Ferroelectric and piezoelectric properties of new NaNbO<Subscript>3</Subscript>–Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> lead-free ceramics

New lead-free ceramics (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ have been fabricated by the conventional ceramic sintering technique, and their ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ diffuses into the NaNbO₃ lattices to form a new perovskite-type solid solution with orthorhombic symmetry. The addition of a small amount of Bi_0.5K_0.5TiO₃ (x ≥ 0.025) transforms the ceramics from antiferroelectric to ferroelectric. The ceramic with x = 0.10 possesses the largest remanent polarization P _r and thus exhibits the optimum piezoelectric properties, giving d ₃₃ = 71 pC/N, k _p = 16.6% and k _t = 39.7%. The ceramics with low doping level of Bi_0.5K_0.5TiO₃ are normal ferroelectrics and the ferroelectric-paraelectric phase transition becomes diffusive gradually with the doping level x of Bi_0.5K_0.5TiO₃ increasing. Our results show the (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ ceramics is one of the good candidates for lead-free piezoelectric and ferroelectric materials.     

Structure and piezoelectric properties of new ternary K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript>–LiSbO<Subscript>3</Subscript>–CaTiO<Subscript>3</Subscript> lead-free piezoceramics

New ternary (1−x)K_0.5Na_0.5NbO₃–x(0.80LiSbO₃–0.20CaTiO₃) lead-free ceramics were fabricated by a conventional ceramic technique and their structure and piezoelectric properties were studied. The results of X-ray diffraction reveal that LiSbO₃ and CaTiO₃ diffuse into the K_0.5Na_0.5NbO₃ lattices to form a new solid solution with a perovskite structure. After the addition of LiSbO₃ and CaTiO₃, the cubic-tetragonal and tetragonal-orthorhombic phase transitions shift to lower temperatures. Coexistence of the orthorhombic and tetragonal phases is hence formed in the ceramics with 0.03 < x < 0.07 at room temperature, leading to a significant enhancement of the piezoelectric properties. For the ceramics with x = 0.04–0.06, the piezoelectric properties become optimum: d ₃₃ = 172–253 pC/N, k _P = 49.9–55.5%, k _t = 49.2–52.1% and T _C = 348–373 °C. The ceramic with x = 0.04 also exhibits a good thermal stability of piezoelectric properties.     

Enhanced dielectric and piezoelectric properties of (100) oriented Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–SrTiO<Subscript>3</Subscript> thin films

The (100) oriented and random oriented 0.755Bi_0.5Na_0.5TiO₃–0.065BaTiO₃–0.18SrTiO₃ (BNT–BT–ST) thin films were deposited on LaNiO₃ (LNO) buffered Pt(111)/Ti/SiO₂/Si substrates by the sol–gel processing technique. The orientation is controlled by the concentration of solution. The structure, dielectric and piezoelectric properties of the thin films are significantly affected by the crystallographic orientation. The (100) oriented BNT–BT–ST thin film has improved dielectric and piezoelectric properties. For the (100) oriented and random oriented BNT–BT–ST thin films, the dielectric constants are 660 and 550, the dielectric losses are 0.045 and 0.076 and the effective piezoelectric coefficients are 140 and 110 pm/V, respectively. The large piezoelectric response is attributed to the uniform microstructure and increased lattice distortion along (100) direction.     

Phase formation and dielectric properties of ceramics in the BiFeO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–Bi(Mg<Subscript>0.5</Subscript>Ti<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> system

We have studied the effect of Bi(Mg_0.5Ti_0.5)O₃ additions on the phase formation, structural parameters, microstructure, and dielectric properties of solid solutions in the region of a morphotropic phase boundary in the BiFeO₃–BaTiO₃ system. Single-phase samples with the perovskite structure have been obtained and the addition of Bi(Mg_0.5Ti_0.5)O₃ has been shown to raise the Curie temperature of the ceramics and improve their dielectric properties.     

