Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Preparation and phase formation of perovskite Pb(Ni<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> by a reaction-sintering process

Pyrochlore-free Pb(Ni_1/3Nb_2/3)O₃ perovskite ceramics produced by a simple and effective reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂ and Nb₂O₅ was pressed and sintered directly into PNN ceramics. Density of 98.5% of theoretical value was obtained after sintered at 1230 °C for 2 h in air. 99.3% of theoretical density was obtained after sintered at 1,200 °C for 2 h in PbO compensated atmosphere. PNN ceramic with dielectric constant 1,680 at 25 °C and 1 kHz has been obtained.     

Dielectric responses in Mg<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>-replaced Pb[(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>),Ti]O<Subscript>3</Subscript> ceramics

Octahedral lattice sites of Pb[(Zn_1/3Nb_2/3),Ti]O₃ were replaced by 20 at.% Mg_1/3Ta_2/3 complex to enhance perovskite development, especially at Pb(Zn_1/3Nb_2/3)O₃-rich compositions. Resultant changes in the perovskite formation and associated dielectric responses were investigated. A perovskite structure was identified at Pb(Zn_1/3Nb_2/3)O₃-rich compositions by X-ray diffraction, although the development was rather incomplete. Phase transition modes in the dielectric constant spectra changed from diffuse to sharp ones, regardless of the introduction of Mg_1/3Ta_2/3. Dielectric maximum temperatures of the ceramics shifted linearly with the compositional change.     

Microwave dielectric properties of Bi(Sc<Subscript>1/3</Subscript>Mo<Subscript>2/3</Subscript>)O<Subscript>4</Subscript> ceramics for LTCC applications

A novel microwave dielectric ceramics Bi(Sc_1/3Mo_2/3)O₄ with low firing temperature were prepared via the solid reaction method. The specimens have been characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy and DC conductivity. The Bi(Sc_1/3Mo_2/3)O₄ ceramics showed B-site ordered Scheelite-type structure with space group C2/c. Raman analysis indicated that prominent bands were attributed to the normal modes of vibration of MoO₄ ^2? tetrahedra. The dielectric loss of Bi(Sc_1/3Mo_2/3)O₄ ceramics can be depended strongly the bulk conductivity by DC measurement. The superior microwave dielectric properties are achieved in the Bi(Sc_1/3Mo_2/3)O₄ ceramic sintered at 875 °C/4 h, with dielectric constant?~?25, Q?×?f ~?51,716 GHz at 6.4522 GHz and temperature coefficient of resonance frequency ~???70.4 ppm/°C. It is a promising microwave dielectric material for low-temperature co-fired ceramics technology.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Synthesis and characterization of pseudo-ternary Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ferroelectric ceramics via a B-site oxide mixing route

Perovskite phase formation and dielectric/ferroelectric properties of the pseudo-ternary Pb(Fe_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ (PFN-PZ-PT) ferroelectric ceramics have been investigated as promising materials for multi-layer ceramic capacitors. Complete solid solution with pure perovskite phase can be formed in this system in the whole composition range studied using conventional solid-state reaction method via a B-site oxide mixing route. Crystal lattice of the ceramics obtained shrinkages with the increase of the concentration of Pb(Fe_1/2Nb_1/2)O₃ (PFN) and expands with the increase of the content of PbZrO₃ (PZ). With the increase of the concentration of PbTiO₃ (PT), crystal structure of PFN-PZ-PT changes from pseudo-cubic ferroelectric phase to tetragonal one while retains the fraction of PFN as constant. A morphotropic phase boundary (MPB) forms at the composition of 42 mol% PT regardless of whatever concentration of PFN, and the content of PFN affects little on the composition of MPB. The preliminary phase diagram of the PFN-PZ-PT system is determined by X-ray diffraction (XRD) measurements combining with dielectric/ferroelectric characterization. Dielectric measurements indicate that the value of dielectric maximum (ɛ_m) and the temperature where ɛ_m appears (T_m) increase with the increase of the concentration of PT. However, PFN exhibits opposite effects, i.e., ɛ_m increases with the increase of the concentration of PFN accompanied by the decrease of T_m.     

