Synthetic Aragonite (CaCO3) as a Potential Additive in Calcium Phosphate Cements: Evaluation in Tris‐Free SBF at 37°C

Conventional SBF (simulated/synthetic body fluid) solutions are buffered at pH 7.4°C and 37°C using 50 mM Tris [(HOCH₂)₃CNH₂]. Tris is not present in human blood or metabolism and its high concentration makes it the third major component of SBF solutions. All three crystalline polymorphs of calcium carbonate (calcite, aragonite and vaterite) have never been tested simultaneously in an SBF solution. This study presents the SBF‐testing of the particles of these polymorphs at 37°C in Na‐L‐lactate (22 mM)‐buffered Lac‐SBF solution. While the calcite rhombohedra remained completely inert in the solution, vaterite spherulites and aragonite needles accrued apatitic CaP (calcium phosphate) deposits on their surfaces. Mg‐doped (1050 ppm) synthetic aragonite particles did not transform into calcite for 96 h in the Lac‐SBF solution while increasing their BET surface area by about 560% via the apatitic CaP deposits. Given the well‐established use of calcite powders in CaP cement formulations, synthetic aragonite particles may be a potential replacement for calcite due to their rapid response to blood plasma‐like solutions in between 24 and 48 h at 37°C.     

Fabrication of aragonite rosette superstructure through the weak interaction between nonionic polymers and Ca2+

The controlled formation of aragonite by simple method under ambient condition is a big challenge for biomaterial scientists. In this article, we took poly (N‐vinyl pyrrolidone) (PVP) as an example to investigate the influence of water‐soluble nonionic polymers on the polymorphs of CaCO₃ via CO₂ diffusion method under ambient pressure and temperature, and found that the existence of PVP molecules favors the formation of aragonite with rosette superstructure. A possible mechanism is proposed that nonionic polymers can be doped into amorphous calcium carbonate (ACC) particles and further participate in the transformation process from ACC to aragonite and then promotes the formation of rosette superstructure through parallel aggregation by crosslinking the aragonite nuclei. The experiments of CaCO₃ crystallization in presence of poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA) confirmed the mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of phosphate and iron on the extent of calcium carbonate precipitation during anaerobic digestion

The extent to which calcium carbonate deposition in an anaerobic reactor can be reduced by adding inhibitors (phosphate and iron) of calcium carbonate crystal growth was investigated. At several concentrations of the additive, the extent of precipitation was assessed in continuous experiments with laboratory‐scale reactors. In the reactor, phosphate concentrations as low as 0.5–5 mg total‐P dm⁻³ were found to severely inhibit CaCO₃ precipitation. However, iron did not inhibit the deposition of CaCO₃, which was found to be due to the fact that iron, in contrast to phosphate, only inhibits the growth of calcite and not the formation of aragonite. The results led to the conclusion that only additives which inhibit the formation of both aragonite and calcite can be used as effective inhibitors during anaerobic digestion. A chemical equilibrium model was developed and shown to be a useful tool to calculate the extent of calcium carbonate deposition during anaerobic digestion provided the proper apparent solubility product of calcium carbonate can be estimated. © 1999 Society of Chemical Industry     

Polymorph and morphology of CaCO3 in relation to precipitation conditions in a bubbling system

Simulating the typical carbonation step in a mineral CO2 sequestration,precipitated calcium carbonate (PCC) was prepared by bubbling CO2 gas into a rich Ca solution.These carbonation reactions were conducted at three pH ranges,namely 10.0-9.0,9.0-8.0,and 8.0-7.0,in which temperature and CO2 flow rate are additional experimental variables.The PCC obtained in experiments was examined by Fourier transform infrared spectroscopy (FrIR) and X-ray diffraction (XRD).It was found that supersaturation determined by pH value and flow rate of CO2 has significant influence on polymorph of PCC.Vaterite was preferably formed at high supersaturation,while dissolution of metastable vaterite and crystallization of calcite occurred at low supersaturation.High temperature is a critical factor for the formation of aragonite.At 70 ℃,vaterite,calcite and aragonite were observed to coexist in PCC because transformation from vaterite to aragonite via calcite occurred at this temperature.Scanning electron microscopy (SEM) technology was performed on prepared PCC,and various morphologies consistent with polymorphs were observed.     

