Crystallization of calcium sulfate dihydrate at different supersaturation ratios and different free sulfate concentrations

Free Sulfate is a major parameter affecting gypsum crystallization during phosphoric acid production. Gypsum crystal size, shape and filtration rate are significantly affected by the concentration of free sulfate. It is, therefore, important to evaluate the effectiveness of different sulfate levels from 1.5% to 3.5% on induction time and gypsum morphology. The crystallization of gypsum was carried out under simulated conditions of phosphoric acid production by the dihydrate process. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 °C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. With increasing free sulfate concentration, the induction time was significantly decreased. Chemical processing of Central and South Florida phosphate concentrates under different concentrations of free sulfate from 1.5% to 5.5% was carried out. The change on crystal size distribution and filtration rate were traced with free sulfate concentrations. The results show that, filtration rate of phosphogypsum was correlated to the mean diameter of crystals. In addition, induction time and co‐crystallized (lattice) P₂O₅ % in gypsum are decreased with increasing free sulfate content from 1.5% to 3.5%. Morphology of formed gypsum crystals at different sulfate contents and different supersaturation ratios are investigated. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth rate of α-calcium sulfate hemihydrate in K–Ca–Mg–Cl–H2O systems at elevated temperature

Kinetics of calcium sulfate hemihydrate (HH) crystal growth plays an important role in mineralization of calcium sulfate phases in nature. HH crystal growth and the conversion of calcium sulfate phases form the basis for the production and application of gypsum based building material. α-HH crystals have been grown in 3.74 M CaCl₂ solutions at a fixed initial ratio of calcium to sulfate under atmospheric pressure. The variations of sulfate ions were determined to obtain the α-HH crystal growth kinetics information. Effects of Mg²⁺ and K⁺ ions on α-HH growth were investigated to find an optimal composition of solution for α-HH preparation. The orders of α-HH growing in the CaCl₂ solution were found, in most cases, to be near 2.0 in presence or in absence of Mg²⁺ and K⁺ ions. Mg²⁺ ions enhance the growth of α-HH in CaCl₂ solution mainly due to initial supersaturation enhancing effects. K⁺ ions also improve the growth rate, which has been attributed to the reduction of interfacial energy. In a Ca (3.74 M)–Mg (0.20 M)–K (0.09 M) chlorides solution, the growth rate of α-HH increases with temperature from 80 to 100 °C, and the activation energy was calculated to be 40 kJ/mol.     

Effect of trace metals on reactive crystallization of gypsum

The effect of Fe²⁺, Fe³⁺, and Cr³⁺ ions on crystallization of calcium sulfate dihydrate (gypsum) produced by the reaction between calcium hydroxide suspension and sulphuric acid solution was investigated at 3.5 pH and 65°C in the absence and presence of 2500 ppm citric acid concentration. Crystal size distributions, filtration rates, and morphology of gypsum were determined and discussed as a function of ion concentration. Average particle size of gypsum was not affected significantly by the presence of Fe²⁺, Fe³⁺, and Cr³⁺ ions individually. Variation of gypsum morphology depending on ion concentration affected the filtration characteristics. The presence of Fe³⁺ or Cr³⁺ ions besides 2500 ppm citric acid influenced both average particle size and filtration characteristics. The effect of citric acid on gypsum morphology was suppressed at high Fe³⁺ and Cr³⁺ ion concentrations. The change of morphology is related to the complex formation between Fe³⁺ or Cr³⁺ ions and citric acid at high ion concentrations. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydration of calcium sulfate hemihydrate (CaSO4· H2O) into gypsum (CaSO4·2H2O). The influence of the sodium poly(acrylate)/surface interaction and molecular weight

The retarding influence of sodium poly(acrylate) (PANa) on the hydration of calcium sulfate hemihydrate (CaSO₄· H₂O) was investigated. This study reports the influence of sodium poly(acrylate) on hemihydrate dissolution, on homogenous and heterogeneous gypsum (CaSO₄·2H₂O) nucleation as well as on gypsum growth. It is shown that adsorption of PANa does not hinder the dissolution of hemihydrate in the present experimental conditions. The specific interaction of PANa with gypsum can explain the oriented growth of gypsum crystal. The gypsum growth is slowed down but cannot be blocked by the adsorption of PANa. On the other hand, PANa can block the heterogeneous and homogenous gypsum nucleation. As soon as a critical surface density of PANa onto the hemihydrate surface is reached, the heterogeneous gypsum nucleation is prevented and hemihydrate hydration is indefinitely blocked. The interaction between PANa and the hemihydrate surface is of prime importance to control hydration. Also, the influence of the molecular weight of PANa on homogenous nucleation has been investigated. The precipitation of calcium polyacrylate can explain the differences between the two molecular weights used (2100 and 20 000). This work leads to the conclusion that heterogeneous nucleation is the key process that controls hydration of a system in which hemihydrate dissolution, gypsum nucleation and growth are all occurring at the same time in a continuous manner.     

