Dielectric and piezoelectric properties of (Ba0.95Ca0.05)(Ti0.88Zr0.12)O3 ceramics sintered in a protective atmosphere

(Ba_0.95Ca_0.05)(Ti_0.88Zr_0.12)O₃ (BCTZ) ceramics have been produced in a protective atmosphere of industrial N₂ gas for potential piezoelectric applications. For comparison, the ceramics were also sintered at 1200–1400 °C in air. The results revealed that the reducing atmosphere of pO₂ = 5 × 10² Pa had no substantial effect on the phase structure or the microstructure of the BCTZ ceramics. The XRD patterns suggested a tetragonal to pseudocubic phase transition at sintering temperatures above 1300 °C in both atmospheres. The nitrogen-sintered BCTZ samples had higher dielectric constants _r but lower electromechanical coupling coefficients k_p than the air-sintered samples. The piezoelectric constant d₃₃ for the BCTZ ceramics was not significantly influenced by the reducing atmosphere of pO₂ = 5 × 10² Pa. The correlation of dielectric and piezoelectric properties of the BCTZ ceramics with the sintering temperature was explained based on a competing mechanism between phase structure and microstructure.     

Low-temperature firing and microwave dielectric properties of 16CaO–9Li2O–12Sm2O3–63TiO2 ceramics with V2O5 addition

The sintering behaviors and microwave dielectric properties of the 16CaO–9Li₂O–12Sm₂O₃–63TiO₂ (abbreviated CLST) ceramics with different amounts of V₂O₅ addition had been investigated in this paper. The sintering temperature of the CLST ceramic had been efficiently decreased by nearly 100 °C. No secondary phase was observed in the CLST ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLST ceramics with small amounts of V₂O₅ addition could be well sintered at 1200 °C for 3 h without much degradation in the microwave dielectric properties. Especially, the 0.75 wt.% V₂O₅-doped ceramics sintered at 1200 °C for 3 h have optimum microwave dielectric properties of Kr = 100.4, Q × f = 5600 GHz, and TCF = 7 ppm/°C. Obviously, V₂O₅ could be a suitable sintering aid that improves densification and microwave dielectric properties of the CLST ceramics.     

The influence of sintering aids for Nd(Mg0.5Ti0.5)O3 microwave dielectric ceramics properties

The influence of various sintering aids on the microwave dielectric properties and the structure of Nd(Mg_0.5Ti_0.5)O₃ ceramics were investigated systematically. B₂O₃, Bi₂O₃, and V₂O₅ were selected as liquid-phase sintering aids to lower the sintering temperature. The sintered Nd(Mg_0.5Ti_0.5)O₃ ceramics are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microwave dielectric properties. The sintering temperature of Nd(Mg_0.5Ti_0.5)O₃ microwave dielectric ceramics is generally high, about 1500 °C. However, the sintering temperature was significantly lowered about 175 °C from 1500 °C to 1325 °C by incorporating in 10 mol% B₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (_r) value of 26.2, a quality factor (Q × f) value of 61,307 (at 9.63 GHz), and τ_f value of −45.5 ppm/°C. NdVO₄ secondary phase was observed at 10 mol% V₂O₅ addition in the sintering temperature range of 1300–1325 °C, which led the degradation in microwave dielectric properties. The microwave dielectric properties as well as grain sizes, grain morphology, and bulk density were greatly dependent on sintering temperature and various sintering aids. In this study, it is found that Nd(Mg_0.5Ti_0.5)O₃ incorporated with 10 mol% B₂O₃ with lower sintering temperature and excellent dielectric microwave properties may be suggested for application in microwave communication devices. The use of liquid-phase sintering, the liquid formed during firing normally remains as a grain boundary phase on cooling. This grain boundary phase can cause a deterioration of the microwave properties. Therefore, the selection of a suitable sintering aid is extremely important.     

Effects of CaSiO3 addition on sintering behavior and microwave dielectric properties of Al2O3 ceramics

The effects of CaSiO₃ addition on the sintering behavior and microwave dielectric properties of Al₂O₃ ceramics have been investigated. The addition of CaSiO₃ into Al₂O₃ ceramics resulted in the emergence of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which acting as liquid sintering aids can effectively lower the sintering temperature of Al₂O₃ ceramic. The Q × f value of Al₂O₃-CaSiO₃ ceramics decreased with the CaSiO₃ addition increasing because of the lower Q × f value of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈. Compared with the pure CaSiO₃ ceramic, the Al₂O₃-CaSiO₃ ceramic with 20 wt% CaSiO₃ addition possessed good dielectric properties of ?_r = 9.36 and Q × f = 13,678 GHz at the similar sintering temperature.     

