Investigation of BiFeO3 modified PbTiO3-Bi(MgZr)O3-based complex perovskite ceramics

Bismuth containing crystalline solutions of (1 − x)Bi(MgZr)_0.5O₃-xPbTiO₃ (BMZ-PT) and [(BiFeO₃)_y − (BiMg_0.5Zr_0.5)_1−y]_x − [PbTiO₃]_1−x (BMZ-BF-PT) have been developed using conventional ceramic technology. X-ray diffraction analysis reveals that both the systems possess a perovskite structure, in which tetragonal to rhombohedral phase transformation appears for x = 0.55 in BMZ-PT and y = 0.20 in BMZ-BF-PT systems. SEM photographs reveal a uniform grain size distribution in the solid solution matrix with the presence of ferroelectric domains in few of the compositions. Ferroelectric hysteresis (polarization-electric field, P-E) loops reveal that increase in BiFeO₃ in BMZ-PT systems results in a decrease in residual polarization of the system with change and distortion in the shape of the (P-E) loops.     

Ferroelectric and piezoelectric properties of tungsten substituted SrBi2Ta2O9 ferroelectric ceramics

Tungsten substituted samples of compositions SrBi₂(W_xTa_1−x)₂O₉ (x = 0.0, 0.025, 0.050, 0.075, 0.10 and 0.20) were synthesized by solid-state reaction method and studied for their microstructural, electrical conductivity, ferroelectric and piezoelectric properties. The X-ray diffractograms confirm the formation of single phase layered perovskite structure in the samples with x up to 0.05. The temperature dependence of dc conductivity vis-à-vis tungsten content shows a decrease in conductivity, which is attributed to the suppression of oxygen vacancies. The ferroelectric and piezoelectric studies of the W-substituted SBT ceramics show that the remanent polarization and d₃₃ values increases with increasing concentration of tungsten up to x ≤ 0.05. Such compositions with low conductivity and high P_r values should be excellent materials for highly stable ferroelectric memory devices.     

Stabilization of α-SiAlONs using a rare-earth mixed oxide (RE2O3) as sintering additive

α-SiAlONs are commonly produced by liquid phase sintering of Si₃N₄ with AlN and Y₂O₃ as additives. The formation of the α-SiAlONs using a mixed oxide (RE₂O₃), containing yttria and rare-earth oxides, as an alternative additive was investigated. Dense α-SiAlONs were obtained by gas-pressure sintering, starting from α-Si₃N₄ and AlN-Y₂O₃ or AlN-RE₂O₃ as additives. The mixed oxide powder RE₂O₃ was characterized by means of high-resolution synchrotron X-ray diffraction and compared to Y₂O₃. The X-ray diffraction analysis of the mixed oxide shows a pattern indicating a true solid solution formation. The Rietveld refinement of the crystal structure of the sintered α-SiAlON using AlN-RE₂O₃ as additive revealed a similar crystal structure to the α-SiAlON using AlN-RE₂O₃ as additive. The comparison of the microstructures of the both α-SiAlONs produced using pure Y₂O₃ or RE₂O₃, revealed similar grain sizes of about 4.5 μm with aspect ratios of about 5. Both materials show also similar mechanical properties, with hardness of 18.5 GPa and fracture toughness of 5 MPa m^1/2. It could be, thus, demonstrated that pure Y₂O₃ can be substituted by the rare-earth solid solution, RE₂O₃, in the formation of α-SiAlONs, presenting similar microstructural and mechanical properties.     

Spark plasma sintering of BiFeO3

Dense BiFeO₃ ceramics were prepared by a novel spark plasma sintering (SPS) technique. The sintering was conducted at temperatures ranging from 675 to 750 °C under 70 MPa pressure. A bulk density value up to 96% of theoretical density was achieved in the process. This contrast to around 90% of the theoretical density achieved by conventional sintering at around 830 °C. It was found that the tendency to form unwanted Bi₂Fe₄O₉ phase is higher at a high sintering temperature for SPS. The dielectric and ferroelectric properties also improved (with respect to conventionally sintered sample) for spark plasma-sintered samples.     

