Compositional range and electrical properties of the morphotropic phase boundary in the Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 system

We have investigated the Na_0.5Bi_0.5TiO₃–K_0.5Bi_0.5TiO₃ (NBT–KBT) system, with its complex perovskite structure, as a promising material for piezoelectric applications. The NBT–KBT samples were synthesized using a solid-state reaction method and characterized with XRD and SEM. Room-temperature XRD showed a gradual change in the crystal structure from tetragonal in the KBT to rhombohedral in the NBT, with the presence of an intermediate morphotropic region in the samples with a compositional fraction x between 0.17 and 0.25. The fitted perovskite lattice parameters confirmed an increase in the size of the crystal lattice from NBT towards KBT, which coincides with an increase in the ionic radii. Electrical measurements on the samples showed that the maximum values of the dielectric constant, the remanent polarization and the piezoelectric coefficient are reached at the morphotropic phase boundary (MPB) (? = 1140 at 1 MHz; P_r = 40 μC/cm²; d₃₃ = 134 pC/N).     

Synthesis,structure and photocatalytic hydrogen evolution of a silver-linked hexaniobate Lindqvist chain

By using a combination of hydrothermal and diffusional strategies, a one-dimensional polyoxoniobate K₅[H₂AgNb₆O₁₉]·11H₂O (1) has been synthesized. The structure was characterized by single-crystal X-ray diffraction, UV spectroscopy, TG analysis, PXRD and IR spectrum. 1 crystallizes in the hexagonal P63/mmc space group with a = 9.8171(2) Å, c = 16.5442(6) Å, and V = 1380.84(6) Å³. It is the first Ag-containing polyoxoniobate, which consists of [H₂AgNb₆O₁₉]^5 − polyoxoanion and potassium ions. In addition, 1 exhibits the photocatalytic H₂ evolution activity.     

Effects of K0.5Bi0.5TiO3 addition on dielectric properties of BaTiO3 ceramics

(1?x)BaTiO₃–xK_0.5Bi_0.5TiO₃ (abbreviated as BT–KBT, 0.10≦x≦0.15) dielectric ceramics were prepared by a conventional oxide mixing method. The effects of KBT content on the densification, microstructure and dielectric properties of BT ceramics were investigated. The density characterization results show that the addition of KBT significantly lowered the sintering temperature of BT ceramics to about 1280 °C. The XRD results showed that the phase compositions of all samples were pure tetragonal phases. The dielectric constant and dielectric loss firstly increased and then decreased with the increase of KBT. In addition, dielectric constant and dielectric loss versus frequency were characterized in the frequency range from 100 Hz to 2 MHz. It is found that the dielectric constant and the dielectric loss changed with the increase of KBT contents regularly.     

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.     

The decrease of depolarization temperature and the improvement of pyroelectric properties by doping Ta in lead-free 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics

Ta-doped lead-free 0.94NBT-0.06BT-xTa (x=0.0–1.0%) ceramics were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. The depolarization temperature (T_d) shifted to lower temperature with the increase of Ta content. The pyroelectric coefficient (p) of doped ceramics greatly enhanced compared with undoped material and reached a maximum of 7.14×10⁻⁴ C m⁻² °C⁻¹ at room temperature (RT) and 146.1×10⁻⁴ C m⁻² °C⁻¹ at T_d at x=0.2%. The figure of merits, F_i and F_v, also showed a great improvement from 1.12×10⁻¹⁰ m v⁻¹ and 0.021 m² C⁻¹ at x=0.0 to 2.55×10⁻¹⁰ m v⁻¹ and 0.033 m² C⁻¹ at x=0.2% at RT. Furthermore, F_i and F_v show the huge improvement to 52.2×10⁻¹⁰ m v⁻¹ and 0.48×10⁻¹⁰ m v⁻¹ respectively at T_d at x=0.2%. F_C shows a value between 2.26 and 2.42 ×10⁻⁹ C cm⁻² °C⁻¹ at RT at x=0.2%. The improved pyroelectric properties make NBT-0.06BT-0.002Ta ceramics a promising infrared detector material.     

