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1.
《Ceramics International》2016,42(13):14749-14753
Sm2(Zr1–xTix)2O7 (0≤x≤0.15) ceramics have been fabricated by pressureless-sintering method at 1973 K for 10 h in air. The influence of TiO2 doping on microstructure and thermo-optical properties of Sm2(Zr1–xTix)2O7 ceramics is investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy measurements. The partial substitution of Ti4+ for Zr4+ results in a significant increase in emissivity at low wavelengths contrasted with undoped Sm2Zr2O7. Sm2(Zr0.85Ti0.15)2O7 ceramic exhibits a high emissivity of above 0.70 at 1073 K in a wavelength range of 3–16 µm, where the highest value at this temperature is more than 0.90 especially in the wavelength range of 9–14 µm. FT-IR spectra and optical absorption spectra unveil the mechanisms of enhanced emissivity in Sm2(Zr1–xTix)2O7 (0.05≤x≤0.15) ceramics in the intermediate infrared range, especially at the wavelengths of 3–8 µm, due to Ti4+ ion substitution for Zr4+ ion.  相似文献   

2.
《Ceramics International》2019,45(13):15898-15905
Recently, the (Pb,La)(Zr,Ti)O3 antiferroelectric materials with slim-and-slanted double hysteresis loops have been widely drawn in the application of advanced pulsed power capacitors due to its low strain characteristic. In this work, the energy storage properties of (Pb0.895La0.07)(ZrxTi1-x)O3 ceramics with different Zr contents are researched thoroughly because the substitution of Ti4+ by Zr4+ can reduce the tolerance factor t, enhancing the antiferroelectricity. The polarization-electric field hysteresis loops of the PLZT ceramics become slimmer with increasing Zr content. The highest recoverable energy storage density (Wre) of 3.38 J/cm3 and ultrahigh energy efficiency (η) of 86.5% are achieved in (Pb0.895La0.07)(Zr0.9Ti0.1)O3 ceramic. The (Pb0.895La0.07)(Zr0.9Ti0.1)O3 ceramic also hold fairly thermal stability (relative variation of Wre is less than 28% over 30 °C-120 °C), excellent frequency stability (10–1000 Hz) and good fatigue endurance. These results demonstrate that the (Pb0.895La0.07)(Zr0.9Ti0.1)O3 ceramic can be a desirable material for dielectric energy storage capacitors, especially for pulse power technology.  相似文献   

3.
《Ceramics International》2019,45(16):20197-20201
Microwave ceramics are an important classes of materials that are used in microwave communication systems, especially in the area of 5G wireless communication and the internet of things. In this work, to improve the Q×f values and enhance the temperature stability of Ni0.4Zn0.6TiNb2O8 ceramics, the influence of the substitution of Zr4+ ions at the Ti site in Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics was investigated. The Q×f value increases from 32114 GHz to 45733 GHz and the τf value changes from 38.1 ppm/°C to 3 ppm/°C with a slight Zr4+ ion substitution (x = 0.1). Meanwhile, the sample with the Zr4+ ion substitution (x = 0.3) that was sintered at 1120 °C shows a very high Q×f value of 92078 GHz. Furthermore, the XRD results reveal that the phase and structure of the Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics change with the different Zr4+ ion contents. The substitution of the Zr4+ ion can promote the sintering process for the Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics and restrain the Ni0.5Ti0.5NbO4 phase formation. The results obtained from Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics can offer useful information for the study and application of high-frequency microwaves.  相似文献   

4.
《Ceramics International》2017,43(15):11699-11709
The (1 − x)Pb(Zr0.70Ti0.30)O3xBiMn2O5 ceramics (PZT-BM), where x = 0, 0.02, 0.055, 0.11, 0.15, 0.22 and 1, were studied. We determined how addition of nonpolar BM influenced electrical properties of the ferroelectric PZT ceramics. Impedance spectroscopy measurements in broad frequency and temperature ranges were performed and several contributions to impedance response were identified. A crossover to the relaxor state was observed in the PZT-BM ceramics by doping with Bi and Mn ions. The relaxation times for the electric conductivity relaxation and dipole relaxation were estimated from electric modulus representation of the data. Activation energy values of the conductivity process, estimated for T > 510 K, decreased from 0.82 to 0.37 eV when BM content increased. The occurrence of the high-frequency dipole relaxation was assigned to the charge transfer of Ti3+/Ti4+, Zr3+/Zr4+ and Mn3+/Mn4+ ions. Occurrence of the ferroelectric relaxor features were deduced from the non-Arrhenius dependence of the relaxation times. Superposition of the relaxor features and electric relaxations provides high value permittivity (ε′ > 1000) in wide temperature range (~ 250–573 K). This effect corresponds to the disorder and precipitation of ions that were shown using x-ray photoelectron spectroscopy and the time of flight–secondary ion mass spectrometry.  相似文献   

