High piezoelectric properties of BaTiO3-xLiF ceramics sintered at low temperatures

BaTiO₃-xLiF ceramics were prepared by a conventional sintering method using BaTiO₃ powder about 100 nm in diameter. The effects of LiF content (x) and sintering temperature on density, crystalline structure and electrical properties were investigated. A phase transition from tetragonal to orthorhombic symmetry appeared as sintering temperatures were raised from 1100 °C to 1200 °C or as LiF was added from 0 mol% to 3 mol%. BaTiO₃-6 mol% LiF ceramic sintered at 1000 °C exhibited a high relative density of 95.5%, which was comparable to that for pure BaTiO₃ sintered at 1250 °C. BaTiO₃-4 mol% LiF ceramic sintered at 1100 °C exhibited excellent properties with a piezoelectric constant d₃₃ = 270 pC/N and a planar electromechanical coupling coefficient k_p = 45%, because it is close to the phase transition point in addition to high density.     

Sintering behavior and electromagnetic properties of Fe-deficient NiZn ferrites

Sintering behavior and electromagnetic properties of Ni_0.5Zn_0.5Fe_2−xO_4−3/2x ferrite (x = 0, 0.4, 0.8) by the sol–gel method are investigated. Fe deficiency in the composition enhances sintering and retards grain growth. The near fully dense Fe-deficient samples could be obtained at a sintering temperature as low as 1120 °C and the highest relative density appears in the x = 0.8 sample sintered at 1150 °C. Second phase zincite ZnO resulting from Fe deficiency plays an important role in spinel NiZn ferrites by acting as a grain growth inhibitor and the grain growth of NiZn ferrite is effectively suppressed. When the sintering temperature is above 1200 °C, extensive grain growth occurs due to the probability of serious volatilization of zinc at high temperatures. The ratio of Ni to Zn of NiZn ferrites increases with increasing Fe deficiency due to the separation of zinc from spinel lattice, which results in the decrease in initial permeability and the increase in Curie temperature and resonant frequency.     

Enhanced stability in CO2 of Ta doped BaCe0.9Y0.1O3−δ electrolyte for intermediate temperature SOFCs

The influence of Ta concentration on the stability of BaCe_0.9−xTa_xY_0.1O_3−δ (where x=0.01, 0.03 and 0.05) powders and sintered samples in CO₂, their microstructure and electrical properties were investigated. The ceramic powders were synthesized by the method of solid state reaction, uniaxially pressed and sintered at 1550 °C to form dense electrolyte pellets. A significant stability in CO₂ indicated by the X-ray analysis performed was observed for the samples with x≥0.03. The electrical conductivities determined by impedance measurements in the temperature range of 550–750 °C and in various atmospheres (dry argon, wet argon and wet hydrogen) increased with temperature but decreased with Ta concentration. The highest conductivities were observed in the wet hydrogen atmosphere, followed by those in wet argon, while the lowest were obtained in the dry argon atmosphere for each dopant concentration. The composition with Ta content of 3 mol% showed satisfactory characteristics: good resistance to CO₂ in extreme testing conditions, while a somewhat reduced electrical conductivity is still comparable with that of BaCe_0.9Y_0.1O_3−δ.     

Phase structure and nano-domain in high performance of BaTiO3 piezoelectric ceramics

BaTiO₃ ceramics were prepared by conventional sintering technique with a special emphasis on the effects of sintering temperature (1100-1230 °C) on the crystalline structure and piezoelectric properties. XRD patterns indicated that the crystallographic structure changed from tetragonal phase to orthorhombic one with raising sintering temperature from 1160 °C to 1180 °C. Domains were shaped in a stripe and a herringbone in orthorhombic samples for BaTiO₃ ceramics. The domain width and domain density increased with raising sintering temperature. The BaTiO₃ ceramic sintered at 1190 °C showed the excellent electrical properties, d₃₃ = 355 pC/N, k_p = 40%, P_r = 10.2 μC/cm², respectively, which are originated to the contributions of both the crystallographic structure transition and nano-domain.     

