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.     

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.     

Nucleation activity of nanosized CaCO3 on crystallization of isotactic polypropylene, in dependence on crystal modification, particle shape, and coating

A detailed analysis of the effect of calcium carbonate nanoparticles on crystallization of isotactic polypropylene (iPP) is reported in this contribution. CaCO₃ nanoparticles with different crystal modifications (calcite and aragonite) and particle shape were added in small percentages to iPP. The nanoparticles were coated with two types of compatibilizer (either polypropylene-g-maleic anhydride copolymer, or fatty acids) to improve dispersion and adhesion with the polymer matrix.It was found that the type of coating agent used largely affects the nucleating ability of calcium carbonate towards formation of polypropylene crystals. CaCO₃ nanoparticles coated with maleated polypropylene can successfully promote nucleation of iPP crystals, whereas the addition of nanosized calcium carbonate coated with fatty acids delays crystallization of iPP, the effect being mainly ascribed to the physical state of the coating in the investigated temperature range for crystallization of iPP, as well as to possible dissolution by fatty acids of heterogeneities originally present in the polypropylene matrix.     

Biomimetic synthesis of aragonite superstructures using hexamethylenetetramine

In this paper, biomimetic synthesis of aragonite superstructures using a low molecular weight organic-hexamethylenetetramine (HMT) as an additive in the presence of CO₂ supplied by an ammonium carbonate ((NH₄)₂CO₃) diffusion method at room temperature was studied. The products were characterized by scanning or transmission electron microscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffractometry, and selected area electron diffraction. The results showed the aragonite superstructures especially dumbbell-flower-like ones were obtained. The formation process of calcium carbonate (CaCO₃) in HMT aqueous solution was investigated, suggesting that the products transformed from calcite to vaterite primarily, and then changed into a mixture of aragonite and calcite with an increase of reaction time. The formation mechanism of CaCO₃ in HMT solution was also discussed, revealing that aragonite might be controlled by HMT molecules and NH₄⁺ ions together.     

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.     

The Surface Activity of the Hydrated Proton Is Substantially Higher than That of the Hydroxide Ion

The behavior of hydroxide and hydrated protons, the auto‐ionization products of water, at surfaces is important for a wide range of applications and disciplines. However, it is unknown at which bulk concentration these ions start to become surface active at the water–air interface. Here, we report changes in the D₂O–air interface in the presence of excess D⁺_hyd/OD^?_hyd determined using surface‐sensitive vibrational sum‐frequency generation (SFG) spectroscopy. The onset of the perturbation of the D₂O surface occurs at a bulk concentration as low as 2.7±0.2 mm D⁺_hyd. In contrast, a concentration of several hundred mm OD^?_hyd is required to change the D₂O surface. The hydrated proton is thus orders of magnitude more surface‐active than hydroxide at the water–air interface.     

以氨水和碳酸铵为沉淀剂制备氧化铝的对比研究

γ-Al2O3，是一种常用的催化剂载体，它具有比表面大和价廉易得等优点。但对于很多高温反应体系，如汽车尾气催化净化，其热稳定性在很大程度上影响了汽车尾气净化催化剂的活性和稳定性，因此提高γ-Al2O3的高温热稳定性对保持汽车尾气净化催化剂的反应活性、延长催化剂的使用寿命非常重要。     

Effect of polyacrylic acid and polyethylene glycol on the crystallization of calcium carbonates in the presence of magnesium ions

The effect of polyacrylic acid and polyethylene glycol on the crystallization of calcium carbonates in the presence of magnesium ions was studied. It was found that the presence of magnesium ions in solution and the treatment temperature (80°C) influence the formation of the final products of calcium carbonate crystallization. In binary mixtures, low-molecular-weight polyacrylic acid and polyethylene glycol affect synergistically, and such mixtures can be used for selectively influencing the formation of calcium carbonate polymorphs.     

氢氧化钙粉末界面张力的测定

以Washburn方程为理论依据,采用毛细管上升法,设计了简易实验装置,测定了氢氧化钙粉末在水、二甲基亚砜和甘油中的润湿接触角.在此实验结果基础上,利用Y-G-G-F-V方程建立了计算固相表面张力和液-固界面张力的表达式,并分别计算出氢氧化钙粉末的表面张力、氢氧化钙与水、二甲基亚砜和甘油的液-固界面张力,为固体粉末的表...     

