Li2O excess (Na0.51K0.47Li0.02)(Nb0.8Ta0.2)O3 lead free piezoelectric ceramics

1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics were prepared by the conventional mixed oxide method and sintered from 950 to 1200 °C. Also, Li₂O was employed as a sintering aid for high densification and low temperature sintering process. X-ray diffraction results of 1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ lead free piezoelectric ceramics indicated that the specimens were well crystallized and have tetragonal structure. The specimens which sintered at 1050 °C showed the highest piezoelectric properties compared with others. The measured piezoelectric constant and electromechanical coupling coefficient were 231 pC/N and 38.9%, respectively. Curie temperature of (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics was 344.32, 344.4 and 344.5 °C at 1, 10 and 100 kHz, respectively.     

Microwave properties of Ba(Mg1/3Ta2/3)O3, Ba(Mg1/3Nb2/3)O3 and Ba(Co1/3Nb2/3)O3 ceramics revealed by Raman scattering

Five Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperatures (form 1350 to 1550 °C), one Ba(Mg_1/3Ta_2/3)O₃ and a Ba(Mg_1/3Nb_2/3)O₃ sample were examined by Raman scattering to reveal the correlation of the 1:2 ordered perovskite structure with the microwave properties, such as dielectric constant and Q factors. The Ba(Co_1/3Nb_2/3)O₃ sample sintered at 1400 °C, which possesses the highest microwave Q value and the lowest dielectric constant among five Ba(Co_1/3Nb_2/3)O₃ samples, has the narrowest width and the highest frequency of the stretch mode of oxygen octahedron (i.e. A_1g(O) near 800 cm⁻¹). We found that the dielectric constant is strongly correlated with the Raman shift of A_1g(O) stretch modes, and the width of A_1g(O) stretch mode reflects the quality factor Q × f value in the 1:2 ordered perovskite materials. This concludes that the oxygen octahedron play an important role of the material's microwave performance. Based on the results of Q × f values and the lineshapes of A_1g(O) stretch mode, we found that the propagation of microwave energy in Ba(Mg_1/3Ta_2/3)O₃ and Ba(Mg_1/3Nb_2/3)O₃ shows weak damping behavior, however, Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperature exhibit heavily damped behavior.     

Effect of Li2O–V2O5 on the low temperature sintering and microwave dielectric properties of Li1.0Nb0.6Ti0.5O3 ceramics

Li₂O–Nb₂O₅–TiO₂ based ceramic systems have been the candidate materials for LTCC application, due to their high dielectric constant and Q × f value and controllable temperature coefficient in the microwave region. However, the sintering temperature was relatively higher (above 1100 °C) for practical application. In this study, dielectric properties of Li_(1+x−y)Nb_(1−x−3y)Ti_(x+4y)O₃ solid solution were studied with different x and y contents and among them, the Li_1.0Nb_0.6Ti_0.5O₃ composition (x = 0.1, y = 0.1) was selected, due to its reasonable dielectric properties to determine the possibility of low temperature sintering. The effects of 0.17Li₂O–0.83V₂O₅, as a sintering agent, on sinterability and microwave dielectric properties of Li_1.0Nb_0.6Ti_0.5O₃ ceramics were investigated as a function of the sintering agent content and sintering temperature. With addition of 0.17Li₂O–0.83V₂O₅ above 0.5 wt%, the specimens were well densified at a relatively lower temperature of 850 °C. Only slight decrease in apparent density was observed with increasing 0.17Li₂O–0.83V₂O₅ content above 0.75 wt%. In the case of 0.5 wt% 0.17Li₂O–0.83V₂O₅ addition, the values of dielectric constant and Q × f reached maximum. Further addition caused inferior microstructure, resulting in degraded dielectric properties. For the specimens with 0.5 wt% 0.17Li₂O–0.83V₂O₅ sintered at 850 °C, dielectric constant, Q × f and TCF values were 64.7, 5933 GHz and 9.4 ppm per °C, respectively.     

