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.     

Growing Innovative Calcium Carbonate Morphologies by Utilizing the Colloidal Gas Aphron System as a Surfactant-Based Template Method

Many studies have been conducted to study the various polymorphs and morphologies of calcium carbonate crystals in nature and living organisms. In this experimental work, a novel method has been employed to crystallize calcium carbonate by using colloidal gas aphron dispersion. The polymorph and morphology of prepared particles were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectrometry techniques. SEM and XRD analyses demonstrated that the morphology of synthesized CaCO₃ can be changed from spherical (vaterite phase) to novel rod and plate-like shapes (mixture of vaterite and calcite phases) with changes in the surfactant concentration. The quantitative examination results of different calcium carbonate polymorph orientations showed that the precursor concentrations had no significant effect on the orientation of calcite phase, but rather they affected the orientation development of vaterite phase at a higher surfactant concentration.     

Mineralization of Calcium Carbonate Induced by Egg Substrate and an Electric Field

Egg substrates, including eggshell, egg membranes, and egg white, exert a significant influence on CaCO₃ biomineralization. CaCO₃ crystallization at different temperatures, concentrations, and with various egg substrates was systematically investigated via rapidly mixing solution method. The crystals were determined by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. As the CaCl₂ concentration increased, the CaCO₃ crystal form gradually changed from calcite to vaterite. Under rising temperature, the single‐hole vaterite and besom‐like aragonite were formed on the raw and boiled egg white substrate, respectively. The effects of electric field on CaCO₃ crystallization were also explored. The findings may offer a novel approach to CaCO₃ synthesis.     

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.     

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.     

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     

Synthesis of calcium carbonate–chitosan composites via biomimetic processing

The crystal growth of calcium carbonate on a chitosan substrate was achieved using a supersaturated calcium carbonate solution, at different concentrations of polyacrylic acid (PAA) as an additive. Several techniques have been employed to characterize the systems. The pH of the solution as the one of indices was used to monitor the crystallization. In the absence of polyacrylic acid, the pH of the solution changed from 6.00 to 8.50 during the crystallization; meanwhile, sporadic nucleation and crystallization was observed via optical microscopy. By introducing polyacrylic acid to the systems, positively charged protonated nitrogen and negatively charged carboxylate ions were produced by reaction between the amino group in chitosan and the carboxyl group in polyacrylic acid, which were detected by ATR-IR and XPS techniques. These charges induced calcium carbonate nucleation of calcite and vaterite crystals on the chitosan-film surface. The average size of the vaterite phase was about 15 nm, determined by XRD. The pH of the solution changed from 5.80 to 9.25 during the crystallization; moreover, the crystals showed spherical morphology, which consisted of a large number of small particles with a diameter of about 0.2 μm. © 1995 John Wiley & Sons, Inc.     

Effect of Organic Additives on Electrochemical Surface Precipitation and Polymorphism of CaCO3

The inhibition effect of three organic additives on the precipitation and polymorphism of CaCO₃ deposited on gold surfaces was investigated using electrochemical and microscopic techniques. Additives, two polyacrylic acid (PAA) polymers with different molecular weights (Mw 2100, Mw 30,000), and 1,2,4,5‐benzenetetracarboxylic acid (BTCA), were either added to the solution before or during deposition. In the presence of 100 ppm of one of the three additives in solution, almost no scale was observed on the surface for at least 24 hours. In the presence of lower concentrations of PAA Mw 2100, only distorted calcite crystals were obtained while with PAA Mw 30,000 the polymorph was spherical vaterite. A mixture of calcite and vaterite was observed with the BTCA additive. Addition of the polymers inhibits further nucleation and growth even if added after partial deposition of CaCO₃ while BTCA has no effect once nucleation has started. The results indicate that the inhibit ion effect of the PAA polymers is due to adsorption on the electrode surface while the effect of BTCA is related to chelation of calcium ions in solution.     

