团簇连接对Cu10Ag90快速凝固中晶体结构的影响

快速凝固得到的晶体通常都会形成多种孪晶结构,但其成因一直是一个谜.本文采用分子动力学模拟Cu10Ag90合金在0、20和40 GPa压强下的快速凝固过程,分别形成了五重孪晶、层片状孪晶和复杂晶体,通过最大标准团簇方法(LaSCA)分析了短程有序结构的演变和晶体团簇之间的连接形式.结果发现,结晶转变温度Tc随着压强的增大而升高,平均原子势能也随之增加.非晶共有近邻子团簇(CNS)会在温度降至Tc时转变为晶体CNS,同时晶体团簇数量急剧增加,结构有序度提升.此外,通过分析晶体团簇之间的连接方式发现,五重孪晶中心团簇截边十面体(tDh)只能与具有相同S422的HCP相连形成五重孪晶轴;FCC与HCP有相同的S421,但只能以彼此的顶层或者底层原子作为彼此的中心原子连接形成层片状结构;BCC与FCC、HCP虽然没有共同的CNS,但是可以通过D-S6结构及其变形体连接,其连接方式的多样性是形成复杂晶体的主要原因.这些结果为研究晶体结构不同排列方式提供了新的理解.

3,5-二氯水杨醛缩-4-氨基安替比林Cu(Ⅱ)和Zn(Ⅱ)配合物的合成、晶体结构及抗肿瘤活性研究

利用3,5-二氯水杨醛与4-氨基安替比林,通过缩合反应,合成3,5-二氯水杨醛缩-4-氨基安替比林希夫碱配体(HL),配体与CuCl_(2)·2H_(2)O、Zn(Ac)_(2)·2H_(2)O,利用溶剂热反应合成两个新型的希夫碱配合物[CuL_(2)](配合物1)和[ZnL_(2)](配合物2)。对合成的配合物进行了红外光谱、热重分析、PXRD表征,用X射线单晶衍射确定了配体(HL)、配合物1和配合物2的分子结构,单晶衍射分析结果表明,配体(HL)晶体属于单斜晶系,空间群为P2_(1)/n,配合物1晶体属于单斜晶系,空间群为C2/c,配合物2晶体属于单斜晶系,空间群为P2_(1)/c,配合物1是四配位的四方形结构,配合物2是扭曲的六配位的八面体结构。MTT法检测了配体(HL)及配合物对3种人体肿瘤细胞株(MDA-MB-231、CNE-2Z、A-549)体外抗肿瘤活性。检测结果显示,配合物对癌细胞的抑制作用明显比配体好,配合物1对MDA-MB-231细胞和CNE-2Z细胞抗增殖活性最好,其IC_(50)值分别为(1.215±0.07)μmol/L、(4.417±0.28)μmol/L均低于顺铂IC_(50)值,配合物2对A-549细胞和MDA-MB-231细胞也表现出较好的抗增殖活性。

基于KNSBN∶Cu晶体的光折变联合变换相关器

给出基于 KNSBN∶ Cu晶体的光折变二波耦合联合变换相关器 ( TBJTC) .以KNSBN∶ Cu晶体作为平方律转换器 ,将强度较大且携带参考图象和待识别图象联合频谱的信号光波与一强度较弱的相干平面参考光波同时输入于 KNSBN∶ Cu晶体 ,通过光折变二波耦合过程的非线性能量转移 ,实现功率谱转换 ,进而实现相关识别 .理论分析和实验结果表明 ,除输入输出外 ,该光学相关器无需 CCD、L CLV等器件和相应的数字处理 ,是一个全光光学相关器 .

光折变KNSBN掺Cu晶体的生长

用 Czochralski 技术生长了 A 位置非充满型 KNSBN 掺 Cu 晶体,提拉速度为4—8mm/h,转速为15—20r/min;沿提拉方向测量了温场分布,用氩离子激光器测量了晶体的高光折变性能。

Cu∶KNSBN晶体自泵浦与互泵浦相位共轭共存特性的实验研究

利用 Cu∶KNSBN晶体 ,研究了在两束泵浦光对称入射的条件下 ,自泵浦与互泵浦相位共轭共存时相互竞争和相互影响的特性 ,以及共存时的相位共轭特性与两束泵浦光的入射位置、入射夹角和泵浦比之间的关系 。

