超导Ag/Bi1.6Pb0.4Sr2Ca2Cu3O10-x复合氧化物摩擦磨损性能

为适应20℃～-200℃ 温度的适用范围,采用固相法制备了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导材料,用摩擦磨损试验机测试了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x从液氮温度至室温的摩擦学性能。结果表明 : 在室温 20℃下,Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x与对偶件轴承钢盘对摩时,摩擦系数约为0.35,当温度降到超导转变温度以下时(液氮温度-170℃)摩擦系数大幅度降低,Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导态摩擦系数为正常态值的一半,实验证明了电子激励对摩擦能量耗散的作用。为改善室温下Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x摩擦学性能,掺杂不同质量分数 Ag作为润滑组元,制备了Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x超导固体润滑复合材料,取得良好耐磨减摩效果。Ag掺杂不影响Ag/Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x复合材料的超导性,在正常载荷和滑动速度下10 wt%Ag/ Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10-x复合材料摩擦系数为0.2~0.3,磨损率为4.57×10-4 mm3·(N·m)-1。     

电场激活燃烧合成( TiB2)PNi/Ni3Al/ Ni功能梯度材料

采用电场激活压力辅助合成技术(FAPAS)制备了(TiB₂)_PNi/(TiB₂)_PNi₃Al/Ni₃Al/Ni梯度材料,主要研究电场激活燃烧合成过程中电场对材料合成及层界面扩散连接的作用。分析了梯度材料各层的界面微观组织及相组成和材料的硬度分布。结果表明,采用FAPAS 技术结合机械合金化工艺制备的(TiB₂)_PNi/(TiB₂)_PNi₃Al/Ni₃Al/Ni 功能梯度材料具有快速、简便和组织均匀密实的特点。梯度材料的陶瓷复合层、Ni₃Al层和Ni板的界面区产生成分的互扩散,形成了良好的冶金结合。从Ni板到陶瓷复合层的硬度呈梯度分布。     

超导PbO/YBa2Cu3O7-δ复合氧化物摩擦磨损性能

为适应从低温到高温宽温范围的使用条件,用溶胶-凝胶法制备了YBa₂Cu₃O_7-δ超导材料,用摩擦磨损试验机测试了YBa₂Cu₃O_7-δ从室温至液氮温度的摩擦学性能。结果表明：室温20℃下,YBa₂Cu₃O_7-δ与对偶件不锈钢盘对摩时,摩擦因数在0.5左右,当温度降到超导转变温度以下时（液氮温度-196℃）摩擦因数大幅度降低,YBa₂Cu₃O_7-δ超导态摩擦因数是正常态值的一半,实验直接证明了电子激励对摩擦能量耗散的作用。为改善室温下YBa₂Cu₃O_7-δ摩擦学性能, 掺杂不同质量分数PbO作为润滑组元,制备了PbO/YBa₂Cu₃O_7-δ超导固体润滑复合材料,取得良好效果。PbO掺杂不影响PbO/YBa₂Cu₃O_7-δ复合材料的超导电性,在正常的载荷和滑行速度下15%PbO/YBa₂Cu₃O_7-δ复合材料摩擦因数为0.2至0.3,磨损率为4.35×10-4 mm3·（N·m）-1,分析了PbO/ YBa₂Cu₃O_7-δ复合材料减摩耐磨机制。     

