Investigation on ferromagnetic and ferroelectric properties of (La,K)-doped BiFeO3–BaTiO3 solid solution

Multiferroic materials of BiFeO₃–BaTiO₃ solid solution have been fabricated in order to improve ferromagnetic and ferroelectric properties. The effects of La (1 mol%) and K (varied from 0.5–5 mol%) doped 0.75BiFeO₃–0.25BaTiO₃ on phase formation, ferromagnetic and ferroelectric properties have been investigated and discussed. The rhombohedral perovskite phase of specimens was characterized by XRD technique. Fracture morphology reveals the grain growth characteristics with increasing K content. (La, K)-doped 0.75BiFeO₃–0.25BaTiO₃ with La=1 mol% and K=3 mol% exhibits the highest remnant polarization and remnant magnetization.     

Dielectric properties and related ferroelectric domain configurations in multiferroic BiFeO3–BaTiO3 solid solutions

Dielectric properties and ferroelectric domain configurations of multiferroic xBaTiO₃–(1 ? x)BiFeO₃ (x = 0.10–0.33) solid solutions synthesized by conventional solid-state reaction, were reported. A structural transition from rhombohedral to pseudo-cubic structures appeared around x = 0.33, and the formation of impurity phase of Bi₂Fe₄O₉ was effectively depressed by doping BaTiO₃. Dielectric constants of xBaTiO₃–(1 ? x)BiFeO₃ solid solutions decreased with increasing the frequency, and the degree of decrease was related to the doping content of BaTiO₃. Transmission electron microscopy images revealed that the ferroelectric domain configurations in the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry, exhibited a wavy character whereas a predominant intricate domain structure with fluctuating mottled contrast was observed in the multiferroic BiFeO₃–BaTiO₃ solid solution with pseudo-cubic phase structure. The presence of 1/2{1 1 1} superlattice spots in the selected area electron diffraction patterns taken from the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry indicated that the ordered regions have a doubled perovskite unit cell.     

Fabrication of piezoelectric particle-dispersed ceramic nanocomposite

The goal of this study is to fabricate perovskite type ferroelectric particles-dispersed ceramic nanocomposites though conventional hot-pressing or pulse electric current sintering (PECS). This type of nanocomposite is expected to show ferroelectricity or piezoelectricity with retaining mechanical properties. Magnesia (MgO) and barium titanate (BaTiO₃) were selected as a matrix and secondary phase dispersoid. From X-ray diffraction analysis, the BaTiO₃ was the phase compatible with the MgO matrix, and there were no reaction phases between the matrix and BaTiO₃. It was found that the BaTiO₃ enhanced the sinterability of the MgO ceramics. Relative density of pure MgO was lower than 80%, while dense MgO/10 vol% BaTiO₃ nanocomposites could be successfully prepared by sintering at 1200°C for 10 min through PECS method. Fine BaTiO₃ particles were homogeneously dispersed within the MgO matrix grain as well as at grain boundaries. Sintering behavior and microstructure development of the MgO/BaTiO₃ nanocomposites were discussed in terms of BaTiO₃ content and sintering temperatures.     

Structure and properties of plasma sprayed BaTiO3 coatings after thermal posttreatment

Previously published results on electrical and mechanical properties of BaTiO₃ coatings prepared by atmospheric plasma spraying showed anomalies in their dielectric response. This paper provides a study of electrical and mechanical properties of BaTiO₃ coatings after thermal posttreatment. The spraying was carried out by a direct current gas-stabilized plasma gun. BaTiO₃ was fed into the plasma jet as a feedstock powder prepared by reactive sintering of micrometer-sized powders of BaCO₃ and TiO₂. In the next step the coatings were annealed in air. Microstructure and phase composition are reported and discussed in relation to electric and mechanical properties. Dielectric properties are reported for the radio frequency (RF) range.     