Dielectric characteristics of Pb(Zn<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ceramics with/without PbTiO<Subscript>3</Subscript> modification

Stabilization tendencies of the perovskite structure in a Pb(Zn_1/3Ta_2/3)O₃-BaTiO₃ pseudobinary system with/without compositional modification by 20 mol% PbTiO₃ introduction were compared. In order to promote perovskite phase formation, the B-site precursor method (which is conceptually similar to the columbite process) was employed in this study. Dielectric properties of sintered samples were investigated as functions of composition and measurement frequency. Dielectric constant spectra, in the paraelectric temperature region, were further analyzed in terms of diffuseness. Microstructures of sintered specimens were also investigated and correlated with perovskite stabilization.     

Effect of excess PbO and sintering temperature on the templated grain growth of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.67</Subscript>Ti<Subscript>0.33</Subscript>O<Subscript>3</Subscript> polycrystals

The effect of excess lead oxide and sintering temperature on the microstructure evolution in the templated grain growth (TGG) of the Pb(Mg_1/3Nb_{2/ 3})_0.67Ti_0.33O₃ (PMNT67/33) polycrystals was investigated. By adding excess PbO in the precursor of PMNT ceramics, the textured structure of PMNT polycrystals was obtained near SrTiO₃ (ST) template by the conventional ceramic technique. The texture profiles developed progressively with increasing the concentration of excess PbO. A suitable sintering temperature is also very essential to grow a thick textured layer and avoid a second phase. Furthermore, the through-thickness of the PMNT textured layer is strongly influenced by the uniaxial compact-pressure of preparing the ST seeded PMNT specimen.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Phase developments in Pb(Mg<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> and Pb(Zn<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> via B-site precursor route

Phase formation stages of MgWO₄ and ZnWO₄ (precursor compositions for following steps) were investigated by monitoring the reactions of oxide chemicals at various temperatures. Developed phases were examined by using X-ray diffraction (XRD). Successive attempts were also conducted for Pb(Mg_1/2W_1/2)O₃ (PMW) and Pb(Zn_1/2W_1/2)O₃ (PZW) by reacting PbO with the precursor compounds. Stages of phase development in the two compositions were also analyzed. The results are compared with those of another tungsten-containing perovskite Pb(Fe_2/3W_1/3)O₃ (PFW) and its B-site precursor Fe₂WO₆. After PbO addition to the precursor powders, a perovskite phase formed directly (i.e., without any intermediate phases) in the case of PMW. For PbO + ½ZnWO₄, in contrast, the decomposition of ZnWO₄ and preferential reaction with PbO resulted in Pb₂WO₅ and ZnO, instead of the perovskite PZW.     

Microstructure and properties of lead-free (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3 </Subscript>based piezoelectric ceramics doped with different cations

Different cations doped lead-free piezoelectric (Bi_1/2Na_1/2)TiO₃ ceramics with the general formula Na_0.4995Bi_0.4995Ba_0.001Ti_0.998M_0.002O₃ (M = Nb, Ta, and Sb) were fabricated. The effects of processing parameters and doping on phase content, microstructure, dielectric and piezoelectric properties of the materials were discussed. Experimental results show that Nb doped (Bi_1/2Na_1/2)TiO₃ exhibits superior polarization performance over the existing lead-free ceramics with a d₃₃ value of 122 pC/N obtained when poled at 60 kV/cm at room temperature. The best piezoelectric properties were achieved in (Bi_1/2Na_1/2)TiO₃ doped with Ta having a measured d₃₃ value of 164 pC/N for samples poled at 100 °C under the applied field of 50 kV/cm.     

Synthesis of anisotropic NaNbO<Subscript>3</Subscript> seed crystals and fabrication of textured (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-based ceramics

