Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Phase,domain, and microstructures in Sr2+ substituted low-temperature sintering PZT-based relaxor ferroelectrics

The Ag-Pd internal electrode of multilayer piezoelectric ceramics needs to be sintered below 1000°C, and lead wires and components need to be welded with lead-free solder at 260°C. PNN–PMW–PZT–xSr piezoelectric ceramics with high Curie temperature (T_c > 260°C) were synthesized at a low sintering temperature (960°C) to meet the requirements of multilayer piezoelectric devices. The relationship between structures (phase, domain, and microstructures) and electrical properties (piezo/ferroelectric properties, and dielectric relaxation) in the Sr²⁺ substituted ceramics was investigated. Rietveld refinement and Raman spectra show that Sr²⁺ substitution can cause the phase change and increase the force constant of [BO₆] octahedron. The piezoelectric response increases with increasing the content of the tetragonal phase (CTP) in the rhombohedral-tetragonal (R-T) coexisted ceramics. The ceramics with 0.6 mol% Sr²⁺ substitution have minimum activation energy for domain wall movement (E_a) of 0.0362 eV which favors the formation of nanometer-sized domains, and possess excellent electrical properties (d₃₃ = 623 pC/N, d₃₃^* =783 pm/V, T_c =295°C). The higher the CTP, the lower the E_a. The lower E_a favors the rotation of polarization direction and extension, and is beneficial to the generation of the nanometer-size domains, resulting in high piezoelectric properties.     

Structural dependence of microwave dielectric properties in ilmenite-type Mg(Ti1-xNbx)O3 solid solutions by Rietveld refinement and Raman spectra

Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were prepared by the conventional solid-state reaction method. The phase composition, sintering characteristics, microstructure and dielectric properties of Ti⁴⁺ replacement by Nb⁵⁺ in the formed solid solution Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were systematically studied. The structural variations and influence of Nb⁵⁺ doping in Mg(Ti_1-xNb_x)O₃ were also systematically investigated by X-ray diffraction and Raman spectroscopy, respectively. X-ray diffraction and its Rietveld refinement results confirmed that Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics crystallised into an ilmenite-type with R-3 (148) space group. The replacement of the low valence Ti⁴⁺ by the high valence Nb⁵⁺ can improve the dielectric properties of Mg(Ti_1-xNb_x)O₃ (x = 0–0.09). This paper also studied the different sintering temperatures for Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics. The obtained results proved that 1350 °C is the best sintering temperature. The permittivity and Q × f initially increased and then decreased mainly due to the effects of porosity caused by the sintering temperature and the doping amount of Nb₂O₅, respectively. Furthermore, the increased Q × f is correlated to the increase in Ti–O bond strength as confirmed by Raman spectroscopy, and the electrons generated by the oxygen vacancies will be compensated by Nb⁵⁺ to a certain extent to suppress Ti⁴⁺ to Ti³⁺, which was confirmed by XPS. The increase in τ_f from ?47 ppm/°C to ?40.1 ppm/°C is due to the increment in cell polarisability. Another reason for the increased τ_f is the reduction in the distortion degree of the [TiO₆] octahedral, which was also confirmed by Raman spectroscopy. Mg(Ti_0.95Nb_0.05)O₃ ceramics sintered at 1350 °C for 2 h possessed excellent microwave dielectric properties of ε_r = 18.12, Q × f = 163618 GHz and τ_f = ?40.1 ppm/°C.     

Nonlinear dielectric response and positive dielectric tunability in antipolar CaTiSiO5

Dielectric tunability has been extensively investigated in ferroelectric materials, which exhibit a negative tunability of dielectric permittivity in an external electric field. In contrast, positive tunability is rare and has been reported only in a few antiferroelectric materials. We present positive (and negative) tunability in the titanite, CaTiSiO₅. The dielectric property of CaTiSiO₅ was measured up to an extraordinarily high electric field of 40 MV/m. A nonlinear polarization field loop with no hysteresis was obtained. The dielectric permittivity of ε_r ~ 25 increases up to ε_r ~ 40 at 20 MV/m and room temperature. Although titanite has an antipolar structure and is expected to be “antiferroelectric,” its dielectric response in high electric fields up to ~40 MV/m differs from that of conventional antiferroelectrics. We demonstrate that the phase-transition temperature and dielectric tunability could be modulated through the chemical substitution of Ca_1−xLa_xTiSi_1−xAl_xO₅, in which the destabilization of the long-range antipolar order is revealed by transmission electron microscopy analysis. These results indicate that the observed dielectric response to an electric field may originate from the unique features of the antipolar and domain structures in CaTiSiO₅.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

