Growth and characterization of gel grown calcium pyrophosphate tetrahydrate crystals

Formation of calcium pyrophosphate dihydrate (CPPD) crystals in soft tissues such as cartilage, meniscus and synovial tissues lead afflictions. The appearance of these crystals in the synovial fluid give rise to acute arthritis attack, which is known as pseudo‐gout. The growth of calcium pyrophosphate crystals in gel medium can mimic the growth in a body. In the present study, calcium pyrophosphate tetrahydrate (CPPT) crystals are grown by a single diffusion gel growth technique and characterized by powder XRD, FT‐IR spectroscopy, TGA, kinetic and thermodynamic studies of dehydration and dielectric studies. Monoclinic crystals structure, presence of P‐O bonds and four water molecules are confirmed from powder XRD, FT‐IR and TGA studies, respectively. The dielectric investigation suggests the reduction in dielectric constant with increase in frequency. (© 2007 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.     

Influence of Bacillus subtilis on the growth of calcium oxalate

The influence of the bacteria Bacillus subtilis (B. subtilis) on the nucleation, growth and aggregation of calcium oxalate (CaOx) crystals in aqueous solution has been studied. The crystals obtained were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray powder diffractometry. The results show that, in the presence of B. subtilis, quasi‐hexagonal calcium oxalate monohydrate (COM) crystals are obtained after 24 hours of reaction at a temperature of 30°C ± 1K. However, without the presence of the bacteria, irregular CaOx crystals were obtained which contain two crystal phases: COM and calcium oxalate dihydrate (COD). This suggests that B. subtilis may promote the crystallization of COM, the major component of urinary stone. The formation mechanism of CaOx crystals in the presence of B. subtilis is explored, indicating that the cell walls and extracellular proteins of the bacteria may act as templates to induce the nucleation, growth and aggregation of CaOx crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Using an electrochemical technique to study the effective variables on morphology and deposition of CaCO3 and BaSO4 at the metal surface

In this work using an electrochemical technique, deposition and crystal growth of calcium carbonate and barium sulphate at a stainless steel electrode is investigated through a rotating disk electrode involving oxygen reduction under diffusion condition. The influence of some parameters such as pressure, temperature, surfactant, cosalt and pH on morphology and deposition of CaCO₃ and BaSO₄ at surface of the stainless steel are studied. The results of the temperature tests reveal that the surface deposition is reduced by increase of the temperature and decrease of pH. The pressure also proves to have a significant influence on the morphology and the structure of calcium carbonate and barium sulphate deposition at the metal surface. With establishing a flow condition at high pressure, nucleation and deposition of calcium carbonate and barium sulphate at the metal surface generate the nano size of CaCO₃ and BaSO₄ crystals and leads to reduction of the coverage of the surface. In the presence of surfactant, it is shown that deposition of the calcium carbonate decreases the surface coverage so that after the point of the critical molar concentration of surfactant, a reduction of deposition of the calcium carbonate and barium sulphate at the surface can be clearly observed. Finally, influence of monovalent cosalts such as NaCl and KCl are investigated so that it does not present any certain trend in the deposition; however the morphology of the deposited crystal considerably changes.     

Size and morphology controlled synthesis of barium sulfate

In this work submicron barium sulfate (BaSO₄) particles were synthesized successfully by chemical precipitation technique. We focused on the effects of pH and additives on the size and morphology of BaSO₄ crystals. Polyacrylic acid, polyvinyl sulfonic acid and ethylenediaminetetraacetic acid were used as crystal growth modifiers. BaSO₄ crystals were characterized using scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared resonance techniques. The results show that the submicron BaSO₄ particles have been synthesized successfully and the particle size of the barium sulfate was effectively controlled under the experimental conditions. Experimental studies revealed that the additive concentration and pH had great effect on the morphology and size of barium sulfate.     

