Effect of BaTiO<Subscript>3</Subscript> heat treatment on the microstructure and dielectric properties of BaTiO<Subscript>3</Subscript>-based ceramics

We have studied the effect of heat treatment of the starting BaTiO₃ powder on the dielectric properties and microstructure of X7R-type BaTiO₃-based ceramics. The results demonstrate that annealing of BaTiO₃ stabilizes the degree of tetragonality in the crystal lattice of the ceramics. Microstructural analysis shows that the annealing temperature has no effect on the average grain size of the ceramics. Increasing the BaTiO₃ annealing temperature increases the dielectric permittivity of the core phase and reduces the temperature coefficient of capacitance (TCC). We obtained an X7R-type BaTiO₃-based ceramic material (BaTiO₃ annealing temperature, 1150°C; firing temperature, 1160°C) with the following properties: ɛ_25°C = 2230, TCC = ±12% (−55 to 125°C), and tanδ_25°C = 0.013.     

Synthesis and microstructure of SrTiO<Subscript>3</Subscript> and BaTiO<Subscript>3</Subscript> ceramics by a reaction-sintering process

Strontium titanate and barium titanate ceramics prepared by a reaction-sintering process were investigated. The mixture of raw materials of stoichiometric SrTiO₃ and BaTiO₃ was pressed and sintered into ceramics without any calcination stage involved. A density 4.99 g/cm³ (97.5% of the theoretic value) was found in SrTiO₃ after 6 h sintering at 1,370 °C. Grains less than 1.5 μm were formed at 1,300–1,330 °C and became 2.2–3.3 μm at 1,350–1,370 °C SrTiO₃. A density 5.89 g/cm³ (97.9% of the theoretic value) was found in BaTiO₃ after 6 h sintering at 1,400 °C. Merged grains were observed in BaTiO₃ and were less than 10 μm after sintered at 1,400 °C.     

Processing of chemical solution-deposited BaTiO<Subscript>3</Subscript>-based thin films on Ni foils

BaTiO₃ films on base metal foils are of interest for capacitor applications, but the processing requires reducing atmospheres that influence the film defect chemistry and density. In this study, powders dried from barium titanate solutions and barium titanate films were studied by X-ray diffraction, differential scanning calorimetry, thermal gravimetric analysis, infrared spectroscopy, and spectroscopic ellipsometry at various points in the processing. It was found that atmospheres designed to minimize Ni oxidation delay decomposition of organics, leading to retained carbonate phases. Thus, crystallization of the barium titanate occurs via decomposition of a barium carbonate phase. Retained organics that are present during high temperature processing can cause porosity in the films. On annealing at 1000 °C, there is slightly increase in the refractive index of the film due to further crystallization and densification. The final refractive index is comparable to that of 95% dense barium titanate ceramics. Re-oxidation did not change the refractive index of the film over the wavelength range from 350 to 650 nm.     

First principles study of three-component SrTiO<Subscript>3</Subscript>/BaTiO<Subscript>3</Subscript>/PbTiO<Subscript>3</Subscript> ferroelectric superlattices

The geometrical, chemical and ferroelectric properties of a new nanoscale short-period three-component SrTiO₃/BaTiO₃/PbTiO₃ perovskite superlattice are investigated using a first principles density functional approach. The study focuses on varying the thickness of each component in the superlattice and determining the resulting lattice distortion and total polarization. Thicknesses of up to three unit cells in a single component are considered and the in-plane lattice constants normal to the [001] stacking direction are fixed to the bulk SrTiO₃ values to simulate a rigid substrate. It is found that the PbTiO₃ layers play a key role in strain and polarization enhancement. By increasing the amount of PbTiO₃ in the superlattices the strain in the other components increases significantly resulting in an enhanced total polarization of the superlattice relative to bulk BaTiO₃. Increasing the number of BaTiO₃ layers also improves the overall polarization. All the SrTiO₃ layers in each superlattice are found to be highly polarized. Many of the calculated features are similar to those found previously by others for the SrTiO₃/BaTiO₃/CaTiO₃ superlattice, although in the present study significantly greater enhancement factors and polarization values are found. The predicted enhancement of the polarization is mostly attributed to lattice strain due to mismatch of the in-plane lattice constant of the three-component materials.     

