Elastic anomalies near phase transitions of lead-free （Na,Bi）TiO3 and （Ba,Zr）TiO3 ferroelectric ceramics

We have investigated the temperature dependence of elastic modulus for various ferroelectric ceramics in the temperature range of 20–90°C.The Na0.5Bi0.5TiO3(NBT)ceramics has a phase transition at 200°C,thus exhibits minimal change in elastic modulus up to 90°C,while the elastic modulus of the BaZr0.07Ti0.93O3(BZT-7)shows 12.5%change at the phase transition temperature of70°C and that of the BaZr0.15Ti0.85O3(BZT-15)ceramics shows 34.6%change at the phase transition temperature of60°C.The variations of elastic modulus will affect the temperature stability of devices made by these lead-free ferroelectric ceramics.     

Synthesis of antiferroelectric (Bi0.534Na0.5)0.94Ba0.06TiO3 ceramics with high phase transition temperature and broad temperature range by a solid-state reaction method

Antiferroelectric 0.94(Bi 0.534 Na 0.5 )TiO 3 -0.06BaTiO 3 ceramics were prepared using a solid-state reaction method, involving the addition of excessive amounts of Bi2O3 . The resulting ceramics featured a very high phase transition temperature (Tm～330°C), from the antiferroelectric to the paraelectric phase, and a low depolarization temperature (Td<25°C). The broad temperature range, within which antiferroelectric properties are retained, of the prepared materials indicates their higher potential over lead-based antiferroelectric ceramics such as PZT-based materials that exhibit a lower T m ≤170°C. The lower Td and higher T m obtained val- ues, relative to those reported in the literature, are believed to be due to the formation of A-site vacancies originating from the incorporation of excess Bi into the perovskite structure of the studied sample. In addition, the synthesized sample shows a high dielectric constant of ～1460, in a temperature range of 50-150°C at 1 kHz, and a high energy storage density of 0.71 J/cm 3 , which is an asset in energy storage capacitor applications.     

Effect of B2O3 on the aqueous tape casting and microwave properties of Li2O–Nb2O5–TiO2 ceramics

The effect of B2O3 addition on the aqueous tape casting, sintering, microstructure and microwave dielectric properties of Li2O-Nb2O5-TiO2 ceramics has been investigated. The tape casting slurries exhibit a typical shear-thinning behavior without thixotropy, but the addition of B2O3 increases the viscosity of the slurries significantly. It was found that doping of B2O3 can decrease the tensile strength, strain to failure and density of the green tapes. The sintering temperature could be lowed down to 900℃ with the addition of 2 wt% B2O3 due to the liquid phase effect. No secondary phase is observed. The addition of B2O3 does not induce much degradation on the microwave dielectric properties. Optimum microwave dielectric properties of εr 67, Q×f 6560 GHz are obtained for Li2O-Nb2O5-TiO2 ceramics containing 2 wt% B2O3 sintered at 900 1C. It represents that the ceramics could be promising for multilayer low-temperature co-fired ceramics (LTCC) application.     

Microwave sintering of Ca<Subscript>0.6</Subscript>La<Subscript>0.2667</Subscript>TiO<Subscript>3</Subscript> microwave dielectric ceramics

Ca_0.6La_0.2667TiO₃ ceramics were prepared by conventional and microwave sintering techniques and their sinterability, microstructure, and microwave dielectric properties were investigated in detail for comparison. Densified Ca_0.6La_0.2667TiO₃ ceramics were obtained by microwave sintering at 1350°C for 30 min and by conventional sintering at 1450°C for 4 h. An unusual phenomenon was found that some larger grains (grain size range: 8–10 μm) inclined to assemble in one area but some smaller ones (grain size range: 2–4 μm) inclined to gather in another area in the microwave sintered ceramics. The microwave dielectric properties of Ca_0.6La_0.2667TiO₃ ceramics prepared by microwave sintering at 1350°C were as follows: dielectric constant (ɛ _r) = 119.6, quality factor (Qf) = 17858.5 GHz, and temperature coefficient of resonant frequency (τ _f) = 155.5 ppm/°C. In contrast, the microwave dielectric properties of the ceramics prepared by conventional sintering at 1450°C were ɛ _r = 117.4, Qf = 13375 GHz, and τ _f = 217.2 ppm/°C.     