5.
In order to ascertain the structural relationship of zirconolite and pyrochlore for their potential application in HLW immobilization, the Gd-doped zirconolite-pyrochlore composite ceramics (Ca1-xZr1-xGd2xTi2O7) were systematically synthesized with x?=?0.0–1.0 by traditional solid-phase reaction method. The phase evolution and microstructure of the as-prepared samples have been elucidated by XRD and Rietveld refinement, Raman spectroscopy, BSE-EDS and HRTEM analysis. The results showed that zirconolite-2M, zirconolite-4M, perovskite and pyrochlore, four phases were identified in Ca1-xZr1-xGd2xTi2O7 system and could be coexisted at x?=?0.4 composition. With the increase of Gd3+ substitution, the phase evolution was followed by zirconolite-2M→zirconolite-4M→pyrochlore. It is illustrated that the phase transformation from zirconolite-2M to zirconolite-4M was promoted by the preferential substitution of Gd3+ for Ca2+. And the solubility of Gd3+ in zirconolite-2M, zirconolite-4M and pyrochlore increased in sequence. The chemical stability test was also measured by the PCT leaching method. The normalized elemental release rates of Ca, Zr, Ti and Gd in Ca1-xZr1-xGd2xTi2O7 system were fairly low and in the range of 10?6?10?8 g?m?2 d?1, which indicated a potential ceramics composite ensemble of CaZrTi2O7-Gd2Ti2O7 system for nuclear HLW immobilization.  相似文献   

6.
《Ceramics International》2022,48(7):9602-9609
The (La0.2Gd0.2Y0.2Yb0.2Er0.2)2(Zr1-xTix)2O7 (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti4+ content. The average thermal expansion coefficients of the (La0.2Gd0.2Y0.2Yb0.2Er0.2)2(Zr1-xTix)2O7 high-entropy ceramics range from 10.65 × 10?6 K?1 to 10.84 × 10?6 K?1. Importantly, the substitution of Zr4+ with Ti4+ resulted in a remarkable decrease in thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2(Zr1-xTix)2O7 high-entropy ceramics. It reduced from 1.66 W m?1 K?1 to 1.20 W m?1 K?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.  相似文献   

7.
《Catalysis communications》2007,8(11):1772-1780
This study has addressed the effect of surface sites (as Ti4+ and Ti3+) of TiO2 support on the formation of the cobalt-support compound on Co/TiO2 catalyst. A 20% cobalt was prepared on each TiO2 support having the different Ti4+/Ti3+ ratios covering on the surface (1.2, 1.3, 1.4, and 1.6). It can be concluded that the non-reducible compound as a Co-SCF preferred to form on the Co/TiO2 catalyst when the most proportional site of surface TiO2 became Ti4+. This is because the migration of cobalt cluster, which plays the significant role for creating Co-SCF, can be promoted by the increasing of Ti4+ sites resulting in the decrease of cobalt dispersion. The hyperfine patterns of ESR spectra demonstrated that the Co0(HxTiOy) was the simple chemical form of Co-SCF formed after standard reduction. Moreover, the structure of Co-SCF changed to be a higher non-uniform structure when the number of Ti4+ site on TiO2 surface increased. The possible mechanism to form this compound has also been discussed.  相似文献   

