钛酸钡陶瓷制备及介电性能研究

采用钛酸四丁酯和硝酸钡为主要原料的微波辅助草酸盐沉淀法,在最佳的工艺参数下合成晶粒尺寸约为30～ 50 nm的钛酸钡粉末.再通过对纳米粉体造粒、成型、排胶和烧结等工艺处理制备钛酸钡陶瓷.研究陶瓷的最佳烧结温度与烧结时间,并且讨论其对介电性能的影响规律.利用透射电子显微镜分析粉体的形貌,XRD和扫描电子显微镜分别分析陶瓷的物相和断面形貌.结果表明,利用微波辅助草酸盐沉淀法合成的粉体制备陶瓷的烧结温度为1270℃,烧结时间为3h.并且其介电常数在室温下可达到2397.6.     

微波水热法制备ZnO纳米晶

采用微波水热(microwave hydrothermal,M-H)法在MDS-6型温压双控微波水热反应仪中成功地制备出平均晶粒尺寸为30 nm且呈现棒状形貌的ZnO纳米晶.并在一定的水热温度和反应时间下系统研究了微波水热反应过程中[Zn2+]离子浓度、反应釜填充比、反应物浓度比[Zn2+]/[OH]等工艺因素对ZnO纳米晶的晶粒尺寸及形貌的影响.采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和透射电子显微镜(TEM)对所制备的ZnO纳米晶进行表征.结果表明:所制备ZnO的平均晶粒尺寸约为30 nm,ZnO纳米晶呈现棒状形貌.随着[Zn2+]离子浓度的增加,ZnO纳米晶的晶粒尺寸先减小后增大;随着反应釜填充比和反应物浓度比[Zn2+]/[OH]的增大,ZnO纳米晶的晶粒尺寸先减小后增大,并逐渐趋于稳定.制备ZnO纳米晶的最佳反应条件为:[Zn2+]=1.6 mol·L-1;反应釜填充比=70;;[Zn2+]/[OH]=1/2.     

微波辅助草酸盐沉淀法制备四方相钛酸钡纳米粉体

以钛酸四丁酯和硝酸钡为主要原料,采用微波辅助草酸盐沉淀法制备了纯度高、结晶度较好的四方相钛酸钡纳米粉体.分别采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对钛酸钡纳米粉体的结构、粒径及形貌进行表征.结果表明,在钡/钛摩尔比为1,微波温度80 ℃、微波时间30 min,煅烧温度700 ℃,煅烧时间1 h,通过添加表面活性剂OP-10,制备出粒径在50 nm左右且四方度为1.0069的钛酸钡纳米粉体,其中微波合成温度及合成时间对钛酸钡纳米粉体的四方度的影响较大.     

反应温度和添加剂含量对微波合成碳化硼微观形貌的影响

微波烧结由于具有高效、快速、绿色等特点越来越受到人们的关注.本文以天然煤粉(C)和硼酸(H3BO3)为原料,在无气氛保护条件下,利用2.45 GHz的TE666单频微波烧结炉,快速碳热还原反应法制备出纳米碳化硼(B4C)粉体.结果发现:当煤粉(C)和硼酸(H3BO3)质量比为3∶1,微波烧结温度为1400~1800 ℃,保温时间为5 min,即可制备出结晶良好的碳化硼(B4C)晶体,调整相关工艺参数可以控制B4C晶体的形貌,如直径为50~150 nm的球形颗粒或碳化硼片状结构,通过改变Na2CO3添加剂含量(3wt;~9wt;),可得到不同尺寸的碳化硼纳米片(边长为200~800 nm),获得传统电阻烧结条件下无法得到的碳化硼(B4C)晶体.     

微波烧结制备铁酸铋陶瓷的介电性和铁电性

采用微波烧结法制备铁酸铋多铁陶瓷,研究了微波烧结时间对其显微结构、介电性和铁电性的影响.结果表明:在4 kW下烧结35～40 min制备出基本为纯相的铁酸铋陶瓷;随烧结时间增加,铁酸铋陶瓷结构越来越致密,晶粒尺寸有一定程度增大;在-10～90℃范围内,介质损耗随烧结时间增加而增大;随微波烧结时间增加,剩余极化强度增大,而矫顽场强先增加后减小,且铁电性具有明显的频率依赖性;铁酸铋陶瓷的漏电流随微波烧结时间增加而减小,这是结构致密化的结果.     

