Room-temperature multiferroic properties of Co-doped KNbO3 ceramics

KNb_0.95Co_0.05O₃ (KN–Co) ceramic was prepared via a solid-state reaction method, and the effect of cobalt dopant on the structural, electric, and magnetic properties was studied. The KN–Co ceramic with polycrystalline perovskite structure exhibited ferromagnetic and ferroelectric properties simultaneously at room temperature, and the coupling of them was confirmed by a large magnetocapacitance effect (about 13%) near the Curie temperature. The possible causes for the magnetism and magnetoelectric properties are discussed.     

Electrical conduction and magnetoelectric effect of (x) BaTiO3 + (1−x) Ni0.92Co0.03Cu0.05Fe2O4 composites in ferroelectric rich region

Particulate composites with composition (x)BaTiO₃+(1−x)Ni_0.92Co_0.03Cu_0.05Fe₂O₄ in which x varies as 1, 0.85, 0.70, 0.55 and 0 (in mol%) were prepared by the conventional double sintering ceramic technique. The presence of two phases viz. ferromagnetic (Ni_0.92Co_0.03Cu_0.05Fe₂O₄) and ferroelectric (BaTiO₃) was confirmed by X-ray diffraction analysis. The dc resistivity and thermo-emf measurements were carried out with variation of temperature. The ac conductivity (σ_ac) measurements investigated in the frequency range 100 Hz to 1 MHz conclude that the conduction in these composites is due to small polarons. The variation of dielectric constant and loss tangent with frequency (20 Hz to 1 MHz) was studied. The static magnetoelectric conversion factor, i.e. dc (dE/dH)_H was measured as a function of intensity of applied magnetic field. The changes were observed in electrical properties as well as in magnetoelectric voltage coefficient as the molar ratio of the constituent phases was varied. A maximum value of magnetoelectric conversion factor of 536.06 μV/cm Oe was observed for the composite with 70% BaTiO₃+30% Ni_0.92Co_0.03Cu_0.05Fe₂O₄ at a dc magnetic field of 2.3 K Oe. The maximum magnetoelectric conversion output has been explained in terms of ferrite-ferroelectric content, applied static magnetic field and resistivity.     

KF-doped BaTi<Subscript>2</Subscript>O<Subscript>5</Subscript> ferroelectric ceramics by solid-state reaction of KF and sol–gel-derived BaTi<Subscript>2</Subscript>O<Subscript>5</Subscript> powders

We report KF-doping work on the recently found ferroelectric material BaTi₂O₅. The ceramic samples, Ba_1-xK_xTi₂O_5-xF_x, were synthesized by solid-state reaction of mixed KF and sol–gel-derived BaTi₂O₅ powders at 1150 °C. An almost pure phase was obtained for nominal composition x≤0.097, while electron probe microanalysis indicated that the real incorporated K and F contents were less than half of the nominal values. It was observed that KF-doping is beneficial in enhancing the ceramic density to some extent, which is a key issue in sol–gel-derived BaTi₂O₅ ceramics, due to a possible liquid-phase sintering mechanism through the presence of melted KF at the sintering temperature. Scanning electron microscopy images showed that these porous ceramic samples are composed of sub-micron-sized powder aggregates which, with increasing KF-doping, undergo further agglomeration. Dielectric measurement from room temperature to ∼ 560 °C showed a broad ferroelectric phase transition, with T_C ∼ 430 °C for the undoped sample. As KF-doping increases, T_C decreases, and the magnitude of the dielectric constant maximum also displays a decreasing trend. The strongly reduced dielectric response can be partly understood by regarding the porous ceramic sample as a composite material composed of bulk BaTi₂O₅ and air, where the porosity has a significant influence on the effective dielectric constant. PACS 77.84.-s; 77.84.Dy; 81.20.Fw     

Crossover from ferroelectric to relaxor behavior in BaTi1− x Sn x O3 solid solutions

Dielectric relaxation of BaTi_{1? x} Sn _x O₃ ceramics is investigated by means of dielectric spectroscopy. The gradual crossover from ferroelectric to relaxor behavior is characterized by vanishing of the contribution due to domain walls and appearance of relaxation related to reorientation of polar nanosized regions. Typical behavior of relaxors is observed only in ceramics with x = 0.30, while the compositions with 0.175 ≤ x ≤ 0.25 show coexistence of both ferroelectric and relaxor features. The relaxor properties are supposed to be due to both weak random fields and disorder inherent in pure BaTiO₃.     

