Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Ultrahigh Q values and atmosphere-controlled sintering of Li2(1+x)Mg3ZrO6 microwave dielectric ceramics

Ultrahigh-Q Li_2(1+x)Mg₃ZrO₆ microwave dielectric ceramics were successfully prepared by means of atmosphere-controlled sintering through simultaneously adopting double crucibles and sacrificial powder. This technique played an effective role in suppressing the lithium volatilization and further promoting the formation of the liquid phase, as evidenced by the X-ray diffraction, microstructural observation and the density measurement. Both dense and even microstructure, and the suppression of detrimental secondary phases contributed to low-loss microwave dielectric ceramics with Q×f values of 150,000–300,000 GHz. Particularly, desirable microwave dielectric properties of ε_r=12.8, Q×f=307,319 GHz (@9.88 GHz), and τ_f=−35 ppm/°C were achieved in the x=0.06 sample as sintered at 1275 °C for 6 h.     

Phase structural transition and microwave dielectric properties in isovalently substituted La1−xLnxTiNbO6 (Ln=Ce,Sm) ceramics

Aeschynite-type La_1−xLn_xTiNbO₆ (Ln=Ce, Sm, x=0–1) ceramics were prepared via a conventional solid state method. Analysis of X-ray diffraction, Raman, infrared reflectivity spectra and the microstructures revealed a series of composition-induced phase evolution in sequence: monoclinic→coexistence of monoclinic and orthorhombic→orthorhombic structure, i.e. M→M+O→O. The critical compositions of distinguishing the dominant M or O phase were x=0.15 in La_1−xCe_xTiNbO₆ and x=0.10 in La_1−xSm_xTiNbO₆ ceramics, exactly corresponding to the average ionic radius of rare earth ions (IR) ~1.027 Å. The crystal structure and microwave dielectric properties of RETiNbO₆ (RE=rare earth) ceramics strongly depended on IR. Near-zero τ_f was achieved in the Ce-sample with x=0.153 (ε_r=28.9, Q×f=17,275 GHz@6.54 GHz) as well as in the Sm-sample with x=0.098 (ε_r=28.2, Q×f=19,186 GHz@6.78 GHz). Eventually, RETiNbO₆ would form O euxenite (-τ_f), O aeschynite (+τ_f), and M aeschynite (-τ_f), as IR<0.945 Å, 0.945 Å <IR<1.027 Å, and 1.027 Å<IR<1.032 Å, respectively. The infrared reflectivity study also confirmed that the structural phonon oscillations in the infrared region dominated the dielectric performance in the microwave region for this system.     

Structure and dielectric characteristics of continuous composition spread Ba1−xSrxTiO3 thin films by combinatorial pulsed laser deposition

Ba_1−xSr_xTiO₃ (0≤x≤1, BST-x) continuous composition spread thin films were grown on SrTiO₃ substrates buffered by La_0.9Sr_1.1NiO₄ (LSNO) electrodes using combinatorial pulsed laser deposition. The effects of Sr concentration on the structure and dielectric properties of the Au/BST-x/LSNO capacitors were investigated. X-ray diffraction patterns and reciprocal space maps revealed that both the in-plane and out-of-plane BST-x lattice parameters decreased with the increment of Sr content. Impedance measurements showed that the dielectric constant and tunability simultaneously changed with Sr concentration and reached the maximum at about x=0.5, which is comparable to that of BST-x individual thin films or bulks. Our results showed the large potential of combinatorial method in optimizing materials properties and even finding new materials.     

Structure and electrical properties of Ca2+-doped (Na0.47Bi0.47Ba0.06)TiO3 lead-free piezoelectric ceramics

