钒酸钇(Nd3+：YVO4；YVO4)晶体的原料合成

本文介绍了钒酸钇(Nd3+:YVO4;YVO4)剩料最多的固相和液相合成方法.使用该法合成的原料用提拉法生长出φ30×40mm～φ35×40mm的优质大尺寸单晶.剩料最多可以重复使用10～15次,仍能生长出优质晶体.     

非线性光学材料Ca_9Y_(0.5)La_(0.5)(VO_4)_7的固相合成、液相合成与晶体生长

采用固相合成和液相合成两种方法成功制备了Ca9Y0.5La0.5(VO4)7晶体的多晶原料,并采用提拉法生长了尺寸分别为30 mm×33 mm(固相合成多晶原料)和20 mm×27 mm(液相合成多晶原料)的Ca9Y0.5La0.5(VO4)7晶体。测试了该晶体在紫外、可见和近红外区域的透过率,采用Kurtz法测试了晶体的粉末倍频效应。结果表明,采用液相合成原料生长的晶体透过率大于采用固相合成原料生长的晶体约10%。前者粉末倍频效应约为KDP的1.8倍,后者约为KDP的2.5倍。晶体化学腐蚀实验表明采用液相合成原料生长的晶体具有更少的缺陷。采用液相合成方法制备多晶原料有利于提高晶体的光学质量。     

Nd∶YVO4杂质引入途径分析

运用ICP方法分析了一次蒸馏水和二次蒸馏水中的离子含量.应用二次蒸馏水合成钒酸钇原料,并生长出Nd∶YVO4晶体.采用色谱对原料样品和晶体样品中的杂质元素和杂质基团进行分析,发现钒酸钇晶体内部含有VO,YO,NdO,YVO2,YVO3,Y2O2基团,含K、Na、Ca等碱金属和稀土元素.在晶体中含有杂质离子铯和铅.     

掺钕钒酸钇原料合成与熔体特性的关系

钒酸钇原料(熔料)在高温氧气氛中钒的氧化物具有预蒸发,而在高温缺氧的气氛中高价钒离子(V5+)会分解成低价钒离子(V4+或V3+)以及在晶体生长过程中存在着掺质Nd3+的分凝效应等特性.因此,在原料合成中,除了强调原料合成规范化(保纯性、均匀性及重复性)外,还要对初始原料及添加料的组分和掺质浓度进行适度调节.其目的是在熔体剩料多次重复使用时,所生长的晶体中Nd3+浓度基本不变,而且所生长的晶体能保持单相生长.     

Nd：YVO4杂质引入途径分析

运用ICP方法分析了一次蒸馏水和二次蒸馏水中的离子含量。应用二次蒸馏水合成钒酸钇原料，并生长出Nd:YVO4晶体。采用色谱对原料样品和晶体样品中的杂质元素和杂质基团进行分析，发现钒酸钇晶体内部含有VO，YO，NdO，YVO2，YVO3，Y2O2基团，含K、Na、Ca等碱金属和稀土元素，在晶体中含有杂质离子铯和铅。     

晶格匹配氮化镓和氧化锌基外延薄膜衬底材料ScAlMgO4晶体生长研究

采用提拉法成功生长了氮化镓和氧化锌基外延薄膜晶格匹配的ScAlMgO4单晶衬底材料,晶体呈透明白色,尺寸为30mm×59mm,表面部分沿解理面有裂纹.粉末X射线衍射(XRD)分析表明经1400℃固相反应烧结的原料基本合成了ScAlMgO4多晶相.初步的偏光显微镜观察、晶体的粉末XRD表征、透过光谱和双晶摇摆测试表明晶体具有较好的光学性质和结晶质量.研究表明晶体本身的层状结构、较大的温度梯度和热应力的不均匀性是生长过程中引起晶体开裂的几个主要原因.     

BaWO4多晶料的合成与优质单晶的生长

以99.99;的BaCO3和WO3为原料通过固相反应直接合成BaWO4多晶料,采用提拉法沿a轴和c轴均可生长出φ22mm×80mm的无色透明的BaWO4单晶.X射线粉末衍射实验确定所获BaWO4晶体的结构属于四方晶系,空间群I41/a.通过浮力法测得其密度为6.393g/cm3.用莫氏硬度计测得BaWO4晶体的莫氏硬度为4.用V型棱镜法测得BaWO4晶体的折射率在1.84左右.     

