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.     

Preparation of calcium sulfate whiskers using waste calcium chloride by reactive crystallization

Calcium sulfate whiskers, owing to its good thermal stability, chemical resistance and good compatibility with rubber and plastics, has a strong potential in the application of polymer reinforcing composite materials. This work deals with the preparation of calcium chloride whiskers by reactive crystallization process with sulfuric acid and calcium chloride discharged from Solvay process. Firstly, the orthogonal experiments were carried out using both CaCl₂ and H₂SO₄ in analytic grade as feedstock, and the reactive crystallization conditions were optimized, which included reaction temperature, reactant concentration, reaction time and stirring speed. Based on the optimized reactive crystallization conditions, the new process for the preparation of calcium chloride whiskers was studied using the reactive crystallization process with sulfuric acid and calcium chloride discharged from Solvay process, and the effects of impurity ions in the waste solutions on the growth of whiskers were evaluated. It was found that calcium sulfate whiskers with stable and structured fine crystals (its aspect ratio up to 190) can be prepared using waste CaCl₂ in Solvay process. The experimental results will provide the valuable information for the reasonable disposal of waste CaCl₂ solution from Solvay process. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

一步水热法制备无水硫酸钙晶须

以生石膏为原料,六水氯化镁为形貌控制剂,采用水热法一步合成了无水硫酸钙晶须.借助SEM、TEM、XRD和XPS等测试手段考察了水热条件对无水硫酸钙晶须的影响,研究了无水硫酸钙晶须的生长过程.结果表明:镁/钙摩尔比n(MgCl2·6H2O)/n(CaSO4· 2H2O)=2.5,反应温度180℃,反应时间2h,可生长出长度为20 ～ 40 μm,直径0.5～2 μm的无水硫酸钙晶须.无水硫酸钙晶须生长过程为:片状CaSO4·2H2O-纤维状CaSO4·0.5H2O-纤维状CaSO4.     

Preparation of copper aluminum borate whiskers via flux method

Single‐crystal and uniform copper aluminum borate whiskers have been synthesized by heating a mixture of boric acid, copper sulfate and aluminum sulfate with potassium sulfate as flux at 870 °C for 4 h. The synthesized whiskers exhibit a well‐crystallized, one‐dimensional structure with diameters ranging from 100 nm to 5 μm, lengths from 5 to 100 μm. Heating temperature and flux addition affect the aspect ratio and morphology of the copper aluminum borate whiskers. A possible growth mechanism of the whiskers is proposed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

柠檬酸废渣制备硫酸钙晶须的研究

硫酸钙晶须是具有良好的力学性能和广泛应用前景的增强材料,利用柠檬酸废渣制备硫酸钙晶须,不仅可以生产出具有较高利用价值的材料,而且大大降低了成本并处理了废渣,起到"变废为宝"的作用.本文针对硫酸钙难溶的特性,采用了水热合成法成功制备了硫酸钙晶须,并讨论了多种因素对其影响,初步探讨了其生长机理,为其工业化生产提供理论基础.     

Preparation of dendritic‐like CdS by hydrothermal method and its photocatalytic performance

In this article, dendritic‐like CdS has been prepared by a hydrothermal method using thiourea as the sulfur source, and the effects of experimental conditions on the morphologies of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and the fluorescence and photodegradation properties of CdS have also been investigated. The XRD result indicates that the dendritic‐like CdS are of hexagonal phase and they are highly crystallized. Also, the FESEM results show that the ratio of raw material affects the yield of CdS, the reaction time affects the morphology of CdS. The best morphology of CdS is dendritic structures and the length is about 6 μm. The fluorescence spectrum shows three peaks at 470 nm, 513 nm and 547 nm, which indicates that the dendritic‐like CdS mainly emits green and blue fluorescence. Moreover, the dendritic‐like CdS exhibits good photocatalytic activity and its photodegradation rate to methylene blue can reach 92%. The growth mechanism for the formation of CdS with dendritic structure is also described.     