Calcium oxalate crystallization in the presence of amino acids,proteins and carboxylic acids

Reactive crystallization of calcium oxalate was investigated in the presence of amino acids, proteins and carboxylic acids at different pH and temperatures. Average particle size, filtration rates of calcium oxalate crystals obtained in the absence and presence of additives were determined. The influence of pH, temperatures and additives on crystal morphology of calcium oxalate were also investigated and discussed by SEM analysis. TG‐DTA, FT/IR and XRD analysis were carried out for all investigated conditions. Average particle size of calcium oxalate was affected significantly by the additive type and concentration. Variation of crystal morphology depending on type and concentration of the additives affected the filtration characteristics. Majority of calcium oxalate crystals occurred in the form of calcium oxalate monohydrate except those in the presence of tartaric acid. TG‐DTA, FT/IR and XRD analysis proved that calcium oxalate monohydrate and calcium oxalate dihydrate mixtures are formed in the presence of tartaric acid. The effect of all additives on scale formation was also investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and spectral studies on gypsum crystals under simulated conditions of phosphoric acid production with and without organic and inorganic additives

In the dihydrate process to produce phosphoric acid, phosphate ore [Ca₁₀F₂(PO₄)₆] is leached with sulfuric and weak phosphoric acids to produce phosphoric acid and gypsum as a by‐product. Crystallization of gypsum occurs as the leaching is taking place. The effect of organic and inorganic additives on the structure and spectrum of gypsum crystals under simulated conditions of phosphoric acid production is studied using x‐ray diffraction and infrared spectroscopy. Structure and spectrum of formed gypsum crystals in the absence of additives are slightly different from the standard gypsum crystals (card No. 6‐0046), which reflect the effect of preparation medium on the crystal structure of gypsum crystals. Presence of additives such as cetyl trimethyl ammonium bromide and 1,2‐dihydroxybenzene‐3,5‐disulfonic acid, Al³⁺ and Mg²⁺ increase the crystallinity of gypsum, while presence of additives such as citric acid and sodium dodecyl sulfate decrease the crystallinity of gypsum. Presence of Al³⁺ and Mg²⁺ as additives lead to the formation of calcium sulfate hemihydrate beside calcium sulfate dihydrate. Presence of sodium dodecyl sulfate as an additive inhibits the crystallization of gypsum and leads to the formation of anhydrite and calcium sulfate hemihydrate.     

Optimization of the mineral content in polymeric gels: The effect of calcium to phosphate molar ratio

The influence of calcium to phosphate (Ca/P) molar ratio on the extent of mineralization in a model (poly)acrylamide gel was investigated under simulated physiological conditions. We hypothesized that the optimal growth of hydroxyapatite crystals will take place at the stoichiometric Ca/P molar ratio of 1.67. Phosphate ions were incorporated during the polymerization of the gel and mineralization was initiated by submersion of the gel in calcium acetate solution. Ca/P molar ratios were varied in the range of 0.5–5.0. The mineralized gel was characterized by Raman spectroscopy, scanning electron microscopy (SEM) and mineral weight fraction analysis via ashing. Raman spectra captured across the bulk of the gels indicated the presence of mineral at the core section. The phosphate symmetric stretching peak was observed in the range of 955–960 cm⁻¹ which is characteristic of hydroxyapatite. SEM images showed that crystals formed at Ca/P=2.0 were denser and larger in size than at other molar ratios. In agreement with SEM images, the dry weight fraction of mineral reached the maximum at the molar ratio of 2.0 and the extent of mineralization rapidly declined as the molar ratio diverged from 2.0. Also, the crystallinity of the mineral was optimum at the molar ratio of 2.0. Thus it appears that for effective mineralization, the molar ratio of the two ions needs to be in excess of the stoichiometric requirement, suggesting that ions are expended in processes other than the formation and growth of hydroxyapatite crystals. Therefore, the optimal level of mineralization in biomimetic-based growth of calcium phosphate crystals in sol–gel environment requires consideration of a range of molar ratios as opposed to using the molar ratios corresponding to that of the crystal species intended to grow.     

Main regularities of crystallization of calcium oxalate in the presence of amino acids

Processes of crystallization of calcium oxalate from aqueous solutions are investigated. Main regularities of the nucleation and crystal growth of calcium oxalate during mass crystallization without admixtures and in the presence of amino acids are established. The inhibiting action of the aspartic and glutamic amino acids on the growth of calcium oxalate crystals is demonstrated. Addition of amino acids does not affect the nucleation kinetics.     

