简化共沉淀法制备CaCu3Ti4O12陶瓷及其介电性能研究

具有巨介电常数的CaCu₃Ti₄O₁₂陶瓷是一种理想的高储能密度电容器材料.本文以草酸为沉淀剂、以乙酸铵为调节pH值的定量缓冲剂,获得制备CaCu₃Ti₄O₁₂陶瓷的简化共沉淀法.确定了pH=30为制备前驱粉料的最佳反应条件.通过显微分析和介电性能测量,发现在1040℃—1100℃范围内,随着烧结温度的提高,陶瓷的品粒尺寸增大,非线性系数上升,电位梯度和介电损耗下降,1100℃烧结的试样tanδ最低达到0.04.认为CaCu₃Ti₄O₁₂陶瓷介电损耗包含直流电导分量、低频松弛损耗和高频松弛损耗.低频松弛活化能为0.51 eV.,对应于晶界处的Maxwell-Wagner松弛极化;高频松弛过程活化能为0.10 eV,对应晶粒内部的氧空位缺陷.烧结温度的升高导致晶界电阻下降.     

CaCu3Ti4O12陶瓷的微观结构及直流导电特性

采用传统固相反应法制备了CaCu₃Ti₄O₁₂陶瓷.XRD证实其CaCu₃Ti₄O₁₂相;SEM观察到明显的晶粒晶界结构,晶界区亦由小晶粒构成;结合EDS结果,判定晶界区小晶粒为CuO.在较宽的温度范围内,CaCu₃Ti₄O₁₂陶瓷的介电常数保持在10⁵左右;当频率为10³ Hz温度小于150 K时,介电常数迅速下降.在173—373 K温度范围内,通过其I-V特性,得到CaCu₃Ti₄O₁₂陶瓷直流电导随温度的变化：直流电导与温度的关系可分为三部分,对应的活化能分别为0.681 eV,0.155 eV和0.009 eV,这与CuO陶瓷直流电导活化能一致.可以认为晶界区的CuO小晶粒在CaCu₃Ti₄O₁₂陶瓷的直流电导中占主导,这为解释CaCu₃Ti₄O₁₂陶瓷反常的介电性能提供了新的思路. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 微观结构 直流电导 介电特性     

CaCu3Ti4O12 陶瓷松弛损耗机理研究

CaCu₃Ti₄O₁₂介电损耗较大且损耗机理尚不明确, 因此限制了其应用.本文采用固相法和共沉淀法合成CaCu₃Ti₄O₁₂陶瓷, 利用宽带介电温谱研究在交流小信号作用下, 双Schottky势垒耗尽层边缘深陷阱的电子松弛过程、 载流子松弛过程以及CaCu₃Ti₄O₁₂陶瓷的介电损耗性能. 研究发现, 在低频下以跳跃电导和直流电导的响应为主, 而高频下主要为深陷阱能级的松弛过程所致, 特别是活化能为0.12 eV的深陷阱浓度, 这是决定CaCu₃Ti₄O₁₂陶瓷高频区介电损耗的重要因素.降低直流电导, 有利于降低低频区介电损耗; 而高频区介电损耗的降低, 需要降低深陷阱浓度或增大晶粒尺寸. 共沉淀法制备的CaCu₃Ti₄O₁₂陶瓷, 有效降低直流电导及控制深陷阱浓度, 介电损耗降低明显. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 介电损耗 松弛过程 Schottky势垒     

CaCu3Ti4O12陶瓷的介电特性与弛豫机理

本文采用Novocontrol宽频介电谱仪在-100 ℃–100 ℃温 度范围内、0.1 Hz–10 MHz频率范围内测量了表面层打磨前 后CaCu₃Ti₄O₁₂陶瓷的介电特性, 分析了CaCu₃Ti₄O₁₂陶瓷的介电弛豫机理. 首先, 基于对宏观“壳-心”结构的定量分析, 排除了巨介电常数起源于表面层效应的可能性; 其次, 基于经典Maxwell-Wagner夹层极化及其活化能物理本质的分析, 排除了巨介电常数起源于经典Maxwell-Wagner极化的可能性; 最后, 依据晶界Schottky势垒与本征点缺陷的本质联系, 提出了巨介电常数起源于Schottky势垒边界陷阱电子弛豫的新机理. 陷阱电子弛豫机理反映了CaCu₃Ti₄O₁₂陶瓷本征点缺陷、 电导、介电常数之间的本质关系. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 介电弛豫 Schottky势垒 点缺陷     