Preparation and characterisation of the magneto-electric xBiFeO3–(1 − x)BaTiO3 ceramics

The solid solutions of BiFeO₃–BaTiO₃ have been prepared via solid state with a view to obtaining magnetoelectric properties, i.e. ferroelectric and magnetic activity in the same range of temperatures. Optimum calcination and sintering strategy for obtaining pure perovskite phase, dense ceramics (>97% relative density) and homogeneous microstructures have been determined. The sample of composition 0.7BiFeO₃–0.3BaTiO₃ reported in the present work is pseudo-cubic at room temperature. The permittivity is ɛ_r ≈ 150 at the room temperature and shows a broad ferro-para phase transition at around 175 °C where ɛ_r ≈ 1600. This diffuse maximum of the permittivity, similar to that in relaxors, is due to the chemical inhomogeneity in both A and B sites of the perovskite unit cell ABO₃. Higher losses, tan δ > 1, appear above 200 °C and other different conduction mechanisms start to be active particularly at temperatures higher than 400 °C, when the ceramic becomes conductive. The magnetic properties show a succession of transitions from weak ferro/ferrimagnetism-to-antiferromagnetism and antiferromagnetism-to-paramagnetism at T_N1 ≈ 10 K and T_N2 ≈ 265 K. Below T_N2 the ceramic 0.7BiFeO₃–0.3BaTiO₃ can present magnetoelectric coupling, due to the fact that is simultaneously ferroelectric and antiferromagnetic.     

Phase–composition and temperature dependence of electrocaloric effect in lead–free Bi0.5Na0.5TiO3–BaTiO3–(Sr0.7Bi0.2□0.1)TiO3 ceramics

The (0.94–x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–x(Sr_0.7Bi_0.2□_0.1)TiO₃ (BNT–BT–xSBT, 0 ≤ x ≤ 0.24) solid solution ceramics were synthesized via a conventional solid–state reaction method and the correlation of phase structure, piezoelectric, ferroelectric properties and electrocaloric effect (ECE) was investigated in detail. The ECE in lead–free BNT–BT–xSBT ceramics was measured directly using a home–made adiabatic calorimeter with maximum adiabatic temperature change ΔT = 0.4 K with x = 0.08 under the electric field E = 6 kV/mm at room temperature. The position of maximum ECE was found in the vicinity of nonergodic and ergodic phase boundary, where the maximum change in entropy occurs as a result of the field–induced phase transformation between the ergodic and long–range ferroelectric phase. Besides, the mechanism for the shift of ECE peak is discussed in detail. Finally, the temperature dependence of ECE for BNT–BT–xSBT (x = 0, 0.04 and 0.08) was also investigated. This work may present a guideline for designing BNT–based ferroelectric relaxor ceramics for EC cooling technologies.     

Microstructural evolution and electric properties of mechanically activated BaTiO3 ceramics

Ceramic materials with a perovskite related structures such as non-doped and doped barium titanate ceramics are attracting much interest for their application as capacitor dielectrics, resistors, thermal sensors, etc. Since mechanical activation can be used in order to modify properties of these materials, in this study microstructure evolution and electric properties of mechanically activated BaTiO₃ have been analyzed. The sintering process of high purity non-doped mechanically activated BaTiO₃ was monitored using a sensitive dilatometer with a heating rate of 10 °C/min. Investigation of the microstructure evolution of mechanically activated BaTiO₃ was performed using scanning electron microscope (SEM) and digital pattern recognition (DPR) methods. A dielectric study of the paraelectric–ferroelectric phase transition in the barium titanate ceramics was performed by recording the temperature dependence of dielectric permittivity.     

Enhanced energy storage properties in La(Mg1/2Ti1/2)O3-modified BiFeO3-BaTiO3 lead-free relaxor ferroelectric ceramics within a wide temperature range

A new ternary lead-free (0.67-x)BiFeO₃-0.33BaTiO₃-xLa(Mg_1/2Ti_1/2)O₃ ferroelectric ceramic exhibited an obvious evolution of dielectric relaxation behavior. A significantly enhanced energy-storage property was observed at room temperature, showing a good energy-storage density of 1.66 J/cm³ at 13 kV/mm and a relatively high energy-storage efficiency of 82% at x = 0.06. This was basically ascribed to the formation of a slim polarization-electric field hysteresis loop, in which a high saturated polarization P_max and a rather small remnant polarization P_r were simultaneously obtained. Particularly, its energy storage properties were found to depend weakly on frequency (0.2 Hz–100 Hz), and also to exhibit a good stability against temperature (25 °C–180 °C). The achievement of these characteristics was attributed to both a rapid response of the electric field induced reversible ergodic relaxor to long-range ferroelectric phase transition and a typical diffuse phase transformation process in the dielectric maxima.     