Cu:KNSBN晶体生长及其光折变效应的研究

在KNSBN晶体中掺进CuO,采用硅钼棒作加热体,以Czochralsk i技术生长Cu:KNSBN晶体。以二波耦合光路,测试晶体的衍射效率和记录时间,计算折射率变化值Δn。Cu:KNSBN晶体的衍射效率,记录速度和折射率变化值皆高于Fe:L iNbO3晶体。尤其记录速度比Fe:L iNbO3晶体高一个数量级以上。测试Cu:KNSBN晶体位相共轭反射率R和自泵浦位相共轭反射率RC。Cu:KNSBN晶体的自泵浦位相共轭反射率RC值达到64%,是纯KNSBN晶体的二倍。以Cu:KNSBN晶体自泵浦位相共轭镜进行消畸变实验。实验结果表明:输出光波确系输入探测光波的位相共轭光波。

同质异构Al-Cu-Mg系混晶粉末冶金制备新方法

为突破传统同质粉末材料均以颗粒尺寸细化作为改性的单一途径禁锢,提出同质异构思想,即通过低能球磨将不同粒径的AA2024合金粉末按照一定比例混合,经热压烧结制备混晶坯料。研究结果表明,传统单一粒径粉末烧结后晶粒形貌趋向于不规则多边形状,而不同粒径粉末混合烧结后晶粒形貌为小颗粒包覆大颗粒的结构形式;与前者相比,当粗粉占比为20%(质量分数)时,抗拉强度增加了38.8%;当粗粉占比为50%时,伸长率提高了14%。粉末混合后的烧结样品呈沿晶断裂和穿晶断裂的混合断裂机制,第二相对位错的钉扎效应更加明显,因此,合金性能得到显著提高。此研究工作为高性能同质异构混晶材料的制备提供了一种新思路。

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Cu(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.

Synthesis,Crystal Structure and Properties of a Nanotubular Metal-organic Framework(MOFs) Based on Cu(Ⅱ) Oxide Chains and Benzenedicarboxylates

A new cooper benzenedicarboxylate metal-organic coordination polymer,[Cu（μH2O）（BDC）]n·nDMF（1,H2BDC = 1,4-benzenedicarboxylate acid,DMF = N,N＇-dimethylfor-mamide）,has been successfully synthesized under hydrothermal conditions and characterized by IR spectroscopy,elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction.This complex crystallizes in triclinic,space group P1 with a = 6.605,b = 10.44780（10）,c = 11.0881（6） ,α = 62.064（11）,β = 73.410（15）,γ = 78.404（16）°,C11H13CuNO6,Mr = 318.76,V = 645.79（8） 3,Z = 2,Dc = 1.639 g/cm3,F（000） = 326,μ = 1.712 mm-1,the final R = 0.0362 and wR = 0.1330 for 2055 observed reflections with I 〉 2σ（I）.The title compound contains infinite inorganic chains constructed by Cu oxygen octahedra by sharing corners and edges.Each chain is connected by BDC linkers to four other chains to form a three-dimensional framework with irregular rhombic channels where the DMF molecules are encapsulated.

Hydrothermal Synthesis and Crystal Structure of a 1D Cu(II) Coordination Polymer: [Cu(bbpy)(H_2bptc)]_n Constructed by a Tetracarboxylic Acid

The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.

Synthesis and Crystal Structure of the Binuclear Complex:[Cu_2(phen)_2(ip)(Hip)_2]·4H_2O

A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.

Crystallization Growth of Single Crystal Cu by Continuous Casting

Crystallization growth of single-crystal Cu by continuous casting has been investigated using self-designed horizontal continuous casting equipment and XRD. Experimental results showed that the crystallization plane of (311), (220) and (ill) were eliminated sequentially in evolutionary process. The final growth plane of crystal was (200), the direction of crystallization was [100], the growth direction of both sides of the rod inclined to axis, and the degree of deviation of direction [100] from the crystal axis was less than 10°. In order to produce high quality single crystal, the solid-liquid interface morphology must be smooth, even be planar.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex with Tridentate Schiff Base and Azido Bridge

A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.

Hydrothermal Syntheses, Crystal Structures and Luminescence Properties of Cu(Ⅱ) and Cd(Ⅱ) Complexes Assembled by 6-Hydroxypicolinic Acid and 1,10-Phenanthroline

Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.

Synthesis,Crystal Structure and Photoluminescence of a Cuprous Dimer with Tetrakis(pyrazol-i-yl)borate Linker

A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.

