Oriented aggregation and novel phase transformation of vaterite controlled by the synergistic effect of calcium dodecyl sulfate and n-pentanol

Calcium dodecyl sulfate (CDS) was used for the first time both as an anionic surfactant and as the source of mineral ions in the precipitation process of calcium carbonate (CaCO3). The simple reaction of the enriched Ca2+ ions at the so-called organic-inorganic interfaces with the slowly bubbled CO2 gas resulted in the metastable vaterite polymorph with various structures. The single-crystalline vaterite of the hexagonal platelets, the lens-shaped structures with hexagonal symmetry, the olive-shaped superstructures and these with a concave at each top of olives, and another metastable polymorph of aragonite were obtained, respectively, depending upon the concentration ratio between CDS and n-pentanol. The synergistic effect of CDS and n-pentanol is believed to play a crucial role in driving the oriented aggregation of metastable nanoparticles. Simultaneously, the novel phase transformation of vaterite to aragonite was observed, implying the possible formation mechanism of aragonite at room temperature and in the absence of magnesium ions.     

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.     

Crystallization of CaCO3 in the presence of sulfate and additives: experimental and molecular dynamics simulation studies

The effects of sulfate and BHTPMP (Bis (hexamethylene) triaminepentakis (methylene phosphonic acid)) on the crystallization rate, phase composition and morphology of calcium carbonate have been studied. It was observed that sulfate reduces the nucleation rate and favors the formation of aragonite form in the calcium carbonate precipitate. Moreover, in the presence of sulfate the rhombohedral morphology of the calcite crystals is modified, and during the formation of calcite, the development of {104} faces are more significantly prohibited than {110} faces. In the presence of sulfate together with BHTPMP, the crystallization process is inhibited and the modified morphology and the dominant calcite form are observed in the solid. The results from molecular dynamics simulations show the more strong combination of sulfate with calcite surface, in particular the {104} face, in comparison with the aragonite surface. The strong interaction of BHTPMP with sulfate and the aragonite surface favors the formation of the dominant calcite phase in the precipitate.     

Properties of amorphous calcium carbonate and the template action of vaterite spheres

The fast mixing of aqueous solutions of calcium chloride and sodium carbonate could immediately result in amorphous calcium carbonate (ACC). Under vigorous stirring, the formed ACC in the precipitation system will dissolve first and, then, transform within minutes to produce crystalline forms of vaterite and calcite. After that, the solution-mediated mechanism dominates the transformation of the thermodynamically unstable vaterite into the thermodynamically stable calcite. Although ACC is the least stable form of the six anhydrous phases of calcium carbonate (CaCO(3)), it could be, however, produced and stabilized by a variety of organisms. To better understand the formation-transformation mechanism of ACC and vaterite into calcite, ex-situ methods (i.e., scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction spectroscopy) were used to characterize the formation-transformation process of ACC and vaterite in aqueous systems without organic additives, showing that ACC sampled at different conditions has different properties (i.e., lifetime, morphology, and spectrum characterization). It is also very interesting to capture the obviously polycrystalline particles of CaCO(3) during the transformation process from vaterite to calcite, which suggests the formation mechanism for the calcite superstructure with multidimensional morphology.     

Quantitative analysis of synthetic calcium carbonate polymorphs using FT-IR spectroscopy

Fourier Transform Infrared Spectroscopy (FT-IR) was used successfully for the simultaneous quantitative analysis of calcium carbonate phases (calcite, aragonite, vaterite) in ternary mixtures. From the FT-IR spectra of pure calcite, aragonite and vaterite powders with KBr, the absorptivities, α, of the absorption bands at 713 cm⁻¹ for calcite, 745 cm⁻¹ for vaterite, 713 and 700 cm⁻¹ for aragonite, were determined. In order to overcome the absorption band overlapping a set of equations based on Beer's law was developed. The detection limits were also established and found to be 1.1×10⁻⁴ mg calcite per mm² of pellet at 713 cm⁻¹, 3.6×10⁻⁴ mg aragonite per mm² of pellet at 700 cm⁻¹, 1.8×10⁻⁴ mg aragonite per mm² of pellet at 713 cm⁻¹ and 3.1×10⁻⁴ mg vaterite per mm² of pellet at 745 cm⁻¹. Analysis of a known ternary mixture of calcium carbonate polymorphs tested the validity of the method.     

