Microstructure and microwave dielectric properties of (1 − x)Ca0.6La0.267TiO3–xCa(Mg1/3Nb2/3)O3 ceramics

(1 ? x)Ca_0.6La_0.267TiO₃–xCa(Mg_1/3Nb_2/3)O₃ ceramics were prepared by a conventional solid-state ceramic route. The microstructure and microwave dielectric properties were investigated as a function of composition and sintering temperature. As the content of Ca(Mg_1/3Nb_2/3)O₃ increased, the temperature coefficient of resonant frequency (τ_f) value decreased gradually. By appropriately adjusting the x value in the present ceramic system, a near-zero τ_f value could be achieved. The appropriate increase of sintering temperature could significantly improve Q·f value by influencing the grain growth. The optimal microwave dielectric properties with a dielectric constant (?_r) of 52.4, Q·f of 36,428 GHz (at 5.8 GHz), and τ_f of 3.4 ppm/°C were obtained for the specimen 0.5Ca_0.6La_0.267TiO₃–0.5Ca(Mg_1/3Nb_2/3)O₃ sintered at 1490 °C for 4 h.     

Dielectric properties of (1−x)La(Mg1/2Ti1/2)O3–xSrTiO3 ceramics

Powders of (1−x)La(Mg_1/2Ti_1/2)O₃–xSrTiO₃ series have been prepared by a non-conventional chemical route based on the Pechini method. Homogeneous solid solutions allowed the sintering of dense and single-phase ceramics for the full composition range (0⩽x<1). Crystal structure of the ceramics was investigated by XRD and several compositional driven structural transformations were observed. The dielectric function of the ceramics was measured at radio, microwave and far infrared (FIR) frequency ranges to help clarifying the relationship between dielectric properties and structure. The FIR data were found to reflect clearly the sequence of structural modifications observed. In order to evaluate the importance of intrinsic mechanisms in the dielectric response at the GHz and MHz ranges, the reflectivity spectra were fit to the Berreman–Unterwald form of dielectric function. The fits showed that the lower frequency dielectric response seems to be dominated by lattice phonons. Microwave permittivity and temperature coefficient of the resonant frequency were found to obey a hyperbolic-type law.     

Investigation of crystal structure,dielectric properties,impedance spectroscopy and magnetic properties of (1-x)BaTiO3 – (x)Ba0.9Ca0.1 Fe12O19 multiferroic composites

Composites having composition (1-x)BaTiO₃?(x)Ba_0.9Ca_0.1Fe₁₂O₁₉ (x = 0.10, 0.20, 0.30) were synthesized by conventional solid-state reaction technique. X-ray diffraction (XRD) was used to examine the phase formation. Rietveld refinement has been done using the FullProf suite which predicted the dual phase symmetry consisting hexagonal (P63/mmc) and tetragonal (P4mm) phases in the prepared composites. The dielectric properties of the obtained composites were investigated at different temperatures as a function of frequency in the range of 100 Hz to 7 MHz. The dielectric constant increases with an increase in Ca doped barium ferrite content. The composites showed usual dielectric dispersive behaviour with increasing frequency. The conduction mechanism and dielectric relaxation were examined by complex impedance spectroscopy (CIS). Nyquist plots of all composites showed two semicircles and their centers lied below the real axis. Magnetic characterization was performed by using a vibrating sample magnetometer (VSM) up to a field of 15 kOe at room temperature. The hysteresis loops reveal the ferromagnetic nature of the composites. The values of saturation magnetization, magnetic moment per formula unit, and corresponding coercivity increases with ferrite content and are maximum at x = 0.3. AC conductivity also increases with ferrite content. The variation of frequency exponent ‘n' of the power-law with temperature suggests that the overlapping large polaron tunneling (OLPT) model is appropriate to explain the mode of conduction in all samples.     

Preparation and microwave dielectric properties of Ca0.6La0.8/3(SnxTi1−x)O3 ceramics

Ca_0.6La_0.8/3(Sn_xTi_1−x)O₃ ceramics were prepared via a conventional solid state reaction method, and the effect of Sn doping on their crystal phase structure and microwave dielectric properties was investigated. Results showed that Sn doping could hinder the formation of the rutile TiO₂ detrimental phase of Ca_0.6La_0.8/3TiO₃ ceramic. Also, the Q×f₀ value was enhanced and the τ_f value was lowered by Sn doping. The best microwave dielectric properties, i. e. ε_r=113 and Q×f₀=8487 GHz were obtained for a Sn doping content of 0.02. The mechanism of the improved properties deriving by Sn doping is discussed.     