Boosting Electrochemical Water Oxidation with Metal Hydroxide Carbonate Templated Prussian Blue Analogues

The development of efficient and stable catalyst systems with low‐cost, abundant, and non‐toxic materials is the primary demand for electrochemical water oxidation. A unique method is reported for the syntheses of metal hydroxide carbonate templated Prussian blue analogues (PBAs) on carbon cloth and their outstanding water oxidation activities in alkaline medium. The best water oxidation activity is obtained with cobalt hydroxide carbonate templated t‐Co^II‐Co^III with an overpotential as low as 240 mV to reach a current density of 10 mA cm^?2. It produces constant current over 50 h in chronoamperometric measurements. Moreover, the catalysts outperform the activities of the PBAs prepared without any template and even the noble metal catalyst RuO₂. Spectroscopic and microscopic studies show that the PBAs are transformed into layered hydroxide–oxyhydroxide structures during electrochemical process and provide the active sites for the water oxidation.     

Tuning the Stability of CaCO3 Crystals with Magnesium Ions for the Formation of Aragonite Thin Films on Organic Polymer Templates

Thin‐film growth of aragonite CaCO₃ on annealed poly(vinyl alcohol) (PVA) matrices is induced by adding Mg²⁺ into a supersaturated solution of CaCO₃. Both the growth rate and surface morphology of the aragonite thin films depend upon the concentration of Mg²⁺ in the mineralization solution. In the absence of PVA matrices, no thin films are formed, despite the presence of Mg²⁺. Molecular dynamics simulation of the CaCO₃ precursor suggests that the transition of amorphous calcium carbonate to crystals is suppressed in the presence of Mg²⁺. The role for ionic additives in the crystallization of CaCO₃ on organic templates obtained in this study may provide useful information for the development of functional hybrid materials.     

氢氧化钡与氯化铵反应实验中结冰成功的关键

对氢氧化钡晶体与氯化铵晶体吸热反应进行实验改进,在反应物中加少量的水,反应小烧杯上面倒扣上一个大一点的烧杯等,使得实验中水结冰成功率高,结冰快,且结冰量增大。结冰水中加入酚酞溶液,结出的冰为红色,既能检验氨的生成,又增添了实验的趣味性。     

A study of the anticorrosion properties of carbonate deposits to protect low-carbon steel from the action of tap water

Effect of electrochemically injected magnesium ions on the process in which carbonate deposits are formed on a corrodible surface of low-carbon steel in water of heat-and-water supply systems was studied. It was found that the anticorrosion efficiency of the deposit, evaluated by the polarization-resistance method and voltammetry, is approximately 1.5 times that of natural deposits formed in the absence of injected magnesium ions. X-ray diffraction analysis with grazing beam incidence, scanning electron microscopy, and energy-dispersive analysis demonstrated that mostly dense polycrystalline calcium carbonate deposits with a structure of aragonite are formed in the presence of magnesium ions. The mechanism by which a protective CaCO₃ layer grows on the corrodible surface of low-carbon steel is discussed.     

Solid‐State Transformation of Amorphous Calcium Carbonate to Aragonite Captured by CryoTEM

Early‐stage reaction mechanisms for aragonite‐promoting systems are relatively unknown compared to the more thermodynamically stable calcium carbonate polymorph, calcite. Using cryoTEM and SEM, the early reaction stages taking place during aragonite formation were identified in a highly supersaturated solution using an alcohol–water solvent, and an overall particle attachment growth mechanism was described for the system. In vitro evidence is provided for the solid‐state transformation of amorphous calcium carbonate to aragonite, demonstrating the co‐existence of both amorphous and crystalline material within the same aragonite needle. This supports non‐classical formation of aragonite within both a synthetic and biological context.     

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.     

