lower calcite precipitation as compared with NB and TB. However, MS has the advantage of being more economical and abundant(waste product from sugar mills and refineries) as compared with other growth media(NB and TB). It was observed that the minimum and the maximum calcite precipitation using MS is 5% and 12%, respectively.The findings using MS in the present study was compared with the literature and found that precipitation of calcite using MS is effective to stabilize soil against wind erosion.

Crystalline-magnetism action in biomimetic mineralization of calcium carbonate

The influence of minor environmental factors,such as the geomagnetic field,on the biomineralization of nacres,is often ignored but a great deal of research has confirmed its important role in the normal mineralization of calcium carbonate.Although the geomagnetic field is weak,its cumulative effects need to be considered given that the biomineralization process can take years.Accordingly,the authors of this paper have investigated the effects of weak magnetic fields(25 Gs or 50 Gs)on calcium carbonate mineralization and analyzed the mechanism involved.The results show that even a weak magnetic field conduces to the formation of vaterite or aragonite,in the induction order of precursor→vaterite→aragonite.The stronger the magnetic field and the longer the time,the more obvious the induction effect.The effect of a magnetic field is strongest in the aging stage and weakest in the solution stage.Inductions by egg-white protein and by a magnetic field inhibit each other,but they both restrict particle growth.These findings highlight the importance of minor environmental factors for biomineralization and can serve as a reference for biomimetic preparation of a CaCO_(3)nacre-like structure and for anti-scale technology for circulating cooling water.

A Primary Study on Mechanical Properties of Heat-Treated Wood via in-situ Synthesis of Calcium Carbonate

This study aims to improve the value of fast-growing wood and extend the heat-treated wood utilization using inorganic calcium carbonate(CaCO_(3))crystals via an in-situ synthesis method.CaCl_(2)and Na 2CO_(3)solutions with a concentration ratio of 1:1 were successively introduced into the thermally modified poplar wood obtained by steam heat treatment(HT)at 200℃for 1.5 and 3 h,resulting in the in-situ synthesis of CaCO_(3)crystals inside the heat-treated wood.The filling effect was best at the concentration of 1.2 mol/L.CaCO_(3)was uniformly distributed in the cell cavities of the heat-treated wood,and some of the crystals were embedded in the fissures of the wood cell walls.The morphology of CaCO_(3)crystals was mainly spherical and rhombic polyhedral.Three main types of CaCO_(3)crystals were calcite,vaterite,and aragonite.The HT of poplar wood at 200℃resulted in degrading the chemical components of the wood cell wall.This degradation led to reduced wood mechanical properties,including the surface hardness(HD),modulus of rupture(MOR),and modulus of elasticity(MOE).After CaCO_(3)was in-situ synthesized in the heat-treated wood,the HD increased by 18.36%and 16.35%,and MOR increased by 14.64%and 8.89%,respectively.Because of the CaCO_(3)synthesization,the char residue of the 200℃heat-treated wood samples increased by 9.31%and the maximum weight loss rate decreased by 19.80%,indicating that the filling with CaCO_(3)cannot only improve the mechanical properties of the heat-treated wood but also effectively enhance its thermal stability.

Comparative Study of Effect of Addition of Calcium Carbonate and Clay on the Performance Properties of Polyvinyl Acetate Wood Glue