Structure study of Bi4Ti3O12 produced via mechanochemically assisted synthesis

Nanosized bismuth titanate was prepared via high-energy ball milling process through mechanically assisted synthesis directly from their oxide mixture of Bi₂O₃ and TiO₂. Only Bi₄Ti₃O₁₂ phase was formed after 3 h of milling time. The excess of 3 wt% Bi₂O₃ added in the initial mixture before milling does not improve significantly the formation of Bi₄Ti₃O₁₂ phase comparing to stoichiometric mixture. The formed phase was amorphized independently of the milling time. The Rietveld analysis was adopted to determine the crystal structure symmetry, amount of amorphous phase, crystallite size and microstrains. With increasing the milling time from 3 to 12 h, the particle size of formed Bi₄Ti₃O₁₂ did not reduced significantly. That was confirmed by SEM and TEM analysis. The particle size was less than 20 nm and show strong tendency to agglomeration. The electron diffraction pattern indicates that Bi₄Ti₃O₁₂ crystalline powder is embedded in an amorphous phase of bismuth titanate. Phase composition and atom ratio in BIT ceramics were determined by X-ray diffraction and EDS analysis.     

Piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 ceramics synthesized by spray drying method

Potassium-sodium niobate was synthesized at 800 °C for 1 h using dried precursors in a powder form obtained by the spray drying method. Different samples were sintered from 1060 to 1120 °C for 2 h reaching a relative density as high as 96% of the theoretical value. Piezoelectric and ferroelectric properties were studied for these samples and some of the most prominent results are: k_p, d₃₁, 2P_r, and 2E_C of 0.36, 39 pC/N, 29 μC/cm² and 16.5 kV/cm, respectively, for the sample sintered at 1080 °C. The methodology presented in this study can be used to synthesize submicrometer powders.     

Dielectric properties and substitution mechanism of samarium-doped Ba0.68Sr0.32TiO3 ceramics

Ba_0.68Sr_0.32TiO₃ ceramics of perovskite structure are prepared by solid state reaction method with addition of x mol% Sm₂O₃, and their dielectric properties are investigated. It is found that, integrating with the lattice parameters and tolerance factor t, there is an alternation of substitution preference of Sm³⁺ for the host cations in perovskite lattice. Owing to the replacement of Sm³⁺ ions for Ba²⁺ ions in the A site, T_c rises with the increase of Sm₂O₃ doping when the doping content is below 0.1 mol%; meanwhile, when the content is more than 0.1 mol%, Sm³⁺ ions tend to occupy the B-site, causing a drop of T_c. Owing to the modifications of Sm³⁺ doping, dielectric constant, dissipation factor and temperature stability of dissipation factor are influenced remarkably, making it a superior candidate for environment-friendly applications. Moreover, the creation of oxygen vacancies controls the dielectric constant when the addition is above 0.1 mol%, so the dielectric constant decreases with increasing of samarium.     

Cation disorder in Bi2Ln2Ti3O12 Aurivillius phases (Ln = La, Pr, Nd and Sm)

The synthesis and structure of triple layered Bi₂Ln₂Ti₃O₁₂ Aurivillius phases (Ln=La, Pr, Nd and Sm), prepared from K₂Ln₂Ti₃O₁₀ Ruddlesden-Popper precursors, has been investigated. These materials adopt a body centred tetragonal structure (space group I4/mmm, with unit cell parameters a∼3.8 Å and c∼33 Å) comprising a regular intergrowth of [Bi₂O₂]²⁺ fluorite-type and [Ln₂Ti₃O₁₀]²⁻ perovskite-type layers. A significant degree of cation disorder is present in the Bi₂Ln₂Ti₃O₁₂ system, involving the cross-substitution of Ln/Bi cations onto the Bi/Ln sites in the fluorite- and perovskite-type layers, respectively. As the size of the lanthanide cation is reduced, Bi/Ln disorder is significantly suppressed due to the effect of bond length mismatch in the perovskite-type layer in the crystal structure of Bi₂Ln₂Ti₃O₁₂. This offers a potential strategy for the chemical control of cation disorder in the Bi₂Ln₂Ti₃O₁₂ system.     