二水硫酸钙间接矿化二氧化碳CTAB对碳酸钙晶型的影响

提升产品附加值对改善二氧化碳矿化过程的经济性具有重要意义。在二水硫酸钙与碳酸铵溶液进行间接矿化反应过程中,采用十六烷基三甲基溴化铵（CTAB）为晶型调节剂,可以获得球霰石晶型的碳酸钙。系统研究了反应时间、反应温度、CTAB加入量对碳酸钙晶型和形貌的影响,通过X射线衍射（XRD）、扫描电镜（SEM）和红外光谱（FT-IR）对碳酸钙的晶型、形貌进行了表征。结果表明：反应过程为先形成亚稳定相的球霰石,再向热力学最稳定的方解石相转化;添加CTAB能够明显地增强球霰石的稳定性;较低温度有利于球霰石的形成;在反应温度为30 ℃、二水硫酸钙和碳酸铵加入量均为0.1 mol/L、CTAB加入量为0.54 mmol/L条件下,碳酸钙中球霰石占比高达80%以上;CTAB在球霰石表面上的吸附降低了其表面能,从而抑制了球霰石向方解石的转化。     

Structural characteristics of poly(vinyl alcohol)–calcium carbonate composites prepared by sequential method

Abstract

Composites of poly(vinyl alcohol) (PVA) and calcium carbonate (CaCO₃) were prepared by a sequential method involving first in situ synthesis of CaCO₃ in PVA solution, then physical crosslinking of synthetic suspension and subsequently washing of resultant elastic gel followed by consolidation. The phase and composition, mechanical properties and microstructure of the composites and possible molecular interactions between both components were evaluated. X-ray diffraction analysis revealed that calcium carbonate was mainly composed of aragonite and calcite. Compression tests confirmed the composites prepared by this sequential method had good mechanical properties and that the compressive strength of the composites increased with higher content of calcium carbonate. PVA formed an interconnected network and needle-like CaCO₃ crystals together with some fine grains were well compatible with PVA. In situ synthesis induced a spectral shift of hydroxyl groups and C–O bonds of PVA and the suppression of the characteristic adsorption of calcite was also observed, according to Fourier transform infrared spectroscopy measurements.     

Nonenzymatic Transformation of Amorphous CaCO3 into Calcium Phosphate Mineral after Exposure to Sodium Phosphate in Vitro: Implications for in Vivo Hydroxyapatite Bone Formation

Studies indicate that mammalian bone formation is initiated at calcium carbonate bioseeds, a process that is driven enzymatically by carbonic anhydrase (CA). We show that amorphous calcium carbonate (ACC) and bicarbonate (HCO₃^?) cause induction of expression of the CA in human osteogenic SaOS‐2 cells. The mineral deposits formed on the surface of the cells are rich in C, Ca and P. FTIR analysis revealed that ACC, vaterite, and aragonite, after exposure to phosphate, undergo transformation into calcium phosphate. This exchange was not seen for calcite. The changes to ACC, vaterite, and aragonite depended on the concentration of phosphate. The rate of incorporation of phosphate into ACC, vaterite, and aragonite, is significantly accelerated in the presence of a peptide rich in aspartic acid and glutamic acid. We propose that the initial CaCO₃ bioseed formation is driven by CA, and that the subsequent conversion to calcium phosphate/calcium hydroxyapatite (exchange of carbonate by phosphate) is a non‐enzymatic exchange process.     

