Di-Ab-An体系远离平衡枝状形貌的演化及枝体结晶学各向异性特征研究

对钠长石(Ab)-钙长石(An)-透辉石(Di)三元体系跨相界线的不同成分点在不同的降温速度条件下快速结晶形成的枝状形貌进行了研究.透辉石为枝晶,斜长石为球粒晶.当降温速度慢于1℃/min后,枝状形貌变为板-柱状形貌(即近平衡形貌).我们的实验结果中没有观察到如E.Brener 和H.Muller等人提出的形貌演化图一样的演化规律.当成分点靠近同结线后,出现两晶共结形成的"中空结构".通过光学显微镜下测试其光学性质发现,透辉石沿c轴方向延长,斜长石沿a轴延长,与晶体结构中的强键链方向一致,即快速结晶时晶体沿着结构中负离子配位多面体共角顶、共棱形成的强键链方向生长形成枝体.     

Di-Ab-An、Q-Lc体系非平衡结晶及枝晶结晶学方向测试研究

本文对两个典型的硅酸盐体系:Di(透辉石)-Ab(钠长石)-An(钙长石)体系和Q(石英)-Lc(白榴石)体中结晶物相系进行了枝状形貌、枝体结晶学方向测试及结晶能力方面的研究.通过偏光显微镜(PL)、扫描电镜(SEM)观察发现:透辉石、低鳞石英、α-方石英都发育为枝晶,而斜长石发育成放射状球粒晶和针状晶体.通过电子背散射衍射(EBSD)测试确定出透辉石是沿<001>方向发育成枝晶的主干、低鳞石英是沿<100>和<010>方向发育成枝晶主干、α-方石英是沿两个<100>方向发育成枝晶的主干.并发现两个体系在相同降温速度下的结晶能力不同.     

铝层厚度对铝诱导非晶硅薄膜晶化过程的影响

基于铝诱导非晶硅薄膜固相晶化方法,利用直流磁控溅射离子镀技术制备了Al/Si/…Al/Si/glass周期性结构的薄膜.采用真空退火炉对Al/Si多层薄膜进行了500℃退火实验,通过透射电子显微镜(TEM)分析了退火前、后Al/Si多层薄膜截面形貌的变化规律,并结合扩散过程探讨了铝层厚度对铝诱导非晶硅薄膜晶化过程的本质影响机理.研究结果表明:在铝诱导非晶硅薄膜固相晶化过程中,随退火过程的进行,Al、Si原子会沿Al/si层间界面进行互扩散运动且在Si层中达到临界浓度Cs的Al原子所在区域整体呈线形平行于Al/Si界面逐渐向铝原子扩散距离增大的方向推进;随着Al层厚度的增加,Al在Si层中达到临界浓度Cs的区域整体向前推进速度加快,已扩散区域产生硅初始晶核的数量也随之增大;随Al/Si层厚比的增大,虽因铝诱导而晶化的硅薄膜均为多晶态,但非晶硅薄膜在晶化过程中的生长晶面数量增多,同时硅晶粒的尺寸有所减小.     

电化学沉积法制备镍枝晶

采用电化学沉积法制备了镍枝晶沉积物,考察了不同的试验参数对枝晶生长过程以及微观形貌的影响.结果表明,枝晶具有典型的自相似性,枝晶容易在高的电流密度下生长,电流密度高,提高了阴极过电位,有利于枝晶形成;电解液里Ni2浓度的增加,沉积层分型更加明显,制备的镍枝晶逐渐稀疏,分叉也相应减小.随着电解液温度的提高,沉积层由开放型向致密型转化.这是因为在很高电流密度下,很容易发生析氢反应,释放大量气泡;金属离子在气泡之间的空隙被还原形成多孔的沉积层.     

NaCl枝状形貌的制备及生长机理探讨

采用溶剂蒸发法,在不同的条件下分别获得了具有四次对称和二次对称的Na Cl枝晶、"Z"字形枝蔓晶以及主要由枝晶呈放射状分布的球粒晶。借助于X射线衍射仪、光学显微镜、扫描电镜以及电子背散射衍射仪(EBSD),对Na Cl枝状形貌进行了测试分析。结果表明,Na Cl球粒晶主要由主干沿着<111>方向生长的一系列枝晶组成。Na Cl晶体(111)面网由同号离子组成,且钠离子层与氯离子层相间分布,层与层之间的联结力强,且(111)的面网间距最小,是导致Na Cl枝晶优先沿<111>方向生长的主要原因。溶剂的蒸发速度等环境因素的变化对Na Cl枝状形貌的形成具有很大的影响。     

一种翡翠仿制品-透辉石微晶玻璃显微结构及晶体化学特征的研究

利用偏光显微镜、电子探针仪及X射线粉晶衍射仪,对一种翡翠的仿制品-人造透辉石微晶玻璃的显微结构、析晶特征、化学成分及物相组成进行了研究.该微晶玻璃外观具有明显的放射状晶花,偏光显微镜下观察及BSE图像反映出透辉石微晶玻璃具有显微斑状结构,且含特征的骸晶.电子探针测试得到该材料内玻璃质基质、主晶相透辉石及少量石英的化学成分,其中透辉石内的镍含量明显高于天然翡翠.X射线粉晶衍射分析确定其主要物相为透辉石和玻璃质,与天然翡翠以硬玉、纳铬辉石等为主要矿物组成不同.     