Polyvinyl alcohol (PVA) stabilized Polyvinyl acetate (PVAc) dispersions-based wood adhesive has poor water and heat resistance. Recently, the addition of fillers in the wood adhesive is one of the most effective ways to enhance the performance of PVAc wood adhesive. Inorganic fillers have unique characteristics to improve the performance of adhesive, such as small size, high surface energy and surface hardness. Hence, the present work investigates the applicability of calcium carbonate and clay incorporated 3% in situ emulsion polymerization PVAc wood adhesive. Effect on physical, thermal and mechanical properties was studied by viscosity, pH, contact angle measurement, differential scanning calorimetry (DSC) and pencil hardness test of films. Emulsions with 3% calcium carbonate and 3% clay were prepared and the shear strength of the applied adhesive on wood was measured. The viscosity of the adhesives was reduced in the case of the addition of calcium carbonate and increased in the case of clay. The mechanical properties like tensile strength of adhesives with calcium carbonate and clay were measured by a universal tensile machine (UTM). Thermal stability was studied by differential scanning calorimetry (DSC). The tensile shear strength demonstrates that clay can improve bonding strength as compared to calcium carbonate of PVAc adhesive in wet conditions. The hardness of PVAc films was also changed positively by the addition of calcium carbonate and clay. Thermal stability of PVAc was significantly improved as calcium carbonate and clay were added to PVAc. Here, we did a comparative study of the effect of the addition of calcium carbonate and clay filler materials in situ polymerization of PVAc on their different properties.

Optimization by the Taguchi Method of a Robust Synthesis Protocol of Calcium Carbonate Phosphate

The experimental processes are difficult to model by physical laws, because a multitude of factors can intervene simultaneously and are responsible for their instabilities and their random variations. Two types of factors are to be considered;those that are easy to manipulate according to the objectives, and those that can vary randomly (uncontrollable factors). These could eventually divert the system from the desired target. It is, therefore, important to implement a system that is insensitive to fluctuations in factors that are difficult to control. The aim of this study is to optimize the synthesis of an apatitic calcium carbonate phosphate characterized with a Ca/P ratio equal to 1.61 by using the experimental design method based on the Taguchi method. In this process, five factors are considered and must be configured to achieve the previously defined objective. The temperature is a very important factor in the process, but difficult to control experimentally, so considered to be a problem factor (noise factor), forcing us to build a robust system that is insensitive to the last one. Therefore, a much simpler model to study the robustness of a synthetic solution with respect to temperature is developed. We have tried to parameterize all the factors considered in the process within a wide interval of temperature variation (60˚C - 90˚C). Temperature changes are no longer considered as a problem for apatitic calcium carbonate phosphate synthesis. In this finding, the proposed mathematical model is linear and efficient with very satisfactory statistical indicators. In addition, several simple solutions for the synthesis of carbonate phosphate are proposed with a Ca/P ratio equal to 1.61.

Evolution Mechanism of Calcium Carbonate in Solution

Calcium carbonate was synthesized in a CaCl2/NaCO3 mixed solution by using ethylenediaminetetraacetic acid （EDTA） as an additive. The thermodynamics and kinetics analyses indicate that although the driving force of amorphous calcium carbonate （ACC） precipitation is always less than that of calcite and vaterite precipitation, the nucleation rate of ACC is greater than that of calcite and vaterite at the initial stage of the precipitation reaction. With the increasing incubation time, vaterite and calcite particles nucleate heterogeneously by using the as-formed particles as active sites. Scanning electron microscopy images indicate that the transformation mechanism of ACC and vaterite to calcite is the dissolution-recrystallisation reaction. The presence of EDTA not only improves the stabilities of ACC and vaterite, but also leads to forming enlongated, connected rhombohedral calcite crystals after incubation 7 days in solutions. The ACC and vaterite are stabler in air than in solutions at room temperature, although the dissolution-recrystallisation reaction occurs on the surface.

Surface modification of calcium carbonate:A review of theories,methods and applications

Calcium carbonate,which is widely employed as a filler added into the polymer matrix,has large numbers of applications owing to the excellent properties such as low cost,non-toxicity,high natural reserves and biocompatibility.Nevertheless,in order to obtain the good filling effect,calcium carbonate needs to be surface modified by organic molecules so as to enhance the dispersion and compatibility within the composites.This review paper systematically introduces the theory,methods,and applications progress of calcium carbonate with surface modification.Additionally,the key factors that affect the properties of the composites as well as the current difficulties and challenges are highlighted.The current research progress and potential application prospects of calcium carbonate in the fields of plastics,rubber,paper,medicine and environmental protection are discussed as well.Generally,this review can provide valuable reference for the modification and comprehensive utilization of calcium carbonate.