Preparation of multiferroic composites of BaTiO3–Ni0.5Zn0.5Fe2O4 ceramics

Magneto-electric coupling in ceramic composites formed by ferroelectric and ferromagnetic phases can be obtained via an adequate mechanical coupling between the individual piezoelectric and magnetostrictive phases (product property). In the present work, the possibility of forming diphase ferroelectric–ferromagnetic ceramics has been investigated. Composites of xBaTiO₃–(1 − x)Ni_0.5Zn_0.5Fe₂O₄ with x = 0.5, 0.6 and 0.7 were prepared according two different procedures: (i) by direct mixing powders of perovskite BaTiO₃ and Ni_0.5Zn_0.5Fe₂O₄ spinel prepared by solid state and (ii) by coprecipitating Fe^III–Ni^II–Zn^II nitric salts in a NaOH solution in which the BaTiO₃ powders were previously dispersed. Optimum processing parameters for good homogeneity, densification and for a reduction of the chemical reactions at the interfaces ferroelectric-ferrite were found. A temperature and composition-dependent magnetic order is present in all the composites, with a dilution effect of the magnetisation due to the presence of the non-ferromagnetic phase. A diffuse ferroelectric–paraelectric transition due to the BaTiO₃ phase was identified by the temperature-dependence of the permittivity and losses, showing that at room temperature the material preserves a ferroelectric order. The interfaces play important roles in the dielectric properties, causing space charge effects and Maxwell–Wagner relaxation, particularly at low frequencies and high temperatures. The combined ferroelectric and magnetic ordering will result in magneto-electric coupling in this material; further investigations are necessary.     

Ferroelectromagnetic characteristic of Na-doped 0.75BiFeO3–0.25BaTiO3 multiferroic ceramics

BiFeO₃-based materials are expected to have both ferroelectricity and ferromagnetism simultaneously. In this study, effects of Na-doping (0.5, 1.0, 3.0, and 5.0 mol%) on ferromagnetic and ferroelectric properties of 0.75BiFeO₃–0.25BaTiO₃ ceramics which have been fabricated by the solid state reaction technique are studied. The effects of Na-doped 0.75BiFeO₃–0.25BaTiO₃ ceramics on the crystal structure, and magnetic and electrical properties were investigated and discussed. Rhombohedrally distorted 0.75BiFeO₃–0.25BaTiO₃ showed weak ferromagnetic and ferroelectric properties. In addition, ferroelectric and ferromagnetic properties of 0.75BiFeO₃–0.25BaTiO₃ have been controlled by Na doping, and the maximum values of magnetization and polarization were observed at 5.0 mol%.     

Synthesis and characterization of electroceramics with magnetoelectric properties

Electroceramics with ferropiezoelectric and ferri-ferromagnetic properties have been studied. These ceramics consist of two phases, a ferroelectric one (commercial BaTiO₃) and a ferromagnetic one (MFe₂O₄, with M = Ni, Zn, Co, obtained through co-precipitation methods), which are later mixed using mechanical milling. A characterization of the previous phases is made by means of electronic microscopy and X-ray diffraction. The results of the magnetic, electric, ferroelectric and piezoelectrical response of the different compound compositions are obtained. The coexistence of phases is made clear, with a greater magnetic response in the samples of ferrite with Co and a greater piezoelectric in the samples of ferrite with Ni. These results are analysed, and the potential of the use of different mixtures is discussed.     