Y2O3添加量对Al2O3/ZrO2共晶陶瓷显微组织及力学性能的影响

为探索第三组元Y₂O₃添加对Al₂O₃/ZrO₂共晶陶瓷显微组织与机械性能的影响,本文利用低温度梯度的高温熔凝法制备了直径为20 mm的Al₂O₃/ZrO₂(Y₂O₃)共晶陶瓷块体,采用SEM、EDS及XRD技术对共晶陶瓷进行微结构分析,并利用维氏压痕法对其硬度和断裂韧性进行测试。SEM结果表明,凝固组织由群集的共晶团结构组成,随着Y₂O₃添加量的增加,共晶团形态由胞状转变为枝晶状,内部相间距在1~2 μm范围内变化。力学测试表明,Y₂O₃摩尔分数小于1.1%时,由于组织内部存在低硬度m-ZrO₂及微裂纹缺陷,故陶瓷硬度较低,约为(9.53±0.22 )GPa;当Y₂O₃摩尔分数为1.1%时,陶瓷硬度最大,约为(18.05±0.27)GPa;当Y₂O₃的摩尔分数大于1.1%时,由于共晶团边界区内气孔缺陷及粗大组织增多,引起陶瓷硬度值略有下降。低Y₂O₃摩尔分数添加时,陶瓷断裂韧性相对较高,约为(6.30±0.16)MPa·m^1/2,这与其内部存在大量微裂纹缺陷有关;随着Y₂O₃添加量的增加,陶瓷的微裂纹数量减少、边界区内缺陷增多,断裂韧性降低。     

原位生成Al2O3/Cu复合材料的新工艺

采用一种新型工艺制备了Al₂O₃/Cu复合材料。高能球磨制备亚稳态的Cu-0.8 wt% Al合金粉,再将Cu₂O粉与其一起进行高能球磨,然后将复合粉末压坯在真空炉中同时进行氧化和烧结。该工艺省略了还原剩余Cu₂O的环节,氧化和烧结时间仅为1 h。生成的Al₂O₃的粒径约250nm,颗粒间距约500 nm,均匀弥散分布;该材料冷加工后性能接近SCM制品性能。该配比的Al₂O₃/Cu复合材料的热稳定性良好,在800℃下循环冷淬20次无裂纹;软化温度为700℃。     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

团簇NiCo2S4的磁学性能

为探究团簇NiCo₂S₄的磁学性能,本文依据密度泛函理论(DFT)在B3LYP/Lan12dz水平下对团簇NiCo₂S₄进行优化计算,确定了三重态下的6种优化构型,并从轨道成单电子数、自旋布居数、磁矩、自旋密度差、轨道态密度图多个角度对构型进行分析。研究表明:团簇NiCo₂S₄的6种构型中,构型2^{(3)性能最优异,而热力学稳定性最好的构型1(3)在磁学性能方面表现一般,其余构型磁学性能相近。对于团簇NiCo₂S₄的磁性强度,在原子轨道上,s、p轨道对团簇NiCo₂S₄整体的磁性强度贡献较小,d轨道对整体的磁性强度贡献最大;Ni原子和自旋向上的α成单电子是团簇整体磁性强度的主要贡献者,其中,s轨道成单电子数的主要贡献者是S原子,p、d轨道主要是金属原子,Ni原子d轨道主要受α成单电子影响,Co、S原子既受α成单电子的影响又受β成单电子的影响。团簇NiCo₂S₄作为磁性材料时采用构型2(3)}作为模型基础,可以通过增大金属Ni比例来增强磁性。     

烧成温度对Al2O3/Ni复合材料的致密化、物相组成和显微结构的影响

首先采用非均相沉淀合成出Ni包裹Al₂O₃粉体,然后热压烧结包裹粉体制备了Al₂O₃/Ni复合材料。本文作者主要研究了不同烧成温度对复合材料致密化、物相组成和显微结构的影响。结果表明:在1400℃保温1h,烧结体获得了最大相对密度,而致密度随Ni含量的增加反而降低;高于1350℃时,除Al₂O₃和Ni相外,在烧结体的表层生成一种由Al,Ni,O,C四种元素组成的新相;随着温度的升高,包裹层的纳米Ni颗粒聚合、长大,并退缩至三角晶界处,在适当的烧结温度(1400℃),少数小的纳米Ni颗粒被卷入Al₂O₃晶内,大的位于三角晶界,当烧成温度为1450℃时,不仅观察到Al₂O₃/Ni界面存在空隙,也发现了Al₂O₃晶粒异常长大现象。     