X-ray photoelectron spectroscopic investigations on cubic BaTiO3, BaTi0.9Fe0.1O3 and Ba0.9Nd0.1TiO3 systems

X-ray photoelectron spectroscopic (XPS) studies were carried out on wet-chemically synthesized cubic BaTiO₃, Ba_0.9Nd_0.1TiO₃ and BaTi_0.9Fe_0.1O_3−δ powders. The compounds were prepared by hydrothermal and gel to crystallite conversion technique; and phases formed readily at 420 K. The phase purity of the powders was confirmed from X-ray diffractometry. Chemical state and chemical environment of the constituent elements in the compositions were examined by XPS. Ba²⁺ was found to exist in two different chemical environments in these titanates. The Ti 2p_3/2 photoelectron peak in BaTi_0.9Fe_0.1O_3−δ was found to be broadened after Fe³⁺ substitution. Any resolvable broadening was not observed distinctly in the Ti 2p peak for Ba_0.9Nd_0.1TiO₃, unsintered BaTiO₃ and BaTiO₃ annealed in hydrogen (8% H₂ + Ar) at 1000 K. The prevalence of mixed-valent titanium and iron in BaTi_0.9Fe_0.1O_3−δ composition was evident from the XPS results and was further supported by the enhanced electrical conductivity at 298-550 K for BaTi_0.9Fe_0.1O_3−δ in comparison to BaTiO₃ and Ba_0.9Nd_0.1TiO₃. Hydroxyl incorporation was facilitated by substituting Nd³⁺ in Ba-sublattice. The presence of hydroxyls was observed from the broadening of the O 1s peak in XPS studies of the compounds.     

Fe掺杂量对双层复合结构BaTi1-zFezO3+δ-Tb1-xDyxFe2-y中磁电耦合的影响

采用溶胶凝胶方法制备了Fe掺杂钛酸钡多晶系列陶瓷BaTi_1-zFe_zO_3+δ(0.005≤z≤0.02) (BTFO).X射线衍射实验显示,所制备的BTFO的结构仍然为四方相钙钛矿.差热分析表明,该BTFO样品的铁电-顺电转变温度及相变潜热随掺杂量z的增加而下降.将该BTFO极化后与Tb_1-xDy_xF 关键词： 磁电耦合 掺杂效应 掺杂钛酸钡     

X-ray and dielectric characterization of Co doped tetragonal BaTiO3 ceramics

ABSTRACT

The crystal structure modifications of BaTiO₃ induced by cobalt doping were studied. The polycrystalline (1 ? x)BaTiO₃ + xCo₂O₃ samples, with x ≤ 10 wt.%, were prepared by high temperature sintering conventional method. According to X-ray phase and structural characterization, performed by full-profile Rietveld refinement technique, all synthesized samples showed tetragonal symmetry perovskite structure with minor amount of parasitic phases. Pure single-phase composition has been detected only in the low level of doping BaTiO₃. It was indicated that substitution of Co for the Ti sites in the (1 ? x)BaTiO₃ + xCo₂O₃ series led to decrease of tetragonality (c/a) of the BaTiO₃ perovskite structure. This effect almost vanished in the (1 ? x)BaTiO₃ + xCo₂O₃ samples with nominal Co content higher than ～1 wt.%, in which precipitation of parasitic Co-containing phases CoO and Co₂TiO₄ has been observed. Based on the results, the solubility limit of Co in Ti sub-lattice in the (1 ? x)BaTiO₃ + xCo₂O₃ series is estimated as x = 0.75 wt.%.     

Investigation of exchange bias in 0.1MFe2O4/0.9BiFeO3 (M=Co, Cu, Ni) nanocomposite

The 0.1MFe₂O₄/0.9BiFeO₃ (M=Co, Cu, Ni) nanocomposite samples were synthesized by the sol-gel method. Phase composition analysis was carried out, which showed that these bulk samples were composed of a ferrimagnetic MFe₂O₄ (M=Co, Cu, Ni) and a ferroelectric antiferromagnet (FEAF) BiFeO₃ phases, respectively. The magnetic properties of all the samples were investigated by measuring their magnetization as a function of temperature and magnetic field. These results indicated that the magnetic hysteresis loops of 0.1CuFe₂O₄/0.9BiFeO₃ sample sintered in air atmosphere at 550 °C for 3 h exhibited a negative shift and an enhanced coercivity at low temperature ascribed to strong exchange coupling between the BiFeO₃ and CuFe₂O₄ grains. However, there were no magnetic hysteresis loops in both the 0.1CoFe₂O₄/0.9BiFeO₃ sample and the 0.1NiFe₂O₄/0.9BiFeO₃ sample. In view of these results, we tend to think the CuFe₂O₄/BiFeO₃ nanocomposite system may be a useful multifunctional material.     

