Effect of alcohols additives on hydrothermal formation of magnesium hydroxide sulfate hydrate whiskers

Two different organic alcohols, ethylene glycol and 1, 2‐propanediol, were used in hydrothermal formation of MgSO₄·5Mg(OH)₂·2H₂O (MHSH) whiskers. Compared with the MHSH whiskers without alcohols, the crystallinity and defect of products were improved. It could also be observed that not only aspect ratio but also crystallinity and purity of the products were improved when 1, 2‐propanediol was used. A reasonable model was proposed to explain the growth process derived from the organic alcohol. In addition, the room temperature photoluminescence (PL) indicated that the spectrum intensity of MHSH whiskers used 1, 2‐propanediol was also significantly improved.     

丁醇-变频微波-水热法制备优质碱式硫酸镁晶须及表征

以MgSO4·7H2O、NaOH为原料,采用丁醇-变频微波-水热法制备了优质碱式硫酸镁晶须.样品用XRD,SEM,TEM,TG-DTA进行了物相、粒度、晶体形貌结构和热分析.考察了传统的水热法、变频微波-水热法、丁醇-水热法、丁醇-变频微波-水热法四种工艺对碱式硫酸镁晶须晶形、结构、分散性的影响.实验发现,在水热反应体系中加入体积分数为25;的丁醇,并采用变频微波加热,调节微波炉反应温度T=130 ℃,反应时间t=9 h时可获得粒度分布均匀、晶形好、分散性好、表面光滑、缺陷少的优质碱式硫酸镁晶须.透射电镜下估算晶须直径约为0.8～1.1 μm,长度约为60～100 μm.初步分析了微波、丁醇对碱式硫酸镁晶须生长的作用.     

Influence of solvents on the hydrothermal formation of one‐dimensional magnesium hydroxide

The influence of solvents on the hydrothermal formation of one‐dimensional (1D) magnesium hydroxide (Mg(OH)₂) was investigated in this paper. Uniform 1D Mg(OH)₂ with a length of 10‐20 μm, a width of 100‐200 nm and a preferential growth along [110] direction have been synthesized by treating magnesium oxysulfate (5Mg(OH)₂·MgSO₄·3H₂O, abbreviated as 513MOS) nanowires in NaOH ethanol solution at 180 °C for 2.0 h. The experimental results indicated that the solvent of ethanol and NaOH concentration were essential for the conversion of 513MOS nanowires to 1D Mg(OH)₂. The slow release of MgSO₄ from 513MOS and the heterogenous precipitation of Mg(OH)₂ at the defects left by MgSO₄ dissolution promoted the formation of 1D Mg(OH)₂. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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 strontium carbonate rods and hierarchical branches in the presence of two organic additives

In this paper, strontium carbonate (SrCO₃) crystals have been synthesized in the presence of two organic additives, including sodium citrate and hexamethylenetetramine (HMT). Scanning electron microscopy, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, X‐ray powder diffractometry and selected area electron diffraction (SAED) were used to characterize the products. The results indicate that SrCO₃rods with the ratio of length to diameter about 20 are obtained in the aqueous solution containing sodium citrate. While polycrystalline SrCO₃ hierarchical branches with about 10 μm length are produced by using HMT.The possible formation mechanism of the SrCO₃crystals obtained in above two systems is discussed, which can be interpreted by particle‐aggregation based non‐classical crystallization laws. Sodium citrate and HMT may direct the formation of SrCO₃ rod‐like or branch‐like structures by adsorbing onto certain facets of SrCO₃ crystals. (© 2010 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.     

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.     

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.     

In situ measurement of growth kinetics of {100} KDP crystal faces in the presence of polyphosphate impurities

The face growth rate and critical supersaturation of {100} face were in situ measured using the laser‐polarization‐interference technique in the presence of potassium pyrophosphate, trimetric sodium phosphate and sodium hexametaphosphate impurities. The polyphosphate impurities inhibit the growth rate of prismatic faces. The face growth rate as a function of supersaturation at different impurity concentrations, as well as critical supersaturation as a function of impurity concentrations, was found in good agreement with a two‐dimensional nucleation model in the pure system and Kubota and Mullin's model in the presence of impurities. The average distance L between active sites available for impurity adsorption as well as the edge free energy was calculated. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Direct and outer-sphere coordination of the magnesium ions in the crystal structures of complexes with 2-furancarboxylic acid (I) and 3-furancarboxylic acid (II)

(I) Mg₂C₂₀H₂₄O₁₈ monoclinic,PT,a=10.760(2) Å,b=11.052(2) Å,c=12.822(3) Å, α=105.31(3)^o, β=98.18(3)^o, γ=91.59(3)^o,Z=2. (II) MgC₁₀H₁₄O₁₀, monoclinic,C2/c,a=30.817(6)Å,b=10.499(2)Å,c=9.000(2)Å, β=91.31(3)^o,Z=8. Magnesium in complexes with furoic acids reveals two ways of coordination: direct, when furoic anions are bonded to Mg²⁺ in an ionic fashion and outer-sphere, when cations bind water in the first coordination sphere and furancarboxylic ligands are hydrogen bonded to the water molecules. This results in the formation of three bridging systems: ?Mg?O_carboxyl?C?O_carboxyl?Mg?, ?Mg?O_water ?O_carboxyl?C?O_carboxyl?C?O_carboxyl?Mg?, and ?Mg?O_water?O_carboxyl?C?O_carboxyl?O_water?Mg?. Magnesium 2-furancarboxylate (I) is dimeric, while magnesium 3-furancarboxylate (II) exhibits a polymeric structure.