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.

Cu-Fe合金凝固过程中结构变化研究

采用分子动力学模拟方法研究了Cu_(100-X)Fe_(X)(X=1%、3%、5%)合金在冷却速率为2×10^(10)K/s条件下合金凝固过程.研究表明,Fe含量为1%时,随着合金温度的降低Fe原子始终保持均匀分布的状态,未出现Fe原子聚集现象,晶体结构是以FCC为主的Cu基体,Fe原子以固溶形式存在于基体中.Fe含量为3%时,随着合金温度的降低Fe原子有聚集趋势,但BCC晶体结构占比较小,晶体结构仍是以FCC为主的Cu基体.Fe含量为5%,随着合金温度的降低Fe原子发生明显聚集,最终形成以FCC、HCP晶体类型为主镶嵌Fe原子的Cu基体.研究了Fe团簇的形成过程,结果表明,Fe团簇的形成、长大是一个连续的过程,该过程受形核生长机制控制,不同阶段形成Fe团簇的大小和数量受Fe-Fe原子相互作用力、Fe原子的扩散能力以及Fe团簇与Cu基体间的界面能三个因素共同影响.

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.

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.

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 Photoluminescence of a TADF Cuprous Complex

A cuprous mononuclear copper complex [Cu（adpypz）CH3CNPPh3]BF4·CH2Cl2（1, adpypz = 9,9-dimethyl-10-（6-（3-phenyl-1H-pyrazol-1-yl）pyridin-2-yl）-9,10-dihydroacridine） was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388（4）, b = 13.4569（4）, c = 16.2561（6） ？, α = 97.154（3）, β = 92.187（3）, γ = 114.119（4）°, V = 2235.38（13） ？3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm^3, F（000） = 996, μ = 2.62 mm^–1, GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm（1）, lifetimes 235 μs and quantum yields（ф = 0.279） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.

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,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.

Studies of Photorefractive Crystals of Cu-Doped (K_(0.5) Na_(0.5))_(0.2)(Sr_(0.75)Ba_(0.25))_(0.9)Nb_2O_6

In this paper, photorefractive crystals of Cu-doped (K0.5Na0.5)0.2 (Sr0.75Ba0.25)0.9Nb2O6 (KNSBN) are systematically studied. A series of Cu-doped KNSBN crystals have been grown and the samples with Cu-dopant in different levels and thicknesses have been fabricated. Their photorefractive properties including two-wave coupling gain coefficients and response rate are experimentally studied in details. The results show that (1) with high Cudopant cocentration, the crystal has larger coupling gain coefficient, higher effective charge carrier density, and faster time response; (2) thinner sample shows larger coupling gain coefficientl (3) at shorter wavelength 9 the crystal sample shows larger coupling gain coefficient and faster time response. The Cu-doping mechanisms were briefly referred. The analyses of the relationships among the crystal’s two-wave coupling, absorption property and the self-pumped phase conjugation are given. All the results show that Cu-doped KNSBN crystals are a kind of very promising photorefractive materials.

Synthesis and Crystal Structure of[Cu(dppb)(NO_3)]_2(dppb=1,4-Bis(diphenylphosphino)butane)

The synthesis and molecular structure of a new dinuclear copper（Ⅰ） complex [Cu（dppb）（NO 3）] 2 are reported.The compound crystallizes in the monoclinic system,space group P2 1 /n with a=12.830（3）,b=10.899（2）,c=19.666 （4）,β=104.69（3）°,V=2660.1（9）3,Z=4,D c=1.378 g/cm 3,F（000）=1144,the final R=0.0600 and wR=0.0668 for 2951 observed reflections with I 2σ（Ⅰ）.The complex contains a folded Cu 2 P 4 core structure,with two Cu（Ⅰ） atoms being bridged by a pair of dppb ligands to form a 14-membered Cu 2 P 4 C 8 zigzag ring.The ligand sphere of each metal center is completed by a nitrate anion in a chelating fashion.

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) ?.