Structural and Dielectric Properties of (1-x) (Al0.2La0.8TiO3) + (x) (BiZnFeO3) (x = 0.2 − 0.8) nanocomposites

Journal of Inorganic and Organometallic Polymers and Materials - (1-x) (Al0.2La0.8TiO3)?+?(x) (BiZnFeO3) (x?=?0.2–0.8) [ALTBZFO] nanocomposites were synthesized via...     

Microstructure and mechanical properties of Al2O3–YSZ spherical polycrystalline composites

The mechanical behavior and microstructure of highly densified, spherically shaped, polycrystalline Al₂O₃–YSZ composites, processed from pseudoboehmite powders by sol–gel is reported here. Processing was carried out by combining nanometric sized α-Al₂O₃ (120 nm) seeds and YSZ particles of tetragonal structure. The YSZ particles were homogeneously distributed in a coarse-grained matrix of alumina, both inside grains and along grain boundaries. Fracture surfaces, achieved by impact tests showed toughening effects of the zirconia particles. The tetragonality of the YSZ phase stability even after fracture events and fracture toughness measurements by Vickers indentation, where the crack tip interacts with YSZ particles, are all provided and discussed. The local mechanical properties, such as elastic modulus, indentation hardness and the onset of plastic deformation or fracture contact pressure of both YSZ particles and the Al₂O₃ matrix were quantified by nanoindentation. Evidence of coercive contact pressure was observed in YSZ from indentation stress–strain curves.     

Microstructure and microwave dielectric properties of Li2Ti1−x(Zn1/3Nb2/3)xO3 ceramics

Li₂Ti_1?x(Zn_1/3Nb_2/3)_xO₃ (0≤x≤0.5) ceramics were prepared by a solid state ceramic route, and the phase purity, microstructure, and microwave dielectric properties were investigated. The XRD results suggest the formation of solid solutions for all studied compositions (0≤x≤5). The dielectric properties are strongly dependent on the compositions, the densifications and the microstructures of the samples. The Q×f value increases with x up to x=0.2 and then decreases with the further increase of x. The best microwave dielectric properties of ε_r=20.5, Q×f =75,257 GHz, and τ_f =15.4 ppm/°C could be obtained when x=0.2.     

Nonlinear optical properties of (1−x) CaFe2O4–xBaTiO3 composites

In this paper, we report nonlinear optical properties of a composite nanostructure with the general formula (1−x) CaFe₂O₄–(x) BaTiO₃ (x=0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1) prepared by sol–gel and conventional solid-state reaction methods. Structural properties and chemical compositions of the samples were characterized using XRD and HRTEM. Basic optical constants, band gap energy and linear absorption coefficient were calculated through optical absorbance measurements. The nonlinear optical properties were investigated using the single-beam open aperture Z-scan technique. The obtained nonlinearity fits to Two-photon absorption process and all samples display high nonlinear absorption effect. The incorporation of BaTiO₃ into CaFe₂O₄ systems show a significant improvement in the nonlinear optical properties. These composite that exhibit efficient optical limiting can have potential applications in photonic devices.     

Synthesis,structure and dielectric properties of (1−x)[0.9BiFeO3–0.1DyFeO3]–xPbTiO3 pseudo-binary ceramics

In order to develop multiferroics with large magnetization and polarization, we have prepared a series of (1?x)[0.9BiFeO₃–0.1DyFeO₃]–xPbTiO₃ [BDF–xPT] solid solution ceramics by solid state reaction. X-ray diffraction reveals that, with the increase of PbTiO₃ concentration, the solid solution transforms from a rhombohedral to a tetragonal phase with the presence of a morphotropic phase boundary (MPB) region located at 0.28≤x≤0.40 at room temperature, in which the rhombohedral, tetragonal and orthorhombic phases coexist. The temperature dependence of the dielectric permittivity indicates that the Curie temperature decreases with the increasing amount of PbTiO₃. Based upon the structural analysis and dielectric characterization, a preliminary phase diagram for the BDF?xPT pseudo-binary system has been proposed. It is found that the ceramics of compositions around the MPB exhibits much better dielectric properties with dielectric constant of the BDF–0.37PT ceramics reaching 459 at 1 kHz, confirming the beneficial effects of the MPB on the dielectric performance.     