热处理对Bi2O3-B2O3-SiO2凝胶玻璃粉体结构与性能的影响

采用溶胶-凝胶法制备了一种Bi₂O₃-B₂O₃-SiO₂系玻璃粉体,在200 ℃、400 ℃、600 ℃和800 ℃温度下分别对凝胶玻璃粉体进行热处理,借助SEM、TEM、XRD、FT-IR、Raman、XPS、DSC、热膨胀仪及“纽扣”烧结实验分别测定了经不同温度热处理后玻璃粉体的结构与性能,分析了其结构变化对玻璃粉体转变温度T_g和烧结特性的影响。结果显示,在实验温度范围内,随热处理温度升高,Bi³⁺逐渐进入玻璃网络中,[BiO₆]八面体和[BiO₃]三角体、[BO₄]四面体和[BO₃]三角体分别与[SiO₄]四面体以顶角相连的方式构建玻璃网络结构。O1s和Bi4f的电子结合能逐渐增大,B1s的电子结合能减小,玻璃网络结构稳定性增强,导致玻璃转变温度T_g及玻璃膨胀软化点温度T_d升高、 润湿性降低且热膨胀系数略有降低。经600 ℃热处理后,玻璃粉体具有较优的烧结性能,T_g、T_d分别约为485 ℃及542 ℃,热膨胀系数α约为7.067×10-6/℃。     

Development of random access memory in Nd0.7Ca0.3MnO3/YBa2Cu3O7 heterostructure

The effects of electrode on the resistive switching in Nd_0.7Ca_0.3MnO₃(NCMO)/YBa₂Cu₃O₇(YBCO) heterostructure are investigated at room temperature. For Cu/NCMO/YBCO, resistance can be switched on-and-off from a high- to low-resistance state at a steady ratio of 25% with a pulsed-voltage of ± 3 V. On the other hand, a giant resistance-change as large as 1350% is observed with ± 5 V for Ag/NCMO/YBCO with a fast decay down to 550%. Our experimental results show clear evidences that the nature of interfaces can be modified by the electric field and it dictates the resistive switching behavior of these heterostructure devices, which are the potential candidates for the random access memory.     

Behavior of N atoms after thermal nitridation of Si1 − xGex surface

Behavior of N atoms after thermal nitridation of Si_1 − xGe_x (100) surface in NH₃ atmosphere at 400 °C was investigated. X-ray photoelectron spectroscopy (XPS) results show that N atomic amount after nitridation tends to increase with increasing Ge fraction, and amount of N atoms bonded with Ge atoms decreases by heat treatment in H₂ at 400 °C. For nitrided Si_0.3Ge_0.7(100), the bonding between N and Si atoms forms Si₃N₄ structure whose amount is larger than that for nitrided Si(100). Angle-resolved XPS measurements show that there are N atoms not only at the outermost surface but also beneath surface especially in a deeper region around a few atomic layers for the nitrided Si(100), Si_0.3Ge_0.7(100) and Ge(100). From these results, it is suggested that penetration of N atoms through around a few atomic layers for Si, Si_0.3Ge_0.7 and Ge occurs during nitridation, and the N atoms for the nitrided Si_0.3Ge_0.7(100) dominantly form a Si₃N₄ structure which stably remains even during heat treatment in H₂ at 400 °C.     

Synthesis and blue to near-infrared quantum cutting of Pr/Yb co-doped Li2TeO4 phosphors

Near-infrared (NIR) quantum cutting luminescent materials Li₂TeO₄ doped with Pr³⁺ and Yb³⁺ were synthesized by solid-state reaction method. The dependence of Yb³⁺ doping concentration on the visible- and NIR-emissions, decay lifetime, and quantum efficiencies of the phosphors are investigated. Quantum cutting down-conversion involving 647 nm red emission and 960-1050 nm broadband near-infrared emission for each 487 nm blue photon absorbed is realized successfully in the resulting phosphors, of which the process of near-infrared quantum cutting could be expressed as ³P₀(Pr³⁺) → ²F_5/2(Yb³⁺) + ²F_5/2(Yb³⁺). The maximum quantum cutting efficiency approaches up to 166.4% in Li₂TeO₄: 0.3 mol%Pr³⁺, 1.8 mol%Yb³⁺ sample corresponding to the 66.4% value of energy transfer efficiency.     