Effect of citric acid and 1,2‐dihydroxybenzene 3,5‐disulfonic acid on crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production

The effect of citric acid and 1,2‐dihydroxybenzene 3,5‐disulfonic acid (DHBDSA), as additives, on the crystallization of gypsum was studied under simulated conditions of the of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 °C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. Addition of citric acid increased the induction time and decreased the growth efficiency while addition of DHBDSA decreased the induction time and increased the growth efficiency compared with in absence of additives. The crystals mean and median diameters were found to decrease in the presence of citric acid and increased in the presence of DHBDSA. The surface energy decreased with citric acid and increased with DHBDSA compared to the baseline (without additives). Interestingly, the majority of the formed crystals are tabular with DHBDSA and needle‐like type with citric acid and baseline     

Nucleation kinetics of the formation of low dimensional calcium sulfate dihydrate crystals in isopropyl alcohol medium

Calcium sulfate dihydrate, constituted as uniform crystals of low dimensions, is a potential biomaterial for clinical applications like bone graft substitution and drug delivery. In this work, isopropyl alcohol has been used as a solvent to obtain low dimensional calcium sulfate dihydrate crystals from calcium nitrate ‐ sulfuric acid system. Reactants in 0.5 molar concentration at ambient conditions generated uniform rod‐shaped crystals of length 3–5 µm. Analysis using X‐ray Diffractometry and Fourier Transform Infrared Spectrometry showed the material to be well crystallized, phase‐pure calcium sulfate dihydrate. The nucleation kinetics has been studied by observing the induction time of phase formation in solutions of millimolar concentrations through turbidimetry at 300 K. The data have been analysed using classical nucleation theory to deduce parameters like interfacial tension (or surface free energy), nucleation rate and critical radius. The surface free energy obtained (5.6 mJ/m²) is comparatively lower than that reported for aqueous precipitation, which could be attributed to the presence of isopropyl alcohol. On escalating the supersaturation ratio, the nucleation rate drastically increased and the critical radius decreased exponentially. Particles formed at supersaturation 1.39 showed a monomodal distribution centered at 8.2 nm in Dynamic Light Scattering analysis. Comparable particle sizes were obtained in Transmission Electron Microscopy.     

Coarse crystal layer growth and liquid entrapment study with gradient freeze technology

The coarse crystal layer growth and liquid entrapment processes were investigated with gradient freeze technology in this paper. The research system was hemihydrate phosphoric acid (H₃PO₄·0.5H₂O) crystal‐phosphoric acid aqueous solution. The distribution coefficients of ions (Ca²⁺, Fe³⁺ and Na⁺) in this system were measured. The effect of supercooling degree gradient on layer growth and the effect layer growth rate on ions redistribution were studied. The result indicated that the layer growth rate increased with supercooling degree gradient as an exponential curve. The distribution coefficient tended to increase as an approximate ‘S’ curve when coarse crystal layer growth rate increased. The ‘three region’ theory was applied to explain this phenomenon. Each ion's diffusion parameter was obtained, which contributed to explain the separation differences between different ions. The work in this paper also indicated that layer crystallization was an effective separation technology for electronic grade phosphoric acid preparation.     

Calcium sulphate hemihydrate hydration leading to gypsum crystallization

The hydration of calcium sulphate hemihydrate (CaSO₄·0.5H₂O) leading to the crystallization of gypsum (calcium sulphate dihydrate – CaSO₄·2H₂O) has been the subject of several investigations over a long period and a vast amount of data is widely distributed throughout in the literature. In this review article an overall picture of the subject is presented. The properties of the two hemihydrates (α- and β-), their hydration characteristics, the mechanism of their hydration and the crystal growth of gypsum are discussed. Additives modify the microstructures of the hardened gypsum and reduce its strength. A probable mechanism is discussed.     