烧结升温速率对钛酸钡陶瓷压电性能的影响

采用固相反应方法在不同烧结升温速率下制备了BaTiO3陶瓷,并对陶瓷样品的晶体结构、表面形貌、介电、压电和铁电性能进行了测试和分析.结果表明:当烧结升温速率为3 ℃/min和5 ℃/min时陶瓷均为四方钙钛矿晶格结构,随升温速率的增大,四方相程度增强,材料平均晶粒尺寸减小,压电系数和铁电性能随之降低,但介电常数随之增大,当烧结升温速率为5 ℃/min介电常数最大,其值为3144.当烧结升温速率为1 ℃/min时陶瓷为正交钙钛矿晶格结构d33和Pr最大,其值为Pr=10 μC/cm2和d33=193 pC/N.     

锆钛酸钡陶瓷的超低温烧结及其介电特性

利用钛酸四丁酯、硝酸锆、氢氧化钡为原料在室温下,直接合成了颗粒尺寸均匀,组分连续可调的高性能锆钛酸钡纳米粉体.在此基础上,通过添加不同比例的Bi2O3和Li2CO3为助烧剂,实现了900℃下的陶瓷的超低温烧结.确立了烧结时间与陶瓷微观结构之间的相关性.研究表明,助烧剂的加入,可以使介电峰强烈地向低温方向移动,室温介电常数可大于5000以上.某些情况下使介电峰分裂,由单一峰变为明显的双峰,这样使得介电常数的温度稳定性得到提高.     

Sr2+置换改性Ca0.25(Li1/2Sm1/2)0.75TiO3陶瓷的微波介电性能研究

采用固相法制备了(Ca1-xSrx)0.25(Li1/2Sm1/2)0.75TiO3(CSLST-x)( x= 0～1/10)系列微波介质陶瓷材料,研究不同含量的Sr2+含量对该体系的相组成、烧结性能和微波介电性能影响.在x=1/22～1/10范围内,Sr2+的掺杂不会改变晶体的结构;在1175～1200 ℃烧结时,相同烧结温度下随着Sr2+含量的增加,介电常数εr增大,无载品质因数与谐振频率乘积Qf值降低;置换离子Sr2+的添加使该体系的烧结温度降低了近200 ℃,并保持良好的微波介电性能.其中,x=1/16的CSLST陶瓷在1200 ℃烧结,保温5 h时具有较好的微波介电性能:εr=97.2,Qf=2490 GHz,τf =14.74 ppm/℃.     

微波辅助水热合成条件对直接合成纳米HZSM-5晶体性质的影响

利用微波辅助水热合成法直接制备了纳米HZSM-5晶体.采用XRD、FT-IR、SEM、BET和NH3-TPD等手段对合成样品进行了分析表征,研究了晶化温度和时间对合成产物晶体性质的影响.结果表明,晶化温度和时间对微波辅助水热直接合成产物微观形貌、晶粒尺寸和分散度影响明显.较低的晶化温度和较短的晶化时间均难以形成形貌规则的HZSM-5晶体.随着晶化温度的升高,合成样品逐渐变为球形晶粒、晶粒尺寸逐渐增大、分散度逐渐提高,继续提高晶化温度达180 ℃时,晶粒长大使比表面积稍有降低;随着晶化时间的延长,样品的微孔和介孔增多,比表面积和孔容逐渐增大,继续延长晶化时间,晶体内微孔可能的收缩和晶粒的长大使得样品孔容和比表面积减小.160 ℃和1.5 h条件下制备的HZSM-5分子筛晶体形貌呈球形,晶粒尺寸约为60 nm,分散程度较好;其比表面积、孔容和平均孔径分别为398.45 m2·g-1、0.63 cm3·g-1和6.27 nm;晶体表面具有弱酸特征.     

锆钛酸钡钙压电陶瓷的晶粒尺寸效应研究进展

锆钛酸钡钙无铅压电陶瓷具有可与锆钛酸铅媲美的压电性能,受到国内外广泛关注.晶粒尺寸是影响锆钛酸钡钙陶瓷电性能的重要因素,其晶粒尺寸效应已成为研究的热点.为此,综述了粉体制备方法、烧结方法、烧结温度和保温时间对锆钛酸钡钙陶瓷的晶粒尺寸及其电性能的影响,并提出了研究中亟待解决的问题.     

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.     

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.     

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 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.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.