Synthesis and characterization of A-site deficient rare-earth doped BaZrxTi1−xO3 perovskite-type compounds

A-site deficient rare-earth doped BaZr_xTi_1?xO₃ (BZT) ceramics were prepared from a soft-chemistry route and by solid-state reaction (SSR). Perovskite-like single-phase diagrams for the BaTiO₃–La_2/3TiO₃–BaZrO₃ system were constructed for each method of synthesis. Infrared spectroscopy on (Ba_1?yLa_2y/3)Zr_xTi_1?xO₃ solid solution revealed a dramatic stress on the M–O (M = Ti, Zr) bonds due to the combined effect of A-site vacancies and the lower ionic radius of La³⁺ than that of Ba²⁺. A relationship between the M–O stretching vibration (υ) and the tolerance factor (t) was determined. (Ba_1?yLn_2y/3)Zr_0.09Ti_0.91O₃ (Ln = La, Pr, Nd) samples synthesized by SSR were selected for detailed studies. X-ray diffraction data were refined by the Rietveld method. Scanning electron microscopy on sintered compacts detected abnormal crystal growth and grain sizes in the range of about 1 μm up to 10 μm when the dopant concentration is 6.7 at. %. Impedance measurements exhibited that ferroelectric to paraelectric phase-transition temperature shifted to lower values as increasing rare-earth content. (Ba_1?yLn_2y/3)Zr_0.09Ti_0.91O₃ system showed a diffuse phase transition with a relaxor-like ferroelectric behaviour. Furthermore, the dielectric constant was enhanced with respect to non-doped BZT system.     

Room temperature photoluminescence of amorphous BaxSr1−xTiO3 doped with chromium

ABO₃ amorphous materials, such as BaTiO₃ (BT), SrTiO₃ (ST), PbTiO₃ (PT), and Ba_xSr_1−xTiO₃ (BST) have recently attracted a good deal of attention due to their ferroelectric and electro-optical properties. Intense photoluminescence at room temperature was observed in amorphous titanate doped with chromium (Ba_xSr_1−xTi_1−yCr_yO₃) prepared by the polymeric precursor method. Results indicated that substantial luminescence at room temperature was achieved with the addition of small Cr contents to amorphous Ba_xSr_1−xTi_1−yCr_yO₃. Further addition of Cr or crystallization were deleterious to the intensity of the luminescent peak obtained for excitation using λ=488.0 nm.     

Luminescent and structural properties of the series Ba6−xEuxTi2+xTa8−xO30 and Ba4−yKyEu2Ti4−yTa6+yO30

The series Ba_6−xEu_xTi_2+xTa_8−xO₃₀ and Ba_4−yK_yEu₂Ti_4−yTa_6+yO₃₀ have been synthesized at 1400°C in air. They exhibit efficient excitation at about 400 nm and typical emission of Eu³⁺ at about 580-620 nm, form solid solutions within 0.0?x?2.0 and 0?y?4 respectively, and crystallized in P4/mbm at room temperature with Eu atoms occupied at centrosymmetric site (0, 0, 0). Their conductivity is very low (2.8×10⁻⁶ Ω⁻¹ cm⁻¹ at 740°C for Ba₆Ti₂Ta₈O₃₀).     

Electrical,dielectric and pyroelectric behavior of neodymium substituted barium zirconium titanate

Neodymium (Nd) substituted barium zirconium titanate with nominal composition (Ba_1−xNd_x)(Zr_0.52Ti_0.48)O₃ [x = 0.1, and 0.2] were synthesized using solid state reaction method. X-ray analysis confirmed the formation of perovskite structure along with minor pyroclore phase of neodymium. The change in grain size revealed the influence of Nd-ions on the microstructure. The sintered samples exhibited negative temperature coefficient of resistance (NTCR) and superior semiconducting behavior. Addition of Nd³⁺varies the room temperature resistivity of Ba(Zr_0.52Ti_0.48)O₃. As the concentration of Nd-ion increased, the value of temperature dependent dielectric constant decreased whereas the Curie temperature of the ceramics shifted toward higher temperature side showing diffuse phase transition. This is attributed to decrease in average grain size. Temperature dependent pyroelectric current exhibited combination of primary and secondary pyroelectric effect.     