Calcium carbonate solubility: a reappraisal of scale formation and inhibition

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.     

Calcium Carbonate Polyamorphism and Its Role in Biomineralization: How Many Amorphous Calcium Carbonates Are There?

Although the polymorphism of calcium carbonate is well known, and its polymorphs—calcite, aragonite, and vaterite—have been highly studied in the context of biomineralization, polyamorphism is a much more recently discovered phenomenon, and the existence of more than one amorphous phase of calcium carbonate in biominerals has only very recently been understood. Here we summarize what is known about polyamorphism in calcium carbonate as well as what is understood about the role of amorphous calcium carbonate in biominerals. We show that consideration of the amorphous forms of calcium carbonate within the physical notion of polyamorphism leads to new insights when it comes to the mechanisms by which polymorphic structures can evolve in the first place. This not only has implications for our understanding of biomineralization, but also of the means by which crystallization may be controlled in medical, pharmaceutical, and industrial contexts.     

Controlled growth of calcium carbonate by poly(ethylenimine) at the air/water interface

Two metastable calcium carbonate polymorphs, hemispherical vaterite and needle-like aragonite, are selectively formed at the air/water interface by the mediation of poly(ethyleneimine)(with molecular weights of 25000 and 2000, respectively) dissolved in supersaturated calcium bicarbonate solution.     

Quantitative determination of binary and tertiary calcium carbonate mixtures using powder X-ray diffraction

The ability to determine the calcium carbonate polymorphic ratio of calcite, aragonite and vaterite in a mixture is important for a variety of applications, particularly the fields of biomineralisation and crystal engineering. Raman spectroscopy and powder X-ray diffraction were used to quantitatively determine the polymorphic composition of both binary and tertiary mixtures of calcium carbonate. It was found that the quantitative detection limits of powder X-ray diffraction were superior to both Raman and infrared spectroscopy.     

Homogeneous Precipitation of Calcium Carbonates by Enzyme Catalyzed Reaction

Catalytic decomposition of urea by urease in aqueous calcium chloride solutions was used to rapidly prepare calcium carbonate polymorphs at room temperature. The nature of the resulting particles depended on the concentration of the enzyme and, in a strong manner, on the agitation of the reacting solutions. In an undisturbed system an amorphous precipitate is formed first, which readily crystallized to vaterite and upon aging changed to calcite. Under the influence of magnetic stirring, the amorphous phase could be not observed; instead smaller particles were initially obtained, which aggregated to vaterite and calcite. Similarly, the application of ultrasonic energy produced small vaterite particles at the early stages. It is apparent that enzyme macromolecules are important in the development of calcite faces and, as such, they exert significant influence on calcite morphology, without being present in detectable amounts in the resulting solids. Copyright 2001 Academic Press.     

X-ray diffraction and scanning electron microscopy studies of calcium carbonate electrodeposited on a steel surface

Calcium carbonate was deposited on a stainless steel surface with the use of an electrical potential of 10 V. The crystals formed on the surface were examined with X-ray diffraction and with scanning electron microscopy, which revealed that calcite, vaterite and amorphous calcium carbonate was formed. Two different surface active polymers were added to the solution and their effect on the crystal structure was investigated. It was found that the more hydrophilic of the two polymers promoted calcite growth and suppressed vaterite growth. The more hydrophobic polymer completely inhibited vaterite growth. Both polymers decreased the amount of crystals formed on the steel surface, the more hydrophobic polymer being the most effective. The crystal inhibition efficiency was enhanced close to the cloud point of the polymers. The results were compared with the effect of poly(acrylic acid), a commonly used antiscalant. It was found that poly(acrylic acid) was about as efficient as the more hydrophobic polymer in decreasing the amount of calcium carbonate. At higher concentrations of poly(acrylic acid), almost all of the calcium carbonate precipitated in the amorphous form.     