Cu过渡层对冷喷涂CuCrZr涂层性能的影响

目的针对冷喷涂CuCrZr涂层与CuCrZr板材在界面处的开裂问题,采用Cu涂层为过渡层,并探究Cu过渡层对CuCrZr涂层组织及性能的影响。方法采用高压氮气为工作气体,使用冷喷涂技术在CuCrZr基板上先制备一层Cu涂层打底,再继续喷涂多层CuCrZr涂层。通过金相显微镜、扫描电镜、显微硬度仪和激光热导仪,对涂层的组织和性能进行表征。结果Cu+CuCrZr涂层与基板界面结合良好,涂层的孔隙率约为0.624%,CuCrZr颗粒的扁平率为(43.62±4.54)%。Cu涂层的平均硬度约为153HV,冷喷涂CuCrZr涂层的平均硬度约为173HV。采用Cu涂层打底获得的CuCrZr涂层的热导率随温度的升高而升高,在500℃时与基体相当。结论Cu过渡层促进颗粒与基体之间发生良好结合,有效防止Cu CrZr涂层与CuCrZr板材开裂。采用Cu+CuCrZr涂层能满足CuCrZr结晶器力学与导热性能的要求。

Crystallization kinetics of amorphous Zr_(65)Cu_(25)Al_(10) alloy

Crystallization behavior of amorphous Zr 65 Cu 25 Al 10 alloy under isothermal annealing condition was investigated by DSC and XRD. It is found that two exothermic peaks appear in the DSC curve of amorphous Zr 65 Cu 25 Al 10 alloy, indicating that the crystallization proceeds through double stage mode. The crystallization process of amorphous Zr 65 Cu 25 Al 10 alloy under isothermal annealing condition is mainly controlled by nucleation and one dimensional growth with the crystallized volume fraction smaller than 70%. With the crystallized volume fraction ranging from 70% to 90%, crystallization process is mainly dominated by the growth of three dimensional pre existing quench in nuclei. And when the crystallized volume fraction reaches above 90%, transient nucleation becomes the master of the crystallization process.

Electronic structure of single-crystalline graphene grown on Cu/Ni(111) alloy film

Graphene with a Dirac cone-like electronic structure has been extensively studied because of its novel transport properties and potential application for future electronic devices.For epitaxially grown graphene,the process conditions and the microstructures are strongly dependent on various substrate materials with different lattice constants and interface energies.Utilizing angle-resolved photoemission spectroscopy,here we report an investigation of the electronic structure of single-crystalline graphene grown on Cu/Ni(111)alloy film by chemical vapor deposition.With a relatively low growth temperature,graphene on Cu/Ni(111)exhibits a Dirac cone-like dispersion comparable to that of graphene grown on Cu(111).The linear dispersions forming Dirac cone are as wide as 2 e V,with the Fermi velocity of approximately 1.1×10^6 m/s.Dirac cone opens a gap of approximately 152 meV at the binding energy of approximately 304 meV.Our findings would promote the study of engineering of graphene on different substrate materials.

Crystal structure and thermal stability of martensite in Cu-24Al-3Mn alloy

The crystal structure and thermal stability of the martensite in Cu 24Al 3Mn (mole fraction, %) alloy were studied by X ray diffraction, electron diffraction, V - t curve measurement. The 18R martensite with fairly perfect long range order can be obtained by water quenching the alloy. The atoms distribution on the basal plane of the martensite is as follows: Ⅰ, 3/25 Mn+22/25 Cu; Ⅱ, 3/25 Al+22/25 Cu; Ⅲ, 18/25 Al+7/25 Cu, correspondingly, the parent phase may have Heusler structure. From the electron diffraction result, the crystal structure is determined to be of a modified 18R type but closely approaching orthorhombic 18R type, its lattice parameters are determined to be a = 0.447?4?nm, b = 0.522?9?nm, c = 3.815?nm and β =89.6° from the X ray diffraction results. The obtained alloy has a higher thermal stability than that of the conventional Cu Zn Al alloy.