Influence of the concentration in Fe-doped BaTiO3 on magnetoelectric couping of layered composites BaTi1−xFexO3–Tb1−yDyyFe2−z

Perovskites BaTi_1−xFe_xO₃ has been synthesized with the concentration x ranging from 0.01 to 0.02. Their transformation point of ferroelectric to paraelectric and the corresponding latent heat of the phase transformation were observed to decrease with increasing the doping level of Fe³⁺. Bonded layered composites BaTi_1−xFe_xO₃–Tb_1−yDy_yFe_2−z have been fabricated and their magnetoelectric effect has been investigated. The sample containing a layer of perovskite BaTi_0.985Fe_0.015O₃ was found to show the maximum transverse ME voltage coefficient, which is about 1422 mV Oe⁻¹ cm⁻¹ under a magnetic field of 1580 Oe, in these bilayers. Analysis shows that the Fe-doped BaTiO₃ with doping level at about 1.5% should have largest piezoelectric coefficient in these ceramics BaTi_1−xFe_xO₃.     

Ferroelectric relaxor behavior in hafnium doped barium-titanate ceramic

Temperature and frequency dependence of the real (ε′) and imaginary (ε″) parts of the dielectric permitivity of cubic Ba(Ti_0.7Hf_0.3)O₃ ceramic has been studied in the temperature range of 100 K to 350 K at the frequencies 0.1 kHz, 1 kHz, 10 kHz, 100 kHz for the first time. Diffuse phase transition and frequency dispersion is observed in the permittivity-vs-temperature plots. This has been attributed to the occurrence of relaxor ferroelectric behavior. The observed relaxor behavior has been quantitatively characterized based on phenomenological parameters. A comparison with the Zr doped BaTiO₃ has also been presented. For Hf doped samples transmission electron microscopy (TEM) characterization do show the presence of highly disordered microstructure at length scales of few tens of nano-meters.     

单相Bi0.9Ba0.1Fe0.85Mn0.15O3陶瓷中的多铁性

溶胶-凝胶法制备了Bi_0.9Ba_0.1Fe_0.85Mn_0.15O₃陶瓷样品,XRD分析显示其为单相菱方钙钛矿结构,明显的磁滞回线和电滞回线说明其在室温具有弱铁磁性和铁电性,介电常数随外磁场的变化显示双掺样品具有更大的磁容效应. 关键词： 溶胶-凝胶法 多铁材料 磁容效应     

The optimized preparation and electrochemical properties of LiMn1.95Co0.05O4 and Al2O3-coated LiMn1.95Co0.05O4

Cathode material LiMn_1.95Co_0.05O₄ for lithium ion battery was synthesized via solid state reaction, and calcination temperature and time were investigated, respectively. Thermogravimetry (TG) and differential thermal analysis (DTA) measurements were utilized to determine the calcination temperature of precursor sample. The optimized calcination temperature and time are 850 °C and 15 h. The surface of LiMn_1.95Co_0.05O₄ cathode is coated using Al₂O₃ coating materials. The phase structures, surface morphologies, and element types of the prepared LiMn_1.95Co_0.05O₄ and Al₂O₃-coated LiMn_1.95 Co_0.05O₄ were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy spectrum analysis (EDS). The 0.5 wt% Al₂O₃-coated compound exhibited better specific capacity and capacity retention than bare sample. The initial discharge capacity was 140.9 mAh/g and capacity retention was 96.7 % after 10 cycles at 0.1 C. Such enhancements are attributed to the presence of a stable Al₂O₃ layer which acts as the interfacial stabilizer on the surface of LiMn_1.95Co_0.05O₄.     

BaTiO3–ferrite composites with magnetocapacitance and hard/soft magnetic properties

BaTiO₃–ferrite multiphase composites were prepared starting from di-phase mixtures of α-Fe₂O₃ and BaTiO₃ powders. During the sintering step, the formation of small amounts of secondary phases with multifunctional character as BaFe₁₂O₁₉ or Ba₁₂Ti₂₈Fe₁₅O₈₄ was promoted. The resulting multiphase ceramic compounds show interesting dielectric, magnetic and small magnetocapacitance effect at low temperature. The coexistence of different magnetic phases with contrasting coercivities (hard/soft) was detected by the presence of ‘wasp-waisted’ M(H) hysteresis loops and first-order reversal curve analysis. The present approach demonstrates that active materials can be realised by controlling in situ reactions at the interfaces in ferroelectric–magnetic oxide composites.     