无光釉中LiAlSiO4-SiO2固溶体的枝晶研究

本文研究了无光釉中LiAlSiO4-SiO2固溶体的枝晶形貌、物相、成分、形成温度及其关系.六枝雪花状枝晶为六方晶系的β-石英固溶体,十字状枝晶为四方晶系的凯石英固溶体,即枝晶形貌反映了晶体结构的对称.枝晶的成分与基质玻璃的成分分异与形成温度和机制有关.枝晶形成时存在两种机制,其生长基元分别为原子(分子)生长或晶核切变生长.枝晶分枝程度和形成机制除与过冷度有关外,还与枝晶对称性有关.四方凯石英枝晶多以原子(分子)生长,其分枝少;六方β-石英枝晶多以晶核切变机制生长,其分枝多.     

热处理制度对透辉石微晶玻璃析晶与导热性能的影响

以SiO2、CaO和MgO为主要原料,采用传统高温熔融工艺制备了基础玻璃,并通过一步析晶热处理工艺制备了透辉石微晶玻璃.利用X射线衍射仪、电子扫描显微镜和激光导热仪分别研究了热处理温度和时间对透辉石微晶玻璃析晶和导热性能的影响.结果表明:随着热处理温度的升高,微晶玻璃的结晶度增加,晶粒尺寸增大,导热系数先增大后减小;随着热处理时间的延长,微晶玻璃的晶粒尺寸增大,导热系数先增大后减小.当热处理温度890℃,热处理时间120 min,升温速率为10℃/min,微晶玻璃晶粒尺寸为0.3～0.4μm,结晶度为79;,导热系数达到最大值2.59 W/(m·K).     

硫酸钾枝状晶的生长与EBSD测定

采用单玻片溶液蒸发法、双玻片溶液蒸发法以及凝胶法,在不同条件下分别获得了硫酸钾枝晶和枝蔓晶,并利用EBSD技术对硫酸钾枝晶和枝蔓晶的结晶学取向进行了测试和分析.研究表明:硫酸钾(K2SO4)枝晶的主干主要沿着＜ 111＞方向生长;而硫酸钾(K2SO4)枝蔓晶中,组成枝蔓晶的相邻枝晶(晶粒)之间存在典型的双晶关系,其双晶轴为＜011＞,双晶面为(053).     

钛源对CaTiO3枝晶结构的光催化性能影响

通过改变不同钛源,在无模板或表面活性剂条件下采用溶剂热法制备了CaTiO3枝晶结构.样品用X射线衍射、扫描电子显微镜和比表面积分析仪进行了表征,并用紫外-可见吸收光度计测试样品的光吸收.研究不同钛源种类对CaTiO3样品的微观结构和光降解率的影响.结果表明:钛源为钛酸丁酯所制备的CaTiO3样品呈现发育良好的枝晶结构,其降解罗丹明B溶液的降解率最高.这主要是由于样品的结晶度高、枝晶结构使其具有低的反射率,因此样品呈现出较高的光降解率.     

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.     

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。     

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.     

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).     

Phase Properties of Hexanedioldiacrylate/E7 Blends

Abstract

Equilibrium phase diagrams of uncured and UV-cured difunctional hexanedioldiacrylate and the eutectic mixture of low molecular weight liquid crystals E7 are established by polarized optical microscopy and differential scanning calorimetry. Data are analyzed using the Maier-Saupe model of nematic order. In the case of the uncured system the Flory-Huggins free energy of isotropic mixing is applied while for the cured system, the Flory-Rehner elastic free energy model is used. A good correlation between experimental and theoretical phase diagrams is found in both systems.     

C–H...O,C–H...π and π–π stacking interactions in 3-(2,4-dimethylphenyloxymethyl)-3,4-dihydroisocoumarin

3-(2,4-Dimethylphenyloxymethyl)-3,4-dihydroisocoumarin (C₁₈H₁₈O₃) was prepared by the alkylation of o-lithio N-methyl benzamide with 2-(2,4-dimethylphenoxy)methyl oxirane, followed by alkaline hydrolysis. The compound crystallizes in the orthorhombic space group Pbca with unit cell parameters : a = 8.239(2) Å, b = 14.918(5) Å, c = 24.831(9) Å, Z = 8. The crystal structure was solved by direct methods and refined to R = 0.0514 for 1564 observed reflections. The heterocyclic ring adopts a distorted half-chair conformation. Molecules are connected by π–π interactions between phenyl rings of the isocoumarin nucleus forming dimers. Dimers are connected via C–H...O hydrogen bonds forming chains. Further intermolecular C–H...π hydrogen bonds link the dimer chains to form supramolecular structure.     

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.     

A new method for the investigation of orientation relationships in meteoritic plessite

The orientation relationship (OR) between the bcc and fcc phase in the plessite microstructure of the iron meteorites Watson, Agpalilik and Gibeon has been analysed in a scanning electron microscope using electron back‐scattered diffraction (EBSD). A very strong OR exists, independently on the analysed plessite type and the observed spreading of single orientation data. The agreement between the experimental orientation distribution and existing models varies for each meteorite. The black plessite in the Agpalilik corresponds to the Nishiyama‐Wassermann model whereas the duplex plessite of the Gibeon meteorite shows an OR close to the Kurdjumov‐Sachs model. The Watson meteorite is strongly deformed so that a general OR is difficult to determine due to the blurred experimental orientation distribution. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.