Role of interface on electrical conductivity of carbon nanotube/alumina nanocomposite

Interface of multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites have been studied using TEM. At low sintering temperature (T_sin=1500 °C), a 3–5 nm thick amorphous interface region was noticed. Nanocomposite sintered at 1700 °C possessed a well-defined graphene layer coating on matrix grains as the interface between CNT and Al₂O₃. A mechanism of such layered interface formation has been proposed. No traceable chemical reaction product was observed at the interface even after sintering at 1700 °C. It was noticed that while DC electrical conductivity (σ_DC) of 1500 °C sintered 2.4 vol% MWCNT/Al₂O₃ nanocomposite was only~0.02 S/m, it raised to ~21 S/m when sintering was done at 1700 °C. Such 10³ times increase in σ_DC of present nanocomposite at a constant CNT loading was not only resulted from the exceptionally high electron mobility of CNT but the well-crystallized graphene interface on insulating type Al₂O₃ grains also significantly contributed in the overall increase of electrical performance of the nanocomposite, especially, when sintering was done at 1700 °C.     

Sintering behavior and microwave dielectric properties of a new low-permittivity ceramic system Ca(Mg1−xAlx)(Si1−x/2Alx/2)2O6

The diopside ceramics with a formula of Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆ (x=0.01–0.3) were synthesized via a traditional solid-state reaction method, and their solid solubility, sintering behavior and microwave dielectric properties were investigated. The results revealed that the solubility limit of Al₂O₃ in Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆, which is defined as x, was between 0.15 and 0.2, and a second phase of CaAl₂SiO₆ presented when the x value reached 0.2. Appropriate Al³⁺ substitution for Mg²⁺ and Si⁴⁺ could promote the sintering process and lower the densification temperature, and a broadened densification temperature range of 1250–1300 °C was obtained for the compositions of x=0.08–0.15. With the increase of the x value, the dielectric constant (ε_r) increased roughly linearly, and the temperature coefficient of frequency (τ_f) showed a rising trend. The Q×f values increased from 57,322 GHz to 59,772 GHz as the x value increased from 0.01 to 0.08, and then they were saturated in the range of x=0.08–0.2. Further increase of the x value (x≥0.25) deteriorated the microwave dielectric properties. Good microwave dielectric properties of ε_r=7.89, Q×f=59,772 GHz and τ_f=−42.12 ppm/°C were obtained for the ceramics with the composition of x=0.08 sintered at 1275 °C.     

Re-examination of bulk and grain boundary conductivities of Ce1−xGdxO2−δ ceramics

Powders of gadolinium-doped ceria solid solutions, Ce_1−xGd_xO_2−δ (x = 0.05, 0.1, 0.2, 0.3 and 0.4), were prepared by a freeze-drying precursor route. Dense ceramic pellets with average grain sizes in the range of several microns were obtained after sintering at 1600 °C. Cobalt nitrate was added to the powders to obtain dense ceramic samples with grain sizes in the submicrometer range at 1150 °C. The ionic conduction was analysed by impedance spectroscopy in air, to de-convolute the bulk and grain boundary contributions. The bulk conductivity at low temperature clearly decreases with increasing content of Gd whereas the activation energy increases. An alternative method is proposed to analyse the extent of defect interactions on conduction. For samples without addition of Co, the specific grain boundary conductivity increases with increasing Gd content. Addition of cobalt does not alter the bulk properties but produces an important increase in the specific grain boundary conductivity, mainly in samples with lower Gd-concentration (x = 0.05 and 0.1). Segregation of Gd and its strong interaction with charge carriers may explain the blocking effects of grain boundaries.     

Effect of Bi2O3 additives on sintering and microwave dielectric behavior of La(Mg0.5Ti0.5)O3 ceramics

Bi₂O₃ was selected as liquid phase sintering aid to lower the sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics. The sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics is generally high, about 1600 °C. However, the sintering temperature was significantly lowered about 275 °C from 1600 °C to 1325 °C by incorporating in 15 mol% Bi₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (?_r) value of 40.1, a quality factor (Q × f) value of 60,231 GHz, and the temperature coefficient (τ_f) value of 70.1 ppm/°C. During all addition ranges, the relative dielectric constants (?_r) were different and ranged from 32.0 to 41.9, the quality factors (Q × f) were distributed in the range of 928–60,231 GHz, and the temperature coefficient (τ_f) varies from 0.3 ppm/°C to 70.3 ppm/°C. Noticeably, a nearly zero τ_f can be found for doping 5 mol% Bi₂O₃ sintering at 1325 °C. It implies that nearly zero τ_f can be achieved by appropriately adjusting the amount of Bi₂O₃ additions and sintering temperature for La(Mg_0.5Ti_0.5)O₃ ceramics.     