Phases in the crystallization process of Zr_(65)Al_(7.5)Ni_(10)Cu_(17.5)metallic glass

The crystallization process of metallic glass Zr_(65)Al_(7.5)Ni_(10)Gu_(17.5)(atom fraction in percent) were studied by transmission electron microscopy and X-ray diffraction.Two stages of crystallization process, which are indicated by the two exothermic peaks in thedifferential scanning calorimetry diagram, were studied separately. It is found that the phases inthe various stage of the crystallization are different. In the first stage, it consists mainly oftI-CuZr_2 and tP-Al_2Zr_3 phases, between which a definite orientation relationship is found. Whilein the second stage, in addition to the above phases, phase hP^2-Al_2NiZr_6 and phase hP^3-alpha-Zrappear, between which another orientation relationship is also found. At the same time, a comparisonis made based on the study of the phases exist in the arc-melted master ingot. The latticeparameters of the identified phases were determined and some interesting similarities were found.According to these similarities, all the phases were classified into two groups. The first is: oB,tI-CuZr_2 and hP^3-alpha-Zr; the other is: hP^2, tP-Al_2NiZr_3 and hP^1-Al_2NiZr_6. Therelationships between phases in these two groups were investigated and the probable reasons that mayresult in these relationships were discussed.

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.

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b = 9.473（4）, c = 9.535（3）A, α = 117.214（10）, β = 108.251（9）, γ = 91.560（6）°, V = 562.3（4）A^3, Z = 1, Mr = 591.30, F（000） = 298, Dc = 1.746 g/cm^3, μ（MoKα） = 2.385 mm^-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones （Ⅰ〉 2σ（Ⅰ））. In the title complex, each copper（Ⅱ） atom is located at the center of a distorted trigonal bipyramid of five coordination atoms （two nitrogen and three chlorine atoms）. Two copper（Ⅱ） atoms were bridged by two chlorine anions （Cl（2） and Cl（2a）） to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity with the distance between two copper（Ⅱ） atoms of 3.398 （A）.

Synthesis,Crystal Structure and Photoluminescence of a Dinuclear Cuprous Complex with Thiocyanate Bridges

A cuprous dinuclear copper complex [PPh_2PAr_2Cu（μ-SCN）_2CuPPh_2PAr_2]（1,PPh_2PAr_2 =（1-bis（2-methylphenyl）-phosphine-2-diphenylphosphino）benzene） was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225（2）,b = 11.360（2）,c = 13.420（3） ？,α = 95.81（3）,β = 93.45（3）,γ = 113.78（3）°,V = 1410.4（5） ？~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm^3,F（000） = 616,μ = 3.029 mm^（–1）,GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu（I） is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu（μ-SCN）_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_（max）= 478 nm（1）,lifetimes 4.7 μs and quantum yields（ф = 0.43） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ^（1,3）MLCT excited states.

Synthesis,Crystal Structure,and Photo-and Electro-luminescence of a TADF Cu(Ⅰ)Complex

A four-coordinate mononuclear cuprous complex [Cu（ac1m）POP]BF4·0.5（C6H14）· 0.5（C2H5OH）（1, ac1 m = 2-（2-ethoxyphenyl）-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-（dipenylphosphino）phenyl]ether） was synthesized and characterized by elemental analysis, NMR, UV-vis, cyclic voltammetry and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group P21/c with a = 17.0546（19）, b = 15.4650（17）, c = 23.685（2） A, β = 104.007（11）°, V = 6061.1（12）A^3, Z = 4, Mr = 1171.46, Dc = 1.284 g/cm^3, F（000） = 2432, μ = 1.50 mm^–1, GOOF = 1.070, the final R = 0.059 and wR = 0.1640 for 8952 observed reflections with I 〉 2σ（Ⅰ）. Compound 1 is composed of a BF4-anion and a [Cu（ac1m）POP]^＋ cation. The Cu（Ⅰ） ion adopts a tetrahedral coordination geometry defined by two nitrogen and two phosphorous atoms. The complex exhibits yellow luminescence with maximum emission peaks at 546 nm, lifetimes 15.1 μs and quantum yields（ф = 0.130） at room temperature. The complex displays thermally activated delayed fluorescence（TADF） at room temperature, which is proved experimentally and theoretically. And the organic light-emitting diode（OLED） with 1 as the light emitting material has the maximum current efficiency of 5.86 cd/A and the highest brightness of 3215 cd/m^2.