Biomineralization of calcium carbonate by adding aspartic acid and lysozyme

Calcium carbonate is one of the most abundant materials present in nature. Crystal structures of CaCO₃ become three polymorphic modifications, namely calcite, aragonite and vaterite. Polymorphic modifications are mediated by adding aspartic acid (Asp) and lysozyme. Lysozyme, which is a major component of egg white proteins, has influenced the calcification of avian eggshells. The influence of Asp and lysozyme on the crystallization of CaCO₃ was investigated by adding these additives and calcium chloride solution into sodium carbonate solution in a crystallization vessel. CaCO₃ crystals were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectrometry (FT-IR). XRD was used to select the intensities and crystal structure of specific calcium carbonate. SEM was employed for the analysis of the morphology of the precipitation and particle size. Two kinds of crystals were identified by FT-IR spectrum. Hexagonal crystals of vaterite were affected by the Asp in the crystallization solution. However, rhombohedral crystals of calcite by lysozyme were formed without any sign of vaterite.     

反应-萃取-结晶过程制备碳酸钙的晶型转变与结晶机理

氨碱法制碱过程中产生的大量蒸氨废液制约了纯碱工业的发展。本文对反应-萃取-结晶耦合工艺产物碳酸钙的晶型转变和结晶机理进行了研究。结果表明,在此耦合过程中,二氧化碳优先被有机相吸收,然后传递到水相进行反应,首先生成的是碳酸氢钙,之后迅速分解为无定形碳酸钙。温度对碳酸钙晶型影响显著,温度较高时,无定形碳酸钙优先转变为针状文石;温度较低时,无定形碳酸钙优先转变为球状球霰石。随后文石和球霰石均会通过溶解-重结晶作用逐渐转变为稳定的菱形方解石。常温下,反应过程中同时进行着新的球霰石的生成和球霰石转变为方解石两个过程,参与反应的二氧化碳浓度越高,晶体中球霰石的含量越高。     

Influence of crystallization conditions on crystal morphology and size of CaCO3 and their effect on pressure filtration

The temperature, supersaturation, seeding procedure, stirring speed and other parameters were varied in crystallization experiments of calcium carbonate performed in aqueous solutions to control size, particle size distribution and morphology of the particles. Particle size information was obtained by focused beam reflectance measurements and the Coulter Counter Multisizer. Crystals of CaCO₃ could be crystallized as spherical polycrystalline particles of the vaterite polymorph, needle‐like crystals of aragonite and both cube‐like and novel plate‐like crystals of calcite. Filtration experiments for calcium carbonate, performed at a constant pressure difference of 2 bar, show that spherical particles with a larger size show better filterability and that spheres with a wider size distribution, as a result of high supersaturation and nucleation, give higher average cake resistance values. Comparing different particle morphologies, plate‐like crystals and needle‐like crystals show worse filterability than spherical particles and cube‐like particles. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

聚天冬氨酸与磁场协同效应对碳酸钙晶型及阻垢性能的影响

研究了单独使用环保型高分子聚合物——聚天冬氨酸、磁场以及磁场与聚天冬氨酸的协同作用对碳酸钙晶型和阻垢性能的影响.利用扫描电子显微镜和X射线衍射等技术对碳酸钙晶体进行观察和晶型分析,结果表明：与普通水比较,磁化水可使碳酸钙结晶中文石与方解石的比例由1∶3转变为1∶1.3;聚天冬氨酸的存在可使碳酸钙晶体几乎全部转化成球霰石结构;聚天冬氨酸对Ca²⁺有螯合作用,磁场与聚天冬氨酸的协同作用可进一步提高对Ca²⁺的螯合作用.利用自行设计的带有加热系统的循环水动态实验装置,测定了不同条件下传热面上的结垢情况.实验结果表明,磁化水的阻垢率为32.2%,浓度为3 mg·L^-1的聚天冬氨酸溶液阻垢率为55.2%,磁场与聚天冬氨酸协同作用时的阻垢率为69.5%,具有很好的协同阻垢作用.     