Strain correlated effect on structural,magnetic, and dielectric properties in Ti4+ substituted Bi0.8Ba0.2Fe1−xTixO3

Ti⁴⁺ substituted Bi_0.8Ba_0.2Fe_1−xTi_xO₃ for x = 0.0, 0.1 and 0.2 are prepared by modified solid state reaction method. The prepared samples sintered at 850 °C for 1 h show a single phase nature. A structural change was observed on Ti⁴⁺ substitutions are confirmed through X-ray Diffraction, Fourier Transform Infrared spectroscopy and Raman spectra. An anomalous phase transition is observed in Bi_0.8Ba_0.2FeO₃ at 1173 K. The absence of ferroelectric transition and enhancement of decomposition temperature is observed in the substituted samples from the thermal analysis. A dielectric spectroscopic measurement shows that on Ti⁴⁺ substitutions, the magnitude of dielectric constant and loss tangent (tan δ) value is decreased. Vibrating Sample Magnetometer (VSM) study shows both antiferromagnetic and ferromagnetic phases coexist in the M−H curve. On Ti⁴⁺ substitutions in Bi_0.8Ba_0.2FeO₃, the antiferromagnetism dominates over the ferromagnetic phase. In corroboration to magnetisation process, ZFC–FC measurement confirms it that on Ti⁴⁺ substitution, the antiferromagnetic behaviour gets dominated. The report suggests that the interplay of strain upon Ti⁴⁺ substitution causes the structural and magnetic phase transition.     

Structural Characterization of the Complex Perovskites Ba1−xLaxTi1−xCrxO3

The series Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤1) was synthesized at 1400°C for about 60 h. Their structure was carefully analyzed by the use of powder X-ray diffraction and Rietveld analysis software GSAS (General Structure Analysis System). Four solid solutions are found in this series: tetragonal solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤0.029), cubic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.0365≤x≤0.600), rhombohedral solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.700≤x≤0.873), and orthorhombic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.956≤x≤1). There are corresponding two-phase regions between the adjacent two solid solutions. The detailed lattice parameters are presented. The relationship between the lattice parameters and the composition of the solid solutions is developed.     

Synthèse et stabilité sous irradiation électronique d'une céramique Ba1,16Al2,32Ti5,68O16 de structure hollandite envisagée pour le confinement de césium radioactif

Synthesis and stability under electron irradiation of a hollandite structure-type Ba_1.16Al_2.32Ti_5.68O₁₆ ceramic envisaged for radioactive cesium immobilization. Hollandite structure-type Ba_xCs_y(M,Ti)₈O₁₆ (x + y < 2, M trivalent cation) ceramics are currently envisaged as a specific waste form for radioactive cesium immobilization. In order to simulate the effect of cesium β decay on this kind of matrix, the structural modifications and the paramagnetic point defects induced by external electron irradiations near room temperature in a simplified Ba_1.16Al_2.32Ti_5.68O₁₆ hollandite composition were studied mainly by EPR and NMR. Modifications of Al³⁺ and Ti⁴⁺ ions' environment were observed and are due to both the formation of oxygen vacancies and to barium ions displacement. Electron (Ti³⁺) and hole (O₂⁻) centres were observed. The stability of these centres was good at room temperature but thermal treatments performed between 50 and 850 °C generated new paramagnetic defects originating from previous defects. These new defects correspond to titanyl-type Ti³⁺ ions located on grain surface and to oxygen aggregates in their bulk.     

Hydrothermal synthesis, structure and property of nano-BaTiO3-based dielectric materials

A series of Ba_1-xSr_xTi_1-yZr_yO₃ (0≤x≤0.5, 0≤y≤0.4) and BA_1?xZn_xTi_1?ySn_yO₃ (0≤x≤0.3, 0≤y≤0.3) solid solutions were synthesized by low-temperature/low-pressure hydrothermal method below 170°C, 0.8 MPa. XRD pattern and cell parameters-composition figures of these prepared powders demonstrated that they are completely miscible solid solutions based on BaTiO₃. Furthermore, TEM showed that they have a shape of uniform, substantially spherical particles with an average particle size of 70 nm in diameter. The sintered ceramics of those powders doped by Sr²⁺ and Zr⁴⁺ or Zn²⁺ and Sn⁴⁺ have dielectric constant twelve times higher than and dielectric loss 1/6 those of pure BaTiO₃ phase at room temperature.     