Mechanochemical synthesis of BaTiO<Subscript>3</Subscript> from barium titanyl oxalate

The effect of mechanochemical processing in air and water on the physicochemical transformations of barium titanyl oxalate has been studied using X-ray diffraction, thermal analysis, FTIR spectroscopy, temperature-programmed argon desorption, and particle size measurements. The results demonstrate that mechanochemical processing of barium titanyl oxalate in air leads to the formation of structurally imperfect barium titanate. During subsequent air calcination at 550°C, this material transforms into well-crystallized cubic BaTiO₃, whereas thermal decomposition of barium titanyl oxalate only yields cubic BaTiO₃ starting at 800°C. Mechanochemical processing in water leads to partial amorphization of barium titanyl oxalate, and conversion of the product to BaTiO₃ requires heat treatment at 700°C. All of the BaTiO₃ samples obtained via mechanochemical processing have a larger specific surface in comparison with samples prepared by conventional calcination of barium titanyl oxalate or other known processes.     

Synthesis and characterization of BaTiO<Subscript>3</Subscript>-based X9R ceramics

The effects of (Na_0.5Bi_0.5)TiO₃ (NBT) and MgO addition on the dielectric properties and microstructures of BaTiO₃ (BT) ceramics were investigated. NBT was first added to Nb₂O₅-doped BT system. As NBT content increases from 0 to 0.2 mol, the Curie temperature of the systems shifts to high temperatures and dielectric constant peak at T _c is suppressed evidently. The variation of capacity (ΔC/C _20 °C (%)) of the system at 200 °C decreases with increasing NBT content from 0.1 to 0.2 mol, but that of −55 and 125 °C increases monotonously. The stable temperature characteristics of the dielectric properties improved by NBT doping would be connected with the distortion and deformation of the structure induced by substitution of Na⁺ and Bi³⁺ into Ba sites. MgO was employed to further flatten the ΔC/C _20 °C–T curve. It is very helpful for this ceramic system to satisfy the requirement of EIA-X9R specification on ΔC/C _20 °C and still keep a satisfied dielectric constant. The addition of MgO improved effectively the temperature stability of the dielectric properties. Changes of the crystalline structure and microstructure induced by MgO doping might contribute to these improvements.     

Effect of wall thickness on the ferroelastic domain size of BaTiO<Subscript>3</Subscript>

Extremely regular self-organized patterns of 90° ferroelastic domains have been reported in free-standing single crystal thin films of ferroelectric BaTiO₃. Lukyanchuk et al. [Phys Rev B 79, 144111 (2009)] have recently shown that the domain size as a function of thickness for such free standing films can be well described assuming that the domains are due to stress caused by a surface tension layer that does not undergo the paraelectric–ferroelectric transition. From the starting point of Lukyanchuk’s model, it is shown here that the “universal” relationship between domain size and domain wall thickness previously observed in ferroelectrics, ferromagnets and multiferroics is also valid for ferroelastic domains. Further analysis of experimental data also shows that the domain wall thickness can vary considerably (an order of magnitude) from sample to sample even for the same material (BaTiO₃), in spite of which the domain size scaling model is still valid, provided that the correct, sample dependent, domain wall thickness is used.     

Ferromagnetism in Fe-doped BaTiO<Subscript>3</Subscript> Ceramics

Polycrystalline samples of BaTi_1?xFe_xO₃ (x = 0.00–0.30) are prepared by solid-state reaction method and their structural and magnetic properties are studied. Detailed investigation of XRD patterns reveal the coexistence of tetragonal (space group P4mm) and hexagonal phases (space group P6 ₃/mmc) for x ≥ 0.1. Magnetic measurements reveal room-temperature ferromagnetism in x = 0.15–0.3 samples, and their ferromagnetic transition temperature increases from 397 K for x = 0.15 to 464 K for x = 0.3. The initial magnetization curves for x = 0.15–0.3 are analyzed in terms of bound magnetic polaron (BMP) model. The analysis of susceptibility data in the paramagnetic region by Curie-Weiss law confirms the ferromagnetic transition for x ≥ 0.15 and the effective magnetic moment systematically increases with increase in Fe concentration.     

Effect of temperature and time on solvothermal synthesis of tetragonal BaTiO<Subscript>3</Subscript>

Tetragonal BaTiO₃ nanoparticles are synthesized via solvothermal route in an ethanol water mixture. Ba(OH)₂·8H₂O is used as Ba precursor and TiO₂ (P25 Degussa ∼25 nm, 30% anatase, 70% rutile) is used as Ti precursor in the Ba : Ti molar ratio 2 : 1. Effect of temperature and time study on solvothermal synthesis of BaTiO₃ revealed that a moderate reaction temperature i.e. 185°C and longer reaction time favour tetragonal phase stabilization. Dissolution–precipitation appears to be the transformation mechanism for the crystallization of BaTiO₃ from particulate TiO₂ precursor.     