Preparation of calcium carbonate particles coated with titanium dioxide

The preparation of a new mineral composite material, calcium carbonate particles coated with titanium dioxide, was studied. The mechanism of the preparation process was proposed. The new mineral composite material was made by the mechanoehemieal method under the optimum condition that the mass ratio of calcium carbonate particles to titanium dioxide was 6.5：3.5. The mass ratios of two different types of titanium dioxide （anatase to rutile） and grinding media to grinded materials were 8：2 and 4：1 respectively, and the modified density was 60%. Under this condition, the new material was capable of forming after 120-min modification. The hiding power and oil absorption of this new material were 29.12 g/m^2 and 23.30%, respectively. The results show that the modification is based on surface hydroxylation. After coating with titanium dioxide, the hiding power of calcium carbonate can be improved greatly. The new mineral composite materials can be used as the substitute for titanium dioxide.

Preparation of poly （methyl methacrylate）／nanometer calcium carbonate composite by in-situ emulsion polymerization

Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

CO_(2) mineralization of carbide slag for the production of light calcium carbonates

The production of polyvinyl chloride by calcium carbide method is a typical chemical process with high coal consumption,leading to massive flue gas and carbide slag emissions.Currently,the carbide slag with high CaO content is usually stacked in residue field,easily draining away with the rain and corroding the soil.In this work,we coupled the treatment of flue gas and carbide slag to propose a facile CO_(2)mineralization route to prepare light calcium carbonate.And the route feasibility was comprehensively evaluated via experiments and simulation.Through experimental investigation,the Ca^(2+) leaching and mineralization reaction parameters were determined.Based on the experiment,a process was built and optimized through Aspen Plus,and the energy was integrated to obtain the overall process energy and material consumption.Finally,the net CO_(2)emission reduction rate of the entire process through the life-cycle assessment method was analyzed.Moreover,the relationship between the parameters and the CO_(2)emission life-cycle assessment was established.The final optimization results showed that the mineralization process required 1154.69 kW·h·(t CO_(2))^(-1) of energy(including heat energy of 979.32 kW·h·(t CO_(2))^(-1) and electrical energy of 175.37 kW·h·(t CO_(2))^(-1)),and the net CO_(2)emission reduction rate was 35.8%.The light CaCO_(3)product can be sold as a high value-added product.According to preliminary economic analysis,the profit of mineralizing can reach more than 2,100 CNY·(t CO_(2))^(-1).

Experimental study on mitigating wind erosion of calcareous desert sand using spray method for microbially induced calcium carbonate precipitation

Wind erosion is one of the significant natural calamities worldwide, which degrades around one-third of global land. The eroded and suspended soil particles in the environment may cause health hazards, i.e.allergies and respiratory diseases, due to the presence of harmful contaminants, bacteria, and pollens.The present study evaluates the feasibility of microbially induced calcium carbonate precipitation(MICP)technique to mitigate wind-induced erosion of calcareous desert sand(Thar desert of Rajasthan province in India). The temperature during biotreatment was kept at 36℃ to stimulate the average temperature of the Thar desert. The spray method was used for bioaugmentation of Sporosarcina(S.) pasteurii and further treatment using chemical solutions. The chemical solution of 0.25 pore volume was sprayed continuously up to 5 d, 10 d, 15 d, and 20 d, using two different concentration ratios of urea and calcium chloride dihydrate viz 2:1 and 1:1. The biotreated samples were subjected to erosion testing(in the wind tunnel) at different wind speeds of 10 m/s, 20 m/s, and 30 m/s. The unconfined compressive strength of the biocemented crust was measured using a pocket penetrometer. The variation in calcite precipitation and microstructure(including the presence of crystalline minerals) of untreated as well as biotreated sand samples were determined through calcimeter, scanning electron microscope(SEM), and energydispersive X-ray spectroscope(EDX). The results demonstrated that the erosion of untreated sand increases with an increase in wind speeds. When compared to untreated sand, a lower erosion was observed in all biocemented sand samples, irrespective of treatment condition and wind speed. It was observed that the sample treated with 1:1 cementation solution for up to 5 d, was found to effectively resist erosion at a wind speed of 10 m/s. Moreover, a significant erosion resistance was ascertained in15 d and 20 d treated samples at higher wind speeds. The calcite content percentage, thickness of crust,bulk density, and surface strength of biocemented sand were enhanced with the increase in treatment duration. The 1:1 concentration ratio of cementation solution was found effective in improving crust thickness and surface strength as compared to 2:1 concentration ratio of cementation solution. The calcite crystals formation was observed in SEM analysis and calcium peaks were observed in EDX analysis for biotreated sand.

