Direct transformation of FGD gypsum to calcium sulfate hemihydrate whiskers: Preparation,simulations, and process analysis

Calcium sulfate hemihydrate (CSH) whiskers were synthesized by phase transition in CaCl₂ solution under atmospheric pressure. Analytical-grade calcium sulfate dihydrate (AR CSD) was used as the raw material for the synthesis of CSH whiskers, according to orthogonal experiments. The effects of reaction temperature, AR CSD content, H₂SO₄ content, and reaction time were investigated, and the crystallization conditions were optimized. The as-prepared CSH whiskers displayed a regular morphology and a highly uniform size, with an aspect ratio of 105. A simulation system was also established by blending various sulfates with AR CSD, to evaluate the effects of impurities in flue gas desulfurization (FGD) gypsum. The main aim was to prepare CSH whiskers directly from FGD gypsum, without any purification, using the optimized conditions. This is a facile potential alternative process for large-scale production of CSH whiskers using abundant FGD gypsum as source materials.     

Preparation of calcium sulfate whiskers from FGD gypsum via hydrothermal crystallization in the H2SO4–NaCl–H2O system

Little attention has thus far been paid to the potential effect of solution composition on the hydrothermal crystallization of calcium sulfate whiskers prepared from flue-gas desulfurization (FGD) gypsum. When purified FGD gypsum was used as raw material, the morphology and phase structure of the hydrothermal products grown in pure water, H₂SO₄–H₂O, NaCl–H₂O, and H₂SO₄–NaCl–H₂O solutions as well as the solubility of purified FGD gypsum in these solutions were investigated. The results indicate that calcium sulfate whiskers grow favorably in the H₂SO₄–NaCl–H₂O system. When prepared using 10–70 g NaCl/kg gypsum −0.01 M H₂SO₄–H₂O at 130 °C for 60 min, the obtained calcium sulfate whiskers had diameters ranging from 3 to 5 μm and lengths from 200 to 600 μm, and their phase structure was calcium sulfate hemihydrate (HH). Opposing effects of sulfuric acid and sodium chloride on the solubility of the purified FGD gypsum were observed. With the co-presence of sulfuric acid and sodium chloride in the reaction solution, the concentrations of Ca²⁺ and SO₄²⁻ can be kept relatively stable, which implies that the crystallization of the hydrothermal products can be controlled by changing the concentrations of sulfuric acid and sodium chloride.     

Hydrothermal synthesis of ZnO whiskers from ɛ-Zn(OH)2 in NaOH/Na2SO4 solution

The influence of Na₂SO₄ on the formation of ZnO whiskers was investigated in this paper. ZnO whiskers with aspect ratios of up to 50 were synthesized by dissolving ɛ-Zn(OH)₂ precursor in NaOH/Na₂SO₄ solution at room temperature, followed by aging of the resulting solution at 140 °C for 6 h. Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy analyses revealed that SO₄²⁻ ions were primarily adsorbed on the (1 0 0) plane of the ZnO whiskers via an outer-sphere complex configuration (OH···O), thereby promoting the one-dimensional growth of ZnO whiskers along the c-axis.     

Structural characteristic and formation mechanism of hemihydrate calcium sulfate whiskers prepared using FGD gypsum

Hemihydrate calcium sulfate whiskers (HH-CSWs) were hydrothermally synthesized in a sulfuric acid solution at 120 ℃ for different holding times (20,40,and 60 mi...     

Influence of disodium hydrogen phosphate dodecahydrate on hydrothermal formation of hemihydrate calcium sulfate whiskers

The influence of Na₂HPO₄·12H₂O on the hydrothermal formation of hemihydrate calcium sulfate (CaSO₄·0.5H₂O) whiskers from dihydrate calcium sulfate (CaSO₄·2H₂O) at 135 °C was investigated. Experimental results indicate that the addition of phosphorus accelerates the hydrothermal conversion of CaSO₄·2H₂O to CaSO₄·0.5H₂O via the formation of Ca₃(PO₄)₂ and produces CaSO₄·0.5H₂O whiskers with thinner diameters and shorter lengths. Compared with the blank experiment without Na₂HPO₄·12H₂O, the existence of minor amounts (8.65 × 10⁻⁴–4.36 × 10⁻³ mol/L) of Na₂HPO₄·12H₂O led to a decrease in the diameter of CaSO₄·0.5H₂O whiskers from 1.0–10.0 to 0.5–2.0 μm and lengths from 70–300 to 50–200 μm.     

