非晶态Cu_(56)Zr_(44)合金的结构及其等温退火晶化过程的研究

利用X射线衍射技术、差示扫描量热分析技术和透射电子显微镜研究了非晶态Cu56 Zr4 4合金的结构及其等温退火条件下的晶化过程 .实验结果表明 ,非晶态Cu56 Zr4 4合金在室温下的短程结构类似于硬球无规密堆积分布 .在70 3K过冷液相区内等温退火时发现 ,当退火时间为 3min时 ,晶化产物主要为Cu8Zr3相 ;当退火时间为 6min时 ,Cu8Zr3相完全消失 ,而Cu1 0 Zr7相大量析出 ;当退火时间达到 3 0min以上时 ,其晶化产物转变为Cu1 0 Zr7,CuZr2 ,Cu8Zr3等多种化合物 .由此提出了非晶态Cu56 Zr4 4合金等温退火晶化过程的扩散机理 .     

First-principles study of structural, electronic and elastic properties of single crystal CuZr

Investigations into the structural, electronic and elastic properties of intermetallic CuZr compound had been conducted by the plane-wave pseudopotential method. The calculated lattice constant was consistent well with the experimental value. The absence of band gap and finite value of the density of states (DOS) at the Fermi level reveal the metallic behavior of CuZr crystal, and Zr 4d states give rise to the electrical conductivity. The calculated elastic constants for single crystal CuZr at zero pressure obey the cubic mechanical stability condition, which indicates that the cubic CuZr crystal is mechanical stable at zero pressure. By analyzing the ratio between the bulk and shear moduli, we conclude that CuZr crystal is ductile in nature. The present theoretical investigations might give prediction to polycrystalline CuZr system.     

固态电解质锂镧锆氧(Li_7La_3Zr_2O_(12))制备及第一性原理研究

固态电解质(SSE)是锂离子电池(LIB)的关键材料.Li_7La_3Zr_2O_(12)(LLZO)固体电解质是全固态锂离子电池开发中的关键部分.采用高温固相法制备了不同烧结温度后的四方Li_7La_3Zr_2O_(12)(t-LLZO)和立方Li_7La_3Zr_2O_(12)(c-LLZO),分析了两种样品的结构性能.800℃下烧结12小时的t-LLZO呈四方相,晶格尺寸为a=b=13.13064?,c=12.66024?,离子电导率为3.42×10~(-8)S·cm~(-1);1000℃下烧结12小时的c-LLZO呈立方相,晶格尺寸为a=b=c=13.03544?,离子电导率为8.48×10~(-5)S·cm~(-1).另基于密度泛函理论(DFT)的第一性原理计算了四方相和立方相的LLZO固体电解质材料的能带结构、晶格参数、态密度和键布居.通过理论计算解释了四方相LLZO离子电导率低于立方相LLZO的原因.     

清代红绿彩瓷器无损分析研究

红绿彩瓷器是我国陶瓷史上一种重要的釉上彩瓷器,分析其彩料的化学组成和物相结构对其烧制工艺的研究有很重要的意义.但由于瓷器表面的不平整和彩料分布的不均匀性,导致其不满足传统的1 mm×10 m m线光源的X射线衍射仪对样品的测试要求.而毛细管聚焦的X射线衍射仪采用点光源的方式照射样品,毛细管X光透镜对Cu-Kα 的能量有...     

第一性原理研究Nb、Sn、Cu、Fe和Cr对Zr (0001)晶面抗疖状腐蚀性能的影响

采用密度泛函理论研究Nb、Sn、Cu、Fe和Cr 5种合金元素对氧在Zr(0001)晶面吸附能的影响, 发现Nb、Sn和Cu会促进氧在Zr(0001)晶面吸附, Fe和Cr对氧吸附的影响因吸附的位置不同而存在差异。研究5种合金元素对氧化后Zr(0001)晶面化学键的破坏情况, 发现Nb对Zr(0001)晶面破坏程度最小而且可以迅速复原, Sn可以使(0001)晶面相邻的两个化学键都变长, 对晶面的破坏性大。最后讨论5种合金元素在Zr(0001)晶面的偏聚能, 发现Sn、Fe和Cr偏聚能为负值, 容易偏聚到Zr(0001)晶面, 而Nb和Cu偏聚能为正值, 不易在Zr(0001)晶面偏聚。综合以上分析, Nb可以促进氧在Zr(0001)晶面的吸附行为, 氧化后(0001)晶面可以快速复原, 从而阻碍其他氧原子进入, 抑制疖状腐蚀的发生。Sn容易偏聚到Zr(0001)晶面, 可以促进氧在Zr(0001)晶面吸附, 氧化后会造成Zr(0001)晶面较大的破坏, 促进氧进入Zr(0001)晶面, 促进疖状腐蚀的发生。     

