ZBL低温助烧CaCu3Ti4O12高介电陶瓷的研究

采用固相合成CaCu_3Ti_4O_(12)(CCTO)微波介质陶瓷基体粉体,通过XRD衍射仪、SEM扫描电镜表征掺杂ZnO-B_2O_3-La_2O_3(ZBL)低软化点玻璃助烧剂的(CCTO)陶瓷的物相组成及结构特点,研究ZBL玻璃的掺杂量对CCTO样品烧结性能及微波介电性能的影响。研究表明:添加10%(质量分数)ZBL玻璃的CCTO陶瓷在960℃烧结3h,能够获得较好的介电性能:εr=112,tanδ=0.0027,τf=-2×10-6/℃。     

第一性原理对CaTiO3和CaCu3Ti4O12的对比研究

通过Ca替换CaCu_3Ti_4O_(12)晶胞中的所有Cu,建立了包含TiO6八面体扭转的CaTiO3;通过Cu替换CaTiO32×2×2超胞中3/4的Ca,建立了不包含CuO_4正方形的CaCu_3Ti_4O_(12)。采用Materials Studio软件的CASTEP模块,对比了上述晶体和标准晶体成键状况、能带结构、态密度及介电函数,分析了TiO6八面体扭转和CuO_4正方形的影响,发现了Cu-O键或CuO_4正方形对CaCu_3Ti_4O_(12)光频介电常数的关键性作用。研究结果提供了通过内禀机制优化CaCu_3Ti_4O_(12)材料介电性能的新途径。     

Al2O3颗粒增强纯铝基复合材料的研究

本文探讨了用粉末冶金法,采用常规的冶金加工设备和工艺,制造Al₂O₃颗粒增强纯铝基复合材料的可行性。研究了不同Al₂O₃体积含量复合材料的显微组织及力学性能。初步试验了二次热挤压变形对颗粒分布和对基体强化的影响。结果表明,Al₂O₃颗粒与纯铝粉混合,加压烧结制备的复合材料,组织致密,颗粒分布均匀,随Al₂O₃含量增加,复合材料强度、硬度及弹性模量大大提高,Al₂O₃含量小于10%时,塑性不降低。二次热挤压有助于提高颗粒分布的均匀性;并使基体显著强化。     

La2O3-TiC/W复合材料组织结构与力学性能

采用真空热压烧结法制备La₂O₃-TiC/W复合材料,并对其组织结构和力学性能进行了研究。结果表明：在一定成分范围内,La₂O₃和TiC的加入提高了复合材料的力学性能,La₂O₃和TiC共同作用时的强化效果强于La₂O₃和TiC单独作用的强化效果,但La₂O₃-TiC/W复合材料的密度和相对密度随TiC含量的增加而下降,并进而影响硬度和弹性模量的提高, 适量的La₂O₃有益于相对密度的提高;抗弯强度在1%La2O3 5%TiC/W成分含量时出现最大值901MPa,而断裂韧性在成分含量为0.5%La₂O₃-10%TiC/W时出现最大值10.07MPa·m1/2。本研究中,1%La₂O₃-5%TiC/W成分配比时具有较好的综合力学性能。La₂O₃-TiC/W复合材料的强化机制为细晶强化和载荷传递,韧化机制为细晶韧化、裂纹偏转和桥接。     

不同纳米材料与石墨混合填充PTFE复合材料摩擦磨损性能

利用MM-200型磨损试验机考察了载荷对纳米SiO₂、TiO₂、Al₂O₃与石墨混合填充PTFE复合材料摩擦磨损性能的影响,采用扫描电子显微镜观察分析磨损表面形貌及磨损机理。结果表明,纳米材料及其与石墨混合都可以不同程度地提高PTFE的耐磨性,而它们对PTFE耐磨性的提高程度各不相同,其中以纳米SiO₂-石墨填充PTFE复合材料的磨损质量损失最小,纳米Al₂O₃-石墨填充PTFE复合材料的磨损质量损失较大;填充PTFE复合材料同钢对磨时的摩擦系数表现出不同的性能,纳米SiO₂-石墨填充PTFE的摩擦系数与纯PTFE相差不大。     