Effect of the synthesis route on the structural and dielectric properties of SrBi<Subscript>1.8</Subscript>Y<Subscript>0.2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

This work is devoted to the synthesis and characterization of yttrium-doped SrBi₂Nb₂O₉ ceramics prepared by three methods: solid state reaction, co-precipitation, and hydrothermal. Multiple characterizations, specifically scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR), were used to validate the structural feature. The crystallite size was estimated by Scherrer’s formula and the Williamson–Hall plot. The effect of the process on the band intensities of the FTIR spectra was investigated. The crystallite size and microstructure of ceramics prepared from different synthesis processes were strongly influenced by the sinterability. SEM images revealed nanograin ceramics for materials prepared by co-precipitation and hydrothermal methods and micrograin ceramics prepared by the solid state method. The synthesized compounds underwent phase transitions at 480–465°C. The dielectric and electrical properties of these Y-doped SrBi₂Nb₂O₉ ceramics appear to be dependent on the grain size.     

Effect of CuO addition on the sintering temperature and microwave dielectric properties of CaSiO3– Al2O3 ceramics

CuO-doped CaSiO3–1 wt% Al2O3 ceramics were synthesized via a traditional solid-state reaction method, and their sintering behavior,microstructure and microwave dielectric properties were investigated. The results showed that appropriate CuO addition could accelerate the sintering process and assist the densification of CaSiO3–1 wt% Al2O3 ceramics, which could effectively lower the densification temperature from1250 1C to 1050 1C. However, the addition of CuO undermined the microwave dielectric properties. The optimal amount of CuO addition was found to be 0.8 wt%, and the derived CaSiO3–Al2O3ceramic sintered at 1100 1C presented good microwave dielectric properties of εr?7.27,Q f?16,850 GHz and τf? 39.53 ppm/1C, which is much better than those of pure CaSiO3 ceramic sintered at 1340oC(Q f?13,109 GHz).The chemical compatibility of the above ceramic with 30 Pd/70 Ag during the cofiring process has also been investigated, and the result showed that there was no chemical reaction between palladium–silver alloys and ceramics.& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.     

Microstructure, crystalline phase and electrical properties of Li0.06(Na0.5K0.5)0.94Nb(1−2x/5)Mg x O3 lead-free piezoelectric ceramics

MgO-modified Li_0.06(Na_0.5K_0.5)_0.94NbO₃ (L₆NKN) lead-free piezoelectric ceramics were synthesized by normal sintering at a relatively low temperature of 1000°C. The crystalline phase, microstructure, and electrical properties of the ceramics were investigated with a special emphasis on the influence of MgO content. The addition of MgO effectively improves the sinterability of the L₆NKN ceramics. X-ray diffraction analysis indicates that the morphotropic phase boundary (MPB) separating orthorhombic and tetragonal phases for the ceramics lies in the range of Mg doping content (x) from 0.3at% to 0.7at%. High electrical properties of the piezoelectric constant (d ₃₃=238 pC/N), planar electromechanical coupling coefficient (k _p=41.5%), relative dielectric constant (? _r=905), and remanent polarization (P _r=38.3 μC/cm²) are obtained from the specimen with x=0.5at%, which suggests that the Li_0.06(Na_0.5K_0.5)_0.94Nb_(1?2x/5)Mg _x O₃ (x=0.5at%) ceramic is a promising lead-free piezoelectric material.     