Pyroelectric,ferroelectric, piezoelectric and dielectric properties of Na0.5Bi0.5TiO3 ceramic prepared by sol-gel method

Sodium bismuth titanate (BNT) nanopowder of molar composition 50/50 (Na_0.5Bi_0.5TiO₃) was prepared by a sol-gel processing method. The structure and microstructure of the precursor gel as well as the ferroelectric, pyroelectric, dielectric and piezoelectric properties of the BNT were studied. BNT crystallized in the rhombohedra perovskites structure Na_0.5Bi_0.5TiO₃ was obtained from the precursor gel by heating at 700 °C for 2 h in air. The BNT ceramic at 1100 °C sintering temperature present high crystallinity, good dielectric properties at 1 kHz (ε′=885, tan δ=0.03, T_c=370 °C), piezoelectric properties (k₃₃=0.39, c₃₃=105 GPa, e₃₃=12.6 C/m², d₃₃=120 pC/N), high remnant polarization (P_r=47 μC/cm²) and pyroelectric coefficient ($p$=707 μC/m² K) and low coercive field (E_c=55 kV/cm). Hence, the BNT prepared by sol-gel method could be used for silicon based memory device application where a low synthesis temperature is a key requirement.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Effects of K nonstoichiometry in bismuth layer-structured K0.5+xBi4.5Ti4O15 ceramics

The effects of K nonstoichiometry on phase formation, grain morphology, dielectric and piezoelectric properties of K_0.5+xBi_4.5Ti₄O₁₅ (KBT) were studied in the range of excess up to +2 mol% and deficient down to ?8 mol% of K_0.5. The relative densities of the sintered KBT ceramics with various K contents prepared by a solid state reaction method were all higher than 95%. In all samples, a bismuth layer-structured phase was confirmed, although a secondary phase appeared as K deficiency became larger than ?6 mol%. Piezoelectric coefficient (d₃₃) increased, showing a high of 16 pC/N at x = ?3 mol%, and then decreased with further K deficiency while Curie temperature (T_C) decreased showing a low of 540 °C at x = ?8 mol% from 551 °C at x = 0 mol%. Mechanical quality factor (Q_m) of all samples was in the range of 900–1860.     

Enhancement of pyroelectric properties of lead-free 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics by La doping

Lead-free 0.94NBT-0.06BT-xLa ceramics at x = 0.0–1.0 (%) were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. With increasing La³⁺ content pyroelectric coefficient (p) and figures of merits greatly increase; however, the depolarization temperature (T_d) decreases. p is 7.24 × 10⁻⁴C m⁻² °C⁻¹ at RT at x = 0.5% and 105.4 × 10⁻⁴C.m^−2 °C⁻¹ at T_d at x = 0.2%. F_i and F_v show improvements at RT from 1.12 (x = 0%) to 2.65 (x10 ⁻¹⁰ m v⁻¹) (x = 0.5%) and from 0.021 to 0.048 (m².C⁻¹) respectively. F_i and F_v show a huge increase to 37.6 × 10⁻¹⁰ m v⁻¹ and 0.56 m² C⁻¹ respectively at T_d at x = 0.2%. F_C shows values of 2.10, 2.89, and 2.98 (x10⁻⁹C cm⁻² °C⁻¹) at RT at 33, 100 and 1000 (Hz) respectively. Giant pyroelectric properties make NBT-0.06BT-xLa at x = 0.2% and 0.5% promising materials for many pyroelectric applications.     

Reversible ferroelectric phase transition of 1,4-diazabicyclo [2,2,2]octane N,N′-dioxide di(perchlorate)

1,4-Diazabicyclo [2,2,2]octane N,N′-dioxide di(perchlorate), C₆H₁₄N₂O₂^2 +·2ClO₄⁻, was synthesized and separated as colorless block crystals. Differential scanning calorimetry detected that this compound underwent a reversible phase transition at ca. 216 K with a hysteresis of 5.5 K width, which was also confirmed by dielectric measurements. Single crystal X-ray diffraction data suggested that there was a transition from a room temperature phase with the space group of P2₁/c (a = 6.815(7) Å, b = 12.644(13) Å, c = 8.676(9) Å, β = 101.466(15)°, V = 732.7(13) ų, Z = 4) to a low temperature one with a space group of P2₁ (a = 9.892(8) Å, b = 12.559(10) Å, c = 17.401(13) Å, β = 92.065(8)°, V = 2160(3) ų, Z = 2). Crystallographic analysis showed that it belonged to chiral space group P2₁ with ferroelectric behaviors, and a typical ferroelectric feature of electric hysteresis loop was obtained in the low temperature phase. The disorder-order transformation of H₂-Dabcodo^2 + cation and ClO₄⁻ anion as well as the change of hydrogen bonds may drive the phase transition.     