ZrO2掺杂对(Ba0.9Ca0.1)TiO3陶瓷性能的影响

采用新型溶胶凝胶制粉技术和传统陶瓷工艺相结合,对(Ba0.9Ca0.1)TiO3陶瓷进行ZrO2掺杂,对陶瓷晶相特征及铁电、介电、压电性能进行了研究。结果表明,ZrO2的加入对(Ba0.9Ca0.1)TiO3陶瓷的铁电性能略有改善,Curie峰前移和展宽,提高了介电常数ε和介电损耗tanδ,压电常数d33却降低了。当ZrO2掺杂量为0.14mol时,陶瓷的介电常数有最大值2559.43,介电损耗有最小值0.027,此时压电常数为35。     

Electrical properties of (La0.9Ca0.1)(Co1−xNix)O3−δ cathode materials for SOFCs

Modified perovskite ceramics (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ (x = 0–0.3) cathodes for solid oxide fuel cells (SOFCs) were synthesized by solid state reaction. The lattice parameters, electrical conductivity, activation energy, and microstructures of these specimens were investigated systematically in this study. The results exhibited that all specimens are rhombohedron structures and their tolerance factors were greater than 0.97, indicating that the perovskite was not distorted by Ni²⁺ cation substitution for the B site of (La_0.9Ca_0.1)CoO_3?δ. The microstructures of the (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ specimens showed good densification, and were well-sintered, with few pores. The electrical conductivity behavior conformed to the nature of a semiconductor, for all specimens. As x = 0.1, the electrical conductivity reached the maximum value of 750.3 S/cm at 800 °C, and the activation energy calculated from the Arrhenius plot of the electrical conductivity versus the reciprocal of temperature is 7.1 kJ/mol.The novelty of this study is its introduction of the concept of defect chemistry to explain the relationship between compensation mechanisms and electrical conductivity. The information gleaned regarding charge compensation mechanisms and defect formation may be valuable for a better understanding of the cathode of (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ ceramics used for SOFCs. Moreover, the information about oxygen content versus temperature is useful for expressing the relationship between electrical conductivity and composition. Therefore, we also used thermogravimetric analysis combined with the room-temperature oxygen content which was determined by iodometric titration to investigate the oxygen content from room temperature to high temperature, in air. Based on the experimental results, the (La_0.9Ca_0.1)(Co_0.9Ni_0.1)O_3?δ specimen shows high electrical conductivity. Consequently, it is identified as a promising candidate for cathode SOFC applications.     

Crystal structure and microwave dielectric properties of La2(Zr1−xTix)3(MoO4)9 (0 ≤ x ≤ 0.1) ceramics

La₂(Zr_1−xTi_x)₃(MoO₄)₉ (0 ≤ x ≤ 0.1) ceramics were prepared by the traditional solid-state reaction method. XRD analysis showed that La₂(Zr_1−xTi_x)₃(MoO₄)₉ (0 ≤ x ≤ 0.1) ceramics belonged to a trigonal system. Based on the chemical bond theory, the consequences of bond energy, bond ionicity, lattice energy, and thermal expansion coefficient of ceramics on microwave dielectric properties were discussed. As Ti⁴⁺ addition was increased, the reduction in dielectric constant was ascribed to the fact that the polarizability of Ti⁴⁺ is smaller than Zr⁴⁺, and the downward trend was related to the bond ionicity. Besides, the tendency of Q·f value depended on the packing fraction and the lattice energy. The improvement in τ_f value, the increase in bond energy, and the decrease in the coefficient of thermal expansion were all correlated. The far-infrared spectra implied that the absorptions of structural phonon oscillation were the main reason for the maximum polarization contribution. La₂(Zr_0.92Ti_0.08)₃(MoO₄)₉ ceramics sintered at 750°C for 4 hours exhibited the best dielectric properties (ε_r = 10.33, Q·f = 80 658 GHz, and τ_f = 3.48 ppm/°C).     

