Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

Preparation of lead magnesium niobate by a coprecipitation method

The ferroelectric complex perovskite lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), was prepared by a coprecipitation method. As the niobium component, niobium oxalate was used. Among the various precipitants, tetramethylammonium hydroxide was effective for the formation of single-phase PMN without pyrochlore phase. The dielectric constant and the dissipation factor of PMN changed either the sintering temperature or the grain size. The maximum dielectric constant at the Curie point was obtained by sintering at 1220 °C in air for 2 h.     

Perovskite phase formation in the PbMg1/3Nb2/3 O3-PbZrO3-PbTiO3 system by the columbite route

The reaction mechanism of PbMg_1/3Nb_2/3O₃-PbZrO₃-PbTiO₃ (PMN-PZT) perovskite phase prepared by the columbite route has been studied in the temperature range from 600 to 800 °C. The effects of heating and cooling rate during the calcination of 3PbO +MgNb₂O₆+PZT powder mixtures have also been investigated. Nearly pure perovskite phase, 0.9 PMN-0.1 PZTsolid solution with no pyrochlore phase, as determined by X-ray diffraction, could be prepared at 800 °C for 2 H. From DTA/TGA, dilatometry and XRD data the reaction mechanism of PMN-PZT solid solution formation could be divided into three steps: (i) decomposition of columbite (MgNb₂O₆) by reacting with PbO at 350 to 600 °C (ii) the formation of a B-site-deficient pyrochlore phase Pb₂Nb_1.33Mg_0.17O_5.50 at close to 650 °C, and (iii) the formation of perovskite phase PMN-PZT solid solution from the reaction of Pb₂Nb_1.33Mg_0.17O_5.50 pyrochlore phase with MgO and PZT above 650 °C.     

Processing and properties of Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3 ceramic relaxors

The shrinkage phenomenon during the reaction-sintering of PMN-PZT from low-temperature pre-reacted 3PbO + MgNb₂O₆ + PZT powder mixtures has been studied. It was assumed that the pre-reaction treatment leads to the formation of a pyrochlore phase containing very active MgO small particles, and that the strong shrinkage occurring up to 800 °C took place by the diffusion of Mg²⁺ cations into the pyrochlore phase particles, thus controlling the reaction-sintering shrinkage phenomenon. Above that temperature the densification was enhanced by a liquid-phase sintering process. The ceramics sintered at 1050 °C for 2 h showed 96% of the theoretical density, and the dielectric constant of such a sintered ceramic showed a maximum value of 17 000 at 1 kHz. It was also found that the dielectric constant decreased with increasing grain size. Although the role of PZT in enhancing the dielectric constant of otherwise low-purity PMN ceramics is not clear, the increase in K is assumed to be a solid-solution effect. The presence of impurities and the PbO stoichiometry could be influencing the not too high dielectric constant value of PMN-PZT ceramics.     

Synthesis of a solid solution of PbTiO3-PbZrO3-Pb (Mg1/3Nb2/3)O3 system through use of 8-quinolinol and its properties

A new method for the synthesis of a solid solution of PbTiO₃-PbZrO₃-Pb (Mg_1/3Nb_2/3)O₃ system (PZTMN) has been developed. An aqueous solution of Ti⁴⁺, Zr⁴⁺, Mg²⁺ and Nb⁵⁺ was dropped into a solution of 8-quinolinol in aqueous ammonia. The precipitate formed was washed, dried and fired, then an oxide (ZTMN) was obtained. The best firing temperature for the precipitate was 700 °C. The ZTMN powder was then mixed with PbO powder: when this mixture was fired, PZTMN was formed directly. By a conventional solid-state reaction among PbO, ZrO₂, TiO₂, MgO and Nb₂O₅ ([P + Z + T + M + N] method), PbTiO₃ and Pb(Mg_1/3Nb_2/3)O₃ were formed as intermediate products during the reaction. The single phase of PZTMN was obtained at 1200 °C for the [P + Z + T + M + N] method and at 800 °C for the new [P + ZTMN] method. The compositional fluctuation of PZTMN prepared by the [P + ZTMN] method was very small, and its dielectric constant was much higher than that of PZTMN prepared by the [P + Z + T + M + N] method. The density of PZTMN prepared by the [P + ZTMN] method practically attained the theoretical density under conditions of calcining at 800 °C and sintering at 1100 °C for 1 h.     