Membrane autopsy to investigate CaCO3 scale formation in pilot‐scale,submerged membrane bioreactor treating calcium‐rich wastewater

BACKGROUND: Membrane scaling is an area of research interest because it can deteriorate membrane performance. The extent to which membrane scaling is produced varies depending upon the concentration of scale‐forming species such as calcium on the membrane surface. Bench‐scale tests have been conducted to better understand membrane scaling in submerged membrane reactors (MBR). However, relatively few studies of membrane scaling in pilot‐scale, submerged MBR have been reported. The objective of this study was to perform membrane autopsy work to analyze membrane scaling in a submerged MBR treating calcium‐rich wastewater. RESULTS: Membrane autopsy work provided evidence that deposition of calcium carbonate (CaCO₃) scale occurred on the membrane surface at the completion of pilot‐scale, submerged MBR operation. The CaCO₃ scaling resulted in significant external fouling on the surface of the membrane. The membrane scaling increased the rejection of calcium with MF membranes. However, the level of CaCO₃ scaling as internal fouling (in the pores) was almost negligible. This autopsy work also showed that aeration did not play a major role in controlling CaCO₃ scaling at the membrane surface in a submerged MBR. Chemical cleaning using citric acid solution efficiently removed CaCO₃ scale from the membrane. Combining citric acid with sodium hypochlorite pretreatment provided synergistic effects, further reducing CaCO₃ scale formation. CONCLUSION: The carbonate salt of calcium leads to precipitation resulting in surface fouling of membranes, and this cannot be removed physically by aeration in a submerged MBR treating calcium‐rich wastewater. It is necessary to combine properly‐selected cleaning strategies with submerged MBR treating wastewater containing a high potential for inorganic chemical precipitates. Copyright © 2009 Society of Chemical Industry     

Controllable synthesis of calcium carbonate polymorphs at different temperatures

Calcium carbonate with various structures and morphologies were prepared by double injection of the CaCl₂ and NH₄HCO₃ solutions with molar ratio of 1:1 at 30-80 °C. The lamellar vaterite particles, the mixture composed of vaterite, aragonite and calcite, and the aragonite whiskers were formed at 30-40 °C, 50-70 °C and 80 °C, respectively. Thermodynamic calculation showed that the value of [CO₃²⁻]/[Ca²⁺] decreased with the increase of temperature, which may be one of the reasons for the formation of the lamellar vaterite at 30-40 °C and the aragonite whiskers at 80 °C.     

Comparison of calcite and vaterite as precursors for CO3Ap artificial bone fabrication through a dissolution–precipitation reaction

Carbonate apatite (CO₃Ap) artificial bone is fabricated in an aqueous solution using calcium carbonate as a precursor. CO₃Ap has attracted attention because it demonstrates high osteoconductivity and can replace a damaged bone based on the bone remodeling process. This study aims to compare vaterite and calcite, which are metastable and stable polymorphs of calcium carbonate, respectively, as precursors. When the vaterite granules, which have higher solubility and consist of smaller crystals than calcite, prepared from calcium oxide granules were immersed in disodium hydrogen phosphate solution, the compositional transformation to CO₃Ap was quicker than that of calcite. Based on the investigations on rabbit femurs, it was observed that the remodeling of CO₃Ap to a new bone was faster when vaterite was used as a precursor compared to when calcite was used as a precursor. It is concluded that vaterite can be a better precursor than calcite for CO₃Ap artificial bone fabrication.     

以白云石为原料氨碱法制备球霰石及其生成机理研究

采用仿Solvay氨碱法,以白云石为起始原料,在碱性环境下制备出高球霰石含量的碳酸钙。XRD和SEM表征结果显示,碳化温度为20~40 ℃时的产品为球霰石;40~60 ℃时的产品为方解石;60~90 ℃时的产品为文石。球霰石的高倍SEM发现产品有许多微孔结构,对产品进行比表面积测定为32.653 m²/g,孔径为2.972 nm,为生物分子的装载提供了良好的空间。对球霰石的形成机理分析表明,NH₄⁺-NH₃缓冲体系不仅可以增加碳酸钙的过饱和度,还可以改善溶液环境,为球霰石的生长提供了一个良好的溶液环境,溶液中微量的Mg²⁺起到了促进完好晶型形成的作用。     

Effects of sodium dodecyl benzenesulfonic acid (SDBS) on the morphology and the crystal phase of CaCO<Subscript>3</Subscript>

The effects of anionic surfactant on the morphology and crystallization of calcium carbonate precipitated from CaCl₂ and Na₂CO₃ were investigated. Although reaction temperature did not have an effect on the morphology of calcium carbonate, it did have an effect on the cluster size. The cluster size became bigger with high reaction temperature. With the addition of sodium dodecyl benzenesulfonic acid (SDBS), the morphology of precipitated calcium carbonate changed from cubic to porous spheres with over 98% of the crystal phase transformed from calcite to vaterite. The analysis of precipitates formed by the reaction of CaCl₂ solution (from limestone (CaO 50% content)) and Na₂CO₃ found that the morphology of precipitated calcium carbonate changed from cubic to spherical, and the crystal phase changed from calcite to over 94% vaterite with the addition of sodium dodecyl benzenesulfonic acid. These vaterite structures were solid spheres rather than hollow ones.     