Investigation of Calcium Carbonate Scaling Inhibition and Scale Morphology by AFM

The calcium carbonate scale inhibition by two inhibitors, polyacrylic acid (PAA) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), has been studied in two heat transfer systems: recirculating cooling water and pool boiling systems. It is found that PBTCA has a better inhibition effect than PAA under identical conditions. The inhibition effect increases with increasing fluid velocity for the cooling water system, whereas in the presence of inhibitors, the fluid velocity has less effect on the scaling behavior. When the initial surface temperature increases, the inhibition efficiency decreases. In the presence of inhibitors, the scaling behavior is insensitive to the change of surface temperature. The relationship between the inhibition effect and the fractal dimension has also been investigated. The results show that the fractal dimension is higher in the presence of inhibitors. The better the inhibition effect, the higher the fractal dimension. XRD and FTIR analyses demonstrate that for the CaCO₃ formed in the pool boiling system, the content of vaterite increases with the increase of inhibition effects. The metastable crystal forms of vaterite and aragonite are stabilized kinetically in the presence of inhibitors. The step morphology has been observed by atomic force microscopy. It is shown that the step space on the CaCO₃ surface increases in the presence of inhibitors. Moreover, with the increase in inhibition effect, both the step space and the fractal dimension increase. Step bunching is also found and discussed in this paper.     

Bioinspired mineralization of inorganics from aqueous media controlled by synthetic polymers

The formation of inorganic structures in nature is commonly controlled by biogenic macromolecules. The understanding of mineralization phenomena and the nucleation and growth mechanisms involved is still a challenge in science but also of great industrial interest. This article focuses on the formation and mineralization of two archetypical inorganic materials: zinc oxide and amorphous calcium carbonate (ACC). Zinc oxide is selected as a model compound to investigate the role that polymers play in mineralization. Most of the effort has been devoted to the investigation of the effects of double-hydrophilic block and graft copolymers. Recent work has demonstrated that latex particles synthesized by miniemulsion polymerization, properly functionalized by various chemical groups, have similar effects to conventional block copolymers and are excellently suited for morphology control of ZnO crystals. Latex particles might serve as analogues of natural proteins in biomineralization. The second example presented, ACC, addresses the issue of whether this amorphous phase is an intermediate in the biomineralization of calcite, vaterite, or aragonite. Conditions under which amorphous calcium carbonate can be obtained as nanometer-sized spheres as a consequence of a liquid-liquid phase segregation are presented. Addition of specific block copolymers allows control of the particle size from the micrometer to the submicrometer length scale. The physical properties of novel materials synthesized from concentrated solution and their potential applications as a filler of polymers are also discussed.     

A quasi-time-resolved CryoTEM study of the nucleation of CaCO3 under langmuir monolayers

Calcium carbonate biomineralization uses complex assemblies of macromolecules that control the nucleation, growth, and positioning of the mineral with great detail. To investigate the mechanisms involved in these processes, for many years Langmuir monolayers have been used as model systems. Here, we descibe the use of cryogenic transmission electron microscopy in combination with selected area electron diffraction as a quasi-time-resolved technique to study the very early stages of this process. In this way, we assess the evolution of morphology, polymorphic type, and crystallographic orientation of the calcium carbonate formed. For this, we used a self-assembled Langmuir monolayer of a valine-based bisureido surfactant (1) spread on a CaCl2-containing subphase and deposited on a holey carbon TEM grid. In a controlled environment, the grid is exposed to an atmosphere containing NH3 and CO2 (the (NH4)2CO3 diffusion method) for precisely determined periods of time (reaction times 30-1800 s) before it was plunged into melting ethane. This procedure allows us to observe amorphous calcium carbonate (ACC) particles growing from a few tens of nanometers to hundreds of nanometers and then crystallizing to form [00.1] oriented vaterite. The vaterite in turn transforms to yield [10.0] oriented calcite. We also performed the reaction in the absence of monolayer or in the presence of a nondirective monolayer of surfactant containing an oligo(ethylene oxide) 2 head group. Both experiments also showed the formation of a transient amorphous phase followed by a direct conversion into randomly oriented calcite crystals. These results imply the specific though temporary stabilization of the (00.1) vaterite by the monolayer. However, experiments performed at higher CaCl2 concentrations show the direct conversion of ACC into [10.0] oriented calcite. Moreover, prolonged exposure to the electron beam shows that this transformation can take place as a topotactic process. The formation of the (100) calcite as final product under different conditions shows that the surfactant is very effective in directing the formation of this crystal plane. In addition, we present evidence that more than one type of ACC is involved in the processes described.     