NiCo2O4/氧化石墨烯复合材料制备与电化学性能研究

为了研究NiCo₂O₄/氧化石墨烯(NiCo₂O₄/GO)复合材料的电化学性能,本文通过先水热合成前驱体再煅烧的方法制备了一系列NiCo₂O₄/GO复合材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学方法对其进行物理表征,其中以GO质量浓度为1 mg/mL悬浊液制备出的NiCo₂O₄ /GO-3复合材料呈类海胆状结构.在1 M KOH水溶液中使用循环伏安法、恒电流充/放电法和交流阻抗法研究了NiCo₂O₄/GO复合材料电化学性能.研究表明,与纯NiCo₂O₄相比,制备的NiCo₂O₄ /GO复合材料的比容量和赝电容性能均有明显提高,这主要是由于NiCo₂O₄ /GO复合材料中NiCo₂O₄与GO纳米片的相互作用形成的高孔隙率复合结构;NiCo₂O₄ /GO-3复合材料在电流密度为0.5~3.0 A/g时,比电容超过650 F/g,具有良好的倍率性能和高比容量.采用本文方法合成的NiCo₂O₄/GO复合材料,既提高了其倍率性能又保证了高比容量,是一种良好的超级电容器电极材料.     

填充型聚合物基介电储能复合材料的研究进展

聚合物薄膜电容器具有功率密度超高、击穿场强高、易于生产和密度小等特点,因而被广泛地应用于电力电子设备中.但是由于聚合物本身低的介电常数而导致其能量密度较低,限制了其在新兴领域的应用.通过复合的方式向聚合物基体中加入不同形貌与特性的填料是提高聚合物能量密度的有效途径.本文综述了近年来国内外关于填充型聚合物基介电储能复合材料的研究现状,分类讨论了各种填料的优势与不足,探究了填料与聚合物基体间的界面及相互作用对复合材料介电性能的影响,阐述了填充型聚合物基介电储能复合材料存在的问题和未来的发展方向.     

Al2O3短纤维/Al-12Si复合材料启裂特征的TEM原位观察研究

利用挤压铸造法制备了Al₂O₃(15%)/Al-12Si复合材料,并采用透射电镜动态拉伸技术对复合材料的裂纹形成及微观断裂过程进行了原位观察,发现该复合材料的纤维/基体界面是破坏路径之一,并发现了纤维中裂纹形成及扩展至完全破坏的现象.     

纳米Al2O3颗粒增强新型铜基自润滑复合材料

以Cu-Ni-Y₂O₃-MoS₂-Graphite混合粉为基体,加入质量分数分别为0%、1%、2%、3%、4%的纳米Al₂O₃增强相,采用粉末冶金方法制备纳米Al₂O₃增强新型铜基自润滑复合材料。结果表明：随着铜合金粉末中纳米Al₂O₃颗粒含量的增加 , 所制备自润滑复合材料样品的密度下降,但硬度和压溃强度先上升后下降,在Al₂O₃含量为2%时硬度从HV 23.7增加到HV 35.1,压溃强度从189 MPa提高到276 MPa。由石墨和MoS₂组成的混合固体自润滑材料的摩擦系数小且稳定,约0.12。Al₂O₃质量分数为2%的样品磨损量最小,是未加Al₂O₃试样磨损量的1/7～1/8。铜基体经过镍、纳米Al₂O₃等弥散颗粒强化和固体润滑相石墨和MoS₂的加入,所制备的材料已具有一定的自润滑性能。     

Co3O4-Sn复合材料对锂离子电池性能的影响

锂电子电池的性能与电池负极材料密切相关,研究了锡掺杂氧化钴复合材料的水热合成及锡掺杂量对Co₃O₄-Sn复合材料的形貌、结构及电池性能的影响。利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等测试手段对材料进行表征。结果表明,Sn在导电基底Ti箔上以无定形态存在,且均匀分布在材料内部。同时,随着锡掺杂量的增加,会在材料表面生长一层小片状或颗粒。电化学性能测试结果表明:锡的引入可以改善锂离子电池的电化学性能,当锡掺杂量过多或过少时,都会使得电池性能下降。而且原始掺杂比例Co与Sn为1∶0.4时,电池性能最好。     