High aspect ratio patelike NaNbO₃ particles with pure perovskite structure have been successfully synthesized by topochemical microcrystal conversion (TMC) from plate-like precursor particles of the layer-structured Bi_2.5Na_3.5Nb₅O₁₈. By changing the Bi_2.5Na_3.5Nb₅O₁₈/Na₂CO₃ ratio, large and thin NaNbO₃ particles with a thickness of approximately 0.5 μm and a width of approximately 20 μm were obtained. The obtained NaNbO₃ particles is quite suitable for fabricating textured (K_0.5Na_0.5)NbO₃-based ceramics. Using the fine platelike NaNbO₃ particles as templates, dense <001> -oriented (K_0.5Na_0.5)NbO₃-0.5 mol %MnO₂ ceramics with high texture quality (Lotgering factor F ₀₀₁ = 87 %) and excellent piezoelectric properties were produced by templated grain growth. Compared with randomly oriented ceramics, textured samples show greatly enhanced properties. The room-temperature strain S, the piezoelectric coefficient d ₃₃ ^* and d ₃₃ reach up to 0.093 %, 233 pm/V and 195pC/N, respectively, which are all about 1.5 times larger than those of non-textured ceramics.     

Fabrication and dielectric properties of textured Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ceramics by RTGG method

Grain-oriented Na_0.5Bi_0.5TiO₃-BaTiO₃ (NBTBT) ceramics were fabricated by reactive-templated grain growth using plate-like Bi_2.5Na_3.5Nb₅O₁₈ (BNN) as templates. The specimens are composed of NBTBT perovskite phase and BNN lay-structured phase. Textured ceramics have a brick-wall microstructure with strip-like grains aligning in the direction parallel to the casting plane and exhibit an {h00} preferred orientation. The texture fraction increases initially, and then decreases with increasing sintering temperature. The optimal sintering temperature is 1,185 °C where the texture fraction has a maximum value of 0.58 and d₃₃ is 98 pC/N. The textured NBTBT ceramics show evidence of relaxor ferroelectrics with diffuse phase transition and frequency dispersion because of composite biphasic structure.     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

Si<Subscript>3</Subscript>N<Subscript>4</Subscript>/TiN composites produced from TiO<Subscript>2</Subscript>-Modified Si<Subscript>3</Subscript>N<Subscript>4</Subscript> powders

Si₃N₄/TiN composites have been produced by hot pressing at temperatures from 1600 to 1800°C in a nitrogen atmosphere, using silicon nitride powders prepared by self-propagating high-temperature synthesis and surface-modified with titanium dioxide nanoparticles. We examined the effect of TiO₂ content on the microstructure, phase composition, and mechanical strength of the ceramics. It is shown that titanium nitride can be formed by the reaction Si₃N₄ + TiO₂ → TiN + NO + N₂O + 3Si. The Si₃N₄/TiN composites containing 5–20% TiN have a low density, high porosity, and a bending strength of 60 MPa or lower. In Si₃N₄/TiN ceramics produced using calcium aluminates as sintering aids, the silicon nitride grains are densely packed, which ensures an increase in strength to 650 MPa.     

Effect of La substitution on structural and electrical properties of Ba(Fe<Subscript>2/3</Subscript>W<Subscript>1/3</Subscript>)O<Subscript>3</Subscript> nanoceramics

The nanocrystalline fine powders (∼80 nm) of (Ba_1−x La _x )(Fe_2/3W_1/3)_1−x/4O₃, (BLFW) (x = 0.0, 0.05, 0.10 and 0.15) were synthesized with a combined mechanical activation and conventional high-temperature solid-state reaction methods. Preliminary X-ray structural analysis of pellet samples (prepared from fine powders) showed formation of a single-phase tetragonal system. Detailed studies of dielectric properties (ε_r and tan δ) exhibit that these parameters are strongly dependent on frequency, temperature and La composition. The La-substitution increases the dielectric constant and decreases the tan δ up to 10% substitutions of La at the Ba-site, and then reversed the variation, and hence this composition is considered as a critical composition. This observation was found valid for structure, microstructures, dielectric constant, electrical conductivity, J–E characteristics and impedance parameters also. Like in other perovskites (PZT, BZT), La substitution plays an important role in tailoring the properties of Ba(Fe_2/3W_1/3)O₃ ceramics.     

