The effect of sodium alginate on the crystal growth of calcium carbonate

The effect of sodium alginate in supersaturated solutions of calcium carbonate was investigated under plethostatic conditions. The rates of crystal growth measured in the presence of sodium alginate at concentrations as low as 0.83 × 10^-7mol dm^-3 were drastically reduced. Kinetic analysis according to a Langmuir-type adsorption isotherm led to the calculation of an affinity constant K _aff = 999.8 × 10^-4mol dm^-3. The apparent order found from kinetic data was 3.0±0.2 suggesting a surface nucleation mechanism.     

The growth of self-aligned calcium carbonate precipitates on inorganic substrates

Calcium carbonate has been found to precipitate into tablets which were self-aligned with respect to each other on limestone aggregates in Portland cement-based materials. A surface layer of water and reaction in 100% relative humidity air environments were critical for alignment of precipitates. The organization of the calcium carbonate precipitates resembled the cross-section of nacre, but without an organic phase. Possible implications for organized material synthesis, as well as biomineralization, are discussed. © 1998 Kluwer Academic Publishers     

Development of macropores in calcium carbonate body using novel carbonation method of calcium hydroxide/sodium chloride composite

Calcium carbonate is one of the bioceramics and has been used clinically as a bone substitute in dental and orthopedic surgery. Introduction of macropores into the bioceramics is highly recommended because those pores enable tissue ingrowth and accelerated osteointegration. We tried to prepare calcium carbonate body with macropores through the new carbonation method of calcium hydroxide/sodium chloride composite. Sodium chloride acted as a water-soluble porogen in developing macropores in calcium carbonate body and was removed completely by washing with distilled water after carbonation. We investigated effects of sodium chloride content and molding pressure on the porosity and the mechanical strength of the calcium carbonate body. Through this study, it was found that the porosity of body increased with the sodium chloride content in composite and was hardly affected by molding pressure. On the other hand, the mechanical strength was increased with the molding pressure and reduced with the porosity. In addition, the increase in content of sodium chloride caused the enlargement of hole size as well as the enhancement of extent of interconnection among pores through hole. Especially, the calcium carbonate body with over 90% porosity could be prepared when 90 wt.% sodium chloride was used under 10 MPa molding pressure. Its average pore and hole size were 177 and 80 μm, respectively.     

碳酸钙晶须合成及其应用

本文介绍了碳酸钙晶须的制备方法，性能特征及其应用。     

The effect of acetaminophen on the crystal growth of calcium carbonate

The effect of acetaminophen, a well known analgesic and fever-reducing medicine, on the calcium carbonate crystal growth was investigated under plethostatic conditions. The calcification rates measured was reduced by 9.1–63.2% in the presence of acetaminophen. Kinetic analysis according to a Langmuir-type adsorption isotherm lead to the calculation of an affinity constant K _aff = 8.33 × 10² dm³ mol⁻¹. The apparent order found from kinetic data was two suggesting a surface diffusion controlled spiral growth mechanism.     

The co-effect of collagen and magnesium ions on calcium carbonate biomineralization

The process of calcium carbonate biomineralization in the solution containing collagen and magnesium ions was studied in this paper. The results were characterized by using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect rules were obtained by the cooperation of collagen and magnesium ions in different concentration. The experiment results showed that in the presence of both collagen and magnesium ions, aragonite and vaterite were precipitated at low Mg/Ca ion concentration ratio, while only aragonite with regular spherical morphology was precipitated at high Mg/Ca ion concentration ratio. It indicated that collagen has a promotional effect on magnesium ions in controlling the polymorph of calcium carbonate crystal. A much wider range of calcium carbonate morphologies was observed in the presence of both collagen and magnesium ions. The experiments suggested that collagen acts in combination with magnesium ions to inhibit calcite crystal growth, while favoring the formation of aragonite crystals.     

Kinetics of calcium molybdate crystallization

Kinetics of crystallization of calcium molybdate from unstirred molten solutions of lithium chloride of low to medium supersaturation in platinum crucibles by the process of continuous cooling at 5° C hr⁻¹ from temperaturesT ₀=700 and 750°C are investigated. The crystal size measured by optical microscopy for different crystallization periods reveals that both crystal length and width generally increase with cooling period. The degree of crystallizationα _t,also increases with cooling period, attaining a maximum of 0·90. The diffusion rate constants,K _Dlat 700 and 750°C are 0·0776 and 0·1138 respectively. The effect of variation of the crystallization temperature on the crystal size and their number is also studied.     