Microwave dielectric properties of (Zn1/3B2/3)0.5(Ti0.8M0.2)0.5O2 (B = Nb5+, Ta5+, M = Sn4+, Ge4+) ceramics

Dielectric properties of (Zn_1/3Nb_(2?x)/3Ta_x/3)_0.5(Ti_0.8Sn_0.1Ge_0.1)_0.5O₂ (x = 0, 1, 2) and/or (Zn_1/3Nb_1/3Ta_l/3)_0.5(Ti_0.8Sn_0.2(l?y)Ge_0.2y)_0.5O₂ (y = 0, 0.5, 1) were investigated at the microwave frequencies. For the compositions with single phase of rutile structure, the dielectric constant (K) of specimens was not only dependent on the dielectric polarizabilities, but also on the bond length ratio of apical bond (d_apical) to equatorial bond (d_equatorial) of oxygen octahedron in the unit cell. Temperature coefficients of the resonant frequencies (TCF) of the specimens with B = Nb⁵⁺ and/or M = Sn⁴⁺ was larger than those with B = Ta⁵⁺ and/or M = Ge⁴⁺. These results could be attributed to the changes of the degree of oxygen octahedral distortion. Quality factors (Qf) of the specimens with B = Ta⁵⁺ and/or M = Sn⁴⁺ were larger than those with B = Nb⁵⁺ and/or M = Ge⁴⁺.     

Microwave dielectric properties of BaO–Ta2O5–TiO2 system

Microwave dielectric properties of the BaO–Ta₂O₅–TiO₂ system were investigated by the solid-state reaction method. It was recognized that the Ba₁₀Ta_7.04(Ti_1.2 − xSn_x)O₃₀ solid solutions have the higher Q · f value in comparison with the Ba₈(Ta_4 − xNb_x)Ti₃O₂₄ solid solutions. The limit of the Ba₁₀Ta_7.04(Ti_1.2 − xSn_x)O₃₀ solid solutions was approximately x = 0.75; the lattice parameter c of the solid solutions, which is related to the change in the B(1)O₆ octahedron, was significantly increased in the composition range from 0 to 0.75. The Q · f values of the Ba₁₀Ta_7.04(Ti_1.2 − xSn_x)O₃₀ solid solutions are remarkably improved by the Sn substitution for Ti; the highest Q · f value of 59,100 GHz is obtained at x = 0.75. Moreover, the ɛ_r and τ_f values of the Ba₁₀Ta_7.04(Ti_1.2 − xSn_x)O₃₀ solid solutions at x = 0.75 were 25.6 and 30.3 ppm/°C, respectively.     

Doping behaviors of NiO and Nb2O5 in BaTiO3 and dielectric properties of BaTiO3-based X7R ceramics

Doping behaviors of NiO and Nb₂O₅ in BaTiO₃ in two doping ways and dielectric properties of BaTiO₃-based X7R ceramics were investigated. When doped in composite form, the additions rendered higher solubility than that doped separately due to the identical valence between the complex (Ni_1/3²⁺Nb_2/3⁵⁺)⁴⁺ and Ti⁴⁺. NiO–Nb₂O₅ composite oxide was more effective in broadening dielectric constant peaks which was responsible for the temperature-stability of BaTiO₃ ceramics. A reduction in grain size was observed in the specimens with 0.5–0.8 mol% NiO–Nb₂O₅ composite oxide, whereas the abnormal growth of individual grains took place in the 1.0 mol% NiO–Nb₂O₅ composite oxide-doped specimen. When the specimen of BaTiO₃ doped with 0.8 mol% NiO–Nb₂O₅ composite oxide was sintered at 1300 °C for 1.5 h in air, good dielectric properties were obtained and the requirement of (EIA) X7R specification with a dielectric constant of 4706 and dielectric loss lower than 1.5% were satisfied.     