Fe掺杂CaCu3Ti4O12陶瓷的介电性能与弛豫特性研究

采用固相反应法制备了CaCu₃Ti_4-xFe_xO₁₂(0≤x≤0.2)陶瓷，通过X射线衍射、扫描电子显微镜、介电频谱和阻抗谱等手段研究了Fe对CaCu₃Ti₄O₁₂陶瓷的结构和介电性能的影响.研究发现：CaCu₃Ti_4-xFe_{x关键词： 巨介电常数 双阻挡层电容模型 界面极化}     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

CaCu3Ti4O12-MgTiO3陶瓷的介电性能与I-V非线性特征

采用固相反应法制备了一系列CaCu₃Ti₄O₁₂-xMgTiO₃(x = 0, 0.25, 0.5, 1.0)复相陶瓷,研究了MgTiO₃掺杂对CaCu₃Ti₄O₁₂(CCTO)陶瓷相结构、显微组织、介电性能和I-V非线性特征的影响.研究发现:MgTiO₃掺杂不仅使CC 关键词： I-V非线性系数')" href="#">I-V非线性系数 巨介电常数 压敏电压     

添加Nb对CaCu3Ti4O12陶瓷介电性能的影响

采用固相反应法制备了CaCu₃Ti_4-xNb_xO₁₂(x=0，0.01，0.04，0.08，0.2)陶瓷，样品在x取值范围内形成了连续固溶体.在40Hz—110MHz频率范围对样品进行了介电频谱分析，实验结果表明，与纯CaCu₃Ti₄O₁₂不同，含Nb试样除了在频率大于10kHz范围内出现的德拜弛豫 关键词： 巨介电常数 德拜弛豫 阻挡层电容 等效电路     

巨介电常数氧化物CaCu3Ti4O12的介电和阻抗特性

采用固相烧结法合成了单相巨介电常数氧化物CaCu₃Ti₄O₁₂（CCTO）.用阻抗分析仪分析了10—420 K温度范围内的介电频谱和阻抗谱特性,并结合ZVIEW软件进行了模拟.结果表明：温度高于室温时,频谱出现两个明显的弛豫台阶,低频弛豫介电常数随温度升高而显著增大,表现出热离子极化特点;温度低于室温时,频谱表现出类德拜弛豫,且高、低平台介电常数值基本不随温度变化,表现出界面极化特点和较好的温度稳定性.频谱中依次出现的介电弛豫对应于阻抗谱中 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 介电频谱 阻抗谱 Cole-Cole半圆弧     

CaCu3Ti4O12陶瓷的微观结构和电学性能

利用传统的固相反应工艺，在不同的烧结温度下制备了一系列的CaCu₃Ti₄O₁₂陶瓷样品，考察了其微观结构以及介电和复阻抗方面的电学性质.研究发现这些样品在微观结构方面可分为三种类型，高介电性与微观结构有着密切的关联性.室温下，样品的低频介电常数随陶瓷晶粒尺寸的增大而提高.随着测试温度的升高，不同微观结构类型的样品呈现出不同的电学性质的变化，但其中也存在着一些相同的特征.高温下，介电频谱呈现出一个低频介电响应和两个类Debye型弛豫色散，复阻抗谱呈现出三个Cole-Cole半圆弧.将实验上观测到的电学性质的起因归于陶瓷多晶微结构中的晶畴、晶界和晶粒内的缺陷. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 微观结构 电学性质     