Factors affecting the phase and morphology of CaCO3 prepared by a bubbling method

Precipitated calcium carbonate (PCC) was prepared by bubbling a CO₂/N₂ mixed gas into a CaCl₂ solution. The influence of preparation conditions on the phase and morphology of PCC was discussed with the help of XRD and SEM measurements. The results showed that the initial CaCl₂ concentration, flow rate and temperature play an important role on the morphology of PCC. At low initial CaCl₂ concentration or high flow rate, spherical vaterite was preferably formed. Otherwise, the rhombic calcite was ready to form. Temperature is a determining factor on the formation of aragonite. Needle-like aragonite was precipitated at 60 °C. The results also indicated that both the bubbling time and stirring rate have a minor effect on the phase and morphology of PCC.     

Influence of relative humidity on the carbonation of calcium hydroxide nanoparticles and the formation of calcium carbonate polymorphs

A consolidating product based on nanoparticles of slaked lime (Ca(OH)₂) dispersed in isopropyl alcohol was exposed under different relative humidities (RH), 33%, 54%, 75% and 90% during 7, 14, 21 and 28 days. The characterization of the calcium hydroxide nanoparticles and the formed calcium carbonate polymorphs have been performed by Micro Raman spectroscopy, Transmission Electron Microscopy (TEM), Environmental Scanning Electron Microscopy (ESEM) with Energy Dispersive X-ray Spectroscopy (EDS) and X-ray Diffraction (XRD). Precipitation and transformation of calcium carbonate polymorphs strongly depend on the relative humidity (RH). Higher RH (75%–90% RH) gives rise to amorphous calcium carbonate and monohydrocalcite, calcite, aragonite and vaterite, faster carbonation and larger particles sizes with higher crystallinity compared to lower RH (33%–54% RH) that gives rise mainly to portlandite and vaterite, slower carbonation and smaller particle sizes with lower crystallinity.     

Casein phosphopeptides–vaterite calcium carbonate enhance cytocompatibility and osteoinductivity of poly(l‐lactic acid)

Although calcium carbonate has been proved to be effective in neutralizing the acid degradation products of poly(l ‐lactic acid) (PLLA), it has no osteoinductivity. In this study, casein phosphopeptides (CPPs)‐containing CaCO₃ vaterite were synthesized by fast precipitation in an aqueous solution of CaCl₂, Na₂CO₃, and 2 mg/ml of CPPs. CaCO₃–PLLA composite membranes (P‐vaterite–CPP) were prepared (CaCO₃/PLLA =1:2) and exhibited uniform structure and increased hydrophilicity. These composite membranes enhanced hydroxyapatite formation after incubated in simulated body fluid at 37°C for 7 days. The P‐vaterite–CPP membranes promoted human bone marrow stromal cells (hBMSCs) proliferation 4 and 7 days after seeding. Scanning electron microscope images of hBMSCs on the composite membranes exhibited a polygonal and unevenly spreading morphology. Immunofluorescent staining of cytoskeleton and focal adhesion showed that hBMSCs had more stress fibers and were more spreading, indicating a good cell adhesion on the CPPs‐containing composite membranes. Osteogenesis related genes (alkaline phosphatase, collagen type, osteocalcin, and osteopontin) expressions were significantly higher on the CPPs‐containing membranes than those on the CPPs‐free membranes (P < 0.05). It can be concluded that the addition of CPPs induces vaterite formation and thus improve cytocompatibility and osteoinductivity of PLLA. POLYM. COMPOS., 36:1213–1223, 2015. © 2014 Society of Plastics Engineers     

Synthesis of single phase aragonite precipitated calcium carbonate in Ca(OH)2-Na2CO3-NaOH reaction system