Low temperature sintering of lead-free Bi0.5(Na0.82K0.18)0.5TiO3 piezoelectric ceramics by co-doping with CuO and Nb2O5

Effect of excess CuO additive on the sintering behavior and piezoelectric properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ ceramics was investigated. The addition of small amount of excess CuO as low as 1 mol% was quite effective to lower the sintering temperature (T_s) of BNKT ceramics down to 975 °C while their piezoelectric properties were degraded by Cu doping. However, the electric field-induced strain was markedly enhanced by further addition of Nb₂O₅ with CuO without elevating T_s. The normalized strain S_max/E_max of 427 pm/V was obtained with a specimen sintered with 0.02 mol CuO and 0.03 mol Nb₂O₅ in excess.     

Low-temperature sintering and microwave dielectric properties of Ba5Nb4O15 with ZnB2O4 glass

The Influence of ZnB₂O₄ glass addition on the sintering temperature and microwave dielectric properties of Ba₅Nb₄O₁₅ has been investigated using dilatometry, X-ray diffraction, scanning electron microscopy and network analyzer. It was found that a small amount of glass addition to Ba₅Nb₄O₁₅ lowered the sintering temperature from 1400 to 900 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases such as Ba₃B₂O₆. The Ba₅Nb₄O₁₅ ceramics with ZnB₂O₄ glass, sintered at a low temperature, exhibited good microwave dielectric characteristics, i.e., a quality factor (Q × f) = 12,100 GHz, a relative dielectric constant (ɛ_r) = 40, a temperature coefficient of resonant frequency (τ_f) = 48 ppm/°C. The dielectric properties were discussed in terms of the densification of specimens and the influence of glassy phases such as Ba₃B₂O₆ and ZnB₂O₄.     

Crystallography,microstructure and morphology of Mg4Nb2O9/MgO and Mg4Ta2O9/MgO interfaces formed by topotaxial solid state reactions

Mg₄Nb₂O₉/MgO and Mg₄Ta₂O₉/MgO interfaces of definite crystallography were formed by topotaxial thin film solid state reactions in the systems MgO–Nb₂O₅ and MgO–Ta₂O₅. MgO (0 0 1) single crystal substrates, heated to different temperatures, were subjected to Nb–O and Ta–O vapors generated by e-beam evaporation in high vacuum. Thin films mainly containing the phases Mg₄Nb₂O₉ and MgNb₂O₆, respectively Mg₄Ta₂O₉ and MgTa₂O₆, were formed by gas–solid reactions. The crystallographic relationships between the product phases and the MgO substrate were systematically studied by X-ray diffractometry and transmission electron microscopy (TEM). Surprisingly pole figure analysis revealed more than one orientation relationship for some of the phases: Mg₄Nb₂O₉ and Mg₄Ta₂O₉ grew with (1 1 .4), (1 1 .6) and (1 1 .9) orientations, depending on temperature. Selected area diffraction patterns and high resolution TEM images show that these three orientations have a common Mg₄(Nb/Ta)₂O₉ $[1\overline{1}.0]$/MgO $[1\overline{1}0]$ axis and differ by the angle between the Mg₄(Nb/Ta)₂O₉ (0 0 .1) and MgO (1 1 1) planes. Crystallographic illustrations of this phenomenon are given, and possible origins and consequences for the solid state reaction are discussed. Indications for two different interfacial reaction mechanisms are found.     

Domain structures in hot-press sintered SrBi2Ta1.6Nb0.4O9 and SrBi2Ta2O9 ferroelectric ceramics

SrBi₂Ta_1.6Nb_0.4O₉ (SBTN) and SrBi₂Ta₂O₉ (SBT) ceramics with typical bismuth layered perovskite structure were synthesized by hot-press sintering at 1000 °C for 2 h. The maximum relative density of as-sintered SBTN and SBT materials is 98.97%. The domain structure of SBTN and SBT was systemically characterized by means of TEM and HRTEM. The 90° domain walls were identified by the 90° rotation relationship of the electron diffraction pattern along the [0 0 1] zone axis. Irregular shaped and highly curved 180° domain wall were also observed in SBTN ceramics. The traditional α-fringes can be found in SBT, which are the evidence of large strains in hot-press sintering ceramics. Rod-like SrTa₂O₆ precipitates are also analyzed as well as its interface with the matrix.     

