Synthesis of rhombohedral strontium carbonate aggregates at the water/hexamethylene interface with cetyltrimethylammonium bromide

Unusual rhombohedral strontium carbonate (SrCO₃) aggregates have been synthesized in situ from strontium nitrate by the slow release of carbon dioxide by alkaline hydrolysis of diethyl carbonate at the water/hexamethylene interface in the presence of cetyltrimethylammonium bromide (CTAB). Transmission electron microscopy, Fourier transform infrared spectroscopy and X‐ray powder diffractometry were used to characterize the products. The results indicate that rhombohedral SrCO₃ aggregates are obtained with weaker crystallinity and sizes of several micrometers. The possible formation mechanism of the SrCO₃ aggregates at the interface is discussed, which can be interpreted by particle‐aggregation based non‐classical crystallization laws. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of hierarchical calcium carbonate crystals templated by biomolecules of lotus root

In this paper, crystal growth of calcium carbonate (CaCO₃) in the presence of biomolecules of lotus root was investigated. Scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray powder diffractometry were used to characterize the products. The results indicate that calcite spherical particles were constructed from small rhombohedral subunits. Similar CaCO₃ crystals were also gained when crystal growth of CaCO₃ in aqueous solution containing extracts of lotus root was performed, suggesting that the soluble biomolecules of lotus root play a crucial role in directing the formation of hierarchical calcite spherical particles. The possible formation mechanism of the CaCO₃ crystals by using lotus root is also discussed, which can be interpreted by particle‐aggregation based non‐classical crystallization laws. The biomolecules of lotus root might induce and control the nucleation and growth of calcium carbonate crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of calcium carbonate polymorphs in the presence of polyacrylic acid

Calcium carbonate precipitates are prepared from a solution of CaCl₂ and K₂CO₃ in the presence of polyacrilic acid. The effect of polyacrilic acid incorporation in the [25–80 °C] temperature range on crystal morphologies and CaCO₃ precipitated polymorph concentrations are investigated using scanning electron microscopy and X-ray diffraction quantitative microstructural and phase analysis. Large changes in morphology and phase proportions are observed in the presence of polyacrylic acid, which strongly depend on the solution temperature. While crystallization of vaterite is favoured in the presence of polyacrilic acid up to 50 °C, it is largely destabilized at higher temperatures. Our process also enables the elaboration of particles in the range 10–20 nm.     

Preparation of calcium carbonate crystals in the presence of trisodium citrate

The dumbbell‐like calcium carbonate (CaCO₃) crystals were synthesized in the presence of trisodium citrate. Different morphologies were obtained by changing the reaction temperature and the trisodium citrate concentration. The obtained samples were characterized by means of X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that the morphology of CaCO₃ crystals was markedly affected by the reaction temperature and citrate anion concentration. The possible growth mechanism of CaCO₃ crystals was proposed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

绒毛球状碳酸锶的沉淀法制备与表征

以柠檬酸三钠为晶形控制剂,采用简单沉淀法合成了绒毛球状SrCO3晶体.用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)、热重分析仪(TG)、透射电镜(TEM)和能谱仪(EDX)等对样品的结构和形貌进行了表征.结果表明,绒毛球状SrCO3的主体结构为微米级实心球,实心球壳表面被一层稠密的粒径为5～15 nm、长度为100 ～ 150 nm的毛发状晶体所覆盖;机理分析认为绒毛球状SrCO3的形成可以用“棒状-束状-哑铃形-球形”的生长机理(RBDS)进行解释.     