Mechanical properties of LaFeO3 ceramics

The fracture strength, fracture toughness and apparent Young’s modulus of LaFeO₃ ceramics in the temperature region 25–800 °C are reported. The fracture strength of the material was observed to increase from 202 ± 18 MPa at room temperature to 235 ± 38 MPa at 800 °C. The room temperature fracture toughness was 2.5 ± 0.1 MPa m^1/2. The fracture toughness decreased to 2.1 ± 0.1 MPa m^1/2 at 600 °C, followed by an increase to 3.1 ± 0.3 MPa m^1/2 at 800 °C. The temperature dependence of the fracture toughness correlates well with the crystallographic strain, |(a−c)|/(a+c), and ferroelastic toughening of LaFeO₃ materials is inferred. Non-elastic stress–strain behaviour of the LaFeO₃ materials due to ferroelasticity was confirmed by cyclic compression experiments, and residual strain was observed in the material after unloading.     

Synthesis and characterisation of La(Co1/2Ti1/2)O3

Single phase, dense La(Co_1/2Ti_1/2)O₃ (LCT) ceramics have been fabricated using conventional solid state synthesis. Samples were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and their dielectric properties were studied at radio and microwave frequencies. X-ray and electron diffraction conclusively revealed that LCT contained in-phase and antiphase rotations of the O-octahedra, consistent with and a⁻a⁻c⁺ tilt system in the Glazer classification. However, XRD indicated that the Co and Ti ions were disordered on the B-site whereas TEM and Raman spectroscopy exhibited reflections and modes which suggested that partial ordering may be present. Moreover, some Raman bands could only be explained by assuming that at least some of the octahedra exhibited a Jahn–Teller distortion. Dielectric measurements indicated that LCT is insulating with low dielectric loss, 0.0024 at 1 MHz and frequency independent relative permittivity, ε_r=25. A quality factor, Q×f_o=38,000 was obtained at microwave frequencies along with a temperature coefficient of the resonant frequency, TCF=−42 MK⁻¹.     

Dielectric and ferroelectric properties of (1 − x)BaTiO3–xBi0.5Na0.5TiO3 ceramics

Lead-free (1 − x)BaTiO₃–xBi_0.5Na_0.5TiO₃ (x = 0.01, 0.02, 0.05, 0.1, 0.2, 0.3) ferroelectric ceramics were fabricated by the conventional ceramic technique. Sintering was made at 1200 °C for 2–4 h in air atmosphere. The crystal structure was investigated by X-ray diffraction. The dielectric and ferroelectric properties were also studied. Room temperature permittivity was found to decrease as Bi_0.5Na_0.5TiO₃ (BNT) content increases. Only the sample with 0.3 mol BNT was found to have relaxor behaviour. The T_c shifted slightly only for BNT addition lower than 0.1 mol. The highest T_c (about 150 °C) was obtained for 0.2 mol BNT addition. The remanent polarization, P_r, decreases whereas the coercive field, E_c, increases monotonously as the BNT content increases.     

Structural determination and microwave properties of (x)Re(Co1/2Ti1/2)O3–(1 − x)CaTiO3 (Re = La and Nd) solid solutions

Solid solutions of (x)Re(Co_1/2Ti_1/2)O₃–(1 − x)CaTiO₃ (Re = La and Nd, abbreviated to xLCT and xNCT, respectively) where x = 0, 0.25, 0.5, 0.75 and 1 have been fabricated using solid state synthesis. Samples have been examined using X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM) and their dielectric properties measured at microwave (MW) frequencies. Formation of single phase solid solutions were confirmed by XRD and the measured lattice parameters varied linearly from LCT (a = 5.66 Å, b = 7.867 Å and c = 5.494 Å) and NCT (a = 5.636 Å, b = 7.914 Å and c = 5.461 Å) to CT (a = 5.596 Å, b = 7.731 Å and c = 5.424 Å). XRD and TEM confirmed both in-phase and antiphase rotations of O-octahedra consistent with an a⁻a⁻c⁺ tilt system across the entire solid solution series. Electron diffraction revealed that LCT and NCT have reflections associated with B-site cation ordering which is absent for x ≤ 0.75. MW dielectric measurements showed that LCT and NCT were highly insulating with microwave quality factor (Qf₀) values of 39,000 and 34,000, respectively. Compositions anticipated to have a zero temperature coefficient of resonant frequency (τ_f) are 0.48LCT-CT and 0.52NCT-CT with ɛ_r = 45 and Qf₀ ∼ 5000 and ɛ_r = 43 and Qf₀ ∼ 4000, respectively.     

