The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Improved properties & fatigue resistant behaviour OF Ba(Zr0.15Ti0.85)O3 ferroelectric ceramics

The microstructure, dielectric and piezoelectric properties of Zr doped BaTiO₃ ceramics sintered at optimum temperature, are investigated. High energy ball milling technique is adopted to realize nano-sized powders of Ba(Zr_0.15Ti_0.85)O₃ ceramics. Increased boundary mobility of fine powders aided to obtain a relative density of >98.8% of theoretical density corresponding to ceramics under study. Internal stresses in these ceramics are found to be relieved by grain-boundary sliding. The Ba(Zr_0.15Ti_0.85)O₃ ceramics synthesized at relatively low sintering temperatures exhibit remarkable, enhanced dielectric properties viz. improved polarization, high unipolar strain values comparable to Zr doped BaTiO₃ single crystals of same composition, at relatively lower electric fields and also exhibit better fatigue tolerant properties. The underlying mechanisms responsible for superior dielectric, ferroelectric and piezoelectric properties are discussed.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

Dielectric and magnetic properties of low-temperature fired NiCuZn-BaTiO3 composites

The composition effects on the dielectric and magnetic properties of NiCuZn-BaTiO₃ composites fired at low temperature were investigated. The coexistence of perovskite BaTiO₃ and spinel ferrite phases in the composites were observed; no significant chemical reactions occurred between BaTiO₃ and NiCuZn ceramics during sintering. The nanosized BaTiO₃ powders favored a decrease in grain size. The saturation magnetization, remanent magnetization and real permeability continuously decreased with increasing BaTiO₃ content. And the real permittivity continuously increased with the BaTiO₃ content. The Q-factor (quality factor) exhibited relatively high values with 20-30 wt% BaTiO₃. All composite materials exhibited a low dielectric loss below 100 MHz. Synthetically considerations, the composites with 20-30 wt% BaTiO₃ could obtain relatively high real permeability and real permittivity values, and the magnetic and dielectric losses were relatively low, so they were the best candidates to produce LC-integrated chip elements.     

Microstructure and dielectric properties of Li2CO3 doped 0.7(Ba,Sr)TiO3–0.3MgO ceramics

Microstructure and dielectric properties of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃–0.3MgO ceramics for the low temperature sintering and microwave applications will be presented. In these days, low temperature sintering process has been widely spread out for the integrated electronic modules for the communication systems such as front-end modules, antenna modules, and switching modules. We have added Li₂CO₃ and MgO to (Ba,Sr)TiO₃ material to reduce the sintering temperature and improve dielectric properties such as loss tangent, and frequency dispersion.In this paper, we have discussed the crystalline properties, dielectric properties, and the microstructures of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃–0.3MgO ceramics. No pyro phase was observed in the X-ray diffraction method. Very weak frequency dispersion (<0.7%) of dielectric permittivity was observed from the 1 kHz to 1 MHz range. We found that the grain size of BST is around 2 μm, while the grain size of Li₂CO₃ dope 0.7BST–0.3MgO is around 4 μm from the SEM analysis.     

Low-temperature sintering of KNN with excess alkaline elements and the study of its ferroelectric domain structure

In the present work, lead-free K_0.48Na_0.52NbO₃ (KNN) ceramics were synthesized by conventional ceramics processes. The excess 3.3 mol% Na₂CO₃ and 1.1 mol% K₂CO₃ were added to decrease the sintering temperature to 990 °C and effectively promote the densification of KNN ceramics. X-ray diffraction results indicated that the excess Na₂CO₃ and K₂CO₃ would induce the formation of the A-site riched secondary phase with the sintering temperature. Compositional segregation phenomenon enhanced by different sintering temperature, spurs the formation of secondary phase in KNN-AEe ceramics. In addition, the difference between ferroelectric domain structure of the poled and as-sintered KNN-AEe samples for 990 °C was investigated. Via XRD analysis and SEM observation, it was found that the domain orientation was urged during the poling process.     

Ferroelectricity and ferromagnetism in fine-grained multiferroic BaTiO3/(Ni0.5Zn0.5)Fe2O4 composites prepared by a novel hybrid process

Dense, homogeneous, and fine-grained multiferroic BaTiO₃/(Ni_0.5Zn_0.5)Fe₂O₄ composite ceramics are synthesized by a novel powder-in-sol precursor hybrid processing route. This route includes the dispersion of nanosized BaTiO₃ ferroelectric powders prepared via conventional sold-state ceramic process into (Ni_0.5Zn_0.5)Fe₂O₄ ferromagnetic sol-gel precursor prepared via a sol-gel wet chemistry process. The composite ceramics show coexistence of obvious ferroelectric and ferromagnetic hysteresis loops at room temperature. Very low dielectric loss of about 0.02–0.0067 in the range of 10 kHz–10 MHz can be achieved, which is about an order of magnitude lower than the results of many reports using conventional processes at room temperature. The combination of high permeability and permittivity with low losses in the ceramics enables significant miniaturization of electronic devices based on the ceramics.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Effect of Cu-stoichiometry on the dielectric and electric properties in CaCu3Ti4O12 ceramics