The lead-free piezoelectric ceramics (Na_.47Bi_.47Ba_.06)_1-xCa_xTiO₃ (x?=?0, 0.01, 0.02, 0.03, 0.05, and 0.08, abbreviated as BNBTC/0, BNBTC/1, BNBTC/2, BNBTC/3, BNBTC/5, and BNBTC/8, respectively) were obtained using the solid-state reaction method. The structure, electric conductivity, and dielectric, ferroelectric, and piezoelectric properties of the Ca²⁺-doped (Na_.47Bi_.47Ba_.06)TiO₃ ceramics were thoroughly investigated. The ceramics sintered at 1200?°C exhibit dense microstructures, having relative densities higher than 96%. The X-ray diffraction results demonstrate that all ceramics have a pure perovskite structure. The mean grain sizes of the ceramics are related to the Ca²⁺ quantity. A small quantity of Ca²⁺ ions (x?≤?0.03) improves the piezoelectric and ferroelectric properties of the samples. The dielectric behavior of the samples is sensitive to the Ca²⁺ content and electric poling. The results demonstrate that the electrical properties of the (Na_.47Bi_.47Ba_.06)TiO₃ lead-free ceramics can be well tuned by varying the Ca²⁺ quantity.     

Control of coring effect in BaTi4O9 microwave dielectric ceramics by doping with Mn4+

In the present work, we have attempted to reduce the effect of coring effect in the titanate ceramic system BaTi₄O₉ (BT4) by doping it with Mn⁴⁺. The microwave dielectric BaTi₄O₉ ceramics doped with 0, 0.5 and 1.0 mol% Mn⁴⁺ were synthesized by conventional ceramic processing route. The XRD studies confirmed a single phase crystalline structure for all the ceramic samples studied. The SEM micrographs of the ceramics reveal a microstructural change leading towards a more uniform grain size distribution as the Mn⁴⁺ content increases to 1.0 mol%. In the low frequency region (100 Hz to 1 MHz), the temperature stability of dielectric properties exhibits a marked improvement with the increasing amount of Mn⁴⁺ in the ceramic system. In the microwave frequency region (9.3 GHz), Q-factor increases from 11,625 GHz to 46,500 GHz for BaTi₄O₉ ceramic doped with 1.0 mol% Mn⁴⁺. The present paper reveals that the commonly observed degradation of dielectric properties due to coring effect in the BaTi₄O₉ ceramic system can be controlled by doping it with an appropriate quantity of Mn⁴⁺.     

Direct and facile synthesis of Li–Sr–Zn ferrites via low temperature solution combustion route

Li–Sr–Zn nanoferrites i.e. Li_0.25Sr_0.5–xZn_xFe_2.25O₄, where ‘x’ varies from 0–0.5, have been synthesized using a low temperature solution combustion method which proves to be an efficient and economical technique for synthesizing these type of nanoferrites. The as-synthesized nanoferrites have cubic spinel structure as characterized by X-ray powder diffraction. Powder XRD and TEM (Transmission Electron Microscopy) characterization also evidence that the crystallite and particle size are in close agreement to each other. Mössbauer spectroscopy studies demonstrate that there is a gradual transition from ferrimagnetic to superparamagnetic character, which is also supported by the saturation magnetization and coercivity values. At room temperature, the nanoferrites were found to be superparamagnetic with negligible coercivities approaching towards zero while saturation magnetization values were found to be in the range 6.87–30.10 emu g⁻¹. The frequency dependent dielectric constant and loss values are in accordance with Koop׳s model. These nanoferrites show great potential in high density recordings, magnetic nanodevices and biomagnetic applications.     

Electrical properties of niobium doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

Nb-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ intergrowth ceramics have been prepared by modified oxalate route. XRD phase analysis confirmed the formation of single phase compound. Nb-doping does not affect the basic crystal structure of the intergrowth. SEM micrographs showed that the grain size of the ceramics decreases with Nb-doping. The temperature dependence of dielectric constant and losses was investigated in the temperature range 30–800 °C and frequency range 1 kHz–1 MHz. With Nb-doping, the T_c of the ferroelectrics reduces and peak permittivity increases. Doping also introduces small relaxor behavior in the ferroelectrics. The dc conductivity of the ceramics decreases with doping. The remnant polarization (P_r) of the intergrowth ferroelectrics is increased with Nb doping.     