Crystal structure and electrical conductivity of lanthanum-calcium chromites-titanates La1−xCaxCr1−yTiyO3−δ (x=0-1, y=0-1)

Five series of perovskite-type compounds in the system La_1−xCa_xCr_1−yTi_yO₃ with the nominal compositions y=0, x=0-0.5; y=0.2, x=0.2-0.8; y=0.5, x=0.5-1.0; y=0.8, x=0.6-1.0 and y=1, x=0.8-1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)?1, the phase diagram of the CaTiO₃-LaCr^IIIO₃-CaCr^IVO₃ quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCr^IVO₃-CaTiO₃-LaCr^IIIO₃. The solid solution La_{(1−x′−y)}Ca_(x′+y)Cr^IV_x′Cr^III_{(1−x′−y)}Ti_yO₃ exists by up to 0.6-0.7 mol fractions of CaCr^IVO₃ (x^′<0.6-0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La_0.1Ca_0.9TiO₃, La_0.2Ca_0.8TiO₃, La_0.4Ca_0.6Cr_0.2Ti_0.8O₃ and La_0.3Ca_0.7Cr_0.2Ti_0.8O₃ in the system La_1−xCa_xCr_1−yTi_yO₃ were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO₂=6×10⁻¹⁶-0.21×10⁵ Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10⁻¹⁵-0.21×10⁵ Pa, the compounds with x>y (acceptor doped) are p-type semiconductors and those with x<y (donor doped) and x=y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite structures: [Cr³⁺]/[Cr⁴⁺] and [Ti⁴⁺]/[Ti³⁺]. The maximum electrical conductivity at 900 °C and pO₂=10⁻¹⁵ Pa was found for the composition La_0.1Ca_0.9TiO₃ (near 50 S/cm) and in air at 900 °C for La_0.5Ca_0.5CrO₃ (close to 100 S/cm).     

Powderless processing of ceramics: Thin-layer electroceramics

A review is made of progress on the sol-gel processing of dense insulating electroceramics by polymeric condensation routes. Up until the past ten years, powders and porous coatings were principally made for optical and conductive applications. Much effort was expended on silica (SiO₂) and silicate-based systems. Recently, these approaches have been extended to non-silicate systems [1]. In this paper information is presented for the powderless processing of selected electroceramics in thin-layer form. Materials include PbTiO₃, BaTiO₃, Ba_1–x Pb _x TiO₃, PbZrO₃, Pb(Zr_1–y Ti _y )O₃ and (Pb_1–x La _x )(Zr_1–y Ti _y )O₃ which find applications in ceramic capacitors, piezoelectric transducers and electrooptic modulators. The approach is to avoid powders, and the attendent problems of powder handling, flow, packing, etc., and make use of polymerization condensation reactions to form extended networks with chemical linkage. Data are reported for the synthesis and low temperature processing routes for amorphous and polycrystalline ceramics.     

Structural,optical and dielectric relaxor properties of neodymium doped cubic perovskite (Ba1−xNd2x/3)(Zr0.3Ti0.7)O3

Neodymium doped Barium Zirconate Titanate (Ba_1−xNd_2x/3)(Zr_0.3Ti_0.7)O₃ (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were prepared using the solid state reaction route. Structural characterizations of the materials were done by using X-ray diffraction and Raman spectroscopy. XRD study suggested that all the compositions were of single phase cubic perovskite structure with space group Pm-3m while Raman spectra revealed that the replacement of the Ba²⁺ ions by Nd³⁺ ions significantly reduced the intensity of the Raman active modes and shifted them towards higher energy side. Room temperature optical property was analyzed by photoluminescence spectroscopy, which confirmed formation of shallow defects in the band gap. Photoluminescence property was attributed to the presence of polar [TiO₆] distorted clusters in the globally cubic matrix. As a result PL emission spectra of these materials were found to belong to violet–blue regions. Microstructural study of sintered pellets revealed that the grain sizes increase with increase in doping concentration. The temperature dependence of the dielectric properties was investigated in the frequency range 1 kHz to 1 MHz. The broadening in the dielectric constant peak around the phase transition temperature and shifting of the temperature maximum towards higher temperatures with increase in frequency indicated a relaxor type of behavior.     