Water as the Key to Proto‐Aragonite Amorphous CaCO3

Temperature and pH value can affect the short‐range order of proto‐structured and additive‐free amorphous calcium carbonates (ACCs). Whereas a distinct change occurs in proto‐vaterite (pv) ACC above 45 °C at pH 9.80, proto‐calcite (pc) ACC (pH 8.75) is unaffected within the investigated range of temperatures (7–65 °C). IR and NMR spectroscopic studies together with EXAFS analysis showed that the temperature‐induced change is related to the formation of proto‐aragonite (pa) ACC. The data strongly suggest that the binding of water molecules induces dipole moments across the carbonate ions in pa‐ACC as in aragonite, where the dipole moments are due to the symmetry of the crystal structure. Altogether, a (pseudo‐)phase diagram of the CaCO₃ polyamorphism in which water plays a key role can be formulated based on variables of state, such as the temperature, and solution parameters, such as the pH value.     

Preparation and thermal decomposition of indium hydroxide

Summary Indium hydroxides were prepared by the mixing of aqueous indium nitrate solution with sodium or ammonium hydroxide solutions under various conditions. The thermal decomposition of the resulting materials was examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectroscopy. It has been found that sodium hydroxide solution is more suitable than the addition of ammonium hydroxide solution to prepare indium hydroxide in well crystallization; the thermal decomposition of indium hydroxide, in which the composition is In(OH)₃·xH₂O where x￡2, proceeds according to the following process: In(OH)₃·xH₂O?cubic In(OH)₃?cubic In₂O₃     

The Displacement of Sr from Organic Chelates by Hydroxide, Carbonate, and Calcium in Concentrated Electrolytes

The effects of calcium, hydroxide, and carbonate on the displacement of Sr from four organic chelates: ethylenedinitrilotetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenedinitrilotriacetic acid (HEDTA) nitrilotriacetic acid (NTA), and iminidiacetic acid (IDA) was studied in solutions with high base and carbonate concentration. Comparison of solutions with and without added chelators allowed the speciation changes in solution to be directly determined. Increases in both carbonate and calcium concentration were effective in displacing Sr from the chelators even under high carbonate concentration. Increases in hydroxide were ineffective in removal of Sr from the chelators, even at base concentrations as high as 6M. Under certain specific conditions, most notably when both CaCO₃(s) and SrCO₃(s) are present in solution, chemical equilibrium constraints result in cancelation of activity coefficient changes for aqueous Sr and Ca organic chelate complexes. Under such conditions the predicted ratios of chelated Ca and Sr become independent of the ionic media and predictive relations using known equilibrium constants give very good representations of the experimental data. These results indicate that manipulation of metal ion displacement reactions during chemical processing of Sr–chelate solutions can result in the displacement of Sr from organic chelators. The implications of such strategies in processing high level waste supernatants stored at Department of Energy (DOE) sites is discussed.     

以两种季铵碱为模板剂合成A形体富集Beta沸石及其晶化过程

以三甲基环己基氢氧化铵和二甲基乙基环己基氢氧化铵为模板剂或结构导向剂(SDA), 采用超浓水热方法合成了A形体富集的Beta沸石, 用粉末X射线衍射(XRD)、 扫描电子显微镜(SEM)、 ²⁹Si固体魔角自旋核磁共振(²⁹Si MAS NMR)以及氮气吸附等表征手段对其进行了详细表征, 探索了最优合成条件, 研究了其晶化过程. 结果表明, 在晶化初期产物中己出现A形体过量特征, 随着晶化的进行, A形体的过量程度无显著变化.     

Supersaturation control in aragonite synthesis using sparingly soluble calcium sulfate as reactants

Sparingly soluble calcium salts were studied as reactants in the synthesis of needle-like precipitated calcium carbonate (PCC). The morphology and aspect ratio of the PCC particles were characterized with SEM. Polymorphs and crystal size were characterized using X-ray diffraction. The counterions of the sparingly soluble salts influenced the growth kinetics of PCC as well as the polymorphism and morphology of product particles. Either chrysanthemum-like or needle-like aragonite can be synthesized from calcium sulfate and sodium carbonate depending on the supersaturation and synthesis conditions. Low concentration and slow addition rate of sodium carbonate solution were favorable to the formation of aragonite. Addition of sodium sulfate to the reaction system (calcium chloride and sodium carbonate) promoted the formation of aragonite and decreased the crystal size of aragonite due to the decrease of supersaturation and adsorption of sulfate ion. Too much added sodium sulfate, however, did not further increase the aragonite fraction. An optimal temperature for the formation of aragonite was found to be ca. 60 degrees C. Slow dissolution kinetics of sparingly dissoluble salt also is very important for controlling PCC polymorphism and morphology.