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, ferroelectric and piezoelectric properties of (1 − x)[Pb0.91La0.09(Zr0.60Ti0.40)O3]–x[Pb(Mg1/3Nb2/3)O3], 0 ≤ x ≤ 1

The dielectric, ferroelectric, and piezoelectric properties of ceramic materials of compositions (1 − x)[Pb_0.91La_0.09(Zr_0.60Ti_0.40)O₃]–x[Pb(Mg_1/3Nb_2/3)O₃], x = (0, 0.2, 0.4, 0.6, 0.8, and 1.0) were studied. The above compositions were prepared by mixing the individual Pb_0.91La_0.09(Zr_0.60Ti_0.40)O₃ (PLZT) and Pb(Mg_1/3Nb_2/3)O₃ (PMN) powders in order to design materials with different combination of piezo and dielectric properties. The powders were calcined at 850 °C for 4 h. The presence of various phases in the calcined powders was characterized by X-ray diffraction (XRD) technique. The compacts were prepared by uniaxial pressing and were sintered at 1250 °C for 2 h. The sintered compacts were electroded, poled at 2 kV/mm dc voltage and their dielectric, ferroelectric, and piezoelectric properties were measured. In general, it was observed that the dielectric constant, loss factor and the slimness of the ferroelectric curves increase with the PMN content while the remnant polarization, saturation polarization, and the coercive fields were decreased. It is now possible to design materials with a wide combination of d ₃₃, K, and loss factor by varying PLZT and PMN ratio.     

Low-temperature fabrication of 0.65 PMN–0.35 PT by a mixed oxide method

Single-phase perovskite 0.65 PMN–0.35 PT was achieved at low temperature by a conventional mixed oxide method. It was prepared by ball-milling a mixture of PbO(orthorhombic), TiO₂, Nb₂O₅ and (MgCO₃)₄Mg(OH)₂·5H₂O instead of MgO and heat treatment at 800 °C for 2 h. The formation was studied by means of DSC, FT-IR, Coupled TG-Mass, XRD, and SEM. It proceeded via formation of PbO(tetragonal) and Pb₂Nb₂O₇(P₂N) intermediates to form perovskite phase. The pure perovskite PMN-PT powder was obtained in particle size of 0.5–0.8 μm, agglomerate-free, and pseudo-cube. The powder calcined at 600 °C was sintered to 97% T.D. at 900–1000 °C for 2 h and showed room temperature dielectric constant of 3200, loss of 1–2%, and specific resistance of 5 × 10¹¹ Ω cm.     

Synthesis and dielectric/ferroelectric characteristics of Ta-modified PMN0.6·PZN0.2·PT0.2 ceramics

Ceramic powders of a [Pb(Mg_1/3Nb_2/3)O₃]_0.6·[Pb(Zn_1/3Nb_2/3)O₃]_0.2·[PbTiO₃]_0.2 system (with Nb replaced by Ta) were prepared via solid-state reaction routes. The structures developed in the B-site precursor and perovskite systems are discussed. Weak-field low-frequency dielectric characteristics as well as the polarization behavior of the perovskite ceramics are presented. The relaxation modes of the dielectric constant spectra are analyzed in terms of diffuseness parameters. A very high maximum dielectric constant of 37 900 (@1 kHz) was obtained when 1/4 of Nb was replaced by Ta. Internal microstructures of the sintered samples are also reported.     

Preparation and characterization of two new dielectric ceramics Ba4NdTiNb3O15 and Ba3Nd2Ti2Nb2O15

Two new cation-deficient hexagonal perovskites Ba₄NdTiNb₃O₁₅ and Ba₃Nd₂Ti₂Nb₂O₁₅ were prepared in the BaO–Nd₂O₃–TiO₂–Nb₂O₅ system by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction and scanning electron microscope (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. Ba₄NdTiNb₃O₁₅ has a dielectric constant of 38.15, a high-quality factors (Q _u ×f >18 700 at 5.4422 GHz), and a small temperature coefficient of resonant frequency ( _f )+12 ppm °C^–1 at room temperature; Ba₃Nd₂Ti₂Nb₂O₁₅ has a higher dielectric constant of 46.83 with high-quality factors Q _u ×f >19 500 at 5.0980 GHz, and _f +28 ppm °C^–1.     