Characteristics of Soybean Urease Mineralized Calcium Carbonate and Repair of Concrete Surface Damage

The C60 concrete blocks with surface crack damage under high temperature environment were soaked by adding appropriate amount of soybean urease into the CO(NH_(2))_(2)-CaCl_(2) solution,the soybean urease mineralized calcium carbonate were characterized,and the effect of repairing concrete surface crack damage were evaluated by the surface sedimentation of C60 concrete blocks in the study.The experimental results showed that the activity of soybean powder was statistically significant,and its productivity of urease was comparable with that of urease-producing bacteria.After immersion in a soybean solution,a layer of complete and continuous white sediment covered the concrete surface.The cracks on the concrete surface were completely shielded,and the rising temperature on infrared thermal image of the concrete after repair was lower than before.Besides,through analysis by SEM,EDS,and XRD,the products formed after repair were found to be calcite-type CaCO_(3) with high purity,and the crystals exhibited different morphological features.The above results indicate that soybean urease can regulate and induce the formation of calcium carbonate,and the precipitate is innocuous and harmless,suitable for a new type of concrete crack repair material.

Mechanism of Calcium Carbonate Scale Deposition under Subcooled Flow Boiling Conditions

Fouling of heat transfer surfaces during subcooled flow boiling is a frequent engineering problem in process industries. It has been generally observed that the deposits in such industrial systems consist mainly of calcium carbonate （CaCO3）, which has inverse solubility characteristics. This investigation focused on the mechanism to control deposition and the morphology of crystalline deposits. A series of experiments were carried out at different surface and bulk temperatures, fluid velocities and salt ion concentrations. It is shown that the deposition rate is controlled by different mechanism in the range of experimental parameters, depending on salt ion concentration. At higher ion concentration, the fouling rate increases linearly with surface temperature and the effect of flow velocity on deposition rate is quite strong, suggesting that mass diffusion controls the fouling process. On the contrary, at lower ion concentration, the fouling rate increases exponentially with surface temperature and is independent of the velocity, illustrating that surface reaction controls the fouling process. By analysis of the morphology of scale, two types of crystal （calcite and aragonite） are formed. The lower the temperature and ion concentration, the longer the induction period and the higher the percentage of calcite nreciDitated.

Distribution of Calcium Carbonate in the Process of Concrete Self-healing

The complete deposition distribution process of calcium carbonate is summarized in three directions of cracks. Distribution of calcium carbonate in the self-healing process of microbial concrete is studied in detail, with the help of a variety of analytical techniques. The results show that carbonate deposits along the x-axis direction of the cracks. The farther from the crack surfaces of concrete matrix in x-axis direction, the more the content of the substrate, the less content of calcium carbonate. Gradual accumulation of calcium carbonate along the y-axis direction is like building a house with bricks. Different repair points are gradually connected, and ultimately the whole of cracks are completely filled. In the z-axis direction, calcium deposits on the surface of fracture direction, when the crack is filled on the surface, because the internal crack hypoxia in the depths of cracks hardly produces calcium carbonate.