Good temperature stability of K0.5Na0.5NbO3 based lead-free ceramics and their applications in buzzers

(K_0.5−xLi_x)Na_0.5(Nb_1−ySb_y)O₃ (KLNNSx–y, x = 0–4 mol% and y = 0–8 mol%) lead-free piezoelectric ceramics were prepared by the conventional mixed oxide method. The denser microstructure and better electrical properties of the ceramics were obtained as compared to the pure K_0.5Na_0.5NbO₃ ceramic. The temperature stability of the electrical properties of the ceramics was also investigated. The experimental results show that the KLNNS2.5–5 ceramic exhibits good electrical properties (k_p  49%, k₃₁  30% and , tan δ  0.019), and possesses good temperature stability in the temperature range of −40 to 85 °C. The related mechanisms for improved electrical properties and temperature stability were also discussed. Moreover, buzzers based on the KLNNS2.5–5 ceramic have been fabricated and their characterization is presented. These results show that the KLNNS2.5–5 ceramic is a promising lead-free material for practical application in buzzers.     

Effects of Al2O3 addition on the sintering behavior and microwave dielectric properties of CaSiO3 ceramics

The effects of Al₂O₃ addition on the densification, structure and microwave dielectric properties of CaSiO₃ ceramics have been investigated. The Al₂O₃ addition results in the presence of two distinct phases, e.g. Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which can restrict the growth of CaSiO₃ grains by surrounding their boundaries and also improve the bulk density of CaSiO₃-Al₂O₃ ceramics. However, excessive addition (≥2 wt%) of Al₂O₃ undermines the microwave dielectric properties of the title ceramics since the derived phases of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈ have poor quality factor. The optimum amount of Al₂O₃ addition is found to be 1 wt%, and the derived CaSiO₃-Al₂O₃ ceramic sintered at 1250 °C presents improved microwave dielectric properties of ?_r = 6.66 and Q × f = 24,626 GHz, which is much better than those of pure CaSiO₃ ceramic sintered at 1340 °C (Q × f = 13,109 GHz).     

Performance of Pd catalysts supported on nanocrystalline α-Al2O3 and Ni-modified α-Al2O3 in selective hydrogenation of acetylene

Nanocrystalline α-Al₂O₃ and Ni-modified α-Al₂O₃ have been prepared by sol–gel and solvothermal methods and employed as supports for Pd catalysts. Regardless of the preparation method used, NiAl₂O₄ spinel was formed on the Ni-modified α-Al₂O₃ after calcination at 1150 °C. However, an addition of NiO peaks was also observed by X-ray diffraction for the solvothermal-made Ni-modified α-Al₂O₃ powder. Catalytic performances of the Pd catalysts supported on these nanocrystalline α-Al₂O₃ and Ni-modified α-Al₂O₃ in selective hydrogenation of acetylene were found to be superior to those of the commercial α-Al₂O₃ supported one. Ethylene selectivities were improved in the order: Pd/Ni-modified α-Al₂O₃–sol–gel > Pd/Ni-modified α-Al₂O₃-solvothermal ≈ Pd/α-Al₂O₃–sol–gel > Pd/α-Al₂O₃-solvothermal  Pd/α-Al₂O₃-commerical. As revealed by NH₃ temperature program desorption studies, incorporation of Ni atoms in α-Al₂O₃ resulted in a significant decrease of acid sites on the alumina supports. Moreover, XPS revealed a shift of Pd 3d binding energy for Pd catalyst supported on Ni-modified α-Al₂O₃–sol–gel where only NiAl₂O₄ was formed, suggesting that the electronic properties of Pd may be modified.     