Dispersion of CoCl2 into γ-Al2O3 studied by positron

Co²⁺/γ-Al₂O₃ samples were prepared by incipient wetness impregnation of γ-Al₂O₃ with different concentration solution of CoCl₂ and dried at 40 °C. We measured the positron lifetime spectra of the samples of different Co²⁺ mass fractions (0%–8.24%) heated at different temperatures (100–500°C). All lifetime spectra were resolved into four components, in which the third and the fourth components were related to the surface state of the micropores and the secondary pores of the γ-Al₂O₃. The experimental results showed that the Co²⁺ was mainly located in the micropores and the secondary pores near to the exterior of the support. For low Co²⁺ mass fraction samples, when the heating temperature was above 400 °C, dispersal was almost finished. When the Co²⁺ mass fraction was above 5.59%, Co²⁺ and Cl⁻ were dispersed into the secondary pores in the form of multiple layers.     

Abnormal thermal shock behavior in electrical conductivity of Ti2SnC

Some ternary carbide and nitride ceramics have been demonstrated to exhibit abnormal thermal shock behavior in mechanical properties. However, the influence of thermal shock on other properties is not clear. This work reports on the influence of thermal shock on electrical conductivity of Ti_2SnC as a representative member of ternary carbides. Abnormal change in electrical conductivity was first demonstrated during quenching Ti_2 SnC in water at 500-800 ℃. The residual electrical conductivity of the quenched Ti_2SnC gradually decreased with increasing temperature, but abnormally increased after quenching at 600 ℃. The microstructure of surface cracks was characterized. The main mechanism for the abnormal electrical conductivity recovery is that some narrow branching cracks are filled by metallic Sn precipitating from Ti_2SnC.     

Effect of KNbO3 content on the crystal structure and electrical properties of (1 − x)PbZr0.54Ti0.46O3-xKNbO3 piezoelectric ceramics

(1 ? x)PbZr_0.54Ti_0.46O₃-xKNbO₃ (0 ≤ x ≤ 25mol%) (abbreviated as PZT-xKN) piezoelectric ceramics were successfully fabricated by a traditional sintering technique at 1225°C for 30 min. The influence of KNbO₃ content on the crystal structure and electrical properties of the PZT-xKN piezoelectric ceramics was studied. Samples with 0 ≤ x ≤ 0.20 show a pure perovskite structure, indicating that all KNbO₃ diffused into the crystal lattice of PZT to form a single solid solution in this compositional range. A second Pb₃Nb₄O₁₃ phase is observed in the PZT-0.25KN sample, showing that the maximum solid solubility of KNbO₃ in PZT matrix ceramic is less than 25mol%. Compared with pure PZT piezoelectric ceramics, samples containing KNbO₃ have smaller crystal grains. PZT-0.15KN exhibits excellent piezoelectric properties with d ₃₃ = 209 pC/N.     

Synthesis of nonstoichiometric M-type barium ferrite nanobelt by spark plasma sintering method

This study investigated the feasibility of ultrafast crystallization of M-type barium ferrite when the coprecipitation precursors in stoichiometric proportions as BaFe12O19, Fe(OH)3 and BaCO3 nanoparticles, had been heated by spark plasma sintering (SPS) process. The results show that SPS method may realize the ultrafast crystallization of M-type barium ferrite, absolutely prevent the crystallization of intermediate phase α-Fe2O3, and significantly decrease the crystallization temperature of M-type barium ferrite. The sintered samples obtained at 800℃ by sintering the precursors for 10 minutes are a kind of multiphase ferrites composed of major phase M-type barium ferrite and trace amount of BaFe0.24Fe0.76O2.88. It is discovered that M-type barium ferrites in the holes of the sintered samples are in nanobelt microstructure about 100-300 nm in width and several micrometers in length. These M-type barium ferrite nanobelts are non-stoichiometric and may be expressed as BaFe12 xO19 1.5x (-4.77≤x≤6.50). Their composistions suggest completely random Fe-rich or Ba-rich domains.     

Thermal shock resistance and crack growth behavior of Aurivillius phase Bi_4Ti_3O_(12)-based ferroelectric ceramics

A type of W/Cr co-doped Bi₄Ti₃O₁₂(ab. BTWC) ceramics were synthesized utilizing the traditional solid-state reaction process, and its thermal shock resistance(TSR) as well as the crack growth behavior was systematically investigated by water quenching technology. It can be found by the succeeded fractographic analysis that many edge thermal cracks began to appear in the samples subjected to thermal shock with ΔT=400°C. According to an integrated TSR model, the cr...     