Fabrication of lead-free piezoelectric (Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript> ceramics using electrophoretic deposition

Electrophoretic deposition (EPD) process has certain advantages such as it can be applied for a mass production and also can be combined with magnetic crystal alignment technique. In this work, we prepared lead-free 85(Bi_0.5Na_0.5)TiO₃–15BaTiO₃ (85BNT–15BT) piezoelectric ceramics by conventional uniaxial pressing and EPD process. Various conditions were optimized such as suspension media, applied electrical field, and deposition time in order to yield dense green ceramics of 85BNT–15BT composition using EPD process. 85BNT–15BT ceramics prepared using EPD process revealed the Curie temperature of about 250 °C, coercive field of about 30 kV/cm, and piezoelectric constant (d ₃₃) of 75 pC/N. The EPD-processed samples exhibited structural and electrical properties similar to that of the conventionally processed one suggesting the successful fabrication of 85BNT–15BT piezoelectric ceramics by EPD method without composition deviation. This study lays a foundation on the fabrication of Bi-based lead-free piezoelectric ceramics by an alternative route other than the conventionally practiced solid-state reaction method maintaining the similar chemical composition, moreover, leaving a large space to explore more in the future.     

Dual relaxation behaviors and large electrostrictive properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Sr<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> ceramics

Lead-free ceramics (1???x)Bi_0.5Na_0.5TiO₃–xSr_0.85Bi_0.1TiO₃ (BNT–xSBT, x?=?0.4, 0.5, 0.6 and 0.7) were prepared by a solid-state reaction process. Coexistence of ferroelectric relaxation at low temperature and Maxwell–Wagner dielectric relaxation at high temperature was revealed for the first time in this system. Meanwhile, hysteresis-free P–E loops combined with a very high piezoelectric strain coefficient (d₃₃) of 1658 pC/N concurrently with large electrostrictive coefficient Q?=?0.287 m⁴C^?2 were achieved. The ferroelectric relaxor behavior and large electrostrictive strain might be linked to easy reorientation and reversal of ergodic PNRs and the combined effect of Bi off-center position and lone pair electrons.     

Ferroelectric and antiferroelectric polarisation switching characteristics of Bi(Mg<Subscript>0.5</Subscript>Ti<Subscript>0.5</Subscript>)O<Subscript>3</Subscript>–PbTiO<Subscript>3</Subscript> ceramics

Bi(Mg_0.5Ti_0.5)O₃–PbTiO₃ (BMT–PT) ceramics, with BMT–PT ratios ranging from 70-30 to 50-50, were prepared by a conventional solid state reaction process. The 50-50 BMT–PT ceramic possessed a tetragonal perovskite structure with a c/a ratio of ~1.037. Increasing BMT content led to a reduction of tetragonality and a change of structure to a rhombohedral or pseudo-cubic phase. Dielectric measurements, carried out during heating, indicated the occurrence of two phase transformations, which were identified as relaxor ferroelectric to antiferroelectric (at a temperature in the range from 150–300 °C) and antiferroelectric to paraelectric (at a temperature around 500 °C). The antiferroelectric nature of the 60-40 and 70-30 BMT–PT ceramics in the intermediate temperature range was confirmed by polarisation-electric field hysteresis measurements.     

Dielectric and piezoelectric properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–BaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xBaNb₂O₆ (BNT–BN100x), a new member of the BNT-based group, was prepared by conventional solid state reaction. X-ray diffraction showed that BaNb₂O₆ (BN) diffused into the lattice of Bi_0.5Na_0.5TiO₃ to form a solid solution with perovskite-type structure. The temperature dependence of dielectric constant ε_r revealed that the solid solution underwent two phase transitions from ferroelectric to anti-ferroelectric and anti-ferroelectric to paraelectric. Both the transition temperature T _d and T _m were shifted to lower with the increasing content of BaNb₂O₆. The temperature dependence of dielectric constant at different frequency revealed that the solid solution exhibited obviously dielectric relaxation characteristics. The sample with x = 0.6 mol% exhibited excellent electrical properties, piezoelectric constant d ₃₃ = 94 pC/N; electromechanical coupling factor k _p = 0.185. The results showed that BNT–BN100x ceramics were good candidates for use as lead-free piezoelectric ceramics.     