Preparation of stabilized Pb(Zn1/3Nb2/3)O3(PZN) films by the sol-gel method

Pb(Zn_1/3Nb_2/3)O₃ thick films with the perovskite structure were prepared by the sol-gel method. Niobium ethoxide Nb(OC₂H₅)₄, lead acetate Pb(CH₃COO)₂, and Zinc 2-ethylhexanoate Zn(O₂C₈H₁₅)₂ were reacted in 2-methoxyethanol to form the precursor. Titanium isopropoxide, Ti(O·i-C₃H₇)₄ and barium isopropoxide Ba(O·i-C₃H₇)₄ were added into the precursor solution to stabilize the formation of the perovskite phase. Films of upto 10 m thickness were obtained by controlling the viscosity of the solution and the dipping speed of silicon wafers. The phase evolution was investigated using differential thermal analysis (DTA) and X-ray diffraction techniques. The thickness-dependent dielectric constant of the resultant films is also reported.     

Dielectric characteristics of bismuth-modified lead magnesium niobate ceramics

Aliovalent Bi was substituted for Pb in Pb(Mg_1/3Nb_2/3)O₃ with required alteration in the Mg/Nb ratio. Resultant changes in the perovskite developments, lattice parameters as well as dielectric characteristics were investigated. Powders were prepared via a two-step B-site precursor route to enhance the perovskite formation. The perovskite structure persisted up to the range of 30 mol% Bi(Mg_2/3Nb_1/3)O₃ substitution. Values of the maximum dielectric constant decreased drastically, while the dielectric maximum temperatures changed only moderately. Meanwhile, the diffuseness exponent values decreased continuously with the Bi modification.     

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.     

Structure analysis on the Ba3Mg(Ta1−xNbx)2O9 ceramics: Coexistence of order and disorder

The Ba₃ZnTa₂O₉ (BZT) and Ba₃MgTa₂O₉ (BMT) ceramics, a family of A₃B²⁺B⁵⁺₂O₉ complex perovskites, are extensively utilized in mobile based technologies due to their intrinsic high unloaded quality factor, high dielectric constant and a low (near-zero) resonant frequency temperature coefficient at microwave frequencies. The preparation conditions as well as size and nature of B cations have a profound effect on the final dielectric properties. In this article, we report the effect of Nb⁵⁺ at the Ta⁵⁺ site on the BMT structure prepared at four synthesis temperatures (1300, 1400, 1500 and 1600 °C). The analysis has been carried out using the Rietveld technique on the X-ray powder diffraction data. Results suggest that both the preparation temperatures and Nb⁵⁺ content have significant effect on the ordering of B cations in the Ba₃Mg(Ta_1−xNb_x)₂O₉ solid solution. A disordered (cubic) structure is preferred by the 1300 °C compounds. The weight percentage of the ordered (trigonal) phase escalates, for a given composition, with increasing calcination temperature. A fully ordered trigonal arrangement exists only for x = 0.0 and 0.2 compounds calcined at 1600 °C, and the rest are biphasic (cubic and trigonal). The increase in the cubic fraction upon Nb⁵⁺ augmentation suggests that the solid solution leans more toward the disordered structural arrangement of B²⁺ and B⁵⁺ cations.     