A tetranuclear pyrophosphate-bridged Cu(II) complex with 4,4′-bipyridine and 1,10-phenanthroline: Synthesis,structural, and magnetic properties

A new tetranuclear pyrophosphate-bridged Cu(II) complex with 4,4′-bipyridine and 1,10-phenanthroline [Cu₄(phen)₄(bpy)₂(P₂O₇)₂]·10H₂O (1) has been hydrothermal synthesized and characterized by single-crystal X-ray analysis, element analysis, IR spectroscopy, TG analysis, and UV–vis spectra. Variable-temperature magnetic susceptibility measurements show the occurrence of antiferromagnetic interactions between the neighbor Cu(II) centers in 1. The analysis of the magnetic data in the whole temperature range allows the determination of the value of the intramolecular magnetic coupling (J = − 13.16 cm^− 1).     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

Reversible water inclusion in a porous magnetic material synthesized from copper(II) incorporated metal-organic framework showing alternate ferro- and antiferromagnetic interactions

X-ray structural analysis shows that {[Cu₂(CTA) (H₂O)] · 5 H₂O}_n constitutes infinite one-dimensional parallel chains along the c-axis with water columns running down the crystallographic a-axis. The inclusion of water molecules is reversible and is confirmed by X-ray powder diffraction studies. The magnetic data (2–300 K) reveal that there are alternate ferro- (J = 0.29 cm⁻¹) and antiferromagnetic (J = −2.5 cm⁻¹) interactions.     

Oxygen ionic transport in SrFe1−yAlyO3−δ and Sr1−xCaxFe0.5Al0.5O3−δ ceramics

The oxygen permeability of mixed-conducting Sr_1−xCa_xFe_1−yAl_yO_3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO₂ gradient of 0.21/0.021 atm vary from 3.7×10⁻¹⁰ mol s⁻¹ cm⁻² to 1.5×10⁻⁷ mol s⁻¹ cm⁻² at 950 °C. The maximum solubility of Al³⁺ cations in the perovskite lattice of SrFe_1−yAl_yO_3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr_1−xCa_xFe_0.5Al_0.5O_3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO₃-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe_0.5Al_0.5O_2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe_0.7Al_0.3O_3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO₂ stability limits of Sr_1−xCa_xFe_1−yAl_yO_3−δ seem essentially independent of composition, varying between that of LaFeO_3−δ and the Fe/Fe_1−γO boundary. Thermal expansion coefficients of Sr_1−xCa_xFe_1−yAl_yO_3−δ ceramics in air are 9×10⁻⁶ K⁻¹ to 16×10⁻⁶ K⁻¹ at 100–650 °C and 12×10⁻⁶ K⁻¹ to 24×10⁻⁶ K⁻¹ at 650–950 °C. Doping of SrFe_1−yAl_yO_3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.     

Synthesis and ion responsiveness of optically active polyacetylenes containing salicylidene Schiff-base moieties

Acetylenic monomers containing salicylidene Schiff-base groups (1a and 1b) as well as Schiff-base and hydroxy groups (1c) were synthesized and polymerized with [(nbd)RhCl]₂/Et₃N catalyst to afford the corresponding polymers 2a–c with high molecular weights (M_n = 2.6–7.2 × 10⁵) in high yields (75–97%). Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that the polymers formed helical structures with a predominantly one-handed screw sense. The addition of metal ions to salicylidene Schiff-base-containing polymers 2a and 2b produced insoluble polymer/metal complexes through ionic cross-linking as a result of salicylaldimine–metal ion complexation. Polymers 2b and 2c underwent a helix–coil transition upon the addition of HSO₄⁻, whereas these polymers did not exhibit responsiveness to other anions, such as F⁻, Cl⁻, and Br⁻.     

Temperature-insensitive dielectric and piezoelectric properties in (1-x)K0.5Na0.5Nb0.997Cu0.0075O3-xSrZrO3 ceramics

Systematic investigation on phase transition, dielectric and piezoelectric properties of (1-x)K_0.5Na_0.5Nb_0.997Cu_0.0075O₃-xSrZrO₃ (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15, abbreviated as KNNC-100xSZ) ceramics was carried out. Due to the coexistence of orthorhombic and tetragonal phase in a wide temperature range, a diffused polymorphic phase transition (PPT) region was achieved in KNNC with x ≥ 0.06. KNNC-12SZ ceramics exhibited high dielectric permittivity (∼1679), low dielectric loss (∼0.02) and small variation (Δe'/ε'_25 °C ≤ 15%) in dielectric permittivity from −78 °C to 237.3 °C. KNNC-6SZ ceramic possessed a high level of unipolar strain (∼0.15%) and maintained a smaller variation of ±12% under the corresponding electric field of 60 kV cm⁻¹ at 10 Hz from 25 °C to 175 °C. d₃₃^*, which was calculated according to the unipolar strain at 60 kV cm⁻¹, was 230 pm V⁻¹ and remained stable below 100 °C. Therefore, our work provided a new promising candidate for temperature-insensitive capacitors and piezoelectric actuators.