Ceramics Based on Powder Mixtures Containing Calcium Hydrogen Phosphates and Sodium Salts (Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>, Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>, and NaPO<Subscript>3</Subscript>)

Ceramic materials in the Na₂O–CaO–P₂O₅ system have been produced using powder mixtures containing calcium hydrogen phosphates (monetite/brushite: CaHPO₄/CaHPO₄ ? 2H₂O) and sodium salts (Na₂CO₃ ? H₂O, Na₄P₂O₇ ? 10H,O, and NaPO₃). These salts were used as precursors to the following high-temperature phases: Сa₂P₂O₇, Na₂O, Na₄P₂O₇, and NaPO₃. The amount of the salts in the powder mixtures was such that the oxide composition of the ceramics corresponded to 10 mol % sodium oxide for each mixture in the Na₂O–CaO–P₂O₅ system. The powder mixtures were prepared using mechanical activation in acetone, which was accompanied by monetite rehydration to brushite. X-ray diffraction characterization showed that, after firing, the phase composition of the ceramics produced from the powder mixtures thus prepared lay in the Сa₂P₂O₇–NaCaPO₄–Na₂СaP₂O₇–Са(РО₃)₂ phase field. The resultant ceramic materials contain biocompatible and bioresorbable phases and can be recommended for bone implant fabrication.     

Dielectric properties,microstructure and diffuse transition of Al-doped Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> ceramics

Pure and Al-doped BaZr_0.2Ti_0.8O₃ (short for BZT) ceramics are prepared via the conventional solid state reaction method. The microstructures, dielectric properties, and diffuse transition of Al-doped BaZr_0.2Ti_0.8O₃ ceramics were investigated. These results indicate that aluminum ions enter the unit cell maintaining the perovskite structure of solid solution. The addition of aluminum leads to the change of the Curie temperature. The dielectric loss of the Al-doped BZT ceramics is higher than that of pure BZT ceramics, and increases as aluminum content increases. The diffuseness of the phase transition of Al-doped BZT ceramics weakens with the increasing of aluminum content. There is no obvious frequency dispersion around the dielectric constant peaks for Al-doped BZT ceramics. The coercive electric field (E _C) increases as Al content increases, and the remanent polarization (P _r) of Al-doped BZT ceramics is lower than that of pure BZT ceramics.     

Effect of Pb(Ti,Sn)O<Subscript>3</Subscript> on the dielectric properties of high dielectric constant X8R BaTiO<Subscript>3</Subscript>-based ceramics

The high dielectric constant X8R dielectric materials could be sintered at 1,240 °C by doping 2.5 mol% Pb(Ti,Sn)O₃ additives into the BaTiO₃ ceramics, with a dielectric constant greater than 3,400 at 25 °C, dielectric loss lower than 2.0% and temperature coefficient of capacitance (TCC) less than ±15% from −55 to 150 °C, which satisfied X8R specification. The effects of Pb(Ti,Sn)O₃ on the microstructure and dielectric properties of BaTiO₃-based ceramics were investigated. Doped with Pb(Ti,Sn)O₃ additives, the partial solid solution was formed between Pb(Ti,Sn)O₃ and BaTiO₃. Due to the high Curie point of Pb(Ti,Sn)O₃, the Curie point of the ceramics was markedly shifted to higher temperature about 150 °C, and the temperature coefficient of capacitance curves was flattened. The increase of the tetragonality (c/a ratio) and the fine microstructure were resulted in the increase of dielectric constant. With Pb(Ti, Sn)O₃ content up to 3 mol%, the depression of Ti⁴⁺’s polarization and the decrease of the tetragonality (c/a ratio) were resulted in the decrease of dielectric constant.     

Microstructure and electrical properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript> lead-free piezoelectric ceramics sintered in low pO<Subscript>2</Subscript> atmosphere

Pure K_0.5Na_0.5NbO₃ lead-free piezoelectric ceramics without any dopants/additives were sintered at various temperatures (950–1125 °C) in low pO₂ atmosphere (pO₂?~?10^?6 atm). All ceramics exhibit high relative densities (>?94%) and low weight loss (<?0.6%). Compared to the ceramics sintered in air, the ceramics sintered in low pO₂ exhibit improved electrical properties. The piezoelectric constant d₃₃ and converse piezoelectric constant d₃₃* are 112 pC/N and 119 pm/V, respectively. The ceramics show typical ferroelectric behavior with the remnant polarization of 21.6 µC/cm² and coercive field of 15.5 kV/cm under measurement electric field of 70 kV/cm. The good electrical properties of the present samples are related to the suppression of volatility of the alkali cations during the sintering process in low pO₂ atmosphere.