Preparation and characterisation of fluorapatite whiskers

Fluorapatite (FAp) whiskers were prepared by using Molten Salt Synthesis (MSS) technique. β‐tricalcium phosphate (TCP) and various fluorine salts, along with potassium sulphate as a flux salt were used as starting materials for preparing FAp whiskers. Effects of flux to powder weight ratio, temperature and soaking time on the morphology were studied. The optimum temperature to obtain FAp whiskers was found to be 1175°C. The phase purity of the prepared FAp whiskers were confirmed by powder X‐ray diffraction and FTIR spectra, and the whiskers were further characterized by laser Raman spectra, chemical analysis and DTA/TGA thermal analysis. The morphology of the FAp whiskers were investigated by scanning electron microscope (SEM) analysis. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于电石渣的硬硅钙石晶须的制备与表征

利用水热合成工艺,以电石渣作钙源合成了硬硅钙石晶须.用HCl对电石渣进行酸洗除杂,采用控制电石渣浆pH值,Ca(OH)2选择性溶解的方法去除电石渣中的其它杂质.采用ICP、XRD、SEM和DSC-TG分析了电石渣酸洗后的杂质含量及产品的晶相组成、微观形貌和耐温性.结果表明:控制pH值让电石渣中的化学组分选择性溶出,可使电石渣得以净化,成为制备硬硅钙石晶须的钙源;不同酸洗pH值、水热合成温度及保温时间对电石渣钙回收率、杂质去除率及合成的硬硅钙石晶须形貌具有很大的影响.比较适宜的制备条件是:电石渣酸洗pH=8、水热合成工艺参数220 ℃保温20 h.制备出的硬硅钙石晶须长径比为100～400,最高使用温度可达1000 ℃.     

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 and morphology of silicon carbide whiskers from polycarbosilane

The growth rate of silicon carbide whiskers grown from polycarbosilane was measured and the growth morphology was investigated. The plot of whisker length vs. growth time was almost linear up to a certain growth time but tended to become time-saturated, independent of growth temperature. Cessation of whisker growth was caused by a change of the growth process from vapor–liquid–solid (VLS) to vapor–solid (VS). Decrease in whisker length with growth time was observed in the higher temperature range. Arrhenius plots of growth rate were almost linear in the lower temperature range, but deviated markedly from linearity in the higher temperature range. This deviation was caused by the coexistence of the VS process and the VLS process during whisker growth.     

Synthesis of magnesium oxysulfate whiskers in the presence of sodium dodecyl benzene sulfonate

Uniform magnesium oxysulfate (5Mg(OH)₂·MgSO₄·3H₂O) whiskers with a length of 10‐15 µm and a diameter of 0.4‐1.0 µm were synthesized in the presence of sodium dodecyl benzene sulfonate (Na‐SO₃‐C₆H₄‐C₁₂H₂₅) at 200°C for 1 h, using MgSO₄·7H₂O and NaOH as the reactants. Mg(OH)₂ precursor with poor crystallization and small crystal size was formed owing to the adsorption of sodium dodecyl benzene sulfonate on the Mg(OH)₂ surface. The quick dissolution of Mg(OH)₂ precursor in the subsequent hydrothermal reaction inhibited the occurrence of the sector‐like byproduct and promoted the formation of magnesium oxysulfate whiskers with uniform morphology. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Synthesis of bamboo‐like SiC whiskers from waste silica fume

A process for the utilization of wasted silica fume is proposed in this work. Silicon carbide (SiC) whiskers several tens of micrometers in length and with a bamboo‐like morphology have been successfully synthesized by a carbothermal reduction process using purified silica fume as the silicon source. The morphology and structure of SiC whiskers were investigated by X‐ray diffraction, Raman spectroscopy, scanning electron microscopy, and high‐resolution transmission electron microscopy. Studies found that the as‐synthesized whiskers were grown as single‐crystalline β‐SiC along the (111) growth direction. The whiskers consisted of hexagonal stems randomly decorated with larger‐diameter knots along their whole length. On the basis of the characterization results, a vapor–solid process was discussed as a possible growth mechanism of the β‐SiC whiskers.     