ZrO2掺杂对(Ba0.9Ca0.1)TiO3陶瓷性能的影响

采用新型溶胶凝胶制粉技术和传统陶瓷工艺相结合，对（Ba0.9Ca0.1）TiO3陶瓷进行ZrO2掺杂，对陶瓷晶相特征及铁电、介电、压电性能进行了研究，结果表明，ZrO2的加入对（Ba0．9Ca0．1）TiO3陶瓷的铁电性能略有改善，Curie峰前移和展宽，提高了介电常数ε和介电损耗tanδ，压电常数d33却降低了。当ZrO2掺杂量为0.14mol时，陶瓷的介电常数有最大值2559．43，介电损耗有最小值0.027，此时压电常数为35。     

Microstructure and improved mechanical properties of Al2O3/Ba-β-Al2O3/ZrO2 composites with YSZ addition

Al₂O₃/Ba-β-Al₂O₃/ZrO₂ composites were fabricated by solid-state reaction sintering of Al₂O₃, BaZrO₃, and yttria stabilized zirconia (YSZ) powders. The effects of YSZ addition on microstructure and mechanical properties have been investigated. The incorporation of YSZ promoted the densification of the composites and formation of tetragonal ZrO₂ phase. The microstructure of the composites was characterized by elongated Ba-β-Al₂O₃ phase and equiaxed ZrO₂ particles including added YSZ and reaction-formed ZrO₂. The Al₂O₃/Ba-β-Al₂O₃/ZrO₂ composites with YSZ addition exhibited improved fracture toughness, as a result of multiple toughening effects including crack deflection, crack bridging, crack branching, and martensitic transformation of ZrO₂ formed by the reactions between Al₂O₃ and BaZrO₃. Moreover, owing to the grain refinement of Al₂O₃ matrix, dispersion strengthening of the added YSZ particles, and an increase in density of the composites, the Vickers hardness and flexural strength of Al₂O₃/Ba-β-Al₂O₃/ZrO₂ composites were dramatically enhanced in comparison with the composites without YSZ addition.     

Electrical properties of La2-xPrxTi2O7 (x = 0–0.3) ceramics

The electrical properties of La₂Ti₂O₇ (LTO) ceramics have been enhanced through the substitution of La³⁺ ions by Pr³⁺ ions. Almost all doped Pr³⁺ ions will get at A - site without causing a change on monoclinic phase of LTO. The average grain size is 17.8 μm for La_1.9Pr_0.1Ti₂O₇ ceramics. The relaxation activation energy which is contributed by defect dipoles that are formed from TiO₆ oxygen octahedrons’ distortions in grains is 1.6 eV for La_1.8Pr_0.2Ti₂O₇ ceramics. This kind of defects will be activated from 520 °C and completely be activated until 650 °C. The piezoelectric coefficient d₃₃ = 3.0 pC/N of La_2-xPr_xTi₂O₇ ceramics maintains stable when the Pr³⁺ doping content x ranging from 0.1 to 0.3.     

Microstructure and electrical properties of ZnO–ZrO2–Bi2O3–M3O4 (MCo,Mn) varistors

Phase evolution, microstructure and the electrical properties of ZrO₂-added pyrochlore-free ZnO–Bi₂O₃–M₃O₄ (MCo, Mn) varistors have been studied as functions of ZrO₂ content up to 10 vol% and the sintering temperature between 900 and 1300 °C. Zirconia remained as intergranular second phase particles up to 1100 °C, which retarded densification and inhibited the grain growth of ZnO. At higher temperatures, on the contrary, ZrO₂ particles began to be entrapped in ZnO grains and irreversibly transform from monoclinic to stable cubic phase dissolving transition metal ions. The grain size of ZnO decreased with increasing ZrO₂ content, and increased with the increase of the sintering temperature. Accordingly breakdown voltage changed with both ZrO₂ content and the sintering temperature as was expected. Nonlinear coefficient (α) depended primarily on the sintering temperature: it increased to >40 up to 1000 °C, and significantly decreased to <30 at higher temperatures probably due to the volatilization of Bi₂O₃. While the specimens sintered at 1200 °C or above had relatively high leakage current (I_L) and large clamping ratio (C_R), those with ZrO₂ content of 0.5–5.0 vol% and sintered below 1200 °C revealed low I_L of ⩽20 μA/cm² and C_R well below 2.0. In spite that varistor characteristics of ZrO₂-added system could not match those of commercial ZnO varistors, its low temperature sinterability and ease of breakdown voltage control via ZrO₂ content without a serious loss of its figures of merit are worth noticing, particularly for multi-layered chip varistor (MLV) application.     