The mechanochemical route of vaterite synthesis using sodium hexametaphosphate as an inorganic additive

Vaterite is a metastable phase of CaCO₃ and was prepared mechanochemically for the first time with the assistance of sodium hexametaphosphate (SHMP). First, CaCO₃ was prepared without SHMP and was characterized using X-ray diffraction (XRD) to study the effect of milling times and speeds on the polymorphs of product. The results indicate that the reaction is complete at 60 minutes producing only calcite. Additionally, amorphous CaCO₃ (ACC) was obtained at a milling speed of 300 rpm, while calcite was obtained at 600 and 1000 rpm. Then, the effect of SHMP concentration on the fraction of vaterite was investigated, and the vaterite fraction increased with increasing SHMP amount. Subsequently, the effect of milling speed in the presence of 0.8 g of SHMP was studied, and the vaterite fraction increased with decreasing milling speed. Finally, gentler manual milling was employed, and the effect of the amount of added SHMP on vaterite formation was evaluated. The results confirmed that vaterite increased with increasing amounts of SHMP, and that vaterite formed more readily via manual milling than via mechanical milling. Observations with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that calcite and vaterite particles formed by mechanical milling were irregular agglomerates composed of primary nanoparticles while calcite particles formed by manual milling were irregular microparticles. Moreover, vaterite readily aggregated into spherical particles as the amount of SHMP increased. To investigate the reaction process and mechanism, the ethanol-washed product was characterized using XRD, SEM/EDS and TEM/SAED. The results demonstrate that ACC and calcite were concomitant during the milling process, and ACC transformed into vaterite during subsequent water washing.     

Effects of magnetic field on calcium carbonate precipitation: Ionic and particle mechanisms

There are two most widely reported mechanisms to study the effect of magnetic fields on calcium carbonate (CaCO₃) precipitate, namely ionic and particle mechanisms. The effects are most debatable because they are contrary to each other. This study explored the effects of both mechanisms in CaCO₃ deposit and total CaCO₃ precipitation using ionic and particle methods. The ionic method showed reductions in CaCO₃ deposit and total precipitation rate of CaCO₃, whereas the particle method showed the opposite results. The particle number decreased and the average particle diameter of CaCO₃ deposit increased in the ionic method. Meanwhile in the particle method, the particle number increased, average particle diameter decreased and particle aggregation of CaCO₃ was observed. XRD measurement on all deposits showed that the crystal deposit was mostly of calcite and the traces of vaterite. However, the amount of the crystal in the particle method was observed to be less than that in the ionic method, indicating that CaCO₃ deposit was more amorphous. Particle mechanism decreased the Ca²⁺ ion concentration in solution during magnetization, and ionic mechanism reduced scale (CaCO₃) formation after magnetization and separation processes. This method could be applied for decreasing water hardness and prevent the formation of scaling.     

Effect of polyethylene glycol on phase and morphology of calcium carbonate

Calcium carbonate (CaCO₃) with different phases and morphologies were prepared and characterized by scanning electron microscopy (SEM), powder X‐ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. The effect of polyethylene glycol (PEG) with different molecular weight and concentrations on the phase and morphology of CaCO₃ was studied. The results showed that aragonite was the only phase in the solution without PEG, while calcite phase could be obtained by the use of PEG as the additive. The possible crystallization mechanism for the formation of CaCO₃ polymorphs in the presence of different PEG was also discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The crystallization behavior of calcium carbonate in ethanol/water solution containing mixed nonionic/anionic surfactants

Crystallization of CaCO₃ was performed in an ethanol/water solution containing Pluronic F127 (EO₉₇PO₆₈EO₉₇) and sodium dodecyl sulfate (SDS). The effects of the ethanol/water volume ratio, concentration of surfactants, and aging temperature (30-90 °C) on the morphology and polymorphs of CaCO₃ were investigated using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). The presence of both F127 and SDS in solution favored the vaterite phase of CaCO₃. A binary calcite-vaterite mixture and a ternary calcite-vaterite-aragonite mixture were produced at low (< 60 °C) and high temperatures, respectively. Spherical, plate-like, flower-like, and rod-like crystals were obtained at different ethanol/water volume ratios. Controllable synthesis of nearly pure flower-like vaterite and rod-like aragonite can be realized by adjusting the ethanol/water volume ratio. The formation mechanism of flower-like CaCO₃ crystals is discussed.     