燃烧法合成La_2Zr_2O_7粉及其光谱性能

以La_2O_3,Zr(NO_3)_4和甘氨酸为原料,采用燃烧法合成La_2Zr_2O_7粉。分别用发射光谱法(ICPAES)、能谱法(EDAX)、X衍射法(XRD)、红外光谱法(IR)和热重-差热法(TG-DTA)等对La_2Zr_2O_7粉进行表征。分别研究了热处理温度对La_2Zr_2O_7粉的X衍射谱和红外光谱的影响。La_2Zr_2O_7粉的ICP-AES和EDAX分析结果表明,用燃烧法可合成出La_2Zr_2O_7粉。不同温度热处理后La_2Zr_2O_7粉的XRD分析结果表明,当热处理温度为600℃时,出现一个衍射峰,且衍射峰较宽,该结构为半晶型结构;提高热处理温度,衍射峰逐渐尖锐,峰形变窄,衍射峰逐渐增多;热处理温度在750~800℃范围,可得到烧绿石结构的La_2Zr_2O_7粉。在650~750℃热处理后La_2Zr_2O_7粉的红外光谱分析结果与XRD分析结果相同,热处理温度为750℃时,可得到烧绿石结构的La_2Zr_2O_7粉。La_2Zr_2O_7粉的TG-DTG分析结果表明,在120~1 600℃范围,La_2Zr_2O_7粉的结构稳定。     

Condensation and Crystal Nucleation in a Lattice Gas with a Realistic Phase Diagram

We reconsider model II of Orban et al. (J. Chem. Phys. 1968, 49, 1778–1783), a two-dimensional lattice-gas system featuring a crystalline phase and two distinct fluid phases (liquid and vapor). In this system, a particle prevents other particles from occupying sites up to third neighbors on the square lattice, while attracting (with decreasing strength) particles sitting at fourth- or fifth-neighbor sites. To make the model more realistic, we assume a finite repulsion at third-neighbor distance, with the result that a second crystalline phase appears at higher pressures. However, the similarity with real-world substances is only partial: Upon closer inspection, the alleged liquid–vapor transition turns out to be a continuous (albeit sharp) crossover, even near the putative triple point. Closer to the standard picture is instead the freezing transition, as we show by computing the free-energy barrier relative to crystal nucleation from the “liquid”.     

The energetics of mercury adsorption on Cu(100)

We have investigated the adsorption of mercury overlayers on Cu(100) by atom beam scattering, low energy electron diffraction and angle resolved photoemission. From our data we have calculated the isosteric heats in the adsorbed Hg layer on Cu(100) and compared these with results obtained for mercury on Fe(100), W(100) and Ni(100). We observe changes in the isosteric heat of adsorption that can be associated with the ordering of a c(2 × 2) Hg overlayer phase and the transition from a c(2 × 2) overlayer to a c(4 × 4) overlayer. The isosteric heat of adsorption is 0.50 ± 0.07 eV/atom (48 ± 7 kJ/mol) at zero coverage and reaches a maximum of 0.73 ± 0.04 eV/atom (70 ± 4 kJ/mol). From a combination of ABS and LEED, the structures of the two equilibrium ordered phases of Hg on Cu(100) have been identified, as well as the structures of several non-equilibrium phases.     

L12型铝合金的结构、弹性和电子性质的第一性原理研究

运用第一性原理方法研究了L12型铝合金相Al3Sc和Al3Zr的晶体结构、电子结构和弹性.结合能和形成能的计算表明,两种合金具有较强的合金化能力,且Al3Zr较Al3Sc具有更强的结构稳定性.电子结构分析表明,费米能级以下较多的价电子数决定了Al3Zr具有较强的结构稳定性.计算并分析比较了两种合金相的单晶弹性常数(C11,C12和C44)以及多晶弹性模量(体弹性模量B、剪切模量G、杨氏模量Y、泊松比ν和各向异性因子A).通过对比实验和其他理论计算结果,进一步分析和解释了两种合金相的力学性质.     

Mechanism of Cu deposition on the alpha-Al(2)O(3) (0001) surface

The growth mechanism of the Cu/alpha-Al(2)O(3) (0001) interface is studied by first-principles molecular-dynamics simulations as a function of the transition-metal coverage (theta) and the temperature of the system. On the anhydrous surface growth of Cu(0) 3D clusters is predicted. On the partially hydroxylated surface, a Cu(I) monolayer, relatively stable upon the temperature rising, is first observed (theta<1/3 ML). Increasing Cu loading leads to Cu(I)/Cu(0) mixed phases that when heated aggregate into 3D particles increasing the number of Cu(0) atoms, in agreement with the Auger spectra of Kelber et al.     

