Structural and dielectric properties,and nonlinear electrical response of the CaCu3-xZnxTi4O12 ceramics: Experimental and computational studies

CaCu_3-xZn_xTi₄O₁₂ ceramics (x = 0, 0.05, 0.10) were successfully prepared by a conventional solid-state reaction method. Their structural and dielectric properties, and nonlinear electrical response were systematically inspected. The X-ray diffraction results indicated that single-phase CaCu₃Ti₄O₁₂ (JCPDS no. 75–2188) was obtained in all sintered ceramics. Changes in the lattice parameter are well-matched with the computational result, indicating an occupation of Zn²⁺ doping ions at Cu²⁺ sites. The overall tendency shows that the average grain size decreases when x increases. Due to a decrease in overall grain size, the dielectric permittivity of CaCu_3-xZn_xTi₄O₁₂ decreases expressively. Despite a decrease in the dielectric permittivity, it remains at a high level in the doped ceramics (~3,406–11,441). Besides retention in high dielectric permittivity, the dielectric loss tangent of x = 0.05 and 0.10 (~0.074–0.076) is lower than that of x = 0 (~0.227). A reduction in the dielectric loss tangent in the CaCu_3-xZn_xTi₄O₁₂ ceramics is closely associated with the enhanced grain boundary response. Increases in grain boundary resistance, breakdown electric field, and conduction activation energy of grain boundary as a result of Zn²⁺ substitution are shown to play a crucial role in improved grain boundary response. Furthermore, the XPS analysis shows the existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, indicating charge compensation due to the loss of oxygen lattice. Based on all results of this work, enhanced dielectric properties of the Zn-doped CCTO can be explained using the internal barrier layer capacitor model.     

Threshold computation for fault detection in linear discrete‐time Markov jump systems

This paper proposes a threshold computation scheme for an observer‐based fault detection (FD) in linear discrete‐time Markovian jump systems. An observer‐based FD scheme typically consists of two stages known as residual generation and residual evaluation. Even information of faults is contained inside a residual signal, a decision of faults occurrence is consequently made by a residual evaluation stage, which consists of residual evaluation function and threshold setting. For this reason, a successful FD strongly depends on a threshold setting for a given residual evaluation function. In this paper, Kalman filter (KF) is used as a residual generator. Based on an accessibility of Markov chain to KF, two types of residual generations are considered, namely mode‐dependent and mode‐independent residual generation. After that threshold is computed in a residual evaluation stage such that a maximum fault detection rate is achieved, for a given false alarm rate. Without any knowledge of a probability density function of residual signal before and after fault occurrence, a threshold is computed by using an estimation of residual evaluation function variance in a fault‐free case. Finally, a detection performance is demonstrated by a numerical example. Copyright © 2013 John Wiley & Sons, Ltd.     

Ge4+ doped CaCu2.95Zn0.05Ti4O12 ceramics: Two-step reduction of loss tangent

CaCu₃Ti₄O₁₂ ceramics have been extensively studied for their potential applications as capacitors in recent years; however, these materials exhibit very large dielectric losses. A novel approach to reducing the dielectric loss tangent in two steps, while increasing the dielectric permittivity, is presented herein. Doping CaCu₃Ti₄O₁₂ with a Zn dopant reduces the loss tangent of the ceramic material from 0.227 to 0.074, which is due to the increase in grain boundary (GB) resistance by an order of magnitude (from 6.3× 10³ to 3.93 × 10⁴ Ω cm). Zn-doping slightly changes the microstructure and dielectric permittivity of the CaCu₃Ti₄O₁₂ ceramic, which reveals that the primary role of the Zn dopant is to tune the intrinsic properties of the GBs. Surprisingly, the addition of the Ge⁴⁺ dopant into the Zn²⁺-doped CaCu₃Ti₄O₁₂ ceramic sample led to a further decrease in the loss tangent from 0.074 to 0.014, due to enhanced GB resistance (3.1 × 10⁵ Ω cm). The grain size increased remarkably from 2–3 μm to 85–90 μm, corresponding to a significant increase in the dielectric permittivity (~1–4 × 10⁴). The large increase in GB resistance is due to the intrinsic potential barrier height at the GBs and the segregation of the Cu-rich phase in the GB region. First-principles calculations revealed that Zn and Ge are preferentially located at the Cu sites in the CaCu₃Ti₄O₁₂ structure. The substitution of the Ge dopant does not hinder the role of the Zn dopant in terms of improving the electrical properties at the GBs. These phenomena are effectively explained by the internal barrier layer capacitor model. This study provides a way of improving the dielectric properties of ceramics for their practical use as capacitors.     

First-principles calculations and experimental study of enhanced nonlinear and dielectric properties of Sn4+-doped CaCu2.95Mg0.05Ti4O12 ceramics

High dielectric permittivity (ε′ ≈ 2000―6900) was accomplished in Sn⁴⁺-doped CaCu_2.95Mg_0.05Ti₄O₁₂ ceramics while retaining a low loss tangent (tanδ ≈ 0.027―0.075). Further, significant improvements in the nonlinear electrical properties, such as high values of the breakdown electric field (E_b ≈ 1.2―1.3 × 10⁴ V cm^?1) and nonlinear coefficient (α ≈ 31), were achieved. In addition, the nonlinear electrical parameters significantly improved, which is consistent with the increase in the electrical resistivities of the grains and grain boundaries due to the decrease in the Cu⁺/Cu²⁺ ratio. According to our first-principles calculations, the Sn atom at the Ti site prefers to be close to the Mg atom at the Cu site, while the oxygen vacancy prefers to be located at large distances from the Sn and Mg co-dopants. This confirms that the dielectric behavior and the nonlinear electrical properties originate from the interface between the grain and grain boundary.