New vacancied and Gd3+-doped lead molybdato-tungstates and tungstates prepared via solid state and citrate-nitrate combustion method

New Pb_1-3x⌷_xGd_2x(MoO₄)_1-3x(WO₄)_3x (0<x≤0.1774) and Pb_1-3x⌷_xGd_2xWO₄ (0<x≤0.1154, ⌷ denotes vacancy) solid solutions were synthesized via solid state reaction route and citrate-nitrate combustion method. XRD and SEM data showed that as-prepared ceramics crystallize in the tetragonal scheelite type symmetry (space group I4₁/a) with the crystallite size varying between ~10 and ~40 µm (solid state method) or ~500 nm and 2 µm (combustion synthesis). A change in lattice constants (a and c), lattice parameter ratio c/a and progressive deformation of MoO₄/WO₄ tetrahedra with an increase of Gd content was observed. The melting point of each Gd-doped sample is lower than the melting point of adequate scheelite matrix. Ceramics under study are insulators with indirect band gap (E_g)>3 eV. EPR investigation revealed a difference among spectra obtained for varied gadolinium content, whereas synthesis method has no influence on EPR results.     

ZnLi2/3Ti4/3O4: A new low loss spinel microwave dielectric ceramic

A new low loss spinel microwave dielectric ceramic with composition of ZnLi_2/3Ti_4/3O₄ was synthesized by the conventional solid-state ceramic route. The ceramic can be well densified after sintering above 1075 °C for 2 h in air. X-ray diffraction data show that ZnLi_2/3Ti_4/3O₄ ceramic has a cubic structure [Fd-3m (227)] similar to MgFe₂O₄ with lattice parameters of a = 8.40172 Å, V = 593.07 Å³, Z = 8 and ρ = 4.43 g/cm³. The best microwave dielectric properties can be obtained in ceramic with relative permittivity of 20.6, Q × f value of 106,700 GHz and τ_f value of −48 ppm/°C. The addition of BaCu(B₂O₅) (BCB) can effectively lower the sintering temperature from 1075 °C to 900 °C and does not induce much degradation of the microwave dielectric properties. Compatibility with Ag electrode indicates that the BCB added ZnLi_2/3Ti_4/3O₄ ceramics are good candidates for LTCC applications.     

Microwave dielectric characteristics of ceramics in Mg2SiO4–Zn2SiO4 system

(Mg_1−xZn_x)₂SiO₄ ceramics were prepared and characterized. The densification temperatures of the present ceramics are much lower than those for Mg₂SiO₄ and Zn₂SiO₄ end-members. Small solid solution limits of Zn in Mg₂SiO₄ and Mg in Zn₂SiO₄ are observed, and the bi-phase structure is confirmed in (Mg_1−xZn_x)₂SiO₄ ceramics with x = 0.1–0.9. Even though, it is clear that the Qf value of Zn₂SiO₄ ceramics can be significantly improved together with a suppressed temperature coefficient of resonant frequency τ_f by substituting Mg for Zn. (Mg_0.4Zn_0.6)₂SiO₄ ceramics indicate a good combination of microwave dielectric characteristics: _r = 6.6 Qf = 95,650 GHz, and τ_f = −60 ppm/°C.     

Structural,magnetic, vibrational and impedance properties of Pr and Ti codoped BiFeO3 multiferroic ceramics

Single-phase (Bi_1−xPr_x)(Fe_1−xTi_x)O₃ ceramics (x=0.03, 0.06, and 0.10 as BPFT-3, BPFT-6 and BPFT-10, respectively) were synthesized by conventional solid state reaction method. The effect of varying Pr and Ti codoping concentration on the structural, magnetic, dielectric and optical properties of the BPFT ceramics have been investigated. X-ray diffraction indicated pure rhombohedral phase formation for BPFT-3 and BPFT-6 ceramics, however, a structural phase transition from a rhombohedral to an orthorhombic phase has been observed for BPFT-10 ceramic. The maximum remnant magnetization of 0.1824 emu/g has been observed in BPFT-6. With increasing codoping concentration the room temperature dielectric measurements showed enhancement in dielectric properties with reduced dielectric loss. UV–vis diffuse reflectance spectra demonstrated the strong absorption of light in the visible region for a band gap variation 2.31–2.34 eV. Infrared spectroscopy indicated the shifting of Bi/Pr–O and Fe/Ti–O bonds vibrations and change in Fe/Ti–O bond lengths. Decrease in the conductivity on increasing Pr and Ti concentration in BFO is attributed to an enhancement in the barrier properties leading to suppression of lattice conduction path arising due to lattice distortion as confirmed from impedance analysis.     