The structure of formate on Cu(100)

There is some controversy over the question of the correct adsorption site for formate on Cu(100). On the basis of SEXAFS and NEXAFS studies Stöhr et al. favour a bridge site with oxygen atoms near fourfold hollows, while Woodruff et al. bring photoelectron diffraction studies to bear argue for a bridge site with the oxygen atoms almost on top of Cu atoms. We calculate the total energies for the two arrangements, optimising the distance of the formate from the Cu surface, using a self-consistent Hartree-Fock scheme with a Gaussian basis. We find the Woodruff structure more stable by some 0.38 eV per formate radical. We calculate the binding energy to be 1.74 eV per formate radical.     

Do superconductors have zero resistance in a magnetic field?

We show that dc voltage versus current measurements of a YBa(2)Cu(3)O(7-delta) film in a magnetic field can be collapsed onto scaling functions proposed by Fisher et al. [Phys. Rev. B 43, 130 (1991)] as is widely reported in the literature. We find, however, that good data collapse is achieved for a wide range of critical exponents and temperatures. These results strongly suggest that agreement with scaling alone does not prove the existence of a phase transition. We propose a criterion to determine if the data collapse is valid, and thus if a phase transition occurs. To our knowledge, none of the data reported in the literature meet our criterion.     

HRTEM and TEM studies of amorphous structures in ZrNiTiCu base alloys obtained by rapid solidification or ball milling

Amorphous structure of Ti(25)Zr(17)Ni(29)Cu(29) composition was studied. Alloys were prepared either by rapid solidification using melt spinning or by high-energy ball milling. The composition of multi-component eutectic in slowly cooled samples of ZrNiTiCu alloy was determined using EDS measurements in scanning microscope of slowly cooled cast samples. The alloys of eutectic composition were melt-spun or ball-milled. Transmission electron microscopy (TEM) studies of melt-spun ribbons from alloys near eutectic composition did not show presence of nanocrystals within the amorphous structure. TEM studies of ball-milled powders showed presence of nanocrystallites of size 2-5 nm. The electron diffraction pattern showed intense diffused ring due to the presence of the amorphous phase and a weak spot due to crystalline phases which were difficult to identify. The high temperature high-pressure compaction in vacuum of amorphous ball-milled powders resulted in a similar structure like in the powders showing nanocrystals embedded in the amorphous matrix. The crystallites were imaged using HREM. Interplanar distances were measured in pictures obtained by inverse fast Fourier transform (IFFT) of atomic planes to obtain better contrast. Analysis of the IFFT from high-resolution micrographs allowed to identify Cu(10)Zr(7) phase. Point analysis and elemental mapping performed using nondispersive X-ray energy spectroscopy showed uniform elements distribution indicating that chemical segregation to nanocrystals is within measurement error.     

粉末状态对激光立体成形Zr55Cu30Al10Ni5块体非晶合金晶化行为的影响

基于金属熔体结构的遗传性, 激光熔池的快速熔凝导致粉末的晶化状态可能会对最终成形件的晶化产生重要影响, 理清其影响规律对于制备大块非晶合金具有重要意义. 本文选取等离子旋转电极法所制粉末和1000 K退火态粉末为沉积材料, 采用激光立体成形技术沉积Zr₅₅Cu₃₀Al₁₀Ni₅块体非晶合金, 考察了粉末中已有晶化相对熔池及热影响区晶化行为的影响. 结果发现, 原始粉末组织由非晶相及粗大的Al₅Ni₃Zr₂相组成; 当激光线能量较低时, 相应熔覆层的熔池和热影响区皆含有Al₅Ni₃Zr₂相; 随着线能量的提高, 熔池中Al₅Ni₃Zr₂相消失, 保持了非晶态, 但热影响区晶化加重, 并有大量Al₅Ni₃Zr₂相析出; 当采用退火态粉末时, 即使线能量较小, 相应熔覆层仍主要由非晶构成, 几乎无Al₅Ni₃Zr₂相析出. 这是由于原始粉末在退火时其微观结构发生重排, 与Al₅Ni₃Zr₂相关的原子短程/中程有序结构减少, 导致已沉积层非晶区的热稳定性提高, 不利于Al₅Ni₃Zr₂相析出. 可见, 提高线能量将会加剧非晶沉积体的晶化, 而粉末中的Al₅Ni₃Zr₂团簇相状态对Zr₅₅Cu₃₀Al₁₀Ni₅合金沉积层的晶化有重要影响.     

