磷石膏常压酸化法制备无水硫酸钙晶须的实验研究

以磷石膏为原料,一步常压酸化法制备无水硫酸钙晶须.采用单因素实验方法研究了盐酸浓度、反应温度、反应时间和固液比4个因素对制备硫酸钙晶须的影响.采用X射线衍射(XRD)、扫描电子显微镜(SEM)对反应产物样品的物相、微观形貌进行了表征.结果 表明:在盐酸浓度为5 mol/L、反应温度为90℃、反应时间为3h和固液比为0.10g/mL的条件下,一步法制备出了直径为1～4μm、长径比为3～8的无水硫酸钙晶须.分析认为,无水硫酸钙晶须是在二水硫酸钙溶解量达到其过饱和度后从溶液中结晶形成的.     

添加CaSO4·2H2O为晶种制备磷石膏半水硫酸钙晶须

以固体废弃物磷石膏为原料,在传统常压醇水热法的基础上添加CaSO₄·2H₂O为晶种制备半水硫酸钙晶须。采用单因素试验法探究了晶种含量、丙三醇含量和磷石膏质量分数对晶须结构和形貌的影响,确定晶须的最佳制备工艺条件。采用SEM和XRD对样品进行表征分析,实验结果表明:添加CaSO₄·2H₂O晶种制备晶须的长径比(49.29)比只添加丙三醇的样品的长径比(30.99)提高了近60%;当丙三醇与水的体积比(V)为1、晶种含量为1%、磷石膏质量分数为5%时制备的晶须的平均直径为0.65 μm,长径比达到了62.15,晶须的尺寸均匀。这说明添加1%CaSO₄·2H₂O晶种、V为1的丙三醇和质量分数为5%的磷石膏在常压下能制备出高长径比和尺寸均匀的半水硫酸钙晶须。     

基于响应面法的半水硫酸钙晶须制备工艺优化

本研究以氯化钙、硫酸为主要原料,采用常压酸化法制备半水硫酸钙晶须.以长径比、长度为主要指标,在单因素实验的基础上,运用响应面法中的Box-Behnken design对反应温度、硫酸浓度、反应时间、搅拌速度进行优化,建立半水硫酸钙晶须制备工艺的数学模型,研究制备的最优工艺条件.结果表明,制备半水硫酸钙晶须的最优工艺条件为:反应温度103℃、硫酸浓度7.4;、反应时间60 min、搅拌速度288 r·min-,得到的晶须样品形貌规整、均一,平均长径比为82.2,φ90为53.3,平均长度为562 μm.     

混合助晶剂促进大长径比硫酸钙晶须的调控研究

以预处理后的磷石膏为原料,氯化镁、丙三醇、丙三醇/无水乙醇、丙三醇/硬脂酸为助晶剂,采用水热法制备了硫酸钙晶须,利用XRF、SEM、XRD和FT-IR分别对硫酸钙晶须的成分含量、表面形貌、物相特征等进行了表征.结果表明,混合助晶剂能够明显增大硫酸钙晶须的长径比,提高晶须合成率,改善晶须形貌.在丙三醇/无水乙醇体系中,当V(无水乙醇)/V(丙三醇)=0.8时,硫酸钙晶须的合成率为96;,长径比可达90.在丙三醇/硬脂酸体系中,当m(硬脂酸)/m(磷石膏)=2;时,硫酸钙晶须的合成率为94;,长径比可达75.     

机械力活化对脱硫石膏制备硫酸钙晶须的影响

对脱硫石膏原料进行机械力活化,然后采用降温重结晶法制备出硫酸钙晶须.借助扫描电镜、图像粒度分析仪和相关软件进行表征,并初步讨论了机械力活化对晶须成核和生长过程的影响.结果表明:经过机械力活化的脱硫石膏可以制备有较大长径比的硫酸钙晶须.在水浴反应温度为75℃,硫酸浓度为2.5 mol/L,机械力活化时间为3.5 h,浆料浓度为2;的条件下,制备的硫酸钙晶须平均长径比为150,平均直径为2.1μm.     

微波外场强化电石渣制备硫酸钙晶须及其机理分析

本文以电石渣为原料,在稀硫酸溶液中制备硫酸钙晶须.在常规水热法最佳制备条件的基础上,不添加表面活性剂,利用微波反应器强化硫酸钙晶须结晶过程.分析了微波反应时间,微波辐射能量对结晶产物的影响.利用X射线衍射仪和扫描电子显微镜对制备的产物进行表征.结果 表明,电石渣与稀硫酸溶液在微波强化的条件下反应10 min,微波辐射能量400 W时,制备的硫酸钙晶须形貌尺寸均一,晶须平均直径为2.2 μm,平均长径比70.在此基础上,进一步分析了微波效应与硫酸钙晶须的生长机理.     

脱硫石膏晶体提纯脱色的研究

以H2O-HCl-CaCl2溶液为反应介质采用两步法在常压下对脱硫石膏脱色;考察了HCl浓度、CaCl2浓度、料浆浓度对水热反应时间的影响和转晶温度、转晶时间、料浆浓度对产品白度和收率的影响。得出的较适宜条件为:HCl浓度为1.21mol/L,CaCl2浓度为0.27mol/L,料浆浓度为6.98%,转晶温度25℃、转晶时间18h,该条件下水热反应时间缩短至120min,脱色产品的白度和纯度分别提高至90%和96%。脱色提纯过程的母液反复利用5次后,产品性能与初次配料时无明显差异。以提纯脱色后的脱硫石膏为原料制备的半水硫酸钙晶须白度达到95.22%。     

脱硫石膏重结晶法制备硫酸钙晶须及其除砷性能初探

以电厂脱硫石膏为原料,利用重结晶原理制备二水硫酸钙晶须.考察了溶液过饱和度、硫酸浓度、陈化温度/时间以及降温速率对晶须生长特性的影响,并初步研究了硫酸钙晶须对含砷水溶液的除砷性能.结果表明:所研究的操作条件对晶须形貌、尺寸均有一定影响.在H2SO4溶液重结晶体系中,控制硫酸钙过饱和度为0.5、陈化温度为20℃、陈化时间为3h并采用自然降温时,制备的二水硫酸钙晶须结晶度较好、形貌尺寸均匀,长径比为50～200.该二水硫酸钙晶须在pH为12时,能将初始浓度低于1 mg/L的含砷水溶液净化至满足地表水标准(0.05mg/L),展示了其在砷污染水体净化方面的应用潜力,可配合石灰-硫酸亚铁两段法除砷,降低废水处理成本.     