Oxygen ion conductivity studies of bismuth and bismuth-calcium co-doped ThO2

A series of trivalent (Bi³⁺) doped and divalent (Ca²⁺) co-doped ThO₂ samples i.e., Th_0.50-xCa_xBi_0.50O_2-δ (x = 0.00, 0.05, 0.10, 0.15 and 0.20) have been synthesized by citrate-nitrate solution combustion route and investigated in the context of oxygen ion conductivity and dielectric relaxation phenomena. The Rietveld refinement of the Powder X-ray diffraction data confirmed monophasic fluorite structures (S.G. Fm$\stackrel{￣}{3}$m) for calcium concentrations up to 20 mol %. The optical band gap decreased with the increase in Ca²⁺ concentration up to 10 mol %. In contrast, the defect band's intensity in the Raman spectra increased due to oxygen vacancies on divalent addition. The quantitative aspect of oxygen vacancy and defect concentration was derived from Raman spectra. The crystallographic index application was further employed to interpret the optimum doping concentration to maximize oxide ion conductivity. Remarkably high oxide ion conductivity (~10^?3 S/cm) was observed for Bi³⁺ doped (50 mol %), and Bi³⁺ (50 mol %)-Ca²⁺ (10 mol %) co-doped ThO₂ samples at 773 K. The Nyquist plot exhibited grain contribution for low dopant levels. Both grain and grain boundary contribution were present in the higher dopant concentrations. Conductivity, dielectric, and modulus properties of doped and co-doped samples have been compared, from which 10 mol % of Ca²⁺-doping was identified to be the optimum concentration.     

Structural and physical properties of microwave synthesized orthorhombic perovskite erbium chromite ErCrO3

Rare-earth chromite ErCrO₃ powder was synthesized from metal nitrate precursors using microwave synthesis. (Micro-) structural characterizations were performed using X-ray diffraction, Rietveld refinement, High Resolution Transmission Electron Microscopy and Electron Micro-Diffraction. Magnetization vs. temperature measurements revealed anti-ferromagnetism with T_Neel ≈ 135 K. An anti-ferrimagnetic moment of ≈0.4 μ_B was determined from magnetization vs. applied field measurements. Temperature dependent impedance spectroscopy (IS) indicated 3 dielectric relaxation processes: electrode interface, grain boundary and bulk. The intrinsic bulk activation energy was found to be 0.27 eV and the dielectric permittivity ?_r was ≈23 in excellent agreement with Clausius-Mossotti predictions and showed no perceptible temperature dependence. This and the low ?_r value suggested that ErCrO₃ is a dielectric rather than ferroelectric compound. IS measurements with applied dc bias revealed the signs of an unconventional type of Schottky barrier at the metallic Au electrode/ceramic ErCrO₃ interface.     

Relaxor behavior and ferroelectric properties of a new Ba4SmFe0.5Nb9.5O30 tungsten bronze ceramic

Unfilled tungsten bronze ceramics with a composition of Ba₄SmFe_0.5Nb_9.5O₃₀ were prepared by the conventional solid-state sintering method. The phase, microstructure, dielectric and ferroelectric properties were studied. Room temperature XRD results indicated that the ceramic occurs in the tetragonal space group P4bm phase with cell parameters of a=b=12.4712(2) Å and c=3.9430(2) Å. The temperature-dependent dielectric properties, XRD data and Raman spectra data indicated that BSFN ceramics exhibit no phase changes from 35 °C to 450 °C. Fitting of a Vogel-Fulcher relationship with an activated energy E_a of 0.11 eV indicates an unambiguous dielectric relaxor state near room temperature. Furthermore, the BSFN ceramics exhibited residual polarization and coercive field of 3.45 µC/cm² and 24.65 kV/cm, respectively.     