BaTiO<Subscript>3</Subscript> and SrBiO<Subscript>2.5</Subscript> two phase system NTC thermistors

BaTiO₃-based materials doped with SrBiO_2.5 only show negative temperature coefficient effect over a wide temperature range. X-ray diffraction analysis displays that major phases present in the sintered bodies were the Ba_0.5Sr_0.5TiO₃ compounds with a cubic structure and the BaBiO₃ compounds with a monoclinic structure. The mean grain size of samples remains unchanged with an increase from 20 to 50 in SrBiO_2.5 content. The values of ρ ₂₅ and B _25/125 constants of thermistors decreased with an increase in SrBiO_2.5 content. The resistivity measured at other temperatures showed basically the same behavior as that at room temperature, irrespective of the measuring temperature.     

Synthesis and Characterization of CoFe<Subscript>2</Subscript><Emphasis Type="Italic">O</Emphasis><Subscript>4</Subscript>/BaTiO<Subscript>3</Subscript> Multiferroic Composites

Three composite modes of CoFe₂ O ₄/BaTiO₃ (CFO/BTO) were created with appropriate stoichiometric proportion. They are nitrate solution of CFO mixed with BTO (SCB), self-propagating precursor of CFO mixed with BTO (PCB), and the made-up CFO mixed with BTO (MCB) separately. The microstructural, ferroelectric, and ferromagnetic properties of SCB, PCB, and MCB bulk composites were investigated. SCB, PCB, and MCB bulk composites with a molar ratio of 2:8 were calcined at 1020, 1120, and 1160 ^°C, respectively. And X-ray diffraction (XRD) analysis showed that they all correspond to the CFO with cubic spinel structure and the BTO with tetragonal perovskite structure. The formation temperature of BTO with hexagonal structure is related to the distance of inter-diffusion and Co ²⁺ concentration in the CFO/BTO bulk composite. The wet chemical routing is of benefit to inhibit the agglomeration of the BTO in the CFO/BTO bulk composite. The maximum polarization of 5.24 μC/cm ² was received in the MCB bulk composite sintered at 1160 ^°C with a molar ratio of 1:9. The maximum saturation magnetization of 31.609 emu/g and the remnant magnetization of 10.336 emu/g were obtained in the MCB bulk composite sintered at 1160 ^°C with a molar ratio of 4:6. The threshold ferromagnetic phase content of percolation which has an effect on the MCB bulk composite is less than 40 mol %.     

Grain-size effects on thermal properties of BaTiO<Subscript>3</Subscript> ceramics

Dense nanocrystalline BaTiO₃ ceramics are successfully prepared by the high pressure assisted sintering. Microstructures are observed by scanning electronic microscopes. The grain sizes are estimated to be about 30 and 150 nm. In comparison, BaTiO₃ ceramics with the grain size of 600 nm and 1.5 μm are fabricated by conventional pressure-less sintering. The thermal properties of BaTiO₃ ceramics with different grain sizes are investigated by differential scanning calorimetry and thermal expansion. The results suggest that the enthalpy values for the tetragonal-cubic transition decreased and the thermal expansion values increased with decreasing grain size. Furthermore, the Curie temperature shifts to lower temperature with decreasing grain size.     

Ultrafine Cr-Doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Prepared by Detonation Synthesis

Data are presented on the phase composition, particle size distribution, EPR, and luminescence of ultrafine chromium-doped alumina powders prepared by detonation synthesis. The largest particles in the powders are shown to consist mainly of a Cr₂O₃ solid solution in α-Al₂O₃. The luminescence spectrum of fine particles shows, in addition to lines characteristic of ruby, extra lines which are tentatively attributed to Cr³⁺ ions incorporated substitutionally into θ-Al₂O₃.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 948–954.Original Russian Text Copyright © 2005 by Lyamkina, Chiganova, Slabko, Vorotynov, Taranova.     

Microstructure and dielectric properties of BaTiO<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-SnO<Subscript>2</Subscript> ceramics

We have studied the effect of codoping with CeO₂ and SnO₂ (2 to 3.5 wt %) on the microstructure and dielectric properties of BaTiO₃. Doping with CeO₂ and SnO₂ inhibits grain growth in BaTiO₃ and enables the fabrication of ceramic materials with a grain size below 1 μm. The temperature coefficient of permittivity of the ceramics increases with CeO₂ + SnO₂ content, firing temperature, and firing time.     