Quantitative Description of the Influence of the Inhibitor Concentration on the Growth Rate of Barium Sulfate Crystals in Suspension (III)

To describe quantitatively the effect of a growth inhibitor on the growth rate of barium sulfate crystals, suspended in a supersaturated solution, the “strength of inhibition” has been introduced. The strength of inhibition is defined as the ratio of the mean linear growth rates without and with inhibitor at the same value of the growth affinity. It has been shown that the strength of inhibition, exerted by 1-hydroxyethylidene-1, 1-bisphosphonic acid (HEDP) and aminomethylene-bisphosphonic acid (AMDP) on the growth process, not only depends on its concentration, but also on the growth affinity, or probably even on both the growth affinity and the changes in the geometry of the crystals due to their growth in the presence of an inhibitor.     

The mechanism of biological mineralization

The control of supersaturation and the nucleation and growth of crystals in calcium phosphate systems are important in relation to the physiological deposition of bone and tooth. Other calcium salts such as the carbonate and oxalate hydrates are significant components of pathological mineral deposits. The use of a highly reproducible seeded growth technique has enabled kinetic studies to be made of the crystal growth of these minerals. Under conditions of relatively high supersaturation, secondary nucleation may be induced upon the surface of the seed crystals. In the case of the calcium phosphates, temperature, supersaturation, surface concentration, pH, ionic strength and presence of foreign ions are very important in determining the nature of the phase which grows upon the added seed crystals. Kinetic considerations are of overriding importance in determining the course of the reactions. It is not possible to predict the phase which forms purely on the basis of thermodynamic solubility data. Thus, in solutions appreciably supersaturated with respect to both dicalcium phosphate dihydrate (DCPD) and hydroxyapatite (HAP), the addition of low concentrations of HAP seed results in the exclusive formation of DCPD whereas this phase is absent when the seed concentration is increased. The kinetic results for calcium oxalate and phosphates are discussed in terms of the important problems relating to tooth mineralization and the origin and growth of renal calculi.     

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)     

Effects of pH and temperature on CaCO3 crystallization in aqueous solution with water soluble matrix of pearls

Water soluble matrix (WSM) was extracted from pearls originated from Hyriopsis cumingii in Zhuji, Zhejiang province, China. WSM was regarded as an additive in mineralization experiments in order to study the effect of WSM on CaCO₃ crystallization. The experiments were carried out at different pH and temperatures by gas diffusion method and solution titration method, respectively. Scanning electron microscopy (SEM) and Raman spectroscopy (Raman) were used as powerful techniques to analyze the co-effect of pH value, temperature and WSM on crystal growth of CaCO₃. The results showed that WSM could induce aragonite at different pH values of mineralization solution, and the pH value had remarkable influence on morphology of calcite rather than aragonite due to distinct supersaturation and ionic strength related to various pH values. At different solution temperatures, WSM had little effect on crystal growth of calcium carbonate while the solution temperature had notable effect on polymorph and morphology of CaCO₃ crystals. This work can provide some basic information for the polymorph and morphology control of calcium carbonate.     

Growth of calcium carbonate in polyacrylamide hydrogel: Investigation of the influence of polymer content

The growth of calcium carbonate crystals has attracted growing attention as a model system for biomineralisation processes. Organic molecules and gelatinous matrices are known to play an essential role in the formation of hard tissues. For the investigation of the function of specific influence factors, a model experiment is necessary. Several hydrogels were previously tested as growth matrices for calcium carbonate.

For laboratory experiments, a double diffusion set-up for the growth of crystals in gels was established earlier. Calcium carbonate crystals were grown in polyacrylamide hydrogels.

Here the influence of the polymer content in the hydrogels on the crystallisation behaviour is reported. Time-resolved and spatially resolved crystallisation experiments were conducted. The collected calcium carbonate precipitates were analysed by light microscopy, scanning electron microscopy and X-ray diffraction.

The morphology of the developing crystals was found to be dependent on the polymer content of the hydrogels.     