Effect of consolidation parameters on structural,microstructural and electrical properties of magnesium titanate ceramics

The aim of this study is to explore the influence of the processing route on the structural and physical properties of bulk MgTiO₃ ceramics. Commercially available MgO and TiO₂ powders were mechanically activated in a planetary ball mill. Green bodies were formed by an isostatic pressure of 300 MPa. The sintering of these samples was done either by the Two-Step Sintering (TSS) approach or by conventional pressureless sintering followed by Hot Isostatic Pressing (post-HIPing). The first set of compacts was sintered by TSS in air at 1300 °C for 30 min and the next step was performed at 1200 °C for 20 h. The density of the obtained samples after the two-step sintering reached almost 90% of the theoretical density (%TD). The second set of compacts was sintered at 1400 °C for 30 min in air. The samples without open porosity were post-sintered by the HIP at 1200 °C for 2 h in an argon atmosphere at a pressure of 200 MPa. The density significantly increased up to 96%TD. The differences between samples prepared by these two techniques were also analyzed by XRD and SEM. The lattice vibration spectra were obtained using Raman spectroscopy and they indicate a high degree of lattice disorder, as well as high values of the oxygen vacancy concentration. Electrical characteristic were established in the frequency range from 10 kHz to 10 GHz. The choice of the processing route had considerable influence on structural and physical properties of MgTiO₃ ceramics.     

Microwave dielectric properties of multi-ions Ba(Zn,Ta)O3-based perovskite ceramics

In this study, Ba(Zn_1/3Ta_2/3)O₃-based complex perovskite compounds, including Ba(Zn_1/3Ta_2/3)O₃, Ba(Zn_1/3Ta_1/3Nb_1/3)O₃, Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃, and Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃, were prepared and characterized. There was no second phase formation shown in the XRD patterns. Though it has been suggested that substitutions of multiple ions over A-site or B-site of the Ba(Zn_1/3Ta_2/3)O₃ ceramics may not be beneficial to their microwave dielectric properties, the Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ and Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramics in this study were found to perform in a fairly acceptable manner. The Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramic (sintered at 1575 °C for 6 h) and the Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramic (sintered at 1550 °C for 6 h) reported the following characteristics after annealing at 1400 °C for 10 h: 24.9 and 27.0 for dielectric constants (?_r), 83,000 and 32,100 GHz for quality factors (Q × f) values and −12.8 and −22.6 ppm/°C for temperature coefficients of resonance frequency (τ_f).     

Microstructure and optical properties of electrodeposited Al-doped ZnO nanosheets

This study grew A1-doped ZnO nanosheets on polycrystalline zinc foils using cathodic electrodeposition in an aqueous solution consisting of 0.02 M Zn(NO₃)₂ and 0.001 M Al(NO₃)₃ at 90 °C. The effects of the electrodepositing potential and thermal annealing on the physical properties of the Al-doped ZnO sheets were investigated. This study observed a high quality sheet-like structure of the electrodeposited Al-doped ZnO for the applied potential larger than −1.1 V, and the sheets were interconnected over the area of interest. The X-ray diffraction patterns showed that the intensity of the Bragg reflections of the electrodeposited Al-doped ZnO sheets increases with the electrodepositing potential because a larger applied potential results in the Al-doped ZnO sheets having a larger lateral dimension and thickness. However, the appearance of the Al-doped ZnO sheets becomes coarse and rough after thermal annealing at 400 °C in ambient air for 4 h. The intensity of the Bragg reflections of the Al-doped ZnO sheets was markedly increased through the thermal annealing due to the improvement of the crystalline quality of the annealed Al-doped ZnO sheets. Annealing caused a large decrease in structural defects of the Al-doped ZnO sheets electrodeposited at −1.3 V causing the sheets to exhibit a sharp photoluminescence peak at ∼380 nm.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Temperature dependence of macroscopic and microscopic PZT properties studied by thermo-mechanical analysis,dielectric measurements and X-ray diffraction

The main objective of the paper is to point out the influence of composition and of poling state (poled and unpoled samples) on the evolution of various parameters (?_r, dilatation coefficients, lattice parameters) at different scales (lattice, bulk) using X-ray diffraction (XRD), thermo-mechanical analysis (TMA) and dielectric methods. The transition temperatures have been determined from the above measurements and compared. The composition has an influence on the transition temperature and not on the dilatation coefficient value. The poling state influences only the macroscopic dilatation evolution and not the value of the transition temperature. A scale effect is only observed on majoritary tetragonal compositions which show different values of transition temperatures from microscopic and macroscopic methods.