The formation behavior of precipitated calcium carbonate polymorphs was investigated in three different supersaturation levels. Because the most easily adjustable and influential variable determining supersaturation is the ion concentration of the major reactants — Ca²⁺ and CO3 ₃ ²⁻ — the supersaturation can be adjusted by changing the ion concentration of these two ions. At high supersaturation, free energy is necessary for a decrease in nucleation, promoting the formation of a sphere-shaped vaterite, while aragonite and calcite were seen to co-exist at medium supersaturation. At low supersaturation, aragonite was mainly formed by mixing with some calcite. Hence, we considered that lower supersaturation was necessary to obtain a single phase aragonite. Furthermore, we found that the solubility of Ca(OH)₂ was decreased with the addition of NaOH by a common ion effect. Thus, it is possible to perform an experiment at a lower Ca²⁺ concentration. The aragonite was synthesized by adding the Na₂CO₃ solution to the Ca(OH)₂ slurry containing several concentrations of NaOH solution at 75°C and under the addition rate of Na₂CO₃ at 3 ml/min. The formation yield of calcite decreased when the NaOH concentration was increased. In conclusion, in the case of the reaction of the 2.5 M NaOH solution over 210 minutes, single-phase aragonite with an aspect ratio of 20 was obtained.     

Effects of PAA and PBTCA on CaCO3 Scaling in Pool Boiling System

Formation of mineral scales on heat exchangers is a persistent and expensive problem. In the presentpaper, the calcium carbonate scale inhibition by two inhibitors, polyacrylic acid (PAA) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) has been studied in a pool boiling system. It is found that PBTCA has abetter inhibition effect than PAA under the identical conditions. X-ray diffraction(XRD) and Fourier transform-infrared(FTIR) analyses demonstrate that the content of vaterite increases as inhibition effects increase. Themetastable crystal forms of vaterite and aragonite are stabilized kinetically in the presence of inhibitors. Therelationship between the inhibition effect and the fractal dimension has also been investigated. The result showsthat the fractal dimension is higher in the presence of inhibitors. The better the inhibition effect, the higher thefractal dimension. The step morphology was observed by atomic force microscopy (AFM) images. It is shown thatthe step space on the calcium carbonate surface increases in the presence of inhibitors. Moreover, with the increaseof inhibition effect, both the step space and the fractal dimension increase. The step bunching is found on thecalcium carbonate by AFM. The better the inhibition effect of the inhibitor, the slower the step velocity in theunbunched location. As a result, the step space becomes wider in the presence of PBTCA than that in the presenceof PAA.     

CaCO<Subscript>3</Subscript> crystallization with feeding of aspartic acid

Aspartic acid (Asp) was employed as the organic template in inducing the nucleation and growth of calcium carbonate. Crystallization experiments were carried out by the addition of Asp into the solution of sodium carbonate and calcium chloride. The effects of reaction time, dropping velocity of Asp and Na₂CO₃ solution were tested. The CaCO₃ crystals were analyzed by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Fourier transform infrared spectrometry (FT-IR). Two kinds of crystals were identified by FT-IR spectrum. In the presence of Asp, formation of vaterite is induced in crystallization solution. Also, under the initial condition of an excess amount of Asp, vaterite morphology is the major one. Various morphologies of CaCO₃ are made by changing dropping velocity of added Asp and Na₂CO₃.     

Calcium carbonate inhibition by a phosphonate-terminated poly(maleic-co-sulfonate) polymeric inhibitor

The precipitation of calcium carbonate scale on heat transfer surfaces widely occurs in numerous industrial processes. For the control of calcium carbonate scale and in response to environmental guidelines, the new low phosphonic copolymer was prepared through reaction of maleic anhydride with sodium p-styrene sulfonate in water with redox system of hypophosphorous and hydrogen peroxide as initiator. The anti-scale property of the low phosphonic copolymer towards CaCO₃ in the artificial cooling water was studied through static scale inhibition tests, and the effect on formation of CaCO₃ was investigated with combination of scanning electronic microscopy (SEM), X-ray powder diffraction (XRD) analysis and Fourier transform infrared spectrometer, respectively. The results showed that the low phosphonic copolymer was excellent calcium carbonate scale inhibitor in artificial cooling water. The crystallization of CaCO₃ in the absence of inhibitor was rhombohedral calcite crystal, whereas a mixture of calcite with vaterite crystals was found in the presence of the low phosphonic copolymer. For actions of carboxyl and phosphonic acid groups, the calcite was inhibited and the metastable vaterite was stabilized in the presence of the low phosphonic copolymer during the CaCO₃ formation process.