氧化铝/钼自润滑结构陶瓷表面三维复合润滑层的制备与摩擦学性能研究

应用先进的激光表面加工技术,在Al_2O_3/Mo层状自润滑结构陶瓷表面制备了微坑型织构.将织构图案作为固体润滑剂的贮存槽,通过在其中引入固体润滑剂形成三维复合润滑层.考察了复配润滑剂对织构化氧化铝/钼复合陶瓷在室温至800℃连续加热过程中的协同润滑作用,并通过磨损表面分析探讨了其在宽温域下的润滑机理.结果表明:通过集成固体润滑剂优异的减摩抗磨性能和微织构特殊的结构特征,可使氧化铝/钼复合陶瓷在室温、中温区域的摩擦学性能得到显著改善,实现了材料在较宽温度范围内的连续润滑.复合Graphite/BaSO_4/CaF_2-BaF_2的表面在室温至800℃温度范围内的摩擦系数均保持在0.45以下.     

Synthesis and characterization of superhydrophobic magnesium oxysulfate whiskers

Superhydrophobic materials have attracted much attention for their special wettability. In this study, magnesium oxysulfate (MOS) whiskers were surface modified by vinyltrimethoxysilane (VTMS) and prepared as superhydrophobic materials, which are expected to be widely used in self-cleaning, corrosion prevention, and oil-water separation. The factors of silane concentration, hydrolysis time, reaction temperature, and reaction time were investigated. The superhydrophobic MOS whiskers were synthesized. SEM and XRD turned out that there were no apparent changes in the morphology and crystallization behavior of whiskers before and after modification, while the surface was uniformly coated with a layer of non-crystal material, and the surface of the whiskers employed a chemical bond Si–O–Mg covalently connected. The thermogravimetric analysis ultimately demonstrated that surface modification was beneficial to the improvement of the thermal stability of MOS whiskers. Superhydrophobic MOS whiskers showed good compatibility with organic solvents through oil-water separation experiments, and demonstrated excellent self-cleaning performance. The methodology for the surface treatment of MOS whiskers to prepare superhydrophobic whiskers in this work may be extended for other whiskers or fillers, which may be promising for the preparation of superhydrophobic materials.     

Structural characteristic and formation mechanism of hemihydrate calcium sulfate whiskers prepared using FGD gypsum

Hemihydrate calcium sulfate whiskers (HH-CSWs) were hydrothermally synthesized in a sulfuric acid solution at 120 °C for different holding times (20, 40, and 60 min). The phase structures and morphologies were characterized by XRD and SEM, respectively. The XRD pattern of the sample under 60 min was refined via the Rietveld fitting method. The structure models of the HH-CSW sample under a 60-min holding time was established based on Rietveld fitting results. No difference in the positions of diffraction peaks was determined. The as-prepared holding time increased the intensity and aspect ratio of the diffraction peaks of both samples. In the prepared HH-CSW structure, Ca–O polyhedron is a 12-sided polyhedron similar to that in the gypsum structure; the Ca atom is located in two positions in the one-unit cell; the H₂O channel along the c-axis similar is O-shaped and bigger than that in hexagonal and monoclinic CaSO₄·0.5H₂O structures. Therefore, although the prepared HH-CSW crystals’ structure are similar to that of the reported hexagonal and monoclinic CaSO₄·0.5H₂O structures, they are not the same. The formation mechanism of HH-CSW from flue gas desulfurization (FGD) gypsum is discussed based on the analysis of gypsum structure.     

Preparation and properties of magnetic iron oxide nanotubes

Magnetite (Fe3O4) nanotubes were prepared by reducing synthesized hematite (α-Fe2O3) nanotubes in 5% H2+95% Ar atmosphere,and then maghemite (γ-Fe2O3) nanotubes were obtained by re-oxidizing the Fe3O4 nanotubes.The nanotube structure was kept from collapsing or sintering throughout the high temperature reducing and re-oxidizing processes.The coercivities of the Fe3O4 and γ-Fe2O3 nanotubes synthesized were found to be 340.22 Oe and 342.23 Oe,respectively,both higher than other nanostructures with the same phase and of similar size.Both adsorbed phosphate and the nanotube structure are considered responsible for this high coercivity.     