Phenomenon of multiple field-induced phase transition in PLZST antiferroelectric ceramics

The multiple field-induced phase transition in 4 at.% La modified Pb(Zr,Sn,Ti)O 3 family with temperature from -40℃ to 45℃ in reported. Two electric field-induced transitions from a metastable antiferroelectric phase to two ferroelectric phases are observed is polarization at the applied field of 4 MV/m. The critical field of phase transition between two ferroelectric phases is not larger than 2.5 MV/m, about ten to twenty percent of that ever found in PZT based ceramics. Lattice structure is shown to be orthorhombic by X-ray diffraction. Dielectric investigation reveals a relaxor-like ferroelectric behavior. Temperature-electric field phase diagram is also presented. An appreciate kind of materials is provided to investigate multiple field-induced phase transition with PZT-based ceramics.     

Phase stability and thermal conductivity of ytterbia and yttria co-doped zirconia

Rare earth oxides doping has been extensively investigated as one of the effective methods to lower thermal conductivity of 4.55 mol% Y2O3stabilized ZrO2(YSZ) thermal barrier coatings(TBCs).In the present work,5–6 mol% Yb2O3and Y2O3co-doped ZrO2ceramics were synthesized by solid reaction sintering at 1600 1C.The phase stability of the samples after heat treatment at 1500 1C was investigated.Yb2O3and Y2O3co-doped zirconia,especially when Yb2O3/Y2O3≥1,contained less monoclinic phase than single Yb2O3or Y2O3phase doped zirconia,indicating that co-doped zirconia was more stable at high temperature than YSZ.The thermal conductivity of the 3 mol% Yb2O3+3 mol% Y2O3co-doped ZrO2was 1.8 W m 1K 1at 1000 1C,which was more than 20% lower than that of YSZ.     

Microstructure and electrical conductivity of 10% Yb-doped SrCeO3 ceramics

As a candidate material for hydrogen separation, Yb-doped SrCeO₃ has attracted increasing attention in recent decades. In the present study, Yb-doped SrCe_0.9Yb_0.1O_3-α ceramics were prepared by the dry pressing and sintering approach, with the microstructure evolution and the micro morphology investigated. It was indicated that the ceramics sintered in air were of a pure perovskite structure, and that the sintering temperature had a significant effect on the growth of ceramic grains. The average grain size increased from 1 ​μm to 10 ​μm with an increase in sintering temperature from 1300 to 1500 ​°C. Further investigation of the thermodynamics and kinetics of grain growth revealed that the grain boundary diffusion was the main driving force of grain growth during solid phase sintering, with a grain growth index of 4 and an activation energy of approximately 61.23 ​kJ ​mol⁻¹. These results illustrate an obvious tendency of grain size growth. By electrochemical workstation with different atmospheres the effects of sintering temperature on the conductivity were characterized in the temperature range of 700–900 ​°C. The electrical conductivities σ of SrCe_0.9Yb_0.1O_3-α ceramics in different atmospheres were as follows: σ(wet hydrogen) ​> ​σ(dry hydrogen) ​> ​σ(dry air) ​> ​σ(wet air). In the test atmosphere containing water and hydrogen the conductivity of protons increased with increasing temperature because of the protons jump between lattices in the form of interstitial hydrogen ions or bare protons.     

Influence of O2/Ar ratio on the properties of transparent conductive niobium-doped ZnO films

Niobium-doped ZnO transparent conductive films are deposited on glass substrates by radio frequency sputtering at 300℃. The influence of O2/Ar ratio on the structural, electrical and optical properties of the as-deposited films is investigated by X-ray diffraction, Hall measurement and optical transmission spectroscopy. The lowest resistivity of 4.0×10^-4Ω· cm is obtained from the film deposited at the O2/Ar ratio of 1/12. The average optical transmittance of the films is over 90%.     