Precipitation-induced healing of Nb2O5

Precipitation-induced stimulated-healing of Nb₂O₅ was carried out through the extrinsic addition of silver oxide nanoscale elemental inclusions to form ternary oxides at the crack site. Nb₂O₅ cylindrical pellets, 13 mm in diameter and 10 mm in length, were produced from powders using a cold isostatic press. The pellets were subsequently sintered at 1100 °C. A scratch was created in the sintered Nb₂O₅ pellets and was subsequently filled with Ag₂O. The pellets were annealed to stimulate the self-healing process. X-ray diffraction was used to explore the evolution of phases, chemical compositions, and structural properties of the sintered samples before and after the stimulated-healing process. Energy dispersive X-ray spectroscopy revealed the elemental composition in the healed region. The on-site composition of the healed sample was determined by Raman spectroscopy and was compared to the spectrum outside of the scratch. Raman spectroscopy confirmed that precipitation proceeded via the following chemical reaction which was facilitated at elevated temperature: Nb₂O₅ + Ag₂O → 2AgNbO₃. In addition, a 3D reconstructed stylus profilometry image of the crack region confirmed that healing occurred. Healing by recovering 89% of the original material strength was confirmed using the three-point bend test.     

Effect of V2O5 on sintering behaviour,microstructure and dielectric properties of textured Sr0.4Ba0.6Nb2O6 ceramics

The acicular Sr_0.39Ba_0.48K_0.32Nb₂O₆ single crystal particles were first prepared by the reaction of SrCO₃, BaCO₃ and Nb₂O₅ in molten K₂SO₄ at 1300 °C for 3 h. By using these single crystal particles as seeds and V₂O₅ as additives, textured Sr_0.4Ba_0.6Nb₂O₆ (SBN40) ceramics were obtained. The effect of V₂O₅ on sintering behaviour, microstructure and dielectric properties of textured SBN40 ceramics was investigated. The experimental results show that the addition of V₂O₅ can accelerate the densification rate of the material and encourage the texture of SBN40 ceramics, which further improves the anisotropy in dielectric properties between different directions of textured SBN40 ceramics.     

Microwave dielectric properties and microstructures of Nb2O5-Zn0.95Mg0.05TiO3 + 0.25TiO2 ceramics with Bi2O3 addition

The effects of Bi₂O₃ addition on the microwave dielectric properties and the microstructures of Nb₂O₅-Zn_0.95Mg_0.05TiO₃ + 0.25TiO₂ (Nb-ZMT′) ceramics prepared by conventional solid-state routes have been investigated. The results of X-ray diffraction (XRD) indicate the presence of four crystalline phases, ZnTiO₃, TiO₂, Bi₂Ti₂O₇, and (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ in the sintered ceramics, depending upon the amount of Bi₂O₃ addition. In addition, in order to confirm the existence of (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ phase in the samples, the microstructure of Nb-ZMT′ ceramic with 5 wt.% B₂O₃ addition was analyzed by using a transmission electron micrograph. The dielectric constant of Nb-ZMT′ samples was higher than ZMT′ ceramics. The Nb-ZMT′ ceramic with 5 wt.% Bi₂O₃ addition exhibits the optimum dielectric properties: Q × f = 12,000 GHz, ?_r = 30, and τ_f = ?12 ppm/°C. Unlike the ZMT′ ceramic sintered at 900 °C, the Nb-ZMT′ ceramics show higher Q value and dielectric constant. Moreover, there is no Zn₂TiO₄ existence at 960 °C sintering. To understand the co-sinterability between silver electrodes and the Nb-ZMT′ dielectrics, the multilayer samples are prepared by multilayer thick film processing. The co-sinterability (900 °C) between silver electrode and Nb-ZMT′ dielectric are well compatible, because there are no cracks, delaminations, and deformations in multilayer specimens.     