Preparation and structure of calcium peroxide‐templated porous calcium carbonate crystals

Crystalline calcium carbonate with randomly dispersed porous structure was prepared through co‐ crystallization with calcium peroxide and the following template elimination by a post heating treatment and washing with water. The artificial CaCO₃ possess abundant macro‐mesopores structures and high surface area. This approach may open a new general route for the preparation of crystals with high porosity and structure specialty. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The precipitation of calcium carbonate via a bubbling method in the presence of Mg2+ and glucose

Abstract

The effect of Mg²⁺ on the crystallization of precipitated calcium carbonate (PCC) via a bubbling carbonation method and the mechanism of eliminating its influence by glucose were investigated. The polymorph and morphology of crystals were characterized by field emission-scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. These results demonstrated that Mg²⁺ and Mg/Ca molar ratio played significant roles on the morphology of PCC. When the Mg/Ca molar ratio was below 0.5, only spindle-like calcite formed. The rod-like aragonite started to form when the ratio was 0.6. As the ratio increased, the amount of aragonite increased and the length of rod-like aragonite became longer. Notably, the effect of Mg²⁺ could be eliminated efficiently when the 1.5?wt% glucose was added into the carbonation system, in which system, the PCC crystals were all spindle-like calcite. Furthermore, the mechanism of the glucose to eliminate the influence of Mg²⁺ on PCC crystallization was proposed.     

Crystallization habit of calcium carbonate in presence of sodium dodecyl sulfate and/or polypyrrolidone

The synthesis of calcium carbonate (CaCO₃) crystals from aqueous solutions containing sodium dodecyl sulfate (SDS), poly(N-vinyl-1-pyrrolidone) (PVP) or SDS/PVP complexes has been performed through a slow titration method. It was found that aragonite and calcite coexisted in the prepared crystals. The formation of aragonite in the precipitation systems without magnesium ions indicates that at ambient temperature ca. 26.0°C, initially formed amorphous CaCO₃ could also transfer into aragonite in the sedimentary phase, which indicates the controlling factor of organic additives in the nucleation and growth process of CaCO₃ crystals. The appearance of hexagonal crystals in the suspensible phase confirmed the hexagonal crystallization cell of vaterite, and revealed the colloidal-dispersion function of the SDS/PVP complex in the crystallization process of CaCO₃.     

Synthesis of magnesium oxysulfate whiskers in the presence of sodium dodecyl benzene sulfonate

Uniform magnesium oxysulfate (5Mg(OH)₂·MgSO₄·3H₂O) whiskers with a length of 10‐15 µm and a diameter of 0.4‐1.0 µm were synthesized in the presence of sodium dodecyl benzene sulfonate (Na‐SO₃‐C₆H₄‐C₁₂H₂₅) at 200°C for 1 h, using MgSO₄·7H₂O and NaOH as the reactants. Mg(OH)₂ precursor with poor crystallization and small crystal size was formed owing to the adsorption of sodium dodecyl benzene sulfonate on the Mg(OH)₂ surface. The quick dissolution of Mg(OH)₂ precursor in the subsequent hydrothermal reaction inhibited the occurrence of the sector‐like byproduct and promoted the formation of magnesium oxysulfate whiskers with uniform morphology. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

矿化剂和温度对水热法合成碳酸锶晶体形态的影响

以氯化锶、硝酸锶为原料,碳酸氢钠、苯甲酸钠等为矿化剂,利用水热法合成了束状碳酸锶晶体聚集体.采用粉末X射线衍射仪、扫描电子显微镜等仪器对产物的结构和形貌进行了表征,对苯甲酸钠的作用和聚集体形成的机理进行了初步探讨.研究表明:苯甲酸钠对碳酸锶晶体束状聚集体的形成有显著作用,得到的晶体产物束状结构形态特征明显、均匀性好;同时温度的提高有利于晶形完好的碳酸锶晶粒的形成.     

Synthesis and structure of 2D‐ and 3D‐ inorganic‐organic coordination polymers: based on Ag‐hmt subunit

Two new inorganic‐organic complexes, namely, [Ag₂(hmt)₂]Cr₂O₇·H₂O ( 1 ) and [Ag(hmt)(tar)_0.5]·H₂O ( 2 ), (hmt = hexamethylenetetramine, Tar = tartarate,), have been synthesized in H₂O/CH₃CN solvent at room temperature. Both molecules have the common [Ag₃hmt₃]³⁺ layers. Compound 1 is a two‐dimensional structure, and Complex 2 shows three‐dimensional topology. In complex 2 , the tartarate molecules are connected with adjacent layers to form parallelogram pores of 18.55×7.44 Å, which are occupied by two water molecules. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of calcium cations on the precipitation of barium sulfate 2: calcium ions in the presence of organic additives