Hydrothermal synthesis, structure and property of nano-BaTiO3-based dielectric materials

A series of Ba_1-xSr_xTi_1-yZr_yO₃ (0≤x≤0.5, 0≤y≤0.4) and BA_1?xZn_xTi_1?ySn_yO₃ (0≤x≤0.3, 0≤y≤0.3) solid solutions were synthesized by low-temperature/low-pressure hydrothermal method below 170°C, 0.8 MPa. XRD pattern and cell parameters-composition figures of these prepared powders demonstrated that they are completely miscible solid solutions based on BaTiO₃. Furthermore, TEM showed that they have a shape of uniform, substantially spherical particles with an average particle size of 70 nm in diameter. The sintered ceramics of those powders doped by Sr²⁺ and Zr⁴⁺ or Zn²⁺ and Sn⁴⁺ have dielectric constant twelve times higher than and dielectric loss 1/6 those of pure BaTiO₃ phase at room temperature.     

Siliconization of titanium oxycarbides by silicon monoxide

Siliconization of titanium oxycarbides TiC _x O _y by gaseous SiO at 1350°C was studied. The reaction source of SiO was a powder mixture of silicon and silicon dioxide. It was found that the main siliconization product is Ti₅Si₃ and the siliconization of high-carbon (x > 0.70) oxycarbides also gives Ti₃SiC₂ and TiSi₂.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

O NMR studies of local structure and phase evolution for materials in the Y2Ti2O7-ZrTiO4 binary system

¹⁷O MAS NMR and XRD studies of precursor-derived Y_1.6Zr_0.4Ti₂O_7.2 and Y_1.2Zr_0.8Ti₂O_7.4 have been performed to investigate the development of local and long-range order in these materials as they evolve from a metastable amorphous state upon heating. Zirconium titanate (ZrTiO₄) was also investigated to help interpret the ¹⁷O NMR spectra of the ternary compositions. Consistent with earlier studies, crystallization was observed at 800 °C to form a fluorite structure and a small amount of rutile; weak broad reflections were also observed which were ascribed to the presence of small pyrochlore-like ordered domains or particles within the fluorite phase. As the temperature was increased further, the sizes of these domains grew along with the concentration of rutile. At the highest temperature studied (1300 °C), the reflections of the thermodynamic phases, pyrochlore and zirconium titanate (ZrTiO₄), dominated the XRD pattern. The ¹⁷O NMR spectra revealed a series of different peaks that were assigned to different 3- and 4-coordinate O local environments. The data were consistent with the formation of a metastable phase Y_2−xZr_xTi_2−yZr_yO_7+x with pyrochlore-like ordering but with Zr substitution on both cation sites of the pyrochlore structure. At low temperatures, doping on the A (Y³⁺) sites predominates (i.e., x>y), consistent with the fact that the pyrochlore develops out of a more disordered fluorite-like, phase. As the temperature is raised, the Zr doping on the A site decreases and the metastable phase at this temperature can now be written as Y_2−x′Zr_x′Ti_2−y′Zr_y′O_7+x′ (i.e., x′<y′); TiO₂ is also observed, consistent with this suggestion. At high temperatures, doping on the B site decreases and the resonances due to the stoichiometric pyrochlore yttrium titanate (Y₂Ti₂O₇) dominate the NMR spectra. Weaker ¹⁷O NMR resonances due zirconium titanate (ZrTiO₄) are also observed.     

Oxygen nonstoichiometry and defect structure analysis of B-site mixed perovskite-type oxide (La, Sr)(Cr, M)O3−δ (M=Ti, Mn and Fe)