Biomediated Precipitation of Calcium Carbonate in a Slightly Acidic Hot Spring,Yunnan Province

A slightly acidic hot spring named ＂Female Tower＂（t=73.5°C, pH=6.64） is located in the Jifei Geothermal Field, Yunnan Province, southwestern China. The precipitates in the hot spring are composed of large amounts of calcite, aragonite and sulfur. Scanning electron microscopy（SEM） analyses reveal that the microbial mats were formed from various coccoid or rod-shaped filamentous microbes. Transmission electron microscopy（TEM） shows that the intracellular sulfur granules are commonly associated with these microbes. A culture-independent molecular phylogenetic analysis demonstrates that the majority of the bacteria in the spring are sulfur-oxidizing bacteria. In the spring water, H2S concentration is up to 60 ppm, while SO4-（2-） concentration is only about 10 ppm. We speculate that H2S might derive from sulfur-oxidizing bacteria in this hot spring water, leading to the intracellular formation of sulfur granules. Meanwhile, this reaction increased the p H in the micronscale microdomains, which fosters the precipitation of calcium carbonate in the microbial mats. The results of this study indicate that the sulfur-oxidizing bacteria might play an important role in calcium carbonate precipitation in slightly acidic hot spring environments.

Effects of Nano Calcium Carbonate on Strength and Microstructure of Corundum-based Castables

The castables specimens were prepared using white fused alumina particle and powder, α-Al2O3 micropowder, hydrated alumina, nano calcium carbonate or calcium aluminate cement as starting materials. Effects of nano calcium carbonate addition on phase compositions, strength and microstructure of corundum based castables were studied. The calcium aluminate cement-containing corundum based castables with the same CaO amount was also tested for comparison. The results show that, when temperature is higher than 900 ℃ , the phase compositions of nano CaCO3-containing mixture and the calcium aluminate cement containing mixture are the same, but the forming mechanism, modality and distribution of new phases in the castables are different. With temperature rising, the hydration cement dehydrates and reacts inside cement forming calcium aluminate until the alumina in cement is not enough for the reaction （ternperature is 91 400 ℃ ） , then reacts with the surrounding alumina forming cluster CA6 in the castables. The change process of nano CaCO3 in corundum based enstables is that nano calcium carbonate decomposes to CaO after firing at 800℃ which reacts with Al2O3 forming amorphous calcium aluminate that causes an in-situ bonding. With temperature rising, the formed calcium aluminate reacts with Al2O3 in matrix and wholly forms tabular CA6 at 1 600 ℃ , which distributes uniformly in the castables. The cold and hot strength of the castables with nano calcium carbonate are obviously higher than those of the castables without nano calcium carbonate, especially at 800 -1 000 ℃ due to smaller size and higher dispersion of the nano calcium carbonate and its different reaction mechanism with Al2O3.

Regulation of Microstructure of Calcium Carbonate Crystals by Egg White Protein

Crystal growth of calcium carbonate in biological simulation was investigated via egg white protein with different volume fractions,during which calcium carbonate was synthesized by calcium chloride and sodium carbonate.The morphology,thermal properties and microstructure of the calcium carbonate micro-to-nanoscale crystals were characterized by scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,Fourier transform infrared spectroscopy（FTIR）,thermogravimetric analysis（TG） and X-ray diffraction（XRD） analysis.The results show that the volume fraction of egg white protein has great influence on the shape,size and morphology of calcium carbonate crystals.The calcium carbonate crystals were the mixtures of calcite-vaterite-like crystals including spherical and rough surface,which are different from that formed in pure water.With the increase of egg white protein concentration,the diameter of calcium carbonate crystals changed,the amount of formed spherical calcium carbonate particles decreased and that of vaterite increased.These results indicate that the coordination and electrostatic interaction between egg white protein and Ca2＋ significantly affect the calcium carbonate crystalization.