Calcium ions have been implicated in changing the precipitation of barium sulfate when organic additives are present, although whether it inhibits or promotes nucleation and/or growth has been disputed in the literature. We conducted a thorough investigation into the effect of calcium when additives are present and show that calcium cations do indeed promote nucleation of barium sulfate particles when compared to the appropriate control. This result is independent of the analytical method (conductivity or turbidity) used to assess precipitation. The nucleation promotion produces no change in the crystal morphology, thus morphology is not always a good indicator of nucleation or growth behavior. The extent of nucleation promotion depends on the functional group of the additive.     

Impact of magnetic field on the nucleation and morphology of calcium carbonate crystals

The influence of static magnetic field of strength 0.75 T on the nucleation of calcium carbonate crystals has been investigated. Particle size analysis shows that magnetic field can cause marked difference in distribution. One of the major impacts of magnetic exposure is the increase in number of the critical nuclei formed. Also, magnetic field promotes the formation of parallelepipedic calcite crystals and the dissolution of the smaller crystals by Ostwald ripening mechanism. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of calcium carbonate precipitated in the presence of alkanols

The influence of myristyl alcohol (CH₃(CH₂)₁₃OH), cetyl alcohol (CH₃(CH₂)₁₅OH) and behenyl alcohol (CH₃(CH₂)₂₁OH) on the structure, morphology, size and surface properties of calcium carbonate (CaCO₃) has been investigated. Changes in the nature of the washing solvent, in the C_nOH/Ca²⁺ and CO₃²⁻/Ca²⁺ molar ratios and in temperature have been also evaluated. The sole polymorph produced was rhombohedral calcite. At room temperature, while microspheres composed of submicrocubes were produced at a high molar ratio CO₃²⁻/Ca²⁺ and low CH₃(CH₂)₁₅OH concentration, a stoichiometric molar ratio CO₃²⁻/Ca²⁺ and high CH₃(CH₂)₁₅OH concentration induced the formation of microcubes and microboxes. In the presence of this alkanol (12 % molar) a significant enhancement of the water contact angle (ca. 40 °) resulted in a sample obtained with a stoichiometric CO₃²⁻/Ca²⁺ ratio. These results emphasize the key role played by the three non‐ionic surfactants in the formation of materials with variable crystal shape and wettability and thus technological interest for a range of applications.     

Study on crystallization of calcium carbonate from calcium sulfate and ammonium carbonate in the presence of magnesium ions

Batch reactive crystallization of calcium carbonate (CaCO₃) from ammonium carbonate ((NH₄)₂CO₃) and calcium sulfate (CaSO₄) was investigated in the presence of magnesium (Mg²⁺) ions. It was observed that Mg²⁺ ions partly inhibited the conversion of CaSO₄ into CaCO₃. When the content of Mg²⁺ was less than 2%, the reduction in conversion rate of CaSO₄ was less than 2%, and the effect of Mg²⁺ ions could be ignored. Effect of impurity on crystallization kinetics of CaCO₃, including the growth rate and nucleation rate, was investigated. The results revealed that when Mg²⁺ ions content was less than 1%, Mg²⁺ could promote the growth of CaCO₃ and inhibit the nucleation process, which was favorable for the filtration of CaCO₃.When the content of Mg²⁺ ions was greater than 1%, Mg²⁺ inhibited the growth of CaCO₃, which resulted in explosion nucleation and led to a large number of particles in the solution, which was unfavorable for the filtration of CaCO₃. Based on the Bransom model, the particle size distribution equations of CaCO₃ were established. X‐ray diffraction patterns and scanning electron microscopy images exhibited the existence of spherical vaterite of CaCO₃ due to the reaction of CaSO₄ with (NH₄)₂CO₃ under the effect of Mg²⁺ ions, which was inconsistent with the results reported in the literatures.     