Oxidation behavior of the Fe-36Al-0.09C-0.09B-0.04Zr alloy at 1250°C

To explore and study the Fe-Al system alloy presenting exceptional oxidation resistance at high temperature, the Fe-36Al-0.09C-0.09B-0.04Zr alloy was designed and developed. The microstructure and hardness of the backing at 1250°C were analyzed and measured. Thermodynamics and kinetics of the oxidation behavior were also analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. The results show that the microstructure of the Fe-36Al-0.09C-0.09B-0.04Zr alloy is FeAl phase at ambient temperature and is stable at 1250°C. It displays the excellent property of oxidation resistance because the oxide film has only the Al₂O₃ layer, and its oxidation kinetics curve obeys the parabolic law at 1250°C. The oxidation mechanism at 1250°C is presumed that in the early oxidation period, the alloy oxidizes to form a large number of Al₂O₃ and a little Fe₂O₃, then, the enrichment of Al caused by Fe oxidization combines with O to form Al₂O₃.     

Influence of post-annealing on the properties of Ta-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> transparent conductive films

Ta-doped In₂O₃ transparent conductive oxide films were deposited on glass substrates using radio-frequency (RF) sputtering at 300°C. The influence of post-annealing on the structural, morphologic, electrical and optical properties of the films was investigated using X-ray diffraction, field emission scanning electron microscopy, Hall measurements and optical transmission spectroscopy. The obtained films were polycrystalline with a cubic structure and were preferentially oriented in the (222) crystallographic direction. The lowest resistivity, 5.1×10⁻⁴ Ω cm, was obtained in the film annealed at 500°C, which is half of that of the un-annealed film (9.9×10⁻⁴ Ω cm). The average optical transmittance of the films was over 90%. The optical bandgap was found to decrease with increasing annealing temperature.     

Synthesis of glass ceramics from kaolin and dolomite mixture

Cordierite-and anorthite-based binary glass ceramics of the CaO-MgO-Al₂O₃-SiO₂ (CMAS) system were synthesized by mixing local and abundant raw minerals (kaolin and doloma by mass ratio of 82/18). A kinetics study reveals that the activation energy of crystallization (Ea) calculated by the methods of Kissinger and Marotta are 438 kJ·mol-1 and 459 kJ·mol-1, respectively. The Avrami parameter (n) is estimated to be approximately equal to 1, corresponding to the surface crystallization mechanism. X-ray diffraction (XRD) analysis shows that the anorthite and cordierite crystals are precipitated from the parent glass as major phases. Anorthite crystals first form at 850℃, whereas the μ-cordierite phase appears after heat treatment at 950℃. Thereafter, the cordierite allotropically transforms to α-cordierite at 1000℃. Complete densification is achieved at 950℃; however, the density slightly decreases at higher temperatures, reaching a stable value of 2.63 kg·m-3 between 1000℃ and 1100℃. The highest Vickers hardness of 6 GPa is also obtained at 950℃. However, a substantial decrease in hardness is recorded at 1000℃; at higher sintering temperatures, it slightly increases with increasing temperature as the α-cordierite crystallizes.     

Effect of sintering temperature on the physical properties and electrical contact properties of doped AgSnO<Subscript>2</Subscript> contact materials

AgSnO₂ electrical contact materials doped with Bi₂O₃, La₂O₃, and TiO₂ were successfully fabricated by the powder metallurgy method under different initial sintering temperatures. The electrical conductivity, density, hardness, and contact resistance of the AgSnO₂/Bi₂O₃, AgSnO₂/La₂O₃, and AgSnO₂/TiO₂ contact materials were measured and analyzed. The arc-eroded surface morphologies of the doped AgSnO₂ contact materials were investigated by scanning electron microscopy (SEM). The effects of the initial sintering temperature on the physical properties and electrical contact properties of the doped AgSnO₂ contact materials were discussed. The results indicate that the physical properties can be improved and the contact resistance of the AgSnO₂ contact materials can be substantially reduced when the materials are sintered under their optimal initial sintering temperatures.