高长径比三水碳酸镁晶须的合成研究

采用低温水溶液法合成三水碳酸镁晶须,考查了反应温度、反应时间、表面活性剂用量及反应溶液初始pH等因素对三水碳酸镁晶须的长度及长径比的影响.研究结果表明:在反应温度45～50℃、反应时间50～60 min、表面活性剂添加量(质量分数)为1;、反应溶液初始pH =9.5的条件下,可以合成出高长径比三水碳酸镁晶须产品.     

脱硫石膏制备硫酸钙晶须结晶动力学研究

结晶动力学能够揭示结晶过程本质,通过测定溶液中Ca2浓度来确定硫酸钙晶须的转化率,从而确定硫酸钙晶须结晶动力学参数,得到转化率与时间的关系式:X=1/｛1+e6^[-10.01977t(0.0956-c)+1.1188]｝,(0≤t≤6.0).研究了影响硫酸钙晶须结晶动力学的影响因素降温速率和陈化时间,利用SEM对制备的硫酸钙晶须进行表征.结果表明:自然冷却条件下,陈化时间6h,制备出的硫酸钙晶须结晶发育完整,晶须平均长径比达到150,平均直径为2.1 μm.     

CsI-LiCl共晶材料的坩埚下降法生长与闪烁性能研究

本文采用坩埚下降法,在真空密封的石英坩埚中成功生长出CsI-LiCl与CsI-LiCl:Na共晶闪烁体。通过扫描电子显微镜(SEM)观察晶体微结构表明该共晶中LiCl相与CsI相存在周期性的层状排列,CsI相的厚度在5 μm左右。共晶样品的X射线激发发射谱显示在CsI-LiCl和CsI-LiCl:Na共晶样品存在缺陷发光,在CsI-LiCl样品中还观察到了纯CsI的自陷激子(STE)发光。CsI-LiCl样品在α粒子激发下的多道能谱中观察到明显的全能峰,这一结果证明CsI-LiCl共晶可用于热中子探测的潜力。     

静电纺丝法制备CeO2微纳米纤维及其除氟性能

以聚丙烯腈(PAN)为载体,六水合硝酸铈[Ce(NO₃)₃·6H₂O]为原料,采用静电纺丝法制备了Ce(NO₃)₃/PAN纤维,在空气中热处理得到CeO₂微纳米纤维,通过XRD、BET和SEM对CeO₂微纳米纤维进行表征。采用静态吸附实验探讨了CeO₂微纳米纤维去除水溶液中氟离子的性能,考察了溶液pH值、初始氟离子浓度及共存阴离子等对吸附性能的影响。结果表明,pH=3时,CeO₂微纳米纤维对F^-的吸附性能最佳,CeO₂吸附量随着F^-浓度的增大呈上升趋势。CeO₂微纳米纤维对F^-的吸附等温线遵循Langmuir模型,二级动力学模型能很好地描述CeO₂微纳米纤维对F^-的吸附过程。CeO₂微纳米纤维的除氟性能优良,可为其实际应用提供理论参考。     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

X-ray analysis of sideroxol from <Emphasis Type="Italic">Sideritis leptoclada</Emphasis>

Sideroxol (1), a kaurane diterpene which has the ent-7α,18-dihydroxy-15β,16β-epoxykaurane structure (MW = 320.47, C₂₀H₃₂O₃) was obtained from the acetone extract of Sideritis leptoclada plant as well as from some other Sideritis species. It crystallizes in the orthorhombic space group P2₁, 2₁, 2₁ with a = 10.967(3), b = 24.555(5), c = 6.372(4) Å, Dc = 1.240 g cm⁻³, Z = 4, and refines to R = 0.065 for 721 independent reflections. The skeleton consists of three fused six-membered rings and a five-membered ring with fused epoxide. The six membered rings exhibited slightly distorted chair conformation. In addition to sideroxol, two kaurane and five kaurene diterpenes were isolated from the hexane and acetone extracts of the studied plant.     

Photoluminescence characteristics of Mg- and Si-doped GaN thin films grown by MOCVD technique

We have studied the optical, structural and surface morphology of doped and undoped GaN thin films. The p- and n-type thin films have been successfully prepared by low-pressure MOCVD technique by doping with Mg and Si, respectively. The different carrier concentrations were obtained in the GaN thin films by varying dopant concentrations. Photoluminescence (PL) studies were carried to find the defect levels in the doped and undoped GaN thin films at low temperature. In the undoped GaN thin films, a low intensity and broad yellow band peak was observed. The donor–acceptor pair (DAP) emission and its phonon replicas were observed in both the Si or Mg lightly doped GaN thin films. The dominance of the blue and the yellow emissions increased in the PL spectra, as the carrier concentration was increased. The XRD and SEM analyses were employed to study the structural and surface morphology of the films, respectively. Both the doped and the undoped films exhibited hexagonal structure and polycrystalline nature. Mg-doped GaN thin films showed columnar structure whereas Si-doped films exhibited spherical shape grains.