The growth,spectral and thermal properties of the coordination compound crystal‐ strontium malate

Growth of single crystals of the title compound Sr(C₄H₄O₅).3H₂O is achieved using the gel diffusion technique. Multifaceted single crystals of size up to 4x3x3 mm³ are obtained. X‐Ray Diffraction (XRD) pattern of the grown crystal and the Fourier Transform Infra‐Red (FTIR) spectrum in the range 400‐4000 cm^‐1 are recorded. The vibrational bands corresponding to different functional groups are assigned. Thermal behavior of the material is investigated using Thermo Gravimetry (TG) and Differential Thermal Analysis (DTA). Thermal studies are indicative of a five‐stage decomposition scheme. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Synthesis of high purity calcium carbonate micro‐ and nano‐structures on polyethylene glycol templates using dolomite

This research paper describes the synthesis of nano‐ and micro‐structures of high purity precipitated calcium carbonate (PCC) on poly(ethylene glycol)(PEG) templates for broad‐range industrial applications, using readily available and cheap impure dolomitic marbles. In the method, calcium components of impure dolomitic marbles are extracted as calcium sucrate which is then bubbled with carbon dioxide gas using a carbonation column in the presence of PEG. The effects of concentration of PEG, pH of calcium sucrate solution and temperature on the final yield, morphology and polymorphism of PCC have been studied. Vaterite and calcite are the crystalline forms of calcium carbonate found in final PCC products. The vaterite is observed as hollow spheres with particle diameter of 1.5‐2 μm which is formed by aggregation of vaterite nanoparticles with particle size of 20 nm on PEG templates. Optimum conditions for the highest PCC yield of 79.94% are 0.4 mol dm⁻³ of PEG, pH of 6.5 and temperature of 80 °C. The purity of PCC products is about 99%. Therefore, the synthesized PCC products are of required purity and quality for industrial applications.     

Facile preparation of diversified patterns of calcium carbonate in the presence of DTAB

Nano- and micro-sized calcium carbonate (CaCO₃) with various morphologies including multi-petal-flower-shaped, multi-step-cube-shaped, coral-shaped, dendrite-shaped and multi-antenna-shaped was successfully prepared using dodecyltrimethylammonium bromide (DTAB) micellar vevulsant. The effects of temperature, pH and the concentration of DTAB micellar solution on the morphology and crystalline form of CaCO₃ were systematically investigated. The prepared CaCO₃ was characterized by Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The concentration of DTAB micelle, pH and reaction temperature are found to play crucial roles in the morphology, size and crystalline form of the final products. On the base of the characterizations, a possible self-assembled mechanism was proposed. The novel multi-petal-flower-shaped and multi-antenna-shaped CaCO₃ may have some unique properties and potential applications in the future.     

硅酸钠和重烷基苯磺酸盐对碳酸钙物相和形貌的影响

研究了硅酸钠及重烷基苯磺酸盐(HABS)对碳酸钙晶型和形貌的影响,采用FESEM、XRD和FT-IR等手段,对获得的产物进行了表征.结果表明,硅酸钠可促进不同形貌和不规则聚集体状碳酸钙的形成;当硅酸钠浓度大于250 ppm时,可以抑制部分无定形碳酸钙向方解石的转化;当HABS与硅酸钠同时存在时,优先形成麦穗状方解石.     

Growth of aragonite calcium carbonate nanorods in the biomimetic anodic aluminum oxide template

In this study, a biomimetic template was prepared and applied for growing calcium carbonate (CaCO₃) nanorods whose shape and polymorphism were controlled. A biomimetic template was prepared by adsorbing catalytic dipeptides into the pores of an anodic aluminum oxide (AAO) membrane. Using this peptide-adsorbed template, mineralization and aggregation of CaCO₃ was carried out to form large nanorods in the pores. The nanorods were aragonite and had a structure similar to nanoneedle assembly. This aragonite nanorod formation was driven by both the AAO template and catalytic function of dipeptides. The AAO membrane pores promoted generation of aragonite polymorph and guided nanorod formation by guiding the nanorod growth. The catalytic dipeptides promoted the aggregation and further dehydration of calcium species to form large nanorods. Functions of the AAO template and catalytic dipeptides were verified through several control experiments. This biomimetic approach makes possible the production of functional inorganic materials with controlled shapes and crystalline structures.