Rietveld analysis and multiferroic properties of Fe doped Ba0.95Bi0.05TiO3 ceramics

We report on the structural, magnetic and ferroelectric properties of Fe doped Ba_0.95Bi_0.05TiO₃ (Ba_0.95Bi_0.05Ti_1−yFe_yO₃ (0 ≤ y ≤ 0.1)) ceramics prepared by solid state reaction. Rietveld analysis shows that compounds with y ≤ 0.07 have a single phase-tetragonal structure (space group P4mm), and the tetragonality (c/a) decreases as x increases. Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ ceramic shows ferromagnetic order with a Curie temperature of about 700 K and ferroelectric order at room temperature. These results indicate that the Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ can be useful as a multiferroic material.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

The multiferroic properties of Bi(Fe0.95Co0.05)O3 films

Bi(Fe_0.95Co_0.05)O₃ films were prepared on conductive indium tin oxide (ITO)/glass substrates by chemical solution deposition. Well saturated polarization hysteresis loop has been observed with a remnant polarization value of about 22 μC/cm² at room temperature. Weak ferromagnetism with saturation magnetization of about 3 emu/cm³ was observed at room temperature. The clear observation of both room temperature ferroelectric and ferromagnetic properties suggests the potential multiferroic applications of Bi(Fe_0.95Co_0.05)O₃.     

Sol-gel preparation of selected high temperature proton conductors

The sol-gel preparation of the compounds BaCe_0.8Y_0.2O_2.9 (BCY20), BaCe_0.8Gd_0.2O_2.9 (BCG20), BaTiO₃, BaTi_0.9Y_0.1O_2.95 and BaTi_0.9Er_0.1O_2.95 using the acrylamide route is described. The advantages lie in the short reaction time leading to the gels and the large batch sizes possible. In the case of the titanates there was the additional advantage that one of the starting compounds was metallic Ti powder which was dissolved in H₂O₂ and NH₃. Basically, all 5 compounds could be synthesized phase pure. The cerates were well described by PDF 35-1318 and absorb large quantities of water vapor in TG experiments. The doped titanates were cubic and were well characterized by PDF 31-0174. They only absorb relatively small amounts of water vapor but still may be termed proton conductors.     

Strain-dependent magnetic configurations in manganite-titanate heterostructures probed with soft X-ray techniques

We present a detailed study on the strain-induced magnetic domain structure of a (La,Sr)MnO₃ thin film epitaxially grown on a BaTiO₃ substrate through the use of polarization-dependent X-ray photoemission electron microscopy and X-ray absorption spectroscopy. Angular-dependent measurements allow us to detect vector magnetization on a single-domain scale, and we relate the strain-induced changes in magnetic anisotropy of the ferromagnetic film to the ferroelectric domain structure of the underlying substrate using X-ray magnetic circular and linear dichroism spectro-microscopy. Comparisons to measurements on a nearly strain free film of (La,Sr)MnO₃ grown on a (La,Sr)(Al,Ta)O₃ substrate illustrate that the BaTiO₃ ferroelectric domain structure imprints specific domain sizes and wall orientations in the (La,Sr)MnO₃/BaTiO₃ artificial multiferroic heterostructure. Furthermore, a change of the BaTiO₃ ferroelectric domain structure either with temperature or with applied electric field results in a corresponding change in the (La,Sr)MnO₃ ferromagnetic domain structure, thus showing a possible route to obtain room-temperature electric field control of magnetic anisotropy at the nanoscale.     

Magnetic and dielectric behaviors of Ba0.2Sr0.8Co0.8Fe0.2O3-δ oxide

Ba_0.2Sr_0.8Co_0.8Fe_0.2O_3-δ (BSCFO) ceramic oxide has been synthesized by combined citrate-EDTA complexing method and studied with regard to their structural, magnetic and dielectric properties. It is shown that the compound exhibits perovskite-type cubic structure. It depicts hysteresis loop in presence of magnetic field—indicating its magnetic nature. The dielectric properties of sintered oxide were investigated in temperature range (373-873 K) and frequency (100 kHz-1 MHz).The ferroelectric and ferrimagnetic transition temperatures were found to be around 700 K.     

Effect of thermal treatment on room-temperature ferromagnetism in Co-doped ZnO powders

The Co-doped ZnO powders were synthesized by sol-gel method, and treated at different temperatures (673-873 K) in the presence or absence of NH₃ atmosphere for 0.5 and 2 h, respectively. X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) show that better crystal structure can cause larger ferromagnetism and the second phase (Co₃O₄) is the reason for saturation magnetization decrease of the sample sintered at higher temperature in air. XPS and nuclear magnetic resonance (NMR) prove the existence of Co²⁺ ions in the Zn_0.9Co_0.1O and the absence of Co clusters, indicating intrinsic ferromagnetism of the samples treated in air. However, strong ferromagnetism of the samples annealed in NH₃ is ascribed to cobalt nitride formed during annealing.