第一性原理研究Mn和Cu掺杂六钛酸钾(K_2Ti_6O_(13))的电子结构和光学性质

六钛酸钾(K_2Ti_6O_(13))是宽带隙半导体光催化材料,只能响应波长较短的紫外光.为了使K_2Ti_6O_(13)对可见光响应,本文采用第一性原理方法,研究过渡金属Mn和Cu掺杂改性后K_2Ti_6O_(13)的电子结构和光学性质.计算结果表明:Mn,Cu掺杂后K_2Ti_6O_(13)禁带中出现了杂质能级,这些杂质能级由O 2p和Ti 3d与Mn 3d或Cu 3d态杂化而成.对于Mn掺杂的K_2Ti_6O_(13),其带隙值变小,位于能带中间的杂质能级可作为电子跃迁的桥梁,从而实现了对可见光的吸收.对于Cu掺杂的K_2Ti_6O_(13),其带隙值虽略有增大,但是若考虑将与价带相连的杂质能级,带隙值将大大减小,且此杂质能级可抑制光生载流子的复合,使得掺杂后K_2Ti_6O_(13)吸收带边红移至可见光区并在可见光范围内吸收强度明显增强.总的而言,Mn,Cu的掺杂实现了钛酸钾对可见光的吸收,同时Cu掺杂的效果要优于Mn掺杂的效果.研究结果对K_2Ti_6O_(13)在光催化领域上的应用具有重要的意义.     

Dielectric properties and ac-conductivity analysis of Bi3.25La0.75Ti3O12 ceramic using impedance spectroscopy

Investigations have been performed on lanthanum-modified layered ferroelectric bismuth titanate for composition Bi_3.25La_0.75Ti₃O₁₂ (BLT) using impedance spectroscopy to understand the role of microstructure on the dielectric properties of this important material. A wide range of frequency and a wide range of temperature passing through the Curie point were chosen for the measurement. The frequency dependence suggested an interfacial polarization controlled Maxwell–Wagner type relaxation at low frequencies, and the impedance spectrum correlated with the mathematical fitting indicated the presence of two types of interfaces, which were attributed to the metallurgical boundaries and the twinned planes parallel to the bismuth oxide layers inherent to the crystal structure within the metallurgical grains. A careful analysis of the dielectric properties, particularly the ac-conductivity analysis revealed that the grain boundaries did also follow their own Jonscher-like relaxation, and the overall relaxation of the sample changed to a purely grain boundary-limited response at low frequency to a pure grain-limited response at higher frequencies. And overall admittance of the ceramic sample neither follow unmodified nor modified Jonscher's law rather its behaviour can be well described by series addition of Jonscher's admittance corresponding to grain boundary and grain. It was demonstrated that the frequency response of the ac conductivity was related to the microstructure exactly in the same way as any other dielectric function, like the impedance or dielectric constant, a fact, which is not much emphasized in the open literature.     

Lu2Ti2O7和Lu2TiO5陶瓷材料的Kr离子辐照损伤研究

钛酸盐因其优异的物理化学性能，可作为高放射性核废物（HLW）和锕系元素（钚）的重要候选固化材料之一。采用传统的陶瓷烧结工艺制备了多晶的Lu₂Ti₂O₇和Lu₂TiO₅陶瓷材料。在室温下，用800 keVKr2+对两种材料进行辐照，辐照后的样品采用GIXRD进行表征，观察到两种样品都经历了先肿胀、然后再发生非晶相变的过程。不同的是Lu₂Ti₂O₇的晶格肿胀程度大于Lu₂TiO₅。另外，Lu₂TiO₅样品的辐照到2×10₁₄ ions/cm₂时非晶含量达95.54%，而Lu₂Ti₂O₇样品在此剂量下非晶含量只有74.66%。通过第一性原理计算了Lu₂Ti₂O₇晶体的晶格肿胀随反位浓度的变化关系，结果表明，Lu₂Ti₂O₇出现非晶前的晶格肿胀主要由阳离子反位导致，而Lu₂TiO₅是无序的萤石结构，其辐照所导致的晶格肿胀不含阳离子反位的贡献，晶格肿胀程度较低。     

Synthesis, electrical and electromechanical properties of a tungsten-bronze ceramic oxide: Pb0.68K0.64Nb2O6