Liquid State Undercoolability and Crystal Growth Kinetics of Ternary Ni-Cu-Sn Alloys

The liquid state undercoolability and crystal growth kinetics of ternary Ni-5%Cu-5%Sn and Ni-10%Cu-10%Sn alloys are investigated by the glass fluxing method. In these two alloys, experimental maximum undercoolings of 304 K （0.18TL ） and 286K （0.17TL ） are achieved and the dendritic growth velocities attain 39.8 and 25.1 m/s, respectively. The transition of morphology from coarse dendrite into equiaxed structure occurs and the grain size of the a （Ni） phase decreases remarkably when the undercooling increases. Both the lattice constant and microhardness increase obviously with the enhancement of undercooling. The enrichment of Cu and Sn solute contents reduces the dendritic growth velocity, while enhances the lattice constant and microhardness of a （Ni） phase.

Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n

A new complex [Cu（L）（1,10-phen）]n （1, L = N-3-pyridine sulfonyl amino acid） has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P2Jc with a = 11.481 （2）, b = 1 8.094（4）, c = 8.5198（17） ]°, β= 102.26（3）°, V = 1729.5（6） ,/k3, Z = 4, Dc = 1.759 g/cm3, F（000） = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu（ll） ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu（Ⅱ）units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.

A Cu(Ⅱ) Coordination Polymer with 5-Tert-butyl Isophthalate Linker:Synthesis,Crystal Structure,and Magnetic Properties

A new Cu（Ⅱ） metal-organic coordination polymer, {[Cu2（tbip）2（bie）2]·H2O}n （1, H2tbip = 5-tert-butyl isophthalic acid, bie = 1,2-bis（imidazol-1 ＇-yl）ethane）, was assembled under hydrothermal conditions by the reactions of Cu（Ⅱ） acetate with H2tbip and bie. Complex 1 was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in triclinic, space group P1, with a = 9.9145（10）, b = 13.2211（13）, c = 15.4363（15） nm, a = 87.0250（10）, β = 88.3220（10）, γ = 83.8240（10）°, V= 2008.4（3） nm3, Z = 2, Dc = 1.505 Mg/m3, F（000） = 944, g = 1.125 mm^-1, S = 1.030, the final R = 0.0336 and wR = 0.0790. The results reveal that complex 1 is a two-dimensional layered structure. In addition, magnetic properties of I were also investigated.

Morphology-dependent structures and catalytic performances of Au nanostructures on Cu_2O nanocrystals synthesized by galvanic replacement reaction

Au nanostructures were prepared on uniform Cu2O octahedra and rhombic dodecahedra via the galvanic replacement reaction between HAuCl 4 and Cu2O. The compositions and structures were studied by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), High-Resolution Transmission Electron Microscope (HRTEM), X-Ray Diffraction (XRD), X-Ray Absorption Spectroscopy (XAS), X-ray Photoelectron Spectroscopy (XPS) and in-situ DRIFTS spectroscopy of CO adsorption. Different from the formation of Au-Cu alloys on Cu2O cubes by the galvanic replacement reaction (ChemNanoMat 2 (2016) 861-865), metallic Au particles and positively-charged Au clusters form on Cu2O octahedra and rhombic dodecahedra at very small Au loadings and only metallic Au particles form at large Au loadings. Metallic Au particles on Cu2O octahedra and rhombic dodecahedra are more active in catalyzing the liquid phase aerobic oxidation reaction of benzyl alcohol than positively-charged Au clusters. These results demonstrate an obvious morphology effect of Cu2O nanocrystals on the liquid-solid interfacial reactions and prove oxide morphology as an effective strategy to tune the surface reactivity and catalytic performance. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Homogeneous Plastic Flow of Fully Amorphous and Partially Crystallized Zr_(41.2)Ti_(13.8)Cu_(12.5)Ni_(10)Be_(22.5) Bulk Metallic Glass

The homogeneous plastic flow of fully amorphous and partially crystallized Zr(41.2)Ti(13.8)Cu(12.5)Ni(10)Be(22.5) bulk metallic glass (Vitl) has been investigated by compression tests at high temperatures in supercooled liquid region. Experimental results show that at sufficiently low strain rates, the supercooled liquid of the fully amorphous alloy reveals Newtonian flow with a linear relationship between the flow stress and strain rate. As the strain rate is increased, a transition from linear Newtonian to nonlinear flow is detected, which can be explained by the transition state theory. Over the entire strain rate interval investigated, however, only nonlinear flow is present in the partially crystallized alloy, and the flow stress for each strain rate is much higher. It is found that the strain rate-stress relationship for the partially crystaltized alloy at the given temperature of 646 K also obeys the sinh law derived from the transition state theory, similar to that of the initial homogeneous amorphous alloy. Thus, it is proposed that the flow behavior of the nanocrystalline/amorphous composite at 646 K is mainly controlled by the viscous flow of the remaining supercooled liquid.