Effects of polarization on crystallization of calcium phosphate

The acceleration effects of polarized lead zirconate titanium (Pb(Ti,Zr)O₃, PZT) on the crystallization of calcium phosphate were demonstrated when PZT plates were immersed in saturated solutions of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂). Moreover, it is indicated that polarization also had influences on the orientation of the deposited crystals because crystalline layers of OCP (Ca₈H₂(PO₄)₆·5H₂O) were found on the negatively charged surfaces of PZT.     

脲解型微生物诱导碳酸钙沉积研究

研究了钙源种类对脲解型微生物诱导碳酸钙沉积的生物-化学过程的影响。利用电位分析法实时测试了沉积过程中钙离子、铵离子及pH值的变化,并利用显微计数对细菌浓度进行了监测。采用扫描电镜(SEM)、X射线衍射(XRD)和分析红外光谱(IR)对沉积产物进行了研究。结果表明,不同钙源环境下脲解型微生物诱导矿化沉积都存在化学沉淀、微生物诱导矿化沉积和沉淀完全3个阶段;有机钙源环境下细菌的产矿动力比在无机钙源中高,且两种钙源所获得的方解石晶体沉积物在形貌上差异显著。     

Calcium carbonate crystallization in the presence of taurine

The kinetics of calcite (CaCO₃) crystallization on calcite seed crystals in the presence of taurine was investigated by the constant composition method. The presence of taurine (4× 10^{− 5}− 4× 10⁻⁴M) in the supersaturated solutions lead to calcite crystals with a characteristic discontinuous planes of growth and poor habit, as compared to the hombohedral morphology of the seed crystals. The acceleration effect of taurine on the crystal growth rate was 17–96%. The apparent order of the crystal growth was found to be 2.0± 0.2 typical for a surface diffusion-controlled spiral growth processes.     

针状纳米碳酸钙的制备研究

采用鼓泡碳化法，以无机酸A为添加剂，通过对反应温度，反应物浓度，气体流量和气体分布板孔状径大小等各影响因素的控制，得到制备针状纳米碳酸钙的优化工艺条件，最终制得了平均粒径为20nm，长径比约为18,且分散性能良好的纳米碳酸钙，并用TEM和XRD对产物粒子进行了表征。     

The crystallization of Hydroxyapatite in the presence of sodium alginate

The effect of sodium alginate on the crystal growth of hydroxyapatite (HAP) was investigated at sustained supersaturation by the constant composition technique. Sodium alginate was found to inhibit HAP crystal growth at low concentrations and reduced the crystal growth rates by 42–86% for inhibitor concentrations of 2.1 × 10^{− 7}–12.6 × 10^{− 7} mol/l. The inhibition effect on the crystal growth rate may be explained possibly through adsorption onto the active growth sites. A detailed kinetics analysis suggested a Langmuir-type adsorption of the alginate on HAP surface and a value of 1.63 × 10⁷ l/mol was obtained for the affinity constant of sodium alginate for the surface of HAP. The apparent order for the crystallization reaction was determined to be approximately 2, thus suggesting a surface diffusion controlled spiral growth mechanism.     

Doped nanocrystalline calcium carbonate phosphates

The formation of nanocrystalline calcium carbonate phosphates doped with Fe²⁺, Mg², Zn²⁺, K⁺, Si⁴⁺, and Mn²⁺ has been studied by X-ray diffraction, IR spectroscopy, differential thermal analysis, and energy dispersive X-ray fluorescence analysis. The results indicate that the synthesis involves the formation of hydroxy carbonate complexes from the three calcium carbonate polymorphs (calcite, vaterite, and aragonite) in a solution of ammonium chloride and ammonium carbonate, followed by reaction with orthophosphoric acid. This ensures the preparation of a bioactive material based on chlorophosphates, octacalcium hydrogen phosphate, and calcium chloride hydroxide phosphates containing cation vacancies. Particle-size analysis data show that the materials contain nanoparticles down to 10 nm in size. Heat treatment of the doped calcium carbonate phosphates produces calcium hydroxyapatite containing cation vacancies, which can be used as a bioactive ceramic.     