8.
《Ceramics International》2019,45(13):16450-16457
The study underlines the impact of Ti4+ substitution in Gd2Zr2O7 for applications in thermal barrier coatings (TBC). Depending on the Ti4+ content, two different crystal structures of Gd2Zr2O7 namely pyrochlore and fluorite were determined. Ti4+ substitutions in the increasing order induced a gradual contraction of Gd2Zr2O7 unit cell; however, with the accomplishment of concentration dependent crystal structures of either single phase pyrochlore or mixtures of pyrochlore and fluorite. Absorption measurements enunciated the enhanced infra-red reflectance behaviour of Gd2Zr2O7 due to Ti4+ substitutions. A gradual increment in the concentration of Ti4+ substitutions in Gd2Zr2O7 envisaged a simultaneous porous to dense morphological features, which reflected in the resultant mechanical data. Hot corrosion studies ensure the critical role of Ti4+ to retain the crystal structure of Gd2Zr2O7.  相似文献   

9.
《Ceramics International》2016,42(13):14431-14437
Lead zirconate titanate Pb(ZrxTi1−x)O3 films with various Zr/Ti ratios of 20/80, 40/60, 52/48, 60/40 and 80/20 are deposited on highly dense CoFe2O4 ceramics using a simple chemical solution deposition. All Pb(ZrxTi1−x)O3 films are polycrystalline and have no preferential orientations. The dielectric, ferroelectric, piezoelectric and magnetoelectric properties strongly depend on the Zr/Ti ratio. And the Pb(ZrxTi1−x)O3 films with a Zr/Ti ratio close to morphotropic phase boundary exhibit best properties, whose magnetoelectric coefficient is over 1.5 times larger than those of other Zr/Ti ratios. The introduction of a PbO seeding layer between the Pb(Zr0.52Ti0.48)O3 films and CoFe2O4 substrates facilitates the (100)-texture. Therefore, the magnetoelectric coefficient was enhanced by 1.5 times. The further improvement of the magnetoelectric coupling could be anticipated by fabricating Pb(Zr0.52Ti0.48)O3 films with more or absolute (100)-texture and using conductive interfacial layer between two phases.  相似文献   

10.
《Ceramics International》2022,48(13):18730-18738
A series of new negative temperature coefficient (NTC) thermal materials based on (Ba0.85Ca0.15)1-xCex/2(Zr0.1Ti0.9)O3 (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba0.85Ca0.15)1-xCex/2(Zr0.1Ti0.9)O3 ceramics, which were composed of solid solution based on the BaTiO3 phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B300/1200 (1.21 × 104–1.13 × 104 K) and the activation energy Ea300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce4+ and Ce3+ provided by high levels of Ce doping. (Ba0.85Ca0.15)1-xCex/2(Zr0.1Ti0.9)O3 ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba0.85Ca0.15)1-xCex/2(Zr0.1Ti0.9)O3 ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.  相似文献   

11.
The applications of antiferroelectric (AFE) materials in miniaturized and integrated electronic devices are limited by their low energy density. To address the above issue, the antiferroelectricity of the reinforced material was designed to improve its AFE-ferroelectric (FE) phase transition under electric fields. In this present study, the composition of Zr4+ (0.72 Å) and Ti4+ (0.605 Å) at B-site of Pb0.97La0.02(ZrxSn0.05Ti0.95-x)O3 ceramics with orthogonal reflections are synthesized via the tape-casting method. These ceramics are modified to enhance their antiferroelectricity by reducing their tolerance factor. A recoverable energy storage density Wrec 12.1 J/cm3 was obtained for x = 0.93 under 376 kV/cm, which is superior value than reported until now in lead-based energy storage systems. Moreover, the discharge energy density can reach 10.23 J/cm3, and 90 % of which can be released within 5.66 μs. This work provides a new window and potential materials for further industrialization of pulse power capacitors.  相似文献   