CeO2对CaTiO3陶瓷烧结性能以及微观结构的影响

以CaO和TiO2为原料,采用固相反应烧结法合成钛酸钙陶瓷.以CeO2为添加剂,重点研究CeO2掺杂对合成钛酸钙陶瓷烧结性能及微观结构的影响.利用XRD、SEM、EDS等手段对试样的物相组成、显微形貌以及元素分布进行表征.通过X'pert High score Plus软件研究CeO2添加量和煅烧温度对合成钛酸钙的相组成、晶胞参数、缺陷反应的影响.结果表明:随着CeO2加入量的增大,Ce4+与Ti4+及Ce3+与Ca2+之间发生取代,致使钛酸钙的晶体结构发生畸变,晶格常数以及晶胞体积出现了先增大后减小的趋势.CaTiO3结构中取代位置的改变,是造成晶胞体积呈非线性变化趋势的原因.形成的结构缺陷加速了固相烧结反应,钛酸钙晶粒由发育不完全的台阶状转变为规则的多边形.过量的CeO2会抑制晶粒的生长,减小晶粒尺寸.随着煅烧温度的升高,结构中热缺陷浓度增大,促进了钛酸钙的烧结.     

双折射YVO4晶体原料的合成及最佳制备工艺的探讨

本文介绍了液相法合成用于双折射单晶生长的钒酸钇原料的工艺。着重讨论了制备条件对原料纯度的影响,确定了最佳合成方案。为了适应工业化生产的需要,探讨了原料合成的规范化(以保证保纯性,均匀性,重复性),合成出的原料已成功生长出φ42×42mm的大尺寸优质钒酸钇单晶,且剩料可重复使用10次左右。     

Nd:YVO4晶体a向生长研究

采用固-液两相混合,使NdO3、Y2O3和V2O5在近常温条件下初步合成Nd:YVO4多晶原料,降低固相合成反应温度,减少V2O5在多晶原料制备过程中的挥发.讨论了a方向Nd:YVO4单晶生长条件,采用提拉法,以(100)方向进行单晶生长,得到一系列掺杂浓度的Nd:YVO4单晶.     

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 structures of the cis and trans isomers of a tetrathia[3.3.3.3]cyclophane

Both the cis and trans isomers of 3,11,18,26-tetrathiatricyclo[26.2.2.1^5,9.2^13,16.1^20,24] hexatriaconta-5,7,9,20,22,24-hexene have been prepared and structurally characterized. Each of these centrosymmetric tetrathia dimers includes two cyclohexane rings in chair conformations with either 1,4-cis or 1,4-trans bonding and two meta-substituted benzene rings. The cis isomer packs into the monoclinic space group P2₁/a with a = 10.485(3)Å, b = 10.3956(18)Å, c = 14.1343(10)Å, = 105.200(13)°, Z = 2 and refined to an R factor of 0.046. The trans isomer crystallizes in the monoclinic space group P2₁/c with a = 10.7217(12)Å, b = 5.6797(7)Å, c = 25.415(5)Å, = 96.001(12)°, Z = 2 and refined to an R factor of 0.043. In the cis structure each benzene ring faces a cyclohexane ring while in the trans structure the cyclohexane rings face one another.     

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.     

电沉积法制备ZnO纳米棒阵列及其发光特性

本文以掺F的SnO2导电玻璃为基板,以硝酸锌水溶液为电解液,采用三电极恒电位体系电沉积制备ZnO纳米棒阵列,系统考察了硝酸锌浓度和沉积电位等工艺参数对ZnO纳米棒阵列的微观形貌及其发光性能的影响规律.结果表明,硝酸锌浓度和沉积电位对纳米棒阵列的形貌有显著影响,控制适宜的工艺条件可以制备出直径分布均匀、结晶性好且纯度高的六方纤锌矿ZnO纳米棒阵列.荧光光谱分析表明,电沉积制备出的ZnO纳米棒阵列在385 nm附近有一个强荧光发射峰,且发光性能稳定、对纳米棒阵列微观形貌的细微变化不敏感,使其在发光二极管和激光器等领域具有广阔的应用前景.     

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.