Influence of 3d-elements on dielectric properties of BaTiO<Subscript>3</Subscript> ceramics

The microstructure and dielectric properties of Yb-Mn- and Yb-Ni-substituted BaTiO₃ ceramics are investigated in this paper. Both Yb-Mn- and Yb-Ni-substituted BaTiO₃ ceramics satisfy the X8R specification (−55 ^∘C to 150 ^∘C, Δ C = ±15% or less) for automotive application when CaZrO₃ is incorporated in the formulations. It is found that both Mn and Ni ions can suppress the diffusion of Yb and CaZrO₃ into BaTiO₃ grains, resulting in formation of core-shell structures in the grains. It is found that Mn is more favorable to stabilize the core-shell structure in BaTiO₃ ceramics as compared with Ni.     

Effects of addition of BiFeO<Subscript>3</Subscript> on phase transition and dielectric properties of BaTiO<Subscript>3</Subscript> ceramics

Samples of xBiFeO₃–(1 − x)BaTiO₃ (x = 0, 0.02, 0.04, 0.06, 0.07 and 0.08) were synthesized by solid state reaction technique and sintered in air in the temperature range 1,220–1,280 °C for 4 h. X-ray diffraction data showed that 2–8 mol% BiFeO₃ can dissolve into the lattice of BaTiO₃ and form single perovskite phase. The crystal structure changes from tetragonal to cubic phase at room temperature when 8 mol% of BiFeO₃ was added into BaTiO₃. Scanning electron microscope images indicated that the ceramics have compact and uniform microstructures, and the grain size of the ceramics decreases with the increase of BiFeO₃ content. Dielectric constants were measured as functions of temperatures (25–200 °C). With rising addition of BiFeO₃, the Curie temperature decreases. For the sample with x = 0.08, the phase transition occurred below room temperature. The boundary between tetragonal and cubic phase of the BiFeO₃–BaTiO₃ system at room temperature locates at a composition between 7 and 8 mol% of BiFeO₃. The diffusivity parameter γ for compositions x = 0.02 and x = 0.07 is 1.21 and 1.29, respectively. The relaxor-like behaviour is enhanced by the BiFeO₃ addition.     

Upconversion emission of BaTiO<Subscript>3</Subscript>: Er nanocrystals

Here, we report the dopant concentration and pump-power dependence upconversion emission properties of erbium doped BaTiO₃ nanocrystals derived from sol-emulsion-gel method. Green (550 nm) and red (670 nm) upconversion emissions were observed at room temperature from the ⁴ S _3/2 and ⁴ F _9/2 levels of Er³⁺: BaTiO₃ nanocrystals. It is found that at 850 mW of cw excitation power (at 980 nm) the total luminescence was 17130 Cd/m² for 1000°C heated 0.25 mol% Er-doped BaTiO₃ nanocrystals. It is worthwhile to mention that the unusual power-dependent upconversion luminescence (saturation) is observed at higher dopant concentration (2.5 mol%) and high pump power. Our analysis confirms that the depletion of the excited state is responsible for the relevant fluorescence upconversion. We have again confirmed that a twophoton excited state absorption process occurs for all samples.     

Mechanochemical synthesis of BaTiO<Subscript>3</Subscript> using different forms of TiO<Subscript>2</Subscript>

Reactions between barium oxide and different forms of titanium dioxide during milling in air and subsequent heat treatment have been studied by X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. The results indicate that, when the low-temperature forms of TiO₂ are used, milling produces weakly aggregated barium titanate powders with a large specific surface area.     

Phase component and conductivities of Co-doped BaTiO<Subscript>3</Subscript> thermistors

BaTi_1−x Co _x O_3−δ (0.01 ≤ x ≤ 0.4) ceramics were prepared by a wet chemical process polymerized with polyvinyl alcohol. The phases and related electrical properties of the ceramics were investigated. The phase component of the ceramics changes from a tetragonal phase to a hexagonal one with the Co concentration increase. A pure hexagonal phase formed in the ceramic with x = 0.2. The measurement of the temperature dependence of resistances revealed that the ceramic resistivities increase with temperature rising at the temperatures (T) lower than half of the related Debye temperature (Θ_D), and the ceramics show a negative temperature coefficient (NTC) effect at T > Θ_D/2. The material constants B _50/120 of the BaTi_1−x Co _x O_3−δ NTC thermistors were calculated to be 3,187, 2,968 and 2,648 K for x = 0.2, 0.3 and 0.4, respectively. Narrow-band conduction and non-adiabatic hopping models are proposed for the conduction mechanisms at T < Θ_D/2 and T > Θ_D/2, respectively.