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.     

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.     

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.     

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.     

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.     

Preparation of nanocoatings in the presence of precipitated CaCO3 fillers by UV-curing

Various methods were employed to prepare precipitated calcium carbonate (PCC) particles. Particle size and morphology were dependent on reaction conditions as well as temperature, reagents and stirring, either mechanical or by ultrasound probe sonication. Sonication helped to reduce the size of CaCO₃ particles as well as the precipitation time. Sonication was also used to disperse PCC particles in the UV-curable formulations as well as for preparation of the PCC. Formulations containing precipitated calcium carbonates and ground calcium carbonates in various grades were cured by a Mini UV-Cure device. Mechanical and thermal properties of films were characterized with a Dynamic Mechanical Analyzer (DMA). SEM analysis was also used to determine the shape and the size of the PCCs. Sonication decreased the precipitation time of calcium carbonate at least four times more than that of conventional precipitation procedures and the dispersion of particles in the formulations increased to a great extent.     

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.     

Facile control of hydroxyapatite particle morphology by utilization of calcium carbonate templates at room temperature

Hydroxyapatite (HAp, Ca₁₀(PO₄)₆(OH)₂) particles are widely used in orthopedic applications due to their chemical resemblance to the inorganic component of bone tissue. Since physical and chemical properties of HAp particles influence bone regeneration, various synthesis techniques were developed to precisely control the particle properties. However, most of these techniques required high reaction temperatures, which limited the spectrum of obtained HAp particle morphologies. In this study, ellipsoidal, bowknot-like and spherical calcium carbonate (CaCO₃) particles were utilized as solid templates to control the morphology of HAp particles (core@shell, CaCO₃@HAp) under ambient conditions. Since CaCO₃ templates had different properties, i.e. morphology, polymorph and surface area, they induced HAp formation with different efficacies, where ellipsoidal vaterite and spherical calcite particles exhibited higher CaCO₃-to-HAp conversion compared to bowknot-like aragonite particles. In vitro experiments showed that proliferation of human bone cells (hFOB) was higher upon their interaction with ellipsoidal and spherical CaCO₃@HAp particles compared to bowknot-like CaCO₃@HAp particles. These findings highlighted CaCO₃ particles as promising hard templates to control the morphology of CaCO₃@HAp particles under ambient conditions for orthopedic applications.     

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     

Peculiarities of the composition of solid phases formed in aqueous calcium–silicate systems with a medium of variable acidity

The effect of a medium’s acidity on the composition of the solid phase formed in aqueous calcium-silicate systems is investigated. Solutions of Са(NO₃)₂ and Na₂SiO₃ are used for the synthesis; the pH values were varied in the range 7.00–12.00. Freshly precipitated solid phases and products of their annealing at 1000°C were studied by the methods of Fourier IR spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM).     

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.     

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.     

Synthesis and performance evaluation of carboxyl-rich low phosphorus copolymer scale inhibitor

A novel low phosphorus terpolymer scale inhibitor P(IA-MA-SHP) was prepared by aqueous free radical polymerization using itaconic acid (IA), maleic acid (MA), and sodium hypophosphite (SHP) as raw materials. It was mainly used as an efficient scale inhibitor to inhibit CaCO₃. The structures of the copolymers were characterized by Fourier transform infrared, ¹H-NMR, and ¹³C-NMR, and the thermal properties, and scale sample crystal structure morphology of the copolymers were analyzed by thermogravimetric analysis, x-ray diffraction (XRD), and scanning electron microscope (SEM). The effects of dosage, monomer ratio, temperature, and reaction time on the scale inhibition effect were investigated, and the optimal synthesis conditions were determined. The results show that: when the monomer ratio is n(IA):n(MA) = 1.0:1.0, the mass fraction of SHP is 10%, the amount of ammonium persulfate initiator is 12%, the reaction temperature is 90°C, and the reaction time is 4 h, when the dosage of the agent is 20 mg L⁻¹, the scale inhibition rate of CaCO₃ is 94.30%, while it also has a favorable inhibitory effect on CaSO₄. The results of SEM and XRD show that the copolymer scale inhibitor can distort the lattice and has a favorable adsorption and dispersion effect. In addition, it has a positive effect on controlling the scale.     

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.     