How the biaxially stretching mode influence dielectric and energy storage properties of polypropylene films

The most important polymer film used in commercial capacitors is biaxially oriented polypropylene (BOPP), which could be produced by sequentially or simultaneously biaxial orientation after the melt-extrusion. In order to disclose the influence of the stretching technique on the properties of films, the BOPP films with varied thickness were fabricated by sequential and simultaneous orientation, respectively. Compared to the sequentially biaxially stretched films, the crystal grains in the simultaneously biaxially stretched films are more isotropically dispersed. As temperature increases, all the BOPP films exhibit similar dielectric constant, and the simultaneous films have much lower dielectric loss thanks to the finer blended crystalline and amorphous phases. When the film thickness is smaller than 5 μm, the breakdown field strength, energy density and discharging time of the simultaneous films can be increased by at least 10% comparing to the sequential ones, which is very important for reducing the volume of the film capacitors. All the results suggest the simultaneously biaxial orientation mode shows significant advantages in producing thin BOPP films with better mechanical and electrical properties.     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Characterization of barium titanate reinforced acrylonitrile butadiene rubber composites for flexible electronic applications: influences of barium titanate content

The aim of this study was to develop high dielectric constant flexible polymers with a highly efficient and cost‐effective approach using acrylonitrile butadiene rubber (NBR) as the polymer matrix and barium titanate (BT) as the high dielectric constant filler. The BT powder was synthesized with a solid‐state reaction and was characterized using a particle size analyzer, XRD, SEM and Fourier transform infrared spectroscopy. NBR/BT composites were fabricated using an internal mixer with various BT loadings up to 160 phr. The influence of BT loading on the cure characteristics and mechanical, dynamic mechanical, thermal, dielectric and morphological properties was determined. The incorporation of BT in the NBR matrix shortened scorch time and increased delta torque. The mechanical properties, thermal stability and dielectric constant were greatly improved and increased with BT loading. The results suggest that the reinforcement effect was achieved due to strong hydrogen bonding or polar–polar interactions between NBR matrix and BT filler. This is further corroborated by the good dispersion of BT filler in the NBR matrix observed with SEM imaging. These findings can be applied to produce high‐performance dielectric elastomers. © 2020 Society of Industrial Chemistry     

Surface treatment of titanium dioxide nanopowder using rotary electrode dielectric barrier discharge reactor

Titanium dioxide (TiO2) nanopowder (P-25;Degussa AG) was treated using dielectric barrier discharge (DBD) in a rotary electrode DBD (RE-DBD) reactor.Its electrical and optical characteristics were investigated during RE-DBD generation.The treated TiO2 nanopowder properties and structures were analyzed using x-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR).After RE-DBD treatment,XRD measurements indicated that the anatase peak theta positions shifted from 25.3° to 25.1°,which can be attributed to the substitution of new functional groups in the TiO2 lattice.The FTIR results show that hydroxyl groups (OH) at 3400 cm-1 increased considerably.The mechanism used to modify the TiO2 nanopowder surface by air DBD treatment was confirmed from optical emission spectrum measurements.Reactive species,such as OH radical,ozone and atomic oxygen can play key roles in hydroxyl formation on the TiO2 nanopowder surface.     

Theoretical estimation of dielectric loss of oxide glasses using nonequilibrium molecular dynamics simulations

To theoretically explore amorphous materials with a sufficiently low dielectric loss, which are essential for next-generation communication devices, the applicability of a nonequilibrium molecular dynamics simulation employing an external alternating electric field was examined using alkaline silicate glass models. In this method, the dielectric loss is directly evaluated as the phase shift of the dipole moment from the applied electric field. This method enabled us to evaluate the dielectric loss in a wide frequency range from 1 GHz to 10 THz. It was observed that the dielectric loss reaches its maximum at a few THz. The simulation method was found to qualitatively reproduce the effects of alkaline content and alkaline type on the dielectric loss. Furthermore, it reasonably reproduced the effect of mixed alkalines on the dielectric loss, which was observed in our experiments on sodium and/or potassium silicate glasses. Alkaline mixing was thus found to reduce the dielectric loss.