Preparation and colossal magnetoresistance in a trilayer La0.67Sr0.33MnO3/La0.75MnO3/La0.67Sr0.33MnO3 device by dc magnetron sputtering

Epitaxial trilayer films of La_0.67Sr_0.33MnO₃ (LSMO)/La_0.75MnO₃ (L0.75MO)/La_0.67Sr_0.33MnO₃ (LSMO) have been prepared on (0 0 1) oriented LaAlO₃ substrates by dc magnetron sputtering. The structure and MR are studied. All as-deposited trilayer films exhibit a semiconductor to metal transition at temperature ranging from 116 to 185 K. The MR is also shown to be dependent on the thickness of the middle oxide layer. A maximum MR value of 32% (ΔR/R₀) has been obtained at 132 K under 0.4 T magnetic field for a LSMO (300 nm)/L0.75MO (70 nm)/LSMO (300 nm) trilayer film. The MR of trilayer film prefers to that of both LSMO and L0.75MO single layer films.     

Effect of Ce doping and calcination on the photoluminescence of ZrO2 (3% Y2O3) fibers

Ce³⁺-doped ZrO₂ fibers were prepared by spinning method. X-ray powder diffraction (XRPD) shows the formation of only tetragonal phase with different concentrations of Ce³⁺-doped ZrO₂ fibers. The surface of the fibers is smooth and of uniform diameter by scanning electron microscopy (SEM). The photoluminescence (PL) results show typical emission bands centered at 470 and 530 nm; concentration quenching of the luminescence occurs as the molar ratio of Ce³⁺ ions exceeds an optimum value of 5%. No thermal quenching was observed, which was attributed to improved crystallinity of the host lattice, due to the increased calcining temperature.     

New palladium phosphate complexes: K2PdP2O7 and K3.5Pd2.25(P2O7)2 synthesis, single crystal structure and conductivity

Two new diphosphate complexes containing potassium and palladium, K₂PdP₂O₇ and K_3.5Pd_2.25(P₂O₇)₂, have been synthesized and characterized by single crystal X-ray diffraction. K₂PdP₂O₇ exists with layers formed of linked PdP₂O₇ polyhedra, between which are found the potassium ions. K_3.5Pd_2.25(P₂O₇)₂ with a Pd/P₂O₇ ratio of 1.125:1 crystallizes with tunnels of various sizes in which are found the potassium ions. Conductivity measurements reveal the material to be conducting.     

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.     

Structure and ferroelectric properties in (K0.5Bi0.5)TiO3-BiScO3-PbTiO3 piezoelectric ceramic system

(K_0.5Bi_0.5)TiO₃-BiScO₃-PbTiO₃ ceramics were synthesized by conventional solid-state method. A morphotropic phase boundary (MPB) was confirmed with the aid of structural analysis. Two dielectric anomalous peaks were observed, the one around dielectric maximum temperature (T_m) due to phase transformation from ferroelectric to paraelectric while the second one could be ascribed to space charges. Furthermore, the existence of space charges also resulted in the independence of T_m with frequency at low lead composition. A new high temperature piezoelectric ceramic, 0.30(K_0.5Bi_0.5)TiO₃-0.30BiScO₃-0.40PbTiO₃ close to MPB exhibited excellent electrical properties with T_m of 384 °C, d₃₃ of 247 pC/N, k_p of 38.9%, P_r of 19.41 μC/cm², and E_c of 2.25 kV/mm, indicative of a candidate for high temperature application.     

Microwave-hydrothermal synthesis of the multiferroic BiFeO3

In this work, three different methods for preparing BiFeO₃ polycrystals are compared: hydrothermal synthesis, microwave heating in the solid state and the combination of both, that is a hydrothermal method using microwave heating. The best materials, without high purity reactants, are obtained in few minutes by the last procedure, a new, very fast, reproducible and environment-friendly method of synthesis, which is described and discussed here.     