Effect of Bi2O3 on the electrochemical performance of LaBaCo2O5+δ cathode for intermediate-temperature solid oxide fuel cells

The LaBaCo₂O_5+δ−x wt.% Bi₂O₃ (LBCO-xBi₂O₃, x=10, 20, 30, and 40) were prepared as composite cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) via the conventional mechanical mixing method. The effect of Bi₂O₃ on polarization resistance, overpotential, and long-term stability of the LBCO cathode was investigated. An effective sintering aid for LBCO cathode, Bi₂O₃ not only lowers its sintering temperature by ~200 °C, but also improves the electrochemical performance within the intermediate temperature range of 600–800 °C. Electrochemical impedance spectroscopy measurements showed that the addition of 20 wt% Bi₂O₃ to LBCO exhibited the lowest area-specific resistance of 0.020 Ω cm² at 800 °C in air, which was about a seventh of that of the LBCO cathode at the same condition. At a current density of 0.2 A cm⁻², the cathodic overpotential of LBCO-20Bi₂O₃ was about 12.6 mV at 700 °C, while the corresponding value for LBCO was 51.0 mV. Compared to B₂O₃–Bi₂O₃–PbO frit, the addition of Bi₂O₃ significantly improved the long-term stability of cathode. Therefore, LBCO-20Bi₂O₃ can be a promising cathode for IT-SOFCs.     

Synthesis and NTC properties of YCr1−xMnxO3 ceramics sintered under nitrogen atmosphere

YCr_1−xMn_xO₃ (0 ≤ x ≤ 0.8) negative temperature coefficient (NTC) compositions were synthesized by classical solid state reaction at 1200 °C, and sintered under nitrogen atmosphere at 1500 °C and 1600 °C. XRD patterns analysis has revealed that for x ≤ 0.6, the structure consists of a solid solution of an orthorhombic perovskite YCrO₃ phase with Mn substitute for Cr. For x ≥ 0.8, a second phase with a structure similar to the hexagonal YMnO₃ phase appears. SEM images and calculated open porosity have shown that the substitution of Mn for Cr results in a decrease in porosity. Whatever the sintering temperature, the electrical characterizations (between 25 and 900 °C) have shown that the increase in the manganese content involves the decrease in both resistivity and material constant B (parameter which characterizes the thermal sensitivity of material) when x ≤ 0.6. The magnitude order of the resistivity at 25 °C is of 10⁴-10⁸ Ω cm and activation energies vary from 0.28 to 0.99 eV at low and high temperatures, respectively.     

Development of novel perovskite based oxide ion conductor

The phase evolution and electrical conductivity of undoped and calcium-doped GdAlO₃ samples have been investigated. The undoped and doped compositions of GdAlO₃ were prepared through citrate gel process. Analysis of the phases was carried out using X-ray diffraction (XRD). The microstructural evaluation of the samples was carried out by SEM/EDS. The electrical conductivity of Gd_1−xCa_xAlO_3−δ (x = 0-0.3) was measured using ac impedance spectroscopy as a function of temperature ranging from 300 to 1000 °C under air. Among the doped compositions, Gd_0.85Ca_0.15AlO_3−δ exhibited a conductivity of 0.057 S/cm at 1000 °C.     

The phase structure and electric properties of low-temperature sintered (K,Na)NbO3-based piezoceramics modified by CuO

0.25 wt% CuO-doped (Li,K,Na)(Nb,Ta)O₃–AgSbO₃ lead-free piezoceramics with pure perovskite structure were successfully prepared at a sintering temperature below 1000 °C. The sintering temperature of KNN-based piezoceramics was effectively reduced by about 100 °C due to the enhanced densification process induced by the addition of CuO. Besides, the acceptable sintering temperature window was broadened by the addition of CuO. It is found that the CuO-doped samples show slightly higher tetragonal–orthorhombic phase transition point (T_T−O) but a lower Curie point (T_c), compared to undoped ones. The KNN-based piezoceramics became “hard” as CuO was added, supported by an increase of Q_m. Fairly good electrical properties of d₃₃^*=383 pm/V, ε_r=860, Q_m=188 and T_c=215 °C could be obtained in dense CuO-modified KNN-based piezoceramics sintered at 970 °C, demonstrating promising potential in practical applications.     