Synthesis and piezoelectric properties of (Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>)<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>TiO<Subscript>3</Subscript> ceramics prepared by sol–gel auto-combustion method

In this study, NaNO₃, Bi(NO₃)₃·5H₂O, Ba(NO₃)₂, Ti(OC₄H₉)₄ and citric acid were successfully introduced to fabricate lead-free piezoelectric (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ [NBBT] nanopartical powders by a novel modified sol–gel auto-combustion method. The resultant products were characterized by the X-ray diffraction analysis and transmission electron microscope method. (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ + Mn(NO₃)₂ [NBBTM] can be sintered by the traditional solid-state reaction, and the effects of NBBT doped different amounts of Mn(NO₃)₂ at various sintering temperatures upon phase formation, microstructure as well as piezoelectric properties were further studied. The experimental results show that it was helpful to control their chemical ingredients and microstructure to prepare nanocrystalline single phase NBBT powders. Where is the X-ray diffraction result of the corresponding ceramics to prove the existence of the mixing between rhombohedral and tetragonal phases at the MPB compositions. Doping 0.015 mol% Mn(NO₃)₂ into NBBT at 1,090 °C, piezoelectric constant (d ₃₃) and relative dielectric constant (ε_r) reach the superior value of 159pC/N and 1,304, respectively, and dielectric loss (tan δ) and electromechanical coupling factor (K _t) are 2.5% and 65%, respectively.     

Piezoelectric properties of [Bi<Subscript>0.5</Subscript>(Na<Subscript>0.7</Subscript>K<Subscript>0.25</Subscript>Li<Subscript>0.05</Subscript>)<Subscript>0.5</Subscript>]TiO<Subscript>3</Subscript>−Ba(Ti,Zr)O<Subscript>3</Subscript> binary system ceramics

Dense lead-free binary system piezoelectric ceramics (1 − x)[Bi_0.5(Na_0.7K_0.25Li_0.05)_0.5]TiO₃−xBa(Ti_0.95Zr_0.05)O₃ (BNKLT–BZT) were prepared by a two-step sintering process. A phase transition from rhombohedral to tetragonal was observed with increasing BZT fraction in the range x = 0.06–0.1 and the morphotropic phase boundary (MPB) between rhombohedral and tetragonal appears in this range. Ceramics containing 10 mol% BZT with tetragonal phase near the MPB region has the maximum piezoelectric constant d ₃₃(151pC/N).     

Good thermal stability and improved piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>–Bi(Mg<Subscript>0.75</Subscript>W<Subscript>0.25</Subscript>)O<Subscript>3</Subscript> solid solutions

In this paper, (1 ? x)(K_0.5Na_0.5)NbO₃–xBi(Mg_0.75W_0.25)O₃ (x = 0–0.015) lead-free dielectric ceramics were investigated. XRD analysis certified that the Bi(Mg_0.75W_0.25)O₃ has diffused into (K_0.5Na_0.5)NbO₃ to fabricate a new solid solution. The addition of Bi(Mg_0.75W_0.25)O₃ depressed the orthorhombic–tetragonal phase transition temperature from 210 to 176 °C and tetragonal–pseudocubic phase transition temperature (Curie point) from 419 to 400 °C. As x = 0.005, the ceramics exhibited high relative permittivity (ε ~ 1325), low dielectric loss (tan δ < 2.9%) tan δ stability (Δε/ε_168°C ≤ ±15%) in the temperature range of 168 ~ 369 °C. Especially, the ceramics also showed optimized piezoelectric constant (d ₃₃ = 122 pC N^?1) and remnant polarization (P_r = 32.57 μC cm^–2). These results indicated that the BMW added ceramics have potential applications in ferroelectric and thermal stability devices.     