Synthesis and properties of multiferroic 0.7BiFeO3−0.3BaTiO3 thin films by Mn doping

Multiferroic BiFeO₃?BaTiO₃ thin films that simultaneously exhibit ferroelectricity and ferromagnetism at room temperature were prepared by chemical solution deposition. Perovskite single-phase 0.7BiFeO₃?0.3BaTiO₃ thin films were successfully fabricated in the temperature range 600–700 °C on Pt/TiO_x/SiO₂/Si substrates. As the crystallization temperature was increased, grain growth proceeded, resulting in higher crystallinity at 700 °C. Although the 0.7BiFeO₃?0.3BaTiO₃ thin films exhibited poor polarization (P)?electric field (E) hysteresis loops owing to their low insulating resistance. The leakage current at high applied fields was effectively reduced by Mn doping at the Fe site of the 0.7BiFeO₃?0.3BaTiO₃ thin films, leading to improved ferroelectric properties. The 5 mol% Mn-doped 0.7BiFeO₃?0.3BaTiO₃ thin films simultaneously exhibited ferroelectric polarization and ferromagnetic magnetization hysteresis loops at room temperature.     

Effect of plasma sprayed and laser re-melted Al2O3 coatings on hardness and wear properties of stainless steel

Commercially available austenic stainless steel substrate was coated with commercially available, raw Al₂O₃ powder applied by means of plasma spraying method and then re-melted with CO₂ laser beam of various parameters. Tribological and mechanical properties of the 120 J/mm and 160 J/mm laser re-melted coatings were compared with the tribological and mechanical properties of the “as-sprayed” coating. The influence of the laser beam of various parameters on the microstructure, phase constituents, and mechanical and tribological properties of the ceramic coating was investigated by means of scanning electron microscopy, light microscopy, computer tomography, X-ray diffraction technique and nanoindentation tests. The micro sliding wear performance of the coatings was tested using a nanoindenter. The study showed an improvement of the mechanical and tribological properties caused by the laser treatment. The best results were achieved for coating re-melted with 120 J/mm laser beam.     

Effect of Ti particle size on mechanical and tribological properties of TiCN coatings prepared by reactive plasma spraying

Titanium carbonitride (TiCN) coatings were successfully fabricated by reactive plasma spraying (RPS) from agglomerated Ti-graphite feedstock. The effect of Ti particle size on the microstructure and phase composition of plasma sprayed TiCN coatings was investigated. The Vickers microhardness of coatings was measured by a Microhardness Test and the corresponding Weibull distribution were also analyzed. In addition, a pin-on-disk tribometer was employed to determine the trobological properties of coatings. Results show that all the coatings consist of TiC_xN_1−x (0 ≤ x ≤1) and minor Ti₂O phases, and the amount of Ti₂O increases with the increase of Ti particle size. The Weibull distribution of Vickers microhardness of all the coatings shows apparent scattering, while the coating sprayed with Ti particle size of 28 µm exhibits a relatively even distribution. Compared with the coating sprayed with Ti particle size of 14 µm or 48 µm, the coating sprayed with Ti particle size of 28 µm exhibits improved mechanical and tribological properties, which are attributed to the high microhardness and strong bonding strength.     

Structure–property relations of ferroelectric BaTiO3 ceramics containing nano-sized Si3N4 particulates

Barium titanate/silicon nitride (BaTiO₃/xSi₃N₄) powder (when x = 0, 0.1, 0.5, 1 and 3 wt%) were prepared by solid-state mixed-oxide method and sintered at 1400 °C for 2 h. X-ray diffraction result suggested that tetragonality (c/a) of the BaTiO₃/xSi₃N₄ ceramics increased with increasing content of Si₃N₄. Density and grain size of BaTiO₃/xSi₃N₄ ceramic were found to increase for small addition (i.e. 0.1 and 0.5 wt%) of Si₃N₄ mainly due to the presence of liquid phase during sintering. BaTiO₃ ceramics containing such amount of Si₃N₄ also showed improved dielectric and ferroelectric properties.     

Microstructure effects on BaTiO3/BaTi0.8Zr0.2O3 composites properties

The dielectric, pyroelectric and ferroelectric properties of bilayered BaTiO₃/BaTi_0.8Zr_0.2O₃ ceramics are described and correlated with their microstructure. Different sintering times are employed to change the microstructure and promote interdiffusion between the layers. The effects of constrained sintering on both compositions are analyzed and their properties are compared to that of single phase BaTiO₃ and BaTi_0.8Zr_0.2O₃ ceramics. The results show that, at sintering times until 2 h, the bilayer properties are predominantly affected by the presence of residual stresses. Only after 4 h sintering, the properties are predominantly affected by interdiffusion between the layers.     