Gram-scale synthesis and shape evolution of micro-CaCO3

A facile solution precipitation route (between Ca²⁺ and CO₃^2?) for the gram-scale synthesis of uniform micro-CaCO₃ from cubes, to spheres, to ellipses, to oblates, and to rods via control of the type and amount of oriented additives (dodecyl sodium sulfate, cetyltrimethylammonium bromide, Ba²⁺ and Co²⁺) has been demonstrated. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). In the presence of Ba²⁺, dispersed micro-CaCO₃ spheres (average diameter is 2391.1 nm, the majority particles are distributed in the range of 1574.1 to 4068.2 nm) could be vastly obtained in a highly morphological yield (~ 100%). The formation process of these microstructures was clarified as the synergic effect of oriented arrangement and ripening mechanism with face-selective additives adsorption on the growing CaCO₃ particles.     

Curcumin and quercetin as templates in the in vitro biomineralization of CaCO3: A comparative study on phase modulation

Biomineralization of calcium-based biominerals is influenced by organic molecules containing oxygen donor atoms. In this work, we were able to synthesize and stabilize the least stable crystalline phase of CaCO₃, vaterite, using the biologically useful organic molecule curcumin as the template. The vaterite phase formed was stable in solution at least for 18 h. A comparative study with chemically similar molecule quercetin, a flavonoid, was performed. Though quercetin as a template could not stabilize the vaterite phase, an interesting observation was made in terms of the morphology of the calcite particles obtained. A dumbbell-shaped morphology, different from the usual rhombohedral morphology of the calcite crystals was obtained under ambient conditions. The maturation of the CaCO₃ crystals in solution with time was studied to observe the changes in terms of phase and morphology of the particles. Additionally, extended studies were performed to investigate the influence of the change in parameters such as; template concentration, the sequence of addition, temperature and ionic strength on the phase, morphology and size of the particles in the presence of both the templates.     

Synthesis of Nano Calcium Hydroxide in Aqueous Medium

The present work reports a simple, inexpensive method for synthesis of calcium hydroxide [Ca(OH)₂] nanoparticles (CHNPs). The method involves chemical precipitation (CP) in aqueous medium at room temperature. Calcium nitrate dihydrate [Ca(NO₃)₂.2H₂O] and sodium hydroxide were used as precursors. The CHNPs were characterized by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), Rietveld analysis, field‐emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM), BET surface area evaluation as well as particle size distribution analysis techniques. The results confirmed the synthesis of CHNPs as the major phase. The CHNPs exhibited an average size of about 350 nm. In addition, some calcite phase formed due to the inevitable carbonation process. A very minor amount of aragonite phase was also present. A schematically developed new qualitative model is proposed to explain the genesis and subsequent evolution of the various phases at the nanoscale. The model helps to identify the rate‐controlling step. It also highlights the implication of reaction kinetics control in synthesis of predesigned nanophase assembly.     

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 and electrochemical behaviour of tin oxide for use as anode in lithium rechargeable batteries

SnO₂ was synthesized by precipitation from an aqueous solution of SnCl₄ and NH₄OH, followed by a heat treatment. The product was characterized by XRD, SEM, FTIR spectroscopy, DSC and TG. The XRD patterns suggest the formation of phase-pure cassiterite form of SnO₂. SEM imaging indicates that the particles obtained are of sub-micron size with good morphology and size control (around ∼300 nm). Electrodes were fabricated by a slurry-coating procedure and the electrochemical performances of these electrodes were evaluated using galvanostatic cycling tests. The results suggest that the heat treated SnO₂ samples deliver higher capacities when cycled between 1.0 and 0.1 V vs. Li⁺/Li and showed coulombic efficiencies of more than 98% in the tenth cycle.     

Effects of comb copolymer PAA-g-MPEO on rheological and dispersion properties of aqueous CaCO<Subscript>3</Subscript> suspensions

Summary The comb copolymer poly(acrylic acid) (PAA) grafted methoxyl poly(ethylene oxide) (MPEO) (PAA-g-MPEO) as dispersant was used in aqueous CaCO₃ suspensions. The PAA-g-MPEO was adsorbed onto CaCO₃particle surfaces due to the electrostatic attraction. The adsorbed amount increased with increasing PAA-g-MPEO content. The CaCO₃ adsorbed PAA-g-MPEO displayed negative zeta potential. The zeta potential was more negative with increasing PAA-g-MPEO content. Addition of PAA-g-MPEO, the conductivity of aqueous CaCO₃ suspensions decreased firstly, and then increased with increasing PAA-g-MPEO content. Compared to that of aqueous CaCO₃ suspensions, the viscosity of aqueous CaCO₃/PAA-g-MPEO suspension reduced remarkably, and the liquidity of the suspensions was improved. The dispersion of CaCO₃ particles in aqueous CaCO₃/PAA-g-MPEO suspensions was significantly improved due to electrostatic repulsions and steric hindrance between CaCO₃ particles adsorbed PAA-g-MPEO.