The influence of tetrahedral ordering on the microwave dielectric properties of Sr0.05Ba0.95Al2Si2O8 and (M = Al, Ga, M′ = Si, Ge) ceramics

The feldspars Sr_0.05Ba_0.95Al₂Si₂O₈, BaAl₂Ge₂O₈ and BaGa₂Si₂O₈ with S.G. I2/c, and BaGa₂Ge₂O₈ with S.G. P2₁/a, were studied by means of crystal structural and microstructural analyses and dielectric measurements. All the investigated densely sintered single-phase feldspars exhibited a permittivity () of 7–8 and a temperature coefficient of resonant frequency (τ_f) from −20 to −30 ppm/°C. In contrast to the and τ_f the dielectric losses were found to be dependent on the annealing conditions. In Sr_0.05Ba_0.95Al₂Si₂O₈ the Qxf values increased from 42,500 to 92,600 GHz when the annealing time at 1400 °C was increased from 1 to 162 h. Such a difference in the Qxf values as a result of various annealing conditions was attributed to different degrees of tetrahedral ordering. In contrast to aluminosilicate feldspars, Ge-containing feldspars can be sintered and ordered at low temperature. In BaAl₂Ge₂O₈ the Qxf values decreased when the sintering temperature exceeded the order-disorder I2/c ↔ C2/m phase-transition temperature. The BaGa₂Si₂O₈ and BaGa₂Ge₂O₈ feldspars exhibited a rapid decrease of Qxf values when the annealing temperature approached the melting point. However, the BaAl₂Ge₂O₈ and BaGa₂Ge₂O₈ can regain their high Qxf values by annealing at 1000 °C. The BaGa₂Ge₂O₈ stood out from the other investigated feldspars, with a sintering temperature of 1100 °C, Qxf values of 100,000–150,000 GHz and a τ_f of −26 ppm/°C.     

Low temperature sintering of barium titanate ceramics assisted by addition of lithium fluoride-containing sintering additives

By addition of LiF-containing sintering additives to commercial BaTiO₃ powder, more than 98% of the theoretical density was reached at a sintering temperature of 900 °C both on powder compacts and laminates. Dielectric measurements were performed on ceramic samples in the temperature and frequency ranges from −20 °C to 125 °C and from 10³ to 10⁶ Hz, respectively. High relative permittivity (_r  3160) and low dielectric loss (tan δ  0.014) were measured for tapes of the favoured material. The breakdown strength for tapes with a thickness of about 80 μm is 30 kV/mm. The microprobe analysis showed, that no interfacial reaction between the dielectric layer and the Ag-electrode had occurred.The newly developed barium titanate ceramics completely densifying at 900 °C turned out to be promising for integration of buried capacitors in LTCC multilayers.     

Microstructure and dielectric properties of low temperature sintered ZnNb2O6 microwave ceramics

Low sintering temperature ZnNb₂O₆ microwave ceramics were prepared by doping with mixed oxides of V₂O₅–Bi₂O₃ and V₂O₅–Bi₂O₃–CuO. The effects of additives on the microstructure and dielectric properties of the ceramics were investigated. The results show that doping with V₂O₅–Bi₂O₃ can reduce the sintering temperature of ZnNb₂O₆ from 1150 °C to 1000 °C due to the formation of V₂O₅ and Bi₂O₃ based eutectic phases. The combined influence of V₂O₅ and Bi₂O₃ resulted in rod-like grains. Co-doping CuO with 1 wt.% V₂O₅–1 wt.% Bi₂O₃ further lowered the sintering temperature to 880 °C, because eutectic phases could be formed between the CuO, V₂O₅ and Bi₂O₃. A second phase of (Cu₂Zn)Nb₂O₈ also forms when the content of CuO is greater than 2.5 wt.%. A pure ZnNb₂O₆ phase can be obtained when the amount of CuO was 1.0–2.5 wt.%. The Q × f values of ZnNb₂O₆ ceramics doped with V₂O₅–Bi₂O₃–CuO were all higher than 25,000 GHz. The dielectric constants were 22.8–23.8 at microwave frequencies. In addition, theτ_f values decreased towards negative as the content of CuO increased. The ceramic with composition of ZnNb₂O₆ + 1 wt.%V₂O₅ + 1 wt.% Bi₂O₃ + 2.5 wt.% CuO sintered at 880 °C exhibited the optimum microwave dielectric properties, is 23.4, Q × f is 46,975 GHz, and τ_f is −44.89 ppm/°C, which makes it a promising material for low-temperature co-fired ceramics (LTCCs).     