Effect of degree of deprotonation of maleic anhydride-allyl polyethoxy carboxylic acid copolymer on calcium scale

A hydrophilic copolymer (MA-APEA) containing carboxylic acid group and ethylene oxide group is synthesized from maleic anhydride (MA) and allyloxy polyethoxy carboxylic acid (APEA) in free radical polymerization and its structure is characterized using FT-IR, ¹H nuclear magnetic resonance spectrometer and gel permeation chromatographic techniques. Seven polymer solutions with different degrees of deprotonation are prepared by adding caustic solution to the polymer solution. Effects of the degree of deprotonation of the polymer on curbing calcium scale and the corrosion inhibition of low carbon steel are studied. Influences of the operating conditions on inhibition against CaCO₃ scale by the polymer with different degrees of deprotonation are also investigated. Effects of the degree of deprotonation on CaCO₃ deposits/precipitate are analyzed using scanning electronic microscope and X-ray diffraction. The results show that different degrees of deprotonation of the polymer have different influences on different calcium scale and corrosion inhibition of low carbon steel. The performance of the polymer to withstand high alkalinity and high hardness and high temperature decreases with increase in the degree of deprotonation. The change in the degree of deprotonation influences the conversion of aragonite and vaterite to calcite, and hardly impacts the crystal morphology of CaCO₃ crystals. MA-APEA has proven to be an excellent calcium scale inhibitor.     

Facile preparation of cubic calcium carbonate nanoparticles with hydrophobic properties via a carbonation route

Cubic calcium carbonate nanoparticles with hydrophobic properties were prepared by a carbonation route in the presence of dodecanoic acid at 20 °C. The as-prepared products were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and contact angle analysis. It was found that dodecanoic acid not only inhibited the growth of CaCO₃ particles but also changed the surface properties of the final products. The effects of the weight ratio of DA to CaCO₃, the calcium hydroxide concentration and temperature on the morphologies of the as-prepared calcium carbonate were systematically studied. The results showed that temperature, the weight ratio of DA to CaCO₃ and the calcium hydroxide concentration are important parameters for the preparation of cubic calcium carbonate nanoparticles with hydrophobic properties.     

Synthesis of vaterite CaCO3 as submicron and nanosized particles using inorganic precursors and sucrose in aqueous medium

It is reported the synthesis of CaCO₃ vaterite as stable nanoparticles and submicron-sized by a simple and relatively rapid procedure. XRD, SEM and FTIR techniques have been used to characterize the precipitated products. The synthesis is based on chemical precipitation of inorganic salt precursors, calcium nitrate tetrahydrate and sodium bicarbonate, and using the disaccharide sucrose as an additive in aqueous medium. The role of the disaccharide sucrose is to control the vaterite precipitation after nucleation and growth. It has been found that an increase in sugar concentration promotes the crystal precipitation of vaterite with spherulitic morphology, as revealed by SEM, and changed the surface of the precipitated particles. There is a significant difference between CaCO₃ precipitation in the absence and presence of sucrose. Addition of 0% of sucrose leads to 83% of calcite as identified by XRD methods. In contrast, addition of 67% of sucrose in aqueous medium produces 100% vaterite. The present results may be useful to provide a quick, simple, inexpensive and novel method for the controlled synthesis of new advanced biomaterials based on vaterite particles without hazardous chemicals and inert atmosphere, with great possibilities for industrial scale production.     

The synthesis of vaterite and physical properties of PP/CaCO3 composites

Vaterite was synthesized in the emulsion state at 50 ‡C. The mixing method was found to have a significant effect on the shape of vaterite. In order to investigate the effect of CaCO₃ morphology on mechanical property and thermal property of polypropylene, cubic forms of calcite and needle forms of aragonite were also prepared in the emulsion states. When vaterite was used as a filler in the PP/CaCO₃ composites, the crystallization temperature and crystallinity were higher than those with other forms. In addition, the size of spherullite of polypropylene was the finest when vaterite was used. Therefore, the vaterite is considered as a proper nucleating agent for polypropylene.