Extended X-ray absorption fine structure,X-ray diffraction and Raman analysis of nickel-doped Ba(Mg1/3Ta2/3)O3

Raman, X-ray diffraction and extended X-ray absorption fine structure (EXAFS) measurements of xBa(Ni_1/3Ta_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples with x = 0–0.03 were performed to reveal the nickel doping effect on the microwave properties. EXAFS result clearly shows that the nickel is located on the Mg lattice site. We also found that, as the nickel concentration increases, microwave dielectric constant decreases with the TaO and NiO bond distances. X-ray diffraction shows that the 1:2 ordered structure is degraded with the increasing of nickel concentration. The stretching phonon of the TaO₆ octahedra, that is A_1g(O) phonon near 800 cm⁻¹, are strongly correlated to the microwave properties of xBa(Ni_1/3Mg_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples. The large Raman shift and the large width of the A_1g(O) imply rigid but distorted oxygen octahedral structure, therefore, the effect of nickel doping lowers the dielectric constant and the Q × f value of Ba(Mg_1/3Ta_2/3)O₃ ceramic.     

Phase formation and dielectric properties of Ln2(Ln′0.5Nb0.5)2O7 (Ln = rare earth element)

Weberites and pyrochlores (A₂B₂O₇), both fluorite-related superstructures, are attractive dielectric ceramics due to their ability to accommodate diverse cations, thus allowing their properties to be tailored. This study focuses on the fundamental understanding of the structure–dielectric property relationships in fluorite-related oxides. Specifically, Ln₃NbO₇ and Ln₂(Ln′_0.5Nb_0.5)₂O₇ (where the ionic radius of Ln′ is smaller than that of Ln) compounds are investigated. It has been previously shown that weberite-type Ln₃NbO₇ exhibits a composition dependent dielectric relaxation above room temperature. It is here shown that a dielectric relaxation also occurs in La₂(Ln′_0.5Nb_0.5)₂O₇ (Ln′ = Yb³⁺, Er³⁺, and Dy³⁺) compounds near or below ?158 °C. The temperature, at which the maximum permittivity occurs, is different for different compositions (?132 °C for La₂(Yb_0.5Nb_0.5)₂O₇, ?197 °C for La₂(Er_0.5Nb_0.5)₂O₇, and ?187 °C for La₂(Dy_0.5Nb_0.5)₂O₇ at 1 MHz) and is correlated with the distortion of the NbO₆ octahedra. The room temperature dielectric permittivity of all three compounds was measured to be between 40 and 50 at 1 MHz.     

Low temperature sintering of the Ba2Ti9O20 ceramics using B2O3/CuO and BaCu(B2O5) additives

The effects of B₂O₃/CuO and BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of Ba₂Ti₉O₂₀ ceramics were investigated. The B₂O₃ added Ba₂Ti₉O₂₀ ceramics were not able to be sintered below 1000 °C. However, when both CuO and B₂O₃ were added, they were sintered below 900 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the Ba₂Ti₉O₂₀ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the Ba₂Ti₉O₂₀ ceramics. Good microwave dielectric properties of Qxf = 16,000 GHz, ɛ_r = 36.0 and τ_f = 9.11 ppm/°C were obtained for the Ba₂Ti₉O₂₀ ceramics containing 10.0 mol% BaCu(B₂O₅) sintered at 875 °C for 2 h.     

Calcium Cl/OH-apatite,Cl/OH-apatite/Al2O3 and Ca3(PO4)2 fibre nonwovens: Potential ceramic components for osteosynthesis