ZnBO-doped (Ba, Sr)TiO3 ceramics for the low-temperature sintering process

ZnBO-doped (Ba, Sr)TiO₃ ceramics were investigated for low-temperature co-fired ceramics (LTCCs) applications. Until now, B₂O₃ and Li₂CO₃ dopants have been commonly employed as the low-temperature sintering aids. In this paper, we suggest ZnBO as an alternative dopant to the B₂O₃ and Li₂CO₃. To reduce the sintering temperature of (Ba, Sr)TiO₃, we have added 1–5 wt.% of ZnBO to (Ba, Sr)TiO₃. ZnBO-doped (Ba, Sr)TiO₃ ceramics were respectively sintered from 750 to 1350 °C by 50 °C to confirm the sintering temperature with different dopant contents. By adding 5 wt.% of ZnBO to the (Ba, Sr)TiO₃ ceramics, the sintering temperature of (Ba, Sr)TiO₃ ceramics can be reduced to 1100 °C. From the XRD analysis, ZnBO-doped (Ba, Sr)TiO₃ has no pyro phase. By adding ZnBO dopants to (Ba, Sr)TiO₃ ceramics, both of relative dielectric permittivity and loss tangent were decreased. From the frequency dispersion of dielectric properties, the relative dielectric permittivity and loss tangent of 5 wt.% ZnBO-doped (Ba, Sr)TiO₃ were 1180 and 3.3 × 10⁻³, while those of BST were 1585 and 4.8 × 10⁻³, respectively.     

In situ Raman microspectrometry investigation of electrochemical lithium intercalation into sputtered crystalline V2O5 thin films

We report here the first in situ Raman microspectrometry study of the electrochemical lithium insertion and de-insertion reaction into crystalline sputtered Li_xV₂O₅ thin films (0 ≤ x ≤ 0.94) in liquid electrolyte. We show that the orthorhombic Pmmn symmetry of the pristine material is kept upon lithium intercalation in the Li_xV₂O₅ film (0 ≤ x ≤  0.94). In fact, a subsequent and unexpected solid solution behaviour is evidenced, leading to the typical Raman fingerprint of the -LiV₂O₅ phase for the Li₀.₉₄V₂O₅ composition. After the charge, a complete recovery of the local structure is found, in good accord with the excellent electrochemical reversibility exhibited by these thin films. Such limited structural changes differ from that usually observed for the bulk material, which emphasizes the key role of the microstructure and morphology on the nature and magnitude of the structural rearrangements induced by the lithium insertion process.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Improving the oxygen permeability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ membranes by a surface-coating layer of GdBaCo2O5+δ

A GdBaCo₂O_5+δ layer was coated on the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes to enhance their oxygen permeability by employing the fast oxygen adsorption/desorption surface-exchange properties of the GdBaCo₂O_5+δ material. The oxygen flux of the coated and uncoated Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes was measured in the temperature range of 600–850 °C. The results reveal that the oxygen-permeation flux of the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes coated by a GdBaCo₂O_5+δ layer shows significant enhancement. The GdBaCo₂O_5+δ layer coated on the oxygen desorption side (He side) has much effect than that coated on the oxygen adsorption side (air side). At 850 °C, the oxygen flux with a single coating layer on the air side can rise 16%, while a single coating on the helium side will result into a rise of 23%.     

The role of particle size on the electrochemical properties at 25 and at 55 °C of the LiCr0.2Ni0.4Mn1.4O4 spinel as 5 V-cathode materials for lithium-ion batteries

The role of the particle size on the electrochemical properties at 25 and at 55 °C of the LiCr_0.2Ni_0.4Mn_1.4O₄ spinel synthesized by combustion method has been determined. Samples with different particle size were obtained by heating the raw spinel from 700 to 1100 °C, for 1 h in air. X-ray diffraction patterns revealed that all the prepared materials are single-phase spinels. The main effect of the thermal treatment is the remarkable increase of the particles size from 60 to 3000 nm as determined by transmission electron microscopy. The electrochemical properties were determined at high discharge currents (1C rate) in two-electrode Li-cells. At 25 and at 55 °C, in spite of the great differences in particle size, the discharge capacity drained by all samples is similar (Q_dch ≈ 135 mAh g⁻¹). Instead, the cycling performances strongly change with the particle size. The spinels with Φ > 500 nm show better cycling stability at 25 and at 55 °C than those with Φ < 500 nm. The samples heated at 1000 and 1100 °C, with high potential (E ≈ 4.7 V), elevate capacity (Q ≈ 135 mAh g⁻¹), and remarkable cycling performances (capacity retention after 250 cycles >96%) are very attractive materials as 5V-cathodes for high-energy Li-ion batteries.     