Synthesis and characterization of novel nanostructured fishbone-like Cu(OH)2 and CuO from Cu4SO4(OH)6

The Cu₄SO₄(OH)₆ was synthesized by a simple hydrothermal reaction with a yield of ~ 90%. Using Cu₄SO₄(OH)₆ as the starting material, novel fishbone-like Cu(OH)₂ was produced by a direct reaction of Cu₄SO₄(OH)₆ with NaOH solution. The Cu(OH)₂ consists of many needle-like nanorods parallel to each other and perpendicular to the direction of backbone, forming fishbone-like structure. Using the fishbone-like Cu(OH)₂ as the sacrificial precursor, CuO with similar size and morphology was obtained through a simple heat treatment. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, X-ray photoelectron spectroscopy, BET nitrogen adsorption, and UV-Vis absorption spectroscopy were employed to characterize the as-prepared samples. The conversion of the Cu₄SO₄(OH)₆ to the fishbone-like Cu(OH)₂ was visualized by time-dependent SEM images. A mechanism was also proposed based on the observed results.     

Formation of SiGe/β-FeSi2 superstructures from amorphous Si/FeSiGe layers

Growth of SiGe/β-FeSi₂ superstructures by annealing of a-Si/a-FeSiGe layered structures was investigated for control of the strains in β-FeSi₂ by Ge doping. The [a-SiGe/β-FeSi₂(Ge)]_n multi-layered structures were formed after annealing at 700 °C. From the analysis of the X-ray diffraction (XRD) spectra, it was found that β-FeSi₂(Ge) was strained by 0.4-0.5% for the sample with n=1. The strains decreased with increasing n, which was due to that the segregation of the Ge atoms from the a-Fe_0.4Si_0.5Ge_0.1 layers to the a-Si layers became large with increasing n. After annealing at 800 °C, agglomeration of β-FeSi₂ occurred, and nanocrystals of relaxed β-FeSi₂ and c-Si_0.7Ge_0.3 were formed. These demonstrate that the SiGe/β-FeSi₂ superstructures were formed by the Ge segregation. These new structures are useful for formation of opto-electrical devices.     

Effect of high magnetic field on the morphology of (Cu, Ni)6Sn5 at Sn0.3Ni/Cu interface

The effect of high magnetic field on the microstructure of (Cu, Ni)₆Sn₅ intermetallic compound layer in Sn0.3Ni/Cu couples at 250 °C was examined. The applied magnetic field changed the morphology of outer (Cu, Ni)₆Sn₅ crystals on the Sn side from faceted shape to stick shape. The high magnetic field affected the crystal orientations of (Cu, Ni)₆Sn₅ and reduced the Ni content in the outer layer. The morphology evolution of (Cu, Ni)₆Sn₅ is attributed to the content of Ni solute decreased by magnetic field. The effects of high magnetic field on the liquid convection and phase diagram are considered to be responsible for the Ni content.     

Atomic and electronic structures of Cu/α-Al2O3 interfaces prepared by pulsed-laser deposition

Interfacial atomic structures of Cu/Al₂O₃(0001) and Cu/Al₂O₃(11 0) systems prepared by a pulsed-laser deposition technique have been characterized by using high-resolution transmission electron microscopy (HRTEM). It was found that Cu metals were epitaxially oriented to the surface of Al₂O₃ substrates, and the following orientation relationships (ORs) were found to be formed: (111)_Cu//(0001)Al₂O₃, _Cu//[1 00]Al₂O₃ in the Cu/Al₂O₃(0001) interface and (001)_Cu//(11 0)Al₂O₃, [1 0]_Cu//[0001]Al₂O₃ in the Cu/Al₂O₃(11 0) interface. Geometrical coherency of the Cu/Al₂O₃ system has been evaluated by the coincidence of reciprocal lattice points method, and the result showed that the most coherent ORs were (111)_Cu//(0001)Al₂O₃, [11 ]_Cu//[1 00]Al₂O₃ and (1 0)_Cu//(11 0)Al₂O₃, [111]_Cu//[0001]Al₂O₃, which are equivalent to each other. These ORs were not consistent with the experimentally observed ORs, and it was possible that crucial factors to determine the ORs between Cu and Al₂O₃ were not only geometrical coherency, but also other factors such as chemical bonding states. Therefore, to understand the nature of the interface atomic structures, the electronic structures of the Cu/Al₂O₃ interfaces have been investigated by electron energy-loss spectroscopy. It was found that the pre-edge at the lower energy part of the main peak appeared in the O-K edge spectra at the interface region in both the Cu/Al₂O₃(0001) and Cu/Al₂O₃(11 0) systems. This indicates the existence of Cu–O interactions at the interface. In fact, HRTEM simulation images based on O-terminated interface models agreed well with the experimental images, indicating that O-terminated interfaces were formed in both systems. Since the overlapped Cu atomic density in the experimental ORs were larger than that in the most coherent OR, it is considered that the on-top Cu–O bonds stabilize the O-terminated Cu/Al₂O₃ interfaces.     