Growth of calcium oxalate crystals induced by complex films containing biomolecules

Nucleation and growth of calcium oxalate (CaC₂O₄) crystals induced by films composed of phosphatidylcholine (PC), cholesterol (CS) and human serum albumin (HSA), and of PC, CS and dextran have been carried out. The products obtained were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and ultraviolet‐visible spectroscopy. The results indicate that hexagonal calcium oxalate monohydrate (COM) and club‐shaped calcium oxalate trihydrate (COT) crystals are obtained on the PC/CH/HSA film, and the microstructure and properties of the PC/CH/HSA film depend on the weight ratio of PC to CS. With an increase in the PC‐to‐CS ratio, the number of COM crystals decreases gradually, and finally disappear, suggesting that PC inhibits the growth of COM crystals. On the PC/CS/dextran film, irregular COM and COT crystals are formed. The possible formation mechanisms of CaC₂O₄ on the two complex films are discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The aging of silicate glass surfaces in humid air

Slicate glass surfaces were observed over several weeks in normally humid laboratory air by atomic force microscopy. Auger spectroscopy and lateral force microscopy measurements were also made. Samples in the study include; vitreous quartz, bulk insulation glass, bulk and fibrous textile e-glass, and bulk container glass. Various features developed on these surfaces are consistent with patterns seen in crystal growth from supersaturated solution. Auger spectroscopy reveals the presence of chemically bound carbon and supports the hypothesis that these crystals are alkali and alkali earth carbonate species. The presence of these crystals is expected to affect the bonding of a coating to silicate surfaces.     

Study of inclusions and causes of their formation during growth of barium metaborate crystals

The complex study of barium metaborate crystals has been undertaken with the aim to determine the conditions of their growth with the minimum density of inclusions. It is shown that almost all the inclusions are multiphase formations of the melt type, and, in addition to the mixture of the main components of the quasieutectic composition, they can also be enriched with gas-forming impurities not removed during barium metaborate synthesis. It is shown that the amount and the composition of melt-like inclusions in crystals depends on the removal of by-products of the reactions used for barium metaborate synthesis from the system, the patterns of the convective flows in the flux, the character of its flow under the interface, the axial temperature gradient in the solution, and the temperature fluctuations at the crystallization front.     

凝胶体系中生物矿物生长的研究进展

近年来,生物矿化的模拟和仿生材料的研究十分引人注目.凝胶体系是模拟生物矿化的有效介质.本文综述了凝胶中羟基磷灰石、透钙磷石、磷酸钙等磷酸盐,文石、方解石、球霰石等碳酸钙,碳酸钡和草酸钙等生物矿物生长的研究进展,讨论了生长参数如凝胶种类、凝胶化学性质、吸附到凝胶表面的物质种类、介质pH、生长时间等对这些矿物晶体生长的影响,最后指出了该领域所面临的问题和将来的发展方向.     

柠檬酸钾对尿石患者和正常人尿液凝胶中草酸钙晶体生长的影响

采用扫描电子显微镜(SEM)和X射线衍射(XRD)方法,比较研究了防石药物柠檬酸钾(K3cit)在尿石患者尿液和正常人尿液制备的凝胶中对草酸钙(CaOxa)晶体生长的影响.没有加入K3cit时,CaOxa晶体均以一水草酸钙(COM)为主要晶相,加入K3cit后,不但COM晶体变得圆钝,比表面积减小,而且诱导了二水草酸钙(COD)生成.随着K3cit浓度从0.10增加到0.20 mol/L,在正常人尿液凝胶中COD晶体的百分含量从20;增加到45;,而在CaOxa结石患者尿液凝胶中,不但COD含量从10;增加到25;,而且K3cit可诱导草酸钙成核,从而产生大量的小尺寸草酸钙晶体,这有利于阻止草酸钙晶体变大形成尿石.本结果可为临床上治疗CaOxa结石提供启示.     

Growth Kinetics of Barium Sulphate in Suspension

The growth rate of barium sulphate seed crystals from stirred solutions was studied conductometrically at 25°C by a stopped-flow technique. The supersaturation ranged from 3 × 10⁻⁷ to 3 × 10⁻⁸ mol BaSO₄/cm³. The seed crystals were grown in the system during the initial (steady-state) period of the experiment. Crystal size distributions were determined by optical microscopy. The growth rate of barium sulphate under the conditions of the experiments can be expressed by a quadratic function of supersaturation. The results, which suggest an interface rate-controlling mechanism, are discussed with respect to published data.