巨介电常数陶瓷CaCu3Ti4O12的研究进展

CaCu_3Ti_4O_(12)(CCTO)陶瓷具有高介电常数和高热稳定性,这使得CCTO可能在高密度信息储存、高介电电容器、大规模集成电路等领域获得广泛使用。系统地介绍了CCTO高介电常数起源的内禀机制和外禀机制,详细归纳了元素掺杂对CCTO介电特性的影响,阐述了巨介电常数与本征点缺陷的内在关联,肯定了晶粒电导赝极化理论,指出了CCTO巨介电常数陶瓷研究的重点在于:基于外禀机制的IBLC模型,通过晶胞掺杂或晶界掺杂改变晶粒或者晶界的电导,进而调控CCTO的介电损耗,使CCTO保持较高介电常数的前提下,在很宽的频率范围内使介电损耗正切值降低到0.1以下。     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Crystal structure and ferroelectric properties of Ca(Cu3−xMx)Ti4O12 (M = Fe and Ni) ceramics

M-substituted Ca(Cu_3−xM_x)Ti₄O₁₂ (CCMTO) ceramics, where M = Fe and Ni, were synthesized and the influence of M substitutions for Cu on the crystal structure and ferroelectric properties of CCMTO ceramics were investigated in this study. From the variations in the lattice parameters of CCMTO ceramics, the solubility limit of Ni substitution for Cu in CaCu_3−xNi_xTi₄O₁₂ (CCNTO) ceramics was x = 0.2, whereas that of CaCu_3−xFe_xTi₄O₁₂ (CCFTO) ceramics was x = 0.05. The crystal structural analysis of CCMTO ceramics revealed that the single phase of CCMTO ceramics belongs to the I23 non-centrosymmetric space group of I23; as a result, the P_r and E_c values of CCFTO ceramics at x = 0.05 were 1.8 μC/cm² and 40 kV/cm, respectively. The ferroelectric behavior of CCMTO ceramics by the M substitutions for Cu may be related to the displacement of a Ti⁴⁺ cation in the TiO₆ octahedra and tilting of the Ti–O–Ti angle because of the non-centrosymmetric space group.     

Synthesis of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.     

Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

Elastic modulus and hardness of CaTiO3, CaCu3Ti4O12 and CaTiO3/CaCu3Ti4O12 mixture

Three ceramic systems, CaTiO₃ (CTO), CaCu₃Ti₄O₁₂ (CCTO) and intermediate nonstoichiometric CaTiO₃/CaCu₃Ti₄O₁₂ mixtures (CTO.CCTO), were investigated and characterized. The ceramics were sintered at 1100 °C for 180 min. The surface morphology and structures were investigated by XRD and SEM. Elastic modulus and hardness of the surfaces were studied by instrumented indentation. It was observed that CCTO presented the higher mechanical properties (E = 256 GPa, hardness = 10.6 GPa), while CTO/CCTO mixture showed intermediate properties between CTO and CCTO.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.     

Effect of yttrium doping on the dielectric properties of CaCu3Ti4O12 thin film produced by chemical solution deposition

Pure and yttrium substituted CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0, 0.02, 0.1) thin films were prepared on boron doped silica substrate employing chemical solution deposition, spin coating and rapid thermal annealing. The phase and microstructure of the sintered films were examined using X-ray diffraction and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using electrochemical impedance spectroscopy. Highly ordered polycrystalline CCTO thin film with bimodal grain size distribution was achieved at a sintering temperature of 800 °C. Yttrium doping was found to have beneficial effects on the dielectric properties of CCTO thin film. Dielectric parameters obtained for a CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0.02) film at 1 KHz were k ∼ 2700 and tan δ ∼ 0.07.     

BaTiO3纳米线的制备及其复合物介电和储能性能研究

采用两步水热法合成钛酸钡(BaTiO₃)纳米线, 并以此为填充物, 聚偏氟乙烯六氟丙烯(P(VDF-HFP))为聚合物基体制备介电复合物, 研究不同含量BaTiO₃纳米线对复合物的介电及储能性能的影响。采用X射线衍射仪、扫描电镜、透射电镜、阻抗分析仪和铁电工作站等表征BaTiO₃纳米线及其复合物的物相、微观结构、介电和储能性能。结果表明: BaTiO₃纳米线具有典型的四方相, 且在聚合物基体中具有良好的分散性与相容性。相同频率下, 复合物的介电常数随着BaTiO₃纳米线含量的增加而增加。含量为20vol%的复合物, 在1 kHz频率下其介电常数取得最 大值30.69。含量为5vol%的复合物, 在场强为240 kV/mm时, 获得了最大的储能密度与放电能量密度, 分别为4.89和2.58 J/cm³。