Microwave dielectric properties of SnO2-doped CaSiO3 ceramics

SnO₂-doped CaSiO₃ ceramics were successfully synthesized by a solid-state method. Effects of different SnO₂ additions on the sintering behavior, microstructure and dielectric properties of Ca(Sn_1−xSi_x)O₃ (x=0.5–1.0) ceramics have been investigated. SnO₂ improved the densification process and expanded the sintering temperature range effectively. Moreover, Sn⁴⁺ substituting for Si⁴⁺ sites leads to the emergence of Ca₃SnSi₂O₉ phase, which has a positive effect on the dielectric properties of CaO–SiO₂–SnO₂ materials, especially the Qf value. The Ca(Sn_0.1Si_0.9)O₃ ceramics sintered at 1375 °C possessed good microwave dielectric properties: ε_r =7.92, Qf =58,000 GHz and τ_f=−42 ppm/°C. The Ca(Sn_0.4Si_0.6)O₃ ceramics sintered at 1450 °C also exhibited good microwave dielectric properties of ε_r=9.27, Qf=63,000 GHz, and τ_f=−52 ppm/°C. Thus, they are promising candidate materials for millimeter-wave devices.     

Effects of CaTiO3 addition on the densification and microwave dielectric properties of BiSbO4 ceramics

In this study, the effects of CaTiO₃ addition on the sintering characteristics and microwave dielectric properties of BiSbO₄ were investigated. Pure BiSbO₄ achieved a sintered density of 8.46 g/cm³ at 1100 °C. The value of sintered density decreased with increasing CaTiO₃, and sintering at a temperature higher than 1100 °C led to a large weight loss (>2 wt%) caused by the volatile nature of the compound. Samples either sintered above 1100 °C or with a CaTiO₃ content exceeding 3 wt% showed poor densification. SEM micrographs revealed microstructures with bimodal grain size distribution. The size of the smaller grains ranged from 0.5 to 1.2 μm and that of the larger grains between 3 and 7 μm. The microwave dielectric properties of the (1−x) BiSbO_4−x CaTiO₃ ceramics are dependent both on the x value and on the sintering temperature. The 99.0 wt% BiSbO₄–1.0 wt% CaTiO₃ ceramic sintered at 1100 °C reported overall microwave dielectric properties that can be summarized as ε_r≈21.8, Q×f≈61,150 GHz, and τ_f≈−40.1 ppm/°C, all superior to those of the BiSbO₄ ceramics sintered with other additives.     

Optical properties of transparent Pr:YSAG ceramic

Pr-doped Y₃Sc_xAl_(5−x)O₁₂ (Pr:YSAG) powders were prepared with a chemical combustion method. Transparent Pr:YSAG ceramics with up to 40% scandium substitution for aluminum (Pr:Y₃Sc₂Al₃O₁₂) and 4 at.% of Pr doping were successfully fabricated by sintering the powder compact at 1800 °C under H₂ atmosphere. Optical properties of Pr:YSAG transparent ceramics were investigated in detail. It was found that by the scandium substitution for aluminum, the YSAG lattice expanded, which favored the formation of Pr:YSAG solid solution.     

Synthesis and thermal behavior of Cu/Y2W3O12 composite

Cu metal matrix composite with Y₂W₃O₁₂ as a thermal expansion compensator was fabricated by high energy ball milling followed by compaction and sintering, and its thermal properties were explored for the potential applications as heat sinks in electronic industries, high precision optics, and space structures. The volume fraction of reinforcement was varied from 40% to 70% in order to tailor the composite for the simultaneous accomplishment of low thermal expansion and high thermal conductivity. The synthesis technique was optimized by varying the parameters like milling time from 1 to 20 h and sintering temperature from 600 to 1000 °C in order to achieve densified composites. The relative density of the composites is found to be around 90% for the 10 h milled powders followed by compaction at a pressure of 700 MPa and sintering at a temperature of 1000 °C. The thermal expansion of the composites exhibits linear behavior in the temperature range 200 to 800 °C and the low coefficient of thermal expansion (CTE) is found to be for Cu–70%Y₂W₃O₁₂ composite whose value, 4.32±0.75×10⁻⁶/°C, matches with that of Si substrate. The thermal conductivities are found to increase with a decrease in the volume fraction of the reinforcement and decrease with an increase in the temperature for all the samples. The experimentally determined CTE and thermal conductivity values are found to be comparable to those predicted by the thermal expansion based Kerner and Turner model and the thermal conductivity based Maxwell model, respectively.     