Growth and electrical performance of Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Fe1/2Nb1/2)O3 single crystals

For the first time, we have grown ferroelectric single crystals Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-Pb(Fe_1/2Nb_1/2)O₃ (PMN-PT-PFN) from the melt by the simple slow cooling process. The chemical composition of the single crystals PMN-PT-PFN (0.59/0.31/0.10) is near the morphotropic phase boundary (MPB). X-ray diffraction (XRD) was used to study phase structure of the as-grown crystals, energy dispersive X-ray spectrometer (EDS) and electron probe micro-analyzer (EPMA) were employed to confirm the chemical composition and element distribution of the as-grown crystals, respectively. The ferroelectric, dielectric and piezoelectric properties of the as-grown PMN-PT-PFN (0.59/0.31/0.10) single crystal oriented along the (0 0 1) axis were measured, which showed that the remnant polarization (P_r), coercive electric fields (E_c), the Curie temperature (T_c) and the piezoelectric coefficient (d₃₃) were 50.2 μC/cm², 13.9 kV/cm, 158 °C and about 1800 pC/N, respectively. All the results indicated that the PMN-PT-PFN (0.59/0.31/0.10) single crystals are promising for applying to field of high frequency.     

Low-temperature synthesis of BiFeO3 nanoparticles by ethylenediaminetetraacetic acid complexing sol-gel process

This paper reported a novel approach to synthesize pure BiFeO₃ nanoparticles through an ethylenediaminetetraacetic acid complexing sol-gel process at low temperature. The pure BiFeO₃ nanoparticles were attained at much lower temperature as 600 °C by this process, in contrast to above 800 °C for the traditional solid-state sintering process. The SEM results showed that the prepared BiFeO₃ nanoparticles had a better homogeneity and fine grain morphology. The BiFeO₃ nanoparticles show a weak ferromagnetic order at room temperature, which is quite different from the linear M-H relationship in bulk BiFeO₃. The origin of the weak magnetic property in our samples should be attributed to the size-confinement effects of the BiFeO₃ nanostructures.     

Effect of Pr substitution on structural and electrical properties of BiFeO3 ceramics

Investigation on structural, vibrational, dielectric and ferroelectric properties of Bi_1−xPr_xFeO₃ (x = 0.0, 0.15, 0.25) ceramic samples has been carried out. Room temperature Rietveld-refined X-ray diffraction pattern shows the crystal structure of Bi_1−xPr_xFeO₃ is rhombohedral for x = 0 and triclinic for x = 0.15, 0.25. The changes in Raman normal modes with increasing doping concentration infer the structural transformation is due to Pr substitution at A-site in BiFeO₃. Raman spectra also reveal suppression of ferroelectric behavior due to Pr doping. The dielectric parameters, namely, dielectric permittivity (ε′) and loss tangent (tan (δ)) were evaluated as a function of frequency at room temperature. The ferroelectric polarization reduces in Pr doped bulk BFO samples due to structural change.     

Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature

We demonstrate the electrocaloric effect (ECE) of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) lead-free ferroelectric ceramics, which were fabricated by the solid-state reaction method. Based on a Maxwell relation, the ECE was characterized via P–T curves under different electric fields. The polarization of NBT increases monotonically within the temperature range of 25–145 °C. It indicates that the NBT has an abnormal ECE with a negative temperature change (ΔT₁₄₀ = −0.33 K at E = 50 kV/cm) opposite to that of the normal ferroelectrics. The 0.92NBT–0.08BT composition near the morphotropic phase boundary has a normal ECE under low electric fields and an abnormal ECE under high electric fields. The abnormal ECE character originates from the relaxor characteristic between ferroelectric and antiferroelectric phases, while the common ECE is always related to the normal ferroelectric–paraelectric phase transition.     

Stress-induced shifting of the morphotropic phase boundary in sol-gel derived Pb(Zr0.5Ti0.5)O3 thin films

The structure evolution of Pb(Zr_0.5Ti_0.5)O₃ thin films with different thicknesses on the Pt(1 1 1)/Ti/SiO₂/Si substrates has been investigated using X-ray diffraction and Raman scattering. Differing from Pb(Zr_0.5Ti_0.5)O₃ bulk ceramic with a tetragonal phase, our results indicate that for PZT thin films with the same composition monoclinic phase with Cm space group coexisting with tetragonal phase can appear. It is suggested that tensile stress plays a role in shifting the morphotropic phase boundary to titanium-rich region in PZT thin films. The deteriorated ferroelectric properties of PZT thin films can be attributed mainly to the presence of thin non-ferroelectric layer and large tensile stress.