磷石膏蒸压制备半水硫酸钙晶须

以磷石膏为原料,利用蒸压法制备半水硫酸钙晶须.采用均匀设计实验的基础上,进一步考察了料浆固液比、反应时间、蒸压压力对产品长径比的影响,并借助透射偏光显微镜、X射线衍射仪(XRD)等仪器对产品进行表征.结果表明,最佳反应条件:料浆固液比0.15 g· mL-1、反应时间0.5h、蒸压的压力0.3 MPa,在此条件下制备出了长径比99.07、晶须直径约1μm、纯度高、结晶良好的晶须产品.并从微观形貌、晶体结构、物相分析三个方面阐明了半水硫酸钙晶须生长规律.本研究对磷石膏的高值化利用具有指导意义.     

Synthesis of flake‐like crystals by a hydrothermal process

In this study, a hydrothermal method for formation of flake‐like nanocrystals is described. This approach with appropriate surfactant CTAB can be successfully synthesized of compound, noble metals, and semiconductors simple substance, such as lead sulfate, gold and selenium. The products were characterized by SEM image and XRD pattern. The results show that TSA acting as a new class of inorganic scaffolds for the synthesis of materials in crystal engineering and composites design for different applications is versatile reactor and may be extended to the creation of other highly novel inorganic structures with applications in catalysis, novel optical materials and other fields. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of SrMnO3 powders with different morphologies by hydrothermal method

By using two different reagents as the starting materials, SrMnO₃ crystallines with two different morphologies rhombus‐like and rod‐like, have been directly synthesized by hydrothermal conditions. The effects of the hydrothermal parameters on the quality of the SrMnO₃ samples were given for the fist time. And a preparative mechanism for the formation of different morphologies using different reagents during the hydrothermal reaction has been discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

利用脱硫石膏制备高品质二水石膏

利用脱硫石膏在酸性溶液中重结晶的特点,采用重结晶技术对脱硫石膏进行脱色提纯,通过对溶解、结晶过程的控制制备出高纯度、高白度的二水石膏.研究了硫酸浓度、晶种量、料浆浓度、稳定剂、温度、反应时间、陈化时间对二水石膏结晶的影响,并进行了母液循环实验.研究结果表明:常压下,H2SO4用量10.0;,Ca(OH)2用量0.5;,料浆浓度7.4;,聚乙二醇用量0.5;,反应温度120℃,反应时间2.5h,陈化24h后生成的二水硫酸钙结晶形貌良好,白度为94.01;,纯度达99.24;;母液循环3次后生成的二水石膏纯度大于98;.     

Optical properties of flower‐like CdS prepared by a hydrothermal method with SDBS as surfactant

In this article, flower‐like CdS structures have been prepared by a hydrothermal method with SDBS as surfactant. The influences of different experimental conditions on the morphologies, UV‐Vis and fluorescence properties of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet‐visible (UV–Vis) and room‐temperature photoluminescence (PL). The XRD result indicates that the flower‐like CdS structures are of hexagonal phase. The FESEM results indicate that the main role of SDBS is to make the CdS crystals assemble together to form the flower‐like structures. The UV–Vis results show CdS has a strong absorption in the ultraviolet region and visible‐light region. The PL results show CdS has two emission peaks, respectively at 461 nm and 553 nm. The growth mechanism for the formation of flower‐like CdS structures is also described.     

Surface‐morphology evolution of ZnO nanostructures grown by hydrothermal method

Surface‐morphology evolution of ZnO nanocrystals has been observed by the hydrothermal process. The effects of stirring time and ammonia content on the morphology evolution have been discussed, respectively. Extension of stirring time of the precursor results in morphology transformation from star‐like to wire‐like ZnO nanocrystals. ZnO nuclei aggregation and uniform Zn(OH)₂ precipitation can readily explain these two morphologies, respectively. By increasing the ammonia content in the solution, the morphology of ZnO crystals is transformed from an irregular shape to hexagon sheets to nanorods, and the side length of ZnO crystals is decreased accordingly. Hollow structures are realized at the subsequent solution aging process. Variation of zinc ammonic complex and minimum surface energy can well explain the morphology evolution of ZnO nanostructures.