12.
Zr4+/Ti4+‐codoped LiNbO3 plates were prepared by local codiffusion of stacked ZrO2 and Ti metal films coated onto Z‐cut congruent LiNbO3 substrates in wet O2 at 1060°C. The metal and oxide films have different thicknesses and coating sequences. After diffusion, the Zr4+ doping effect on the refractive index of LiNbO3 and the Li2O out‐diffusion issue were studied by the prism coupling technique. The codiffusion characteristics of Zr4+ and Ti4+ were studied by secondary ion mass spectrometry. The results show that the Zr4+ doping has little contribution to the refractive index of the crystal. Li2O out‐diffusion is not measurable. In the Zr4+‐only diffusion case, the diffusivity of Zr4+ is four times smaller than that of Ti4+. In the Zr4+/Ti4+ codiffusion case, the Ti4+ codiffusion assists the Zr4+ diffusion. The Zr4+ diffusivity increases linearly by two more times with the increase in initial Ti film thickness from 0 to 200 nm. On the other hand, the Zr4+ affects the Ti4+ diffusion little. Neither the ZrO2 film thickness nor the coating sequence of Ti metal and ZrO2 oxide films influences the diffusivity of the two ions. All the codiffusion characteristics are explained. A Zr4+/Ti4+ codiffusion model is suggested that consists of two independent diffusion equations with a Zr4+ diffusivity dependent of Ti4+ concentration and a constant Ti4+ diffusivity. In addition, the existence of a waveguide in the Zr4+/Ti4+‐codoped layer is verified experimentally, and the optical‐damage‐resistant feature of the waveguide is verified by two‐beam hologram recording experimental results.  相似文献   

13.
《Ceramics International》2017,43(10):7408-7414
The effect of Ti4+ substitution on the crystal structure and magnetic properties of the Bi0.8Ba0.2FeO3 ceramic nanoparticles was investigated. Bi0.8Ba0.2Fe1−xTixO3 (x=0, 0.05, 0.10, 0.15 and 0.20) ceramics have been prepared by tartaric acid modified sol-gel method. Rietveld refinement of the XRD profile pattern of Bi0.8Ba0.2FeO3 ceramic revealed the formation of pseudo-cubic (Pm3m) phase and confirms structural distortion on incorporation of Ti4+ ions, which consequently transform pseudo-cubic (Pm3m) structure to tetragonal (P4mm) structure. The saturation magnetization increases appreciably on Ti4+ ions substitution in Bi0.8Ba0.2FeO3 and is found to be 0.57 emu/g for Bi0.8Ba0.2Fe0.95Ti0.05O3 ceramic. The increase in the magnetization by the substitution of non-magnetic Ti4+ ions has been ascribed to crystal structure modification made by the Ti4+ ions. However, a sudden decrease in the magnetization has been observed for Bi0.8Ba0.2Fe0.8Ti0.2O3 ceramic nanoparticles. The prominent Ti (3d) – O (2p) hybridization would stabilize the ferroelectric distortion and consequently reduce the magnetization. Scanning Electron Microscope (SEM) image of Bi0.8Ba0.2Fe0.8Ti0.2O3 ceramic sample revealed the formation of dense microstructure with uniform grains size.  相似文献   

14.
The properties of ZrO2 co-stabilized by CeO2 and TiO2 ceramic bulks were investigated for potential thermal barrier coating (TBC) applications. Results showed that the (Ce0.15Tix)Zr0.85-xO7 (x?=?0.05, 0.10, 0.15) compositions with single tetragonal phase were more stable than the traditional 8YSZ at 1573?K. These compositions also showed a large thermal expansion coefficient (TEC) and a high fracture toughness, which were comparable to those of YSZ. However, the phase stability, fracture toughness and sintering resistance of the CeO2-TiO2-ZrO2 system showed a decline tendency with the increase of TiO2 content. The TEC of the ceramic bulks decreased with increase of TiO2 content as well because the crystal energy was enhanced with increasing substitution of Zr4+ by smaller Ti4+. The (Ce0.15Ti0.05)Zr0.8O2 had the best comprehensive properties among the (Ce0.15Tix)Zr0.85-xO2 compositions as well as a low thermal conductivity. Therefore, it can be explored as a TBC candidate material for high-temperature applications.  相似文献   

15.
The (micro)structural and electrical properties of undoped and Er3+-doped BaTi0.85Zr0.15O3 ceramics were studied in this work for both nominal Ba2+ and Ti4+ substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 °C for 3 h. For those materials prepared following the donor-type nominal Ba1?xErx(Ti0.85Zr0.15)O3 composition, especially, Er3+ however showed a preferential substitution for the (Ti,Zr)4+ lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O3?δ-like system, with a solubility limit below but close to 3 cat.% Er3+. The overall phase development is discussed in terms of the amphoteric nature of Er3+, and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials’ grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er3+ content.  相似文献   

16.
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 CaCu3Ti3.8-xZrxNb0.2O12 (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.  相似文献   