Tribological properties of NiCr–ZrO2(Y2O3)–SrSO4 composites at elevated temperatures

The effect of SrSO₄ content on the tribological properties of NiCr–30wt%ZrO₂(Y₂O₃) (NC30Z) cermet was evaluated over a wide temperature range from room temperature to 1000 °C. The results indicated that the inclusion of SrSO₄ effectively improved the friction coefficients and wear rates of NC30Z cermet above 400 °C. NC30Z–5SrSO₄ composite against alumina ball exhibited satisfactory tribological performance, which was attributed to synergistic lubrication of pseudocubic-SrZrO₃ and NiCr₂O₄ between 400 °C and 800 °C and cubic-SrZrO₃, NiCr₂O₄, NiO and Cr₂O₃ at 1000 °C.     

Microstructure and properties of CaO–ZrO2–SiO2 glass–ceramics prepared by sintering

For the development of a new wear resistant and chemically stable glass-ceramic glaze, the CaO–ZrO₂–SiO₂ system was studied. Compositions consisting of CaO, ZrO₂, and SiO₂ were used for frit, which formed a glass-ceramic under a single stage heat treatment in electric furnace. In the sintered glass-ceramic, wollastonite (CaSiO₃) and calcium zirconium silicate (Ca₂ZrSi₄O₁₂) were crystalline phases composed of surface and internal crystals in the microstructure. The internal crystal formed with nuclei having a composition of Ca_1.2Si_4.3Zr_0.2O₈. The CaO–ZrO₂–SiO₂ system showed good properties in wear and chemical resistance because the Ca₂ZrSi₄O₁₂ crystals positively affected physical and mechanical properties.     

Electrical and magnetic properties of La1−xSrxMnO3 (0.1 ≤ x≤ 0.25) ceramics prepared by sol–gel technique

La_1−xSr_xMnO₃ (0.1 ≤ x ≤ 0.25) high density ceramics were prepared by sol-gel method using methanol as solvent. X-ray diffraction analysis showed that all samples exhibited single perovskite structure and no second phase was detected. Scanning electron microscopy images exhibited good particle connectivity on the surface of sample, and grain size increased with the increase in Sr doping. Resistivity-temperature curves of samples were measured by standard four-probe method, and curves exhibited significant differences in studied range of Sr doping. Magnetic measurement results indicated that the variation of susceptibility of different samples was quite different, and the Curie temperature of samples increased with the increase in Sr content. For x = 0.2, temperature coefficient of resistance value of the sample was larger, and corresponding peak TCR temperature was 307.1 K, which is very close to room temperature. Thus, La_0.8Sr_0.2MnO₃ ceramics exhibited high TCR value close to room temperature. Combined with its excellent magnetic properties, La_0.8Sr_0.2MnO₃ ceramics may potentially act as effective candidates for uncooled radiation calorimeter and uncooled magnetic sensor. Applications of La_0.8Sr_0.2MnO₃ ceramics in uncooled infrared radiation calorimeter at room temperature will be highly beneficial.     

Two–step processing of thermoelectric (Ca0.9Ag0.1)3Co4O9/nano–sized Ag composites with high ZT

A two–step processing method, spark plasma sintering (SPS) combined with a heat–treatment, was used to fabricate (Ca_0.9Ag_0.1)₃Co₄O₉/nano–sized Ag composites. Sliver within the lattice generated hole carriers, and silver along the grain boundaries improved the transport path of the charge carriers. Samples sintered using SPS at different temperatures had very different thermoelectric properties. The results showed that when the sample was sintered at 1233 K, the maximum power factor reached 0.43 mW/(m·K²) along with an electrical resistivity of 8.61 mΩ·cm and a Seebeck coefficient of 196.90 μV/K, and the corresponding lattice thermal conductivity was 1.86 W/(m·K). This study shows how to improve the properties and broaden the application of Ca₃Co₄O₉ thermoelectric ceramics.