The relative acidities of gas phase acids for displacement of surface intermediates

The recent work of Barteau and Madix [Surface Sci. 120 (1982) 262] indicated that the stability of surface intermediates with respect to displacements by other species is related to the gas phase acidity difference of the molecules. To further test the generality of this hypothesis, experiments similar to those of Barteau et al. conducted on Ag(110) were performed on Cu(110). The results of those experiments are presented here.     

Two-step disordering of perpendicularly magnetized ultrathin films

We have imaged the stripe domain structure of perpendicularly magnetized fcc ultrathin Fe films grown on Cu(100). The stripe phase has a strong local orientational order and sustains the two kinds of fluctuations predicted by Abanov et al. [Phys. Rev. B 51, 1023 (1995)]: meandering and dislocations. Before reaching the Curie temperature, the stripes transform into a new and so far unobserved domain structure, characterized by domains with predominantly square corners. We argue that this phase is the tetragonal liquid phase proposed by Abanov et al. to separate the stripe phase from the paramagnetic phase. This two-step disordering is reminiscent of a two-dimensional melting process.     

三方和四方相PbZr0.5Ti0.5O3 的结构稳定性和电子结构的第一性原理研究

采用基于密度泛函理论的第一性原理超原胞方法和虚晶近似方法, 在局域密度近似和广义梯度近似下系统研究了三方相和四方相 PbZr_0.5Ti_0.5O₃的能量稳定性、原子结构以及电子结构. 计算结果表明三方相的能量比四方相低, 说明三方相结构更加稳定, 并且发现利用广义梯度近似计算的结构参数与实验值符合得更好. 电子结构表明, 两种相的Ti/Zr的3d电子和O的2p电子间存在明显的轨道杂化, 并且Ti-O之间的作用比Zr-O作用更强;Pb的6s和5d电子与O的2s和2p电子也分别存在轨道杂化. 而三方相中Pb的5d电子与O的2s电子杂化比四方相更强, 进一步说明三方相比四方相结构更加稳定.     

Phase stability and pressure dependence of defect formation in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores

We report dramatically different behaviors between isostructural Gd2Ti2O7 and Gd2Zr2O7 pyrochlore at pressures up to 44 GPa, in which the substitution of Ti for Zr significantly increases structural stability. Upon release of pressure, the Gd2Ti2O7 becomes amorphous. In contrast, the high-pressure phase of Gd2Zr2O7 transforms to a disordered defect-fluorite structure. First-principle calculations for both compositions revealed that the response of pyrochlore to high pressure is controlled by the intrinsic energetics of defect formation.     

Evolution of the commensurate and incommensurate magnetic phases of the S = 3/2 kagome staircase Co?V?O? in an applied field

Single crystal neutron diffraction studies have been performed on the S = 3/2 kagome staircase compound Co(3)V(2)O(8) with a magnetic field applied along the magnetization easy-axis ([Formula: see text]). Previous zero-field measurements (Chen Y et al 2006 Phys. Rev. B 74 014430) reported a rich variety of magnetic phases, with a ferromagnetic ground state as well as incommensurate, transversely polarized spin density wave (SDW) phases (with a propagation vector of [Formula: see text]) interspersed with multiple commensurate lock-in transitions. The magnetic phase diagram with [Formula: see text] adds further complexity. For small applied fields, μ(0)H ≈ 0.05 T, the commensurate lock-in phases are destabilized in favor of the incommensurate SDW ones, while slightly larger applied fields restore the commensurate lock-in phase with δ = 1/2 and yield a new commensurate phase with δ = 2/5. For measurements in an applied field, higher-order scattering is observed that corresponds to the second harmonic.     

Fluorescence of Metal–Ligand Complexes of Mono- and Di-Substituted Naphthalene Derivatives

In this work, metal ion complexes for several naphthalene derivatives have been investigated. Different working pH values were chosen: 2.5 for complexes with Zr(IV), 4.0 for complexes with Fe(III), 5.0 for complexes with Al(III), and 7.5 for complexes with Cu(II). A stoichiometry of 1:1 for all complexes except two has been established by use of the Benesi–Hildebrand method and the stability constants have been calculated. All complexes between naphthalene derivatives and Cu(II) and Fe(III) show fluorescence quenching. In the case of Al(III), all complexes provided enhanced fluorescence. For Zr(IV), only the complex with 3-hydroxy-2-naphthoic acid provided enhanced fluorescence. The value of the stability constants as a function of the substituents of naphthalene derivatives has been analyzed. One can conclude that Cu(II) showed the largest binding affinity for the mono-substituted derivatives. However, Al(III) and Zr(IV) produced greater selectivity for the di-substituted derivatives. Iron(III) showed no specific binding with any of the naphthalene derivatives.