Polycrystalline calcium phosphate ((Cl/OH)Ap = Ca₅(PO₄)₃(OH/Cl); TCP = Ca₃(PO₄)₂) fibres were prepared from aqueous solutions of calcium chloride and phosphoric acid using poly(ethylene oxide) (PEO) as spinning aid. Generation of nonwoven materials was accomplished via rotary jet spinning. Polycrystalline (Cl/OH)Ap fibres 10–25 μm in diameter were obtained with 37% ceramic yield by pyrolysis of the green fibres followed by sintering at 1150 °C in air. X-ray diffraction (XRD) analysis provided evidence for apatite formation starting at 650 °C while (Cl/OH)Ap ceramic fibres were obtained at 1100 °C via transformation through intermediate dicalcium dichloride hydrogen phosphate (Ca₂Cl₂(HPO₄)) and calcium pyrophosphate (Ca₂P₂O₇) phases. A glass-forming Al-based additive was applied to enhance the mechanical properties of the Cl/OH)Ap ceramic fibres and indeed resulted in the formation of (Cl/OH)Ap/Al₂O₃ fibres with improved mechanical stability. Finally, TCP, (Cl/OH)Ap and (Cl/OH)Ap/Al₂O₃ fibres were subjected to seeding with mesenchymal stem cells. Negligible cytotoxicity is observed.     

Electrical properties of (Na2O)35.7(RE2O3)7.2(SiO2)57.1 (RE = Y,Sm, Gd,Dy, Ho,Er and Yb) glasses and ceramics

Fifteen kinds of sodium rare earth silicate glasses and ceramics with (Na₂O)_35.7(RE₂O₃)_7.2(SiO₂)_57.1 (RE = Y, Sm, Gd, Dy, Ho, Er and Yb) composition were synthesized from a mixture of Na₂CO₃, RE₂O₃ and SiO₂. The densities of the glasses were in fairly good agreement with the theoretical densities and were 0.2–0.41 g cm⁻³ larger than those of the polycrystalline ceramics. The conductivities of the glasses are 1–2 orders lower than those of the ceramics and the highest electrical conductivity was achieved for the Yb ceramic sample with the smallest ion radius of RE³⁺. The electromotive force, EMF, of the potentiometric CO₂ gas sensors using (Na₂O)_35.7(Y₂O₃)_7.2(SiO₂)_57.1 glass and ceramic increased linearly with an increase in the logarithm of CO₂ partial pressure, in accordance with Nernst's law. It was suggested from the slope of Nernst's equation that the two electron-transfer reaction associated with the carbon dioxide molecule takes place at the detection electrode above 450 °C.     

Oxidative dehydrogenation of ethane to ethylene over V2O5/Nb2O5 catalysts

V₂O₅/Nb₂O₅ catalysts with various V₂O₅ contents were prepared by impregnation and characterized by various techniques in detail. Oxidative dehydrogenation of ethane was carried out in a fixed bed quartz reactor at 500–600 °C. XPS analysis indicated a clear enrichment of vanadium on the near-surface-region and UV–vis diffuse reflectance spectroscopy revealed the nature of VO_x structures formed. 10 wt.% V₂O₅/Nb₂O₅ catalyst has displayed the best performance (X = 28%, S = 38% at 600 °C) due to enrichment of vanadium in the near-surface-region and formation of optimum amount of monomeric/oligomeric VO_x species.     

Dependence of dielectric properties on structural characteristics of (Zn1/3A2/3)0.5 (Ti1−xBx)0.5O2 (A = Nb5+, Ta5+, B = Ge4+, Sn4+) ceramics at microwave frequencies

The effects of structural characteristics on the dielectric properties of (Zn_1/3A_2/3)_0.5(Ti_1?xB_x)_0.5O₂ (A = Nb⁵⁺, Ta⁵⁺, B = Ge⁴⁺, Sn⁴⁺) (0.1 ≤ x ≤ 0.3) ceramics were investigated at microwave frequency. The sintered specimens showed solid solutions with a tetragonal rutile structure within the solid solution range of compositions. With an increase of BO₂, the temperature coefficient of resonant frequency (TCF) and dielectric constant (K) decreased with a decrease of oxygen octahedral distortion and dielectric polarizabilites, respectively. However, the quality factor (Qf) of the sintered specimens was increased with BO₂ due to the reduction of Ti⁴⁺ ions. The Qf value of the specimens with A = Ta was higher than that of the specimens with A = Nb.