The Setting Behaviour of α‐ and β‐CaSO4 · 0,5 H2O as a Function of Crystal Structure and Morphology

Calcium sulphate subhydrates (CaSO₄ · x H₂O, 0 < x ≤ 0.8) have a honeycomb‐shaped channel structure. The symmetry is either trigonal or a slight deviation thereof. Due to insufficient diffraction data and the high pseudosymmetry of the structure, it is not possible at this point to determine with certainty the specific arrangement of the water molecules in the channels. When the Fourier transformation method is used to calculate the growth form of the hemihydrate (x = 0.5), the calculated crystal form corresponds to the observed form only when the trigonal structural symmetry is largely retained. During dehydration of gypsum or, conversely, during the setting process of hemihydrate, heteroepitaxial growths of hemihydrate are observed on gypsum, or gypsum is grown heteroepitaxially on hemihydrate. The (100) faces of the hemihydrate and (010) of gypsum for the most part run parallel. Using diffraction and spectroscopic methods, it can be shown that a structural difference exists between α‐ and β‐hemihydrates, and that this difference probably accounts for the different setting behaviours. It is in this context that the presence of oxonium ions, particularly in β‐hemihydrate, found in NMR experiments is of interest. Textural studies indicated that the arrangement of gypsum crystals found in hardened gypsum is determined by the hemihydrate.     

Effect of CuCl2 on hydrothermal crystallization of calcium sulfate whiskers prepared from FGD gypsum

Using purified flue‐gas desulfurization (FGD) gypsum as raw material, effects of CuCl₂ on crystal morphology, phase structure, aspect ratio and crystallization of hydrothermal products prepared via hydrothermal crystallization in H₂SO₄‐H₂O solutions were investigated. The results show that dosage of CuCl₂ has a significant effect on the morphology, aspect ratio and crystallization of calcium sulfate whiskers (CSWs), but no effect on their phase transformation . At a dosage of 15 g CuCl₂/kg FGD gypsum, the produced calcium sulfate whiskers had diameters ranging from 1 to 3 μm with average aspect ratio greater than 200 . Transmission electron diffraction patterns and highly magnified surface morphology of CSWs were found different from those of self‐assembly crystals. Compared to self‐assembly crystals, the produced CSWs showed a single crystal structure and their surface was very smooth.     

Influence of citric acid on calcium sulfate dihydrate crystallization in aqueous media

The crystallization of Calcium sulfate dihydrate produced by the reaction between pure Ca(OH)₂ suspension and H₂SO₄ solution was investigated at different pH values, temperatures and citric acid concentrations. Crystal size distributions, filtration rates and zeta potentials of gypsum were determined as a function of citric acid concentrations at pH 3.5 and 65°C. The influence of citric acid on the morphology of gypsum was also investigated and discussed. The average particle size of gypsum was reached to maximum in the presence of approximately 2500 ppm citric acid concentration, where the minimum cake resistance and maximum filtration rate were obtained. In the presence of citric acid, various crystal morphologies such as tabular, plate‐like, double‐taper leaf‐like and flower‐like, etc., were obtained. The change of morphology is related to the preferential adsorption of citric acid on different crystallographic faces. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of phosphonate additive on crystallization of gypsum in phosphoric and sulfuric acid medium

Understanding the mechanisms of growth and inhibition during crystallization of calcium sulfate is of primary importance for many industrial applications. For instance, inhibition of the crystallization process may be required to prevent scale formation in pipes, boilers, heat exchangers, reactors, reverse osmosis membrane surfaces, cooling water systems, secondary oil recovery utilizing water flooding techniques and desalination evaporators, etc. On the other hand, control growth and morphology of gypsum crystals is desired in achieving higher filtration rate and higher productivity of phosphoric acid from phosphate rocks. In this regard, this basic study is carried out to understand effect of Aminotris (methylenephosphonic acid (ATMP) on calcium sulfate dihydrate (gypsum) crystallization. The time elapsed between the achievement of supersaturation and the appearance of a solid phase (termed as induction time) is measured under different supersaturation ratios ranging from 1.018 to 1.979. The data are used to calculate the surface energy, critical nucleus size, and crystal growth rates of gypsum under different conditions. The results show that, the induction time decreases exponentially with increasing the supersaturation ratio. In addition, the surface energy decreases with ATMP compared to the baseline (without ATMP). Interestingly, with addition of the ATMP, the crystals mean and median diameters are found to decrease. The inhibition efficiency ranges from 16% to 59% depending on supersaturation ratio.     

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.     

Preparation of calcium sulfate whiskers by carbide slag through hydrothermal method

In this work, a series of calcium sulfate whiskers were prepared successfully using carbide slag as raw material through hydrothermal method. The prepared gypsum observed is hemihydrate calcium sulfate and the formation of the calcium sulfate whiskers are influenced by preparation parameters. The optimal preparation conditions are as follows: seriflux concentration, 4 %; hydrothermal reaction time, 10 h; hydrothermal reaction temperature, 130°C; seriflux pH, 7; calcium‐magnesium ratio, 12 : 1. Some nanowires appear when seriflux pH is very low (e.g. 1). The length‐diameter ratio of the whiskers is about 60‐80.     