CaCu_3+yTi₄O₁₂ (y=0, ±0.025, ±0.05, ±0.1 and −0.15) ceramics are prepared by the conventional solid-state reaction technique under sintering condition of 1050 ^°C, 10 h. X-ray diffraction shows that they all have the good crystalline structure. Cu-deficient ceramics exhibit the microstructures of uniform grain size distribution, whereas both Cu-stoichiometric and Cu-rich ceramics display microstructures of bimodal grain size distribution. The largeness of low-frequency dielectric permittivity at room temperature is found to be very sensitive to the Cu-stoichiometry. Upon raising the measuring temperature, all of the ceramics present commonly three semicircles in the complex impedance plane. It indicates that there exist three distinct contributions, which are ascribed to arising from domains, grain boundaries and domain boundaries. In addition, the influence of CuO segregation on the dielectric and electrical properties is also discussed.     

The effects of sintering temperatures on dielectric,ferroelectric and electric field-induced strain of lead-free Bi0.5(Na0.78K0.22)0.5TiO3 piezoelectric ceramics synthesized by the sol–gel technique

Lead-free Bi_0.5(Na_0.78K_0.22)_0.5TiO₃ (BNKT) piezoelectric ceramics were synthesized by the sol–gel technique. The effects of sintering temperatures on the crystal structure, microstructure, densification, dielectric, ferroelectric and electric field-induced strain behaviors of the BNKT ceramics were investigated. X-ray diffraction patterns exhibited a pure perovskite structure from 1075 to 1150 °C. A scanning electron microscopy study revealed an increase in grain size with increasing sintering temperature. The density of the ceramics sintered at 1150 °C reaches a maximum value of 5.55 g/cm³, which is 96% of the theoretical density. BNKT ceramics sintered at an optimum temperature of 1150 °C exhibited a high remnant polarization of 18.5 μC/cm², a high electric field-induced strain of 0.20% and dynamic piezoelectric coefficient d₃₃¹ = (S_max/E_max) of 247 pm/V.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

Preparation and characterization of CaTiO 3 –(Li 1/2 Nd 1/4 Sm 1/4 )TiO 3 microwave ceramics by a sol–gel combustion process

A novel sol–gel combustion process was adopted to synthesize reactive ceramic powder with composition of 0.25 CaTiO₃–0.75 (Li_1/2Nd_1/4Sm_1/4)TiO₃, and microwave dielectric ceramics were prepared at different sintering temperatures using the synthesized powder. The combustion behavior of citrate gel and the sintering feature of the synthesized powder were evaluated by using differential thermal analysis–thermogravimetric analysis and thermo-mechanical analysis techniques, respectively. The citrate gel exhibits a self-propagating behavior after being ignited in air at room temperature. The as-burnt powder is so highly reactive that it can be transformed into single-phase perovskite at 900 °C and it can be sintered at 1100 °C. The effects of sintering temperature on the density, microstructure, and dielectric properties of the sintered ceramics were investigated. The maximum values of density, dielectric constant, and Q×f were achieved after sintering at 1200 °C. At 1200 °C, very dense ceramics with uniform grains and good dielectric properties with a dielectric constant of 123.8, a Q×f value of 5110 (at 3.7 GHz), and a τ_f value of +12.5 ppm/°C were achieved via the sol–gel combustion route. PACS 77.84.Dy; 81.20.FW; 77.22.-d     

Microstructures and microwave dielectric properties of La1-xBx(Mg0.5Sn0.5)O3 ceramics

The microwave dielectric properties of La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A maximum apparent density of 6.58 g/cm³, a dielectric constant (ε_r) of 19.8, a quality factor (Q × f) of 41,800 GHz, and a temperature coefficient of resonant frequency (τ_f) of −86 ppm/°C were obtained for La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.     

Effect of calcium substitution on structural,dielectric, ferroelectric,piezoelectric, and energy storage properties of BaTiO3

The effect of calcium substitution on the structural, dielectric, ferroelectric, piezoelectric, and energy storage properties of BaTiO₃ (BT) ceramics has been investigated. XRD confirmed the phase formation of Barium Calcium Titanate (BCT), and structural Rietveld refinement was used to estimate the lattice parameters. It is evident from the SEM data that the average grain size decreases as calcium is added. At Curie temperature (110 °C), BCT 0.10 ceramic has a good dielectric constant of 15834 and a very low dielectric loss of 0.009. According to the ferroelectric and piezoelectric investigations, BCT 0.10 exhibits maximum spontaneous polarization with the highest piezoelectric charge coefficient of 100 pC/N. BCT 0.10 has a maximum energy storage density of 96.8 mJ/cm³ and a good energy storage efficiency of 53.9%, which is around three times that of pure BaTiO₃. These results suggest that the BCT ceramic has good potential for energy storage applications.     