溶液电导率法对碳酸钙结晶动力学的研究

溶液电导率法对碳酸钙结晶动力学的研究;结垢;电导率     

Influence of Calcium Sources on Microbially Induced Calcium Carbonate Precipitation by Bacillus sp. CR2

Stimulation of microbially induced calcium carbonate precipitation (MICCP) is likely to be influenced by calcium sources. In order to study such influences, we performed MICCP using Bacillus sp. CR2 in nutrient broth containing urea, supplemented with different calcium sources (calcium chloride, calcium oxide, calcium acetate and calcium nitrate). The experiment lasted 7 days, during which bacterial growth, urease activity, calcite production and pH were measured. Our results showed that calcium chloride is the better calcium source for MICCP process, since it provides higher urease activity and more calcite production. The influences of calcium sources on MICCP were further studied using Fourier transform-infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses. These analyses confirmed that the precipitate formed was CaCO₃ and composed of predominantly calcite crystals with a little amount of aragonite and vaterite crystals. The maximum yield of calcite precipitation was achievable with calcium chloride followed by calcium nitrate as a calcium source. The results of present study may be applicable to media preparation during efficient MICCP process.     

Use of seeds to control precipitation of calcium carbonate and determination of seed nature

Understanding and controlling precipitation reactions is a major challenge for industrial crystallization. Calcium carbonate is a widely studied system: more than 3000 papers have been devoted to the subject over the past 10 years. The first step of the precipitation of calcium carbonate, from relatively concentrated solutions (0.01 mol/L), involves the formation of an initial gel phase which later transforms into calcite, vaterite, or a mixture of both phases. Our work aimed at controlling this first step. Nanosized seeds (8 nm), formed in situ, were used in order to control the often chaotic nucleation step which normally leads to poor phase selection and broad particle size distributions. Seeding has often been used to avoid spontaneous nucleation in metastable solutions for growth mechanism investigations of single-crystal calcium carbonate. Here the ability of a seeding method to control the precipitation reaction evolution even in the case of high supersaturation is demonstrated. The seeds and the presence of a polymeric additive (poly(acrylic acid)) allow the control of the precipitated polymorph and the specific surface area, while maintaining a narrow particle size distribution in the submicron range. Direct characterization methods did not succeed in identifying these nanoseeds; indirect methods using solubility calculations are used to demonstrate their existence and quantify size and number density of the nanosized seeds.     

蔗糖/精氨酸体系中碳酸钙结晶的仿生合成

该文以更加接近生物矿化的方法研究了蔗糖/精氨酸体系对碳酸钙晶体取向、形貌和晶型的控制作用.XRD 分析表明,在蔗糖/L-精氨酸混合体系中合成的晶体主要为碳酸钙的球霰石晶型及少量的方解石型,在单独的蔗糖或L-精氨酸溶液中基本是球霰石晶型.SEM分析表明,蔗糖和L-精氨酸均可诱导形成特殊形貌的碳酸钙.实验结果表明,蔗糖/精...     

Synthesis of vaterite and aragonite crystals using biomolecules of tomato and capsicum

In this paper, biomimetic synthesis of calcium carbonate (CaCO₃) in the presence of biomolecules of two vegetables-tomato and capsicum is investigated. Scanning electron microscopy and X-ray powder diffractometry were used to characterize the CaCO₃ obtained. The biomolecules in the extracts of two vegetables are determined by UV-vis or FTIR. The results indicate that a mixture of calcite and vaterite spheres constructed from small particles is produced with the extract of tomato, while aragonite rods or ellipsoids are formed in the presence of extract of capsicum. The possible formation mechanism of the CaCO₃ crystals with tomato biomolecules can be interpreted by particle-aggregation based non-classical crystallization laws. The proteins and/or other biomolecules in tomato and capsicum may control the formation of vaterite and aragonite crystals by adsorbing onto facets of them.     

Continuous Preparation of Calcite,Aragonite and Vaterite,and of Magnesium‐Substituted Amorphous Calcium Carbonate (Mg‐ACC)

The three water‐free calcium carbonate polymorphs calcite, aragonite and vaterite were prepared from aqueous solutions without additives using standard laboratory equipment in a continuous process. Variation parameters were the way of mixing, the solution concentrations, and the reactor residence time. The samples were crystallographically and chemically pure, but a thorough elemental analysis revealed the presence of small amounts of sodium carbonate which was not detectable by X‐ray powder diffraction. The continuous process avoids the inherent variability of batch syntheses. By adapting the crystallization parameters, magnesium‐substituted amorphous calcium carbonate (molar ratio of Mg:Ca of 1:2.68) was prepared in this continuous process.