Magnetic and ferroelectric domain structures in BaTiO3–(Ni0.5Zn0.5)Fe2O4 multiferroic ceramics

BaTiO₃–(Ni_0.5Zn_0.5)Fe₂O₄ composites prepared by co-precipitation were investigated. The macroscopic magnetic properties derived from the magnetic phase (low coercivity, almost no M(H) hysteretic behavior and high permeability) are preserved in the composite. The dielectric properties are strongly influenced by interface phenomena (Maxwell-Wagner), due to the local electrical inhomogeneity. At low frequencies, the composites present thermally activated conductivity and relaxation, while at 1 MHz permittivity of around 500 and tan δ < 8% is obtained at room temperature. The multiferroic character was demonstrated at nanoscale by the presence of the magnetic and ferroelectric domain structure in the same region. Imprint polarisation in the regions corresponding to the ferroelectric phase is found, as result of an internal electrical field created at the interfaces between the (Ni,Zn)-ferrite and BaTiO₃ regions.     

Phase stabilization in plasma sprayed BaTiO3

This paper presents a comparison of properties of BaTiO₃ ceramics prepared by two different production methods: gas-stabilized plasma spraying (GSP) and spark plasma sintering (SPS). Samples of both materials were evaluated by various techniques, the goal being to detect the Curie temperature of the ferroelectric transformation between the tetragonal and the cubic phase. All tests, resonant ultrasound spectroscopy, dielectric measurements, differential scanning calorimetry and temperature-resolved X-ray diffraction (XRD), used in combination, proved the absence of this transformation in the case of GSP coating up to 500 °C. Similarly, the tetragonal-to-orthorhombic transition temperature is shifted downwards, this transition probably taking place in a small fraction of the volume of coating. The SPS samples exhibit several anomalies, such as a strong anisotropy of relative permittivity, but their phase transformations were detected in the usual temperature ranges.     

Synthesis,spray granulation and plasma spray coating of lanthanum phosphate nanorods for thermal insulation coatings

Nanorods of lanthanum phosphate obtained by a wet chemical precipitation route were granulated to obtain sizes in the range of 10–15 µm by spray drying from aqueous slurry of 35 wt% solid loading and 2 wt% of PVA binder. The powders thus obtained displayed enhanced flowability and were plasma sprayed on to stainless steel substrates resulting in the formation of adherent coatings of 150–180 µm thickness. These coatings were characterized using electron microscopy, X-ray diffraction analysis and Raman spectroscopy. X-ray analysis indicated phase instability of LaPO₄ during plasma spraying resulting in the formation of oxy and polyphosphates of lanthanum (La₂P₄O₁₃ and La₃PO₇). However, post deposition heat treatment of coated samples at 1100 °C for 2 h resulted in the reversible formation of stoichiometric lanthanum orthophosphate (LaPO₄). Raman spectral analysis was used to confirm the phase structure of the coatings deposited at various plasma input powers. The coatings obtained were found to effectively lower the thermal conductivity of the substrates from ~24 W/mK to less than 19 W/mK (~10%) even at 200 °C.     

Microstructure and electrical properties of relaxor (1 − x)[(K0.5Na0.5)0.95Li0.05](Nb0.95Sb0.05)O3–xBaTiO3 piezoelectric ceramics

In order to solve the low temperature stability of electrical properties in KNN-based ceramics, (1 ? x)[(K_0.5Na_0.5)_0.95Li_0.05](Nb_0.95Sb_0.05)O₃–xBaTiO₃ [(1 ? x)KNLNS–xBT] lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. The introduction of BT stabilizes the tetragonal phase of KNLNS ceramics at room temperature, results in a typical ferroelectric relaxor behavior, and shifts the polymorphic phase transition to below room temperature. Moreover, there is a strong BaTiO₃ concentration dependence of relaxor behavior and electrical properties, and the ceramic with x = 0.005 exhibits optimum electrical properties and typical relaxor behavior (d₃₃ = 269 pC/N, k_p = 0.50, ?_r = 1371, tan δ = 0.03, T_C ～ 349 °C and γ = 1.88024). These results indicate that the BT is an effective way to improve the temperature stability as well as the electrical properties of KNN-based ceramics.