Improving microwave dielectric properties of La2.98/3Sr0.01(Mg0.5Sn0.5)O3 ceramics with CuO additive

The microwave dielectric properties of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were investigated with a view to their application in microwave devices. CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method. The X-ray diffraction patterns of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics exhibited no significant variation of phase with sintering temperature. By adding 0.75 wt.% CuO, a dielectric constant of 20.07, a quality factor (Q × f) of 63,000 GHz, and a temperature coefficient of resonant frequency τ_f (−77.0 ppm/°C) were obtained when La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were sintered at 1500 °C for 4 h.     

Ferroelectric behaviour of 30nm BaTiO3 ceramics prepared by high pressure assisted sintering

Dense nanocrystalline BaTiO3 ceramics with a homogeneous grain size of 30 nm was obtained by pressure assisted sintering. The ferroelectric behaviour of the ceramics was characterized by the dielectric peak at around 120 ℃, the P-E hysteresis loop and some ferroelectric domains. These experimental results indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm. The ferroelectric property decreasing with decreasing grain size can be explained by the lowered tetragonality and the ＇dilution＇ effect of grain boundaries.     

Effect of sintering atmosphere on Ni/PTC composites ceramics

In order to prepare lead-free BaTiO₃-based PTC (positive temperature coefficient) with low room temperature resistivity, metal Ni is added to BaTiO₃-based PTC samples that contain 5, 8, 10, 12, 15, 20 wt% of Ni. The sintering temperature is from 1240 °C to 1260 °C. The sintering atmosphere of Ni/PTC composites ceramics was studied. Two sintering atmospheres were adopted in this experiment; full reducing sintering atmosphere and part reducing sintering atmosphere. Controlling the dose of graphite powder can make these two reducing atmospheres. The experiment data show that the optimal sintering atmosphere is a part-reducing atmosphere. Under on the conditions mentioned above, the room temperature resistivity of the samples can drop to under 10 Ω cm and the PTC jump can reach 10³, which represents a good PTC characteristic.     

All-inkjet-printed Metal-Insulator-Metal (MIM) capacitor

BaTiO₃-resin hybrid composite is one of the most promising candidates to surmount the intrinsic process issues of pure ceramic materials such as the requirement of high temperature sintering, disability to be integrated with dissimilar materials, etc. We utilized the inkjet printing to prepare all-inkjet-printed MIM (Ag/BaTiO₃-resin hybrid film/Ag) capacitor. The microstructures of the MIM capacitor were investigated to confirm the integrity of dissimilar layers within MIM capacitor. The dielectric properties of BaTiO₃-resin hybrid film in MIM capacitor were also investigated by measuring its relative permittivity and loss tangent. The inkjet-printed BaTiO₃-resin hybrid composite film showed that its relative permittivity and loss tangent were 70 and 0.011 at 1 MHz, respectively.     

Preparation and properties of Nd-doped BCTH lead-free ceramics by solid-phase twin crystal method

0.5 mol% Nd-doped (Ba_0.85Ca_0.15)(Ti_0.9Hf_0.1)O₃ (BCTH-Nd) lead-free ceramics were prepared by a solid-phase twin crystal method, where the effects of sintering condition on structure, electrical and optical properties were studied. All the sintered BCTH-Nd ceramics exhibit pure perovskite structure, dense microstructure with several micron grain size, which tends to increase with elevating sintering temperature. All synthesized ceramics have complex dielectric behavior, which presents normal ferroelectrics characteristic with slight dispersion phenomenon. The BCTH-Nd ceramics exhibit excellent piezoelectric and ferroelectric properties and acceptable dielectric performance when sintered at 1480 °C for 2 h. Under 269 nm light excitation, several fluorescent emission peaks are excited with a whole indigo fluorescence, where the strongest emission peak is emitted at 473 nm, corresponding to the ⁴G_3/2 → ⁴I_9/2 energy level transition of Nd³⁺. Multifunctional performance is fulfilled in the lead-free BCTH ceramics via rare earth doping, which can broaden the application fields of piezoelectric-based materials.     

Effect of the solid-state synthesis parameters on the physical and electronic properties of perovskite-type Ba(Fe,Nb)0.5O3 ceramics

Single-phase cubic Ba(Fe,Nb)_0.5O₃ (BFN) powder was synthesized by solid-state reaction at 900, 1000, 1100, 1200 °C for 4 h in air. X-ray diffraction indicated that the BFN oxide mixture calcined at 1200 °C crystallizes to the pure cubic perovskite phase. The crystallite size of the BFN increases slightly with increasing temperature, while the lattice strain progressively decreases. BFN ceramics were produced from this powder by sintering at 1350–1400 °C for 4 h in air. Samples prepared under these conditions achieved up to 97.4% of the theoretical density. The temperature dependence of their dielectric constant and loss tangent, measured at difference frequencies, shows an increase in the dielectric constant with sintering temperature and measurement frequency which is probably due to disorder on the B site ion of the perovskite. The Mössbauer spectra of these sintered BFN ceramics suggests the presence of a superstructure on the B-cation sublattice.