Effect of the level of addition of Nb2O5/Co2O3 and Ba(Nb2/3Co1/3)O3 on the structure, microstructure, and dielectric properties of BaTiO3

In this work attempt is made to study the effects of the level of the addition of two dopant systems, that is, Nb₂O₅/Co₂O₃ and Ba(Nb_2/3Co_1/3)O₃ on the structure, microstructure, and dielectric properties of BaTiO₃(BT) prepared by ceramic route. For the BT samples doped with 2 and 3 at % Nb₂O₅/Co₂O₃ a broad maxima for _r–T variations was observed. Higher levels of addition, that is, 6, 8, and 10 at % Nb₂O₅/Co₂O₃, however, caused a drastic reduction in the magnitude of _r and vanishing of maxima peaks observed. The reduction in the magnitudes of the _r for these samples is related to the observed reduction of the tetragonality of doped BT samples as well as the existence of some non-ferroelectric extra phase, evidenced by our XRD analysis. The existence of this extra phase is also believed to be mainly responsible for the observed increase of the dielectric loss. For the BT samples doped with Ba(Nb_2/3Co_1/3)O₃ perovskite solid solution, the _r maxima peak could only be detected for the samples doped with 2 at %. In the case of the samples doped with 4, 6, 8, and 10 at % perovskite solid solution, however, a very uniform distribution of _r–T was observed. The increase of the level of dopant for these series of samples was also seen to give rise in the reduction of the magnitude of _r. However, this reduction was not as strong as the cases observed for the samples doped with 8 and 10 at % Nb₂O₅/Co₂O₃. XRD patterns obtained for these series of samples also revealed the reduction of tetragonality of the BT samples when doped with Ba(Nb_2/3Co_1/3)O₃. Further, microstructural studies carried out by scanning electron microscopy (SEM) on both series of samples revealed a contrasting picture. While a uniform grain size distribution was observed for the whole series of the samples doped with Ba(Nb_2/3Co_1/3)O₃, a non-uniform size distribution of grain sizes was observed in the case of samples doped with Nb₂O₅/Co₂O₃. This is thought to be due to the possible formation and non-uniform distribution of a liquid phase due to the formation of Ti-rich region in the shell region of Nb₂O₅/Co₂O₃-doped samples. The existence of such liquid phase, in case of Nb₂O₅/Co₂O₃-doped samples, would have the consequence of an increased rate of diffusion of Nb/Co into the BT cores leaving narrow compositional fluctuations for the shell regions.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Top-cooling-solution-growth and characterization of piezoelectric 0.955Pb(Zn1/3Nb2/3)O3-0.045PbTiO3 [PZNT] single crystals

A technique of top-cooling-solution-growth (TCSG) has been developed to grow the piezo-/ferroelectric perovskite single crystals of 0.955Pb(Zn_1/3Nb_2/3)O₃-0.045PbTiO₃ [PZNT95.5/4.5]. The flux composition and concentration, and the thermal parameters have been optimized, leading to the growth of high quality PZNT crystals with a size up to 20 × 15 × 10 mm³. The perovskite crystals are found to form upon slow cooling down to 1020°C, while the undesirable pyrochlore crystals of Pb_1.5Nb₂O_6.5-type start growing upon further cooling from 1020°C to 950°C. By controlling the growth pathway, the formation of the pyrochlore phase can be avoided. The dielectric properties of the grown PZNT95.5/4.5 crystals have been measured as a function of temperature at various frequencies. Upon heating, the phase transition for the rhombohedral R3m to the tetragonal P4mm phase takes place at 132°C, while the tetragonal to cubic phase transition occurs at 160°C. The TCSG developed in this work provides an alternative technique to grow PZNT piezocrystals of medium size at low cost for transducer applications.     

Structural change of hydrothermal BaTiO3 powder

Formation rate of tetragonal BaTiO₃ powder by hydrothermal synthesis and its dielectric property were studied. Submicron tetragonal BaTiO₃ powders were prepared hydrothermally, using Ba(OH)₂ · 8H₂O, TiO₂ (anatase) and KOH as starting chemicals. Characterization via X-ray diffractometry, Field Emission Scanning Electron Microscopy confirmed that increasing calcination temperature (from 1100 to 1300°C) promotes the formation of tetragonal BaTiO₃. Tetragonal BaTiO₃ ceramics obtained from optimum condition (Tetragonal BaTiO₃ powders calcined at 1200°C for 3 h after hydrothermal synthesized at 200°C for 168 h) exhibited submicron size of 0.5–0.7 m, monodispersed type and high relative permittivity.