17.
Pyroelectrics are attracting increasing attention because they enable pyroelectric generators to extract energy from low-gradient-temperature heat for portable electronic devices. High pyroelectric coefficient around room temperature is essential for high-performance energy harvesters, which, unfortunately, is only commonly achieved in lead-based ferroelectrics. Herein we report a high room temperature pyroelectric response of 27.2 × 10?4 C m-2 K-1 in 0.94(Bi0.5Na0.5)TiO3-0.06Ba(Ti0.75Zr0.25)O3 lead-free ceramics by modulating the Zr4+/Ti4+ ratio to tune the ferroelectric-relaxor antiferroelectric-like phase transition point to around ambient temperature, whose pyroelectric response is one order of magnitude higher than that of the sample without Zr and even comparable to those of lead-containing pyroelectrics. The theoretical analysis revealed that introduced Zr4+ could incorporate into the TiO6 octahedral lattices and break the long-range translational symmetry of BaTiO3 lattices, resulting in the reduction of B-site ion displacement activation energy and transition point of ferroelectric-relaxor antiferroelectric-like phase, giving rise to a pronounced room-temperature pyroelectric effect in BNT-BZT.  相似文献   

18.
In order to find materials with increased specific electrical energy, especially for impact fuzes, the irreversible conversion of mechanical to electrical energy in ferroelectric ceramics of the Pb(Zr1-xTix) O3 type with a considerable proportion of zirconium is studied. The depolarization of the ceramics is measured for shock compressions between 0 and 30 kbar. The maximum electrical energy, obtained at about 18 kbar, is of the order of 1.8 J/cm3 with Pb(Zr0.965Ti0.035)03 + 1% Nb2O5 and of the order of 0.8 J/cm3 with a Pb(Zr0.54Ti0.46)03 + 1% Nb205. As an example for application, the initiation of a 3.5 ω bridge wire PETN detonator is described.  相似文献   

19.
Li2Mg3Zr1?xTixO6 (x = 0, 0.2, 0.4, 0.6, 0.8, 1) ceramics were prepared via a solid-state reaction method. Crystal structures, sintering behaviors, micro-structures and microwave dielectric properties of Li2Mg3Zr1?xTixO6 (0 ≤ x ≤ 1) ceramics were investigated by XRD, SEM and chemical bond theory. XRD results showed that a single phase with the rock-salt structure was formed in all ranges. On the basis of the Rietveld refinement and chemical bond theory, several intrinsic parameters were calculated and connections between intrinsic parameters and microwave dielectric properties were investigated. The substitutions of Ti4+ for Zr4+ obviously increased the relative density and improved the quality factors. Variations of εr could be explained by changes of the polarizability. Q·f values showed the similar trend with the packing fractions, average bond valences and lattice energy of Zr–O bonds. τ? values significantly correlated with the bond energy of Zr–O bonds.  相似文献   

20.
The structural and electrical properties of xPb(Mg1/3Nb2/3)O3–(1−x)Pb(Zr,Ti)O3 ternary ceramic system with the composition near to the morphotropic phase boundary (MPB) and of xPb(Mg1/3Nb2/3)O3–(1−x)Pb(Zr0.47Ti0.53)O3 ceramics were investigated as a function of the Pb(Mg1/3Nb2/3)O3 (PMN) content by scanning electron microscopy (SEM), X-ray diffraction (XRD), dielectric and piezoelectric spectroscopy and polarization-electric field measurement technique. Studies were performed on the samples prepared by a columbite precursor method for x=0.125, 0.25 and 0.5. Room temperature SEM investigations revealed common trends in the grain structure with increasing PMN content. XRD analysis demonstrated that with increasing PMN content in xPb(Mg1/3Nb2/3)O3–(1−x)Pb(Zr0.47Ti0.53)O3, the structural change occurred from the tetragonal to the pseudocubic phase at room temperature. Changes in the dielectric and ferroelectric behavior were then related to these structural trends and further correlated with the piezoelectric properties. The results of ferroelectric hysteresis measurements, in conjunction with dielectric spectroscopy, demonstrated an intermediate, relaxor-like behavior between normal and relaxor ferroelectrics in the solid solution system, depending on the PMN content.  相似文献   

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