Temperature dependence of piezoelectric properties on Nd and V co-substituted Bi4Ti3O12 ceramics for ceramic resonator applications

The temperature dependences of the piezoelectric properties of (Bi_4−yNd_y)_1−(x/12)(Ti_3−xV_x)O₁₂ [BNTV-x, y (x = 0.01, y = 0.00–1.00)] were investigated for environmentally friendly lead-free piezoelectric ceramic resonators with low-temperature coefficients of resonance frequency, TC-f. The |TC-f| in the (33) mode improved with increasing concentration of modified Nd ions, y, and exhibited the smallest |TC-f| value of 77.4 ppm/°C at y = 0.75 (BNTV-0.75). The |TC-f| in the other vibration mode (t), was also investigated for the BNTV-0.75 ceramic, and a smaller value of 42 ppm/°C was obtained. The (t) mode of the BNTV-0.75 ceramic showed excellent piezoelectric properties: Q_m = 4200, Q_e max = 31 and TC-f = −49.8 ppm/°C. These properties are very similar to those of commercialized hard PZT ceramics for resonator applications. The BNTV-0.75 ceramic seems to be a superior candidate material for lead-free piezoelectric applications of ceramic resonators.     

Microstructural and electrical behavior of Bi4V2−xCuxO11−δ (0 ≤ x ≤ 0.4)

Cation substituted bismuth vanadate possesses high oxygen ion conductivity at lower temperatures. The ionic conductivity of this material at 300 °C is 50–100 times more than any other solid electrolyte. Three phases (α, β, γ) are observed in the substituted compound; α and γ are low and high conducting phase, respectively. Samples of Bi₄V_2−xCu_xO_11−δ (x = 0–0.4) were prepared by solid-state reaction technique. Impedance spectroscopy measurements were carried out in the frequency range of 100 Hz to 100 kHz using gold sputtered cylindrical shaped pellets to obtain bulk ionic conductivities as a function of the substitution and temperature. The change of slopes observed in the Arrhenius plots is in agreement with the phase transitions for all the compositions. The highest ionic conductivity of the Cu-substituted compound was observed in Bi₄V_1.8Cu_0.2O_11−δ which is attributed to its lower activation energy. Microstructural studies indicated the stabilization of high temperature γ-phase at low temperature in those samples whose ionic conductivity observed was higher.     

The effects of doped Nd on conductivity and phase stability of BaCe0.8Y0.2O3−δ-based electrolyte for solid oxide fuel cell

This study investigates the structure, phase stability, and electrical properties of BaCe_0.8Y_0.2−xNd_xO_3−δ (x = 0-0.2) in humid air. XRD results indicate that a BaCe_0.8Y_0.2−xNd_xO_3−δ sample has an asymmetric orthorhombic structure, and this structure becomes more symmetric as the amount of Nd doping increases. The conductivity of BaCe_0.8Y_0.2−xNd_xO_3−δ depends on the amount of Nd doping and the operation temperature. AC impedance results indicate that the resistance of BaCe_0.8Y_0.2−xNd_xO_3−δ decreases as the temperature increases, with the majority of resistance coming from oxygen ion diffusion. The XRD peak intensity of BaCe_0.8Y_0.2O_3−δ apparently decreased with time, forming Ba(OH)₂ and CeO₂ second phases. The phase stability of BaCe_0.8Y_0.2−xNd_xO_3−δ (x = 0.05-0.2) samples is much better than that of BaCe_0.8Y_0.2O_3−δ, and it exhibited no second phase after tested in an 80 °C water bath for 18 h.     

Effect of Bi-substitution on the microstructure and electromagnetic properties of YCaZrVIG with low sintering temperature

Bi substituted YCaZrVIG ferrites, Y_2.3−xBi_xCa_0.7Zr_0.3V_0.2Fe_4.42O₁₂ (x=0.1, 0.25, 0.4, 0.5, 0.75) ferrites were prepared by conventional oxide method. The addition of Bi₂O₃ promoted the sintering performance and lowered the sintering temperature from 1420–1230 °C. However, it also resulted in the formation of minor second phases and the decrease of grain size. With the increase of Bi concentration, the dielectric constant increases linearly and then remains unchanged. The dielectric loss decreased firstly and then increased. The saturation magnetization (4πM_s) almost retained unchanged as the Bi concentration increased except for the sample with 0.75. The coercivity (H_c) decreased firstly and reached the minimum of 1.32 Oe at 0.25, and then rose when x>0.25, which was related to the facility of magnetic domain wall motion and magnetic moment reverse. Moderate addition of Bi also can increase the remanence (B_r) by improving sintering process. Additionally, we got the optimum electromagnetic properties in the samples with x=0.25 at 1230 °C: RD>97%, ε_r=15.7, tan δ_e=2.48×10⁻⁴, H_c=1.32Oe, 4πM_S=1663 Gs, B_r=583.91 Gs.