基于热老化实验的螺杆马达定子橡胶本构模型研究

随着我国油气资源勘探开发向深部地层迈进,螺杆钻具定子橡胶井下高温热老化问题日益凸显,导致螺杆钻具输出性能衰减,严重影响钻进效率,迫切需要揭示热老化对螺杆钻具定子橡胶力学性能的影响,以在设计之初提出可减小螺杆钻具输出性能衰退的综合方案。本文开展了螺杆马达定子橡胶在不同温度下的热老化实验,通过拉伸实验得出应力应变数据并拟合出Mooney-Rivlin模型常数和Yeoh模型常数;再对所得实验数据及所求得的模型常数数据进行分析;最后,使用确定了基本常数的模型开展了数值计算。计算结果表明,随着温度的上升,Mooney-Rivlin模型常数C_1增大、C_2减小,C_1和C_2呈明显相反变化的趋势,Yeoh模型常数C_(10)和C_(20)增大,C_(30)减小;通过模型计算结果与室内实验测定结果的对比,证明了Mooney-Rivlin模型较Yeoh模型更适合于螺杆马达定子橡胶的力学分析。不考虑环境温度热老化和考虑环境温度热老化,螺杆钻具定子衬套的计算结果存在很大差别,研究工作不仅证明了螺杆钻具定子橡胶热老化研究的必要性,更为螺杆钻具定子橡胶的线型设计和过盈量选取提供了参考。     

锡青铜基自润滑材料的摩擦学特性研究

采用粉末冶金自由烧结工艺制备出锡青铜基自润滑复合材料,对该类复合材料的力学性能与摩擦磨损特性进行了研究,从固体润滑剂角度就其室温与450℃自润滑机理进行了分析与探讨。研究结果表明,该类材料在室温至450℃温度范围内具有良好的机械性能与磨擦磨损特性。XRD分析结果显示：在室温下磨损表面形成的含石墨、Pb和SnO2的复合膜是其具有润滑性能的主要原因;在高温下则由石墨、Pb2O3和CuO组成的复合膜起主要润滑作用。     

An approach to modeling induction period in crystallization fouling

In this study the fouling of calcium carbonate CaCO₃ and calcium sulfate dehydrate CaSO₄·2H₂O each from single salt solutions on stainless steel surfaces as well as modified surfaces was investigated. Based on experimental investigations a mathematical model for estimation of the induction time was developed. The model was integrated in a software code, computed and compared with experimental data. As a criterion for the induction period the corresponding ratio of Biot numbers was applied.     

季铵盐修饰磷钼酸铵纳米微粒作为液体石蜡添加剂的摩擦学性能

采用共沉淀法在溶液中原位合成了季铵盐修饰磷钼酸铵[(NH4)3PMo12O40]纳米微粒,采用透射电子显微镜、X射线衍射仪、示差扫描热分析仪及热重分析仪等观察分析了表面修饰(NH4)3PMo12O40纳米微粒的形貌和热稳定性,并在四球摩擦磨损试验机上考察了其作为液体石蜡添加剂的摩擦学性能。结果表明：表面修饰(NH4)3PMo12O40纳米微粒大小均匀,平均粒径约为20nm;(NH4)3PMo12O40纳米核在300℃左右分解;(NH4)3PMo12O40。纳米微粒作为液体石蜡添加剂,在中低负荷下具有较好的抗磨性和一定的减摩作用,并可提高液体石蜡的极压负荷,采用扫描电子显微镜和X射线光电子能谱对磨斑表面形貌和化学组成进行观察分析发现,(NH4)3PMo12O40纳米微粒在摩擦副接触表面发生了摩擦化学作用,并形成由多种含氧化合物组成的表面保护膜,从而起到减摩抗磨作用。     

Microwave synthesis and spectroscopic characterization of manganese oxalate nanocrystals

The microwave synthesis of MnC₂O₄·2H₂O nanoparticles was performed through the thermal double decomposition of oxalic acid dihydrate (C₂H₂O₄·2H₂O) and Mn(OAc)₂·4H2O solutions using a CATA-2R microwave reactor. Structural characterization was performed using X-ray diffraction (XRD), particle size and shape were analyzed using transmission electron microscopy (TEM). The chemical in the structures was investigated using electron paramagnetic resonance (EPR) as well as optical absorption spectra and near-infrared (NIR) spectroscopies. The nanocrystals produced with this method were pure and had a distorted rhombic octahedral structure.     