Effect of polyvinylpyrrolidone on morphology and structure of In2O3 nanorods by hydrothermal synthesis

Indium oxide (In₂O₃) nanorods were hydrothermally synthesized from aqueous InCl₃ solution in urea with addition of polyvinylpyrrolidone (PVP) as a steric stabilizer. Indium hydroxide, In(OH)₃, was precipitated at 60 °C and was changed into a transient InOOH phase upon calcination at 250 °C in air. X-ray diffractometry revealed that the existence of PVP delays the phase transformation of InOOH. Cubic-structured In₂O₃ phase was then formed when temperature was raised to 350 °C, regardless of the PVP concentration. The In(OH)₃ phase without the PVP showed a rod-based, flower-like morphology of polycrystalline character. Minor addition of the PVP, i.e., 0.1–2 wt.%, resulted in a pronounced evolution in morphology from the three-dimensional, flower-like form to discrete, one-dimensional nanorods aligned in planar form. Both the flower-like and discrete nanorod morphologies were preserved after heat treatments at 250 and 350 °C. This reveals that the morphological change is attributable to preferential adsorption of the PVP molecules on the In(OH)₃ crystallite surface, so that the aggregate attachment responsible for the multipod growth is inhibited.     

Effect of sintering temperature on varistor properties and aging characteristics of ZnO–V2O5–MnO2 ceramics

The microstructure, electrical properties, dielectric characteristics, and DC accelerated aging behavior of the ZVM-based varistors were investigated for different sintering temperatures of 800–950 °C. The microstructure of the ZVM-based ceramics consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂, which acts as liquid-phase sintering aid. The Zn₃(VO₄)₂ has a significant effect on the sintered density, in the light of an experimental fact, which the decreases of the Zn₃(VO₄)₂ distribution with increasing sintering temperature resulted in the low sintered density. The breakdown field exhibited the highest value (17,640 V/cm) at 800 °C in the sintering temperature and the lowest value (992 V/cm) at 900 °C in the sintering temperature. The nonlinear coefficient exhibited the highest value, reaching 38 at 800 °C and the lowest value, reaching 17 at 850 °C. The varistor sintered at 900 °C exhibited not only high nonlinearity with 27.2 in nonlinear coefficient, but also the highest stability, in which %ΔE_1 mA = −0.6%, %Δα = −26.1%, and %Δ tan δ = +21.8% for DC accelerated aging stress of 0.85 E_1 mA/85 °C/24 h.     

Nanocomposite Fe2O3–SiO2 inclusion pigments from post-functionalized mesoporous silicas

High-surface mesoporous silicas with different pore sizes were employed for the first time as silicon precursors in the synthesis of reddish Fe₂O₃–SiO₂ inclusion pigments. Interestingly, the size of included Fe₂O₃ nanoparticles was partially controlled through confinement effects into silica mesopores. Notably, impregnated samples showed a more homogeneous and efficient encapsulation of smaller and monodisperse hematite nanoparticles (sizes around 10–35 nm). Moreover, they resulted in an improved reddish color at 1000 °C within a ceramic glaze. The best red shade (a* ≈ 18) was associated to nanocomposite with smaller hematite nanoparticles (around 5 nm). These promising results suggest the possibility to improve the reddish coloration and thermostability of Fe₂O₃–SiO₂ ceramic pigments through and adequate control of confinement effects into sintered mesoporous silicas.     

Phase relations and electrical properties in the pseudo-ternary La2O3–TiO2–Mn2O3 system in air

Scanning electron microscopy (SEM), electron-probe microanalysis, energy- and wavelength-dispersive X-ray analysis and X-ray powder diffraction were used to investigate the subsolidus phase relations in the pseudo-ternary La₂O₃–TiO₂–Mn₂O₃ system in air (oxygen partial pressure p_O2=0.21   atm) at 1275 °C. The addition of Mn₂O₃ to the starting La₂O₃:3TiO₂ mixture led to the formation of a La-deficient perovskite La_2/3TiO₃ compound. The oxides form two new compounds with the proposed compositions: (i) La_1.7Ti_13.0Mn_6.3O_38−x, with a davidite-like crystal structure, and (ii) La₄₉Ti₁₈Mn₁₃O₁₂₉. There were also several solid solutions existing over a wide range of concentrations.