Increased Solubility of Mg at Ca Site in Cu<Subscript>0.5</Subscript>Tl<Subscript>0.5</Subscript>Ba<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10−<Emphasis Type="Italic">δ</Emphasis></Subscript> Superconductor

The Cu_0.5Tl_0.5Ba₂Ca_2?y Mg _y Cu₃O_10?δ (y=0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0) superconductor has been synthesized at the atmospheric pressure by the solid-state reaction method. The zero resistivity critical temperature is found to increase to 98 K with Mg concentration of y=0.6, but saturates to 97 K with further enhancement of Mg to y=0.8, 1.0, and 1.5. The Mg doped material grows in tetragonal structure and follows P4/mmm symmetry with a &; c-axes lengths of 3.894 Å &; 15.091 Å for y=1.5. The axes lengths were decreased with the increase of Mg content in the unit cell, which shows that anisotropy of the material decreases. The critical current density and the quantity of diamagnetism in the samples with Mg contents are higher than in the samples without Mg. In order to realize the effects of decreased axes lengths on the phonon modes of Cu_0.5Tl_0.5Ba₂Ca_2?y Mg _y Cu₃O_10?δ , we have carried out FTIR absorption measurements.     

Structure of SrCo<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3 − δ</Subscript>-based composites prepared by sol-gel and mechanochemical processes

X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy have been used to investigate the structural phase transformations of SrCo_0.5Fe_0.5O_{3 ? δ}-based mixed-oxide nanocomposites containing fine iron oxide particles. The nanocomposites have been prepared using sol-gel and mechanochemical processes. The addition of iron(III) oxide sol to SrCo_0.5Fe_0.5O_{3 ? δ} xerogel is shown to enhance the thermal stability of the resultant cubic perovskite phase. The stabilization is due to partial shielding of the perovskite surface with a thin Fe₂O₃ layer, which hinders cobalt diffusion to the surface, preventing Co₃O₄ formation.     

Synthesis and study of structural,dielectric, magnetic and magnetoelectric properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript>–CoMn<Subscript>0.2</Subscript>Fe<Subscript>1.8</Subscript>O<Subscript>4</Subscript> composites

Magnetoelectric (ME) composites consisting of K_0.5Na_0.5NbO₃ (KNN) as ferroelectric phase and CoMn_0.2Fe_1.8O₄ (CMFO) as ferrite phase with general formula (x) CoMn_0.2Fe_1.8O₄–(1???x) K_0.5Na_0.5NbO₃ (x?=?10, 20, 30, 40 and 50 wt%) were synthesized using solid state reaction method. X-ray diffraction analysis asserts the existence of component phases including spinel phase of CMFO and orthorhombic phase of KNN. Field emission scanning electron microscopy has been used for studying the morphology and calculation of average grain size. The temperature dependent dielectric properties including dielectric constant (\(\varepsilon ^{\prime}\)) and dielectric loss (tan δ) at different frequencies has been studied and both are found to increase with incorporation of CMFO. Magnetic hysteresis loops have been measured at temperatures of 300 and 5 K. Variation of magnetization versus temperature has been studied in field cooled and zero field cooled modes. Polarization versus electric field (P–E) hysteresis loops are obtained at room temperature indicating presence of ferroelectric ordering in the composites at room temperature. The remnant polarization (2P_r) and coercive field (2E_c) are found to decrease linearly with incorporation of CMFO. ME voltage coefficient (α_ME) has been measured. The maximum value of α_ME is found to be 5.941 mV/cm-Oe for 10% CMFO–90% KNN bulk composite.     

Two-step sintering and electrical properties of sol–gel derived 0.94(Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript>–0.06BaTiO<Subscript>3</Subscript> lead-free ceramics

Two-step pressureless sintering of sol–gel derived 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (BNT-BT) lead-free piezoelectric ceramics were investigated in comparison with conventional sintering. The effect of sintering regimes on the densification, grain growth behavior and electrical properties was discussed in detail. The results indicated that BNT-BT ceramics with a density of 95%, a relatively fine grain size of 850 nm and comparable piezoelectric properties (d₃₃ ~170 pC/N, k_p ~0.26, Q_m ~102) had been achieved by pre-sintering at 1,150 °C to reach a critical density of 78%, and then cooling to a lower temperature of 1,050 °C for 20 h. The critical density value proves important at which the grain boundary diffusion could be maintained but the grain boundary migration suppressed at the same time. Moreover, the volatilization loss of Bi and Na elements could be inhibited by two-step sintering. Both the reduction of the grain size and the inhibition of the stoichiometry deviation together account for the variation of various electrical properties.     