Synthesis of nanocrystals of gadolinium carbonate by reaction crystallization

The formation of nano-sized crystals of gadolinium carbonate via reaction crystallization was studied in a semi-batch crystallizer using gadolinium chloride and ammonium hydrogen carbonate as the reactants. The gadolinium carbonate crystals were formed by the aggregation of primary particles sized about 5 nm. Thereby, the crystallization parameters acting directly on the aggregation of the primary particles, such as the reactant concentrations, non-stoichiometry of the reactants, solution pH, acoustic energy, and agitation speed, were mechanistically investigated. As such, increasing the reactant concentrations enhanced the crystal size due to higher nucleation of the primary particles for the aggregation. Non-stoichiometric reactant concentrations resulted in a significant reduction of the crystal size, due to the adsorption of the excess species on the primary particles. Similarly, the surface charge of the primary particles depended on the solution pH. Thus, the crystal size was reduced when the pH deviated from the neutral point. The acoustic cavitation of the ultrasound was much more effective than the turbulent fluid motion of the agitation in inhibiting the primary particle aggregation. Thus, the crystal size was remarkably reduced, even at a low acoustic energy of 6 watts.     

The role of prenucleation clusters in surface-induced calcium phosphate crystallization

Unravelling the processes of calcium phosphate formation is important in our understanding of both bone and tooth formation, and also of pathological mineralization, for example in cardiovascular disease. Serum is a metastable solution from which calcium phosphate precipitates in the presence of calcifiable templates such as collagen, elastin and cell debris. A pathological deficiency of inhibitors leads to the uncontrolled deposition of calcium phosphate. In bone and teeth the formation of apatite crystals is preceded by an amorphous calcium phosphate (ACP) precursor phase. ACP formation is thought to proceed through prenucleation clusters--stable clusters that are present in solution already before nucleation--as was recently demonstrated for CaCO(3) (refs 15,16). However, the role of such nanometre-sized clusters as building blocks for ACP has been debated for many years. Here we demonstrate that the surface-induced formation of apatite from simulated body fluid starts with the aggregation of prenucleation clusters leading to the nucleation of ACP before the development of oriented apatite crystals.     

Effect of uncoated calcium carbonate and stearic acid coated calcium carbonate on mechanical,thermal and structural properties of poly(butylene terephthalate) (PBT)/calcium carbonate composites

PBT/CaCO₃ composites were prepared in a single screw extruder with particle content varying from 0–30% by weight. The influence of surface treatment of the particles, with and without stearic acid (SA), on the mechanical, thermal and structural properties was studied. The experiments included tensile tests, impact tests, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy. The composite systems containing SA coated CaCO₃ were found to exhibit better mechanical properties as compared to composite systems containing uncoated CaCO₃, with the S3 system (20% of SA coated CaCO₃) exhibiting best combination of mechanical properties. Thermal study revealed that particle type and content had no influence on the melting temperature but the crystallization temperature, % crystallinity and thermal stability increased on increasing the CaCO₃ content in PBT matrix. Morphological observation indicated that in PBT composites containing SA coated CaCO₃, the coupling agent favours a better polymer filler interaction rendering inorganic polymer interface compatible, which is also evident from better mechanical and thermal properties.     

针状纳米碳酸钙制备过程中反应条件的研究

用间歇碳化法制备了针状纳米CaCO3,对它们的形成机理进行了分析,实现了对针状CaCO3的粒度控制.通过对反应物Ca(OH)2浓度、反应温度、添加剂等操作条件对产品粒径和形态的影响考察,发现添加剂的加入时间是影响结晶习性和碳酸钙粉体形状的决定性因素.制得了平均粒径40～50nm、长径比约为10的针状纳米碳酸钙粉体.     

超细碳酸钙的碳化机理探讨

间歇鼓泡碳化法生产超细碳酸钙的碳化过程是一个四相浆态反应过程。本文在双膜理论基础上 ,提出用“四膜模型”的观点来探讨碳化各阶段的动力学区域和碳化机理 ;探讨了包裹返碱现象发生的规律和碳化过程的化学理论基础。