A tungsten-bronze ceramic oxide, Pb_0.68K_0.64Nb₂O₆, has been prepared by a standard solid-state reaction technique. Compound formation and phase identification has been confirmed by X-ray diffraction (XRD) studies. The dielectric permittivity and the loss tangent of the sample have been measured in a frequency range 45 Hz–5 MHz and a temperature range 35–590 °C. Electrical properties of the material were studied using an impedance spectroscopic technique. Detailed analysis of the impedance spectrum suggested that the electrical properties of the material are strongly temperature dependent. The Nyquist plots clearly showed the presence of bulk and grain boundary effect in the compound. The imaginary part of modulus at different temperatures shows a relaxation peak and its position shifts to higher frequency with increase in temperature. This suggests a temperature-dependent relaxation. The frequency dependent ac conductivity at different temperatures indicated that the conduction process is thermally activated process.     

Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

探索基于人工超晶格LaFeO3-YMnO3和自然超晶格n-LaFeO3-Bi4Ti3O12薄膜多铁性

基于纳米尺寸下复合铁电材料和反铁磁性材料是一个探索多铁性材料有效的方法. 利用激光脉冲沉积制备出LaFeO₃-YMnO₃人工超晶格和掺入不同层LaFeO₃, BiFeO₃的Bi₄Ti₃O₁₂的外延薄膜. 通过系统的X射线衍射、透射电子显微术、扫描透射电子显微术下的能量损失谱表征证明这些样品具有原子尺寸上清晰的界面和完整的层状结构. 磁性测试证明这些材料具有亚铁磁性. 特别是在0.5和1.5LaFeO₃-Bi₄Ti₃O₁₂中的亚铁磁性甚至能保持到室温. 就铁电性而言, 铁电性测试显示出LaFeO₃-YMnO₃和插入BiFeO₃的Bi₄Ti₃O₁₂样品中存在较大的漏电流, 而在0.5LaFeO₃-Bi₄Ti₃O₁₂样品中存在铁电性. 因此在0.5LaFeO₃-Bi₄Ti₃O₁₂中能够实现亚铁磁和铁电共存. 其次发现当掺入多层的钙钛矿(3层SrTiO₃或2.5层LaFeO₃)后, Bi₄Ti₃O₁₂ 的层状结构将出现结构失稳现象. 这些工作对于利用纳米复合开发新颖多铁性提供一些实例.     

SrBi4Ti4O15的化学键性质和铁电性研究

通过原子环境计算方法分析了正交相SrBi₄Ti₄O₁₅晶体内的键络结构、各原子的空间配位数及局域团簇结构. 在此基础上, 结合晶体分解理论将SrBi₄Ti₄O₁₅晶体分解为多个二元赝晶体, 根据化学键介电理论计算得到各赝晶体所对应化学键的有效价电子密度、离子性等化学键性质. 通过键偶极矩建立了铁电体自发极化强度与化学键性质之间的关系, 求得正交相SrBi₄Ti₄O₁₅沿a轴方向的自发极化强度为28.03 μC/cm², 与实验结果和其他理论计算值符合较好.     

Infrared optical response of YBa2Cu3O7 and PrBa2Cu3O7 An ellipsometric study

Ellipsometry was used to study (110) and (001) oriented films of YBa₂Cu₃O₇ and PrBa₂Cu₃O₇ in the mid-and near-infrared spectral regions. Below a photon energy of 0.1 eV, the in-plane component of the dielectric tensor of YBa₂Cu₃O₇ is dominated by a Drude term with a squared plasma energy of (3.0 ± 0.3) eV². This “oscillator strength”, and the Lorentzian broadening energy of (0.104 ± 0.005) eV at room temperature, are confirmed by the changes induced in Pr-substituted material, and by low-temperature measurements in the near-infrared. The deviation from the Drude behavior observed above 0.1 eV is accounted for by a broad absorption band with an oscillator strength of (3.6 ± 0.1) eV² in YBa₂Cu₃O₇ which shifts to higher energies and takes over almost all of the oscillator strength of the Drude term when Y is substituted by Pr. The response to electric fields perpendicular to the planes is much weaker, with an upper bound of 0.63 eV² for the squared plasma energy. The in-plane loss function computed from the measured dielectric function follows the Drude-like lineshape, modified by the bound-state absorption band, down to the lowest energy reached in our measurements (0.058 eV).