Vapour-diffusion assisted growth of oriented or-cobalt hydroxide thin films

Layered ,α-cobalt hydroxides Co(OH) 1.65Cl0.35.0.5H2O (1), Co(OH) 1.75(NO3)0.25.0.1H2O (2) with unique macro- and microscale morphologies have been synthesised by a low temperature, ammonia-controlled vapour-diffusion method. The materials have thin film morphologies and were characterized by X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FESEM).     

Comparison of schemes for preparing magnetic Fe3O4 nanoparticles

Magnetic Fe3O4 nanoparticles were prepared by means of coprecipitation using NH3·H2O in water and in alcohol, and using NaOH in water. A series of instruments such as SEM, TEM, HRTEM, FT-IR, XRD and VSM were used to characterize the properties of the magnetic nanoparticles.was the longest. The process using NaOH in water was the simplest and the reaction time was the shortest, but the particle characteristics were inferior to those of the other two methods. The mean size of magnetic Fe3O4 nanoparticles prepared by coprecipitation in alcohol was the smallest among the three, but the nanoparticles aggregated severely. The magnetic Fe3O4 nanoparticles were coated with oleic acid using saturated sodium coated successfully and thoroughly.     

惰性气体对C3H8可燃下极限的影响

为探究CO₂、N₂和Ar对C₃H₈可燃下极限的影响,在5 L爆炸容器中测定了C₃H₈在O₂/CO₂、O₂/Ar、O₂/N₂三种气氛下的可燃下极限。首先分析了稀释气浓度、稀释气种类和氧气浓度对C₃H₈的可燃下极限的影响。结果表明,在O₂/CO₂气氛下,稀释气浓度变化对C₃H₈的可燃下极限影响最大,对O₂/Ar的影响次之,对O₂/N₂的影响最小。在相同稀释气浓度条件下,CO₂对C₃H₈可燃下极限的影响最大,N₂的影响次之,Ar的影响最小。随着O₂浓度的上升,O₂/CO₂气氛的可燃下极限出现较为明显的下降,O₂/N₂和O₂/Ar的氛围的可燃下极限平缓上升。通过建立能量平衡方程分析了稀释气的比热和辐射效应对可燃下极限的影响。结果表明,混合气比热的改变是C₃H₈可燃下极限改变的主要原因,辐射热损失是影响可燃下极限的重要因素。     

A readily monitored and controllable hydrothermal system for the facile,cost-effective transformation of FGD gypsum to calcium sulfate hemihydrate whiskers

The controllable transformation of flue gas desulfurization(FGD)gypsum to calcium sulfate hemihydrate(HH)whiskers under facile,readily monitored,and cost-effective hydrothermal conditions could play a vital role in the preparation of high quality HH whiskers and improve our understanding of the transformation process.This work assessed the conversion of FGD gypsum to HH whiskers in 5×10^-4mol/L H₂SO₄and 1.5 wt%CuCl₂at 120℃while determining the effects of temperature as well as H₂SO₄and CuCl₂concentrations on transformation kinetics.The preparation of HH whiskers was found to involve a solution-mediated transformation from the dihydrate(DH)to theα-HH.This transition was determined to proceed via a dissolution crystallization mechanism,the rate of which was controlled by nucleation and growth of the HH whiskers.An autocatalytic kinetic model was established based on variations in the HH whiskers mole fraction over time,and this model accurately fit the experimental data with R2=0.990.Increasing the temperature or H₂SO₄concentration accelerated the transformation by modifying the super-saturation and water activity in the reaction solution,while increasing the CuCl₂concentration had the opposite effect.The hydrothermal conditions had an important effect on the transformation from FGD gypsum to HH whiskers.     

氧化硼的纳米磨损特性研究

利用原子力显微镜和将纳米力学性能测试仪研究了室温及不同湿度环境下,氧化硼表面上硼酸的形成规律,分析了表面形貌,表面力学性能及微观磨损特性,研究表明,氧化硼表面生成硼酸时,体积发生膨胀,硼酸的形成受环境湿度的影响,而氧化硼的微观磨损率与硼酸的生长速度呈对应关系,硼酸的生长使氧化硼表面软化,强度降低。