The defect chemical relationships in various B-site mixed LaCrO₃-based ceramics were investigated by means of high-temperature gravimetry. The nonstoichiometric deviation, δ, in (La_0.7Sr_0.3)(Cr_1−yTi_y)O_3−δ (y=0.1, 0.2 and 0.3) (LSCT)_, (La_0.75Sr_0.25)(Cr_0.5Mn_0.5)O_3−δ (LSCM) and (La_0.75Sr_0.25)(Cr_0.5Fe_0.5)O_3−δ (LSCF) were measured as a function of oxygen partial pressure, P_O2, at temperatures between 973 and 1373 K.The effects of partial replacement of the donor on Cr-sites were examined in LSCT. In LSCM and LSCF, effects of the partial substitution of isovalent transition metals on Cr-sites are discussed. Oxygen nonstoichiometries of various B-site mixed LaCrO₃-based ceramics were compared with those of A-site substituted perovskite-type oxides, (La_1−xSr_x)MO_3−δ (where x=0-0.3, M=Cr, Mn and Fe). The partial substitution of the different elements on Cr-sites drastically changed the P_O2 and temperature dependence of oxygen vacancy formation in LaCrO₃-based ceramics. The defect equilibrium relationships of the localized electron well explained the oxygen vacancy formation in B-site mixed LaCrO₃-based ceramics. Oxygen vacancy formation in (La_0.7Sr_0.3)(Cr_1−yTi_y)O_3−δ (y=0.1 and 0.2) and (La_0.7Sr_0.3)(Cr_0.7Ti_0.3)O_3−δ was explained by redox reaction of Cr and Ti ions, respectively. The defect equilibrium relationships of LSCM and LSCF were interpreted by redox reaction of Mn ions and Fe ions, respectively. No significant change in valence state of Cr³⁺ ions in LSCM and LSCF was confirmed under the experimental conditions.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Room-temperature synthesis and conductivity of the pyrochlore type Dy2(Ti1−yZry)2O7 (0?y?1) solid solution

Different compositions in a solid solution of general formula Dy₂(Ti_1−yZr_y)₂O₇, showing high oxygen ion conductivity, have been successfully prepared at room temperature via mechanochemical synthesis. Stoichiometric mixtures of the constituent oxides were dry milled together in a planetary ball mill by using zirconia vials and balls. Chemical changes in the powder mixtures as a function of composition and milling time were followed by X-ray diffraction and revealed that, in all cases and after milling for 19 h, the powder mixtures consisted of a single phase. Electrical properties were measured on sintered pellets as a function of frequency, temperature and zirconium content, revealing an increase in conductivity of more than one order of magnitude for y?0.4, which, as observed in the similar Y₂(Ti_1−yZr_y)₂O₇, has been related with the onset of disordering of the anion sublattice. Despite increasing structural disorder with increasing Zr content, conductivity remains almost constant for y>0.6, reaching a maximum value of ∼5×10⁻³ for Dy₂Zr₂O₇ at 900 °C.     

Sur le système BaFeO3−xBi2O3

Investigations, in this system, are limited to the region $\text{0 <}\text{Bi}\text{Ba}\text{< 0.7}$. The oxygen pressure is applied up to 200 bar. The phase diagram results from chemical analysis and X rays diffraction. A perovskite phase is formed with a composition (Ba_1?yBi_y)_A (Fe_1?yBi_y)_BO_3?x. The change of electrical and magnetic properties depends chiefly on the average oxidation number. The dielectric constant is rather high, but with an important angle loss.     

Structural Study of Li1+x−yNb1−x−3yTix+4yO3 Solid Solutions

The structures of Li_1+x−yNb_1−x−3yTi_x+4yO₃ solid solutions within the so-called M-phase field in the Li₂O-Nb₂O₅-TiO₂ system were investigated using high-resolution transmission electron, microscope (HRTEM) and single-crystal X-ray diffraction. The results demonstrated that the phase field is not a solid solution but rather a homologous series of commensurate intergrowth structures with LiNbO₃-type (LN) slabs separated by single [Ti₂O₃]²⁺ corundum-type layers. The thickness of the LN slab decreases with increasing Ti-content from ∼55 to 3 atomic layers in the metastable H-Li₂Ti₃O₇ end-member. The LN slabs accommodate a wide range of Ti⁴⁺/Nb⁵⁺ substitution, and for a given homolog the distribution of Ti and Nb is not uniform across the slab. A single-crystal X-ray diffraction study of a structure composed of nine-layer LN slabs revealed preferential segregation of Ti to the slab surfaces which apparently provides partial compensation for the charge on the adjacent [Ti₂O₃]²⁺ corundum layers. The extra cations in phases with x>0 are accommodated through the formation of Li-rich Li₂MO₃-type layers in the middle of the LN slabs. The fraction of layers with extra cations increases with increasing Ti-content in the structure.