Phase formation and dielectric properties of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> by slow injection sol–gel technique

A simple sol–gel process incorporating slow precursor injection technique was employed to synthesize homogeneous Ba_0.5Sr_0.5TiO₃ nano powders. The Ba_0.5Sr_0.5TiO₃ samples were subjected to calcination temperatures from 600 to 1,100 °C and sintering temperatures from 1,250 to 1,350 °C for the study of phase formation, crystallite size, particle distribution, and dielectric properties. Single phase Ba_0.5Sr_0.5TiO₃ with a cubic perovskite structure was successfully synthesized after calcination at 800 °C. The average size of the nano particles is 42 nm with a narrow size distribution, and a standard deviation of 10%. The highest values recorded within the investigated range for dielectric constant, and dielectric loss measured at 1 kHz are 1,164 and 0.063, respectively, for Ba_0.5Sr_0.5TiO₃ pellets calcined at 800 °C and sintered at 1,350 °C. Leakage current density measured at 5 V for the Ba_0.5Sr_0.5TiO₃ pellet was found to be 49.4 pA/cm².     

BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> films produced from BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> heterostructures

BaFe₁₂O₁₉ hexaferrite films have been produced on thermally oxidized single-crystal silicon (SiO₂/Si) substrates by sequential ion-beam sputtering of BaFe₂O₄ and α-Fe₂O₃ targets in an argon-oxygen atmosphere. Their crystal structure has been studied, and the origin of the impurity phases forming during heat treatment has been identified. The results show that heat treatment may lead to the formation of eutectic melts. As a result, the hexaferrite films may contain spherulites.     

Microwave dielectric properties of Sr<Subscript>0.7</Subscript>Ce<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript>–Sr(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

xSr_0.7Ce_0.2TiO₃–(1???x)Sr(Mg_1/3Nb_2/3)O₃ ceramics, referred to xSCT–(1???x)SMN, were successfully produced by conventional solid-state sintered technology. The compounds, belonging to perovskites with a secondary phase of CeO₂, can be detected even with x down to 0.1 of SCT composition. The overall trend for grain growth illustrates the increase with increasing SCT doping level. The Raman peak at 825 cm^?1 splits into two peaks and causes red shift phenomenon. XPS spectra indicate that Ti and Nb ions exist respectively in tetravalence and pentavalence, and Ce ions exist in trivalence and tetravalence. Dielectrics constant (ε _r ) of SCT–SMN ceramics gradually increases with increasing theoretical dielectric polarizabilities. A wider width of the 825 cm^?1 for FWHM of A_1g mode Raman peaks suggests to a lower Q?×?f value. The increasing tolerance factor in agreement with temperature coefficient of resonant frequency (τ _f ), denotes that the rise of perovskite symmetry. The 0.1SCT–0.9SMN ceramic sintered at 1450?°C for 4 h illustrates excellent microwave dielectric properties with ε _r ?~?35.4, Q?×?f?~?11282 GHz and τ _f ?~?1.7 ppm/°C. Activation energies of 0.1SCT–0.9SMN ceramic at 100, 300 and 500 V, are ~0.436, 0.427 and 0.331 eV, respectively, indicative of a decreased trend with external electric field.     

System ZnO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>-CuO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis and x-ray diffraction data indicate that the ZnO B₂O₃-CuO B₂O₃ join of the ternary system CuO-B₂O₃-ZnO is pseudobinary, with eutectic phase relations and a liquid-liquid miscibility gap in the composition range 25–35 mol % CuO.Translated from Neorganicheskie Materialy, Vol. 41, No. 3, 2005, pp. 339–340.Original Russian Text Copyright © 2005 by Kasumova, Bananyarly.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.