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)     

Investigation on the blue photorefractive properties varied with MgO codoping in Ru:Fe:LiNbO3 crystals

Mg:Ru:Fe:LiNbO₃ crystals with various doping concentration of MgO have been grown by Czochralski method. The type of charge carriers and photorefractive properties in Mg:Ru:Fe:LiNbO₃ crystals were measured by two‐wave coupling method using Kr⁺ laser (476 nm) and He‐Ne laser (633 nm) as light sources. We found that holes were the dominant charge carriers under blue light irradiation while electrons were the dominant charge carriers under red light irradiation. Mg²⁺ ions behaved no longer as damage resistant, but promoter to the photorefractive properties at 476 nm wavelength. The photorefractive properties under blue light improved with the increase concentration of Mg²⁺ ions. The enhancement mechanisms of the blue photorefractive were suggested. Experimental results definitely showed that Mg‐doped two‐centre Ru:Fe:LiNbO₃ was a promising blue photorefraction material for holographic volume storage.     

SQUID magnetometry,EPR and XPS characterization of Y3Al5O12: Co,Si single crystals

Single crystals of garnet Y₃Al₅O₁₂ (YAG): Co and Co, Si were grown by Czochralski method as materials for optoelectronic applications. Silicon doping is responsible for the change of the Co³⁺ ions into Co²⁺ in order to keep charge neutrality of the material and for a coloration of materials. Magnetization and Electron Paramagnetic Resonance measurements show that the most cobalt ions in the silicon co‐doped crystals were Co²⁺ in octahedral positions. Estimated concentration of the Co²⁺ ions were close to Si⁴⁺ nominal concentration. A little excess of Co²⁺ may be ascribed to defects present in the crystals. For the crystal doped only with Co, the concentration of Co²⁺ was about 13% of the nominal Co amount and might be caused by crystal defects. X‐ray Photoelectron Spectroscopy measurements exhibit aluminium deficiency. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of calcium hydrogen phosphate dihydrate crystals from single diffusion gel technique

Calcium hydrogen phosphate dihydrate (CaHPO₄·2H₂O, CHPD) a dissolved mineral in urine is known to cause renal or bladder stones in both human and animals. Growth of CHPD or brushite using sodium metasilicate gel techniques followed by light and polarizing microscopic studies revealed its structural and morphological details. Crystal identity by powder x‐ray diffraction confirmed the FT‐IR and FT‐Raman spectroscopic techniques as alternate methods for fast analysis of brushite crystals which could form as one type of renal stones. P‐O‐P asymmetric stretchings in both FT‐IR (987.2, 874.1 and 792 cm^‐1) and FT‐Raman (986.3 cm^‐1, 1057.6 cm^‐1 and 875.2 cm^‐1) were found as characteristics of brushite crystals. Differential Scanning Calorimetry (DSC) analysis revealed brushite crystallization purity using gel method by studying their endothermic peaks. This study incorporated a multidisciplinary approach in characterizing CHPD crystals grown in vitro to help formulate prevention or dissolution strategy in controlling urinary stone growth. Initial studies with 0.2 M citric acid ions as controlling agent in the nucleation of brushite crystals further support the presented approach. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single‐crystal growth and characterization of mullite‐type orthorhombic Bi2M4O9 (M = Al3+, Ga3+, Fe3+)

Pure and homogeneous single crystals of orthorhombic mullite‐type Bi₂M₄O₉ (M = Al³⁺, Ga³⁺, Fe³⁺), and a mixed Bi₂Fe_1.7Ga_2.3O₉ crystal from an equimolar Ga/Fe composition were grown by the top seeded solution growth (TSSG) method. All these compounds melt incongruently in the range of about 800 and 1100 °C. In case of bismuth gallate and ferrate inclusion‐free crystals with dimensions up to several cubic centimeters can be grown. Limited solubility in Bi₂O₃ and the high steepness of the liquidus curve are the reasons for getting only small imperfect bismuth aluminate crystals. In contrast to ceramic materials preparation reported in literature, divalent calcium and strontium could not be incorporated into the mullite‐type structure during the melt growth process. Several fundamental physical properties like heat capacity, thermal expansion, heat conductivity, elastic constants, high‐pressure behavior and oxygen diffusivity were determined by different research groups using single‐crystalline samples from the as‐grown materials. Furthermore, the refractive indices of Bi₂Ga₄O₉ were measured in the range of 0.430 and 0.700 μm. Such as many other bismuth containing compounds the refractive indices of Bi₂Ga₄O₉ are larger than 2, and Bi₂Ga₄O₉ is an optic biaxial positive crystal. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)