Magneto-optical activity of f–f transitions in elpasolite Rb2NaDyF6

Absorption and magnetic circular dichroism (MCD) spectra of f–f transitions ⁶H_15/2 → ⁶F_3/2, ⁶F_5/2, ⁶(F_7/2 + H_5/2) have been measured in cubic crystal Rb₂NaDyF₆ with Dy³⁺ ions in centrosymmetrical O_h positions. Magneto-optical activities (MOA) of the transitions (the ratio of zero moments of the MCD and absorption bands) have been obtained from the corresponding spectra. Origins of the transitions MOA have been analyzed and theoretical estimations of the MOA values have been made. It turned out, that MOA of the transitions in the centrosymmetrical crystal Rb₂NaDyF₆ (being allowed by odd vibrations) are noticeably larger than those in non-centrosymmetrical compounds, where f–f transitions are allowed by static odd components of crystal field.     

Synthesis and characterization of LiCo0.3−xGaxNi0.7O2 (x = 0, 0.05) as a cathode material for lithium ion battery

The single phase of LiCo_0.3−xGa_xNi_0.7O₂ (x = 0, 0.05) was synthesized by a sol–gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The powders are homogeneous and have a good-layered structure. The synthesized LiCo_0.25Ga_0.05Ni_0.7O₂ exhibits better electrochemical performance with an initial discharge capacity of 180.0 mAh g⁻¹ and a capacity retention of 95.2% after 50 cycles between 2.8 and 4.4 V at 0.2C rate. The study on the structural evolution of the material during the cycling shows that Ga-doping improves the structure stability of LiCo_0.3Ni_0.7O₂ at ambient temperature and 55 °C. Meanwhile, Ga-doping not only suppresses the alternating current (AC) impedance of LiCo_0.3Ni_0.7O₂ but also promotes the Li⁺ diffusion in LiCo_0.3Ni_0.7O₂. Furthermore, thermal stability of the charged LiCo_0.25Ga_0.05Ni_0.7O₂ is improved, which may be attributed to the retard of O₂ evolution in LiCo_0.3Ni_0.7O₂ and the suppression of electrolyte oxidation during cycling by Ga-doping_.     

Reproducibility of transition temperature and critical current density of thin films of YBa2Cu3O7 on (100) LaAlO3

Submicrometer epitaxial films of YBa₂Cu₃O₇(YBCO) on (100) LaAlO₃ were made by coevaporation and furnace annealing. Samples from more than a dozen runs are used in this study. The zero resistance transition temperature (T _c) is high (89 or 90 K) if the film composition is phase pure (Ba/Y=2, Cu/Y=3) or if it is enriched in Ba and Cu. For these compositions the critical current density (J _c) at 77 K has an average value of 2×10⁵ A cm^–2, with a tendency for decreasingJ _c with increasing film thickness (0.2 to 0.8m). Variations inJ _c are not correlated with deviations from ideal stoichiometry. Steeper slopes of the resistance-temperature curves above 100 K and lower values of the room-temperature resistivity are associated with high values ofJ _c. If the film composition is enriched in Y relative to Ba and Cu,T _c decreases by several degrees.